Vous êtes sur la page 1sur 919

PVC PLASTICS

Properties, Processing, and Applications


PVC PLASTICS
Properties, Processing,
and Applications

W. V. TITOW
M.Phil., Ph.D., C.Chem., F.R.S.C., F.P.R.I., C. Text., A. T.I.

ELSEVIER APPLIED SCIENCE


LONDON and NEW YORK
ELSEVIER SCIENCE PUBLISHERS LTD
Crown House, Linton Road, Barking, Essex IGll SJU, England

Sale distributor in the USA and Canada


ELSEVIER SCIENCE PUBLISHING CO., INC.
655 Avenue of the Americas, New York, NY 10010, USA

WITII 120 TABLES AND 149 ILLUSTRATIONS

© 1990 ELSEVIER SCIENCE PUBLISHERS LTD

British Library Cataloguing in Publication Data

Titow, W. V. (Witold Victor) 1926-


PVC plastics.
1. Polyvinyl chloride
I. Title
668.4236
ISBN 1-85166-471-8

Library of Congress Cataloging in Publication Data

Titow, W.V.
PVC plastics: properties, processing, and applications/
W. V. Titow.
p. em.
Includes bibliographical references.
ISBN 1-85166-471-8
1. Polyvinyl chloride. I. Title.
TPll80.V48T58 1990
668.4'237-dc 20 89-71512
CIP

No responsibility is assumed by the Publisher for any injury and/or damage to persons
or property as a matter of products liability, negligence or otherwise, or from any use or
operation of any methods, products, instructions or ideas contained in the material
herein.

Special repletions for readen in the USA


This publication has been registered with the Copyright Clearance Center Inc. (Ccq,
Salem, Massachusetts. Information can be obtained from the CCC about conditions
under which photocopies of parts of this publication may be made in the USA. All other
copyright questions, including photocopying outside the USA, should be referred to the
publisher.

All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted in any form or. by any means, electronic, mechanical, photo-
copying, recording, or otherwise, without the prior written permission of the publisher.
Preface

This book originated from my Publisher's request for anew, concise


account of PVC plastics in terms of their nature, properties, process-
ing, and applications. There is thus, inevitably, an extensive thematic
overlap with my-still relatively recent-PVC Technology (4th edi-
tion), and I have drawn liberally on that source for a substantial
amount of relevant basic material. However, the present book is by no
means merely an abridgement of the earlier one: whilst indeed
considerably shorter, it is not only comparable in scope and general
coverage of the subject, but also contains much new information. I
have made a point of again strongly featuring the numerous standards
relevant-and in many cases cardinal-to the testing and characterisa-
tion of PVC materials and products, and to the evaluation of their
properties and performance: these standards are an indispensable part
of the technology of PVC plastics, and nobody concerned with any
aspect of this complex subject should fail to recognise that fact.
It is ever a pleasure to express appreciation and thanks where they
are due.
I am grateful to Dipl-Ing. H. E. Luben of Brabender OHG,
Duisburg, FRG, not only for the up-to-date information he provided
on Brabender equipment, but also most particularly for his exception-
ally friendly, helpful attitude in all our contacts, and for the trouble he
took to make some illustrations and figures available in the form
convenient for direct reproduction. The courtesy of those other
persons and/or companies to whom I am indebted for the photo-
graphic illustrations is, in each case, acknowledged in the relevant
caption.
Myoid friend and former colleague Mr David Mugridge, of the
Yarsley Technical Centre, Redhill, UK, kindly obtained for me some
v
vi Preface

additional information I needed for Chapter 20. I am most grateful for


this help.
My appreciative thanks go to Mrs Micky Kruger, who typed the
manuscript and provided other secretarial assistance.
As on previous occasions, I have experienced-and much
appreciated-the friendly, courteous cooperation of every member of
the Publisher's team concerned with the preparation and production of
the book.

W.V.T.
Contents

Preface. . . . . . . . . . . . . . . . . . . . . . . . . . v

Section I-Introductory 1

Chapter 1 . . . . . . . . . . . . . . . . . . 3
General Introduction . . . . . . . . . . . . 3
1.1 Some Key Terms, Definitions, and Concepts 3
1.1.1 What is PVC? . . . . . . . . . . 3
1.1.2 The Nature and Make-Up of PVC Materials 4
1.1.3 Abbreviations and Symbols for Material Names 5
1.2 Material and Test Standards . . . . . . . . . . . . 6
1.3 Origins, Historical Development, and Present Position of
pvc . . . . . . . . . . . . . . . . . . . . . 8
1.3.1 Early History . . . . . . . . . . . . . . . . 8
1.3.2 Present Position: (a) PVC as a major, highly
versatile thermoplastic; (b) some topical concerns-
vinyl chloride as a health hazard; some PVC for-
mulation constituents as potential health hazards;
health hazards associated with combustion products
of PVC; disposal of waste PVC products . . . . 10
1.3.3 The PVC Industry-Outline of General Structure 16
References 17
Bibliography 18

Chapter 2 . . . . . . . . . . . . . . . . . . . . . . . . 22
Constitution and Formulation of PVC Materials. . . . . . . 22
2.1 PVC Compositions (Compounds) and Their Formulation 22
vii
viii Contents

2.1.1 General Features and Main Categories . . . . . 22


2.1.2 Constituents of PVC Compositions (Formulation
Components) . . . . . . . . . . . . . . . 24
2.2 The Basics of Formulating PVC Compositions . . . . . 25
2.2.1 General Considerations: (a) processing require-
ments; (b) service requirements-food-contact and
medical applications; outdoor applications; electrical
insulation; (c) material and process cost economy 25
2.2.2 Selection of the Principal Individual Constituents of
a PVC Composition: (a) PVC polymer; (b) heat
stabilisers; (c) plasticisers; (d) lubricants; (e) poly-
meric modifiers; (f) fillers; (g) colourants; (h) other
components of PVC formulations . . . . . . . 27
2.2.3 Some Aids to Formulating: (a) computer-aided
formulating; (b) 'desirability function' in plasticiser
selection for pPVC formulations . . . . . . . . 35
2.2.4 Some Interactions and Mutual Effects of Principal
Components of PVC Formulations: (a) compatibility
effects; (b) synergism; (c) other mutual effects . . 36
2.2.5 Side-Effects of Formulation Components: (a) 'sec-
ondary functionality' effects; (b) undesirable side-
effects. . . . . . . . . . . . . . . . . . . . 37
2.2.6 Examples of Basic Formulations: (a) pipes and
tubing; (b) extruded profiles; (c) sheeting and film;
(d) calendered PVC/asbestos flooring (tiles); (e)
cable covering and insulation; (f) injection mould-
ings; (g) blow-moulded bottles; (h) paste formula-
tions . . . . . . . . . . . . . 38
2.3 Materials Cost of a Formulation . . . . 45
2.4 Compositional Analysis of PVC Materials 46
References . . . . . . . . . . . . . . . . 48

Section 2-Constituents of PVC Compositions 51

Chapter 3 . . . . . . . . . . . . . . 53
PVC Polymers . . . . . . . . . . . 53
3.1 Homopolymers of Vinyl Chloride. 53
3.1.1 Chemical Structure and Molecular Weight. 53
Contents ix

3.1.2 Polymer Morphology and Some Related Properties 59


3.1.3 Production of PVC Polymers: (a) vinyl chloride
monomer (VC); (b) polymerisation processes-
suspension polymerisation; mass (bulk) polymerisa-
tion; emulsion polymerisation . . . . . . . . . 61
3.1.4 Physical Forms of PVC Polymers: (a) suspension
polymer particles; (b) mass polymer particles; (c)
emulsion polymer particles . . . . . . . . . . 67
3.1.5 Effects of Some Polymerisation Process Factors on
Polymer Characteristics 73
3.2 Copolymers of Vinyl Chloride 73
3.2.1 Kinds and Applications 73
3.2.2 Production . . . . . 78
3.3 Commercial PVC Polymers . 78
3.3.1 Polymer Properties Cardinal to Processing and/or
Service: (a) chemical composition; (b) molecular
weight (viscosity number; K value); (c) polymer
particle characteristics; (d) quality (purity) 78
3.3.2 Characterisation and Designation of Commercial
PVC Polymers. . . . . . . . . . . . 81
3.3.3 Some Commercial Sources and Materials 90
3.4 Chlorinated Polyvinyl Chloride (CPVC) 90
3.4.1 Origins and Production Methods 90
3.4.2 Chemical Structure . . . . . . 95
3.4.3 Material Properties. . . . . . 96
3.4.4 Formulation and Processing of CPVC Compositions 97
3.4.5 Commercial CPVC Compounds and Their Applica-
tions 99
References 99

Chapter 4 . . . . . . . . . . . . . . . . 102
Stabilisers . . . . . . . . . . . . . . 102
4.1 Degradation and Stabilisation of PVC. 102
4.1.1 General. . . . . . . . . . . 102
4.1.2 Thermal Degradation: (a) outward manifestations;
(b) chemical aspects-dehydrochlorination and col-
our development; chemical basis of other property
changes; vulnerable sites in the PVC polymer chain;
(c) thermal degradation in melt processing and static
x Contents

exposure to heat; (d) effects of polymer molecular


weight, and some impurities and additives . 103
4.1.3 Photochemical Degradation 109
4.2 Purposes and Functions of Stabilisers in PVC 111
4.3 Heat Stabilisers . 112
4.3.1 General Classification of Heat Stabilisers 114
4.3.2 Lead Compounds 115
4.3.3 Organotin Stabilisers: (a) chemical nature and types;
(b) characteristics and applications; (c) mode of
action. 119
4.3.4 Other Metal-Based Stabilisers: (a) nature, and some
general applicational features; (b) antimony stabili-
sers; (c) calcium stearate; (d) mixed-metal
stabilisers-barium/ cadmium and barium/ cadmium/
zinc stabilisers; calcium/zinc stabilisers; other
mixed-metal stabilisers; mode of action of mixed-
metal stabilisers 124
4.3.5 Organic and Miscellaneous Stabilisers: (a) esters of
aminocrotonic acid; (b) urea derivatives; (c) epoxy
compounds; (d) organic phosphites; (e) other or-
ganic stabilisers 135
4.3.6 Stabiliser/Lubricant Balance and Interactions 140
4.4 Antioxidants and Light Stabilisers 141
4.4.1 Antioxidants. 141
4.4.2 Light Stabilisers: (a) organic UV absorbers; (b)
inorganic (particulate) UV-screening agents; (c)
free-radical scavengers; (d) chromophore quenchers;
(e) some general features of the action of light
stabilisers and antioxidants 143
4.5 Stabilisers in Single-Pack Additive Systems 149
4.6 Some Commercial Stabilisers . 151
4.7 Some General Effects of Stabilisers on Various Properties
of PVC Compositions . 151
4.8 Some Stabiliser-Related Problems 151
4.8.1 Sulphide Staining. 151
4.8.2 Plate-Out . 157
4.9 Testing and Evaluation of Stabilisation Effects 160
4.9.1 The Concept of Stability in Processing, Service, and
Tests. 160
4.9.2 Stability Testing: (a) heat-stability tests-dynamic
Contents xi

stability tests; static stability tests; (b) light-stability


~~. 1~
References 174

Chapter 5. 177
Plasticisers 177
5.1 General Definition and Nature of Plasticisers . 177
5.2 Plasticisation Mechanism, and some Relevant Features of
Plasticiser Structure. . . . . . . . . . . . 179
5.3 Main Outward Manifestations of Plasticisation . 182
5.3.1 Effects of the Level of Plasticisation 182
5.3.2 Stages of Plasticiser-Polymer Interaction 184
5.3.3 Ageing of Plasticised PVC after Processing 185
5.4 Principal Functional Parameters of Plasticiser Action 186
5.4.1 Compatibility and Miscibility: (a) the 11 value; (b)
solubility parameter 6; (c) clear-point temperature
(solid-gel transition temperature); (d) interaction
parameters: Flory-Huggins (X) and Bigg (a); (e)
Api Po ratio; (f) loop and roll compatibility tests; (g)
maximum-torque temperature (fusion point) in con-
trolled mixing . . . . . . . . . . 186
5.4.2 Effectivity (Efficiency) of Plasticisers . . . . . 193
5.4.3 Permanence of Plasticisers. . . . . . . . . . 195
5.5 Plasticiser Types, Their Characteristics and Commercial
Versions. . . . . . . . . . . . . . . . . . . . . 196
5.5.1 General Type Classification . . . . . . . . . 196
5.5.2 Plasticiser Nomenclature: Names, Synonyms, and
Abbreviations . . . . . . . . . . . . . . . . 198
5.5.3 Properties of Individual Plasticiser Types, and Their
Main Effects in PVC: (a) phthalate plasticisers-
lower phthalates; general-purpose phthalates; linear
phthalates; higher phthalates; miscellaneous phtha-
lates; (b) phosphate plasticisers-triaryl phosphates;
trialkyl phosphates; mixed alkyl aryl phosphates;
halogenated alkyl phosphates; (c) trimellitate plas-
ticisers; (d) aliphatic diester plasticisers; (e) polyme-
ric plasticisers; (f) miscellaneous plasticisers-epoxy
plasticisers; chlorinated paraffins and olefins; mono-
esters; glycol and polyglycol esters; other mis-
cellaneous plasticisers; hydrocarbon extenders . . . 201
xii Contents

5.5.4 Transport, Handling, and Storage of Plasticisers 223


5.5.5 Some Commercial Sources and Trade Names of
Plasticisers . . . . . . . . . . . . . . . . 224
5.6 Plasticiser-Inftuenced Properties of PVC. . . . . . . 224
5.6.1 Formulating Considerations-General Points. 224
5.6.2 Softness and Tensile Properties: (a) softness; (b)
tensile strength and elongation at break 230
5.6.3 Low-temperature Properties . 237
5.6.4 Electrical Properties . . . . . . . . 239
5.6.5 Flammability. . . . . . . . . . . . 239
5.6.6 Permanence Properties: (a) volatile loss-
automotive fogging; plasticisation of cable cover-
ings; (b) extraction resistance; (c) migration resis-
tance; (d) high-humidity compatibility . . . . 239
5.6.7 Stain Resistance . . . . . . . . . . . . . . 248
5.6.8 Resistance to Weathering and Photodegradation 249
5.6.9 Resistance to Biological Attack . . . . . . . 250
5.7 Toxicity and Health Aspects . . . . . . . . . . . . 250
5.7.1 Plasticisers in Food-Contact and Medical Applica-
tions . . . . . . . . . . . . . . 250
5.7.2 Plasticiser Handling and Processing. 251
5.8 Standards Relevant to Plasticisers . 255
References . . . . . . . . . . . . . . . . . 255

Chapter 6. . . . . . . . . . . . . . . . . . 258
Fillers . . . . . . . . . . . . . . . . . . . 258
6.1 Definition and General Functions of Fillers 258
6.2 Particulate Mineral Fillers . . . . . . . . 259
6.2.1 Silicates and Silicas: (a) clay; (b) asbestos; (c) talc;
(d) other silicate fillers-wollastonite; mica; nephe-
line syenite . . . . . . . . . . . . . . . . . 259
6.2.2 Alkaline-Earth Metal Sulphates; (a) barium sulph-
ate; (b) anhydrous calcium sulphate . . . . . . 265
6.2.3 Calcium Carbonate Fillers: (a) general: types and
characteristics; (b) whiting; (c) ground limestone,
marble, and calcite; (d) ground dolomite; (e) pre-
cipitated calcium carbonates; (f) filler properties and
selection criteria-maximum particle size; particle
size distribution and mean particle size; dry bright-
ness; refractive index (opacifying effect); oil (plas-
Contents xiii

ticiser) absorption; dispersion characteristics; cost;


(g) applications, and some effects, of filler loading-
flooring; plasticised compounds; rigid compounds 266
6.3 Functional Fillers. . . . . . . . . . . . . . . . . . 281
6.3.1 Reinforcing Fillers: (a) asbestos (chrysotile) fibres;
(b) miscellaneous inorganic microfibres; (c) glass
fibres; (d) microspheres; (e) fine-particle calcium
carbonate. . . . . . . . . . . . . . . . . 281
6.3.2 Flame-Retardant and Smoke-Suppressant Fillers 286
6.3.3 Miscellaneous Functional fillers: (a) carbon black;
(b) metal, or metallised particles and fibres; (c)
wood flour; (d) cellulose fibres; (e) starch 286
6.4 Surface Treatments for Fillers . . . . . . . 288
6.4.1 Stearate Treatments . . . . . . . . 289
6.4.2 Treatment with Silane Coupling Agents 289
6.4.3 Organotitanate Treatments . . . . . 290
6.4.4 Proprietary and Miscellaneous Treatments. 290
6.5 Commercial Fillers 293
References . . . . . . . . . . . . . . . . . . . . 293

Chapter 7. . . . . . . . . . . . 294
Lubricants . . . . . . . . . . . 294
7.1 Functions, Nature, and Effects 294
7.2 Interaction and Co-action of Lubricants with Other PVC
Formulation Components . . . . . . . . . . . . . . 301
7.2.1 Lubricant/Stabiliser Effects: (a) stabilising effects of
lubricants-direct stabilising action; synergistic ac-
tion with stabilisers; indirect stabilising action; (b)
lubricant action of stabilisers. . . . . . . . . . . 301
7.2.2 Mutual Effects of Lubricants and Plasticisers: (a)
primary plasticisers; (b) secondary plasticisers and
extenders . . . . . . . . . . . . . . . . . . 303
7.2.3 Effects of Polymeric Modifiers: (a) impact modifiers;
(b) processing aids . . . . . . 304
7.2.4 Effects of Fillers and Pigments . . . . . . . . . 304
7.3 Assessment of Lubricant Performance. . . . . . . . . 305
7.3.1 Test Methods: (a) sheet 'fluidity' test; (b) two-roll
milling; (c) flow in the moulds and dies-flow in a
spiral mould; flow in a Rossi-Peakes flow tester;
xiv Contents

flow in a piston plastometer; the ASTM capillary


rheometer test; (d) tests using the Brabender Plasti-
Corder-fusion test in a roller mixer attachment;
processability test in a Brabender Extrusiograph
with a rheometric head . . . . . . . . 305
7.3.2 Some Research Equipment and Methods 309
7.3.3 'Lubricant Value' . . . . . . 309
7.4 Some Effects of Incorrect Lubrication 310
7.5 Commercial Lubricants 310
References . . . . . . . . . . . . . . 312

Chapter 8 . . . . . . . . . . . . . 313
Polymeric Modifiers . . . . . . . . 313
8.1 Nature and Functions-General 313
8.2 Processing Aids. . . . . . . . 314
8.3 Impact Modifiers . . . . . . . 316
8.3.1 Impact Resistance-Definition, Significance, and
Measurement . . . . . . . . . . . . . . . . 316
8.3.2 The Impact Resistance of PVC . . . . . . . . . 322
8.3.3 The Nature, Effects, and Applications of Polymeric
Impact Modifiers for PVC: (a) ABS modifiers; (b)
MBS modifiers; (c) acrylic modifiers; (d) rubber-
modified styrene/maleic anhydride copolymers; (e)
nitrile rubbers (acrylonitrile/butadiene copolymers);
(f) E/VAC modifiers; (g) chlorinated polyethylene
(CPE); (h) polyurethane (PUR) elastomers 323
References 333

Chapter 9 . . . . . . . . . . . . 335
MisceUaneous Additives . . . . . 335
9.1 Additives Active in Processing 335
9.1.1 Chemical Blowing Agents for PVC Foams. 335
9.1.2 Cell-Control Agents for PVC Foams . . 343
9.1.3 Minor Additives for PVC Pastes . . . . . 344
9.2 Additives Incorporated for End-Use Properties . . " . 345
9.2.1 Colourants: (a) general; (b) choice of colourant-
colour; processability; stability and performance in
service; health and safety considerations; (c) some
Contents xv

practical tests-heat stability; stability to light and


weathering; colour migration . . . . . . . . . 345
9.2.2 Flame Retardants and Smoke Suppressants . . . 351
9.2.3 Additives for Antistatic and Conductivity Effects:
(a) antistatic surface-active agents; (b) polymeric
antistatic additives; (c) conductive fillers; (d) some
relevant test methods and specifications . . . 354
9.2.4 Odour Control Agents . . . . . . . . . . 359
9.2.5 Matting ('Flatting') and Anti-blocking Agents 360
References 361

Section 3-Production (Compounding) of Solid PVC Composi-


tions. . . . . . . . . . . . . . . . . . . . . . . . . . . 363

Chapter 10 . . . . . . . . . . 365
Solid ('Dry') PVC Compositions 365
10.1 General . . . . . . . . 365
10.2 Types and Forms of PVC Compounds 367
10.3 Some Material Properties of PVC Compounds 370
10.3.1 Physical and Short-Term Mechanical Properties 370
10.3.2 Creep and Fatigue in Rigid Compositions: (a)
creep; (b) fatigue. . 370
10.3.3 Thermal Properties . 379
10.3.4 Electrical Properties 379
10.3.5 Chemical Properties 379
10.3.6 Miscellaneous Properties: (a) optical; (b) water
absorption; (c) others. . . . . . . . . . . . 385
10.4 Characterisation and Standard Designation of Commercial
PVC Compounds . . . 387
10.4.1 Characterisation 387
10.4.2 Designation 388
References . 392

Chapter 11 . . . . . . . . . . . . . . 393
Compounding: Operations and Equipment 393
11.1 General . . . . . . . . . . . . 393
xvi Contents

11.2 Industrial Production of Solid Compounds . . . . . . . 396


11.2.1 Upstream Equipment and Operations: (a) han-
dling, storage, and conveying-polymer and
fillers; plasticisers; other formulation components
(additives); (b) metering-general; major for-
mulation components; minor formulation com-
ponents; control and accuracy in metering in-
stallations; batch assembly. . . . . . . . . . . 396
11.2.2 Compounding Operations and Equipment: (a)
general; (b) production of powder mixes-batch
mixing; continuous mixing; (c) melt-
compounding: objectives and general features; (d)
melt-compounding machinery: continuous
compounding-the Plastifikator (shear-cone com-
pounder); the Buss kneader; the cascade ex-
truder; the Kombiplast equipment; the FCM
continuous mixer; the MPC/V compounder; the
Bitruder BT; the planetary compounder; machine
drives and controls; machine working surfaces and
parts; on-line operational and melt quality con-
trol; (e) further processing-pelletising; pellet
cooling; mixing (blending) of pellets; final han-
dling and delivery; (f) batch compounding in
internal mixers; (g) compounding some recycled
materials . . . . . . . . . . . . . . . . . . 412
11.2.3 Compounding for Direct Feeding of Calenders. 455
11.3 Compounding of Liquid PVC Compositions. . . . . . 455
11.4 Small-Scale (Laboratory) Compounding . . . . . . . 455
11.4.1 General: (a) usual objectives; (b) scope of discus-
sion in this chapter . . . . . . . . . . . . . . 455
11.4.2 Laboratory Compounding Equipment and Its
Uses: (a) some laboratory and pilot-scale counter-
parts of industrial compounding equipment-
powder mixers; two-roll mills; Kombiplast; Buss
Kneader; compounding extruders; internal
mixers; (b) specialised instrumented equipment
for investigation and study of compounding be-
haviour and effects 456
References . 463
Contents xvii

Section 4---Processing of Solid PVC Compositions into Products 465

Chapter 12 . . . . . . . . . . . . . . . . . . . . . . . . 467
Main Types of PVC Products and Methods of Their Production 467
12.1 PVC Products of Greatest Industrial Importance-General 467
12.2 Rigid PVC Products . . . . . . . . . . . . . . " 467
12.2.1 Pipes and Conduit: (a) types of PVC pipes-
principal general kinds; some special pipe forms;
(b) some formulation aspects; (c) important pipe
properties and their determination . . . . . . . 467
12.2.2 Profiles and Cladding (Siding): (a) types and
applications; (b) some formulation aspects; (c)
testing and specifications . . . . . . . . , . 475
12.2.3 Sheeting and Film: (a) terminology; (b) produc-
tion types; (c) some formulation aspects; (d)
properties and applications 481
12.2.4 Blow Mouldings . . . 486
12.2.5 Injection Mouldings . 486
12.2.6 Gramophone Records. 486
12.3 Plasticised PVC Products . . . 486
12.3.1 Electric Cable and Wire Coverings: (a) types and
applications; (b) properties and tests 486
12.3.2 Sheeting and Film . 489
12.3.3 Flooring. . . . . . 493
12.3.4 Tubing and Profiles. 493
12.3.5 Fabric Coatings 495
References 496

Chapter 13 . . . . . . . . . . . . . . . . . . . . . " 497


Extrusion. . . . . . . . . . . . . . . . . . . . . . . . 497
13.1 History and Significance of Extrusion in PVC Processing 497
13.2 Extruders Used in PVC Processing. . . . . . . . . . 498
13.2.1 General. . . . . . . . . . . . . . . . . . 498
13.2.2 Basic Operational Features: (a) the screw; (b) the
barrel; (c) the head and die assembly; (d) the
hopper; (e) main operating characteristics of
single-screw and twin-screw extruders for PVC
processing. . . . . . . . . . . . . . . . . . 499
xviii Contents

13.3 Some General Points Relevant to PVC Extrusion 504


13.3.1 Working Surfaces 504
13.3.2 Use of Gear Pumps. 505
13.3.3 Purging. . . . . . 506
13.3.4 Coextrusion. . . . 507
13.3.5 Extrusion of CPVC . 507
13.3.6 Computerisation and Automation of Extrusion
Lines. . . . 508
13.4 Material Aspects. . . 508
13.4.1 Formulations 508
13.4.2 Feed Types . 508
13.4.3 Stock Transformations in the Course of Extrusion 509
13.4.4 Some Extruded-Product Faults: (a) manifestations
of incomplete gelation; (b) irregularities of par-
ticulate appearance; (c) variation or fluctuation in
dimensions; (d) plate-out . . . . . . . . 511
13.5 Basic Extrusion Lines for Important Extruded PVC
Products . . . . . . . . . 513
13.5.1 Rigid Pipe Extrusion 513
13.5.2 Profile . . . . . 516
13.5.3 Sheeting and Film . 516
13.5.4 Wire Covering. . . 519
13.6 Some Commercial Extrusion Equipment 522
References . 522

Chapter 14 . 524
Calendering. 524
14.1 Origins, and Current Position in the PVC Industry 524
14.2 Equipment and Process: General Aspects. . . . 524
14.2.1 The Calender . . . . . . . . . . . . 525
14.2.2 The Calendering Operation: Main Features and
Their Effects on the Structure and Properties of
Calendered Sheet . . . . . . . . . . . . . 529
14.3 Calender Lines . . . . . . . . . . . . . . . . . . 530
14.3.1 Regular General-Purpose Lines: (a) pre-calender
(compounding and feed) section; (b) calender
section; (c) post-calender section-sheet take-off
and stretching; embossing; cooling; measurement
and control of sheet thickness; edge trimming;
wind-up. . . . . . . . . . . . . . . . . . . 530
Contents xix

14.3.2 Other Lines and Arrangements: (a) lines for


calendered flooring; (b) 'Calandrette' lines; (c)
lamination on or at the calender . . . . . . . 542
14.4 Formulation of PVC Compositions for Calendering 546
14.5 Some Faults and Defects Occurring in Calendered Sheet-
ing. . . . . . . . . . . . . . . 549
14.5.1 Simple Dimensional Faults 549
14.5.2 Structural Defects . . . . 549
14.5.3 Faults Manifested in Appearance -. 550
14.6 Further Processing of Calendered Sheet 552
14.6.1 Press Finishing. . . 552
14.6.2 Press Lamination. . . . . . . 553
14.6.3 Surface Treatments. . . . . . 553
14.6.4 Continuous Lamination away from the Calender 553
14.7 Calendered-Sheet Products: Properties and Applications 554
References . . . . . . . . . . . . . . . . . . . . . . . 559

Chapter 15 . . . . . 560
Blow Moulding . . . 560
15.1 Basic Features. 560
15.2 Blow-Moulding Processes and Their Application to PVC 562
15.2.1 General Characterisation and Principal Features
of Blow-Moulding Techniques and Systems: (a)
extrusion blow moulding-general operational se-
quence; parison programming, and other control;
(b) injection blow moulding; (c) dip blow mould-
ing . . . . . . . . . . . . . . . . . . . . 562
15.2.2 Stretch-Blowing in Blow Moulding. . . . . . 569
15.2.3 Process and Equipment Arrangements in Blow
Moulding . . . . . . . . . . . . . . . . . 570
15.2.4 Cooling Methods. . . . . . . . . . . . . . 571
15.2.5 Miscellaneous Features: (a) mould venting; (b)
removal of waste material; (c) part removal
(take-off) systems; (d) blowing pressures 573
15.3 Industrial Blow Moulding of PVC . . 574
15.4 PVC Compositions for Blow Moulding 577
15.4.1 The Processing Aspect . . . 577
15.4.2 The End-Use Aspect . . . . 579
15.4.3 Formulations: (a) commercial compounds;
xx Contents

(b) formulation components-PVC polymer; sta-


biliser system; impact modifiers; lubrication; other
components . 580
15.5 PVC Blow Mouldings . . . 583
15.5.1 Applications . . . . 583
15.5.2 Properties and Tests 584
References . 586

Chapter 16 . . . . . . . . . . . . . . . . . . . . 588
Injection Moulding . . . . . . . . . . . . . . . . 588
16.1 The Process and its Application to PVC-General 588
16.2 The Material Aspect . . . . . . . . . . . . . 589
16.2.1 PVC Melt Properties and Behaviour . . 589
16.2.2 Moulding Compounds: (a) general points; (b)
'easy flow' moulding compounds; (c) melt flow
tests for moulding compounds . . . . . . . . 591
16.3 Equipment and Process Considerations . . . . . . . . 594
16.3.1 Equipment: (a) features and operation; (b) work-
ing surfaces . . . . . . . . . . . . . . . . 594
16.3.2 Processing: (a) stock temperature, and tempera-
ture settings; (b) rate of injection and injection
pressure; (c) interaction of PVC with acetal
polymers and copolymers . . . . . . . . . . 597
16.3.3 Flow Moulding. . . . . . . . . . . . . . . 600
16.3.4 Moulding Quality Maintenance, and Some Com-
mon Faults . . . . . . . . . . . . . . . . 600
16.4 Some Effects of Processing on the Morphology of Injec-
tion Mouldings . . . . . . . . . . . . 601
16.4.1 Quenching Stresses. . . . . . . 603
16.4.2 Orientation and Related Features 603
16.5 Injection Moulding of CPVC 604
References . . . . . . . . . . . . . . . . . 605

Chapter 17 . . . . . . . . . . . . 607
Other Processes. . . . . . . . . . 607
17.1 Compression Moulding of PVC 607
17.1.1 General . . . . . . . 607
17.1.2 Industrial Applications: (a) production of gramo-
Contents xxi

phone records; (b) compression moulding of thick


sheets (press lamination) 607
17.1.3 Sheet Moulding for Samples and Test Specimens:
(a) unplasticised PVC sheet-preparation of mill
sheet; compression moulding of final sheet in a
picture-frame mould; (b) plasticised PVC sheet 610
17.1.4 Compression Moulding of PVC Paste 613
17.2 Thermoforming 614
17.2.1 General Features . 614
17.2.2 Plastics Materials Used in Thermoforming . 615
17.2.3 Assessment of the Thermoforming Characteristics
of Materials . 616
17.2.4 Thermoforming Methods: (a) main types and
variants; (b) some processing considerations . 619
17.2.5 Thermoforming Equipment: (a) machinery; (b)
moulds-mould materials; applicational features
of main mould types; mould construction 627
17.2.6 Finishing Operations 630
17.2.7 Thermoformed Parts: (a) general design con-
siderations; (b) dimensional stability, and effects
of temperature and draw ratio on part quality 630
17.3 Powder Sintering and 'Lost Filler' Methods in the Produc-
tion of Porous PVC Sheets 632
17.3.1 Sintering of Powder 632
17.3.2 The 'Lost Filler' Method 633
References . 634

Section 5---Liquid PVC Compositions: Nature, Preparation,


Processing, and Applications . . . . . . . . . . . 635

Chapter 18 . . . . . . . . . . . . . . . . . . . . . . 637
PVC Pastes. . . . . . . . . . . . . . . . . . . . . . 637
18.1 The Nature and Terminology of PVC Pastes-General 637
18.2 The Role and Basics of Paste Rheology . . . . . . 638
18.2.1 Viscosity of PVC Pastes: (a) features relevant to
behaviour in processing; (b) basic modes of
rheological behaviour: effects of shear rate, and of
time under constant shear . . . . . . . . . . . 638
xxii Contents

18.2.2 Rheological Effects of the Polymer Component in


a PVC Paste: (a) polymer particle content ('poly-
mer fraction'); (b) polymer particle
characteristics-particle size and size distribution;
particle interactions. . . . . 643
18.3 Measurement of PVC Paste Viscosity . . . . . . . . . 645
18.4 Gelation/Fusion of PVC Pastes . . . . . . . . . . . . 646
18.4.1 General Features of the Transformation of a Paste
into a pPVC Material. . . . . . . . . . 646
18.4.2 Polymer-Plasticiser Interactions during the
Gelation/Fusion of a PVC paste . . . . . 647
18.4.3 Practical Determination of the Completeness of
Fusion in Paste Products . . . . . 651
18.5 The Composition of PVC Pastes. . . . . . . . . . . 653
18.5.1 Paste Formulation-General Points. . . . . . 653
18.5.2 Components of PVC Pastes: (a) paste polymers;
(b) plasticisers; (c) stabilisers; (d) fillers; (e)
additives modifying paste rheology-thickening
agents; viscosity depressants; diluents; (f) mis-
cellaneous additives. . . . . . . . . . . . 653
18.5.3 Pastes for Rigid Products: (a) organosols; (b)
rigisols . . . . . . 659
18.6 Preparation of PVC Pastes . . . . . . . . . . . 661
18.6.1 Some General Points . . . . . . . . . . 661
18.6.2 Small-Scale (Laboratory) Paste Preparation 662
18.6.3 Industrial Production of Pastes. . . . . . 664
18.7 Application of PVC Pastes: Processes and Products 666
18.7.1 Moulding Processes: (a) rotational casting; (b)
slush moulding; (c) dip mOUlding. . . . . . 666
18.7.2 Coating of Objects and Articles: (a) dip coating-
hot-dip coating; cold-dip coating; (b) spray coat-
ing . . . . . . . . . . . . . . . . . . . 668
18.7.3 Coating of Fabrics and Paper: (a) coating pro-
cesses and methods; (b) quality and testing of
paste-coated materials-some coating faults; test-
ing . . . . . . . . . . . . . . . . . . . 670
18.7.4 Paste Casting . . . . . . . . . . . . . . 678
18.7.5 Other Paste-Processing Methods of Minor Sig-
nificance 681
References . 681
Contents xxiii

Chapter 19 . . 683
Solutions. . . 683
19.1 General 683
19.2 Composition of PVC Solutions 683
19.2.1 The PVC Polymers: (a) homopolymers; (b) co-
polymers and terpolymers. . . . . 684
19.2.2 Solvents and Diluents. . . . . . . 688
19.2.3 Other Constituents of PVC Solutions 689
19.3 Preparation of PVC Solutions 692
19.4 Applications 694
References . . . . . . . . . . . 697

Chapter 20 . . . . . . . . . . . . . . . . . 698
PVC Latices . . . . . . . . . . . . . . . . 698
20.1 The Nature and PVC Versions of a Latex 698
20.1.1 Definition and General Characteristics 698
20.1.2 Basic Processing Features 700
20.2 Types of PVC Latices . . . . 702
20.2.1 General. . . . . . . 702
20.2.2 Homopolymer Latices 703
20.2.3 Copolymer Latices . . 703
20.3 Commercial PVC Latices . . . 706
20.4 Formulation and Compounding of PVC Latices 706
20.4.1 General Considerations . . . . . . . 706
20.4.2 Constituents Controlling Latex Stability and Pro-
perties: (a) latex stabilisers (emulsifiers); (b)
wetting agents; (c) thickeners; (d) anti-foaming
(defoaming) agents; (e) pH-modifiers and buffers 707
20.4.3 Additives Incorporated for End-Product Pro-
perties: (a) heat-stabilisers; (b) plasticisers; (c)
fillers; (d) pigments; (e) miscellaneous additives-
matting agents; anti-blocking agents; flame retar-
dants; biostats . . . . 711
20.5 Applications of PVC Latices . . . . . . . . . . . 719
20.5.1 Typical Uses-General . . . . . . . . . . 719
20.5.2 Examples of Basic Formulations for Particular
Applications. . . . . . . . . . . . . 723
20.6 Some Standard Test Methods for Polymer Latices 725
References . . . . . . . . . . . . . . . . . . . . 725
xxiv Contents

Section 6----Post-production Processing of PVC Products . . . . 727

Chapter 21 . . . . . . . . . . . . . . . . . . . . . . . 729
Fabrication, Conversion and Related Processing of PVC Sheet
and Parts. . . . . . . . . . . . . . . . . . . . 729
21.1 Fabrication and Related Operations-General . 729
21.2 Welding of PVC Products. 733
21.2.1 General. . . . . . . . . . . . 733
21.2.2 Hot-Gas Welding. . . . . . . . 734
21.2.3 Heated-Tool (Hot-Plate) Welding 735
21.2.4 Indirect Heated-Element Welding 737
21.2.5 Friction Welding: (a) spin welding; (b) vibration
welding . . . . . . . . 737
21.2.6 High-Frequency Welding . . . . . . . . . 738
21.2.7 Ultrasonic Welding. . . . . . . . . . . . 740
21.3 Bonding of PVC with Solvents, Solvent Cements, and
Adhesives . . . . . . . . . . . . . . . . 741
21.3.1 Solvent and Solvent-Cement Bonding 741
21.3.2 Adhesive Bonding 745
21.4 Cutting and Machining 745
21.4.1 Cutting. . . . . 745
21.4.2 Machining. . . . 750
21.5 Manipulation and Conversion of PVC Film and Sheeting
for Packaging 750
References . . . . . . . . . . . . . . . . . . . . . . . 750

Chapter 22 . . . . . . . . . . . . 752
External Treatments of PVC Products 752
22.1 Decorative Surface Treatments 752
22.1.1 Printing. . . . . 752
22.1.2 Heat Transfers. . . . 754
22.1.3 Hot Foil Stamping . . 755
22.1.4 Embossing: (a) general; (b) emobssing of foamed
sheet products-mechanical embossing; chemical
embossing. . 756
22.2 Surface Marking. . . 759
22.3 Protective Treatments 759
22.3.1 Lacquering . 759
Contents xxv

22.3.2 Other Protective Coatings. . . . . . . . . . 761


22.3.3 Film and Sheet Lamination . . . . . . . . . 762
22.4 Treatment with High-Energy Ionising Radiation (Irradia-
tion for Cross-Linking) . . . . . . . . . . . . . . . 762
22.4.1 Effects of High-Energy Radiation on Essentially
Saturated, Linear Polymers . . . . . . . . . 762
22.4.2 Irradiation of PVC Products: (a) PVC composi-
tions for products cross-linkable by high-energy
radiation; (b) property improvements in irradiated
PVC products; (c) the irradiation treatment 764
References . 768

Section 7-Applications of PVC Products, and Some Important


Application-Related Properties . . . . . . . . . . 769

Chapter 23 . . . . . . . . . . . . . . . . . . . 771
Miscellaneous PVC Products and Their Applications 771
23.1 Cellular PVC Products . . . . . . . . . . . 771
23.2 PVC Fibres and Fibre Products . . . . . . . 777
23.3 Laminates or Laminate-Like Products Involving PVC
Layers . . . . . . . . . . . . . 778
23.4 Sheet-Type Interior Wall Coverings 779
23.5 Powder Coatings and Mouldings. 779
23.6 Medical Applications. . . 781
23.7 Applications in Motor-Cars . . . 782
23.8 Footwear Applications . . . . . 783
23.9 Some Special, Unusual, or Minor Products and Applica-
tions . 783
References . . . . . . . . . . . . . . . . . . . . . . . 785

Chapter 24 . . . . . . . . . . . . . . . . . . . . . . . . 787
PVC Properties of Special Significance in Some Important Usage
Contexts . . . . . . . . . . . . . . . . . 787
24.1 Mechanical and Related Properties . . . . . . . 787
24.1.1 Principal Mechanical Properties . . . . . 787
24.1.2 Environmental Stress Cracking and Crazing 788
24.2 Properties Relevant to Electrical Applications . . . 792
xxvi Contents

24.2.1 Electrical Properties 792


24.2.2 Other Relevant Properties . 793
24.3 Properties Relevant to Some Effects of the Environment
in Service. 798
24.3.1 Properties for Outdoor Applications: (a) stability
to light (UV resistance); (b) resistance to
weathering-definition of weathering; factors in-
strumental in the weathering of PVC; manifesta-
tions of weathering of PVC; ways of promoting
weathering resistance of PVC; evaluation of the
resistance of PVC to weathering 798
24.3.2 Behaviour at Low and High Temperatures: (a)
low-temperature properties; (b) high-temperature
effects-general; maximum 'safe' temperature for
continuous service (in the absence of mechanical
stress); heat ageing of flexible PVC; effects as-
sociated with the thermal softening of PVC at
elevated temperatures. 813
24.3.3 Resistance to Biological Attack: (a) microbiologi-
cal attack (biodegradation); (b) attack by insects
and rodents 819
24.4 Properties Relevant to Barrier and Protective Applications 821
24.4.1 Permeability . 821
24.4.2 Chemical Resistance 833
24.5 Health Hazard Aspects . 833
24.5.1 Vinyl Chloride Monomer 834
24.5.2 PVC Compositions and Their Regular Constitu-
ents. 835
24.5.3 Peripheral Hazards in Production, Processing, and
Bulk Conveyance. 836
24.6 Burning Behaviour, Flammability, and Combustion Pro-
ducts. 836
24.6.1 General Burning Mechanism. 837
24.6.2 Flammability of PVC. 838
24.6.3 Products Generated by Burning PVC: (a) chemi-
cal nature; (b) smoke emission. 840
24.6.4 Burning Tests: (a) small-scale laboratory tests; (b)
larger-scale tests . 842
24.6.5 Tests for Smoke Emission and Properties: (a)
smoke density; (b) acid index; (c) toxicity . 845
Contents xxvii

24.6.6 Some Relevant Publications 847


References . 847

Appendix 1 . . . . . . . . . . . . . . . . . . . . . . 851
Some Material Properties of PVC Products and Compounds 851

Appendix 2 . . . . . . . . . . . . . . . . . . . . . . . 864
Quantities and Units: The SI System: Unit Conversion Tables 864

Appendix 3 . . . . . . . . . . . . . . . . . . . . . . 877
Abbreviations (Letter Symbols) Used in This Book for Some
Polymers, Their Derivative Plastics, and Certain Monomers 877

Index . . . . . . . . . . . . . . . . . . . . . . . . . . 881
Section 1

INTRODUCTORY
CHAPTER 1

General Introduction

1.1 SOME KEY TERMS, DEFINITIONS,


AND CONCEPTS
1.1.1 What is PVC?
In common, widely employed usage, the abbreviation 'PVC' has one
of two meanings, depending on the context in which it appears, viz.

(a) 'polyvinyl chloride', i.e. the homopolymer of vinyl chloride, or


(b) as a noun: a member (or, collectively, the whole) of the large
family of plastics materials based on polyvinyl chloride and/or
vinyl chloride copolymers;
as an adjective: of the nature of, or pertaining to, such member
or family.

In the sense of (b), the term 'vinyl' is also often used in the place of
'PVC' , e.g. in such phrases as 'vinyl flooring', 'flexible vinyl' ,
'processing of vinyls'.
The quality of meaning and its dependence on the context, of
themselves, make the terminology somewhat less than precise; whilst
(b) is also open to some objections on formal grounds (as is, with even
more justification, the use of 'vinyl' for 'PVC'). Some of the objections
have influenced certain relevant standard definitions, notably those in
ISO 472, the ISO plastics vocabulary standard (its British counterpart,
BS 3502, and some ASTM specifications-e.g. ASTM D 1784-are
more inclined to acknowledge living usage). However, the fact
remains that the definitions given above under (a) and (b) do accord
with what 'PVC' means to those who deal with the material(s)
represented by the hard-worked abbreviation.
3
4 PVC Plastics-Properties, Processing, and Applications

1.1.2 The Nature and Make-Up of PVC Materials

A plastic can be defined as a polymer-based material in which the


parent polymer may be virtually the sole constituent, or may be
combined with additives of one kind or another. In PVC plastics the
parent polymers are always associated with additives, some of which
may occasionally be present in predominant proportions (e.g. the
plasticisers in certain soft PVC materials). Indeed, among plastics,
PVC is remarkable for the great variety and range of properties
realised through planned formulation of individual compositions for
particular purposes: one example is the contrast between the soft,
flexible PVC coating on an upholstery fabric (in which the hard, horny
nature of polyvinyl chloride is not apparent) and the rigid, hard
material of a PVC pipe. This scope for wide variation of properties
through appropriate formulation, which is the basis of PVC's great
applicational versatility, is unmatched by any other plastic.
In common technical usage, the intimate blend of a vinyl chloride
polymer or copolymer with the other components of a PVC formula-
tion as first made up for processing into a product, is usually referred
to as a compound or composition (the former term is sometimes
restricted to compositions produced by melt-compounding). There are
also specific terms for particular kinds of PVC compositions (see for
example Chapter 2). 'Formulation' is also sometimes used synony-
mously with 'composition' in the above sense, although there is
justification for restricting the former term to the make-up of a
composition (e.g. as recorded on paper). It is usual to refer to the
polymer constituent of PVC compositions as a PVC resin or PVC
polymer.
PVC materials incorporating significant amounts of plasticisers are
known, collectively and severally, as plasticised PVC (in this book
abbreviated to pPVC-see Section 1.1.3). Flexible PVC and soft pvc
contain plasticisers in proportions high enough to impart these
properties to the material in substantial degree. As implied by the
name, unplasticised PVC (in this book abbreviated to uPVC) contains
no plasticisers; the term is often used interchangeably with rigid PVC
(in that uPVC is indeed a rigid material): such usage is not strictly
correct however, since-whilst, in general, plasticisation reduces
rigidity-the presence of a small proportion of plasticiser (up to about
10% by weight in most cases, but occasionally even higher) can
actually increase it (see 'antiplasticisation' via the Index). Rigid and
1 General Introduction 5

semi-rigid PVC materials (the latter typically containing up to about


25% of plasticiser) exhibit the properties indicated by these terms.
Note: As used in the industry, the last two terms are adequately
descriptive and well understood, but not strictly quantitative.
In standard nomenclature, * a rigid plastic is one that has-
under stated conditions (including, subject to permitted
tolerances, 23°C and 50% RH)-a modulus of elasticity in
flexure (or, if that is not applicable, in tension) greater than
700 MPa (=105Ibf in -2). A semi-rigid plastic is similarly
defined as one having a modulus of elasticity between 70 and
700 MPa (approximately 104-1W lbf in- 2).

1.1.3 Abbreviations and Symbols for Material Names

For the sake of convenience, abbreviations of (letter symbols for) the


names of various polymeric materials, in particular many polymers and
copolymers, are freely used throughout this book. All such abbrevia-
tions are listed, with their meanings, in Appendix 3. The versions used
are in line with the recommendations of the relevant ISO standard
(ISO 1043-1978), but it should be noted that these recommendations
do not fully accord in every case either with those of the other two
relevant English-language standards (ASTM D 1600-83 and
BS 3502:Part 1:1978) or with common usage in industry. A case in
point is the abbreviation for the copolymer of ethylene and vinyl
acetate: 'EVA' is widely used in industry and also recommended by
the ASTM standard, whereas the ISO standard favours 'E/VAC', and
the BS standard 'EVAC'-quis custodiet custodes ipsos? Moreover,
none of the standards provides a truly comprehensive list of abbrevia-
tions (cf. Appendix 3).
The abbreviations uPVC (for unplasticised PVC) and pPVC (for
plasticised PVC) often seen in the technical literature, and used
throughout this book, were originally prescribed by two relevant ISO
standards-ISO 1163:Part 1 and ISO 2898:Part 1. After a subsequent,
relatively short-lived, minor modification to 'u PVC' and 'p PVC' the
two standards have again changed their abbreviations (in the current
editions issued, respectively, in 1985 and 1986) this time to 'PVC-U'
and 'PVC-P'. These latest offerings are not favoured by the present

* As put forward in the three principal English-language plastics vocabulary


standards-ISO 472-1979; BS 1755: Part 1: 1982; ASTM D 883-85.
6 PVC Plastics-Properties, Processing, and Applications

author, who regards them as open to criticism on certain sound


grounds of logical consistency.
The abbreviation 'iPVC' has sometimes been used to designate rigid
PVC materials formulated for high impact resistance ('high-impact'
grades).

1.2 MATERIAL AND TEST STANDARDS

Standardisation of test methods and material property requirements


for plastics has now developed to the point where the standards play
an essential role in the proper running of the industry's technical
operations and quality control, as well as in product specification for
the purposes of tendering and sales.
In the Western World, the most important 'plastics' standards are
found among those developed and issued by four organisations: the
International Organisation for Standardisation* (ISO standards), the
British Standards Institution (BS standards), the American Society for
Testing and Materials (ASTM standards), and the German Institute
for Standardst (Deutsches Institut fur Normung: the DIN standards).
Note: Most other countries have their own standardisation bodies
which issue their national standard specifications. With vir-
tually no important exceptions, each national standardisation
body is a member of ISO, and each acts in its own country as
an agent of ISO, as well as of all other ISO member bodies,
for such purposes as the sale of standard specifications and
related documents and provision of information on standards.
It may be noted in passing that the official national standard-
isation body of the USA is not the ASTM, but the American
National Standards Institute (ANSI). However, a great many
ASTM standards have been adopted by the ANSI as national
standards.
Some ISO, BS, ASTM, and DIN standards are generally applicable
to many plastics (including PVC). Such standards include, for in-
stance, specifications dealing with· terminology, conditioning and test
atmospheres, and test methods for some properties (e.g. mechanical

* With headquarters in Geneva.


t With headquarters in Berlin.
1 General Introduction 7

properties, water absorption, etc.). Many specifications of this kind-


all with some relevance to PVC-are listed in Table 1.3 at the end of
this chapter, and others are referred to, as appropriate, throughout the
book. There are also large numbers of ISO, BS, ASTM, and DIN
standards directly relevant to PVC, and some dealing with important
constituents of PVC materials (e.g. plasticisers). Such standards are
listed at the end of each chapter to which they are relevant, and/or
mentioned in the text.
Some big industrial concerns, as well as user organisations, issue and
operate their own specifications for certain plastics materials and
products. Notable examples are the well-known US military (MIL)
specifications; those of the National Coal Board in the UK (NCB
specifications); and the specifications of major car manufacturers.
Some 'plastics' or plastics-related standards of two independent
organisations of international standing are also important: these are
the relevant specifications issued by Underwriters Laboratories Inc. *
(the UL specifications; exemplified by the much-quoted UL94-the
basis for rating the flammability of plastics materials for moulded parts
in devices and appliances), and those of the International Electrotech-
nical Commissiont (known as lEC publications; some are particularly
relevant to the electrical properties of plastics, including PVC:j:).
References to standard specifications throughout this book (both in
the tabulated lists and in the text) include in almost every case a year
of issue since this can provide a useful point of reference. Most of the
issues so quoted should be still current at the time of the book's going
to press (except where an older specification is deliberately cited) but
it will be appreciated that consecutive issues of national and ISO
standards are periodically brought out under new dates, embodying
the results of more or less regular revision. Some standards are also
being amended, some are occasionally withdrawn, and entirely new
ones are brought out.
Useful information on standard tests for plastics can be found in a
book edited by Brown. 1 Two other books are also relevant as general
reference sources on this extensive subject. 2,3 Numerous tests and

* With headquarters in Northbrook, IL, USA, and several local agencies in


the USA and abroad.
t With headquarters in Geneva.
:j: For example Publication 189-1: Low Frequency Cables and Wires with PVC
Insulation and PVC Sheath-Part 1: General test and measuring methods.
8 PVC Plastics-Properties, Processing, and Applications

evaluation methods for PVC materials and products are cited, listed,
and discussed in a recent book by the present author. 4

1.3 ORIGINS, mSTORICAL DEVELOPMENT, AND


PRESENT POSmON OF PVC

1.3.1 Early History

The following highlights in the early history of PVC may be noted.

1835: Vinyl halides first made in the laboratory, and formation from
them of white, amorphous solids on exposure to sunlight observed (by
V. Regnault).4,5
1872: Vinyl chloride and bromide prepared (by E. Baumann) by the
action of alcoholic potash on dichloroethane, and their prolonged
exposure to sunlight in sealed tubes found to result in the formation of
white, powdery, flaky solids (polymerisation).4,5
1912-1913: Patent disclosures in Germany by Chemische Fabrik
Griesheim-Elektron,6,7 based on work led by F. Klatte,5,8 of the
reaction between acetylene and hydrogen halides as a method of
preparation of vinyl chloride and bromide, referring also to their
polymerisation (still by sunlight) and to some suggested uses for the
vinyl chloride polymer. Patent disclosures in the UK and Germany by
Ostromislensky4 of sunlight-polymerised PVC.
1916: Method suitable for technical-scale preparation of vinyl chloride
(based on the reaction of acetylene with HCI) established at I.G.
Farbenindustrie (now BASF) in Germany by Klatte and co-workers.
1928-1930: Patent disclosures of VC/V AC copolymers by Du Pont
and the Carbon and Carbide Chemicals Corp. in the USA, and I.G.
Farbenindustrie in Germany. 4 A patent obtained for 'polyvinyl hal-
ides' by Ostromislensky in the USA. 9 Vinyl chloride polymers
prepared by emulsion polymerisation by H. Fikentscher and co-
workers at I.G. Farbenindustrie (Ludwigshafen), Germany.5 Prepara-
tion of VC/VAC copolymers by E. W. Reid at the Carbon and
Carbide Chemicals Corp. in the USA,4,5 and at I.G. Farbenindustrie
in Germany (by A. Voss and E. Dickhliuser, who also pioneered
polymerisation of vinyl chloride at elevated temperatures and
pressures).5,10
1 General Introduction 9

The 19308: Plasticisation of PVC by phthalate esters. Introduction in


the USA of 'non-rigid vinyl chloride plastics' by B. F. Goodrich. 4
Suspension polymerisation of vinyl chloride at ICI in England and
Wacker Chemie in Germany.s Technical production of chlorinated
PVC polymer and fibres at I.G. Farbenindustrie, Germany.ll Com-
mercial production of PVC polymers in Germany and USA.4
1942-1943: Commercial production of PVC polymers in England (by
ICI and the Distillers CO.).4

Early attempts at heat-processing vinyl chloride homopolymers were


hampered by the unfortunate combination of the materials' high fusion
temperature and poor thermal stability. This difficulty promoted early
interest in vinyl chloride copolymers (in the first instance with vinyl
acetate): these, whilst in general somewhat less heat-stable than the
homopolymer, could be processed at significantly lower temperatures,
at which their stability was adequate. The role in this respect of the
co-monomer units in the polymer chains-sometimes referred to as
'internal plasticisation'-is well understood today.
The possibility of temporarily plasticising a PVC polymer by the
addition of solvents in amounts insufficient to effect solution, but
producing a dough-like mixture which might be processable (into
blocks, sheets, etc.) even without heating, was suggested in one of the
patents on Klatte's work,7 before the advent of internal plasticisation
by copolymerisation. However, true external plasticisation of the kind
practised today came after the first use of copolymers: it began with
the finding (by several workers 4) in the 1930s that compounding PVC
polymer with dibutyl phthalate (DBP) and some other phthalate esters
would yield a material processable at acceptable melt temperatures,
into products which could be permanently soft and flexible. Although
chronologically a slightly later development, it is the external and not
internal plasticisation that today provides the main route to the
formulation of flexible and most semi-rigid PVC materials. The 1930s
also saw the first use of heat stabilisers in PVC compositions. 4
The early processing of PVC before (and to some extent during)
World War II was largely carried out by methods and on machinery
originally developed for rubber and celluloid. The main processes
involved were compounding, calendering, compression moulding and
extrusion.
Thanks to the work of Kaufman, the history of PVC polymers,
compounds and processing is well recorded and documented. 12 ,13
10 PVC Plastics-Properties, Processing, and Applications

1.3.2 Present Position

(a) PVC as a Major, Highly Versatile Thermoplastic


The original impetus for the development of PVC to its present
eminent position among plastics got under way during World War II,
partly as a result of the realisation that PVC could be an effective
replacement for rubber in some important applications, notably as
insulation and covering for electrical wires and cables.
As illustrated by the 1984 figures in Table 1.1 (and, to a first
approximation, the data should be reasonably representative for the
mid-1980s generally), PVC vies with low-density polyethylene for the
first place among the four leading polymers that jointly account for
some 50-60% of the total polymer consumption. Table 1.2 gives a
general idea, with the aid of 1984 statistics, of the main uses to which
PVC is put. The amounts taken up by a given application differ
somewhat between the two principal economic units--Western Europe
and USA-but the general usage picture (if not the detailed pattern) is
broadly similar, with pipe and conduit, profiles and cladding, and film
and sheeting accounting for the greatest rigid-product tonnages, whilst
cable coverings and flexible film and sheeting are the highest-tonnage
outlets for plasticised PVC.
Even the brief, bare outline of the range of PVC's main applications
demonstrates that this is the most versatile among thermoplastics.

(b) Some Topical Concerns


Three subjects have gained-and maintain-topicality for their social
and commercial as well as technical significance: they are, respectively,
the question of health hazards posed by vinyl chloride monomer and
by some constituents of PVC compositions, the toxicity of PVC
combustion products, and the problem of PVC waste.

VINYL CHLORIDE AS A HEALTH HAZARD


Vinyl chloride, the basic monomer of PVC polymers and copolymers, *
was found in the early 1970s to be capable of causing cancer (albeit of
rather rare kinds).t Since then, increasingly more stringent limits have
been imposed on the amounts of VC released into work-place

* In this context frequently abbreviated to 'VCM' (for 'vinyl chloride


monomer').
t Angiosarcoma (a cancer of the liver), and a form of cancer of the mouth.
TABLE 1.1
Consumption of PVC and Other Leading Polymers in 1984
(Approximate figures based on data published in the technical press.) c:J
~
Polymers PVC LDPE HDPE PP All plastics '"~
(million (% of all (million (% of all (million (% of all (million (% of all (million (%)
;;-
Area tonnes) plastics) tonnes) plastics) tonnes) plastics) tonnes) plastics) tonnes) ~
I:>..
""- ;:
:::to
'0"'
USA 3·01 15·1 3·73 18·7 2·67 13·4 2·21 11·1 19·95 100 ;0
Western Europe 3·88 25·3 3·75 24·3 1·62 10·6 1·81 11·8 15·32 100
UK 0·44 18·2 0·51 21·1 0·21 8·7 0·30 12·4 2·42 100
West Germany 1·13 15·2 0·68 9·2 0·63 8·5 0·42 5·7 7·41 100
Japan 1·21 18·9 1-16 18·1 0·85 13·3 1·23 19·2 6·40 100

-
12 PVC Plastics-Properties, Processing, and Applications

TABLE 1.2
Consumption of PVC Polymers, by Main Application, in Western Europe and
the USA in 1984
(Approximate figures, based on data published in the technical press.)

Area Western Europe USA

(Thousand (% of grand (Thousand (% of grand


Application tonnes) total) tonnes) total)

Rigid PVC
Pipes and conduit 945 24·3 1139 37·8
Profiles and cladding 515 13·3 286 9·5
Sheeting and film 390 10·0 190 6·3
Blow-moulded bottles 315 8·1 97 3·2
Injection mouldings
(incl. pipe fittings) 73 1·9 130 4·3
Records 68 1·8 36 1·2
Miscellaneous 83 2·1 177 5·9
Total rigid 2389 61·5 2055 68·2
Plasticised PVC
Cable coverings 373 9-6 189 6·3
Sheeting and film 320 8·2 208 6·9
Flooring 197 5·1 90 3·0
Tubing and profiles 160 4·1 45 1·5
Fabric coatings 150 3·9 151 5·0
Miscellaneous 150 3-9 94 3·1
Total plasticised 1350 34·8 777 25·8
Other outlets (incl.
latex applications
and adhesives) 145 3.7 181 6.0
Grand Total 3884 100·0 3013 100·0

atmospheres, remaining in the PVC polymers after their production,


and migrating into foodstuffs and beverages packaged in PVC films or
containers. The issue of possible migration had a severely restrictive
effect on the use of rigid and semi-rigid PVC for food contact
applications in some countries, especially the USA * and Japan. In
1975, the American Food and Drug Administration (FDA) was

* Cf. e.g. the % consumption figures for blown bottles and rigid film,
respectively for the USA and Western Europe in Table 1.2.
1 General Introduction 13

contemplating a complete ban on such applications: the proposal was,


however, withdrawn some years later in view of the advances made by
PVC polymer manufacturers in reducing the residual VC content of
their polymers, and also because the principle was accepted that
carcinogens may be tolerated in foods if present in amounts sufficiently
low to be regarded as insignificant (the de minimis principle). Revised
FDA thinking in the late 1980s inclined to making PVC fully
acceptable as single-use or repeated-use food-packaging material
where the maximum residual VC contents do not exceed 10 ppb* in
rigid or semi-rigid PVC, and 5 ppb in flexible PVC. The technical
aspects of the presence of VC in PVC polymers and products are
discussed in Chapter 24 (Section 24.5).

SOME pvc FORMULATION CONSTITUENTS AS POTENTIAL HEALTH HAZARDS


The components of PVC formulations on which attention has been
principally focused in this connection are certain plasticisers-notably
dioctyl phthalate (DOP) and adipate (DOA)-and those stabilisers
and pigments which contain heavy metals, especially lead and cad-
mium. Several studies have been undertaken in the last few years
(some are still in progress) to determine whether some phthalate and
adipate plasticisers, in particular DOP and DOA, are carcinogenic in
man. The question is important, as these plasticisers are widely used in
PVC films for food packaging and in such medical products as
transfusion bags and tubing. This subject is discussed in Section 5.7 of
Chapter 5 (with a brief reference, inter alia, to the cling-film scare in
the UK in 1986), but it may be mentioned here that the case against
phthalate plasticisers as cancer-inducing agents is by no means
established. The intrinsic toxicity of lead and cadmium is not in doubt
(and chromium has also come under scrutiny in this regard), but the
severity of such hazards as may be posed by compounds of these
metals used as stabilisers or pigments in PVC compositions is still to
some extent controversial. One illustration of the way in which official
attitudes differ is the fact that-subject to certain restrictions on
extractability-lead stabilisers are allowed in PVC pipes for potable
water in Europe (as well as in many countries elsewhere), but not in
the USA. Possible hazards associated with heavy-metal compounds
used in PVC are referred to in connection with cadmium and lead

* Parts per American billion (i.e. per 109 ).


14 PVC Plastics-Properties, Processing, and Applications

stabilisers in Chapter 4, and cadmium and chromium pigments in


Chapter 9.

HEALTH HAZARDS ASSOCIATED WITH COMBUSTION PRODUCTS OF PVC


This subject is particularly important in connection with fires involving
PVC products (usually wire and cable coverings, often also pipes, in
fires in such locations as buildings and mines), and also as an aspect of
incineration of PVC waste. The compounds generated in substantial
quantities by burning PVC are hydrogen chloride (HCI) , carbon
monoxide and dioxide (CO; CO2), and aromatic hydrocarbons. HCI is
normally the most plentiful; it is a strong acid corrosive to human
tissue (capable of quickly causing severe damage to the respiratory
tract and lungs) and to many materials. It is often regarded as the
principal hazard in fires in which PVC is burning, although it has been
pointed out that HCI gas or fume can 'decay' fairly quickly in fire
environments by absorption and condensation on available surfaces. 14
The nature, hazards, and assessment of PVC combustion products are
discussed in Chapter 9 (in connection with flame-retardant and
smoke-suppressant components of PVC formulations) and in Chapter
24 (Section 24.6). Anxiety, occasionally bordering on hysteria, has
been voiced from time to time concerning toxic emissions from the
incineration of PVC waste. Even the vexed problem of acid rain has
been blamed on HCI from that source! The facts, as known from the
best evidence to date, are that incineration of waste PVC is not among
the significant causes of atmospheric pollution generally (and of acid
rain in particular) and that, with suitable equipment incorporating
appropriate scrubbing and cleansing devices, it can be carried out
effectively and safely. *

DISPOSAL OF WASTE PVC PRODUCTS


This is another subject receiving continuing attention for its environ-
mental implications as well as for its economical and technical interest.
As with other plastics waste, the two general possibilities are reclama-
tion, i.e. reprocessing for re-use, or permanent elimination, in which

* Compare for example relevant statements at the European Conference on


Packaging, Brussels, 1986; those by the Society of the Plastics Industry (SPI);
and those at the 4th H. F. Mark symposium of the Austrian Plastics Institute,
Vienna 1986; also publications by the Swiss Eidgenossische Anstalt fUr
Wasserversorgnung (A. Scharsach, 1986), and the recent paper by P. Decroly
in Plastics and Rubber International (June 1987, pp. 32-35).
1 General Introduction 15

incineration plays an important part. However, in both these methods


of disposal PVC presents certain special problems. The toxicity and
corrosive nature of PVC combustion products have just been men-
tioned, and whilst effective and safe incineration is possible, the
special measures and equipment required make the operation rela-
tively expensive and not entirely straightforward. Reclamation in most
cases involves dealing with mixed plastics waste with a somewhat
variable PVC content. Reprocessing of such waste may, in principle,
follow one of two lines, viz. the waste may be cleaned and processed
into some useful end-product without separation, or the PVC may be
separated out to be processed into reclaimed PVC products. Industrial
systems for recycling mixed plastics waste are available (e.g. the West
German Recycloplast system, or the Italian Sorema installations), but
they are not primarily intended for PVC. Indeed, for fully effective
reprocessing, with reasonable commercial scope for the end-products,
it is necessary to separate PVC from other plastics waste, as it is not
compatible with polyethylene*-the waste's most abundant
constituent-whilst PVC's own susceptibility to thermal decomposition
can be aggravated by certain contaminants (so that effective purifica-
tion is required also for that reason) and by the presence of any PVC
polymer that has already been partly degraded in the course of past
heat treatment and/or service. Some processes have been claimed to
be effective in recovering PVC from mixed plastics waste (e.g. the
Mesco process, developed in Japan by Mitsui 16), but in general the
scale of industrial recovery of this kind remains modest. Recovered
plasticised PVC is converted into compositions used, for instance, for
cable cores (cable filling), cheap garden hose, soles for cheap
footwear, and low-grade wall skirting (e.g. for caravans).
Note: The compatibility of some PVC wastes can be limited in
certain circumstances, and practical compounding tests are
always desirable. For example, certain plasticisers have been
found to interfere in the formation of a useful blend from a
mixture of pPVC waste with scrap PVC containing an
acrylonitrile/methylacrylate copolymer .17
A fairly common source of mixed plastics waste with a high pPVC
content is provided by scrap cable and wire coverings. Perhaps the

* Although attempts have been made to promote compatibility through the


addition of chlorinated polyethylene. 15
16 PVC Plastics-Properties, Processing, and Applications

most successful case of recovery of rigid PVC scrap is the re-use of


material from discarded PVC bottles. Reprocessing of these into
compounds for the production of certain grades of sewage and
drainage pipes and cable sheathing was initiated in France by Societe
Dorlyl. 18 Currently, in three French industrial operations (still rela-
tively small-scale), reclaimed PVC bottle material is used in composi-
tions for some mOUldings, sheeting, and extrusion of profiles and
vineyard postS. 19 Efforts to develop effective ways of recovery and use
of waste PVC are being continued both by industrial companies (e.g.
Cleveland Reclaim, Cleveland, OH, USA) and organisations promot-
ing the relevant research and development (e.g. in the USA, the
Plastics Recycling Foundation, and the Council for Plastics in Packag-
ing). Normal recirculation, in the same process, of clean PVC scrap
('rework') generated by the process, is, of course, widely practised in
most melt-processing operations.

1.3.3 The PVC Industry-Outline of General Structure

In the broadest terms, the PVC industry may be said to comprise


(a) PVC polymer producers;
(b) compounders (producers of PVC compositions for processing);
(c) processors;
(d) converters, and other companies making and selling finished
products consisting of or containing PVC.
Importers of PVC polymers and compounds are not, strictly speaking,
within the industrial set-up proper, because they do not normally
undertake any technical operations. However, together with the
polymer producers and compounders they make up the wider category
of polymer and compound suppliers.
Some companies engage in more than one of the above activities.
For example, all major polymer manufacturers produce compounds,
and some also make semi-finished products.
The number of PVC polymer producers in any country is very small
compared with that of companies in the other categories (in some
cases a polymer producer has manufacturing plants in several
countries). For many members of category (d), PVC may represent
only a relatively small part of their interests: nevertheless some-such
as motor-car manufacturers for example-can be using very large
quantities of PVc.
1 General Introduction 17

The principal processes used to convert PVC to finished and


semi-finished goods are extrusion, calendering, injection moulding,
and spread coating. Although some processors operate more than one
of these processes, most tend to specialise in one process. In some
cases the processed PVC is marketed directly by the processor (e.g.
unplasticised PVC pipes), whilst in other areas the processor passes on
the PVC in semi-finished form to another company which employs the
material in its products (as for example with calendered PVC sheeting
to be made into inflatables).
In addition to the material producers, converters and users, there
are many companies which specialise in the supply of additives for use
in PVC compounds, e.g. plasticisers, stabilisers, lubricants, fillers,
etc. It may be noted that the value of the total market for some of
these materials exceeds that of many other plastics materials.
Also highly relevant-since without them the PVC industry could
not function-are manufacturers of PVC processing machinery and
auxiliary equipment, including process control devices. Many com-
panies have specialised in this field and, through their development
activities, improved processing as well as wider and also entirely new
applications for PVC have been made possible.
Some reference sources on PVC are listed in the Bibliography
below.

REFERENCES
1. Brown, R. P. (Ed.), Handbook of Plastics Test Methods, 2nd edn. George
Goodwin and the PRI, London, 1981.
2. Vishu Shah, Handbook of Plastics Testing Technology. John Wiley &
Sons, Chichester, 1984.
3. Turner, S., Mechanical Testing of Plastics, 2nd edn, George Goodwin and
the PRI, London, 1984.
4. Titow, W. V., PVC Technology, 4th edn. Elsevier Applied Science
Publishers, London and New York, 1984.
5. W. Forest et al., (Ed.) Ullmans Encyclopiidie der Technischen Chemie,
Vol. 14, p. 201 and Vol. 18, p. 87. Urban & Schwarzenberg, Munich and
Berlin, 1963.
6. DRP 278249 (1912).
7. DRP 281877 (1913).
8. Kaufman, M., Trans. J. Plastics [nst., 365-71.
9. Drukker, H. L., Proc. Symposium on Plastics, ASTM, Philadelphia, PA,
USA, pp. 165-77.
10. DRP 579048 (1928).
18 PVC Plastics-Properties, Processing, and Applications

11. Domininghaus, H., KunststoJfe und ihre Eigenschaften. YDI-Verlag


GmbH, Dusseldorf, p. 566.
12. Kaufman, M., Plast. Polym., 37(129) (1969) 243-51.
13. Kaufman, M., The History of PVC. Elsevier, London, 1969.
14. Anon., Plast. Technol., 32(10) (1969) 135. (Summary of results of study of
the behaviour of HCl gas in fire environments, by the Southwest Research
Institute, San Antonio, Texas.)
15. Paul, D. R., Vinson, C. E. & Locke, C. E., Polym. Engng Sci., U (1972)
157; idem, ibid., 13 (1973) 202 and 308.
16. Trevitt, E. W., Polym. Paint. Col. J., 166(3918) (1976) 193-4.
17. Erwin, L. & Wilson, M. L., Plast. Rubb. Process. Appln, 2(2) (1982)
183-90.
18. Anon, Eur. Plast. News, 6(2) (1979) 3.
19. Mapleston, P., Mod. Plast. Int., 18(1) (1988) 39-41.

BIBLIOGRAPHY

SPE Vinyl Professional Activity Group, A Guide to the Literature and Patents
Concerning Polyvinyl Chloride Technology. SPE, Stamford, CN, USA,
1964.
Dux, J. P., Vinyl chloride polymers. In Encyclopedia of Polymer Science and
Technology, Vol. 14, ed. H. F. Mark & N. G. Gaylord. Wiley-Interscience,
New York, pp. 305-483.
Matthews, G., Vinyl Chloride and Vinyl Acetate Polymers. Plastics Institute
Monograph, Iliffe Books, London, 1971.
Sedlacek, B. (Ed.), Polyvinyl Chloride: Its Formation and Properties.
Proceedings of IUPAC Symposium, Prague 1970. Butterworths, London,
1971.
Sarvetnik, H. A. (Ed.), Plastisols and Organisols. Van Nostrand, New York,
1972.
Yescombe, E. R., Plastics and Rubber: World Sources of Information.
Applied Science Publishers, London, 1978, pp. 151, 177-80, 359.
Burgess, R. H. (Ed.), Manufacture and Processing of pvc. Applied Science
Publishers, London, 1981.
Brydson, J. A., Plastics Materials. 4th edn. Butterworth Scientific, London,
1982, Chapter 12.
Davidson, J. A. & Gardner, K. L., Vinyl polymers (PVC). In Kirk-Othmer
Encyclopedia of Chemical Technology, 3rd edn, Vol. 23. John Wiley &
Sons, New York, pp. 886-936.
Owen, E. D. (Ed.), Degradation and Stabilisation of pvc. Elsevier Applied
Science Publishers, London and New York, 1984.
Titow, W. V. PVC Technology. 4th edn. Elsevier Applied Science
Publishers, London and New York, 1984.
Becker, G. W. & Braun, D. (Eds), KunststoJf Handbuch-PVC. Carl Hanser
Verlag, Munich, 1986.
Nass, L. I. (Ed.), Encyclopedia of pvc. Marcel Dekker, New York, 1986.
General Introduction 19

TABLE 1.3
Some 'Plastics' Standards Relevant to Terminology, and General Testing

Entry Standard specification


no.
Designation Subject (not necessarily the
official title)
Terms and Definitions
1 ISO 472-1979 Plastics-Vocabulary
(3 addenda: 1982; 1983;
1984)
2 ISO 194-1981 Plastics-List of equivalent terms
(four addenda: one-1981; (English, French and Russian)
three-1983 )
3 BS 1755 Glossary of terms used in the plastics
industry
Part 1: 1982 Polymer and plastics technology
Part 2: 1974 Manufacturing processes
4 BS 3558: 1980 Glossary of rubber terms
5 BS 4815: 1972 Glossary of generic names for man-
made fibres
6 BS 5168: 1975 Glossary of rheological terms
7 ASTM C 168-80 Definitions of terms relating to thermal
insulating materials
8 ASTM C 274-68 (1980) Definitions of terms relating to
structural sandwich construction
9 ASTMD 16-84 Definitions of terms relating to paint,
varnish, lacquer and related products
10 ASTM D 883-85 Definitions of terms relating to plastics
11 ASTM D 907-82 (1985) Definitions of terms relating to
adhesives
12 ASTM D 1418-85 Rubber and rubber latices-
Nomenclature
13 ASTM D 1566-86 Definitions of terms relating to rubber
14 ASTM E 6-85 Definitions of terms relating to methods
of mechanical testing
15 ASTM E 12-70 (1986) Definitions of terms relating to density
and specific gravity of solids, liquids
and gases
16 ASTME41-79 Definitions of terms relating to
conditioning
17 ASTM E 206-72 (1979) Definitions of terms relating to fatigue
testing and statistical analysis of
fatigue data
18 ASTM E 284-81 Definitions of terms relating to
appearance of material
(continued)
20 PVC Plastics-Properties, Processing, and Applications

TABLE l.3----contd.

Entry Standard specification


no.
Designation Subject (not necessarily the
official title)

19 ASTM F 17-76 (1982) Definitions of terms relating to flexible


barrier materials
20 ASTM F 141-85 Definitions of terms relating to resilient
floor coverings
21 ASTM F 412-84 Definitions of terms relating to plastic
piping systems
Common names and abbreviations
22 ISO 1043-1978 Plastics-Symbols
23 BS 3502 Schedule of common names and
abbreviations for plastics and rubbers
Part 1: 1978 Principal commercial plastics
Part 3: 1978 Rubber and rubber latices
24 BS 4589: 1970 Abbreviations for rubber and plastics
compounding materials
25 ASTM D 1600-83 Abbreviations of terms relating to
plastics
26 DIN 7723 (1971) Abbreviations for plasticisers
27 DIN 7728
Part 1 (1978) Symbols for terms relating to
homopolymers, copolymers and
polymer compounds
Part 2 (1980) Symbols for reinforced plastics
General test conditions and methods
(a) Conditioning and testing conditions
28 ISO 291-1977 Plastics-Standard atmospheres for
conditioning and testing
29 ISO /R 483-1966 Plastics-Methods for maintaining
constant relative humidity in small
enclosures by means of aqueous
solutions
30 ISO 554-1976 Standard atmospheres for conditioning
and/ or testing-specifications
31 ISO 558-1980 Conditioning and testing-Standard
atmospheres-definitions
32 ASTM D 618-61 (1981) Conditioning plastics and electrical
insulating materials for testing
33 DIN 50013 (1979) Climatic testing-Preferred test
temperatures
34 DIN 50014 (1985) Standard atmospheres
1 General Introduction 21

TABLE l.3-contd.

Entry Standard specification


no.
Designation Subject (not necessarily the
official title)
35 DIN 50015 (1975) Constant test atmospheres
36 DIN 50016 (1962) Testing of materials, components, and
equipment in damp alternating
atmospheres
37 DIN 50017 (1982) Climatic testing-Stress in
environments containing condensed
water
38 DIN 50018 (1978) Corrosion test methods in alternating
atmosphere containing condensation
water and sulphur dioxide
39 DIN 50019
Part 1 (1979) Climates (outdoor)---Graphical and
other data
Part 2 (1963) Testing of materials, structural
components and equipment-Data on
climates (outdoor) (Withdrawn in
1986)
Part 3 (1979) with Climatic patterns: statistically-based
supplement data

(b) Some general test methods


40 ISO 62-1980 Plastics-Determination of water
absorption
41 ISO 171-1980 Plastics-Determination of bulk factor
of moulding materials
42 ISO 3451/1-1981 Plastics-Determination of ash: general
methods
CHAPTER 2

Constitution and Formulation of pvc Materials

2.1 PVC COMPOSmONS (COMPOUNDS) AND


THEIR FORMULATION
2.1.1 General Features and Main Categories
PVC polymers must be modified by the incorporation of appropriate
additives for satisfactory processing and end-use performance. The
necessary modifications are more varied and extensive than those
practised with any other polymer of major industrial importance, but
so also is the applicational versatility of PVC in the form of the
resulting materials.
In this chapter the terms 'composition' and 'compound' are used
generically for the material which results when PVC polymer is first
combined with the necessary additives, and the operations involved in
making a compound (composition) are collectively called
'compounding' .

Note: Compounding may consist of, or include as one of its stages,


mixing and/or melt-compounding. The former term is usually
applied either to the blending together of the appropriate
constituents to produce a solid composition in the form of a
free-flowing powder or powder agglomerate (either of these
may be referred to as 'pre-blend' or 'dry blend', depending
on the context), or to their mixing to form a liquid composi-
tion, i.e. a paste, latex, or solution. Melt-compounding is the
operation (commonly carried out on a mixed pre-blend)
whereby the constituents of a composition are intimately
combined with the resin in the melt, under heat and shear:
the resulting compound is normally pelletised (granulated).
22
2 Constitution and Formulation 23

A compound is processed by the appropriate method to make a


PVC product (e.g. sheet, film, pipe, injection-moulded component,
blow-moulded container, coating on a fabric, etc.); some of the
products may be used to fabricate secondary products by further
processing (e.g. mouldings thermoformed from sheet, wall coverings
made by laminating calendered films). A general outline of this
sequence may be schematically represented as in Fig. 2.1.
The material (and thus, of course, the formulation) of a product is
that of the composition used to make it, but in the product the
material will have had a more extensive 'heat history', having
undergone at least one processing operation after the original
compounding.
Nowadays, ready-made PVC compounds are available in great
variety and profusion, formulated to meet the needs not only of the
main processes and applications, but also of individual process and
application variants, as well as particular standard specifications.
Commercial PVC compounds are discussed in Chapter 10.
As mentioned in Chapter 1, PVC materials and products fall into
two broad categories: unplasticised (uPVC) and plasticised (pPVC).
The former group is also often referred to as rigid PVC (but see

1 - - - - - - ---------1
Compounding I Ph . I f I
1 YSlca orms: I
...--_....L.._! _ _ _ _ _ _ _ _ JSolid: (al Frae-flowing powder or I
Composition powder agglomerate I
'----..---'- - ------1 (prebland; dry blend) I
1 (bl Pellets; granulate I
Processing
: Liquid: (al Paste I

IPcOd~ I
1 (bl Latex I
1 (cl Solution
1_ _ _ _ _ _ - - - - - - - - -
i
I
I

Further processing
1
1
1----*-------,
i Secondary product I
~ - - - ------.1
Fig. 2.1 Stages in the manufacture of PVC products-general outline.
24 PVC Plastics-Properties, Processing, and Applications

Section 1.1.2 of Chapter 1 for the strict definition of this term). pPVC
materials with low plasticiser contents-up to about 20% (i.e. about
30 phr)-are known as semi-rigid; the softest plasticised materials may
contain well over 100 phr of plasticiser(s).

2.1.2 Constituents of PVC Compositions (Formulation


Components)

With the partial exception, not important in the present context, of


some PVC latex and solution compositions (see Chapters 19 and 20),
virtually all PVC compounds undergo heat treatment-as well as, in
most cases, mechanical shearing which also generates heat-in the
course of processing (including the initial compounding). Many
end-uses also entail exposure to heat in service, albeit at temperatures
generally lower than those encountered in processing. As PVC
polymers are inherently prone to heat degradation (see Chapter 4)
they must be protected by the incorporation of stabilisers. A stabiliser
(very often a composite one, and hence frequently referred to as the
'stabiliser system) is thus, next to the polymer, the second most
important constituent of virtually every PVC composition.
A basic formulation for a uPVC composition will also normally
contain a lubricant: this may be a single compound, but is frequently a
composite (and often formulated jointly with the stabiliser system).
The lubricant counteracts sticking of the melt to hot equipment
surfaces in processing ('external' lubrication) and/or reduces frictional
effects within the melt ('internal' lubrication). A processing aid may
also be included (typically a polymeric additive) to improve melt
properties and fusion characteristics. If the product is required to be
resistant to knocks and impacts in service, then an impact modifier will
be incorporated in the composition to impart toughness to the
relatively brittle PVC polymer: impact modifiers are normally poly-
meric additives (although some toughening effect is claimed also for
certain fine-particle calcium carbonate fillers; see Chapter 6).
In a basic formulation for a pPVC composition a piasticiser (or
plasticiser system, if more than one plasticiser is used) is the essential
component in addition to the PVC resin and heat stabiliser. Apart
from its effects on the finished material properties (imparting softness,
flexibility, extensibility, toughness) it plays an important role in
heat-processing by reducing melt viscosity and providing lubricant
action of the internal kind (see Chapter 7, Section 7.1). Certain
2 Constitution and Formulation 25

plasticisers, and especially plasticiser extenders, can also occasionally


provide some external lubrication; otherwise this function may be
discharged by lubricants which are sometimes specially incorporated in
pPVC compositions.
In addition to the basic constituents, other components are often
included in PVC formulations, mainly for particular end-use pro-
perties. Colourants and fillers are common additives. The latter are
often incorporated, in substantial proportions, as cheapening exten-
ders, but even in such cases the attendant effects on some properties
may be useful, e.g. reduced shrinkage, increased hardness and
stiffness. Some fillers have a principally functional role; for example,
glass or asbestos fibres provide reinforcement. Fillers and their effects
are discussed in Chapter 6.
Other formulation components with specific end-use functions in
PVC materials are the following (discussed in Chapter 9, unless
otherwise indicated): flame retardants and smoke suppressants;
antistatic agents; biostatic additives, odour control agents, matting
('flatting') and anti-blocking agents (cf. also Chapter 20); antioxidants
and UV absorbers (see Chapter 4).
Functional components with a processing role include viscosity
control agents for liquid PVC compositions (viscosity depressants,
thickeners, diluents), and blowing agents and cell-control agents for
PVC foam compositions.

2.2 THE BASICS OF FORMULATING


PVC COMPOSITIONS

2.2.1 General Considerations

The basic general principles of formulating a PVC composition (Le.


deciding on the nature and proportion of its constituents) are relatively
straightforward. However, successful practice calls for a great deal of
specialist knowledge and experience.
Note: Nowadays many PVC processors buy-in compositions from
the wide ranges of compounds formulated and produced for
various processes and applications by commercial compoun-
ders. Many compounders will also custom-make compositions
for specific requirements (see also Chapter 10).
26 PVC Plastics-Properties, Processing, and Applications

A formulator normally designs a composition in response to a stated


need for a product, i.e. he starts with the knowledge of the nature and
intended end-use of the product into which the composition will be
processed (these factors will also determine the process to be used): in
the light of this knowledge three main considerations will govern his
choice of the formulation's components and their proportion, viz. the
requirements of processing and service, and cost economy
considerations.
(a) Processing Requirements
To meet these requirements the composition must be in the right form
for use as feed-stock (e.g. dry blend or pellets for extrusion; paste for
spread-coating of fabrics), have the necessary heat stability under the
processing conditions, and other properties appropriate for the par-
ticular process (e.g. the right fusion characteristics and melt rheology
for extrusion or injection moulding; paste rheology and gelation
properties appropriate to a given spread-coating operation; correct
melt cohesion and lubricity in calendering).
(b) Service Requirements
These are dictated by the nature and conditions of the proposed
end-use and must include, inter alia, stability to the service environ-
ment. Some end-uses impose special requirements. The following
application areas are important examples.
FOOD-CONTACT AND MEDICAL APPLICATIONS (e.g. films for food packaging,
beverage bottles, bags and tubing for blood transfusions and drips)
Non-toxicity of all composition constituents is a cardinal requirement
here; there are also restrictions on extractability and migration of
constituents (especially plasticisers and stabilisers). Stabiliser choice is
essentially restricted to a limited number of individual representatives
of four stabiliser classes: a few approved organotin stabilisers; some
stabiliser systems based on compounds of calcium, zinc, and mag-
nesium; some derivatives of aminocrotonic acid; and some epoxy
compounds (notably epoxidised soyabean oil) used as co-stabilisers in
many formulations. The suitability and selection of plasticisers for
food-contact and medical applications are considered in Section 5.7 of
Chapter 5. In general, all formulation components for such applica-
tions should be checked for acceptability against lists of approved or
recommended materials published by organisations concerned with the
health and safety aspects of plastics products (cf. Chapter 5, Section
5.7, and Chapter 24, Section 24.5). In cases of doubt, the organisa-
2 Constitution and Formulation 27

tions should be consulted directly. It may be noted that each of the


materials on the lists is a specific product of a particular manufacturer,
i.e. there are no blanket recommendations for material types. In some
cases a limit is stipulated on the proportion of the material that may be
incorporated in a PVC composition. There are also procedures
prescribed by some relevant authorities (e.g. the Council of Europe l )
for obtaining approval for new non-toxic components in plastics.

OUTDOOR APPLICATIONS (e.g. window frames, rainwater goods, cladding,


flexible sheeting for reservoir or swimming-pool liners)
These applications call for particularly effective stabilisation against
photochemical degradation of the PVC polymer, selection of other
components (especially polymeric modifiers) for resistance to such
degradation, and-in plasticised compositions-use of non-migratory,
low-volatility plasticisers. UV absorbers and stabilising pigments
(carbon black, titanium dioxide) are also often included in PVC
compositions for outdoor use.

ELECfRICAL INSULATION
Compositions formulated for this purpose should contain no conduc-
tive constituents or impurities: emulsion PVC polymers are not used in
such compositions, as they usually contain trace residues of additives
from the polymerisation process (especially emulsifying agents). The
general requirement also affects stabiliser choice: the stabiliser should
not include conductive compounds, or form such compounds in the
course of discharging its stabilising function. Lead stabilisers, which
meet this condition and are also relatively inexpensive, are normally
the first choice for electrical applications. Plasticiser selection is
influenced, inter alia, by any need to cater for the composition's
stability at elevated temperatures.

(c) Material and Process Cost Economy


Except in certain special cases (e.g. some military applications) this is
always a highly important consideration in the formulation of PVC
compositions.

2.2.2 Selection of the Principal Individual Constituents of a PVC


Composition

(a) PVC Polymer


The main properties considered by the formulator in selecting the
PVC polymer for a particular composition are the chemical nature
28 PVC Plastics-Properties, Processing, and Applications

(i.e. whether homopolymer or copolymer), molecular weight, particle


characteristics (which can be of a special importance in processing),
and quality (purity)-a significant factor in many applications. These
properties and their significance are discussed further in Section 3.3.1
of Chapter 3. The type of polymer (i.e. whether suspension, mass, or
emulsion) is also considered in selection, partly in connection with its
influence on particle characteristics. For PVC paste compositions,
paste grades of emulsion polymers are used, although suspension
polymers are sometimes added as extender ('filler') resins: the use of
PVC polymers in pastes is discussed in Chapter 18. Solid compositions
for extrusion, moulding, and calendering are commonly formulated
with suspension or (less frequently) mass polymers, although mixtures
of one of these with an emulsion resin, or even emulsion resins alone,
are occasionally used, especially in Europe, in some uPVC composi-
tions for better melt flow.
Broadly speaking, suspension and mass polymers may be regarded
as equivalent from the point of view of the ultimate product
properties, although a mass polymer may contain fewer impurities
than an otherwise equivalent suspension grade, and hence give better
clarity in transparent compounds. The differences between the two
types of polymer are more strongly. manifested in processing. Mass
polymers tend to have higher bulk densities than suspension polymers
(for comparable polymer molecular weight and particle porosity), with
greater uniformity of particle porosity and shape (and hence more
uniform and rapid plasticiser absorption) as well as greater ease of
gelation (i.e. ease and completeness of fusion in heat processing),
which is of particular interest in the production of large mOUldings. All
these characteristics can offer processing advantages in certain cir-
cumstances and operations; however, the fact should not be over-
looked that-whilst the processing conditions for best results in a
particular process may not be the same for a mass polymer as for a
suspension one-if they are properly optimised for the type used,
each of the two types can be processed satisfactorily.
With regard to the chemical nature of the polymer component of a
PVC formulation, in broad terms homopolymers have better thermal
stability and impart better mechanical properties to a composition than
copolymers, whilst the latter make for easier melt processing and
greater extensibility and filler acceptance in some compositions.
Copolymers are also normally used in PVC-based solution formula-
tions for surface coatings (d. Chapter 19). The melt-processing
2 Constitution and Formulation 29

advantages of copolymers, like those of lower- versus higher-


molecular-weight homopolymers, are more important in rigid com-
positions, as in adequately plasticised ones the fusion and melt
rheology characteristics are governed principally by the plasticiser.
VC/VAC copolymers form the basis of uPVC compounds for
gramophone records and certain types of sheeting; they are also used
in flooring compositions. They are sometimes included (as in some
formulations in Europe) with a homopolymer to improve the ease of
processing of some rigid formulations. VC/VDC copolymers are
employed, alone or in admixture to homopolymer, in some specialised
compounds for calendering, and also as viscosity-reducing extenders in
some paste formulations.
Some formulations call for high-quality polymer, i.e. one of good
colour, free from coarse particles, fish eyes', * and particulate con-
tamination (low 'speck count').
Note: The number and size of fish-eyes in PVC polymer may be
determined by the method of ASTM D 3596-77(1983). Gels*
in a PVC film (which may be synonymous with fish eyes) can
be determined by the standard gel-count method of ASTM
D3351-74 (1980). ISO 1265 provides a method for the
determination of foreign particles in particulate PVC
polymer.
Low grade polymer can be used, in admixture with standard grades or
even alone, in formulations for the cheaper kinds of injection-
moulding compositions, usually fairly heavily filled, used for the
production of cheap moulded footwear (sandals, slipper soles) and
toys.

(b) Heat Stabilisers


Although much has been learnt over the years about the degradation
of PVC and the effects of stabilisers, the stabilisation of PVC
materials is still largely a practical art, relying on the specialist
interpretation and application, in the specific context of a particular
composition, of information and principles stemming mainly from
practical experience. For this reason, and also because a great variety
of stabilisers is available (many of which are not single chemicals but
compositions specially developed for particular types of formulations

* For definitions see Section 3.3.1( d) in Chapter 3.


30 PVC Plastics-Properties, Processing, and Applications

and end-uses), even a skilled formulator will normally seek the advice
of a reputable supplier when formulating a composition of which he
has no previous experience. The proportion of stabiliser(s) in a PVC
formulation will vary-in broad general terms, between about 0·5 and
8 phr~epending on the nature and purpose of the composition, the
nature of the stabiliser itself, and the processing (including the kind of
compounding to be undergone; for example, the completeness of
dispersion achievable with modern compounding machinery reduces
the stabiliser requirement). Heat stabilisers, their uses and effects are
discussed in some detail in Chapter 4; only the most basic points of
general relevance to formulating are mentioned here. The type of
stabiliser to be considered will be determined by the kind of PVC
composition contemplated (always subject to any special require-
ments). Within the general type, the choice of the particular
compound-or today more usually the composite system-will be
dictated by detailed requirement considerations. For flexible PVC
materials, such as sheeting and film, extrusions (profiles, hose),
mouldings, and paste products, the most widely used stabilisers are of
the barium/cadmium, or barium/cadmium/zinc type (predominantly
liquid systems, but also some solid, or mixed liquid/solid). Flexible
cable coverings and insulation compounds are most commonly stabil-
ised with lead stabilisers (in some cases barium/lead systems). Liquid
barium/cadmium or barium/cadmium/zinc stabilisers are occasionally
used in clear insulation compositions. Rigid compounds (e.g. for
pipes) are widely stabilised with lead stabilisers (especially in Europe)
and organotin or antimony stabilisers (especially in the USA). Solid
barium/cadmium stabilisers with phosphite chelators are also some-
times used. Epoxy co-stabilisers are included in many compositions to
improve heat and light stability.

(c) Plasticisers
Plasticisers convert the inherently hard PVC polymer into composi-
tions of varying degrees of softness and flexibility, processable into a
variety of products with diverse properties and uses (determined to
a large extent by the nature and amount of plasticiser(s) present).
Plasticisers and their effects in PVC are discussed in Chapter 5, and
mentioned at various places in this book. Only a few salient points,
therefore, are indicated here.
The proportion of plasticiser in a pPVC composition is always fairly
substantial, and may be very high in very soft materials. For this
2 Constitution and Formulation 31

reason cost considerations are particularly important in plasticiser


selection. In the absence of special processing and/or service require-
ments which may dictate the choice (see below) the formulator will
normally consider first a relatively inexpensive, general-purpose plas-
ticiser. In most cases this will be a phthalate, commonly di-2-ethylhexyl
phthalate ('dioctyl phthalate'; DOP) which offers reasonably good
all-round material properties.
The cost of phthalate-plasticised formulations (and some containing
other plasticisers) can often be reduced by replacing part of the main
plasticiser by a cheaper secondary plasticiser, e.g. a chlorinated
paraffin (which may also reduce the flammability of the plasticised
composition; cf. Chapters 5 and 24), or a hydrocarbon extender (cf.
Chapter 5). Triaryl phosphate plasticisers (which also reduce flam-
mability) are the second most important group of common plasticisers.
However, a member of this group is not often used as the sole
plasticiser, because of the cost (higher than that of general-purpose
phthalates) and the comparatively poor low-temperature properties
(e.g. cold bend, cold flex, toughness) of compositions so plasticised.
For strong enhancement of good low-temperature properties, aliphatic
diester plasticisers are included in the formulation. Some plasticisers
are particularly associated with special properties they promote in the
composition: for example, butyl benzyl phthalate (BBP) is one of the
best-solvating, quickest-fusion plasticisers for PVC, and thus promotes
rapid and easy processing of its compositions; it also imparts particu-
larly good stain resistance to PVC films and surfaces. Ditridecyl
phthalate (DTDP) has a particularly low volatility (for a phthalate) and
hence a high degree of permanence in compounds (useful, for
example, in high-temperature cable coverings). For particularly high
levels of certain properties, beyond what is available even with the
best among general-purpose plasticisers, recourse must be had to
other, special plasticiser types. Selected representatives of these types
(all more expensive, as a rule, than general-purpose plasticisers) are
used in PVC compositions where the particular property or group of
properties they contribute is of special importance. An outline
summary of plasticiser effects is given in Table 2.1.
Where more than one plasticiser is used in a pPVC composition, the
resulting properties will represent a combination of those normally
conferred by each individual plasticiser when present alone. This is an
important feature of plasticiser action, widely utilised in formulating
PVC compositions.
TABLE 2.1
Some General Features of Plasticise.. Usage W
tv

Characteristics required Typically relevant plasticiser type(s) Examples of application

Price economy Selected phthalates, extenders Wide range of cheaper-grade compositions


for various purposes
Important features of behaviour of plas-
'"tl
ticiser in composition:
(a) High compatability with PVC resin Many phthalates, triaryl phosphates Very soft, flexible products, including paste ~
(i.e. suitability for use in high pro- mouldings and coatings ;:!;!
portions in a composition) e::to
(b) Permanence (low volatility, resis- Polymeric plasticisers; for some purposes, Shower curtains, upholstery, gaskets [;l
tance to extraction and migration in trimellitates, high-molecular-weight
compositions) phthalates, solid blending resins (e.g. ~
(:l
chlorinated PE, EVA copolymers,
nitrile rubber) ~::to
Processing properties: ~
(a) Ease of solvation, fusion and BBP, DBP, triaryl phosphates, phthalates Foamed coatings '"tl
gelation (:l
(b) Effect on viscosity of pastes: '~"'
Low viscosity Aliphatic diesters and extenders '"
~.
High viscosity BBP, DBP, triaryl phosphates, polymeric
plasticisers
End-use properties imparted to compositions: l
).
(a) Good colour Phthalates Clear compositions
(b) Good chemical resistance Polymeric plasticisers Protective clothing ~
(c) Good low-temperature properties Aliphatic diesters (sebacates, adipates, Tarpaulins, flexible tubing for use in cold ~
AGS esters) conditions ~.
(d) Electrical properties:
High resistivity Triaryl phosphates
Low resistivity Sebacates
(e) Food-contact applications Individual plasticisers (high-purity grade) Packaging films
as permitted by relevant authorities
(f) Mechanical properties:
High tensile strength Triaryl phosphates
High extensibility Sebacates
2 Constitution and Formulation 33

(d) Lubricants
The functions of lubricants in PVC compositions are:
(i) to reduce the friction at, and adhesion to, working surfaces
when the composition is being processed (external lubrication);
and/or
(ii) to lower the inter-particle and inter-molecular friction in pro-
cessing (internal lubrication); this reduces the effective melt
viscosity and heat build-up.
Some lubricants discharge only, or mainly, one of these two
functions and are, accordingly, referred to as internal or external
lubricants; others act in both ways. The main factor determining the
type of lubricant action is the lubricant's compatibility with PVC: a
true external lubricant is poorly compatible, and a good internal
lubricant fairly compatible, with the polymer. In selecting a lubricant,
or lubricant system, for a particular formulation, its mutual suitability
and joint effects with the stabiliser(s) must be carefully considered.
This aspect is discussed further in Chapter 7.

(e) Polymeric Modifiers


These fall into two broad categories: processing aids and impact
modifiers (which improve the toughness of uPVC compositions). The
nature and uses of these additives are discussed in Chapter 8.

(f) Fillers
Various fillers, and their applications in PVC compositions, are
considered in detail in Chapter 6. However, two general points
relevant to formulating with fillers may be mentioned here. In many
compositions a filler is included, often at very high loading levels, as a
cheapening extender. Calcium carbonate fillers are commonly
employed for this purpose. When present in substantial amounts, such
fillers will-as will virtually all mineral fillers in plastics generally-
affect some physical properties of the PVC composition: the common
effects are reduced tensile strength, elongation at break, moulding
shrinkage, and thermal expansion coefficient, and increased hardness.
A particularly important point concerning the general effects of
mineral fillers in plastics compositions, including PVC, is that even at
loadings which in many cases do not bring about substantial changes in
other properties, the density of the composition may increase
significantly; it will also continue rising with further increases in filler
34 PVC Plastics-Properties, Processing, and Applications

content. Since the compositions are sold on a weight basis (whilst


ultimately used, in the form of products, on a volume basis-see
Section 2.3), the overall material cost saving may drop progressively
(in some cases quite rapidly) with increased filler loading.

Note: For example, if a given volume of product (say a moulding)


weighs 1 kg when produced from a compound of density
1·1gcm-3 , the weight of compound of density 1·4gcm-3
needed to produce it will be 1·4/1·1 = 1·27 kg (to the second
decimal place).

It is useful to remember that-to the extent to which the generalisa-


tion can validly be made-with particulate mineral fillers, the larger
the particle size, the greater the reduction of surface gloss of the
composition, and the higher the water absorption and the tendency to
'stress whitening' (see Chapter 6). However, the finer the filler, the
greater the plasticiser demand in pPVC compositions and the tendency
to absorb lubricants in uPVC compositions, except where the particles
are effectively surface-coated (see Chapters 6 and 7).

(g) Colourants
A colourant must be able to impart the desired colour, in adequate
strength, to a PVC composition when present in a relatively low
proportion (normally up to a few phr at most). Completeness of
colourant dispersion is of paramount importance for optimum colour
effect in a PVC material, whilst ease of handling and dispersibility of
the colourant in compounding are equally important from the point of
view of operational efficiency and economy. Colourants are available
in forms particularly suited to these requirements, viz. as pre-
compounded colour concentrates of various kinds, or as integral
components of multicomponent 'single-pack' additive systems in which
they are intimately interdispersed with other additives for direct, joint
incorporation in a PVC composition in the course of its compounding.
The aspects of colourants relevant to formulating are among those
covered in Section 9.2 of Chapter 9. Colourant manufacturers are, as a
rule, very technically minded and their advice and recommendations in
connection with specific formulation problems are readily available
and worth having.
2 Constitution and Formulation 35

(h) Other Components of pvc Formulations


Discussion of the other formulation components in the various
relevant chapters and chapter sections includes, inter alia, the points
of direct concern to the formulator.

2.2.3 Some Aids to Formulating

(a) Computer-Aided Formulating


Relevant laboratory data can be processed by computer to provide
reasonably accurate predictions of the likely performance of a PVC
formulation when several of its features are treated as variables. This
approach can be applied to the selection of a formulation which, at the
lowest cost, can meet a particular specification. 2 ,3 Such predictions can
be especially useful at times of price and availability fluctuations.
However, the development of the appropriate programs calls for
considerable expertise, and a large body of reliable data on the effects
of the amounts and nature of the relevant formulation components
upon the composition's properties relevant to the requirements of the
specification concerned.

(b) 'Desirability Function' in Plasticiser Selection for pPVC


Formulations
This concept was first put forward 4 to assist in the selection of
plasticisers for applications requiring several properties of the product,
some of which may be conflicting. The method also takes account of
the price factor.
Briefly, the 'desirability function' is a single number representing the
combination of all the important property factors-each at least at the
minimum level of acceptability-for the application under considera-
tion. For the purpose of the calculation, each of the properties being
considered is allocated a value representing its desirable or admissible
level in the compound. The scale of values is in arbitrary units;
therefore both the measurable properties (e.g. cold flex temperature,
resistivity, etc.) and subjective ones (e.g. odour, irritation) can be
accommodated. Cost can also be one of the properties. One of the
attractive features of the method is that it gives a result strongly
reflecting the effect of a possible particularly low desirability value in
respect of a single property. This is analogous to the rejection by a
prospective user of an otherwise excellent compound because of, say,
36 PVC Plastics-Properties, Processing, and Applications

poor transparency. It has been claimed for the method that com-
pounds within the (properly calculated) range of desirability values
between 0·65 and 0·90 (1·00 represents maximum desirability) are
virtually certain to be suitable for the purpose for which they are being
formulated.

2.2.4 Some Interactions and Mutual Effects of Principal


Components of PVC Formulations

Some of the interactions between the constituents of a PVC composi-


tion arise in normal consequence of the constituents' exercise of their
intended functions, e.g. plasticisation of the PVC polymer by the
plasticiser(s) in pPVC, reactions of stabilisers with polymer decom-
position products, lubrication of the composition by the lubricant(s).
However, other interactions can also occur, and should be taken into
account by the formulator. The kinds of such secondary interactions
are indicated briefly in this section: more detailed discussion of some
of their aspects will be found in other chapters.
(a) Compatibility Effects
As has been mentioned, it is a cardinal general requirement that the
components of a formulation should be compatible with one another
in both processing and service conditions.
Possible effects of one component on the mutual compatibility of
some of the others should also be borne in mind. For example, the
compatibility of an external lubricant with the PVC resin (which
should be relatively limited, for the lubricant to exercise its function
properly) may be increased by the presence of plasticisers or certain
polymeric modifiers: more external lubricant will then be required in
the particular formulation than in a comparable one where the effect
does not arise (cf. Chapter 7, Section 7.2). Similarly, the presence in
the composition of an appreciable quantity of fine-particle filler (or
pigment) able to absorb plasticisers or lubricants may necessitate the
inclusion of these additives in proportions higher than would otherwise
be required, whilst the use of a surface-coated grade of the same filler
(with absorptivity reduced by the coating) would obviate the need for
such compensatory increase (cf. Chapter 6, Section 6.2, and Chapter
7, Section 7.2).
(b) Synergism
The action of some stabilisers can be synergistically enhanced by
certain other stabilisers or lubricants. Examples are the effect of
2 Constitution and Formulation 37

organic phosphite and epoxy co-stabilisers on the heat stability and


resistance to weathering of PVC stabilised with certain stabilisers (see
Chapters 4 and 24), and the synergism of glycerol ester lubricants with
sulphur-containing tin stabilisers, or that of calcium stearate lubricant
with antimony mercaptide stabilisers (see Chapter 7, Section 7.2).

(c) Other Mutual Effects


Noteworthy examples are the activating effect of some stabilisers on
blowing agents in the production of cellular PVC materials, and the
discolouration which may result through interaction of some lead
stabilisers with impurities in lubricants of the glycerol ester type (cf.
Chapter 7, Section 7.2), or through the interaction of sulphur-
containing organotin stabilisers with lead-containing pigments (due to
formation of coloured sulphides).

2.2.5 Side-Effects of Formulation Components

Some constituents of a PVC composition can, in addition to the


function for which they are incorporated, also exert effects which are
the primary functions of other constituents; undesirable side-effects
may also arise. The following examples illustrate some of the effects in
each category.

(a) 'Secondary Functionality' Effects


Such effects are illustrated and exemplified by the following.
(i) Stabilising action of some lubricants and lubrication action of
certain stabilisers (both permitting the use of the other com-
ponent in proportions lower than would otherwise be
necessary-see Chapter 7, Section 7.2).
(ii) Flow-promoting action (i.e. processing aid effect) of some
polymeric impact modifiers (see Chapter 8, Section 8.2).
(iii) Internal lubrication by plasticisers and their impact-modifying
effects.
(iv) External-lubricant effect of some plasticisers (see Chapter 7,
Section 7.2).
(v) Flame-retardant effects of phosphate plasticisers and
chlorinated-paraffin secondary plasticisers [cf. Section 2.2.2(c)
above; Chapter 5, Section 5.6.5, and Chapter 9, Section 9.2].
(vi) Stabilising action of epoxy plasticisers (cf. Chapter 4, Section
4.3; Chapter 5, Section 5.5.3).
38 PVC Plastics-Properties, Processing, and Applications

(vii) Light-stabilising effect of carbon black, the common black


pigment used in plastics compositions including PVc.

(b) Undesirable Side-Effects


Examples of such side-effects include
(i) Opacifying effects of fillers, many impact modifiers and other
formulation components, which must be considered when
formulating clear compositions.
(ii) Susceptibility to 'sulphide staining' (through formation of
coloured sulphides) associated with the presence of stabilisers
which are heavy-metal compounds (especially lead and
cadmium-see Chapter 4, Section 4.8).
(iii) Detrimental effect of emulsion PVC polymer on the electrical
resistance of compositions based on this type of polymer [cf.
Section 2.2.1(b) above, and Chapter 3, Section 3.3.1(d)].
(iv) Lowering of heat stability of PVC compositions by most
antistatic agents (cf. Chapter 9, Section 9.2.3).
(v) Tendency to 'stress whitening' promoted by the presence of
some fillers (see Chapter 6, Section 6.2) and polymeric modi-
fiers (see Chapter 8, Section 8.3.3).

2.2.6 Examples of Basic Formulations

The following examples illustrate something of the principal features


of basic outline formulations for some PVC products of the main
groups listed in Table 1.2, Chapter 1.

(a) Pipes and Tubing

(i) Rigid pipe (lead-stabilised):


PVC polymer (S* or M, t K value 65-68) 100
Stabiliser/lubricant (co-precipitate):
Tetrabasic lead sulphate 1·2 phr
calcium stearate 1·2 phr
polyethylene wax 0·1 phr
Filler: CaC0 3 (fine-particle-size grade: precipitated, 2-4phr
or ultrafine ground whiting; surface-coated)

* Suspension type.
tMass type.
2 Constitution and Formulation 39

Absence of impact modifier makes this a 'non-impact-resistant'


formulation.
(ii) Clear, flexible tubing (non-toxic-1or medical use):
PVC polymer (S or M, K value 65-70) 100
Stabiliser: Ca/Zn type 1·5-2·0 phr
Co-stabiliser: epoxidised soya bean oil 2 phr
Plasticisers: DOP 10 phr
high-molecular-weight polyester (e.g. 37 phr
Reoplex 43O-Ciba-Geigy)
Lubricant: a glycerol monoester (e.g. Loxiol G 10) 0·0-0·6 phr

(b) Extruded Profiles

(i) High impact uPVC:


PVC polymer (S or M, K value 60) 100
Stabilisers: tribasic lead sulphate 6phr
dibasic lead stearate 1 phr
Lubricants (internal/external): fatty acid ester type 1·9-2·0phr
calcium stearate 0·4-0·8phr
Impact modifier: ABS type 6-1Ophr
Processing aid: acrylic type 1·8-2·2 phr
(ii) Flexible composition:
PVC polymer (S or M, K value 68-70) 100
Stabiliser: a Ba/Cd soap complex (e.g. Irgastab BC 1·2-1·5 phr
247)
Co-stabiliser: an organic phosphite (e.g. decyl 0·4-0·5 phr
diphenyl phosphite, Irgastab CH 301)
epoxidised soyabean oil 5 phr
Plasticiser: DOP 47 phr
External lubricant: stearic acid 0·1-0·4 phr
This is a non-transparent composition which may be pigmented. The
BalCd stabiliser provides some lubrication, reinforced as necessary by
the stearic acid.
(c) Sheeting and Film
(i) Calendered clear uPVC-1ood packaging grade:
PVC polymer (S or M, K value 60) 100
Stabiliser: a di-n-octyl tin (e.g. Irgastab 17 MOL- 1·1-1·5 phr
Ciba-Geigy)
40 PVC Plastics-Properties, Processing, and Applications

Lubricants:
Internal: fatty alcohol type (e.g. Irgawax 365- 1·2-2·0phr
Ciba-Geigy)
Internal/external: fatty acid ester type (e.g. 0·2-0·5phr
Irgawax 370)

If an impact modifier is included it should be of the MBS type (and


fully compatible with the lubricant system) to maintain transparency.
For maximum clarity the polymer should be of high-purity, fish-eye-
free grade.

(ii) Calendered, clear pPVC with good stability to light-general-


purpose and horiticultural applications:
PVC polymer (S or M, K values 69-72) 100
Stabiliser: Ba/Cd liquid (e.g. Irgastab BC 26) 1·3-1·6phr
Co-stabilisers: epoxidised soyabean oil 5phr
an organic phosphite (chelator) 0·4-0·5 phr
Plasticisers: DOP 55phr
triaryl phosphate lOphr
UV absorber: (light stabiliser, e.g. Tinuvin P) 0·2-0·3phr
External lubricant: stearic acid 0·2-0·4phr

(iii) Extruded (blown) filled pPVC film-industrial grade:


PVC polymer (S or M, K value 68-71) 100
Stabiliser: a Ba/Cd soap complex (e.g. Irgastab BC 0·9-1·8 phr
247)
Co-stabiliser: an organic phosphite (e.g. Irgastab CH 0·3-0·6phr
301)
Plasticiser: DOP 42phr
Plasticiser extender: chlorinated paraffin 13phr
(50-52% CI)
Filler: whiting (a coated grade) 40phr

The barium/cadmium soap stabiliser has some external lubricant


action in this composition, so additional external lubrication may not
be necessary. Otherwise about 0·3 phr of stearic acid may be added. It
is good practice to use a chelating co-stabiliser with solid
barium/cadmium stabilisers (in the respective proportions of 1 to 3) to
improve the initial colour and light stability of the composition.
2 Constitution and Formulation 41

(d) Calendered PVC/Asbestos Flooring (Tiles)


Vinyl chloride/acetate copolymer (K value 55, 13- 100
15% VA)
Stabiliser: A Ca/Zn complex powder (e.g. Irgastab 2·0-4·0phr
CZ 45M)
Co-stabiliser: epoxidised soya bean oil 6·0-8·0phr
Plasticiser: DOP 15phr
External lubricant: stearic acid 1·0-2·0phr
Pigment: titanium dioxide 10-15 phr
Fillers: asbestos (chrysotile) 100phr
whiting 160phr
Special grades of solid calcium/zinc complex stabilisers are produced
by most manufacturers for vinyl/asbestos fiooring compositions. These
stabilisers combine good compatibility with VC/VA copolymer and
asbestos, with very good heat stabilisation (even when a substantial
proportion of scrap is added to the compound) and freedom from
sulphide staining of the fiooring in contact with rubber objects in
service. They have no appreciable lubricating action; an external
lubricant should, therefore, be included in the formulation; stearic
acid is particularly useful since, in addition to its lubricant effect, it can
also enhance stabilisation. The amount required will normally increase
with increasing calcium carbonate filler loading (as well as when
substantial amounts of pigment are incorporated): 0·1 phr stearic acid
per 8 phr filler may be taken as a general guideline (but with
surface-coated filler grades the effect of the presence of the coating
should be taken into account-see Chapter 7, Section 7.2).

(e) Cable Covering and Insulation

(i) High-temperature cable compound:


PVC polymer (S or M, K value 68) 100
Stabiliser: dibasic lead phthalate 7phr
Plasticiser: tri-Linevol 79 trimellitate (e.g. Reomol 70phr
LTM-Ciba-Geigy)
External lubricant: calcium stearate 1phr
Flame retardant: antimony trioxide 6phr
In this composition calcium stearate contributes to heat stabilisation
whilst acting as lubricant. Ditridecyl phthalate (DTDP) may be used as
42 PVC Plastics-Properties, Processing, and Applications

plasticiser instead of the more expensive trimellitate for all but the
most severe conditions (but the efficiency of the latter is better, so that
a lower proportion is required, and trimellitate-plasticised composi-
tions retain their properties better after heating at high temperatures).
An antioxidant is desirable, especially if the compound is to be used
in thin sections. Reomol LTM already contains 0·2% of an effective
antioxidant (Irganox 1010).
(ii) General-purpose insulation:
PVC polymer (S or M, K value 68) 100
Stabiliser: basic lead carbonate 7phr
Plasticiser: di-iso-octyl phthalate (DIOP) 30phr
Plasticiser extender: chlorinated paraffin 30phr
(50-52% CI)
External lubricant (with stabilising action): 1·3 phr
calcium stearate
Filler: whiting (a coated grade) 70phr

(f) Injection Mouldings


(i) Clear, plasticised compound:
PVC polymer (S or M, K value 65~67) 100
Stabiliser: liquid Ba/Cd/Zn (e.g. Irgastab Be 206) 1·5-2·5 phr
Co-stabiliser: epoxidised soyabean oil 5phr
External lubricant: liquid, non-polar type (e.g. 0·3-0·5phr
Irgawax 360)
The lubricant used should be chosen, inter alia, for its suitability in a
clear formulation.
(ii) Oil-resistant soling compound:
PVC polymer (S, K value 66-70) 100
Stabiliser: solid Ba/Cd 4phr
Co-stabiliser: epoxidised soyabean oil 5phr
Plasticiser: DIOP 80phr
Polymeric modifier: nitrile rubber 33phr
(g) Blow-Moulded Bottles
(i) For mineral water:
PVC polymer (S or M, K value 58) 100
Stabilisers: zinc octoate 0·15-0·20 phr
calcium stearate 0·05-0·10 phr
2 Constitution and Formulation 43

Co-stabilisers: distearyl pentaerythrityl diphosphite 0·4-0·5 phr


epoxidised soyabean oil 3·0phr
Impact modifier: MBS type 1O·0phr
Processing aid: acrylic type 0·5-1·0phr
All additives in a formulation for this purpose must be of special purity
grade (as well as permitted for food contact) because mineral water
picks up taints easily. For the same reason the use of permitted
organotin stabilisers is not recommended. The epoxy co-stabiliser has
some plasticising action. If the lubricating effect of the calcium stearate
is not sufficient in a particular moulding process, lubricant(s) best
suited to the conditions should be incorporated.
(ii) General-purpose, clear:
PVC polymer (S or M, K value 54-58) 100
Stabiliser: liquid thiotin 1·4-1·6 phr
Impact modifier: MBS type 10-12 phr
Processing aid: acrylic type 1-2phr
Lubricant (internal/external): fatty-acid ester type 1·0-1·5 phr

(h) Paste Formulations


(i) Cold dipping paste:
PVC polymer (E, * K value 69-72) 100
Stabiliser: basic lead carbonate 2phr
Plasticisers: DOP 65phr
DOS 17phr
(ii) Conveyor belting:
PVC polymer (E, K value 69-72) 100
Stabiliser: tribasic lead sulphate 2·0-3·0pbr
Plasticiser: triaryl phosphate 40phr
Plasticiser extender: chlorinated paraffin (45% CI) 35phr
Flame retardant: antimony trioxide 5phr
Antistatic agent: e.g. Lankrostat LA3 (Lankro 10phr
Chemicals)
(iii) Composite coating for upholstery fabric:
Base coat
PVC polymer (E, K value 70) 100
Stabiliser: liquid Ca/Zn (e.g. Irgastab CZ 57) 1·5-3·0phr

* Emulsion type.
44 PVC Plastics-Properties, Processing, and Applications

Co-stabiliser: epoxidised soyabean oil 5·0phr


Plasticiser: OOP 85phr
Filler: Whiting 20phr

Intermediate (expanded) coat


PVC polymer (E, K value 68-70) 100
Stabiliser/activator: liquid, zinc-containing (e.g. 1·5-2·5phr
Irgastab ABC2)
Co-stabiliser: epoxidised soyabean oil 6·0-8·0phr
Plasticisers: OOP 45phr
BBP 30phr
Blowing agent: azodicarbonamide (paste, 1: 1 in 2·5-4·5 phr
OOP)
Filler: fine-ground whiting 5phr

The zinc-based stabiliser is selected to act also as an activator


('kicker') for the blowing agent in this foaming composition. The BBP
(butyl benzyl phthalate) is a highly solvating plasticiser, widely used in
PVC foam formulations for rapid, uniform fusion of the composition.

Top coat
PVC polymer (E, K value 70-72) 100
Stabiliser: liquid Ba/Cd/Zn complex (e.g. Irgastab 1·5-2·5 phr
BC 206)
Co-stabiliser: epoxidised soyabean oil 5·0phr
Plasticiser: OOP 52phr
Pigment: titanium dioxide 0·0-3·0phr
Filler: whiting 0·0-10·0 phr
Colourant: as required

The stabiliser is one suitable for clear PVC to enable the formulation
to be used for unpigmented, unfilled compositions.

2.3 MATERIALS COST OF A FORMULATION

It is usual to express the formulation of a PVC composition in terms


of 100 parts by weight of the PVC resin, using the abbreviation 'phr'
(parts per hundred resin) for the content of each component so
expressed.
2 Constitution and Formulation 45

A EXTRACT Evaporate ether .® SOLVENT -FREE


EXTRACT
1 Org.anic st.bilisers (including
most organotins and
epoxidised soyabean oil).
2 Monomeric plasticisers and
plasticiser extenders
(chlorin.ated paraffins;
hydrocarbons) .
3 Most org.anic lubricants
(e.g- glycerol esters; stearyl
, - , - , - - - - - , Extract (SoxhleO esters).
4 Light stabilisers
with
{UV-absorbers}.

Precipitate
gradually
with
ethanol

C EXTRACT Evaporate.~SOLVENT_
methanol FREE
~
.3
B.7
EXTRACT
B RESIDUE Extract (Soxhlet) B.8
ExtractCSoxhlet) E EXTRACT
wIth methanol (36h)
with 8.1

[J
1 PVC resin(s). D RESIDUEtetrahydro1uran 8.4
2 Most inorg.mic stabilisers
'1 (24h)
(based on e.a,Ca,Cd,Pb, B.2
Sb,Zn) .and phosphorus- 64-66
containing chelators).
3 Polymeric plasticisers.
4 Polymeric modifers
5 Metal-soap lubricants
(e.g. Ca and Pb stearates).
6 Inorgoiilnic fillers and
pigments.
7 Antistatic agents.
S Polymerisation residues
(suspending agents;
emulsifiers) .

Fig. 2.2 Analysis of a PVC material: a general separation scheme.


Relevant final identification methods are as follows.
Components of extract A I : gas chromatography (GC); thin-layer chromat-
ography (this can also serve as a final separation method for individual
components): infrared spectrophotometry (IR). Light stabilisers can be
identified by UV-absorption spectroscopy. 24
Components of extract C: GC; IR.
Components of residue F: IR; chemical analysis.
Components of first precipitate G and solution H: IR.

Whilst it is convenient to formulate a PVC composition on the


weight basis, the material when made into products will ultimately be
sold effectively on a volume basis (e.g. as lengths of pipe or profile of
particular dimensions, numbers of mouldings, etc.). Thus it is relevant
to know both the weight-cost and the volume-cost of the components
of a formulation. Moreover, given two basically similar compositions
which, however, differ in density (say because the denser one contains
a heavy mineral filler used as a cheapening extender), although the
46 PVC Plastics-Properties, Processing, and Applications

materials cost of the denser compound may be lower on a weight basis


it can be more expensive on a volume basis.

2.4 COMPOSmONAL ANALYSIS OF PVC MATERIALS

As indicated in Sections 2.2.1 and 2.2.2 above, and made evident by


other relevant parts of this book, the composition of PVC materials
can be quite complex: in consequence, so is the analysis of a PVC
material whose formulation is not known. After a preliminary visual
inspection, which will normally show whether the material is uPVC or
pPVC and can also indicate possible presence of colourants and fillers,
the analysis proper will comprise separation of components (or at least
groups of components), followed by identification of the components
(or their characteristic part-constituents-e.g. the metals in stabilisers
and pigments). Two useful separation schemes are shown, in broad
outline, in Figs 2.2 and 2.3: both relate to plasticised compositions
since the analysis of these encompasses also uPVC, in that the first
step is the removal of plasticisers whereupon the remainder becomes,
in effect, a uPVC composition. The scheme of Fig. 2.2 has evolved on
the basis of the early methods of plasticiser extraction from pPVC
materials. 5 That of Fig. 2.3 is currently the subject of an ASTM
standard,6 whose formal scope is restricted specifically to the separa-
tion, identification, and determination in a PVC composition, of only
those components named in the figure's caption. For the separation
treatments of Figs 2.2 and 2.3 the material should be comminuted (if
not already in powder form, e.g. a dry blend) for intimate contact with
the reagents. Comminution may be effected for example by grinding
after cooling in liquid nitrogen or solid CO2 , slicing with a microtome
or buffing on a coarse grinding wheel.
The techniques most widely used (often jointly) to identify the
constituents of a PVC composition after separation are IR spectropho-
tometry and gas or gas/liquid chromatography. Thin-layer chromatog-
raphy is also used (both as a final separation method for individual
liquid or solvent-soluble components, and for their identification).
Nuclear magnetic resonance is employed in some cases as a final
identification technique, as is-somewhat less widely nowadays--'wet'
chemical analysis. Examination under the microscope can be helpful in
identifying some fillers, notably asbestos fibres, glass fibres, and some
grades of calcium carbonate; crystals of some crystallisable com-
-~-----..
~ @SOLVENT-FREEEXTRACT

Extract
PVC
MATERIAL (Soxhlet) with
diethyl ether ©SUPERNATANT LIQUID
(comminuted:
(BATCHED THF EXTRACTS)
approx.lg) (6h) N

~
~
(a) Heat with tetrachloroethane ~'
until all solubles dissolved g.
,.-_:=---, (b) Add tetrahydrofuran, shake
for 30 min ~
(cJ Centrifuge for 30min
~
L----=-_----' (d) Decant supernatant liquid
(e) Repeat (b)-(d)twice(to
~
extract all PVC resin)
~
@RESIDUE Dry. ~ @ DRY RESIDUE
§"
and weigh

Fig. 2.3 Separation procedure for identification (by infrared spectrophotometry) of some components of a PVC
material,6 viz.
In Extract AI: dioctyl phthalate, tricresyl phosphate, and epoxidised soyabean oil.
In supernatant liquid C: PVC resin.
In Residue D1: lead stabilisers (basic lead carbonate, tribasic lead sulphate, diabasic lead phthalate); inorganic fillers
(calcium carbonate, chalk, antimony trioxide). ~
48 PVC Plastics-Properties, Processing, and Applications

ponents (e.g. stearic acid where used as a lubricant) can sometimes be


identified under high magnification.
Several publications can serve as sources of further, detailed
relevant information on the following subjects.

Analysis of plastics materials (including PVC): Books by Haslam et


al. 7 Crompton8 and Hummel & Scholl;9 papers by Arnold & Willis, 10
Kagarise & Weinberger l l (IR spectra), and Tryon & Horowitz 12 (IR
spectra).

Analysis of pVC: Papers by Haslam & Newlands,13 Burley &


Bennett 14 (spectroscopic analysis), and Haslam & Soppett15 (deter-
mination of chlorine in PVC resins).

Analysis and identification of plasticisers: ASTM D 3421-75 16 (total


plasticising additives and DOP); publications by Kendall et al. 17 (IR
spectra), and Haslam et al. 18

Analysis and identification of other components of pvc


compositions: Books by Crompton/ 9 Scholl,2° and Lawson;21 papers
by Miller & Wilkins,22 and Hunt et af. 23

REFERENCES

1. Anon., Substances Used in Plastics Materials Coming into Contact with


Food, 2nd edn. Council of Europe Publications Section, Strasbourg, 1982.
2. Tang, Y. P. & Harris, E. B., SPE ]., 23(11) (1967) 91-5.
3. Pugh, D. M. & Wilson, A. S., Eur. Plast. News, 3(9) (1976) 37-42.
4. Harrington, C. E., Ind. Qual. Control, 21 (1965) 494-8.
5. Kainer, F., Polyvinylchlorid und Vinylchlorid Mischpolimerisate, Springer
Verlag, Berlin, 1951, p. 245.
6. ASTM D 2124-70 (1984). Analysis of Components in Poly(vinyl chloride)
Compounds Using an Infrared Spectrophotometric Technique.
7. Haslam, J., Willis, H. A. & Squirrell, D. C. M., Identification and
Analysis of Plastics, 2nd edn. Iliffe Books, London, 1973.
8. Crompton, T. R., The Analysis of Plastics, Pergamon Press, Oxford,
1984.
9. The Hummel/Scholl Atlas of Polymer and Plastics Analysis. Vols 1-3.
Current edition. Carl Hanser Verlag, Munich, Vienna and VCH Pub-
lishers, New York, Weinheim, Basel, Cambridge. NB. The latest edition
of Vol. 2 is 1988.
2 Constitution and Formulation 49

10. Arnold, P. & Willis, H. In Polymer Science, ed. A. D. Jenkins.


Northern-Holland Publishing Co., Amsterdam and London, 1972, Ch. 24.
11. Kagarise, R E. & Weinberger L. A., Infrared Spectra of Plastics and
Resins. OTS Publication PB 11438, US Dept of Commerce, 1960.
12. Tryon, M. & Horowitz, E. In Analytical Chemistry of Polymers, Part 2,
ed. G. M. Kline. Interscience Publishers, New York, 1962, Ch. 8.
13. Haslam J. & Newlands, G., 1. Soc. Chem. Ind., 69 (1950) 103-12.
14. Burley, R A. & Bennett, W. J., Applied Spectroscopy, 14 (1960) 32-41.
15. Haslam, J. & Soppett, W. W., 1. Soc. Chem. Ind., 67 (1948) 33-42.
16. ASTM D 3421-75. Extraction and Analysis of Plasticiser Mixtures from
Vinyl Chloride Plastics. (Discontinued in 1989.)
17. Kendall, D. N., Hampton, R. R, Hausdorff, H. & Pistera, F., Applied
Spectroscopy, 7 (1953) 179-88.
18. Haslam, J., Soppett, W. W. & Willis, H. A., 1. Appl. Chem., 1 (1951)
112-19.
19. Crompton, T. R., Chemical Analysis of Additives in Plastics, 2nd edn.
Pergamon Press, Oxford, 1977.
20. Scholl, F., Additives and Processing Aids: Spectra and Methods of
Identification, Vol. 3 of Ref. 9 above.
21. Lawson, K. E., Infrared Absorption of Inorganic Substances. Reinhold,
New York, 1961.
22. Miller, F. A. & Wilkins, C. H., Analytical Chemistry, 24 (1952) 1253-8.
23. Hunt, J. M. Wishert, M. P. & Bonham, L. C., Anal. Chemistry, 22 (1950)
1478-89.
24. Ruddle, H. L. & Wilson, J. R., Analyst, 94 (1969) 105-15.
Section 2

CONSTITUENTS OF PVC
COMPOSITIONS

51
CHAPTER 3

PVC Polymers

3.1 HOMOPOL YMERS OF VINYL CHLORIDE

3.1.1 Chemical Structure and Molecular Weight

The basic repeat unit of the PVC polymer chain is [-CH2-CHCI-].


The units are linked essentially 'head-to-tail' (Le. -CH2-CHCI-
CH2-CHCI-), with very few head-to-head junctions (see Table 3.3).
In commercial PVC polymers the average number of repeat units in
the molecular chain (Le. the degree of polymerisation) can range
between about 500 and 1500; this corresponds to a theoretical
molecular weight range of about 31000-94000.
Note: As with other polymers, the numerical values from deter-
minations of weight-average (Mw), number-average (Mo), and
viscosity-average (My) molecular weight of the same sample
of polyvinyl chloride are in the sequence Mw> My > Mo, with
My closer to Mw than to Mo.
In industrial practice, dilute-solution viscosity of PVC polymers is
normally determined (by direct measurement of solution and solvent
flow times) as an index of the molecular weight. The results are
commonly expressed in terms of the K value or viscosity number, but
sometimes also as specific viscosity or inherent viscosity (logarithmic
viscosity number). Where the actual value of My is required, it can be
calculated, under certain assumptions, from the Mark-Houwink
equation (also known as the Staudinger-Kiihn equation):l,2
[17] = K(My )'''

where K and Cl' are constants for a given polymer/solvent system at a


53
54 PVC Plastics-Properties, Processing, and Applications

given temperature, and [1'/] is the limiting viscosity number (intrinsic


viscosity) determined by extrapolating to zero-concentration a plot of
the viscosity number (reduced viscosity), or of the inherent viscosity,
versus dissolved polymer concentration. The relationships between the
various viscosity terms are set out in Table 3.1.
The version of the K value in widest use is the Fikentscher K value:
its relation to other K values also sometimes quoted, and to the
various viscosity expressions in common use for PVC polymers, is
shown in Table 3.2; Fig. 3.1 shows the relationship between this K
value and molecular weight. The Fikentscher K value was first
introduced as an index of the molecular weight of cellulose polymers. 3
It is dependent on the nature of the solvent, but little influenced by the
concentration (in generally dilute solutions) and the temperature of
determination. For PVC polymers it is related to the viscosity ratio
1'/11'/0 (see Table 3.2) by the expression
cK (75K )
In (1'/11'/0) = 1000 1.5 cK + 1000 + 1
Most commercial PVC polymers have Fikentscher K values within the
range 50-80. Polymers with much higher values have also been made.
Like those of other thermoplastics, the properties of PVC polymers
are influenced by the average molecular weight and also by the
molecular weight distribution. The ratio Mwl MD (known as the
'dispersion of distribution') is a function of the latter (giving an
indication of the width of the distribution curve but not greatly
influenced by its shape). Commercial PVC polymers usually have a
relatively narrow molecular weight distribution, with Mwl MD values of
suspension polymers typically within the range 2-2·5 (reducing with
increasing polymerisation temperature). The best method for obtain-
ing complete molecular weight distribution curves of PVC polymers is
gel-permeation chromatography (GPC): the data produced by this
technique can also be used to calculate Mw and MD values (shown to be
in good agreement with direct determinations by other methods7,8). A
review of the evaluation of the molecular weight characteristics of
polymers and copolymers of vinyl chloride by GPC has been published
by Janca and Kolinsky.9 ASTM D 3593-80 (1986) gives CPC proce-
dures and Mark-Houwink constants for PVC (inter alia).
Polymerisation temperature is the most important factor governing
the molecular weight of PVC polymers: molecular weight increases
with decreasing temperature, both within the normal temperature
TABLE 3.1
Polymer Solution Viscosity: Terms and Expressions
Terms and symbols Mathematical Remarks
expressionb,c
Original Now recommendeda

Term Symbol Term Symbol

Relative viscosity "r or "rel Viscosity ratio ,,1"0 ,,1 "0


Specific viscosity "sp (" - "0)/"0 Also known as viscosity
increment: represents viscosity
increase attributable to the
dissolved polymer
Reduced viscosity RV Viscosity number (" - "o)/"oc Provides a measure of the specific
....
capacity of the polymer to
increase the viscosity ratio ~
Inherent viscosity IV Logarithmic viscosity [In (" 1"0)]1c ~
number '<'
:I
Intrinsic viscosity [,,] Limiting viscosity [,,] limc-+o [(" - "o)/"oc] The reduced and inherent '"
t:l
number = limc~o [(In" 1"0)1 c] viscosities tend to the same
limit as the dissolved polymer
concentration tends to zero.
The value of the limit (intrinsic
viscosity) is different for the
same polymer in different
solvents because of
polymer 1solvent interactions

a By the International Union of Pure and Applied Chemistry (IUPAC).


b The relationships expressed are valid for practical determinations only when the relevant viscosities are determined under the same
standard conditions.
C Key to symbols used in the expressions: viscosity of dilute polymer solution (or its time of flow in standard conditions); ~
,,=
flo = viscosity of the solvent alone (or its time of flow in the same standard conditions); c = concentration of the polymer, in g per ml of
solution.
Vl
0-
TABLE 3.2
Interrelationship between Some Common Standard Indices of Molecular Weight of PVC Polymers4 .5
(Based in part on a table compiled by Matthews and Pearson of leI, first reproduced, with permission, in the 3rd edition)

\0'
~ ~
'I) 'I)
,eo ,eo
£.l~ '<')
I:: ~ I:: ~
ilr)lr) i£.l • I:> •I:>
~ I:: ~ I::
... ... E: 8~ ..... 'l)l:! ~
8~~ c-<::S c-<::S '1)001;:
'I) 10 ~~ ~~ _~ - ..... <::st:::l f::! El
I "_ I
~
8~", ~~ ... E:..9
001;:
8'1)
'-I::
''I)
~I:: '.
'-'5
eo'l) ~ooI;:
.-
~ooI;:
~ §IO ~.~
- ~.~ ::to
Q
'I) .~~
E~.~ eo I:> '<') I:> Iil "'..9 l:'I) ~ ~ ~
::to,t;l .~C"l~ "r~
'.~- -§~
1:: ..... ;,..... .~~~
..... 8·~
..... '1::1 ..... ~ ~N ;, ;>... .!:;l '"
;,;>... .!:;l f:::Z ;, ... 'is ... I
-t:::l'<::s ;'t:::l'<::s ~;, 6~~ 'is..s! ... ..s! ;t'
.~t:t ~ 'I) ~ 'Il~!:/ ~ ~ Iil"'" 'I) ::t .g
I::~ I:> '" I:> ~ ~ £.l .::! 001;: I:: '" '" E: 'I) - ::t -c",
~ ..... t:::l ~ Eo-< -S $~-S ";'l~1r) ~ ~ooI;: <::Sl:>~ - $ilr)
"''''£.l $i~
;:..,.~ 001;
.~~
: '" E:~
~ ;:..,.~ ;,-§ ~ t:s 0_ is -ce ~8t<') '"~.
"'O'<::s
.!:;l t') I:: ~~~ ~~~ ~8~ 15~
. . -5 ~ ~.~ ~ ..... '5 Q,,'1;:! ~~ ~ ~ ,?l
$:"'I)<::S ~ ..... '5
::.: ..... <::s ~~~ ~~~ t3....... ~C- ~ c-es
;t'
c
50 0·42 0·155 1·216 42 45·3 49 0·25 0·08 275 40000 20000 '"~
52 0·44 0·165 1·227 43 46·2 50 0·26 0·09 310 ~.
54 0·47 0·175 1·237 44 47·1 51 0·27 0·10 350
57 0·49 0·185 1·247 45 47 48·4 52 0·28 0·105 380 54000 26000 §
I:>..
59 0·52 0·195 1·258 46 49 49·3 53 0·29 0·11 415
61 0·55 0·206 1·269 47 51 50·1 54 0·31 0·115 450 30000 ~
"5
:::-:
64 0·57 0·217 1·280 48 52 51·3 55 0·32 0·120 495 ~
1·292 49 53 52·4 56·5 0·34 0·125 525 ::to
67 0·60 0·228 c
70 0·62 0·239 1·304 50 54 53·6 57·5 0·35 0·13 560 70000 36000 ~
73 0·65 0·25 1·316 51 55 54·7 58·5 0·37 0·14 600
77 0·67 0·264 1·329 52 57 56·1 59·5 0·38 0·145 640 40000
80 0·70 0·275 1·342 53 58 57·2 60·5 0·40 0·15 680
83 0·73 0·285 1·355 54 59 58·2 61·5 0·42 0·155 720
87 0·75 0·3 1·369 55 60 59·5 62·5 0·44 0·16 760 100000 45500
90 0·78 0·31 1·383 56 61 60·5 63·5 0·45 0·17 800
94 0·80 0·32 1·397 57 62 61·7 64·5 0·47 0·175 840 50000
98 0·83 0·33 1·412 58 63 62·9 66 0·49 0·18 885
102 0·85 0·34 1·427 59 64 64·1 67·5 0·51 0·19 930
105 0·88 0·36 1·443 60 65 64·9 68 0·53 0·195 975 140000 55000
109 0·91 0·37 1·458 61 66 66·1 69 0·55 0·20 1025
113 0·92 0·38 1·474 62 67 67·1 70 0·57 0·205 1070
117 0·95 0·39 1·491 63 68 68·2 71 0·59 0·21 1120 60000
121 0·98 0·40 1·508 64 69 69·2 72 0·61 0·22 1175
125 1·01 0·41 1·525 65 70 70·2 73 0·63 0·225 1230 200000 64000
130 1·03 0·43 1·543 66 70·5 71·5 74 0·65 0·23 1300
134 1·06 0·44 1·562 67 71 72·4 75 0·67 0·235 1350
138 1·08 0·45 1·581 68 72 73·3 76 0·69 0·24 1420 70000
142 1·11 0·46 1·60 69 73 74·3 77 0·71 0·25 1490 .....
145 1·13 0·47 1·62 70 74 74·9 78 0·73 0·255 1570 260000 73000
~
149 1·16 0·49 1·64 71 75·8 0·75 0·26 1650
153 1·18 0·50 1·661 72 76·7 0·77 0·27 1720 ~
157 1·21 0·51 1·682 73 77·5 0·79 0·275 1810 cl'
~
161 1·23 0·53 1·704 74 78·3 0·81 0·28 1900 80000 ;!
165 1·26 0·54 1·726 75 79·1 0·83 0·29 1980 340000 82000 '"<::l
169 1·28 0·56 1·749 76 79·9 0·85 0·295 2070
173 1·30 0·57 1·772 77 SO·7 0·87 0·30 2170
177 1·33 0·58 1·796 78 81·5 0·89 0·31 2260
181 1·35 0·6 1·821 79 82·2 0·90 0·315 2360 90000
185 1·38 0·61 1·847 80 83·0 0·93 0·32 2460 480000 91500
a The recommended term is logarithmic viscosity number (cf. Table 3.1).
b This method involves measurement of the viscosity of 0·2 g/l00 ml solution of PVC polymer in cyclohexanone at 30°C.
C This is the viscosity ratio less unity (rJlTJo) = (TJ - TJo)/TJo (see Table 3.1).
d In this method specific viscosity is calculated from the results of determination on a dilute solution of PVC polymer in
nitrobenzene (0·4 g/l00 mI). ASTM D 1243-58T and its subsequent (1966) edition have been superseded by
ASTM D 1243-79, the version currently in force. This gives only one method, whereby the viscosity of 0·2 g/l00 ml VI
-.J
solution of PVC polymer in cyclohexanone is determined at 30°C, and the logarithmic viscosity number calculated from
the results.
58 PVC Plastics-Properties, Processing, and Applications

100000 5·8

90000

80000

70000

1'1 60000 52
C1
o
...J
50

5·0.·100000

40000

30000 4·8

--50000
20000
4·6

10000

K ValU4

Fig.3.1 Relationship between the Fikentscher K value (DIN 53726-1983) and


the molecular weight of PVC polymers.

range for industrial production (about 40-75°C) and outside it.


Polymers of very high molecular weight (such as may be produced, for
special purposes, at near-zero temperatures) may require intensive
heating in the solvent for complete dissolution when solutions are
being prepared, e.g. for viscosity measurements or GPC
determinations.lO The effect of polymerisation temperature within the
range 0-70°C on the molecular weight of PVC polymers was examined
by Ravey & Waterman. l l The temperature also affects the degree of
stereoregularity which is present, in relatively low degree, in commer-
cial PVC polymers, in the form of rather short syndiotactic sequences:
the degree of syndiotacticity is higher in polymers produced at lower
temperatures. 12
3 PVC Polymers 59

The chemical structure of the molecules of commercial PVC


polymers deviates from the theoretical ideal of linear chains of vinyl
chloride units joined head-to-tail and terminating in -CH2-CH2CI
and -CHCI-CH3 end groups. The structural irregularities which
have been reliably identified in commercial polyvinyl chloride are
listed in Table 3.3, with the best current estimates of their respective
contents. Two of these irregularities, viz. chain-branch junctions
containing a tertiary chlorine atom, and mid-chain chloroallyl groups,
are thought to be largely responsible for the low thermal stability of
PVC [ef. Chapter 4, Section 4.1.2(b)].

3.1.2 Polymer Morphology and Some Related Properties

Commercial PVC polymers may be regarded as essentially amor-


phous in nature,13 although they do contain small crystallites in
proportions amounting to about 8-10% crystallinity as determined by
X-ray diffraction. 14 Other techniques, viz. thermal analysis (differential
thermal analysis, differential scanning calorimetry, thermomechanical
analysis (DTA, DSC, TMA» and density measurements, give similar
crystalline content values (albeit in some cases with a lower limit of
only about 2%).15-17 The crystallinity is associated with the stereo-
regular (syndiotactic) polymer fraction: 18.19 the crystalline habit of
such material was first characterised in the mid-1950s by Natta &
Corradini. 20
Note: It is also possible that microcrystallites can actually form in
plasticised PVC, where the free-volume increase caused by
plasticisation can facilitate local chain alignment (see Chapter
5, Section 5.2).
There is good evidence that, in addition to fully crystalline material,
a two-dimensionally ordered nematic phase is also present in commer-
cial PVC polymers, in proportions dependent on the processing
history. 21
The glass transition temperatures (Tg) of commercial homopolymers
lie in the range 80-84°C (as determined by DTA, DSC and TMA).13,15
Annealing above the Tg increases crystallinity and also the crystalline
melting temperature (as given by the endothermic peak on DTA
curves).15,17 The density of the crystalline fraction has been reported as
1530 kg m- 3 (1·530 g cm- 3) and that of totally amorphous (quenched)
polymer as 1337 kg m- 3 (1·337 g cm- 3)Y
TABLE 3.3 ~
Irregularities in the Molecular Chain Structure of Commercial PVC Polymers
(Based on data from Refs 4 and 6.)

Irregular grouping Content a Remarks

Head-to·head monomer junctions


(-eHzCHCt-CHCt-CH 2- ) Less than 0·2 per 1000 monomer units ~
Chain branches: [
Chloromethyl (-CHzCI) 4 per 1000 monomer units Associated predominantly with
tertiary hydrogens (-eH-)
I
CHzO i
2-Chloroethyl (-CHz-CHzCl) Less than 0·5 per 1000 monomer Units} .g
2,4·Dichlorobutyl (-CH2-CHCl---CHz-CHzCl) 1 per 1000 monomer units Associated largely with tertiary ~
::to
Longer chain branches Less than 0·5 per 1000 monomer units chlorine (-eCl-) -~
Tertiary chlorine (-eO-) 0·5-1·5 per 1000 monomer units ~
~ g~
Internal allylic chlorine (-eH=CH-CHCl-) 0·1-0·3 per 1000 monomer units .,~
U nsaturation: ~.
Total 1 per molecule } Conjugated double bonds (polyene sequences)
internal double bonds 0·1-0·3 per 1000 monomer units virtually absent: less than 5 x 10- 4 per 1000
monomer units (below limit of detection) l
).
End·groups:
1,2·Dichloroalkane (-eHz-CHCl---CHzCl) 0·8-0·9 per molecule Other end-groups also possible, e.g. ~
1-Chloro-2·alkene (-eHz-CH=CH-CHzCl) Approx. 0·7 per molecule -eH=CHCl; -eHz-CHOz; ~
-eHz-CHzO; -eHCl---CH=CHz ~.
Initiator residues Approx. 0·2 per molecule May be embodied in such end-groups as
-eHZ-OC-C6 H 5 ; -eHz--O-SOz-OR,
and -eHz-OH (where R is an alkyl
group)

a Best estimates from reliable determinations to date.


3 PVC Polymers 61

As would be expected, annealing below the 1'g has no effect on


crystallinity. However, it can increase the density: this has been
attributed to a reduction of the free volume in the polymer without
ordering of its fine structureY
Relatively highly crystalline PVC polymers (up to about 50%
crystallinity) with high syndiotactic material content have also been
prepared, by polymerisation at low temperatures and in the presence
of chain-transfer agents (including solvents acting in that
capacity).16,18,2I-24 The preparation of fibres and films from such
polymers has been reported,25 as well as of plasticised compounds
(with about 50 phr DOp).18,25 The melting points of the highly
crystalline polymers can be as high as 265_273°C22 ,24 (cf. commercial
PVC polymer-about 210°C in the absence of decomposition).
The plasticised compounds just mentioned had higher modulus and
hardness and lower tensile creep at room temperature (but also lower
tensile strength and extension at break), than a similar compound of
ordinary commercial PVC polymer. Below - 25°C the modulus and
hardness were lower (i.e. the flexibility and softness greater) than
those of the ordinary PVC compound. 18
Molecular orientation of the PVC polymer, and the associated
structural anisotropy, can be an important factor in the morphology
(and the properties) of PVC products (especially uPVC). Thus in PVC
mouldings the skin-and-core effects (a well-known, common feature
also of other polymer mouldings) can involve, inter alia, a considerable
degree of orientation in the skin. 26 Biaxial orientation of the polymer
in PVC bottles and films increases impact resistance (cf., for example,
Chapter 15) and reduces permeability. The tensile strength and
retraction on heating of extruded products is strongly influenced by
longitudinal molecular orientation imparted by stretching in produc-
tion, whilst the degree of orientation produced in PVC fibres by the
drawing process in manufacture is responsible for their very high
tensile strength in comparison with other PVC products (cf. Appendix
1). The yield and fracture behaviour of PVC polymers and uPVC
compositions is strongly influenced by the nature and extent of
molecular orientation. Investigational work in these areas has been
reported by several authors. 27-30
3.1.3 Production of PVC Polymers
Commercial PVC polymers are the products of polymerisation of vinyl
chloride (monochloroethene; chloroethylene), CHz-CHCl.
62 PVC Plastics-Properties, Processing, and Applications

(a) Vinyl Chloride Monomer (VC)


Two main routes are used in the industrial production of this
monomer: see Fig. 3.2. The ethylene route via dichloroethane, which
is the most widely utilised, is commonly operated in the form of the
so-called balanced process. This combines the chlorination and oxy-
chlorination of ethylene to dichloroethane, followed by the latter's
pyrolytic dehydrochlorination to vinyl chloride. The HCI formed as a
by-product is re-used in the process to make more dichloroethane by
oxychlorination of some of the feed ethylene through joint reaction
with oxygen (supplied directly or as air):
2CHz==CH2 + 4HCI + O2 - 2CH2 CI-CH2 CI + 2H2 0
The balanced process embodiment of the ethylene route, long
favoured in the USA, has provided the basis of industrial production
of vinyl chloride in most of the major plants set up since the
mid-1960s. The process in which petroleum-derived ethylene is used
affords the greatest economy when run on a large scale, at or near the
full capacity of the plant.
The acetylene route was of prime industrial importance until the
early 1960s, and especially favoured in Europe. Although in com-
parison with the ethylene route it offers the advantages of lower plant
cost and effective operation on a smaller scale (where required), it is
more energy-intensive, and acetylene produced from oil feedstocks is
more expensive than ethylene from that source. However, as acetylene
can also be readily made from coal, this route-which can thus be
completely independent of petrochemicals-remains relevant where

Ethylene route (balanced process)

Cl/catalyst
/ ~
pyrolysis~ CHz-CHCl + HCl
CHz-CH2, high temperature, CH2Cl-CH2Cl ,
O,/catalyst + HCI
t,
,,
~----------------------------------------------I

Acetylene route

catalyst
CH==CH + HCl BO-2SO"C' CH2=CHCl
(excess)
Fig. 3.2 Main reaction routes in industrial production of vinyl chloride.
3 PVC Polymers 63

coal is freely available andl or, as just mentioned, where production is


on a relatively small scale. In the coal-based process, acetylene is
produced from coke and quicklime via calcium carbide:
3C + CaO~ CaCz + CO
(coke)
CaCz + 2H20~ HC==CH + Ca(OHh
The chlorine and hydrogen to make the HCI used in the subsequent
hydrochlorination of the acetylene (see Fig. 3.2) can be produced by
electrolysis of brine (with caustic soda as a saleable by-product).
Integrated plants producing VC from coal by the acetylene route, and
PVC polymer from the monomer, have been successfully operated for
many years (e.g. the AECI 'Coalplex' plant at Sasolburg, RSA).
Vinyl chloride is a colourless gas at room temperature and normal
pressure (boiling point, -13·9°q, with explosive limits of about
4-20% by volume in air. For industrial processing it is normally kept
as a liquid under pressure. It has anaesthetic properties and an odour
resembling that of chloroethane. Because of its carcinogenic effects
discovered in the 1970s [see Chapter 1, Section 1.3.2(b)], VC is
regarded as a health hazard and precautions must be observed in its
handling and processing to prevent direct body contact and to keep the
concentration in the factory air within the permitted maximum limits
laid down by the relevant national authorities. Maximum content
values for VC in PVC polymers are similarly laid down, as are limits
for amounts extractable from PVC products [ef. Chapter 1, Section
1.3.2(b)].

(b) Polymerisation Processes


The polymerisation techniques used to produce PVC polymers are, in
order of commercial importance, suspension polymerisation (about
80% of total commercial polymer production), emulsion polymerisa-
lion (about 10-15%), bulk polymerisation, also called mass polymeri-
sation (about 10%), and solution polymerisation.
The commercial application of the solution process is almost entirely
confined to the manufacture of PVC copolymers for use in surface
coatings (see Chapter 19). The total production probably represents
about 1% of PVC polymer sold in the Western World.
Polymerisation is carried out in a liquid which may be a solvent for
both the monomer(s) and the polymer, or only for the monomer(s) so
that the forming polymer precipitates out of the system ('precipitation
64 PVC Plastics-Properties, Processing, and Applications

polymerisation'). This can also happen in initially homogeneous


systems above a certain degree of conversion. Initiators and selected
chain-transfer agents are included in a typical solution polymerisation
system. The resulting polymers can be of high purity, and the method
affords good control over molecular weight.

SUSPENSION POLYMERISATlON
In a typical suspension polymerisation process, a suspension of
monomer droplets (some 50-150 Ilm in size) is formed by vigorous
agitation in a sealed pressure reactor (autoclave), and the monomer of
the droplets, which contains a monomer-soluble free-radical initiator,
is polymerised at a temperature within the range 40-75°C, under the
autogenous VC vapour pressure corresponding to the reaction tem-
perature (up to 1·5 MPa at 80°C). The reaction is exothermic and
excessive temperature rise is prevented by use of chilled water, and
operation under reflux. Protective colloids (dispersants), nowadays
typically polyvinyl alcohol or soluble cellulose derivatives, are included
in the aqueous phase (typically 0·05-0·06% by weight) to stabilise the
suspension throughout the process, and also buffers to counteract
development of acidity. When some 80-90% of the monomer has
been converted to polymer (the widest conversion range in practice is
75-95%) the reaction is stopped by venting-off excess monomer from
the reactor. The resulting slurry of polymer in water is freed from the
remaining monomer by further evaporation, either in the autoclave
itself or in a separate vessel. This operation is known as stripping: to
secure an effective high degree of removal of residual VC, stripping is
assisted and completed by steam 'sparging'. Different variants, both
batchwise and continuous, of this operation exist, all essentially
involving scrubbing the slurry with steam at an elevated temperature.
Continuous, counterflow scrubbing in an efficient column can reduce
the VC content of the polymer to below 1 ppm. The stripped slurry is
centrifuged to remove free water and the resulting wet polymer 'cake'
is dried by hot air.
Note: In the so-called microsuspension polymerisation the general
composition and physical state of the system are more akin to
those characteristic of emulsion polymerisation, in that an
emulsifying agent is used and the size of the monomer
droplets is comparable with that typical for emulsion systems.
Thus, although a monomer-soluble initiator is employed as in
regular suspension polymerisation-and therefore initiation
3 PVC Polymers 65

takes place inside the droplets-the processing is essentially


as in emulsion polymerisation.

MASS (BULK) POLYMERISATION


The polymerisation system comprises only the monomer and a
free-radical initiator (typically an acyl peroxide or peroxycarbonate).
Polymerisation is carried out under pressure (to keep the VC liquid)
and normally at 40-70°C. The process has two distinct stages, run
respectively and consecutively in a vertical reactor (prepolymeriser),
and a larger reactor, the autoclave (originally horizontal, but in the
most recent plants often vertical), each equipped with agitators and
condensers. In the first stage, polymer particles form in, and separate
from, the liquid VC phase (polyvinyl chloride is virtually insoluble in
its monomer), thus forming a heterogeneous system. This stage is
carried out under strong agitation (with a turbine-type stirrer) to
ensure uniformity and correct morphology of the PVC grains. At a
relatively low degree of conversion (around 10%) much of the VC
liquid is absorbed onto the porous polymer grains, and the viscosity of
the slurry becomes too high for effective rapid stirring, whereas the
grains develop enough strength to withstand transfer to the second-
stage reactor. Here further polymerisation and growth of the polymer
particles proceed to completion-under relatively gentle stirring with a
ribbon-blender type of stirrer-in what becomes essentially a solid
(powder) phase. Additional monomer and initiator required for the
second stage are introduced during the transfer. At about 20%
conversion the material has the appearance and consistency of damp
powder, and that of a dry powder (with all the monomer absorbed into
the grains) at about 40% conversion. Agitation, particularly important
in the second stage, is provided by agitators of special design.
Polymerisation is terminated at a predetermined level of conversion
(usually about 80%) by venting-off unreacted Vc. Residual monomer
is stripped from the polymer by degassing (in the reactor or a separate
vessel) assisted by introduction of steam or an inert gas to act as
carrier. The resulting polymer powder is then classified to remove the
small percentage of large particles usually present.
The mass polymerisation process was developed and perfected by
the French company Pechiney-Saint Gobain: subsequently, in conse-
quence of mergers and take-overs, it became the property of Rhone-
Poulenc Industries, which is now part of the nationalised French
chemical industry conglomerate.
66 PVC Plastics-Properties, Processing, and Applications

EMULSION POLYMERISATION
In emulsion polymerisation the system consists of the monomer and
water containing emulsifier(s) (typically anionic) in substantial con-
centration (typically 2-3%) and a water-soluble initiator.
In batchwise operation, polymerisation is carried out in an autoclave
designed for operation at the VC vapour pressure generated at the
reaction temperature (typically 40-60°C), say up to about 1 MPa. In
the presence of the emulsifier(s), agitation of the charge in the
autoclave disperses the monomer into very fine droplets (down to
about O·lllm). The initiator (commonly potassium persulphate or
ammonium persulphate alone or with a reducing agent, or a more
complex redox system, e.g. HzOz/FeS04/ascorbic acid) produces free
radicals in the aqueous phase, where initiation takes place, at the
boundary with the monomer phase. The polymer particles formed
grow progressively in size throughout the process run: this may
necessitate controlled addition of further emulsifier to maintain
emulsion stability. The degree of conversion is normally about 90%,
the reaction being terminated by venting-off excess monomer. The
final stripping of VC from polymer produced by the emulsion process
is similar in principle to that practised with suspension polymer,
although it can be more difficult in practice: some spraying methods
have been claimed to be particularly effective. 31 The polymer particles
are normally separated out and dried by spray-drying, followed by
grinding to modify agglomerate size distribution (and break down
outsize or fused ones), and finally by size classification.
Continuous emulsion polymerisation processes are also operated.
Emulsion polymerisation was the first process to be used for large-
scale commercial production of PVC polymers.
A final product of elementary particle size somewhat larger than
that normally resulting from 'straight' emulsion polymerisation may be
obtained by 'seeding' the initial emulsion system, i.e. by introduction
of a PVC polymer latex on whose particles the new polymer then
forms. Controlled, progressive addition of emulsifier will normally be
necessary to secure such growth of the seed particles without forma-
tion of entirely new, smaller ones.
Microsuspension polymerisation, too, can yield similarly larger
particles; it also affords some control over the elementary particle size
of the final product by virtue of the fact that-since in this process
polymerisation takes place within the original monomer droplets-the
size of the polymer particles ultimately formed is much the same as
that of the droplets.
3 PVC Polymers 67

3.1.4 Physical Forms of PVC Polymers

As indicated in the preceding section, PVC polymers are produced in


particulate (powder) form.
The structure of suspension and mass PVC polymer particles is
complex, and closely similar for the two types. A schematic repre-
sentation is given in Fig. 3.3, with the nomenclature for the various
structural elements which has now been widely adopted. Some of the
main structural features are also briefly mentioned below.
Note: Within the gross, overall morphological characteristics, many
different variants of the fine structure are possible. A good
account of these has been published by Allsopp.34 It is these
variations that make individual polymer grades suitable for
particular formulations and processing methods. The numeri-
cal sizes of the structural elements given in Fig. 3.3 are fairly
representative averages: actual values may vary in practice

""" "
-0---
~ i
Stagem particle "
( polymer powder graIn) '; I
'}I

. . ;. "~/stage II particle
.... ,/"" ./ /'./ (microgranule)
...,/ ,/
/

Eo«
/

. . /",/
/ /

~ 9CQ/s;ageI particle
~ @ - \", (primary particle)
" ,, , \
,, , ,
, \
\," \

\8 Crystallite
~ ~
4nm
(40'&')
approx

Fig. 3.3 Schematic representation (after Hori 32 and Faulkner3) of the


structure of a PVC polymer particle (suspension- or mass-polymerised).
68 PVC Plastics-Properties, Processing, and Applications

depending on polymerisation conditions (cf. Table 3.5 be-


low). Some examples from the literature are given in Table
3.4.

(a) Suspension Polymer Particles


The powder grains (Stage III particles) of a typical suspension polymer
have a fair degree of sphericity. Under the microscope in reflected
light they exhibit a characteristic puckered surface. Viewed in trans-
mitted light (especially when partly transparentised, e.g. by absorption
of plasticiser) the grain is seen to be surrounded by a dense skin
('pericellular membrane'), enclosing a partly porous interior made up
of clusters of small, near-spherical or oblong Stage II particles and the
associated interstitial voids. The skin, which has been likened to a bag
enveloping the Stage II particle clusters,35 is formed at the boundary
between the original monomer droplet (to which the Stage III particle
corresponds) and the aqueous suspending medium in the polymerisa-
tion process: hence, whilst the skin may not be complete (seam-like
gaps are a fairly common feature, for example), and may vary in
thickness (from about 0·5 to 5 .urn), it is always present in suspension
polymer particles and absent from those of mass polymer, being
clearly visible in photomicrographs of suspension polymer particle
sections and in electron-scan micrographs of whole particles. Some

TABLE 3.4
Some Examples of Stage nf and n Particle Sizes of PVC Suspension and Mass
Polymers

Grain Microgranule Type of Reference


(Stage III (Stage II polymer
particle) particle)
size (11m) size (11m)

About 100-500" 'Approaching' l a Mass Marks 35


50-250 'Submicron' Suspension Chartoff37
100-150 'About 2' Suspension Summers et al. 38
100 0·2-1·5 Unspecified Parey & Menges39
100 0·5 Suspension Menges et al. 40
Approx. 200-300 Approx.l Suspension Benjamin41
70-250 Suspension/ mass Clark42

aValues cited as generally representative of those obtainable at high conversion rates in


polymerisation. Stage III particle-size distribution graphs also given-as typical
examples-in this reference indicate a total range of about 30-200 11m (with a mean of
about 130l1m) for a mass polymer, and about 40-260 11m (with a mean of about
160 11m) for a suspension polymer.
3 PVC Polymers 69

excellent photographs of both kinds have been published by Marks. 35


An interesting method for determination of the internal particle
structure of suspension PVC polymers by analysis of the desorption
rate of vinyl chloride has been described by Daniels & Longeway.36
The Stage I microparticles which make up a Stage II particle (see
Fig. 3.3) are the basic polymer elements that are formed in the course
of polymerisation.

(b) Mass Polymer Particles


These are similar in general shape to suspension polymer particles,
although they often have a higher degree of overall sphericity, coupled
with a characteristic 'flat-sided' appearance under the microscope.
Their internal structure is also closely similar, but, as they have no
continuous outer skin, their internal pores are more directly
accessible.

(c) Emulsion Polymer Particles


Viewed under high magnification, and in electron-scan micrographs,
the primary particles of a typical emulsion or microsuspension polymer
appear as solid, smooth-surfaced spheres. They are roughly com-
parable in size with the Stage II particles of suspension or mass
polymers, to which they may be regarded as corresponding: however,
their size range is rather wider-typically about 0·1-3 Ilm for seeded

O·1f.1m - 3·Of.lm
\ I
\ I
\ I
\ I
\ I
\ I
\ I
\ I
\
\
\

Fig. 3.4 Emulsion polymer: primary


particles in an aggregate-schematic
40-50fJ.m representation.
TABLE 3.5 ~
Effects of Some Process Factors on the Characteristics of PVC Polymers Produced by the Three Principal Industrial
Polymerisation Processes

Factor Polymerisation Polymer property Effect Remarks


process affected
Nature Magnitude

Polymerisation Suspension Molecular weight Increases with Very large Cf. Section 3.1.1
~'"tI
temperature decreasing (in absence
~
::to
temperature of chain
modifiers) !:l
Particle porosity Increases with Substantial ~
decreasing ~
temperature ~
Mass Molecular weight Increases with Substantial Temperature in the first stage has ~.
decreasing little effect on the molecular :-
temperature in the weight ~
second stage ~
Particle porosity Increases with Significant If required, particle porosity can ~
decreasing be varied (without affecting the ~.
temperature (in both molecular weight) by varying
stages) the first -stage temperature
§
!:>...
Bulk density of Increases with increasing Significant
polymer powder temperature ~
~
(especially in the first
stage) £
Emulsion and Relatively little effect within the comparatively narrow temperature range used in industrial polymerisation ~.
microsuspension [see Section 3.1. 4(b ) I
Degree of Suspension Particle size Increases with increasing Significant
convergence degree of conversion
Particle porosity Decreases with Moderate Polymerisation rate low above
increasing degree of 95% conversion
conversion within the
normal range
Mass Particle porosity Decreases with Significant Degree of conversion in the first
increasing degree of stage has little effect (but
conversion in the transfer to second stage at low
second stage conversion level promotes
formation of fines)
Bulk density of Increases with increasing Significant
polymer powder degree of conversion
in the second stage
Dispersant Suspension Particle size and Affected by the nature Significant
system size distribution of dispersant (and/or
composition of
dispersant system)
Particle porosity Influenced by the Substantial Low surface activity of dispersant
Bulk density of surface activity of (single or composite) makes for
polymer powder the dispersant(s) low porosity and high bulk
w
density
Emulsifier Emulsion and Particle size and Affected by the nature Substantial Addition of small amounts of ~
system microsuspension size distribution and composition of electrolytes often reduces the
..:::
("')
emulsifier system size and increases the number
of particles (with the same
~
~
emulsifier system) :I
Agitation Suspension Particle size Decreases with Substantial '"
t:l
increasing stirrer
speed, passes through
a minimum, then
increases (due to
droplet coalescence)
Particle porosity Usually increases with Significant
increasing stirrer
speed
Agitation Bulk density of Influenced by stirrer Significant
polymer powder speed
Mass Particle size Decreases with agitator Substantial Little effect of the relatively
tip speed in the first gentle agitation in the second
stage: also influenced stage -.I
by agitator type
(continued)
-
;j
TABLE 3.5-contd.

Factor Polymerisation Polymer property Effect Remarks


process affected
Nature Magnitude

Agitation Microsuspension Particle size Influenced by the Substantial .."


The reaction system (monomer
(continued) homogenising with initiator; emulsifier; ~
pressure water) is pre-mixed then ::E
homogenised (in an ultrasonic ~
:::to
homogeniser, high-speed !:l
pump, or colloid mill), and fed
into the polymerisation reactor ~
Presence of Suspension Particle size Decreases with Large These effects are manifested ~
oxygen increasing oxygen even with very low oxygen ::\.
'"
~.
content contents (of the order of
100 ppm on the VC)
Porosity Decreases with Significant The air space in the charged ~
increasing oxygen reactor is normally ev'acuated ~
content just before final VC addition, '"
~.
to remove all oxygen
Chemical properties A1Iected Significant §
~
and stability
~
~
~
~.
3 PVC Polymers 73

emulsion or microsuspension polymers, down to as low as 0·01-0·2 Jlm


for ordinary unseeded emulsion polymers. In commercial emulsion
PVC powders the primary particles are not separate, but clustered into
somewhat irregularly shaped aggregates which form in the course of
spray-drying after polymerisation, and undergo some size modification
in the subsequent grinding [see Section 3.1.3(b) above]. The aggre-
gates can range considerably in size; however, a mean value of about
40-50 Jlm is fairly representative. Thus both on this score, and as
coherent assemblies of primary, pseudo-Stage II particles, they may be
considered as roughly equivalent to Stage III particles of suspension
and mass polymers. Figure 3.4 shows schematically the features of
emulsion polymers just mentioned.

3.1.5 Effects of Some Polymerisation Process Factors on Polymer


Characteristics

The main effects are summarised in Table 3.5.

3.2 COPOLYMERS OF VINYL CHLORIDE


3.2.1 Kinds and Applications
The oldest, and still most widely used, copolymer of vinyl chloride is
that with vinyl acetate (VC/VAC).
In most of the vinyl chloride copolymers of commercial interest the
co-monomer units are in a minor proportion (and randomly distrib-
uted) in the polymer chain, i.e. most are internal, random copolymers,
with the VC units predominating. Copolymers with vinylidene chloride
(VC/VDC) are a notable partial exception here in that, whilst those
used in certain PVC compositions (e.g. some calendering compounds)
for ease of heat-processing contain relatively small amounts of VDC
co-monomer, in others (e.g. those for making self-supporting, low-
permeability films) it is the VC co-monomer which is the minor
constituent (usually to-15 % ).
Vinyl chloride is also the minority co-monomer in some types of
acrylic copolymer fibres, although the material of the original Dynel
modacrylic* fibre was a 60/40 copolymer of vinyl chloride and
acrylonitrile.

* Modacrylic fibre is defined [ISO 2076-1977 (E)] as consisting of linear


macromolecules having in the chain at least 35% and less than 85% (by mass)
of the recurring unit -CH2-CH(CN}-.
74 PVC Plastics-Properties, Processing, and Applications

Some terpolymers of vinyl chloride are used in surface coatings (see


Chapters 19 and 20), whilst certain graft polymers and terpolymers
serve as base polymers or polymeric modifiers in weathering-resistant
PVC compositions; there is also a graft-terpolymer fibre (see Table
3.6). Graft copolymers are, as a rule, more expensive than main-chain
ones.
As has been mentioned, most copolymers exhibit behaviour as-
sociated with 'internal plasticising' effects of the co-monomer units: in
comparison with homopolymers, the processing temperature is re-
duced, as is the Tg (and hence the softening temperature, and the
temperature of deflection under load); the hardness also usually
decreases, and the extensibility increases.

Note: A partial exception to the general trend, which is of some


practical significance, may be noted: some copolymers of
vinyl chloride with N -substituted maleinimide derivatives 43 ,44
have 1'g values and Vicat softening points significantly higher
than those of vinyl chloride homopolymer: cf., for example,
Hostalit LP HT 5060 (Hoechst), a copolymer containing 5%
of N -cyclohexylmaleinimide. 43

Copolymers are normally more readily soluble than homopolymers:


those used as binders in surface coatings tend to adhere better to
substrates (suitable third co-monomers are often incorporated in the
chain to promote adhesion-see Chapters 19 and 20).
Broadly speaking, the morphology of most copolymers is similar to
that of PVC homopolymer, except that the reduced regularity of the
chain is an extra hindrance to crystallisation. This is the case with
VDC/VC copolymers: the chain structure of PVDC is favourable to
crystallisation and the crystallinity of the homopolymer is normally
high;45,46 however, the structural regularity and hence ease of crystal-
lisation is progressively reduced as the VC unit content of the polymer
chain is increased, until at VC contents ~30% the copolymer becomes
non-crystalline. It is for this reason that VDC/VC copolymer films for
barrier applications contain only about 10-15% VC. This content level
represents a reasonable combination of easement of processing (the
highly crystalline PVDC homopolymer requires high temperatures)
and retention of much of the excellent barrier effect of the homopOly-
mer associated with its crystallinity (crystalline regions in polymers are
normally impenetrable to diffusant molecules).
TABLE 3.6
Some Vmyl Chloride Copolymers
Copolymer Some typical applications a Relevant chapter(s)/Remarks References
(...)

Vinyl chloride/vinyl 1. Unplasticised mouldings Chapters 10, 17; passim in "tl


acetate (VC/VAC) (including gramophone records) others (see Index) ~
and sheeting (including flooring cl'
and sheets for ~
;:
thermoforming)-S
2. Surface coatings-E or SL Chapters 19, 20. The Literature on VC/VAC
'"~
copolymers for some of the copolymers and
applications may contain a terpolymers is extensive;
third component, or the see for example the
VAC may be partly Bibliography at the end
saponified to produce some of Chapter 1
vinyl alcohol residues
3. Adhesives; finishing agents (for
paper; textiles; leather)-E
4. Fibres, e.g. Vinyon HH (FMC
Corp., American Viscose Div.);
Wacker MP (Wacker Chemie)
-.I
(continued) Ul
~

TABLE 3.6----contd.

Copolymer Some typical applications" Relevant chapter(s)/Remarks References


~"tJ
Vinyl chloride/vinyl Fibres-Cordelan (Kohjin, G., Part of the acetate groups
acetate/vinyl alcohol Japan); graft copolymer saponified to --OH ir
~.
Vinyl chloride/vinylidene 1. Unplasticised calendered Chapters 10, 14
chloride (VC/VDC) sheets; mouldings-S
2. Extruded films (packaging}-S Chapter 23 a~
"0:5
3. Viscosity-reducing polymer in Chapter 18 Ref. 25----general nature !ll
::to
pastes-S and preparation of the
~
4. Coatings and finishes-E For some applications copolymers
"tJ
terpolymers are used, with Ref. 46---general review ..,a
a third component in (with 92 references) ~
addition to VC and VDC Ref. 47-packaging films '"
~.
(see Chapter 20)
5. Fibres, e.g. Saran (National Saran is also the generic name ~
Plastics Products Co.) for all VDC copolymer
fibres containing at least ~
"0:5
85%VDC ~
;:,
Vinyl chloride/propylene Extruded film (packaging); Commercially available from Refs 48 and 49--polymer g.
(VC/P) injection mouldings-S Air Products and Chemicals production, structure and i;!
Inc. (USA)-Airco 400 properties
series Ref. 5~olymer
composition and density
Ref. 51---packaging film
Vinyl· chloride/ethylene Similar to VC/P copolymers-S Developed by Union Carbide Ref. 52
(VC/E) Chemical Co.
Vinyl chloride/ethylene/ 1. Extrusions (profiles, esp. See Index Refs 25, 44 and 53---polymer
vinyl acetate window frames); injection preparation, structure and
(VC/E/VAC) mouldings--graft copolymer, properties
e.g. Vinnol K510 (Wacker- Refs 44 and 54--applications
Chemie) or Baymod L (Bayer)
2. Surface coatings; finishing Chapter 20
agents; adhesives--E
Vinyl chloride/ Mainly surface coatings--E Heat after-treatment required Ref. 55
trifluorochloroethylene for good adhesion. In melt
(VC/lFCE) processing, processability
and heat stability improve
with increasing lFCE
content
Vinyl chloride/vinyl cetyl Calendered sheet-S Originally available from the
....
ether Allied Chemical Co. (USA) "1:J
and some Japanese sources ~
Vinyl chloride/acrylic 1. Modifiers--graft copolymers Refs 25, 56 and 57 cl'
ester (a) for outdoor compositions '<'
(esp. window frame §
extrusionsHraft copolymers,
e.g. Vestolit P1982K (Hills)
(b) for uPVC film and bottles
(for clarity, heat weldability
and impact strength)
Vinyl chloride/fumaric 1. For pastes fusible at relatively
ester low temperatures, e.g. Pliovic
Vinyl chloride/maleic
ester
1 AD (Goodyear)--E
2. Extruded products; injection
Vinyl chloride/itaconic mOUldings
ester
l~~~~
aThe usual method of copolymer production for each application is indicated as follows: S = suspension polymerisation; E = emulsion :::i
polymerisation; SL = solution polymerisation.
78 PVC Plastics-Properties, Processing, and Applications

3.2.2 Production

In principle, subject to suitability of co-monomer reactivities, all the


four types of polymerisation process mentioned in Section 3.1.3(b)
may be used for the production of PVC copolymers (although in the
case of bulk polymerisation it is also necessary for the copolymer to be
substantially insoluble in the monomers). The processes commonly
used in practice are indicated in Table 3.6. Incorporation of the
required proportion of a co-monomer into the final polymer is
achieved by adjusting the monomer contents of the reaction mixture in
accordance with the relevant parameters (respective reactivity ratios,
resonance and polarity factors 58), and suitably controlling the poly-
merisation conditions.
The graft copolymers of vinyl chloride and E/VAC, used in
compositions for outdoor applications, are typically made by grafting
polyvinyl chloride chains onto E/VAC backbone chains in a solution
of the E/VAC polymer in vinyl chloride monomer. 44

3.3 COMMERCIAL PVC POLYMERS

3.3.1 Polymer Properties Cardinal to Processing and/or Service

The properties that may be listed under this heading are: chemical
composition (i.e. whether homopolymer or copolymer); molecular
weight; polymer particle characteristics (shape, structure, size and size
distribution), and those bulk properties of polymer powder which are
influenced by the particle characteristics and are important in storage,
conveying, and processing, viz. bulk density, packed density, and
powder flow. Polymer quality, in the sense of freedom from gels (fish
eyes) and impurities, is also important in a number of applications.

(a) Chemical Composition


In broad terms, the formulator's general choice is between a homo-
polymer and a copolymer (in certain specialised formulations the latter
may be included with the former in a modifying role). The
copolymers-of which polyvinyl chloride/acetate is the most important
in the commercial sense-are used in certain cases in preference to
homopolymers largely for ease of melt processing of rigid composi-
3 PVC Polymers 79

tions, or where (as in coating, finishing or adhesive compositions) their


ease of fusion, adhesion properties and-where relevant-their easier
solubility characteristics, are beneficial. In rigid compositions based on
VC/VAC copolymers, the ease of melt flow increases with increasing
VAC content (for the same molecular weight), but the softening point,
hardness, and-to some extent-the heat stability of the products are
also progressively reduced. The commercial VC/VAC copolymers
typically contain 10-16% V AC, although the proportion may be as
low as 2% in some coating copolymers modified with a third
component (see Chapter 19).
Of the three main melt-processing outlets for VC/VAC copolymers,
flooring (where ease of melt flow, and ability to accept large amounts
of fillers are important) and gramophone records (again requiring
good flow, and faithful reproduction of moulding surface detail) call
for polymer of high vinyl acetate content (typically about 15%) and
low molecular weight (K value typically below 50). On the other hand,
for packaging films and foils, where easy melt flow must be combined
with good melt elasticity, and good mechanical properties are required
in the product, a typical choice would be copolymer of about 60 K
value containing about 10% vinyl acetate.
In commercial copolymers of vinyl chloride with ethylene and
propylene (see Table 3.6), the presence of the olefin component
affects the melt viscosity in the same way as that of the vinyl acetate in
VC/VAC copolymers. However, there is comparatively little adverse
effect on heat stability and strength properties. Nevertheless, the use
of these copolymers is very limited, largely because they are con-
siderably more expensive than VC/VAC copolymers. The uses of
other VC copolymers are indicated in Table 3.6.
(b) Molecular Weight (Viscosity Number; K Value)
The molecular weight of the PVC polymer has a substantial influence
on the ease of processing of uPVC compositions, whose melt viscosity
at a given processing temperature rises considerably with increasing
molecular weight of the polymer (the effect is relatively unimportant
with pPVC where it is outweighed by the overall reduction of melt
viscosity promoted by the plasticiser). Polymer molecular weight also
influences the mechanical properties of PVC products (in pPVC rather
less than in uPVC). Both these effects are considered in discussion of
particular processes and applications at a number of places in the
book.
80 PVC Plastics-Properties, Processing, and Applications

(c) Polymer Particle Characteristics


The shape, structure, size, and size distribution of PVC polymer
particles affect the particle packing behaviour and hence the bulk
density and settling (packing) characteristics of polymer powder and
powder compounds, as well as their dry flow in the course of
conveying, metering, hopper-feeding, and processing. Particle mor-
phology is an important factor in the rate and uniformity of absorption
of liquid additives (plasticisers; some stabilisers) in the course of
production and processing of powder blends, and in the rate and
uniformity of fusion in melt processing: the presence of substantial
proportions of fine particles can impair these functions, and adversely
affect dry flow. Rheological properties of PVC pastes are strongly
influenced by the particle size and size distribution of the paste
polymer particles (see Chapter 18).
The main reason for the very large variety of PVC polymer grades
offered by manufacturers is that each represents an attempt to gear
and harmonise the above properties for maximum suitability in a
particular combination of process (or even a process variant) and
ultimate application.
Several standard characterisation tests in wide use (see Section
3.3.2) are directly relevant to the handling and processing behaviour of
commercial PVC polymer powders. Thus, the results of bulk density
and compacted bulk density determinations relate to the production
rate in melt-compounding and in extrusion of rigid products (profile;
pipe) from powder blends (higher rates at high bulk densities). These
two properties as determined in the tests were shown (by Ravey &
Waterman59) to correlate linearly with one another, and hyperbolically
with the specific surface of the polymer powder. The results of the
ASTM dry-flow test in conjunction with those of the test for plasticiser
absorption are significant as a guide to hopper-feeding characteristics
of plasticised dry blends (cf. ASTM D 1755-81, Subsection 16.2).

(d) Quality (Purity)


Whilst not of such basic significance as the characteristics considered in
(a)-(c) above, polymer purity is important in some applications, e.g.
high-clarity compositions for blow-moulded bottles or packaging films.
In such compositions purity is essentially a matter of freedom from fish
eyes and external contamination.
3 PVC Polymers 81

Note: ISO 472-1979 defines 'fish eye' as 'a small globular mass
which has not blended completely into the surrounding
material and is particularly evident in a transparent or
translucent material'. In PVC, fish eyes (also called gels) are
hard specks of polymer which are not dispersed in processing
and thus persist in the finished product. They can originate in
polymer production, but may also be formed in melt process-
ing as a consequence of non-uniform fusion. In opaque PVC
materials they can show up as 'nibs' in the surface.
In the general context, purity may also be impaired by the presence in
the polymer of processing residues (e.g. residual protective colloids,
emulsifiers, etc.) in significant amounts; inter alia, such impurities can
affect electrical properties. Adventitious external contaminants may
reduce heat and light stability and strength properties, apart from any
adverse effects on appearance and electrical properties.
3.3.2 Characterisation and Designation of Commercial PVC
Polymers
Certain polymer properties are very widely and commonly determined
by the manufacturers and processors, and their values quoted for the
purposes of characterisation, quality control, and technical specific-
tions. The principal standards relevant to the properties and testing of
PVC polymers are listed in Table 3.7. Designation systems for
commercial polymer grades normally include code indications of at
least some of these properties, as well as an indication of the
applicational purpose (e.g. whether a 'general-purpose' grade for
melt-processing, or a paste polymer, etc.). Three major standards
provide designation systems, with the relevant characterisation tests,
for PVC polymers: ISO 1060, DIN 7746, and (jointly) ASTM D1755
and D2474. The DIN system is in substantial technical agreement with
the ISO one. The latter and the ASTM designation system both follow
the principle of indicating the selected designatory polymer charac-
teristics by code references to the relevant groups of data (called 'data
blocks' in the ISO system). However, the two systems differ in the
actual coding, and the contents and arrangement of the blocks. The
following two examples illustrate something of the ISO designation
system, in which the information belonging to a 'block' is separated
from that of the next 'block' by a comma (two commas after the third
'block' if the optional fourth block is also included).
~
TABLE 3.7
Standards Relevant to the Properties and Testing of PVC Polymers and Copolymers

Entry Standard specification


no.
Designation Subject (not necessarily the official title) ~."
General (Designation, coding, characterisation) [
~.
1 ISO 1060/1-1982 Plastics-Homopolymer and copolymer resins of vinyl chloride
Part 1: Designation
2 ISO 1060/2-1985 Part 2: Determination of properties ~
~
3 ISO 6186-1980 (1985) Plastics-Determination of pourability ~
4 ASTM D 1755-81 Specification for poly( vinyl chloride) resins
'"
'"~.
Note: this standard refers to several of the ASTM test methods
listed below
5 ASTM D 2474-81 Specification for vinyl chloride copolymer resins
~
~
6 ASTM D 2873-70 (1982) Interior porosity of PVC resins by mercury intrusion porosimetry '"
~.
7 DIN 7746 s::.
Part 1 (1986) Vinyl chloride homopolymers: classification and designation 5.
Part 2 (1979) Vinyl chloride homo- and co-polymers: determination of properties )..

Viscosity and molecular weight


:g
[
8 ISO 174-1974 Determination of viscosity number of PVC resins in dilute solution g.
9 ISO 1628/1-1984 Guidelines for the standardization of methods for the determination ~
of viscosity number and limiting viscosity number of polymers in
dilute solution
Part 1: General conditions
10 ISO 3219-1977 Polymers in the liquid, emulsified or dispersed state-Determination
of viscosity with a rotational viscometer working at a defined shear
rate
11 BS 2782: Part 7
Method 730 A: 1979 (*- ISO 1628/1) Determination of reduced viscosity (viscosity number) and intrinsic
viscosity of plastics in dilute solution
Method 730 B: 1978 (== ISO 3219) Determination of the viscosity of polymers in the liquid, emulsified
or dispersed state using a rotational viscometer at a defined shear
rate
12 ASTM D 1243-79 (1984) Test for dilute viscosity of vinyl chloride polymers
13 ASTM D 3591-77 (1985) Determining logarithmic viscosity number of poly(vinyl chloride) in
formulated compounds
14 ASTM D 3592-77 Determining molecular weight (Aln) by vapour-pressure osmometry
15 DIN 53726 (1983) Determination of viscosity number and K value of vinyl chloride
polymers
I..>
Chlorine content
16 ISO 1158-1984 Determination of chlorine in vinyl chloride homopolymers and ~
copolymers
17 ASTM D 1303-55 (1979) Test for total chlorine in vinyl chloride polymers and copolymers cl'
~
(Discontinued in 1986) ~
18 DIN 53474 (1976) Plastics-Determination of the chlorine content <:!
Vinyl acetate content of vc /VAC copolymers
19 ISO 1159-1978 Determination of V AC in VC/VAC copolymers
Ash and/or sulphated ash content
20 ISO 1270-1975 PVC resins-Determination of ash and sulphated ash
[N.B. Revision document (ISO/DIS 3451-5) in 1987]
21 BS 2782: Part 4
Method 454 A: 1978 (1983) Determination of ash
Method 454 B: 1978 (1983) Determination of sulphated ash
(== ISO 1270)
(continued) ~
~
TABLE 3.7-contd.

Entry Standard specification


no.
Designation Subject (not necessarily the official title)
~
Volatile matter
22 ISO 1269-1980 (1985) Determination of volatile matter (including water) in PVC r5'
homopolymers and copolymers
23 BS 2782: Part 4
Method 454 D: 1978 (1983) Determination of volatile matter (including water) in PVC resins a~
(=ISO 1269)
1
24 ASTM D 3030-84 Test for volatile matter (including water) in vinyl chloride resins j-
Impurities and foreign matter ~
~
25 .ISO 1265-1979 (1986) PVC resins--Determination of number of impurities and foreign ~
particles s·
Test for methanol extract of vinyl chloride resins ~
26 ASTM D 2222-66 (1984)
Bulk density ~
)..
27 ISO 60-1977 (1985) Determination of the apparent density of material that can be :g
poured from a specified funnel ir
28 ISO 61-1976 Determination of the apparent density of moulding material that g.
cannot be poured from a specified funnel ~
29 ISO 1068-1975 Determination of compacted apparent bulk density of PVC resins
30 BS 2782: Part 6
Method 621 A: 1978 (1983) Essentially as ISO 60 (entry no. 27 above)
(=IS060)
Method 621 B: 1978 (1983) Essentially as ISO 61 (entry no. 28 above)
(=IS061)
Method 621 D: 1978 (1983) Essentially as ISO 1068 (entry no. 29 above)
( == ISO 1068)
31 ASTM D 1895-69 (1979) Test for apparent density, bulk factor, and pourability of plastic
materials
N.B. Method A == ISO 60
Method C == ISO 61
Particle size
32 ISO 1624-1978 Vinyl chloride homopolymer and copolymer resins-Sieve analysis in
water
33 ISO 4576-1978 (1984) Plastics-Aqueous dispersions of homopolymers and copolymers-
Determination of gross particle content by sieve analysis
34 ISO 4610-1977 Vinyl chloride homopolymer and copolymer resins-sieve analysis .....
using air-jet sieve apparatus
35 BS 2782: Part 4
Method 454 F: (1978) (1983) Essentially as ISO 4610 (entry no. 34 above) ~
( == ISO 4610) :;p
~
36 ASTM D 1705-82 Particle size analysis of powdered polymers and copolymers of vinyl ~
chloride <:!
Bromine number
37 ISO 3499-1976 Aqueous dispersions of homopolymers and copolymers of vinyl
acetate--Determination of bromine number
pH of aqueous extract
38 ISO 1264-1980 (1985) Homopolymer and copolymer resins of vinyl chloride-Determination
of pH of aqueous extract
39 BS 2782: Part 4
Method 454 C: 1978 (1983) Determination of pH of aqueous extract of PVC resins
(== ISO 1264)
(continued) ~
TABLE 3.7-contd. ~

Entry Standard specification


no.
Designation Subject (not necessarily the official title)
~
Miscellaneous properties relevant to processing ~
40 ISO/R 182-1970 Determination of thermal stability of PVC polymers and copolymers :::s:!
and their compounds, by splitting off HCI El
PVC resins for general use-Hot plasticiser absorption

41 ISO 4574-1978
42 ASTM D 2396-79 (1985) Powder-mix time of PVC resins using a torque rheometer 'f
43 ASTM D 2538-79 (1985) Fusion test of PVC resins using a torque rheometer .g~
44 ASTM D 3367-75 (1986) Test for plasticiser sorption of PVC resins under applied centrifugal '"3-.
force -~
45 ASTM D 3596-77 (1983) Determination of gels (fish eyes) in general-purpose PVC resins
46 ASTM D 4202-82 Thermal stability of PVC resins g~
~
VC monomer content '"

47 ISO 6401-1985 PVC homopolymers and copolymers-Determination of residual VC ~
monomer-Gas-chromatographic method
48 ASTM D 3680-78 Residual VC monomer content by solution injection method (for PVC i).
homopolymers, copolymers and compounds) ~
49 ASTM D 3749-78 Determination of residual VC monomer content of vinyl chloride ~
homopolymers by gas chromatography (head-space method) '5'".
50 ASTM D 3834-80 Determination of the purity of VC by gas chromatography ~
51 ASTM D 4434-84 Determination of residual VC monomer content in parts per billion in
vinyl chloride polymers and copolymers
52 DIN 53743 (1979) Determination of VC in polyvinyl chloride by gas chromatography
3 PVC Polymers 87

Homopolymer for melt processing:


ISO 1060---PVC-S G, 121-56
homopolymer j~
suspension-produced
general-purpose
(i.e. not for paste)
viscosity number------'
bulk density of 0·56 g ml- 1- -.. . .
Copolymer for melt processing:
ISO lO60-VC/VAC 88-S, G, 080-75, 17 X

vinyl chloride/acetate
88% vinyl chloride-derived
j JJ 1
suspension-produced
general purpose - - - - - - - - - - '
viscosity number ( 8 0 ) - - - - - - - - '
bulk density 0·75 gml- 1 - -_ _ _ _- '
particle size limits (by reference - - - - - - '
to numbered 'classes'-here classes 1 and 7)
plasticiser absorption by particles - - - - - - - - '
(X indicates that the value is not
specifically designated)
A fairly typical set of standard characterisation tests is shown in
Table 3.8. The standard tests are widely used although some manufac-
turers have their own versions of certain tests (e.g. the ICI compaction
test for compacted bulk density; the Coulter counter test for particle
size analysis), and/or a wider range of tests that they apply.
Apart from the common test procedures used regularly for routine
purposes, other methods are also available for use in more fundamen-
tal investigations and research. Some of these are listed below.
Chemical structure characterisation: Infrared spectrophotometry;21
nuclear magnetic resonance;21 various chemical methods, and study of
model compounds. 4 ,21
Determination of molecular weight: 1 Osmometry (£10 ) ; light-
scattering methods (Mw) which also provide information on molecular
configuration in solution (dissymmetric scattering); fractional sedi-
mentation (£1w).
gg

"tI
;::;
::s!
El
~.
TABLE 3.8
PVC Polymer Properties: Common Standard Characterisation Tests

Property Test methods


1
-%
::I.
'"
'"~.
ISO ASTM
~
Dilute solution viscosity ISO 174 (viscosity number) D 1243 (inherent viscosity) g
~
Apparent (bulk) density ISO 60 (determined in g cm -3) D 1895 (test also gives bulk factor and '"
~.
pourability)
Compacted bulk density ISO 1068 (determined in gem -3)
Particle size and size ISO 1624 (sieve analysis of wet D 1921 (sieve analysis: general methods ~
).
distribution slurry) standard); ~
D 1705 (sieve analysis of wet PVC powder
slurry)
Powder mix time D2396
ISO 6168 (time of flow through D 1755 (time of flow through standard funnel)
Flowability (dry flow)
standard funnel)
r
Plasticiser absorption at room ISO 4608 (phr of DOP sorbed in test D 1755 (phr of DOP sorbed in test conditions)
temperature conditions)
Hot plasticiser absorption ISO 4574 (phr min- 1 of DOP
sorbed in test conditions)
Chlorine content (virtually ISO 1158 (determined as % by D1303
never determined on weight)
commercial polymers)
Porosity D 2873 (determined in cm3 g-l by Hg intrusion)
Volatile matter ISO 1269 D3030
pH of aqueous extract ISO 1264 D 1755 (determination of electrical
conductivity)
Thermal stability ISO/R 182 D793; D2115
Vinyl acetate contene (of ISO 1159 (hydrolysis of the acetate Designation requirements for comonomer
copolymers) groups, and back-titration) (vinyl acetate and others) content stated in
D 1755, but no test method given
Specific gravity (of D792
copolymers) '-'>
Ash and sulphated ash ISO 1270
Preparation of a paste ISO 4612 ~
Apparent viscosity of a paste ISO 4575 (Severs rheometer) ~
ISO 2555 (rotating viscometer) ~
'Fish eyes' Mentioned in ISO 1060/2 but no D3596 ::I
ISO method yet available <.:!
'"
aSome manufacturers use IR spectrophotometry, involving comparison with specially prepared reference spectra. A
rapid IR method for the analysis of a number of copolymers of vinyl chloride has been described by Grisenthwaite. 60

~
90 PVC Plastics-Properties, Processing, and Applications

Determination of molecular weight distribution: 1 GPC; fractional


precipitation; fractional sedimentation; fractional dissolution.
Particle size and size distribution: Sedimentation methods;42,61,62
optical-microscope methods: 61 ,62 electrical sensing zone method (Coul-
ter counter);61,62 centrifugal liquid sedimentation methods;61,62 laser
diffraction;42 light blockage. 42
Particle morphology: Electron-scan microscopy;35 optical
microscopy;42 specific surface area (gas sorption) determinations. 42 ,62
Bulk powder flow: Angle of repose determination;42 shear-cell
tests. 42
3.3.3 Some Commercial Sources and Materials
Some large producers of PVC polymers operate in more than one
country; some also provide technical know-how and backing (under
licence or other arrangements) to local producers in other countries. It
is also not unusual for one producer to supply bulk quantities of
monomer to another. In some countries, imported polymers account
for a significant proportion of the PVC resin market. Some major PVC
polymer producers are listed in Table 3.9.
Table 3.10 gives an indication of polymer types suitable for various
applications. Further illustrations will be found in various formulations
cited in this book.

3.4 CHLORINATED POLYVINYL CHLORIDE (CPVC*)


3.4.1 Origins and Production Methods
CPVC was first produced commercially in the mid-1930s in Germany
by chlorination of PVC polymer in solution (in a chlorinated hydro-
* The abbreviation currently favoured by ISO is 'PVC-C'. However, its logical
consistency with accepted letter symbols for other polymers is questionable.
Virtually all such symbols are groups of capital letters, without hyphens, each
group reflecting the chemical nature of the actual molecular species of the
polymer, in some cases in a very general way (e.g. PA for polyamide; UF for
urea formaldehyde; UP for unsaturated polyester-cf. ISO 1043-1978). Chlor-
inated PVC is a chemically distinct molecular species and should, by the same
token, be abbreviated to CPVc. The congruity is highly suspect-to say the
least-of constructing the abbreviation on the same pattern as the present ISO
letter symbol for PVC compositions (Le. no longer the polymer itself)
containing externally added plasticisers (PVC-P), or the one indicating what is
essentially simply the absence of external plasticisation, i.e. PVC-U for
unplasticised polyvinyl chloride compositions.
TABLE 3.9
Some Major PVC Polymer Manufacturers
(Sources: Ref. 4; published technical press data.)

Manufacturer Country Trade name Production Remarks


capacity (1984)
(thousand
tonnes/year)

AECI Republic of South Corvic 135 ICI associate


Africa
Air Products and Chemicals USA Airco 225
\.,;,
Inc.
ATO Chimie (Atochem) France Lacqvyl; Lucovyl 500 Approx. half the PVC capacity in .."
France. First in copolymers. Big ~
producer of paste polymers cl'
BASF West Germany Vinoflex; Vinidur; 235 ~
Lutofan ~
B. F. Goodrich USA Geon; Dalvin (B. F. 1000 Ranked world first before the formation Zl
Goodrich, Canada) of European Vinyls Corporation (see
below)
Borden Chemical Div., USA 300
Borden Inc.
Certain Teed Corp. USA 100
Chemische Werke Hiils West Germany Vestolit 380
Chemopetrol Czechoslovakia Neralit
Chisso Corp. Japan Nipolit
Conoco Chemicals Co. USA Conoco PVC polymer and feed-stock business
acquired by Vista Polymers (see
below)
(continued) -.0
-
TABLE 3.9-contd.
~
Manufacturer Country Trade name Production Remarks
capacity (1984)
(thousand
tonnes /year)

Denki Kagaku Japan Denkavinyl "a


Dutch State Mines (DSM) Netherlands Varian 335 Joint capacity with SAV shown (see ~
below)
Electro Chem. Israel Epivyl l
Electroclor Argentina Corvic ICI associate B'
EniChem Italy Ravinil; Vipla; 775 Ranked world fifth before joining ICI in
Viplavil European Vinyls Corporation (see
~
.g.,.
(copolymer) below). The EniChem group was
formed in 1983 incorporating all l
business of Anic, Societa Italiana
Resine, Liquichirnica, Enoxy, and
Montedison
l~
European Vinyls Belgium Corvic; Ravinil; Not yet operating Formed in 1986, combining the PVC S·
~
Corporation (EVC) (headquarters) Vipla; Viplavil in 1984 business of Enichem and ICI: gained s::o
world first ranking as a result E.
Formosa Plastics Formosa and USA 940 Ranked world second in 1984
USA 398 Formed in 1985 to acquire PVC business ~
'1::i
Georgia Gulf
of Georgia-Pacific Corp. (whose 1984 ~
s::o
capacity is shown in the preceding g.
column) ill
Goodyear Tire & Rubber USA Pliovic 45 Producer of paste polymers only
Co., Chemical Division
Hoechst West Germany Hostalit 235
ICI UK (headquarters) Corvic 860 With associates ranked world third in
1984. Now partner with Enichem in
European Vinyls Corporation (see
above)
Kanegafuchi Chemical Japan Kaneka
Industry
Mitsui Toatsu Chemicals Inc. Japan Vinychlon
Norsk Hydro Norway and UK Norvinyl 315
Occidental Chemical Corp. USA Tenneco 290 In 1986 purchased all PVC business of
Tenneco Polymers Inc. (see below).
As a result now next to B. F.
Goodrich in PVC polymer production
capacity
Produit Chimiques Ugine France Ekavyi Subsidiary of Elf Aquitaine
Kuhlman
Rhone-Poulenc Ind. France Lucovyl Subsidiary of Enterprise Miniere et
Chimique I.>
Saudi Basic Industries Corp. Saudi Arabia 200 ~
(SABIC) (in 1986)
Shell Netherlands Carina
~
280
Shinetsu Chemical Industry Japan Shinetsu ~
-?
Co. l!
Shin tech Inc. USA Shintech 450 ~
Singapore Polymer Corp. Singapore SPC
Societe Artesienne du France Artevyl 335 Joint capacity with DSM shown (see
Vinyle (SAV) above)
Solvayet Cie. Belgium Solvic 800 Ranked world fourth in 1984
Stauffer Chemical Co. USA SCC
Tenneco Polymers Inc. USA Tenneco 425 (See note for Occidental Chemical Corp.
above)
Union Carbide Corp. USA Bakelite; Ucar 65
(solution
copolymers)
Vista Polymers USA Conoco Formed at end of 1984 (see note for
Conoco above) -0

Wacker Chemie West Germany Vinnol


....
~

"'tI
TABLE 3.10 ~
Polymer Types for Some AppHcations ~
Sl
~.
Application Rigid inj. or Rigid pipes Battery Plasticised Rigid sheeting, Gramophone Paste (Gen.
blow moulding; and profiles separators profiles; extruded or records; purpose spread ~
calendered (incl. window cables calendered (jor flooring coating) .g
Polymer type ~ sheeting profiles) thermoforming) ~
~.
Nature· H H H H C(ll) C(14) H
Kindb SorM SorM E S S S E (paste "'tI
grade) <:!
(')

K value 57-58 65-68 69-72 67-80 57 46-48 70-72 ~


""
~.
Examples of grades· that Corvic S57/116 Corvic S68/173 Corvic E72/660 Corvic S67/105 Corvic C57/350 Corvic C47/488 Corvic 72/755
may be considered Ravinil S230CT Ravinil S2265 Ravinil S575 Ravinil C57 Ravinil C48 Vipla P700 §
!:l..
• H, homopolymer; C, VA/VAC copolymer (% VAC content in brackets). )..
b S, suspension polymer; M, mass polymer; E, emulsion polymer. ~
C European Vinyls Corporation polymers. [
5"
i:;
3 PVC Polymers 95

carbon solvent, typically tetrachloroethane or chloroform) at elevated


temperatures (50 to about 100°C). CPVC made by this process is more
soluble in solvents than the parent PVC. The early commercial
materials, e.g. Igelit PC (I.G. Farbenindustrie) and Rhenoflex
(Dynamit Nobel), were used in solution-applied surface coatings and
adhesives. CPVC fibres were also spun from solvent solutions.
Around 1960 the dispersion process came into use. In the originally
patented version of this process,25,45 PVC polymer in aqueous disper-
sion is treated with a large excess of chlorine at relatively low
temperatures (up to 60°C) in the presence of a swelling agent (a
chlorinated hydrocarbon, e.g. chloroform) under UV light. The early
commercial polymers produced on this way are exemplified by·
Trovidur HT (Dynamit Nobel) and Geon HT (Goodrich).
3.4.2 Chemical Structure
In both processes chlorination takes place mainly at the -CH2-
groups of the PVC polymer chain (i.e. the 1,2-chlorinated configura-
tion, -CHCI-CHCI-, is preferentially formed) so that the resulting
chain structure becomes virtually that of a copolymer of vinyl chloride
with 1,2-dichloroethylene* [(a) in Fig. 3.5], rather than that of a vinyl
chloride/vinylidene chloride copolymer [(b) in Fig. 3.5] which would
be given by preferential 1, I-chlorination. t The large preponderance of
the 1,2-chlorination is shown by the IR spectra of CPVc. It is also
evidenced by the products of thermal decomposition. 4
Complete chlorination of polyvinyl chloride would give a pOlymer
very similar to the symmetrical polydichloroethylene [(c) in Fig. 3.5];
however, the degree of chlorination of commercial CPVC polymers
is considerably lower than this (cf. Table 3.11).
Dispersion-chlorinated CPVC polymers are less soluble than those
produced by the solution process, and their thermal stability is better.
These differences are thought to be associated with differences in the
distribution of the additional chlorine atoms among the -CH2-
groups of the original PVC molecular chains,4 arising as a result of
differences in accessibility of the molecules respectively in the dis-
solved and dispersed states. 25

* Production by direct polymerisation of the monomer is impracticable,


although some brittle, low-molecular-weight products have been obtained in
attempts to prepare the homopolymer.45
t In the dispersion process the tendency to 1, I-chlorination can be increased at
high temperatures if the chlorine concentration is allowed to fall. 45
96 PVC Plastics-Properties, Processing, and Applications

-CHCl-CHCl-CHz-CHCI-CHCI-CHCI-CHCl-CHCI-
(a) Vinyl chloride/l,2-dichloroethylene copolymer or a chlorinated
PVC
-CHz-CClz-CHz-CHCl-CHz-CClz-CHz-CClz-
(b) Vinyl chloride/vinylidene chloride copolymer
-CHCI-CHCl-CHCI-CHCl-CHCl-CHCI-CHCl-CHCI-
(c) Homopolymer of 1,2-dichloroethlene

Fig. 3.5 Simplified representation of polymer segment structures.

Chlorination of PVC polymers reduces the forces of attraction


between the molecular chains, as evidenced, for example, by the
comparatively greater ease and extent of stretching of CPVC films
above the Tg •63 The essentially amorphous morphology of CPVC
polymers is probably a factor in this effect, as even the small amount
of crystalline material present in commercial PVC polymers would
have a constraining effect (with the crystallites acting as quasi
cross-links) at temperatures up to the crystalline melting point. In
comparison with uPVC, the effect of stretching (especially biaxial
stretching) of CPVC sheet upon some of its properties (increases in
Young's modulus and yield stress) is greater, although the per-
meability to CO2 of CPVC sheet was found to increase with biaxial
orientation, in contrast with the reverse effect observed with UpVC: 63
as pointed out by the investigators, the increase in permeability on
biaxial stretching is characteristic of essentially amorphous polymers
which do not crystallise under tension. 63 ,64 However, the increase in
the impact strength of the CPVC sheet, which was also achieved by
biaxial stretching in the above investigation, was claimed to be greater
than that attainable-in the absence of molecular orientation-
through incorporation of impact modifiers.

3.4.3 Material Properties

The two most important points of difference between PVC polymers


and CPVC are the latter's higher melt viscosity in processing, and its
higher Tg (and hence the Vicat softening point and temperature of
deflection under load). Like the 1'g, the density of CPVC increases
with increasing chlorine content. Some properties of CPVC polymers
are shown in Table 3.11, and those of a number of commercial CPVC
3 PVC Polymers 97

TABLE 3.11
Some Properties of Commercial CPVC Polymers, PVC, and FuUy Chlorin-
ated PVC

Polymer CPVC PVC Fully chlorinated


Property polymer homopolymer PVC homopolymer

Chlorine content, weight % 65·67 56·8 73·2 a


Density, gcm- 3 1·52-1·59b 1-40 1·70
Tg,oC 99-123 80-84 175
Maximum service temperatureC
(for commercial
compounds), °C
Continuous exposure 90 65
Intermittent exposure 110 80

a Theoretical figure for polymer of 1,2-dichloroethylene.


b Density of commercial CPVC compounds: 1·47-1·62. This coincides almost exactly
with the density range specified for CPVC pipes and fittings in ISO 3514-1976.
C In non-aggressive environments.

compounds in Table 3.12. Among the properties, the high continuous-


service temperature is particularly important: it is the property
instrumental in the main application of CPVC, viz. as the material of
pipes and fittings for the conveyance of water and other liquids at
elevated temperatures (in some cases also under pressure).
The chemical resistance of CPVC compositions is generally similar
to that of uPVC, except for somewhat greater susceptibility of CPVC
to a number of organic solvents (ketones, chlorinated hydrocarbons,
esters, higher alcohols, aromatic hydrocarbons).
Its higher chlorine content makes CPVC less readily flammable than
PVC (oxygen index typically about 60).

3.4.4 Formulation and Processing of CPVC Compositions


CPVC compositions are formulated on the same general lines as
uPVC, but both their formulation and processing are influenced by
the much higher melt viscosity of the polymer at processing tempera-
tures, and the lower sensitivity of melt viscosity to temperature.
Note: For example, at relatively low shear rates, an increase of the
temperature of a PVC melt from 195 to 205°C may reduce the
melt viscosity by about half: with a CPVC melt the cor-
responding reduction may be only about 15%.
98 PVC Plastics-Properties, Processing, and Applications

TABLE 3.12
Some Properties of Commercial CPVC Compounds
(Based on manufacturer's published data.)

Compound type Extrusion and Extrusion: Profile


injection pipes and coextrusion
mouldinga profiles b with pPVC:
high -ductility
Property compound c
Tensile strength, lbf in- 2 8200 8400 7300
(ASTMD 1708)
Flexural strength, lbf in- 2 14500 15600 13600
(ASTMD790)
Flexural modulus, lbf in- 2 387000 395000 396000
(ASTMD790)
Izod (notched) impact 2·3 2·0 3·2
resistance, ft lbf in- 1
(ASTMD256)
Deflection temperature 100 102 82
under load (264lb in- 2),
°C
(ASTMD648)
Specific gravity 1·52 1·57 1·47
(ASTMD792)
a Geon 88933.
b Geon 88934.
c Geon 88935.

The higher melt viscosity of CPVC makes effective lubrication (and


hence proper selection of the lubricant system) especially important.
The advice of the polymer or compound suppliers on both the
formulations and equipment requirements should always be sought
(and verified in pre-production trials) when first setting up to process
CPVC. The following few general points may also usefully be borne in
mind.
Unless used directly from freshly opened moisture-proof packages,
CPVC compounds should preferably be dried before processing
(tray-drying in layers 2-3 cm deep for 2 h at 103-105°C, or hopper-
drying for the same period at the same inlet temperature). Accurate
stock temperature control within narrow limits is important in process-
ing. The stock temperature should not be below 215°C; higher
temperatures, up to about 230°C, are in fact preferable for ease of
3 PVC Polymers 99

melt flow. The residence time should be kept to the practicable


minimum, and points of possible material hold-up eliminated: to this
end, all flow channels should be stream-lined, and breaker plates and
screen packs should not be used in extrusion. As in PVC processing,
all working surfaces should be resistant to acid corrosion: polished,
multilayer hard chrome plating is suitable; 420 stainless steel (marten-
sitic 13% chrome stainless steel, grade 420 S37 of BS 970) has been
successfully used as mould material.
3.4.5 Commercial CPVC Compounds and Their Applications

Apart from the Geon CPVC compounds (B. F. Goodrich) shown in


Table 3.12, other examples of commercial CPVC compounds are those
of the Lucalor range (Rhone-Poulenc, France) which includes
Lucalor RB 1266 specially developed for domestic central heating
systems, and the Dekadur compounds (Deutsche Kapillar Plastik,
FRG). The commercial compounds are used mainly for the production
of pipes and pipe fittings for hot-water installations (including,
increasingly, domestic central heating systems), where the general
similarity of properties to uPVC (including, inter alia, suitability for
jointing by solvent welding) combined with the greatly increased
temperature resistance in service, are particularly advantageous. Other
applications include pipes and fittings for potable water (CPVC is
approved for this purpose by several professional and regulatory
bodies), pipework and associated products (fittings, valves, tanks) for
chemical plant, extruded profiles, sheets (including co-extruded
CPVC/pPVC sheets), some electrical appliances, and constructional
applications.

REFERENCES
1. Billingham, N. C. & Jenkins, A. D. In Polymer Science, Vol. 1, ed. A. D.
Jenkins. North-Holland Publishing Co., Amsterdam and London, 1972,
Ch. 1.
2. Addleman, R. L. & Yearsley, F., Plastics and Rubber, 1(2) (1976) 81-2.
3. Fikentscher, H., Cellulosechemie, 13, (1932) 58.
4. Titow, W. V., PVC Technology, 4th edn. Elsevier Applied Science
Publishers, London and New York, 1984.
5. Matthews, G. A. R. & Pearson, R. B., Plastics, 28(307) (1963) 98-9.
6. Hjertberg, T. & Sorvik, E. M. In Degradation and Stabilisation of PVC,
ed. E. D. Owen. Elsevier Applied Science Publishers, London and New
York, 1984, Ch. 2.
100 PVC Plastics-Properties, Processing, and Applications

7. Kolinsky, M. & Janca, J., J. Polym. Sci., Polym. Chem. Ed., U (1974)
1181-91.
8. Sorvik, E. M., J. Appl. Polym. Sci., 21 (1977) 2769-90.
9. Janca, J. & Kolinsky, M., Plasty. u. Kaucuk, 13(5) (1976) 138-41.
10. Tavan, M., Palma, G. & Carenza, M., J. Appl. Polym. Sci., 19(9) (1975)
2625-7.
11. Ravey, M. & Waterman, J. A., J. Polym. Sci., Polym. Chem. Ed., 13(6)
(1975) 1475-8.
12. Liu, N. I., Tong, S. N. & Koenig, J. L., J. Appl. Polym. Sci., 2S (1980)
2205-12.
13. Haward, R. N. (Ed.), The Physics of Glassy Polymers. Applied Science
Publishers, London, 1973, pp. 201-6.
14. Baker, c., Maddams, W. F. & Preedy, J. E., J. Polym. Sci., Polym.
Phys. Ed., 15, (1977) 1041-51.
15. Gray, A. & Gilbert, M., Polymer, 17(1) (1976) 44-50.
16. D'Amato, R. J. & Strella, S., Applied Polymer Symposia, 8, Wiley-
Interscience, New York (1969) 275-86.
17. Ohta, S., Kajiyama, T. & Takayanagi, M., Polym. Engng Sci., 16(7)
(1976) 465-72.
18. Gugelmetto, P., Pezzin, G., Cerri, E. & Zinelli, G., Plast. Polym.,
39(144) (1971) 398-402.
19. Abdel-Alim, A. H., J. Appl. Polym. Sci., 19(8) (1975) 2179-85.
20. Natta, G. & Corradini, P., J. Polym. Sci., 20 (1956) 251-67.
21. Maddams, W. F. In Particulate Nature of PVC, ed. G. Butters. Applied
Science Publishers, London, 1982, Ch. 3.
22. Pezzin, G., Plast. Polym., 37(130) (1969) 295-301.
23. Bockman, O. c., Brit. Plast., 38(6) (1965) 364-5.
24. Guinlock, E. V., J. Polym. Sci., Polym. Phys.Ed., 13(5) (1975) 961-70;
idem, ibid., 13(8) (1975) 1533-42.
25. Bier, G., Kunststojfe, 55(9) (1965) 694-700.
26. Gilbert, M., Marshall, D. E., Voyvoda, J. C. & Copsey, C. J., Plast. Rub.
Process, 3 (1979) 96-108.
27. Rider, J. G. & Hargreaves, E., J. Polym. Sci. A-2, 7 (1969) 829-44.
28. Miller, L. E., Puttick, K. E. & Rider, J. G., J. Polym. Sci. C, 33 (1971)
13-22.
29. Smith, K., Hall, M, G. & Hay, J. N., J. Polym. Sci., Polym. Lett. Ed.
14(12) (1976) 751-5.
30. Brady, T. E., Polym. Engng Sci., 16(9) (1976) 638-44.
31. (a) ICI, British Patent 1553829; (b) Hoechst, US Patent 4158092.
32. Hori, Y., Japan Plastics, 3(2) (1969) 48-53.
33. Faulkner, P. G., J. Macromol. Sci. Phys., B11(2) (1975) 251-79.
34. Allsopp, M. W. In Manufacture and Processing of PVC, ed. R. H.
Burgess. Applied Science Publishers, London, 1982, Ch. 7.
35. Marks, G. C. In Developments in PVC Technology, ed. J. H. L. Henson
& A. Whelan. Applied Science Publishers, London, 1973, Ch. 2.
36. Daniels, C. A. & Longeway, G. D., Polym. Engng Sci., 19(3) (1979)
181-9.
37. Chartoff, R. P., 34th ANTEC SPE, Proceedings (1976) pp. 347-9.
3 PVC Polymers 101

38. Summers, J. W., Isner, J. D. & Rabinovitch, E. B., 36th ANTEC SPE,
Proceedings (1978) pp. 757-9.
39. Parey, J. & Menges, G., J. Vinyl Technol., 3(3) (1981) 152-6.
40. Menges, G., Berndtsen, N. & Opfermann, J., Kunststojfe, 69(9) (1979)
562-9.
41. Benjamin, P., Plast. Rubb. Mat. Appln (Nov. 1980) 151-60.
42. Clark, M. In Particulate Nature of PVC, ed. G. Butters. Applied Science
Publishers, London, 1982, Ch. 1 and 2.
43. Kiihne, G., Andrascheck, H. J. & Huber, H., Kunststojfe, 63(3) (1973)
139-42.
44. Domininghaus, H., Die Kunststojfe und ihre Eigenschaften, VDI-Verlag
GmbH, Dusseldorf, 1976, p. 566.
45. Brighton, C. A. In Advances in PVC Compounding and Processing, ed.
M. Kaufman. Maclaren and Sons Ltd, London, 1962, Ch. 1.
46. Sauntson, B. J. & Brown, G., Reports on the Progress of Applied
Chemistry: Plastics, LVI (1971) 66-76 (Society of Chemical Industry).
47. Oswin, C. R, Plastic Films and Packaging. Applied Science Publishers,
London, 1975.
48. Cantow, M. J. R, Cline, C. W., Heiberger, C. A., Huibers, D. Th. A. &
Phillips, R., Mod. Plast., 46(6) (1969) 126-38.
49. Heiberger, C. A., Phillips, R & Cantow, M. J. R, Polym. Engng Sci.,
9(6) (1969) 445-51.
50. Ravey, M., J. Polym. Sci., Chern. Ed., 13(11) (1975) 2635-7.
51. Briston, J., Packag. Rev., 96(3) (1976) 71-2.
52. Sarvetnik, H. A., Polyvinyl Chloride. Van Nostrand, New York, 1969.
53. Goebel, W., Bartl, H., Hardt, D. & Reischl, A., Kunststojfe, 55 (1965)
329-32.
54. Edser, M. H. & Bulezuik, B. W., Polym. Paint Col. J. (4 December
1974), 1051-6.
55. Ulbricht, J. & Rassler, K., Plaste u. Kaut., 23(7) (1976) 487-90.
56. Albert, W., Kunststojfe, 53(2) (1963) 86-93.
57. Bohn, L., Kunststojfe, 53(2) (1963) 93-9.
58. Burgess, R H. In Manufacture and Properties of PVC, ed. R H. Burgess.
Applied Science Publishers, London, 1982, Ch. 1.
59. Ravey, M. & Waterman, J. A., J. Appl. Polym. Sci., 18 (1974) 2927-33.
60. Grisenthwaite, R J., Plastics, 27 (January 1962) 117-9.
61. BS 3406: Determination of Particle Size Distribution (Relevant part,
current issue).
62. Particle Size Analysis, Proc. Society for Analytical Chemistry; Lough-
borough, England, September 1970. Soc. Analytical Chemistry, London,
1970.
63. De Vries, A. J. & Bonnebat, C., Polym. Engng Sci., 16(2) (1976) 93-100.
64. Hopfenberg, H. B. & Stannett, V., Ch. 9 in Ref. 13.
CHAPTER 4

Stabilisers

4.1 DEGRADATION AND STABILISATION OF PVC


4.1.1 General
It is a fact known since the earliest days of PVC processing and
application, that PVC polymers-unless suitably protected-are strong-
ly susceptible to thermal and photochemical degradation. Indeed, in
contrast with other polymers in wide industrial use, the vinyl chloride
polymers are subject to unacceptable degradation at the temperatures
necessary to bring about the degree of fusion and homogenisation
without which melt-processing into useful products is not practicable.
This is what is meant by the statement, often seen in the literature,
that PVC polymers are thermally unstable 'at normal processing
temperatures' .
This inherent thermal instability is reflected in the low energy of
activation for heat degradation of polyvinyl chloride, which has been
variously quoted as 'approximately 20 kcal per mol',1 and 25·9 kcal per
mol 2 (cf. 55, 46, and 65 kcal per mol similarly quoted! for, respec-
tively, polystyrene, polyethylene, and polypropylene). Also, the
specific energy for the generation of a homogeneous melt of polyvinyl
chloride is considerably higher than the activation energy for heat
degradation.
For the above reasons, PVC polymers cannot be heat-processed
without suitable stabilisers. Heat stabilisation is also necessary for
PVC products that may encounter elevated temperatures in service,
whilst outdoor applications additionally call for stabilisation against
degradation by light.
The original discovery (in the 1930s) that certain lead salts and tin
compounds, as well as some metal soaps, could counteract thermal
102
4 Stabilisers 103

degradation when compounded with PVC polymers, marked the


beginning of practical heat-stabilisation of PVC compositions which
opened the way to successful heat-processing. Nowadays a host of heat
stabilisers is available: most of those supplied commercially are
specialised composite systems (in many cases incorporating also
lubricant additives) developed for particular types of PVC materials,
processing methods, and service conditions. The stabiliser systems
used in PVC compositions for outdoor applications normally provide
dual heat/light-stabilising action.
The modes and mechanisms of PVC degradation and of the action
of stabilisers have been extensively studied since stabilisation first
came to be practised. The findings have resulted in considerable
insight into (but not yet full understanding of) the main aspects of the
entire, extremely complex subject, viz.
(a) the reasons for the instability of vinyl chloride polymers (this is
the best-understood aspect of the three);
(b) the ways in which degradation proceeds, and the resulting
changes in the polymer;
(c) the ways in which stabilisers act, and their relation to (a) and
(b).
However, there is still much to be elucidated before the science of
stabilisation of PVC compositions draws abreast of the highly de-
veloped art. It may be noted in passing that PVC polymers are not the
only constituents of these compositions that can suffer degradation, or
benefit from stabilisation: some others are chlorinated polyethylene
modifiers, chlorinated paraffins (used as plasticiser extenders), and
certain rubbery modifiers (e.g. some ABS types). The first two can be
degraded by heating (undergoing dehydrochlorination with formation
of double bonds and oxidation3,4), whilst the rubbery copolymers may
be photodegraded through the disruption and oxidation of the double
bonds present in their molecules.

4.1.2 Thermal Degradation

(a) Outward Manifestations


The main outward manifestations of thermal degradation of PVC (at
temperatures sensibly below those of pyrolytic decomposition and
combustion, against which no stabilisation is possible) are the evolu-
tion of hydrogen chloride, development of colour (progressing with
the extent of breakdown from light yellow, through reddish brown, to
104 PVC Plastics-Properties, Processing, and Applications

almost black in severe cases) and deterioration of physical, chemical,


and electrical properties.
(b) Chemical Aspects
DEHYDROCHLORINATION AND COLOUR DEVELOPMENT
It is known that the evolution of HCI is due to progressive de-
hydrochlorination of the polymer chains, which can occur at only
moderately elevated temperatures (from about 100°C). It can be
initiated, and is thereafter catalysed, by the presence of HCI (auto-
catalysis) as well as other strong acids.
Conjugated double bond systems (polyene sequences) are formed
in a polymer chain as the hydrogen and chlorine atoms are 'unzipped'
from it. The general effect is illustrated by the summary scheme (1),
without any assumption as to the nature of the actual mechanism
involved (which is still under debate).

H H H H H H H H H
I I I I I I I I I
~C-C-C-C-C-C~-C-~
I ;-1----t-; I I I I I I
H:O H:O H a H a H
l
1_ _ _ _ _ _ _ _ 1

energy;
HCI

H H H H H H H H H
I I I I I I I I I
~C-C=C-C-C-C~~-~
I ~+--h I I I I
H : CI H: CI H CI H
1________ 1

i energy;
HCI
(1)
H H H H H H H H H
I I I I I I I I I
~C-C=C-C=C-C~~~~
I .--I----h I I
H :OH:OH

i
I______ --~

energy;
Hel

H H H H H H H H H
I I I I I I I I I
~C-C=C-C=C-C=C~~~
I ,--~---~--,
H : Cl H:
I . _______ ~

and so on
4 Stabilisers 105

The illustration shows random initiation, i.e. elimination of HCI from


two ordinary neighbouring monomer residues in the polymer chain:
there is good evidence that such initiation does occur in practice,
although much less frequently than initiation at certain more vul-
nerable sites in the chain (see below). As can be seen, the first
elimination of HCI by random initiation and the subsequent steps
generate the grouping """CH=CH-CHCI""", i.e. an intra-chain aUylic
group, whose CI atom should be strongly activated by the neighbour-
ing double bond,5 facilitating further unzipping of HCl under the
catalytic influence of that already formed.
It is fairly generally assumed that the polyene sequences are
primarily responsible for the development of colour* in PVC undergo-
ing degradation. However, the possible contribution must also be
recognised from coloured carbonium salt complexes (polyenyl chloride
ion pairs) which should be formed under an ionic mechanism of
dehydrochlorination [see for example the illustrative scheme (2)]6-8
thought by some recent reviewers9 to be more likely to be operative
than the free-radical mechanism favoured by many earlier
investigators. 5,10 The formation of carbonium-type complexes in PVC
polymer degraded by heat was demonstrated by Schlimper .11,12
Cl-

"""--fCH=CHtCHCl-CHr ;::=::::! """--fCH=CH-tCH-CHr


(I)
(II) 1
-HC)

(2)

'''T
AAA rCH=CH-tCH-CHr
n+l
;::=::::! ~CH=CH-tCHCI-CHr
n+l
(IV) 1- HC) (III)

and so on
On good grounds,9 the stability of the ion pairs D and IV (i.e. their
reluctance to split off HCI) may be expected to increase with the

* Colour appears with as few as seven conjugated double bonds in a polyene


sequence, whilst sequences of up to 30 such bonds can arise in de-
hydrochlorinated pVC,1O with a sequence length of 10 being regarded by
some as a likely average. 9
106 PVC Plastics-Properties, Processing, and Applications

length of the polyene sequence in the cation, to the point where the
polyene propagation ceases after a certain sequence length has been
reached: this is a possible explanation for the limited length of polyene
sequences in degraded PVc.

CHEMICAL BASIS OF OTHER PROPERTY CHANGES


The deterioration of various material properties that accompanies
thermal degradation of PVC is the joint, complex effect of changes
occurring in the polymer, in other susceptible constituents of the PVC
composition concerned, and in the composition as a whole (by way of
inter-reaction of its constituents or their loss by exudation, migration
or volatilisation, and through developing contamination by the
products of degradation of the constituents and of their reactions).
In addition to the dehydrochlorination and polyene formation
already mentioned, the PVC polymer undergoes chain-scission, oxida-
tion (in the presence of air) at vulnerable points in the chain (cleaved
bonds, double bonds, activated sites), cross-linking (with some conse-
quent gel formation), and some cyclisation.
Although the relevant mechanisms is by no means fully established,
there is plausible evidence that a Diels-Alder reaction between
polyene sequences of neighbouring chains [cf. illustrative scheme (3)]
is responsible for much of the cross-linking. 9

-CH=CH~H=CH-CH=CH-CH=CH­
+
-CH=CH-CH=CH-CH=CH-CH=CH-

~H=CH~
1
/CH=CH~ /CH=CH-
(3)

CH' CH
~CH-CH/
/ ~ .
-CH=CH CH=CH-CH=CH-

The mechanism of cyclisation in thermal degradation of PVC


polymer is still in dispute, but the cyclisation is thought to take place
within (rather than between) chains, and benzene and cyclohexadiene
are known to be among the products.
Possible degradative changes in some other constituents of PVC
4 Stabilisers 107

compositions have been mentioned previously. Apart from those,


stabilisers are also used up as they react with some polymer degrada-
tion products, and compounds formed in these reactions appear in the
PVC material (cf. Section 4.3). In plasticised compositions, volatilisa-
tion, exudation or migration of the plasticisers under heating, as well
as their partial breakdown (with oxidation in the presence of air) can
contribute to the overall effect of thermal degradation.

VULNERABLE SITES IN THE PVC POLYMER CHAIN


Theoretical considerations, and the study of model compounds, have
established that, in the absence of sites of reduced stability in the
chain, polyvinyl chloride with the ideal, purely linear head-to-tail
monomer unit arrangement should be much more resistant to de-
hydrochlorination than the commercial PVC polymers in fact are. It is
known that the structure of the molecular chains of these polymers
does deviate in a number of ways from the simple ideal: the structural
irregularities are discussed in Chapter 3 (Section 3.1.1). It is,
therefore, a reasonable assumption-not contradicted by any of the
results of the very numerous investigations to date-that in, or near,
some of these structural features the carbon-chlorine bond is activ-
ated, constituting a favourable site for initiation of dehydro-
chlorination.
Up to the early 1980s, in consequence of much careful investigative
work--on model compounds, exchange reactions of commercial PVC
polymers, and involving evaluation by chemical and IR techniques-
the view was fairly well grounded that the structural features
principally responsible for activated, labile chlorine atoms were
chloroallyl groups, both in, and at the ends of, the molecular chains. S
Whilst it was realised that mid-chain tertiary chlorine atoms (see
Chapter 3, Section 3.1.1) should be as labile as an allylic chlorine,s
available evidence indicated that tertiary chlorines were too scarce to
playa significant role. s However, some of the most recent results,
including those of investigations by very sensitive NMR techniques,
radiochemical methods, and UV spectroscopy, now strongly support
the converse conclusion, viz. that tertiary chlorine is much more
abundant (possibly by a factor of about five) than mid-chain allylic
chlorine, and that it is mainly responsible for the relative ease of
dehydrochlorination of commercial PVC polymers. A recent review9
estimates the respective contributions to the initiation of de-
108 PVC Plastics-Properties, Processing, and Applications

hydrochlorination as 70-80% by tertiary chlorine* at branch points in


the molecular chains (I\N\CClI\N\) and 10-15% each by mid chain allylic
~
chlorine (I\N\CH==CH-CHCII\N\), and regular monomer units serving
as random initiation sites (see illustrative scheme (1) above). This
estimate indirectly brings out the fact that the current balance of
relevant evidence on which it is based points away from the likelihood
that any of the other structural irregularities listed in Table 3.3 of
Chapter 3 playa significant role in the dehydrochlorination of ordinary
PVC polymers.

(c) Thermal Degradation in Melt Processing and Static Exposure to


Heat
The melt processing in which thermal degradation can occur is that
experienced by a PVC composition in compounding and production
operations or in dynamic stability tests (see Section 4.9). Static
exposure to heat may occur in the course of service of a PVC product
or in static stability tests (see Section 4.9).
There is as yet no complete agreement on the mechanisms in-
strumental in the thermal degradation of PVC during melt processing,
and no clear explanation of the role in this complex phenomenon of
the known instability sites in the polymer chains, although such
internal double bonds as are originally present (cf. Table 3.3 in
Chapter 3) are thought to playa significant part. Thermally activated
dehydrochlorination (with the consequent formation -of polyene se-
quences), and its autocatalysis by the HCI formed, are recognised as
major factors. There is some chain scission (partly heat-induced and
partly caused by the mechanical shear experienced by the stock), and
some peroxide and carbonyl formation at the cleaved bond sites; but
the oxygen content of a PVC melt in ordinary processing is normally
low, so that this kind of thermo-mechanical oxidative degradation is
not thought to be extensive.
Considerable similarities have been noted 14 between the IR and UV
spectra of PVC compositions degraded, respectively, in processing and

* Compare Berens' conclusion 13 (drawn as early as 1974 from the results of


degradation experiments on model copolymers) that 1-2 tertiary chlorines per
1000 monomer units would alone adequately account for the thermal
instability of commercial PVC polymers. This may also be compared with the
best current estimate of 0·5-1·5 tertiary chlorine atoms per 1000 monomer
units in such polymers (see Chapter 3, Table 3.3).
4 Stabilisers 109

by static heating in air, although the static degradation produced more


carbonyl groupS.14 Progressive dehydrochlorination autocatalysed by
the HCI evolved is a principal feature also in the degradation under
static conditions.

(d) Effects of Polymer Molecular Weight, and Some Impurities and


Additives
In general, PVC polymers of lower molecular weight are less
heat-stable than the higher-molecular-weight ones. This was originally
attributed to the increase in the end-group content with decreasing
molecular weight (since until recently some end-groups were thought
to have a significant destabilising effect4). However, the more likely
explanation now seems to be the greater 'heat history' (cf. Section 4.9)
associated with the higher polymerisation temperatures used in the
production of lower-molecular-weight PVC polymers (see Chapter 3,
Section 3.1.1 and Table 3.5).
Note: In melt-processing, the tendency to lower heat stability of the
lower-molecular-weight polymers is compensated to some
extent by the fact that their lower melt viscosity entails less
shear heating and permits somewhat lower stock tempera-
tures to be used.
The presence of impurities, both external and internal (e.g. suspend-
ing or emulsifying agents from the polymerisation process), reduces
thermal stability of PVC polymers. It is mainly for this reason that,
other factors being equal, susceptibility to thermal degradation in-
creases in the sequence
mass polymer~ suspension polymer~ emulsion polymer

4.1.3 Photochemical Degradation

The chemical bonds in an ideal PVC polymer chain with no structural


imperfections would all be saturated covalent linkages of three kinds:
C-Cl, C-C, and C-H. The dissociation energies of these bonds are
respectively 78, 81, and 98 kcal mol- 1 (to the nearest unit). In relation
to the photon energies of the radiation making up the spectrum of
sunlight, these dissociation energies are high: they are encompassed
only by those associated with the shortest wavelengths in the UV band
of the sunlight spectrum (viz. the 290-400 nm band) which itself
constitutes the spectrum's most energetic portion.
110 PVC Plastics-Properties, Processing, and Applications

Note: The wavelengths (A) carrying photon energies (E) cor-


responding to the three bond dissociation energies quoted
above are (to the nearest unit):
A, nm 368 351 . 291
E, kcal mol- 1 78 81 98
Thus, in theory (and solely on the basis of the simplest energetic
considerations) the UV component of sunlight received at the earth's
surface should be capable of degrading the notional ideal PVC
polymer. However, the chemical bonds of such a polymer would also
not absorb radiation above about 200 nm, 15 and since without absorp-
tion no interaction can take place between a polymer and the radiation
it receives, no degradation would occur.
In practice, commercial PVC polymers are susceptible to degrada-
tion by UV light. This is attributable to the sensitising effect of some
of the structural irregularities in their molecular chains: the strongest
sensitisation is believed to be due to the unsaturation (double bonds)
that are always present, and to such carbonyl and peroxide groups as
may be present originally, or formed during photodegradation. In
PVC compositions the base polymer can be further sensitised by the
presence of degradation products originating in thermal processing, as
well as by sensitive sites in some of the other formulation components
(e.g. plasticisers I6 ), by some impurities, residual solvents, and the like.
Suitable, effective stabilisation and attention to processing conditions
are therefore especially important in the production of PVC materials
for outdoor applications.
All the main external manifestations associated with thermal
degradation of PVC appear also as a result of photolysis (i.e.
dehydrochlorination, development of colour, and deterioration of
properties). In plasticised compositions, exudation of plasticisers
(resulting in sticky surface layers), embrittiement, and cracking can
also occur in varying degrees. However, in comparison with typical
thermal degradation, there is greater variability in the occurrence of
these effects (for example, more often than not, colour development is
slight or absent altogether) as well as in their onset, progress, and
respective intensities. The situation can be further complicated
where-as is often the case in service-exposure to light is associated
with weathering: this introduces a number of further destructive
factors such as thermal expansion and contraction with temperature
changes, solar heating, water absorption, and possible effects of
atmospheric pollutants.
4 Stabilisers 111

PVC undergoes photodegradation on exposure to light in the


absence of oxygen as well as in its presence. The latter mode is one
more directly relevant to practical service situations, in which air will
almost invariably be present.
Photodegradation of PVC is widely believed to proceed through a
free-radical mechanism. 5,15 The chemical processes involved are com-
plex and still not completely understood, but some general features
are fairly well established. Thus, as has been mentioned, for both
non-oxidative and oxidative photodegradation, the most likely initia-
tion sites in the polymer are double bonds (mid-chain unsaturation,
and possibly also that in some end-groups17), and any adventitious
oxygen-bearing groups that may be present originally (having arisen in
the course of polymer production) or be formed through photo-
oxidation.
The main processes occurring in non-oxidative photodegradation of
PVC polymers are progressive ('unzipping') dehydrochlorination with
polyene formation, chain scission, and cross-linking. The same main
processes are observed in oxidative photodegradation in which, how-
ever, new carbonyl and hydroperoxide groups are formed (whose
presence further sensitises the polymer) through reactions with oxygen
at sensitised or cleaved-bond sites. Polyene sequences forming in the
course of dehydrochlorination may also be interrupted by reaction
with oxygen: this kind of disruption ('photobleaching') of these
colour-inducing formations may be responsible for retarded or
arrested development of colour in PVC undergoing weathering. 18,19
Oxygen-bearing groups arising in photo-oxidation are hydrophilic-
their presence is thought to play a part in the disruptive effects of
atmospheric water in weathering of PVC materials. 20
The rate and extent of dehydrochlorination in photodegradation (in
both the presence and the absence of oxygen) increase with the
intensity of the incident radiation, with its decreasing wavelength
(increasing energy), and with increasing temperature. 19
Exudation of plasticisers from PVC on weathering has been
attributed to their partial exclusion from the areas where some
cross-linking of the polymer has taken place. s

4.2 PURPOSES AND FUNCTIONS OF


STABILISERS IN PVC
Like the mechanisms of degradation of PVC, those of stabiliser action
are still not fully understood. However, it is clear even from quite
112 PVC Plastics-Properties, Processing, and Applications

general considerations that-whatever the mechanisms of its


operation-a good stabiliser should prevent or disrupt the reactions
instrumental in thermal degradation of PVc. To this end it should, in
particular, rapidly bind and inactivate any reaction products which
may further impair stability (especially free HCI generated by de-
hydrochlorination), deactivate potential initiation sites in the PVC
polymer (e.g. by substituting stable groups for labile Cl atoms and
reacting to saturate double bonds), disrupt polyene sequences (without
damaging the polymer chain), react with free radicals, deactivate
oxygen-bearing groups (which would otherwise act as instability sites),
and neutralise the destabilising effects of impurities. A good light
stabiliser should be similarly functional with respect to photodegrada-
tion, as well as preferably, having a screening action against UV
radiation of the sunlight spectrum.
As is largely self-evident, important general requirements that
should also be met by the stabiliser include ease of intimate dispersion
in the PVC composition concerned and compatibility with all its
constituents in processing and service conditions, no adverse effect on
processing behaviour and properties, effectivity at low levels of
addition, and general cost economy. For some applications the
stabiliser may also have to be non-toxic, and/or odourless, and/or
without effect on the clarity, colour or other characteristics of the PVC
material.
When all the above requirements are considered vis-a-vis the great
variety of PVC compositions, their processing conditions and applica-
tions, each of which may (and usually does) impose some special
demands, it is not difficult to see why there are so many commercial
stabilisers for PVC, and why most of these are not single compounds
but composite, multicomponent systems. It is often said that every
PVC composition presents an individual stabilisation problem,
and-from the practical standpoint-this is hardly an exaggeration. In
the absence of prior directly relevant experience, the choice of a
stabiliser or stabiliser system for a particular formulation should be
made in consultation with the stabiliser manufacturer, and should be
verified in practical tests.

4.3 HEAT STABILISERS

All heat stabilisers and stabiliser systems in industrial use are of the
'external' kind in the applicational sense, in that they are additives
4 Stabilisers 113

incorporated in the PVC polymer by physical admixing. * Permanent


'internal' stabilisation of the polymer should, in principle, be possible,
either by operating the polymerisation conditions so as to eliminate (or
at least substantially reduce) the formation of the irregular structures
that constitute sites of instability in the PVC polymer chains, or by
chemically modifying these structures to neutralise their destabilising
effects.
Along the first of these lines, some possibilities have been explored
of counteracting the formation of labile-chlorine groupings (intra-chain
chloroallyl groups and tertiary chlorine) which are known to arise as a
result of chain transfer to polymer during polymerisation. Possible
means of reducing such transfer include increasing the monomer
content of the polymer gel (by raising the polymerisation pressure
and/or temperature),9 use of additives which can temporarily retain
the VC monomer (e.g. tetrahydrofuran9), or employing an anionic
polymerisation system. 9,21 However, none of these possible methods is
free from difficulties, and none has led to an industrially viable
process.
Stabilising modification of the PVC polymer by chemical reaction is
also still of largely academic interest rather than practical significance.
The following exemplify some of the main lines of approach explored
by various investigators.
(i) Substitution of labile chlorine atoms by stable groups: through
reactions with triphenyl aluminium,22 triethylaluminium,23,24
with dibutyltin mercaptide salts (reported25 ,26 to improve ther-
mal stability by factors of 6 and 9, or with alcohol/water
mixtures27 (said to have produced some promising results in
industrial-scale trials9).
(ii) Saturation of double bonds: through limited chlorination,9 or
addition of hydrogen fluoride. 9
Heat stability superior to that of commercial PVC polymers has also
been claimed for a copolymer of vinyl chloride and lead
undecylenate. 28

* Even if a stabiliser is added to the polymerisation mixture in the reactor


('in-kettle' stabilisation-usually with an organotin stabiliser-practised by
some US pipe manufacturers who produce their own PVC polymers) it still
functions as an additive, although its effectivity is maximised by the very
intimate degree of dispersion attained: its presence also protects the polymer
formed against heat degradation in the drying operations which conclude the
production cycle.
114 PVC Plastics-Properties, Processing, and Applications

4.3.1 General Classification of Heat Stabilisers

There is no official, rigid classification of heat stabilisers, although for


the purposes of discussion or review of their properties and effects
they are very often grouped on a somewhat mixed basis relating partly
to their chemical nature and partly to the types and areas of
application. The classification adopted here is based mainly on
chemical type. On this basis, the compounds used as heat stabilisers
for PVC may be divided into the following general groups:
(i) lead compounds:
(ii) organotin compounds;
(iii) compounds of other metals;
(iv) organic stabilisers.
In many instances [and with groups (iii) and (iv) predominantly]
individual members of these groups are used not singly, but in
combination with other compounds from the same or another group,
to make up composite stabiliser systems. The majority of commercial
stabilisers are such composites, specially designed for particular types
of composition and application, often with a view to utilising synergis-
tic effects between the components and avoiding undesirable interac-
tions. Stabilisers and stabiliser systems are also available in combina-
tion with other PVC additives (lubricants, colourants, antistatic
agents, etc.) in 'single-pack' additive systems marketed by suppliers
for specific purposes and types of PVC composition. The mutual
effects of stabilisers with lubricants (whether as members of the same
single-pack system or when incorporated individually in the PVC
composition) are of particular importance (see Chapter 7, Section
7.2).
Other things being equal, the effectivity of a stabiliser increases with
the thoroughness of its dispersion in a PVC composition.
The first step in selecting a stabiliser for a particular application is to
consider which of the above general types is likely to be the most
appropriate. In this connection it is also particularly important to
consider the total compound and manufacturing costs, with proper
regard to the fact that the cheapest possible stabiliser is not necessarily
the wisest choice. For example, such factors as the recycling of rejects
and general rework can involve extra demands on the stabiliser's
effectivity, and large hidden costs that may overshadow differences in
stabiliser prices.
4 Stabilisers 115

4.3.2 Lead Compounds

These are either lead salts or lead 'soaps' (salts with stearic acid). The
main technical advantages of these old-established stabilisers are good
heat-stabilising power (in some cases combined with UV absorption),
and particular suitability for use in electrical insulation (because of
their complete non-conductivity and the inert nature of the chlorides
formed by reaction with Hel). However, they are not suitable for
clear compositions (although some may be used in translucent ones),
where freedom from sulphur staining is necessary, or where their
toxicity presents a hazard, as, for example, in food-contact applica-
tions (e.g. packaging films, containers), products for medical use, or
children's toys. Lead stabilisers are comparatively cheap. Although
they are the heaviest (costing is often on a volume basis), and are
generally used at relatively high-loadings, they can frequently prove
most cost-effective. Subject to their above-mentioned limitations they
are, therefore, always worth considering first. Typical application
areas include pipes, pipe fittings, rainwater goods, interior and
exterior profiles, cable coverings, conveyor belting and electrical
insulation tape.
Lead compounds represent a health hazard, and exposure must be
minimised. In most Western countries stringent limits are laid down by
the appropriate regulatory bodies for maximum lead concentrations to
which people may be exposed in particular circumstances and
conditions.
In the handling and processing of lead stabilisers there are two
general, mutually complementary routes to reducing exposure. Firstly,
the stabilisers are available in forms which do not contain, or give rise
to, dust that may be inhaled. These forms are: 'dustless' powders
(stabiliser powder damped down with a small proportion-varying
with absorptivity, but in general about 1%-{)f plasticiser or mineral
oil, or treated with PTFE); liquid dispersions (pastes) in a suitable
plasticiser; agglomerated forms (granules, flakes, or 'pearls'); and
'strands' (thin miniature rods, typically 5-10 mm long and 0·5-1·5 mm
in diameter). The agglomerates and strands have the additional
advantage (over powders) of better dry flow. Finally, the stabiliser can
be supplied packaged within a sealed polyethylene bag (the pack may
also contain lubricants and other additives) for addition direct and
whole into a high-speed mixer. The mixer shreds the bag, and the
small amount of polyethylene may contribute a little external lubrica-
,...
,...
0\

TABLE 4.1 ~

Lead Stabilisers for PVC ~


~
Lead compound Main applicational features Advantages and limitations Remarks !:l

Basic lead carbonate ('white Low-cost, general-purpose Not suitable for compositions melt-processed at Oldest lead stabiliser; still
'"I
lead') stabiliser. Special high- high rates and temperatures (decomposes at popular for some non- .g~
purity grades available. about 200°C, with CO2 and water-vapour critical applications.
gassing). '"~
'"~.
Non-lubricating. Opacifying.
Tribasic lead sulphate Very common component Strong heat-stabilising action. Non-lubricating. Often used with dibasic ~
of composite lead stabili- Opacifying. lead phosphite in com- ~
sers; widely used in lead- posite heat/light lead ~
~.
stabilised PVC composi- stabilisers.
tions for melt-processing.
Tetrabasic lead sulphate As tribasic lead sulphate, but still more powerful stabilising action (highest proportion of available PbO
~
~
among lead stabilisers); some UV absorption. ~
Dibasic lead phosphite Virtually standard com- Good heat stabiliser with pronounced UV- Virtually standard light-
ponent of composite lead screening and antioxidant functionality. Non- stabilising component
~
stabilisers for outdoor- lubricating. Opacifying. of composite heat/light
~.
service PVc. lead stabilisers.
Lead stearate Main use as lubricating Only moderate heat-stabilising power, but May be used with other
component of composite strong lubricant action. Will not give clear metal-stearate stabili-
lead stabilisers (espe- compounds above about 0·75 phr (general sers, e.g. calcium and
cially ones based on lead use level 0·5-1·5 phr). strontium stearates.
sulphates) .
Dibasic lead stearate Main use as high- Moderately good heat stabiliser with strong
temperature lubricant in lubricant action. More suitable for clear com-
composite lead positions than lead stearate.
stabilisers.
Lead salicylate Used in composite lead Heat stabiliser with some light -stabilising ac-
stabilisers for PVC com- tion. Chelator for iron (prevents iron-
positions containing iron- promoted colour deVelopment). Non-
bearing constituents (e.g. lubricating.
asbestos-filled PVC
flooring).
Lead silicate Used as component of Effective heat stabiliser (high PbO yield). Suit- Main applications in
composite lead able for translucent compositions (refractive pPVC including some
stabilisers. index approximates that of PVC polymer). paste products.
Non-lubricating. .j>"

Dibasic lead phthalate Used in lead stabilisers in Good heat stabiliser with some light-stabilising c;"
accordance with its func- action. Good dispersibility in PVC resins. S
<:0-
tional characteristics (see Activator ('kicker') for chemical blowing
~
next column). agents in PVC foam compositions. Non- '"<;!
lubricating. Opacifying.
Tribasic lead maleate Used in lead stabilisers for Effective heat stabiliser with some light-
pipe and sheeting, and in stabilising action. Useful stabiliser for CPVC.
some translucent
compositions.
Tetrabasic lead fumarate Main use in gramophone Good heat stabiliser, highly compatible with
records and cable PVC resin.
coverings.

- .I
-
118 PVC Plastics-Properties, Processing, and Applications

tion in subsequent processing. Secondly, automatic or semi-automatic


handling systems are operated in many PVC compounding plants
(especially large-scale ones) so that the stabiliser can be delivered in
bulk and conveyed to weighing and mixing stations with no direct
contact with any operatives.
Methods of monitoring such parameters as 'lead in air' and 'blood
lead' levels are available, so that, provided that proper precautions are
observed, it is possible to handle lead stabilisers and other hazardous
materials with safety. Relevant information is readily available from
stabiliser suppliers. 29
The lead compounds used as stabilisers (nowadays most commonly
as constituents of composite stabilisers) for PVC are listed in Table
4.1.
Stabiliser suppliers invariably provide recommendations on the
amount of any of their stabilisers to be used in a particular kind of
PVC composition, as well as specific formulations incorporating the
stabilisers. However, on the rare occasions when a completely new
formulation may have to be devised without such assistance, two
points should be borne in mind, viz. that the stabilising action of a lead
stabiliser (i.e. the effectiveness and duration of protection afforded) is
dependent on the amount of lead monoxide (PbO) potentially
available in the compound, and that only a part of that amount should
be counted as the actual stabilising agent. This part is sometimes
referred to as 'safe PbO', because if it is exhausted (as the stabiliser is
being used up in the course of discharging its function) and further
PbO is drawn upon, the consequent further decomposition of the
stabiliser may result in 'gassing'* or in liberation of residues which may
disturb the stabiliser/lubricant balance, e.g. excess stearic acid liber-
ated from lead stearate.

Note: With a basic lead stabiliser, only the PbO from the base part
of the compound should be regarded as available for stabili-
sation, and the total amount of stabiliser to be used calcu-
lated accordingly. For example, in white lead-basic lead
carbonate, 2PbC0 3 ·Pb(OH)z- the total PbO available (ex-
pressed as a fraction) is 3PbO/2PbC03 = 0·863, whereas the

* Release of gas, normally CO2 during hot processing can be promoted or


aggravated by acidity of plasticisers in plasticised compositions.
4 Stabilisers 119

'safe' proportion may be taken as about 0·31. The respective


'safe' PbO figures for tribasic lead sulphate and dibasic lead
phosphite are 0·65 and 0·60.
The main mechanism whereby the lead stabilisers exert their effect
is thought to be neutralisation of nascent hydrogen chloride. 5 This
view accords with their basic nature, their mode and rates of reaction
with HCI,30 and the fact that lead chloride is formed in lead-stabilised
PVC materials in the course of their heat treatment and service.
Unlike the chlorides of some other stabiliser metals, lead chloride does
not promote degradation of PVC polymer. Its inactivity in this regard
is most probably the main reason why, as is well known, the
performance of lead stabilisers is not much improved by the presence
of co-stabilisers (especially the chelators or metal carboxylates used as
components of mixed-metal stabiliser systems), * in that deactivation of
stabiliser decomposition products and impurities is believed to be one
of the main functions of such additives.

4.3.3 Organotin Stabilisers

(a) Chemical Nature and Types


Commercial organotin stabilisers are mainly compounds of the general
formula V, with some of those represented by formulae VI and VII
also in use (commonly in mixtures with formula V compounds, the
respective proportions being adjusted for particular effects).

In the three formulae, R can be an alkyl or an ester group (see below),


and A is normally derived either from
(i) mercapto compounds (mercaptoacids and their esters; mercap-
tides), or
(ii) carboxylic acids and their esters (e.g. maleic or lauric acids;
maleic esters and half-esters).

* But addition of cadmium/barium stabilisers to lead stabilisers can improve


both heat- and light-stability.
120 PVC Plastics-Properties, Processing, and Applications

Most commonly the A groups are all mutually the same, although
compounds in which they differ are not unknown among commercial
organotin stabilisers (e.g. Thermolite 17, M&T Chemicals, USA:
dibutyl laurate-maleate). Alkyltin stabilisers in which the A sub-
stituents are mercapto compounds are usually referred to as thiotin
stabilisers, or simply 'thiotins' (occasionally 'sulphur tins'), and those
with A substituents of the sulphur-free carboxylic acid or ester type as
tin carboxylates: the most numerous members of this latter group
among commercial stabilisers are dibutyltin carboxylates. However,
the nomenclature commonly employed in the industry for organotin
stabilisers is predominantly associated with the nature of the sub-
stituent groups R, as shown schematically in Fig. 4.1, so that the
compounds V, VI and VII may be referred to as di-substituted,
mono-substituted and tri-substituted respectively.
Note: Recent work31 indicates that organotellurium compounds
have a stabilising action similar to that of the organotins.
Dialkyltellurium maleates were found to be the most effective
(but still inferior to the corresponding tin compounds).
The alkyltin compounds most effective individually as heat stabili-
sers for PVC are those of type V, closely followed by type VI
compounds. However, a great many commercial alkyltin stabilisers are
composite systems in which the presence of type VI compounds and,
in some cases also type VII ones, jointly with type V compounds,
confers considerable synergistic benefits. The tri-substituted alkyltins
(R3SnA), formed alongside the other two kinds in the course of
production of organotin stabilisers by the industrial processes,5 are
more toxic, and less effective in their stabilising action, than the
compounds of types V and VI.

Organotin stabilisers
I
I I
Alkyltin compounds Estertin compounds
(R = an alkyl group) (R = an ester group:
I R'·OOC·CH2 ·CH2- )
~I----~I--~--~I------~I
Methyltin Butyltin Octyltin Lauryltin
compounds compounds compounds compounds
(R = -CH3 ) (R = -C4H9) (R = -CRH 17 ) (R = -C 12H 2S )
Fig. 4.1 General nomenclature of organotin stabilisers in relation to the
substitute group R (see formulae V, VI).
4 Stabilisers 121

The estertin stabilisers are relatively new, having been first intro-
duced (by Akzo Chemie) in the mid-1970s. Since then several
commercial representatives have been available, e.g. in the Stanclere
(Akzo Chemie), Irgastab (Ciba-Geigy), and Interstab (Interstab
Chemicals) ranges. The lauryltins-a Japanese development-are even
more recent.
The preparation and evaluation of an interesting group of polymeric
p-benzoquinone-tin compounds has been described by Yassin &
Sabaa,32 who claim a high degree of stabilising action in PVC for these
compounds.
(b) Characteristics and applications
The organotins are powerful heat stabilisers, imparting excellent short-
and long-term stability to PVC compositions, and-for the most
part-a high degree of clarity in transparent products. They are
relatively expensive, although the 'compounded' cost can be competi-
tive with that of other types of stabilisers, especially when considered
on the basis of performance, because of the comparatively low
incorporation levels (rarely more than 2 phr, and only fractional phr in
many formulations). Most organotins are toxic: however, several
commercial tin stabilisers based on dioctyltin compounds* are allowed
in many countries (with restriction on maximum content), because of
their low level of toxicity and good resistance to extraction. These
permitted tin stabilisers are important in the production of uPVC
food-packaging film and bottles for edible oils and beverages, where
a combination of non-toxicity with high degrees of heat stability and
clarity is a primary requirement. Some commercial estertins have also
gained food-contact approval.
The stabilising effectivity of organotin compounds is primarily
influenced by the nature of their A substituent groups (cf. formulae
V, VI, VII). In general, the thiotins-and especially dialkylthiotins-
are the most powerful and effective heat stabilisers known, suitable
for use with PVC polymers of all types and grades (even emulsion
resins stabilised with alkali, which can give problems with some
stabilisers of other types), many copolymers, and blends with modify-
ing polymers.
A partial restriction on the use of thiotins is that, as mercapto
compounds, they can impart an unpleasant odour to PVC composi-

* For example di-n-octyltin maleate; or di-n-octyltin bis(iso-octyl thioglyco-


late), listed in the US Federal Register as di-n-octyl-tin-S,S'-bis-iso-octyl-
Dlercaptoacetate.
122 PVC Plastics-Properties, Processing, and Applications

tions, perceptible in processing and tending to persist in products


(more so in pPVC ones). Also, the divalent sulphur in thiotins can
form coloured sulphides with the metals of cadmium and lead
stabilisers of pigments ('cross-staining').
The thiotins have relatively little UV-stabilising action. Where a
thiotin-stabilised composition may be called upon to undergo outdoor
exposure, the stabiliser system should be augmented by a tin carboxy-
late or other light-stabilising component (e.g. an epoxy stabiliser).

Note: Some commercial stabilisers are mixtures of this kind, e.g.


Irgastab T68 (a tin mercaptide with a dibutyltin carboxylate)
or Irgastab 170 MO [di-n-octyltin bis(2-ethylhexyl thioglyco-
late) with epoxidised soyabean oil].

Incorporation in the composition of titanium dioxide (12-14 phr)


also improves resistance to UV, and weathering generally. In transpa-
rent compositions for outdoor use, organic UV stabilisers are normally
included.
The heat-stabilising power of the sulphur-free tin carboxylates,
whilst generally good, is rather less than that of the thiotins, and their
cost tends to be higher. However, they impart good stability to light
(excellent in some cases, e.g. with some modified butyltin maleates).
Like the thiotins they are suitable for all types and grades of PVC
polymers. They are also odour-free and do not cause cross-staining
with heavy-metal compounds. When used in PVC pastes (in appropri-
ate cases; pastes are not widely stabilised with organotins), they do not
greatly affect the paste viscosity.
The first-generation estertins (all of the liquid thiotin type) are
comparable in performance with the established non-lubricating
alkylthiotins in the major applications (calendering, extrusion, injec-
tion moulding, blow moulding). They are also somewhat better than
alkylthiotin stabilisers in regard to weathering resistance (although
inferior to tin carboxylates); low volatility and extractability are
further general advantages.
Organotin stabilisers are available in both liquid and solid forms.
Most, and especially the liquid ones, are non-lubricating. Suitable
lubricants may either be obtained with the stabiliser in a multicom-
ponent 'single-pack' additive system, or selected separately by the
formulator in the light of relevant criteria. As mentioned in Section
4.3.6, the stabiliser/lubricant balance must always be carefully con-
4 Stabilisers 123

sidered and, inter alia, use can be made in some formulations of


synergistic effects that can arise between the thiotins and some
lubricants, notably internal lubricants of the partial-glyceride type.
Conversely, these lubricants (both liquid and solid) can impair the
heat stability of compositions stabilised with tin carboxylates (which
give very good results when used in conjunction with lubricants of the
fatty alcohol ester type).
Lubricant capability can be built into methyl, butyl, and octyl tin
compounds by suitable choice of the ligand (substituent group A).
Thus some alkyltin mercaptides with a long aliphatic chain in the
ligand have lubricating properties (e.g. dibutyltin bis(lauryl-
mercaptide), used in some rigid compositions in Europe), as have
members of the group of 'reverse-ester' alkyltin mercaptides de-
veloped in the USA for rigid pipe compositions, in which the A
substituents are esters of a mercaptan (such as thioethanol).
In lauryltin compounds the presence of the lauryl group is conducive
to lubricant action but the overall effect is influenced also by the
nature of the A substituent. In estertins significant lubricant effects can
be obtained by the appropriate choice of the R' substituent in the ester
groups.
In the USA, where lead compounds are not permitted in PVC water
pipes, alkyltin stabilisers are used in this large-scale application. Their
relatively high cost, and the vigorous competition among their
manufacturers, prompted the development of alkyltin stabiliser sys-
tems effective in rigid PVC pipe compositions at very low incorpora-
tion levels (down to about 0·3 phr). Among the main trends in such
systems have been increased use of monoalkyl tins, exploitation of
synergists (e.g. some organotin sulphides), and introduction of the
lubricating tin stabilisers.
Note: An analogy may be drawn between the practical effect of the
monoalkyl compounds in composite tin stabiliser systems, and
that of zinc in barium/cadmium/zinc stabilisers (cf. Section
4.3.4): both promote good initial colour and enhance long-
term stability. In some blown-bottle and rigid-film formula-
tions, an increased proportion of mono alkyl compound in
the alkyltin stabiliser system, coupled with suitable lubricant
choice, can reduce the stabiliser requirement to below 1 phr.
In addition to the references already cited, a publication edited by
Wilkinson33 and a paper by Ayrey & Poller34 are noteworthy sources
124 PVC Plastics-Properties, Processing, and Applications

of information on the production and chemistry of organotin com-


pounds, and their stabilising effects in PVC, respectively.
Gamma-ray sterilisation-as practised in hospital~f medical-use
PVC products stabilised with organotins, can cause the development
of colour, ranging from light yellow to deep amber. Special 'gamma-
shielding' grades of tin stabilisers* (as well as calcium/zinc stabilisers
for flexible PVC compositionst) should be used to avoid this effect.:j:
PVC products stabilised in this way are commercially available,
including medical-grade sheeting (e.g. Krene sheeting; Dynamit
Nobel, FRG).

(c) Mode of Action


On good evidence from work with model compounds and with actual
PVC compositions stabilised with organotins, it is widely accepted that
these stabilisers function in a number of ways to prevent and
counteract degradation of PVC polymers. These modes of action are
thought to be: deactivation of labile chlorine atoms (tertiary and
allylic) in the polymer chain (including their replacement by the ligand
groups of the stabiliser); binding the HCI evolved in the course of
incipient degradation; reaction with the double bonds of polyene
sequences and with other chromophoric groups; scavenging of free
radicals; and decomposition of peroxide groups in the polymer chain.
The most likely mechanisms whereby these functions are discharged
have been investigated, but not yet conclusively and finally estab-
lished. Some of the mechanisms have been reviewed in 1984 by Titow5
and Owen. 35

4.3.4 Other Metal-Based Stabilisers

(a) Nature, and Some General Applicational Features


Apart from those of lead and tin, certain compounds of other metals
act as heat stabilisers in PVC. Those in widest use are compounds of

* For example Gammashield 401 and 801 (M&T Chemicals); Mark 1955, 2242
A and 2244 (Argus Chemical).
t For example Interstab GS 4562, GS 4563 and GS 4571 (Interstab Chemicals).
:j: A typical gamma-radiation dose for sterilisation would be 2·5 Mrad, (=
25 kGy). PVC materials properly formulated with 'gamma-shielding' stabilisers
should withstand this without any discolouration. For conversion of rad to Gy
see footnote in Section 22.4.1 of Chapter 22.
4 Stabilisers 125

cadmium, barium, zinc, calcium, and antimony; strontium and mag-


nesium compounds are also used in certain stabiliser systems; finally
those of sodium, potassium, lithium, and aluminium are also
occasionally included as constituents of some composite stabilisers,
sometimes partly for their lubricant action.
The antimony compounds used in commercial stabilisers are nor-
mally antimony mercaptides. The other metal compounds are virtually
all carboxylates. In line with the rather loose, unsystematic terminol-
ogy still found in the industry, they may be divided into the three
general groups (not very clearly demarcated) of 'soaps', 'salts' and
'complexes' (the 'salts' are sometimes grouped with the 'complexes'
under the latter name). The 'soaps' are metal compounds of higher
aliphatic carboxylic acids, typically stearic and lauric (occasionally also
others, e.g. myristic or palmitic); they are normally solids with some
lubricant action in PVC compositions (but liquid composite stabiliser
systems, in which the metal soaps are dissolved or pasted-up in a liquid
carrier, are strongly represented among commercial stabilisers). The
'salts' are compounds of relatively lower aliphatic acids, such as metal
hexoates, heptoates or octoates, occasionally also caprates and unde-
cylates. The 'complexes' are the least well defined group, * which
includes compounds of the stabiliser metals with some organic acids
(e.g. benzoic), substituted phenols, and petroleum-derived acid and
phenolic mixtures (naphthenic and cresylic acids).
In some PVC compositions an individual antimony mercaptide may
constitute the sole stabiliser. Occasionally a calcium soap may also be
used alone, especially calcium stearate (as for example in certain paste
compositions, or compounds for potable-water pipes). But otherwise
all the metal compounds of this section are normally employed in
mixtures, constituting composite stabiliser systems. In such a system,
compounds of two or three different metals mutually supplement, and
sometimes synergistically enhance, one another's stabilising effects. In
many cases the mixture is further augmented by epoxy and phosphite
('chelator') co-stabilisers, which are present as regular constituents of
some proprietary mixed-metal stabiliser systems, or may be added
separately as required.

* Clarity is not aided by the fact that a combination of metal compounds in a


commercial stabiliser is sometimes referred to as a 'complex stabiliser' or
'stabiliser complex', or simply a 'complex' (especially if synergistic additives
are also present), even if the main components are metal soaps.
126 PVC Plastics-Properties, Processing, and Applications

(b) Antimony Stabilisers


Liquid grades, based on antimony trimercaptide, were the first to be
introduced commercially (in the mid-1970s, after some early, explora-
tory use in the 1950s). Since then the range, available from a number
of suppliers, has been widened. The usage and effects of antimony
mercaptide stabilisers are, in general, similar to those of conventional
thiotins. Some proprietary versions, and uPVC compounds in which
they are used, have the approval of the American National Sanitary
Foundation (NSF) for application in potable-water pipes (with some
restrictions on the maximum content levels). At low levels of
incorporation, up to about 0·8 phr, the antimony mercaptides can be
more efficient than the thiotins; they can also be more effective in
compounds subjected to moderately high temperatures over long time
periods. However, the resistance to sulphur staining and to UV
radiation (especially in transparent compositions) is, in general, lower
than that imparted by the organotins (in opaque compositions ade-
quate levels of addition of titanium dioxide will promote good
resistance); they may also form orange-coloured antimony sulphide
when exhausted. Strong synergistic effects are possible when antimony
mercaptide stabilisers are used in conjunction with calcium stearate. 36
Stabilisers based on antimony/tin combinations have also been de-
veloped for rigid pipe compounds for single-screw extrusion and for
thick-walled, large-diameter pipe. 37 In Europe antimony-based stabili-
sers are recommended, inter alia, for some VC/VA copolymer
gramophone record compositions.
Examples of commercial antimony mercaptide stabilisers are
Irgastab S 110 (Ciba-Geigy, UK) and in the USA Synpron 1027
(Synthetic Products Co.), with corresponding products in the Argus
Chemical and Ferro Chemical ranges (respectively, Mark 2115 and
Therm Check 1514).

(c) Calcium Stearate


Although other calcium compounds (e.g. calcium laurate) are also
available individually from stabiliser suppliers, calcium stearate is the
only one that is used as the sole stabiliser in some PVC compositions;
in others it may serve as a lubricating co-stabiliser (with synergistic
effects in some cases) in conjunction with organotin and antimony
compounds, or as a synergist with certain lead stabilisers (e.g. Irgastab
L600 or L601; Ciba-Geigy). The other calcium compounds find
4 Stabilisers 127

application as regular constituents of mixed-metal stabiliser systems in


which they are variously combined with zinc, barium or magnesium.
Whilst it is not a highly powerful stabiliser, calcium stearate has a
reasonable heat-stabilising action. It is useful with emulsion-type PVC
polymers and finds application in certain paste formulations (especially
in the UK), including some that are required to be non-toxic (e.g. for
toy production). Its non-toxic character in also utilised in uPVC
compositions for potable-water pipes in France, which widely are
stabilised with calcium stearate, often in conjunction with organic
co-stabilisers (not epoxy compounds, as these are susceptible to
microbiological attack).

(d) Mixed-Metal Stabilisers


It is in certain advantageous combinations with one another that some
of the metal compounds mentioned in Section 4.3.4(a) enjoy a
prominent position as stabilisers for Pvc. In such combinations the
effects of the individual components are mutually complementary, to
the overall benefit of the system. A characteristic example is the
barium/cadmium system, in which the cadmium compounds contribute
good initial colour hold, whilst their unsatisfactory long-term stabilis-
ing performance is compensated by the good properties in this respect
of the barium component (whose own initial colour hold is poor).
Synergistic effects also arise in this system, as they do in some other
mixed-metal stabilisers.
Versions of the principal types of mixed-metal stabiliser systems are
available in solid (e.g. powder, flake), liquid, or paste forms. More
recently, concentrates of some systems in PVC polymer have also been
coming onto the market, as have low-dusting (plasticiser-dampened)
powder forms. Such materials are exemplified, respectively, by some
barium/cadmium powder stabilisers 'encapsulated' in PVC resin at a
1: 1 ratio (in the Poly-Chek MP series of Ferro Chemical, USA), and
low-dusting powder grades of the same metal system in the Mark 8100
series of the Argus Chemical Corp., USA. The concentrates are added
to PVC compositions at twice the normal levels, with 1 part of PVC
polymer omitted from the composition for every 2 phr of concentrate.
These developments parallel the forms in which some lubricants and
lead stabilisers are being offered, and involve similar advantages (cf.,
respectively, Section 7.5 in Chapter 7 and Section 4.3.2 of the present
chapter).
128 PVC Plastics-Properties, Processing, and Applications

BARIUM/CADMIUM AND BARIUM/CADMIUM/ZINC STABILISERS


In terms of the amounts used, this is the most important group among
PVC stabilisers, with particularly wide application in flexible and
semi-rigid formulations, both opaque and clear.
In the barium/cadmium/zinc combinations the zinc compound
improves the initial colour hold of the PVC composition, its long-term
stability, and resistance to cross-staining with sulphur compounds to
which cadmium stabilisers are prone. Zinc compounds (e.g. the
octo ate ) are effective as activators ('kickers') for chemical blowing
agents used in the production of PVC foams. The amounts of zinc
compounds in barium/cadmium/zinc stabilisers can vary (typically
within the range 0·1-0·5 phr) depending on the other components of
the particular system and the zinc sensitivity of the PVC polymer in
the composition in which the stabiliser is to be used.

Note: The degree of sensitivity to zinc varies with the type and
grade of the PVC polymer, and also in different compositions
(e.g. plasticised, filled compositions of VC/VAC copolymers
are among the least sensitive). The variations in response of
emulsion PVC polymers to zinc compounds are well known
to occur, but the actual effects in individual cases normally
have to be checked by test. Where the sensitivity is substan-
tial, degradative discolouration ('zinc burn') can occur at
elevated temperatures.
Both liquid and solid barium/cadmium and barium/ cadmium/zinc
systems are available. The latter are combinations of the metal soaps.
Liquid systems are dispersions of the components in solvent-type
carriers. A typical basic composition of a system of this kind as
evolved over the years might be: 38

Barium nonyl phenolate 30-50%


Cadmium octo ate 10-30%
Zinc octoate 5-15%
Alkyl aryl phosphite 10-30%
White spirit 5-15%

The actual proportions would be governed by the specific application.


Subsequent, fairly recent developments gave rise to a new gener-
ation of 'high-efficiency' liquid systems with higher metal concentra-
tions and lower solvent contents, the solvents being less volatile. Such
4 Stabilisers 129

systems can be used in somewhat lower proportions than the orthodox


ones; many are self-lubricating, with less tendency to plate-out.
The barium/cadmium and barium/cadmium/zinc systems (as well as
some of the newer, high-efficiency barium/ zinc stabilisers) can impart
high degrees of thermal stability, good light stability, and be
compatible with good clarity in transparent compounds. Their effects
are improved (and especially the light stability increased) by the
addition of epoxy co-stabilisers and organic phosphite 'chelators':
these synergists are normally included either by the formulator or ab
initio as constituents of the composite proprietary system. Weathering
properties can be further improved by addition of UV-absorbers.
Liquid barium/cadmium and barium/cadmium/zinc systems are par-
ticularly widely used in flexible PVC materials, typically at levels of
1-2 phr (with about 0·5-1·0 phr of a chelator and up to about 5 phr of
an epoxy co-stabiliser where appropriate).
Whilst appropriate solid systems can be used in both rigid and
flexible compositions, in some of the former, the lubricant action they
can provide in some degree may be of particular interest; they also
affect the softening temperature of the product less than do the liquid
systems. However, some of the latter have-by virtue of their solvent
carrier-a solvating effect on PVC resin, contributing to effective, fast
fusion in processing. One example is the barium/cadmium liquid
Interstab BC-4528 (mainly for melt-compounded compositions) or
BC-4531 (for dry blends).
The incorporation levels for solid systems are, as a general
guideline, 2-3 phr of the mixed-metal composition, with about 0·7-
1·0 phr (i.e. 1: 3 on the main stabiliser) of a phosphite chelator if
included (for improved initial colour, transparency and light stability);
an epoxy co-stabiliser (about twice the amount of the main stabiliser,
i.e. around 4-6 phr) may also be included for further improvements in
general stability and light and weathering resistance. Combinations of
solid and liquid systems may be used for optimum flow and
lubrication characteristics in particular compositions.
The main general limitations of barium/cadmium and
barium/cadmium/zinc systems are: differing effectiveness in different
types of PVC* (also influenced, in a given type of composition, by the
ratio-and respective contents----of the barium and cadmium com-
ponents, the amount of zinc component if present, and the nature of

* Generally unsuitable for alkali-prestabilised emulsion grades.


130 PVC Plastics-Properties, Processing, and Applications

the organic parts of the compounds); variable tendency to plate-out in


processing; and susceptibility to sulphur-staining (minimised in zinc-
containing systems).

CALCIUM/ZINC STABILISERS
Representatives of this system are the most widely used non-toxic
stabilisers for PVC (although not all its commercial variants have
approval, or the same wide approval, in different countries). Stearates
and octoates* of the two metals, and many of their proprietary
combinations, are permitted in most countries for use in rigid and
plasticised compositions for the production of food-packaging materials
and containers, medical goods, and toys.
Calcium/zinc combinations are not among the most powerful
stabilisers, although some newly developed versions, intended as
non-toxic replacements for the more effective barium/cadmium/zinc
systems, represent considerable improvements (cf. for example
Lankromark LZ 847, LZ 935 and DP 6401; see also below).
Wherever practicable (and this is permitted for many 'non-toxic'
applications) they are used in conjunction with epoxy co-stabilisers
(which are components of many proprietary calcium/zinc systems) to
improve the stabilising effects against both heat and light, and with
organic phosphite synergists (which improve the initial colour, and
transparency in clear compositions). Other synergists available for use
(alone or in conjunction with organic phosphites) to improve the
stabilising action and efficiency of calcium/zinc systems include
stearoylbenzoylmethane (Rhodiastab 50; Rhone-Poulenc, France)
and some proprietary polyol compounds (mostly based on mannitol or-
sorbitol). These compounds, used in proportions of 0·02-0·5% with
solid calcium/zinc systems, are claimed to improve the stability of
some PVC compositions by factors of up to x2. The composite
calcium/zinc polyol systems are sometimes prone to plate-out, but the
newer proprietary versions (e.g. some marketed by Swedstab AB,
Sweden) are designed to be free from this tendency.
The calcium/zinc stabilisers are available in both solid and liquid
forms. In addition to the conventional powders, the solid versions now
include particulate concentrates in PVC polymer (e.g. Ferro-Chek
NT-3; Ferro Chemical Corp.). Where a liquid system consisting of
calcium and zinc soaps in a liquid carrier is to be used for a 'non-toxic'

* Salts of C8 carboxylic acids (often 2-ethylhexanoic or caprylic).


4 Stabilisers 131

application it is necessary to ascertain that the carrier is acceptable for


the purpose. For flexible, medical-use PVC products (e.g. tubing,
components of open-heart surgery kits) that may have to be sterilised
by gamma radiation, special 'gamma-shielding' grades of calcium/zinc
stabilisers are available to make the products resistant to discoloura-
tion under irradiation [see Section 4.3.3(b)].
Typical incorporation levels may be illustrated by the following
figures: liquid calcium/zinc system for paste compositions 1·5-3 phr
(with up to 5 phr epoxy co-stabiliser); solid (powder) system for
sheeting compositions 1-2 phr (rigid sheeting), O· 5-1· 5 phr (flexible
sheeting), in each case with the addition of an epoxy co-stabiliser.
Outside the non-toxic field, a common use for technical grades of
calcium/zinc stabiliser systems is in asbestos-filled PVC flooring. Such
compositions are subject to discolouration during heat processing, due
to the catalytic action of iron present in the asbestos. In compositions
otherwise adequately stabilised with barium/cadmium or lead systems
the discolouration can be severe, but it can be effectively prevented by
the use of an appropriate calcium/zinc stabiliser [see also Chapter 2,
Section 2.2.6(d)].
Apart from the special applicability of the non-toxic grades, the
advantages of calcium/zinc stabilisers include moderate price, and
virtual freedom from odour in finished products and from sulphide
staining. * The soap compositions have some lubricant action. The
main limitations are: the relatively low stabilising power already
mentioned; rapid progress of degradation, once commenced, in
Ca/Zn-stabilised compositions; and limited suitability for crystal-clear
compositions. *

OTHER MIXED-METAL STABILISERS


Since the late 1970s increasing attention has been directed to the
potential hazards of cadmium in its own processing and as a
component of pigments and stabilisers. Studies and discussions have
been proceeding in several countries, and in some (such as Sweden,
Denmark and Switzerland) restrictions-statutory or voluntary-are
already in operation. These events have, inter alia, stimulated efforts
by many stabiliser manufacturers to develop alternatives to the
cadmium-containing stabilisers that would be free of that heavy metal

* Haze may develop in transparent compositions in contact with sulphur


compounds: see Section 4.8.1.
132 PVC Plastics-Properties, Processing, and Applications

(and preferably also of lead). The task is difficult, because of the very
good stabilising performance of mixed-metal stabilisers incorporating
cadmium compounds, and their consequent wide, long-established
usage. However, considerable progress has been made, and the
alternatives now offered, some of which are claimed to approach the
cadmium-containing stabilisers in performance, include-apart from
the new calcium/zinc compositions already mentioned (characterised
by improved heat-and also light-stabilising performance )-also
barium/zinc, barium/calcium/zinc, and magnesium/zinc compositions.
References to some of these stabilisers are included among the
following examples intended to illustrate something of the nature and
applications of various mixed-metal stabilisers.

Barium/zinc: Commercial versions of this kind of stabiliser


system-several of which are offered as replacements for
barium/cadmium stabilisers-are exemplified by those cited below:
(i) Synpron 1531 (Synthetic Products Co., USA), a liquid, low-
barium, high-zinc system incorporating a phosphite synergist
(for use in calendered, extruded and paste products, at about
2 phr);
(ii) Mark 2181 and 4004 (Argus Chemical), both liquid barium/zinc
combinations, for use in paste-produced PVC flooring (at
1·S-2·Sphr, with 3-lOphr of epoxy co-stabiliser) where they
can confer good clarity (top 'wear' layers), initial colour hold,
stability to ageing at moderate temperatures, and long-term
stability;
(iii) Naftovin BZ stabiliser series (Chemetall, FRG), self-lubricating
and with little tendency to plate-out;
(iv) Stavinor BZ 329 (Ceca SA,* France), for paste-produced
flooring compositions;
(v) Irgastab BZ 590 series (Ciba-Geigy), claimed to combine good
long-term stability with freedom from plate-out;
(vi) Lastab DC 45, 48 and 49 (Lagor SpA, Italy), another group of
barium/zinc stabilisers offered as replacements for cadmium
(and also lead) systems.

Magnesium/zinc: Selected combinations of this type may be used


(in conjunction with phosphite chelators) for stabilising flexible and

* Which took over the Stavinor stabiliser line from Rousselot in 1985.
4 Stabilisers 133

semi-rigid compositions for many calendered, extruded and paste


products. A degree of UV-resistance, and freedom from sulphur
staining, are useful general features of compositions stabilised with
some proprietary veisions of this system. Its solid-soap variants (e.g.
Synpron 1534; Synthetic Products Co., USA) also have some lubricant
action.

Strontium/zinc/tin: This is another of the combinations offered as


replacements for barium/cadmium based systems in some applications.
Resistance to sulphur staining, and low tendency to plate-out (of some
commercial versions, e.g. Nuostabe V 1925; Tenneco Chemicals,
USA) are advantageous features.

Strontium/zinc: The commercial strontium/zinc systems are ex-


emplified by strontium/zinc laurate co-precipitates* (e.g. Lankromark
M; Lankro Chemicals, UK) used mainly in plasticised compositions
(at about 2 phr, with about 5 phr of an epoxy co-stabiliser), where
freedom from sulphur staining, and low toxicity, are of interest.

Calcium/antimony: The already-mentioned combination of anti-


mony mercaptide with calcium stearate effected by some formulators
for its synergistic and lubricant features is also embodied in some
proprietary stabilisers. An example is Stavinor SB-739 (Ceca), a
liquid system for high-fidelity gramophone records (a powder version
is used in lower-quality records, where initial high sound fidelity and
fidelity retention are less crucial).

Calcium/aluminium/zinc: Commercial versions of this system, e.g.


Lankromark LA 105 and Lankromet LA 175, are used in paste
compositions for rotational moulding where, inter alia, they promote
good mould-release.
Cadmium/zinc: Systems of this type are useful in compositions for
chemically blown cellular PVC products (e.g. injection-moulded
microporous shoe soles; foamed layers of coated fabrics) in which they
act both as stabilisers (alone or in conjunction with other stabilisers,

* Mixed-metal systems may be physical mixtures of the components (in which


the organic parts of each metal compound may be different, or mutually the
same) or 'co-precipitates' in which the organic portion is normally the same for
all the metal constituents present. This is the case also with composite lead
stabilisers and lead-based stabiliser/lubricant systems (cf. Section 4.3.2).
134 PVC Plastics-Properties, Processing, and Applications

usually barium/cadmium systems) and activators ('kickers') for the


blowing agent (normally azodicarbonamide). Typically (for example
with a Ciba-Geigy commercial version-Irgastab ABC 2) about
0·5 phr would be required for the activator function, and up to about
2·5 phr for stabilising effects.

Cadmium/lead: Such systems have been used in PVC window


profile compositions. An example of a single-pack version is Haro-
Mix YJ-l09 (Haagen Chemie BV, The Netherlands).

Barium/cadmium/lead: This is another example of the kind of


mixed, lead-containing plasticiser system for window profiles. Some
commercial versions, like Stavinor BCP 866, include lubricants.
These systems can offer very good performance in processing, and
weathering protection.

MODE OF ACTION OF MIXED-METAL STABILISERS


These stabilisers have long been known to act as HCI acceptors, and
also believed to remove labile CI atoms from PVC molecules,
substituting their own carboxyl residue to form a relatively stable
grouping. The current understanding of their general mode of
operation is in line with these ideas, and there is a substantial body of
evidence, largely from studies of model compounds, supporting also
the general explanation of the co-action and synergistic effects
between the individual components of the composite systems. The
detailed mechanisms and individual reaction steps involved have not
been entirely worked out.
Taking the barium/cadmium and cadmium/zinc carboxylate systems
as typical examples, the stabilisation process may be summarised by
the following scheme:
Ml(OOCR)z + 2(Pol·Cl)- M1Cl2 + 2(Pol·OOCR) (4)
M2(OOCR)z + M1C12_ Ml(OOCR)z + M2Ch (5)
M2(OOCR)z + 2HCI- M2Ch + 2RCOOH (6)
where R is a straight- or branched-chain alkyl radical, and Pol is a
PVC polymer chain. Ml is a metal which is an effective stabiliser in the
sense that it readily exchanges its carboxylating group for a labile
chlorine atom in PVC, thereby 'esterifying' the site involved to a
stable condition [eqn (4)], but whose chloride, formed in the process,
is a strong catalyst for dehydrochlorination of PVC. Zinc and cadmium
are such metals, ZnCh being even more effective than CdCh in
4 Stabilisers 135

promoting dehydrochlorination. M2 is a metal (such as barium or


calcium) whose chloride is relatively inactive in this detrimental sense,
but whose carboxylate is capable of regenerating that of the MI metal
from its chloride [eqn (5)]. The M2 metal carboxylate also disposes
safely of HCI generated by dehydrochlorination [by converting it to
harmless M2C12 : see eqn (6)]; whereas the reaction of eqn (6) involving
an M2 metal carboxylate would generate the destructive M1C12. It may
be noted that increasing concentrations of ZnClz and stearic acid were
detected and monitored in the course of a dynamic heating experiment
on PVC compositions stabilised with a zinc/calcium stearate system?9
It is when the regenerative component (the M2 carboxylate) is
used-up to the point where its concentration drops below the effective
level, that the destructive catalytic effect of the now accumulating
M1Cl2 speeds up degradation, which becomes catastrophic. The latter
factor is also responsible for the unsuitability of cadmium and zinc
compounds as sole stabilisers.
The main functions of an epoxy compound when used as a
co-stabiliser with mixed-metal systems are direct binding of nascent
HCI and assistance in the transfer of labile CI atoms to the main
stabiliser [see Section 4.3.5(c)].

4.3.5 Organic and Miscellaneous Stabilisers

None of the organic, non-metal compounds used in the stabilisation of


PVC compositions can be described as a powerful primary stabiliser.
However, some are used as sole stabilisers in compositions for
food-packaging products, whilst others (epoxy compounds and
phosphite 'chelators') are very important as synergistic co-stabilisers
used with many primary stabilisers (notably barium/cadmium and
other mixed-metal systems). Because some are liquids, and others
melt at PVC-processing temperatures, the organic stabilisers are
uniformly and intimately dispersible in PVC compositions (but some
have limited compatibility with plasticisers, or particular
plasticiser/resin combinations in pPVC-see below).

(a) Esters of Aminocrotonic Acid


Typically these are aminocrotonates of the general formula

NH2 H 0
I I "
H3 C-C=C-C-OR
136 PVC Plastics-Properties, Processing, and Applications

Many commercial stabilisers based on these compounds are approved


for food-packaging applications in several European countries, includ-
ing the UK, West Germany, France and Italy. They are used mainly in
uPVC compositions, based on suspension and emulsion polymers of
vinyl chloride copolymers, for use in the production of packaging film
and blow-moulded containers. Typical incorporation levels range
between 1 and 2 phr, in conjunction with an epoxy co-stabiliser (up to
about 4 phr) to improve both heat and light stability. Some proprietary
aminocrotonate stabilisers have limited compatibility with plasticisers
in pPVC; or example, Irgastab Gl* is recommended for use mainly as
a co-stabiliser in plasticised compositions, at up to 0·4 phr to avoid
exudation, whereas Irgastab A 70t causes no difficulties at normal
incorporation levels.
In most cases, uPVC compositions stabilised with the aminocroton-
ates, require lubricants, although some proprietary versions may have
lubricant action.

(b) Urea Derivatives


Representatives of this group in common use are

H 0 H
I \I I
phenylurea (C6H5)-N-C-N-H;
0 H H
\I I I
diphenylurea (C6H5)-N-C-N-( C6H 5);
H S H
I \I I
diphenylthiourea (C6H5)-N-C-N-(C6H5)·

These compounds may be used as heat stabilisers (with little light-


stabilising effect) for compositions based on alkali-prestabilised emul-
sion polymers, and especially in plasticised compositions of this kind
(yellow discolouration may occur in semi-rigid and rigid PVC).
Typical incorporation levels are relatively low, around 0·3-0·5 phr,
because of the low compatibility of these stabilisers with plasticised
PVc. Long-term stability can be substantially improved by the

* Ciba-Geigy: a solid (waxy flakes) mixture of esters of aminocrotonic acid


with 1,4-butylene glycol and some fatty alcohols (C 16-C18).
t Thiodiethylene glycol bis(p-aminocrotonate), sold as a free-flowing powder.
4 Stabilisers 137

presence of an epoxy co-stabiliser (up to about 3 phr). At tempera-


tures above IS0 aC some commercial urea stabilisers may start decom-
posing with evolution of ammonia: this point should be checked with
the supplier in individual cases (and preferably also by tests) with
reference to the processing method and equipment used, as such
gassing can give rise to porosity in products.
The main effect of stabilisers of this type is thought to be
neutralisation of any hydrogen chloride evolved as a result of thermal
dehydrochlorination: this mode of action would be in keeping with the
basic nature of these compounds. They are also thought to have some
antioxidant action.

(c) Epoxy Compounds


Many epoxy compounds, including the epoxy plasticisers, have a
stabilising effect in PVC compositions. Whilst this is not strong enough
to enable their general use as main or sole stabilisers, such epoxy
compounds as epoxidised soyabean oil (ESO) and some epoxy esters
are very important and widely used as strongly synergistic co-
stabilisers for metal-based stabiliser systems, as well as for some
organic stabilisers (see above). Their uses and benefits are referred to
at various places throughout this book (see Index), the main effects
being substantial improvements in heat and light stability. Further-
more, in rigid compositions their plasticising action (even at the
'stabilising' level of only a few phr) improves flow properties in
processing (although the softening point may be lowered), whilst the
use of a suitable epoxy plasticiser in a PVC paste can reduce viscosity
where this effect is desirable in processing, in addition to improving
the heat- and light-resistance of the product. Epoxy stabilisers/
plasticisers are resistant to extraction and migration: several (but not
normally epoxidised soyabean oil) improve the low-temperature flexi-
bility and 'cold-crack' resistance of plasticised PVC. Many proprietary
products (notably epoxidised soyabean oils) are approved in most
countries for food-contact applications, and-at incorporation levels of
up to 3 phr-do not affect the clarity of transparent PVC composi-
tions. The polarity of the epoxy groups makes epoxy compounds
effective as dispersion aids for solid additives (pigments, fillers,
polymeric modifiers) in both rigid and flexible compositions.
Features which impose some limitations on the use of epoxy
compounds in PVC compositions are their susceptibility to microbio-
logical attack, and the possibility of exudation, with formation of tacky
138 PVC Plastics-Properties, Processing, and Applications

surface deposits, in some cases where-in discharging its stabilising


function-the compound loses its epoxy groups through the chemical
reactions involved, so that its compatibility with PVC is reduced. This
effect can be a potential problem, especially in weathering or ageing
situations. The compositional factors which promote it are the use of
the epoxy compound as the sole stabiliser and/or its presence in a
relatively high proportion as a component of the plasticiser system.
Thus, to prevent this kind of problem, an epoxy compound should not
be used as the only stabiliser, and its level of incorporation as a
component of the plasticiser system should perferably not be higher
than 25% of the total system in PVC compositions likely to
experience any but mild ageing or weathering conditions.
Note: Interaction of epoxy compounds with unsaturated additives in
a PVC composition (e.g. ricinoleates or oleates which might
be present in stabilisers or plasticisers) can also lead to
permanent chemical modification (loss) of epoxy groups, with
consequences similar to those just described. Thus was the
cause of development of surface tack in, for example,
calendered sheeting when, in the early days, the barium
component of barium/cadmium stabiliser systems then
coming into use was frequently barium ricinoleate.
The main mode of action of epoxy stabilisers is widely thought to
be5 the binding of HCl through reaction with their oxirane groups:
-CH-CH- + HCl- -CH-CH-
""'/ I I
o OH CI
These groups are also believed to participate in the role the epoxy
co-stabilisers may play in the transfer of HCI to the main stabiliser,40
and the exchange of the PVC polymer's labile chlorine atoms for
stabiliser groupS.41

(d) Organic Phosphites


These are not primary stabilisers, but valuable co-stabilisers, used
mainly with mixed-metal stabiliser systems (and widely with the
principal types based on barium/cadmium and calcium/zinc combina-
tions). Many proprietary phosphite co-stabilisers are acceptable, in
conjunction with suitable calcium/zinc combinations, for use in
food-packaging film and containers (e.g. blown bottles), and in other
'non-toxic' applications. Numerous commercial stabilisers are variants
of this kind of composite system containing an approved organic
4 Stabilisers 139

phosphite as one of the components, and in many cases also a


permitted epoxy-co-stabiliser.
It is well known that, when used in conjunction with suitable
primary stabilisers, the organic phosphites improve the clarity of
transparent PVC compositions, weathering and light stability gene-
rally, as well as heat stability (especially in pPVC). Although the
mechanisms of their action are not fully elucidated, they are believed
to be numerous and complex, and to include reactions of the stabiliser
(or in some cases the products of its transformations) with the
following: 5 ,35 HCI, hydroperoxides, free radicals, metal salts, and
ketoallyl groups. The clarity improvements often effected by phosph-
ites have been attributed to the formation, in the course of stabilising
reactions, of PVC-soluble complexes with the normally insoluble
chlorides of the stabiliser metals, which are themselves formed as
these stabilisers exercise their functions. It is because of this that the
phosphite stabilisers are often referred to as 'chelators'.
Commercial organic phosphite co-stabilisers (typically liquids, with
no appreciable lubricant effect in PVC) are either individual com-
pounds, or mixtures of compounds of the general formula:
RO OR
"-/
P
I
OR
in which R can be a simple (but relatively long-chain) alkyl, or aryl
(usually phenyl), or alkyl-aryl, group or a polyhydric alcohol deriva-
tive (e.g. a partial ester of pentaerythritol); the R groups of the same
compound may not all be identical.
Examples of organic phosphites available as proprietary chelator
co-stabilisers for PVC include triphenyl phosphite, tridecyl
phosphite,42 distearyl pentaerythrityl diphosphite, * tris(nonylphenyl)-
phosphite, t and mixtures consisting of a dialkyl phenyl phosphite with
the corresponding alkyl diphenyl phosphite, triphenyl phosphite and
trialkyl phosphite (e.g. Irgastab CH 300, CH 301, and CH 343).
The levels of incorporation of phosphite chelators are, typically,
about 1 phr (fractional phr in many cases). With solid

* Used in some formulations for PVC bottles in place of the common


combination of tris(nonylphenyl) phosphite and 2-phenylindole.
t Commercial versions (e.g. Irgastab CH 55-Ciba-Geigy; Phosclere P315-
Interstab Chemicals Inc.) are approved in many countries for food-contact
applications.
140 PVC Plastics-Properties, Processing, and Applications

barium/cadmium systems it is fairly usual to add 1 part of the chelator


per 3 parts of the metal stabiliser combination; but, in general, the
optimum amount should be verified by tests.

(e) Other Organic Stabilisers


Stearoylbenzoylmethane and certain polyols have already been men-
tioned [in Section 4.3.4(d)] as synergistic co-stabilisers for use with
calcium/zinc stabiliser systems. Their modes of action are believed to
be similar to those of the phosphites. However, as mannitol and
sorbitol-their frequent constituents-would be expected to decom-
pose to a considerable extent at processing temperatures, it appears
possible that their stabilising effects may in fact be exerted by their
decomposition products. Another organic co-stabiliser of industrial
interest is 2-phenylindole:

~~
~NH~
One use of this additive is as a co-stabiliser (at a level of about
0·3-0·5 phr) in uPVC bottle compositions, frequently non-toxic ones,
stabilised with a calcium/zinc stabiliser and containing also an epoxy
compound and phosphite chelator as the other components of the
co-stabiliser system. It is also used in some pipe and sheeting
formulations.

4.3.6 Stabiliser/Lubricant Balance and Interactions

When choosing a stabiliser, single or composite, for a particular type


of PVC formulation and processing conditions (e.g. a uPVC pipe
composition for twin-screw extrusion, a semi-rigid sheet composition
for calendering, etc.), careful thought must be given also to the proper
selection of the lubricant or lubricant system, to secure what is usually
known as correct stabiliser/lubricant balance. This is important for a
number of cogent reasons which are significant technical factors, viz.
because some lubricants have a stabilising action and some stabilisers
a lubricant action; because synergistic effects can arise between some
stabilisers and lubricants; and because, whilst lubricants reduce the
frictional and work heat experienced by PVC stock in processing (see
Chapter 7, Section 7.1), they do not all do so equally effectively.
Undesirable interactions which can occur between some stabilisers and
4 Stabilisers 141

lubricants, leading for example to plate-out or (less frequently) to


cross-staining, must also be considered.
Note: The mutual effects and interactions of lubricants and stabili-
sers are discussed in some detail in Section 7.2 of Chapter 7.
In any given case, the achievement of proper stabiliser/lubricant
balance will in effect yield a harmonised, composite stabiliser/lubricant
system, in which the beneficial factors among those just mentioned are
utilised through mutual adjustment, and negative effects such as
over-lubrication, plate-out, or cross-staining are avoided. This in turn
should promote the optimum practicable ease and effectivity of
processing, whilst minimising the danger of heat degradation (and
generally the heat history) of the material and securing the maximum
sensibly attainable cost savings. Most stabiliser suppliers provide
single-pack stabiliser /lubricant systems for various combinations of
PVC composition and processing method.
Where, for whatever reason, a formulator sets out to devise his own
stabiliser/lubricant system, he should always seek recommendations
from the suppliers of the stabilisers and lubricants he is considering.
In the course of developing the system it is necessary to carry out
laboratory tests (in a suitably equipped torque rheometer, e.g. a
Brabender Plasti-Corder, or on a laboratory-scale extruder, calender,
or two-roll mill, as appropriate) and then, in the final stage, also to
perform in-plant trials, as the laboratory-test results may not always
correlate sufficiently well with those obtained on production
equipment.

4.4 ANTIOXIDANTS AND LIGHT STABILISERS

4.4.1 Antioxidants

The oxidative breakdown mentioned in passing in Section 4.1.3,


involving a free-radical chain reaction (sometimes referred to as
'autoxidation,)43 is one of the modes of degradation of PVC polymers
by both heat and light. Some heat stabilisers (notably those that also
exhibit light-stabilising effects) have an antioxidant action in PVC.
Special antioxidant additives are also often incorporated, either
individually or as constituents of composite commercial stabiliser
systems.
142 PVC Plastics-Properties, Processing, and Applications

Antioxidants used in plastics may be divided into two general


groups: primary antioxidants, which act as free-radical scavengers to
interrupt or prevent oxidation reactions (which are believed to
proceed by free-radical mechanisms43 •44-see also Section 4.1.3); and
secondary antioxidants, which react with hydroperoxide groups-
whose formation is a stage in the oxidation reaction chain-to convert
them to non-radical products. 5 The primary antioxidants employed in
PVC compositions are typically compounds containing sterically hin-
dered phenolic OR groups: they are popularly known as 'hindered
phenols'. An example is Ciba-Geigy's Irganox 1076. * This additive was
for many years its supplier's main antioxidant for PVc. Irganox 245, a
bisphenolic hindered phenol compound of somewhat higher molecular
weight, which is less labile, is also applicable, and can be more
cost-effective in some formulations. The other main class of compound
in the primary antioxidant group comprises secondary aromatic
amines: with a few exceptions [see 4.4.2(c) below] these are not,
however, important in the PVC context, being mainly used in rubber
compositions (especially dark-coloured ones, as they can cause strong
discolouration) .
The secondary antioxidant group consists of certain phosphites
[including organophosphite chelators and dibasic lead phosphite: see
Section 4.3.5(d) and Table 4.1 respectively], phosphites, and
thioethers. Useful synergistic effects can sometimes be obtained by the
joint use of some primary and secondary antioxidants.

Note: One route through which oxidative degradation of some


polymers can proceed, even at room temperature, is a
redox-type breakdown of hydroperoxide groups in the pre-
sence of metal ions (introduced-sometimes as impurities-
with fillers, pigments, and other additives). Metal-deactivator
additives which are sometimes employed to counteract this

* Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate:
t-Bu 0
HO <Q>-cH2.CH2.~.O.C18H37.
t-Bu

Since the relevant Ciba-Geigy patents expired in 1984 this compound is also
available as Ultranox 276 (Borg-Warner Chemicals) and Naugard 76 (Uni-
royal Chemical).
4 Stabilisers 143

process could therefore be classified among secondary anti-


oxidants, although some are hindered phenols (e.g. Irganox
MD 1024).
In PVC, autoxidation is both a degradation mechanism in its own
right and a factor increasing the rate of dehydrochlorination (cf.
Section 4.1.3). Thus incorporation of antioxidants can improve the
heat stability of many PVC compositions. Where they are added
individually, and not introduced as constituents of composite
proprietary stabiliser systems, primary antioxidants may typically be
used at levels of the order of 0·1 phr (in compositions such as some
cable sheathing and high-temperature insulation compounds, some
injection-moulding compounds, and plasticised compounds for chain-
link wire covering).
Some antioxidants, e.g. Irganox 1010 (Ciba-Geigy)-a tetrakis-
phenolic compound~an be used (generally in very low proportions,
e.g. 200 ppm) as additives to the polymerisation mixture in the
production of PVC polymers, to improve the polymer's resistance to
the relatively intense heat treatment necessary to strip off residual VC
monomer down to acceptably low levels.

4.4.2 Light Stabilisers

The UV component of the sunlight reaching the earth's surface


(waveband 280-400 nm), and especially its more energetic part (wave-
lengths up to about 320 nm*), as well as any UV radiation of
wavelengths below 290 nm, can cause photodegradation of PVC
polymers.
The light stabilisers used in polymeric compositions may be grouped
into four main general functional types: organic UV absorbers;
inorganic (particulate) UV-screening agents: free-radical scavengers;
and chromophore quenchers. This classification is not strict or formal,
and there can be a certain functionality overlap between some of the

* Wavelengths of 310-320 nm are regarded as particularly damaging to


polyvinyl chloride, and 327 nm (sometimes also 364 nm) is often quoted as a
wavelength to which VC/VAC copolymers are sensitive.
Principally in the medical context (from the point of view of scope for
damage to skin and other tissue) the UV spectrum is sometimes divided into
three bands: A (least harmful), 320-380 nm; B (medium severity), 280-
320 nm; C (most harmful) < 280 nm.
144 PVC Plastics-Properties, Processing, and Applications

types. Primary antioxidants acting as free-radical scavengers, and


secondary antioxidants functional as hydroperoxide decomposers, can
also contribute to light stabilisation.

(a) Organic UV Absorbers


These stabilisers operate by absorbing the damaging UV radiation and
re-emitting the energy thus acquired at a lower level (longer wave-
length) as infrared radiation (Le. heat) which is relatively harmless to
the polymeric material. The ideal UV absorber should absorb com-
pletely the wavelengths between 280 and 400 nm, but none in the
visible region, so as not to impart colour to transparent or white
compositions: although many commercial UV absorbers are good in
these respects, none meets completely both these ideal requirements
(especially with regard to 100% absorption of the entire UV band).
The types of organic compound in widest commercial use as UV
absorbers for PVC compositions are modified benzophenones (espe-
cially certain alkoxy derivatives of 2-hydroxy- or 2,2-dihydroxy-
benzophenone), and benzotriazole derivatives. Proprietary additives
of the first type are exemplified by Cyasorb UV9, UV 24, and UV 531
(American Cyanamid Co, Polymers and Chemicals Dept, and Cyana-
mid of Great Britain Ltd); Uvinul D 408 (BASF); UV-Chek 541 A and
AM-300 (Ferro Corp., Chemical Div.); and Carstab 700 (Carstab
Corp.). Benzotriazole compounds figure prominently in the Ciba-
Geigy Tinuvin light-stabiliser range (e.g. Tinuvin P, 320, 326 and
327). Another commercial example is Vanox UV-1 (R. T. Vanderbilt
Co.). Normal use levels of both types are in fractional phr (typically
0·1-0·8).
Other organic compounds represented among proprietary UV
stabilisers available for PVC include substituted cyanoacrylates (e.g.
ethyl 2-cyano-3,3-diphenylacrylate-cf. also Uvinul N-35 and N-559;
BASF) , phenyl salicylate (Salol; Dow Chemical Co.), oxalic anilide
(Sanduvor; Sandoz), and phenyl formamidine (Givsorb UV-2;
Givaudan Corp., USA).
Polymeric UV stabilisers are exemplified by a polymer of 2,4-
dihydroxybenzophenone, originally applied45 with a view to reducing
the ease of diffusional migration of the stabiliser to the surface of the
PVC material (and subsequent loss by volatilisation, leaching and
wear) to which non-polymeric benzophenone UV absorbers are more
prone.
In most cases the degree of UV protection afforded increases with
4 Stabilisers 145

the additive's concentration within the useful range. However, the


protective effect is also known to be dependent on the thickness of the
PVC material, in that-for the same concentration of stabiliser-it is
markedly less in fine fibres, very thin films, and surface layers of
thicker products. This phenomenon accords with the reported finding 46
that, at a given stabiliser concentration, the amount of UV radiation
reaching a point in the substrate drops exponentially with the distance
of the point from the material's surface. These facts are in line with
the expectation that the degree of obstruction of the path of an
incident ray by particles or molecules of evenly dispersed stabiliser
(Le. the probability that one or more particles or molecules will lie
directly in the path) should increase fairly sharply with distance into
the material: interaction of the radiation with the PVC material itself
must also be a factor progressively reducing the amount of radiation
with distance of penetration. *
It may be noted that, because of the purely physical nature of its
mode of operation, a typical UV absorber of the kind discussed in this
section does not undergo any chemical changes, so that it is not used
up in the course of discharging its function.
Compatibility with the rest of the PVC composition, and any
interactions that may occur, are considerations as relevant in the case
of UV absorbers as they are for any other formulation constituent.
The following practical points may be mentioned in this connection.
Joint use of organic UV absorbers with antioxidants can enhance the
effect of both in many PVC compositions. Their use in conjunction
with a tin carboxylate stabiliser (dibutyltin maleate) has been claimed
to have no beneficial effect on stability in outdoor exposure, and even
to impair it in some cases. 47 Some organic UV absorbers can form
metal complexes with certain metal-based stabilisers, giving rise to
undesirable colour in the PVC material, as in the following cases:

-Yellow colouration (overall or in spots) can develop, in the


presence of alkali, in compositions (especially flexible com-

* In all polymeric materials the extent of degradation by light (and weathering


generally) is also dependent on thickness for purely geometrical reasons, in
that whilst the surface is the most directly exposed to attack, and therefore the
material of the outermost surface layer suffers the earliest and most extensive
degradation, that material will also represent an increasing proportion of the
total as the overall material thickness is decreased (the surface-to-volume ratio
is increased).
146 PVC Plastics-Properties, Processing, and Applications

pounds) stabilised with barium/cadmium or barium/cadmium/zinc


systems in conjunction with certain benzophenone or ben-
zotriazole UV absorbers (normally only those containing pheno-
lic hydroxyl groups which are 'unhindered', i.e. not sterically
protected and thus available to participate in complex-formation);
the alkalinity may be introduced by the heat-stabiliser system
(e.g. some barium/cadmium stabilisers, although neutral versions
are widely available), or where the PVC polymer is an alkali-
prestabilised emulsion resin, or adventitiously from external
source.
-Pink to mauve colour can arise where a benzotriazole UV
absorber and a thiotin stabiliser are used together.

Some dihydroxybenzophenone compounds can develop a yellow


colour in the presence of nitrogen oxides (which may be produced in
the burning of gas, coal, or oil, or when air passes over incandescent
wires). This phenomenon is similar to the 'gas-fume fading' long
known to occur in man-made fibres dyed with aminoanthraquinone
dyes and certain others. 5 However, the alkoxybenzophenones, ben-
zotriazoles, and salicylates used as UV absorbers in PVC are not
normally susceptible. Some UV absorbers can interfere with fluores-
cent colorant effects.
Where non-toxicity is a consideration, selection of organic UV
absorbers should be made in the light of advice from the suppliers and,
if relevant, also from the appropriate authorities.

(b) Inorganic (Particulate) UV -Screening Agents


Carbon black and titanium dioxide, widely used and important as
pigments for plastics, have a light-stabilising effect on many polymers,
including PVC. Because of their particulate nature and their mode of
action, they are often referred to in this context as 'screening agents',
'screeners' or 'light screens'. Each functions as a physical barrier to
radiation, both UV and visible. Carbon black absorbs the radiation
over both these wavelength ranges and, like the organic UV absor-
bers, emits the energy in the IR region: it is also capable of capturing
free radicals: the appropriate, fine-particle grades should be used,
typically at a few phr (not less than 2 phr). Titanium dioxide also has
some UV absorption, but its screening action is principally due to
reflection and scattering of radiation (IR, visible, and UV). This
mechanism is less efficient than that of carbon black, and higher
4 Stabilisers 147

loadings are needed (typically 5-15 phr) of appreciable effect. It is


self-evident that the use of both these pigments as light stabilisers is
ipso facto restricted to opaque compositions (and only black ones in
the case of carbon black).
Zinc oxide is another particulate, inorganic screening agent which
may be considered for those PVC compositions that are not too
zinc-sensitive (cf. Section 4.3.4 above): it can benefit synergistically
from the presence of certain antioxidants, to the point where suitable
combinations of this kind can be more effective than normal amounts
of organic UV stabilisers. Some proprietary zinc oxide/synergist
compositions have been claimed * to nearly double the light-
degradation resistance of such PVC articles as car crash-pads.

(c) Free-Radical Scavengers


As in the case of thermo-oxidative degradation, photo degradation can
be counteracted, or at least retarded, by inclusion in the polymer
composition of additives which can effectively scavenge the free
radicals formed as intermediates in the degradation process. Apart
from the hindered-phenol antioxidants used in PVC, the other
important group of free-radical scavenging additives employed as light
stabilisers in plastics comprises hindered amine light stabilisers
(HALS). Some of these compounds are highly effective, especially in
polyolefins and ABS, but they are not widely used in PVC, because
most impair heat stability in precessing. However, a few have been
used, e.g. Tinuvin 770t and Chimasorb 944.t Both these compounds
are solid, hindered secondary amines (the second is polymeric, with a
number-average molecular weight in excess of 25(0). They have been
used in compositions stabilised with some barium/ cadmiumlzinc and
barium/cadmium stabiliser systems, but not with sulphur-containing
stabilisers, such as the thiotins, because of cross-staining.

(d) Chromophore Quenchers


These are compounds able to deactivate, evidently by resonant energy
transfer, energy-absorbing (chromophoric) groups (e.g. carbonyl)
either originally present, or formed in the polymer chain in the course
of photodegradation, and 'excited'-i.e. raised to a higher energy
level-by absorption of UV radiation (and thereby primed to promote

* For example by Santech Inc., Canada.


t Ciba-Geigy.
148 PVC Plastics-Properties, Processing, and Applications

chain-scission with the formation of free radicals). The mode of action


of quenching additives may be schematically represented as follows:

~+ UV photons - - ~
~+Q--~+Q*

Q* - - Q+heat
where © is a chromophoric group, and * indicates an excited state.
Quenchers are particularly useful in some stabiliser systems for
polyolefins, but are not much used in PVC.

(e) Some General Features of the Action of Light Stabilisers and


Antioxidants
The most general difference in the operation of UV absorbers and
screening agents on one hand and the other kinds of light stabilisers
and antioxidants on the other, is that the UV absorber's task is to
intercept as much as possible of the damaging radiation before it
interacts with the polymer. In contrast, the free-radical scavengers,
quenchers, and peroxide decomposers deactivate in various ways the
intermediate products of the antioxidation reactions (thus counteract-
ing further, more drastic, effects) after these reactions have been
initiated. However, it is also because the products are formed
anywhere in the polymer where initiation has occurred, that the
effectivity of the three last-named types of stabiliser is not limited (as
is that of UV absorbers) by the polymeric material's thickness,
although (as also in the case of UV absorbers) it is influenced by the
concentration and distribution of the stabiliser in the material.
The schematic summary (by Scott43 ) shown in Fig. 4.2 indicates the
functional mechanisms (points of intervention before or in the chain of
autoxidation reactions) of five kinds of stabiliser: free-radical scaven-
gers operating as reaction-chain-breaking electron acceptors (CB-A)
or donors (CB-O); peroxide decomposers (PO); metal deactivators
(MO) and UV absorbers (UVA).
Since UV absorbers are less effective in thin layers, this is so also in
the outermost layer of PVC products; yet it is there that the most
protection is needed, as the surface is the most directly and extensively
exposed to photochemical attack. The problem is particularly relevant
in transparent compositions for outdoor service, in which UV absor-
bers are widely used; surface application, rather than internal incor-
4 Stabilisers 149

°2
RH CB-~
~R ROO

CB-D_~ ~CB-D
MD. ttl
UVA-- - :
PO
ROOH RH

hv. Fig. 4.2 Modes of action of light


M+/M2+ stabilisers: schematic outline. 43

poration of the stabiliser, can be a useful solution in some cases. PVC


sheeting, for example, may be surface-coated with a lacquer contain-
ing a relatively high concentration (say 1-3%) of the stabiliser; such
lacquers, based on vinyl copolymer resins, acrylic resins, or other
binders are available from commercial sources. This approach can
offer cost and protection-efficiency advantages in suitable
circumstances. 48 Surface absorption from solution of a UV stabiliser
(MPB *) into PVC has also been claimed to give good results. 48
Such physical factors as the degree and uniformity of dispersion,
ease of migration through the composition, extractability, and volati-
lity, influence the performance of any additive in PVC: a useful
discussion of their effects on the performance of stabilisers, including
UV stabilisers, has been published by AHara. 25
Antioxidants, UV absorbers, and screening agents are available
individually, as composite light-stabiliser systems, and as components
of polyfunctional 'single-pack' additive combinations. The individual
stabilisers or stabiliser systems are also supplied as ready-made or
custom-compounded concentrates in PVC polymer or other appropri-
ate carriers.

4.5 STABILISERS IN SINGLE-PACK


ADDITIVE SYSTEMS

The PVC processor buying-in stabilisers as, or as part of, single-pack


products secures several advantages. The number of weighing opera-

* 2(2' -Hydroxy-5' -methylphenyl)benzotriazole.


150 PVC Plastics-Properties, Processing, and Applications

tions preparatory to compounding is reduced substantially, and the


need to dose-in such low-level additives as antioxidants (which have to
be accurately weighed in small amounts) is avoided. The formulation
of the stabiliser, and stabiliser/lubricant, systems is carried out by the
stabiliser supplier, so that the processor is relieved of the need to
undertake this highly skilled and often costly development work. The
disadvantages are somewhat reduced formulation flexibility and rela-
tively high stabiliser price.
With mixed-metal stabilisers the use of single-pack systems is a
virtual necessity, as the systems are carefully designed (and optimised
in the course of their development) to make the best use of the
frequently complex synergistic effects. The proprietary systems often
incorporate, where appropriate, such co-stabilisers as organophos-
phites, epoxy compounds, antioxidants (most usually the suitable
hindered phenols), and polyol chelators. The solid metal-soap prod-
ucts, by virtue of the lubricant action of the soaps, can be formulated
to provide their own lubrication as required in the applications for
which they are suitable. The single-pack lead stabiliser systems, either
co-precipitated or composite, have been developed to offer a complete
stabiliser system in one product. This has been taken a stage further by
some suppliers with the incorporation of fillers, processing aids, flame
retardants, and pigments within stabiliser composites. In the USA the
one-pack concept has extended into the tin stabiliser field with the
development of products containing both organotin stabiliser and a
complete lubricant system.
The physical form of a stabiliser product is another important aspect
to consider when selecting a stabiliser system. The ancillary equipment
available such as storage facilities, conveying equipment, and weighing
stations must be capable of handling the stabiliser. Most mixed-metal
complexes and tin stabilisers are liquid and require dosing equipment.
Solid stabilisers, and many one-pack combinations, are available in
various forms, such as dustless powders, flakes, prills and tablets
(about the size of an aspirin tablet).
However, dust is a major inconvenience in handling a solid,
particularly when it can be harmful if inhaled. For this reason,
considerable development work has been carried out by the manufac-
turers of solid stabilisers on forms with low dusting tendencies, and
good handle ability on dosing and conveying equipment (see individual
stabiliser sections in this chapter, and also Chapter 11).
4 Stabilisers 151

4.6 SOME COMMERCIAL STABILISERS

Many proprietary stabilisers have been mentioned or cited by way of


specific examples in this chapter, as well as in some of the other
chapters. Some commercial stabiliser manufacturers are also listed in
Table 4.2, with their product trade names.

4.7 SOME GENERAL EFFECTS OF STABILISERS ON


VARIOUS PROPERTIES OF PVC COMPOSITIONS

These are outlined in Table 4.3.

4.8 SOME STABILISER-RELATED PROBLEMS

The main problems classifiable under this heading are sulphide


staining and plate-out, which may-in some circumstances-be pro-
moted or contributed to by certain stabilisers. Discolouration of some
PVC products for medical use when sterilised by gamma radiation is
also associated with the functionality of the stabiliser system; this topic
has already been discussed in Sections 4.3.3(b) and 4.3.4(d).

4.8.1 Sulphide Staining

PVC compositions containing stabilisers (or other additives, e.g.


pigments) based on cadmium or lead can develop colour on contact
with sulphur compounds. This phenomenon is known as sulphide
staining. In cadmium-containing compositions the colour is yellow,
caused by the formation of yellow cadmium sulphide (CdS). Composi-
tions incorporating lead compounds may turn black-in patches or
overall-due to the formation of black lead sulphide (PbS), or
sometimes dark brown ranging to black: this is probably attributable
to the presence of the reddish-brown lead sulphochloride,
Cl·Pb·S·Pb·Cl.
Note: Zinc-containing additives do not give rise to dark sulphide
staining (zinc sulphide is white), and indeed the zinc
component of a barium/cadmium/zinc stabiliser may retard
colour development. However, turbidity may develop in clear
compositions if enough ZnS is formed (see also Table 4.4).
TABLE 4.2 ....
Ul
N
Some Western Stabiliser Manufacturers and Their Product Trade Names
Manufacturer a Trade names Remarks

UK and Western Europe


Akzo Chemie (Netherlands) Interstab, Stanclere "tI
BASF (W. Germany) Sicostab, Uvinul b ~
Biiropan "tI
Otto Biirlocher (W. Germany)
Ceca SA (France) Stavinor This stabiliser line taken over from Rouss-
e-
~.
elot in 1985
Ciba-Geigy (Switzerland) lrgastab, Tinuvin, b Chimassorb b Also Ciba-Geigy Industrial Chemicals, I
~
C
lrganox UK .§
Chemetall Division of Metallgesellschaft (W. Listab, Naftomix, Naftovin ~
::to
Germany) .01
Chemson (UK and Europe) See 'remarks' column Owned jointly by Cookson America and
Metallgesellschaft. Absorbed the stabili- ~
ser lines of the former Associated Lead 0:
Manufacturers Ltd (UK). ~.
Durham Chemicals (UK) Durostabe Own stabiliser line (single-pack, mixed-
metal) ~
Nuostabe Manufactured under licence from Tenneco ~
Chemicals Inc. (USA) ~
Haagen Chemie (Netherlands) Haro ~
Henkel (W. Germany) 5'
Hoechst (W. Germany) Hostastab, Hostanox i:l
Lagor (Italy) Lastab
Lankro Chemicals Lankromark Company became independent in 1986
after management buy-out from Dia-
mond Shamrock Corp. (USA)
Rhone-Poulenc (France) Rhodiastab
Swedstab (Sweden)
Victor Wolf (UK) Vinco Bought by NL Industries (USA) in 1985
USA
American Cyanamid Co., Polymer Additives Dept. Cyastab, Cyasorb, Cyanox C The Cyastab lead stabiliser line sold to
Anzon Inc. in 1986
American Hoechst Corp. Hostastab
Anzon Inc. Dythal, Dyphos, Leadstar, Lectro, Company formed by merger of Anzon
Tribase America and Associated Lead Inc. in
1985
Argus Chemical Div. of Witco Chemical Corp. Mark
Borg-Warner Chemicals Weston, Ultranox
Cardinal Chemical Co. Cardinal
Carstab/Thiokol Carstab, Advastab
Ciba-Geigy Plastics and Additives Div. Irgastab
-"'-
Eagle-Picher Industries Inc. EPIstatic
Ferro Corp., Bedford Chemical Div. Therm-Chek, Ferro-Chek, Oxy-Chek Also Ferro (GB) Ltd in the UK '"S
0-
Guardian Chemical Div., United-Guardian Inc. Voidox
~
Halstab Div., Hammond Lead Products Inc. Halstab, Halbase, Halcarb, Halphos, '"<.:!
Halthal
Interstab Chemicals, Akzo Chemie America Stanclere, Interstab, Estabex d Plastoflex d
M-R-S Chemicals Inc. MiRaStab
M&TChemicals Inc. Thermolite
Mobay Chemical Corp.
Mobil Chemical Co.
New Jersey Zinc Co. Inc. Zinstabe

a Many of the manufacturers are big international companies: for those based in Europe only the headquarters country is indicated.
b Light stabilisers.
C Antioxidants.

d Epoxy stabilisers.

Vl
t...l
-
TABLE 4.3 ~
-
Some General ElI'ects on PVC Compositions Associated with Various Stabiliser Types

Property Significant Relevant stabiliser types, Remarks


in: factors, and effects
Softening point (uPVC) Service In general, liquid stabilisers tend to This consideration can be important with
lower the softening point of the many rigid PVC products. ~
composition.
Lubrication Processing and service Suitable choice and balance of the cf. Chapter 7, Section 7.2. N.B. Surface- ~
stabiliserllubricant system very im- decoration and heat-sealing properties ~.
portant, especially in uPVC. may be affected by stabiliser exudation.
Electrical properties Service (electrical Lead stabilisers are the first choice (cf. Properties important in this connection are ~
....
insulation) Section 4.3.2). high resistivity, low power factor (esp. .g
for high-frequency cables) and high ~
::1'.
electric strength. .~
Non-toxicity Service Selected octyltin compounds. Ca/Zn
systems (with permitted co- ~
stabilisers) .
Clarity Service Organotin stabilisers. Selected BalCd Clarity is influenced by the refractive indices 5.~
systems (with epoxy and phosphite and mutual compatibility of all com- ~
co-stabilisers). Selected Ca/Zn ponents of the PVC composition con-
system (for non-toxic, clear cerned. N.B. In damp conditions cloudi- ~
compositions). ness can develop in some Ba/Cd- ~
stabilised clear compositions. ~
Weldability Heat welding Organotin stabilisers give best results. ~
Some metal soaps can cause ~.
problems.
Paste viscosity Processing In general, stabilisers should be cf. Chapter 18.
checked for effect on viscosity.
Liquid stabilisers should be used
for reduction (or least increase).
The pH of the stabiliser may have
an effect.
4 Stabilisers 155

The sulphur compounds responsible for sulphide staining may be


encountered by the PVC as atmospheric pollutants, or as components
of materials (e.g. rubber) with which the PVC may come into physical
contact. They may also be present in the PVC composition itself as its
regular components (or impurities in such components); in this case
the internally induced sulphide staining that may result is sometimes
referred to as cross-staining.
Although simultaneous use of sulphur-containing additives with
cadmium or lead compounds (say, for example, thiotin or antimony
mercaptide stabilisers in conjuction with lead or cadmium ones) is
avoided in formulating practice, it can occur in the processing of PVC
scrap of different or uncertain origins. Where fresh stabiliser is to be
added to a batch of scrap material of unknown composition to
'post-stabilise' it for processing and service, or where two or more
such batches are to be mixed in processing, the possibility of
cross-staining should be checked beforehand (even for black material).
A simple compounding test, e.g. on the mill for about 10 min at 180°C,
should be adequate in most cases in practice, and is simpler than
analysis for heavy metals and sulphur. Where the scrap material is to
be post-stabilised with a lead-, cadmium-, or sulphur-containing
stabiliser, the test should be carried out on a sample to which about
3% by weight of the stabiliser has been added, and the sample then
examined for colour development. Absence of discolouration will
indicate that the stabiliser is 'safe' for use with the material; the
appearance of colour (or milky haze in transparent materials) provides
not only evidence of interaction but, from the nature of the
manifestation, also clues for the choice of suitable alternatives (see
Table 4.4). The compounding test should also be carried out where
scrap from different sources is to be processed with or without
post-stabilisation.
Several standard tests are available for susceptibility of PVC
compositions to sulphide staining through external contact. BS
2739:1975 (Appendix D) prescribes immersion (for 30 min) of a sheet
specimen (50 mm 2) in a freshly prepared solution of 55 g of hydrated
sodium sulphide (NaS·9H2 0) in distilled water (1 litre), acidified with
concentrated hydrochloric acid (30 ml). In the method of ASTM
Dl712-83, thin sheet specimens (preferably about 100 mm x 13 mm)
are half-immersed (for 15 min) in a saturated solution of hydrogen
sulphide prepared by rapidly bubbling freshly produced H 2S gas
through 100-150 ml of water for about 5 min. The method of DIN
u.
0\
TABLE 4.4 -
Visible Manifestations of Sulphide-Forming Interactions of the Main Types of Stabiliser in PVC Compositions
Organic Tin
sulphur- free Ca/Zn Ba/Cd/(Zn) carboxylate Lead
"'I:l
Lead ~
::l:!
~
~.
Thiotin
.,~
.g
Tin carboxylate ~.
~
"'I:l
;:l
Ba/Cd/(Zn)
'~"'
'"
~.

Ca/Zn
~
).

Organic ~
sulphur- ctg e~.
Organic No effect
sulphur - free D
Sulphide formation,
with visible effects
~ as indicated
4 Stabilisers 157

53378-1965 involves exposure of film specimens to gaseous HzS


(continuously generated by reaction of sodium sulphide with sulphuric
acid). In all three methods any staining is detected visually, and its
intensity determined, where relevant, in terms of colour change in
comparison with untreated material or/and with the aid of the
appropriate standard grey scale for stain assessment (BS 1006:A03;
DIN 54001).
Note: The standard ASTM test method for the staining of PVC by
rubber-compounding ingredients, ASTM D 2151-68 (1982),
caters for staining resulting from actual migration of such
compounds (especially certain antioxidants) into PVC,
whereupon colour may develop, either immediately or after
exposure to heat or UV radiation.
The development of milky cloudiness when a clear PVC composi-
tion incorporating zinc in the stabiliser system is in contact with some
sulphur-containing gases or materials (see above, and Table 4.4), can
cause varying degrees of loss of transparency. This effect can be
quantitatively assessed, e.g. with the aid of the standard method of
ASTM D 1746. For a rough, qualitative assessment, a simple
comparison may be made by viewing, in good light, a thin-sheet
specimen of the clouded compound, laid on a white page carrying a
few lines of sharp black print, side-by-side with a similar specimen of
the original (unaffected) material.

4.8.2 Plate-()ut

Plate-out is a persistent sticky deposit which may sometimes appear,


and build up, on the working surfaces of PVC-processing equipment.
It can occur in any of such principal processes as extrusion, calender-
ing, and moulding, as well as in ancillary operations (e.g. milling,
embossing). Plate-out deposits are a nuisance in the equipment-
necessitating cleaning-up operations involving loss of time and
output-and detrimental to product quality. When present, for ex-
ample in extrusion dies, pipe-sizing sleeves, or on calender rolls, they
impair product surface finish and dimensional conformity; plate-out on
embossing rolls may blur the emboss, or even obliterate it in severe
cases. The deposit may also be transferred to the product, causing
marks, blemishes or stains on its surface. There is still no complete,
detailed understanding of the mechanism of plate-out formation,
158 PVC Plastics-Properties, Processing, and Applications

which appears to be complex and probably varies somewhat with the


nature of the PVC formulation concerned and the method and actual
conditions of processing. It is known, however, that plate-out deposits
are formed by material exuding from the hot ,PVC stock in
consequence of incompatibility-which may become manifested only
in certain processing conditions~f some constituents of the PVC
composition with one another and with the PVC resin. The exudate
moves out to the surface of the hot stock or melt and thence to the
working surfaces of the processing equipment. The process factor
which can promote plate-out are local changes in temperature,
pressure, and the rate and direction of flow of the stock (melt) in the
equipment. The formulation components particularly implicated in
plate-out formation are some lubricants (especially metal soaps) and
stabilisers; incorrect stabiliser/lubricant balance is often a factor. It is
known that lubricants and stabilisers are normally the predominant
components of a plate-out deposit, which may also contain some of
the other additives, notably fillers and pigments (if those are present
in the PVC composition) occluded by the exudate.
These compositional features are well brought out in a study by
Lippoldt,49,50 who put forward a comprehensive explanation of the
nature and mode of formation of plate-out produced in the course of
extrusion of a PVC compound containing an organotin stabiliser, a
composite lubricant incorporating calcium stearate, a calcium
carbonate filler, and titanium dioxide pigment. Lippoldt's explanation
postulated a fairly complex mechanism, involving a number of
sequential steps. According to this, the hot melt exudes a gel formed
by components of the lubricant and stabiliser system, one of the
components-a hydrocarbon in that particular study-acting as a
temporary solvent while the gel is above its 'critical solution tempera-
ture' (CTS). The gel, which occludes particles of the filler and
pigment, deposits on any working surface whose temperature is below
the critical value (estimated by Lippoldt as 175°C for his particular
system). Loss of the temporary solvent and cooling after deposition
transform the deposited gel into a solid film, resistant to re-dispersion
in the PVC composition and providing a receptive surface for further
deposit build-up. Lippoldt suggested50 the following measures for the
prevention of plate-out: reduction of the CTS by suitable selection of
stabilisers and lubricants; modification of the potential solvent/solute
system of the gel precursor of the plate-out deposit so as to hinder its
formation, e.g. by selecting a stabiliser with low capacity for
4 Stabilisers 159

solubilising fatty-acid salts (calcium stearate and others); and main-


taining the temperature in any pressure-change zones in the equipment
well above the CTS.
The first two of the above suggestions are matters of formulation;
and indeed correct initial formulation, or re-formulation at need, are
the best ways of avoiding plate-out problems. The advice of the
stabiliser, lubricant, and polymer suppliers is always well worth having
in this connection. In some cases, especially where the plate-out is
only slight, it can be cured by including in the composition low
proportions of anti-plate-out additives, like the appropriate grades of
ultra-fine pyrogenic silica or some silicates, e.g. Aerosil 200 or 300
(Oegussa) or Gasil 35 (Joseph Crosfield and Sons). Fine-particle
pigments or fillers, e.g. titanium dioxide or precipitated calcium
carbonate, incorporated at 2-5 phr, can also be helpful on occasion.
The beneficial effect of all such fine particulate additives has been
attributed51 to retention, through adsorption, of the material respon-
sible for plate-out deposits, and to the additive's direct 'scrubbing'
action on the working surfaces.
A laboratory test can sometimes be useful for checking the
tendency of a PVC composition to plate-out, and gauging the effects
on that of formulation modifications. The principle of such tests is that
a test compound, made up to the formulation concerned and contain-
ing additionally a small amount of an appropriate colourant, is run in
suitable laboratory-scale equipment (e.g. a roll-mill, or a Brabender
Plasti-Corder) under conditions relevant to the intended full-scale
processing of the composition. The colourant should be one that will
enter and colour the plate-out deposit-a colourant supplier should be
consulted regarding the choice. After the test run the compound is
completely removed and a white scavenging compound run in the
equipment. The plate-out from the test compound is assessed on the
amount of colour picked up by the scavenging composition.
One variant of this procedure is exemplified by the following
recommendations. 10

Colourant for test compound Sico Red WRC* (0·1 weight % on the
total compound): Run the test compound for 7 min at 165°C
(without friction); sheet and remove from the mixer. Run the
scavenging compound for 3 min: remove and judge the degree of red

* BASF (formerly a trade name of the Siegle Company, FRG).


160 PVC Plastics-Properties, Processing, and Applications

staining (related to the amount of plate-out) by comparison with the


unused portion of this compound. For increased accuracy of
assessment, the comparison specimens may be moulded into sheets
of identical size. Constant, uniform conditions are essential; in
particular the equipment should be in thermal equilibrium (achieved
by running for some hours prior to the test): the tests should be run
by one and the same operator as a continuous series, and each series
completed on the same day.
The recommendations include the following formulation for the
scavenging composition.
PVC polymer: Solvic 239 (Solvay) 100
Stabiliser: dibutyltin maleate (Irgastab OM 18-Ciba- 0·5 phr
Geigy)
Epoxy co-stabiliser: Reoplast 39 (Ciba-Geigy) 5·0phr
Plasticiser: DOP 30phr
Lubricants: stearic acid (Irgawax 330-Ciba-Geigy) O·Sphr
Irgawax 331 O·Sphr
Pigment: Ti02-anatase (Kronos A-Titangesellschaft 1·5 phr
MbH,FRG)

4.9 TESTING AND EVALUATION OF


STABILISATION EFFECTS

4.9.1 The Concept of Stability in Processing, Service, and Tests

The ease and rate of degradation of PVC by heat and light vary with
the composition, and the conditions of treatment or exposure.
Therefore, in the practical context, the stability of a PVC material may
be thought of, and assessed, in terms of the length of time elapsing
before perceptible and/or measurable signs of degradation develop (or
reach a stated level) under the relevant conditions. This approach
provides a basis for quantitative expression and comparison of the
stability of PVC polymers and compositions by reference to the
stability time and/or induction time for degradation, determined in a
suitable way. The way in which these two concepts are defined is
illustrated by Fig. 4.3: the 'degradation index' in the figure can be any
one of the various manifestations of degradation selected as relevant,
and monitored, in the particular conditions or treatment to which the
4 Stabilisers 161

x
CiI
"0
£
c
o
:;:;
C\J
"0
C\J
L.
01
CiI
Cl

Tima ~

Fig. 4.3 Induction time (t j ) and stability time (ts) of a PVC material exposed
to heat or light: schematic representation.

PVC material is exposed. The effects most often used as such indices
in practice are the intensity of colour developed in, or the HCI evolved
by, the PVC material (see also Table 4.5).
Note: In stability tests in which colour development is used as an
index of degradation it is sometimes relevant to make a
distinction between 'time to colour' and 'time to black'.
Blackening of the PVC material-indicating extensive
degradation-may develop progressively, or it may occur
rapidly as a result of accumulation of chlorides of stabiliser
metals which can catalyse decomposition of the PVC polymer
[e.g. zinc or cadmium chloride-d. Section 4.3.4(d)).
Two other concepts of practical significance in connection with the
stability of PVC in processing (and to some extent also in service,
especially at elevated temperatures) are the heat life and heat history of
a PVC composition. The heat life is the total period during which,
under given conditions (or successive sets of different conditions, as
for example in hot compounding followed by heat-processing into a
product and any subsequent heating experienced by the product) the
composition can remain substantially free of significant degradation.
Thus the heat life is closely represented by the stability time (or the
induction time, depending on the way in which 'significant degrada-
tion' is defined) in comparable conditions, and like the stability (or
162 PVC Plastics-Properties, Processing, and Applications

the induction) time it will be shorter the more severe the heat
treatment(s) experienced, or the less effective the stabilisation (see
Figs 4.4 and 4.5). Implicit in the concept of heat life is recognition of
the fact, highly important in practice, that heat treatment-or the
number of consecutive heat treatments-of a given nature, intensity
and duration, i.e. a certain 'heat history', may be considered to use up
a proportion of the heat life: the remainder then represents the
residual, shorter, heat life still available. In this way the extent and
severity of its history determines how close a PVC composition is to
the point of significant degradation, i.e. to the limit of its total heat
life.

4.9.2 Stability Testing

Various procedures and instrumental techniques used in the study of


PVC degradation have been referred to in the preceding sections. The
present section is concerned specifically with test methods of particular
relevance to the practical assessment of stability of PVC materials for
such purposes as formulation development, product specification,
quality control, fault investigation, and the like.
Note: It may be noted in passing, however, that where very low
levels of dehydrochlorination or cross-linking of PVC poly-
mers in the course of degradation need to be detected or
monitored for whatever purpose, laser-Raman spectroscopy
is an applicable, highly sensitive technique. 52,53

(a) Heat-Stability Tests


A heat-stability test normally comprises a suitable treatment of the
PVC material to induce degradation under controlled conditions,
followed by detection, or quantitative determination, of significant
level(s) of the manifestation of degradation which is being used as the
degradation index in the test. Some of the determination methods
employed in such tests can also be applied to PVC materials degraded
by means other than the test treatment (e.g. in actual processing or
service), but reference to a relevant standard (e.g. results of
appropriate calibration tests; specimens exemplifying the effects of
actual service in known, relevant conditions) will normally be neces-
sary to characterise the extent of any degradation detected.
Heat-stability tests are of two general types: dynamic and static. The
test methods often used in the investigation and evaluation of
stabiliser effects are summarised in Table 4.5.
4 Stabilisers 163

A B c
~ -+ _ _ _ _~a~i~u~ ~::e~t~b~e -.!.e~e~o!...d~g.r!~~on
'0
c:
c:
.Q
+'
111
'0
111
'-
01
~
o

Time •
Fig. 4.4 Effect of stabilisation (or severity of treatment) on the stability time
(t) of a PVC composition: schematic representation. A, No stabiliser (or most
drastic conditions); B, moderately effective stabilisation (or medium-severe
heating); C, highly effective stabilisation (or mildest treatment).

100

1
2
3

.
+'

10

2·3 2·2 2·1 2·0


1/EI , K- 1 x 103

Fig. 4.5 Arrhenius plot of log stability time (t .. minutes) as a function of the
reciprocal of absolute temperature (1/ (J) for three PVC compositions of
increasing stability (1) 2 > 3): schematic representation (but values roughly
representative of some uPVC compositions, with HCI emission as the
degradation index).
~

TABLE 4.5
Heat-Stability Tests Relevant to Practical Assessment of the Effects of Stabilisers in PVC ~
~

Manifestation Determination of degradation effects Test treatment References and remarks Ff


of degradation for which
detected or General means Method, and/or determination
measured stability criteria method t
.g
is suitable ~
::t.

Development of Visual Inspection after set time, or at in- Both static and Static: ISO 305;Q ASTM D
.~
colour in PVC tervals, and comparison with dynamic 2115; DIN 53 381 Part 2
material standards. Dynamic: Refs. 10, 54, 55
Evolution of HCl Colour change Colour change (to blue) of a Congo Static ISO/R 182;Q BS 2782, Method
Red paper, or universal indicator 130A: 1986; DIN 53 381
r
~.

sensitive at about pH 3, in contact Part 1, Procedure A §


~
with volatiles evolved during the
test. ~
'1:5
Evolution of HCl Colour change Reduction of colour of Ultra-marine Static Nelson's test: Ref. 57
Blue incorporated in the test
2
specimens, continuously moni-
~.
tored (by photo cell) during heat
treatment in oven. Onset of sig-
nificant degradation (end of sta-
bility time) indicated by sharp
drop in blue-light reflectance
curve-cf. Fig. 4.8.
Evolution of HCI pH Volatiles evolved by specimens in Static ISO/R 182;D BS 2782, Method
determination test treatment passed through a 130B: 1986; DIN 53 381 Part
standard KCI solution. Time pH 1, Procedure C
(continuously monitored) to drop
from about 6 to about 3·9
measured as stability time. b
Evolution of HCI Titration Volatiles evolved by specimens in Static ASTM D 793 (discontinued in
test treatment absorbed in NaOH 1983)
solution, and HCI determined by
back titration. Stability expressed
as mg of HCI evolved per g of
sample during heating period
(30 min).
Evolution of HCI Conductivity Absorption in water of volatiles Static Introduction of test of this
determination evolved by specimens in test kind under consideration for ""'"
c;"
treatment. Stability time meas- a revised version of ISO/R s:;
Q-

ured as time for water conduc- 182;D DIN 53 381, Part 1, ~


<II
tivity to rise by a specified figure. b Procedure B t::!
Melt viscosity rise Torque-time Stability time determined as time to Dynamic Ref. 54
with onset of de- plot reach point of torque rise ('de-
gradation of composition point') on the
composition in torque-time graph.
torque rheometer

D Under revision in 1988.


b Volatile alkyltin chlorides are formed on heating of PVC compositions containing alkyltin stabilisers. These can dissociate in aqueous
solution, and may thus interfere with HCI determination by conductivity and pH methods.

8i
-
166 PVC Plastics-Properties, Processing, and Applications

DYNAMIC STABILITY TESTS


In dynamic tests an appropriate weight of the PVC composition is
worked at an elevated temperature in suitable equipment, typically a
torque rheometer, internal mixer, extruder, or mill. Stability is
assessed by periodically checking the effect used as the degradation
index. This is often the development of colour in the material or-in
instrumented torque-measuring equipment-4ietermination of the sta-
bility time as the period from the commencement of test processing to
'decomposition point', marked by an ultimate, sharp rise in melt
viscosity (and hence the torque) associated with a substantial amount
of cross-linking and incipient carbonisation in the material, occurring
as some of the manifestations of extensive degradation (see Fig. 4.6).
By their nature, dynamic tests are primarily relevant to the stability of
PVC compositions in processing. Indeed, the test equipment, tem-
perature and running conditions are often chosen with a view to
relating the test results t,o a particular process. Because PVC cannot be
processed without stabilisers, dynamic methods are not generally
suitable for the determination of the heat stability of PVC polymers
alone. It is a feature of properly designed dynamic stability tests, in
particular those employing equipment like the Brabender Plasti-
Corder, that they can bring out the important role of lubrication in the
heat stability of PVC in processing. The reduction of frictional heating
by proper internal and external lubrication can substantially increase
the stability of a PVC composition (by reducing the heat history and
hence extending the heat life), in comparison with an unlubricated, or
poorly lubricated, but otherwise identical composition. This factor is
not brought out by static tests, in which the stability time depends
essentially on the stabiliser system and is not significantly influenced
by the lubricants54 (unless these are synergistic with the stabiliser, or
are of the stabiliser-Iubricant type: cf. Chapter 7, Section 7.2.1).
In a typical procedure for a dynamic stability test in a Brabender
Plasti-Corder, the appropriate mixing head is selected, and the mixer
preheated to the required temperature. A weighed quantity of PVC
composition is quickly introduced into the chamber (head cavity) with
the rotors running. The amount of material is selected in relation to
the cavity volume: if it is desired to ensure good exposure of the
composition to air during mixing, the cavity should not be filled
completely. If colour development is used as the degradation index,
samples of the composition are withdrawn for examination at suitably
frequent intervals (say every two minutes). Otherwise the time is
4 Stabilisers 167

Test-Conditions
Order BRABENDER Mixer-Temp. 200 ·C
Operator EICKMEIER Speed 75 l/min
Check-Date 16. MAY 'B8 Meas. Range 5111 Nm
PL-Type 2000-3 Zero-Suppr. III Yo
Mixer-Type W 50 Dampin~ 3
Load. Chute MANUAL + 5 KG Test-Tl.me 15.111 min
Sample PVC Sample-Weight 57.111111 g
Additive Coden umber 2
Start-Temp. 196 "C

Torquelltlll) Telllp [OC]


58 238

45 t·m; ......... ( j . . . .j. 228


. ' ,--:,j, 218
48
35 . . . i......ii . 288

38 ......................... 198

25 188

28 178

15 . . . . ;.... .........L...................................... Llt 168

18 ······t 158

" ~--4----I~'---+---4i----~--+i---4----~i---+~-4t
5
ABX
~ II ::
8.8 3.8 b.8 9.8 12.8 15.8
Tillie [,lin]

Value Time [sJ Torque [NmJ Stocktemp.["C]


Load.Peak 4 48.5 168
Minimum 16 19.7 173
Maximum 32 37.5 188
Decomposition 838 24.3 214

Integration
- Load.Peak to Minimum Wl 2.5 E3 [NmJ
- Minimum to Maximum W2 3.7 E3 CNmJ
--Load.Peak to End W3
W4
159.5
2.7
E3
E3
CNmJ
CNm/gJ
Specific Energ~ (W3/Wei~ht)
-Decomposition nergy (T to TO 152.5 E3 CNmJ

Fig. 4.6 A Brabender Plasti-Corder plot from a dynamic stability test on a


PVC composition illustrating the main process stages, including ultimate
torque rise at decomposition point (D), B, start of gelation; X, completion of
gelation. Courtesy of Brabender® OHG, Duisburg, FRG.
168 PVC Plastics-Properties, Processing, and Applications

determined from the start of mixing to the rise of torque indicating the
decomposition point. The roller speed and the temperature are the
principal variables; their values should be selected in the light of the
purpose of the test. The following examples may be mentioned of
combinations which have been used in investigations of stability of
PVC compositions in relation to their behaviour in industrial process-
ing: roller speeds of 35, 45, 55 and 65 r min- 1 at temperatures of 165,
180 and 185°C;55 or 50 and 100 r min -1 at 140 and 1800C. 54
Note: An interesting study by Collins et al. 55 provided evidence for
good correlation between Brabender thermal-stability values
and those obtained with a capillary rheometer. Data obtained
with the latter instrument also demonstrated, inter alia, a
correspondence between the 'time to black' of PVC composi-
tions and a pronounced increase in melt viscosity (reflected
by the commencement of an upward sweep in a plot of the
extrusion load versus time).
The effects of calendering are among the most difficult to relate to the
results of laboratory tests: in-plant trials are the only complete answer
wherever they are practicable and not precluded by cost considera-
tions. Milling tests are sometimes used to give some indications of the
likely stability in calendering of a PVC composition,5 but the results of
such tests can only be regarded as rough, general guidance. Correla-
tion with results of static tests is less close.

STATIC STABILITY TESTS


In static methods the test treatment essentially consists of heating
specimens of PVC material at the relevant test temperature. The
specimens are most often pieces of sheet, but may also be suitable
amounts of powder or pellets of PVC polymer or composition.
Temperatures of 175-180°C are most commonly used in the tests,
although higher ones are sometimes recommended, e.g. 200°C by the
French Centre Scientifique du Biitiment. 56
Note: For the same PVC composition and test method, stability
times (t s) at different elevated temperatures within a reason-
able range may be expected to conform to an Arrhenius-type
relationship: In ts = -(E / RT) + constant, where E is the
activation energy for the thermal degradation of the PVC
composition in the test, R is the universal gas constant, and T
is the absolute temperature (d. also Fig. 4.5).
4 Stabilisers 169

The sheet from which specimens are cut for a static stability test may
be moulded as described in Sections 17.1.3 and 17.1.4 of Chapter 17.
The relevant standard test specifications (cf. Table 4.5) also usually
include directions for the method and conditions of specimen prepara-
tion. With solid PVC compounds simple milling on a laboratory mill
into a sheet about 0·3 mm thick (uPVC) or about 0·5 mm (pPVC) may
be adequate. 5 In all cases the specimen preparation should be carefully
standardised, so that variations in heat history do not arise to affect
the results of the stability test itself.
The heating equipment may, typically, be an air-circulation oven,
containers for the specimens immersed in a heating bath, or-in some
cases-a press with suitable arrangements for heating and cooling the
platens. Stability is determined in terms of heating time to reach a
certain level of the degradation index used in the test (i.e. stability
time in those terms). This level may be that marked by the
appearance, or attainment of a certain degree, or discolouration in the
composition (cf. the example below), colour change of an indicator in
continuous contact with volatiles evolved by a specimen, or the other
effects mentioned in Table 4.5.
An oven used for static heating tests must be reliable, with good
control, and even distribution, of temperature. ASTM D2115 gives a
useful summary of requirements in this regard. In the interests of the
greatest uniformity of exposure, specimen carriers rotatable during the
test treatment should be provided inside the oven in preference to
ordinary shelves. The carriers may take the form of self-levelling
shelves carried in a horizontally mounted cylindrical frame after the
manner of a 'big-dipper', or a turntable 57 with the specimens placed
around the periphery.
The following recommendations lO are fairly representative of condi-
tions and procedure for a press-heating test. A sheet is prepared under
standard conditions from the PVC composition to be tested. Speci-
mens of suitable size are cut from the sheet and placed in a press
(preferably a multi-daylight one) preheated to the test temperature
(typically 180°C), between chromium-plated metal plates, and within
moulding frames to prevent thickness reduction. Pressures of about
200 MPa (29000 lb in- 2 ) and 100 MPa (14500 lbf in- 2 ) may be used,
respectively, for uPVC and pPVC compositions.
In an oven or press test, the extent of discolouration of the
specimens, graded on a convenient scale, may be used as a semi-
quantitative degradation index. For example, when specimens of the
170 PVC Plastics-Properties, Processing, and Applications

11 A
10
9

01 8
.!::: 7
~6
u
L.. 5
54
°3
U
2

o 10 20 30 40 50 60 70 80 90 100 110
HlZating timlZ, minutlZs

Fig. 4.7 Colour changes in four PVC compositions on heating at 180°C.

four basic compositions listed below were heated in an oven at 180°C,


the results, plotted in terms of degree of discolouration on a scale from
o to 11 versus heating time, gave the curves of Fig. 4.7. 5 The
discolouration scale was: 0, clear; 1, barely detectable change; 2, very
slight change; 3, slight yellow tinge; 4, pale yellow; 5, yellow; 6, faint
tinge of red; 7, pale red; 8, red; 9, deep red; 10, very deep red/black;
11, black. As can be seen, the four plots of Fig. 4.7 reflect the trend
illustrated by their idealised, schematic counterparts in Fig. 4.4. They
also demonstrate the stability improvement promoted by an epoxy
co-stabiliser added to a PVC composition stabilised with a barium/zinc
stabiliser. The compositions used in the determinations are listed in
Table 4.6 (parts by weight).
An oven test developed by Nelson57 (originally for plastisol mate-
rials) is noteworthy for the degree of precision achievable in the
determination of stability time, as well as the good control over the
heating conditions. An effectively insulated, dome-shaped oven is

TABLE 4.6
Compositions used in the Oven Stability Tests (Parts by Weight)
Formulation PVC DOP Barium Zinc Epoxidised Dibutyltin
resin stearate stearate oil dilaurate
A 100 50
B 100 50 2·5 0·5
C 100 50 2·5 0·5 5·0
D 100 50 2·0
4 Stabilisers 171

used, in which a heated air-stream is directed, from above, onto a


turntable (revolving at 1 rmin- 1) on which the PVC specimens are
mounted over holes, so that they are accessible to a light beam
directed at them from below. The specimens are films spread on
microscope slides: they incorporate Ultramarine Blue RS 1, com-
pounded into the composition to act as indicator, in an amount
sufficient to make the colour change (reduction of the blue colour)
distinct when free HCl is evolved at the onset of significant
degradation (0·5 phr of the indicator exemplifies the incorporation
level). This degradation point, which defines the stability time, is
marked by the end of a sharp drop in the reflectance curve of the blue
component of the part of the light beam reflected by the specimens
onto an EEL (Evans Electroselenium Co. Ltd, UK) selenium cell: the
reflectance is continuously measured and recorded from the start of
the test (see Fig. 4.8).
A test method which can give rapid results, and in which the
degradative test treatment is combined with measurement of induction
time, is differential scanning calorimetry (DSC). This may be
applicable where the degradation process is exothermic, so that on the
usual DSC plot of heat flow rate versus time, the period of stability
(induction time) at the heating temperature used is represented by a

.,!
o

ts
Time) minutes

Fig. 4.8 Reflectance of blue light as a function of heating time in Nelson's


stability test with Ultramarine Blue RSI indicator: 57 schematic representation.
t s , stability time.
172 PVC Plastics-Properties, Processing, and Applications

flat portion of the curve, and a subsequent drop marks the end of that
period. 58
The results of static tests are more directly relevant to the effects of
heat in service than in processing of PVC materials. However, because
the equipment required and the test procedures are generally simpler
than those of dynamic tests, static tests are sometimes used also to
obtain indications of the likely stability in processing, albeit correla-
tions with actual process effects (or with those of dynamic tests) may
not be very good. Oven-heating involves free access of air to the PVC
specimens, whilst in the heating-bath methods the containers housing
the specimens can usually be continuously swept with air. Thus either
of these two methods may be employed where accessibility to air is
relevant to the purpose of the test, and their results are sometimes
taken as an indication of the PVC material's likely stability in such
open processes as calendering and coating. Similarly, because heating
between the platens of a press substantially excludes air contact,
press-heating tests may be considered somewhat more relevant (within
the generally limited degree of correlation) to the stability of the
material in injection moulding or extrusion.

(b) Light-Stability Tests


The general format of tests for stability to light is the same as that of
heat-stability tests-i.e. a test treatment producing degradation,
followed (or accompanied) by a determination of its extent. All the
test treatments in common use are static ones. In the practical context,
the ultimate significance of light-stability tests is as sources of guidance
to resistance of the material tested to photodegradation in service
(although good correlations with actual service performance may be
difficult to establish-see Chapter 24, Section 24.3): this is implicit, at
least to some extent, even in the use of such tests for direct
comparison of the stability of similar materials, as criteria of specifica-
tion requirementS, and in quality control. The usual test treatments
consist of exposure of suitable specimens to 'natural' sunlight (with or
without accessibility to general weathering), or to artificial light
sources in the laboratory. The laboratory tests may also include
exposure to heat and water (liquid and/or vapour) to simulate the
effects of these factors in outdoor weathering. The popular tests in
both these categories (including international and national standard
tests), their effects, applications, significance, and limitations are
discussed in Section 24.3 of Chapter 24, in connection with weathering
4 Stabilisers 173

resistance of PVC. As mentioned in that section, laboratory tests


which involve exposure to artificial light with a spectral distribution
resembling that of daylight are not necessarily accelerated tests, as the
degradation effects may take as long to develop as they would on
outdoor exposure. True acceleration of photodegradative effects may
be achieved by using sunlight-concentrating devices, or UV radiation
(for example the QUV apparatus), and/or running tests at elevated
temperatures or higher ambient oxygen concentrations.
The accelerated test treatments may be particularly relevant where
the object is purely to achieve rapid photodegradation, or to examine
the roles and effects of the three factors just mentioned in the
conditions of the test (the effects may differ in magnitude or even
nature under different conditions); or where the stability of generally
similar materials (e.g. PVC of basically the same formulation but with
modifications to the stabiliser system) is to be directly compared.
The applicability of the test results as an indication of the likely
stability of the material on long-term exposure in service will, in each
individual case, cardinally depend on the available evidence and
records of the relevant correlations.
An accelerated test for photochemical stability of polymers and
plastics, including PVC, useful in some circumstances, has been
developed by the Plastics and Rubber Research Institute TNO (Delft,
The Netherlands). In the test, the time scale for degradation effects is
reduced not only by the use-in combination-of UV light, heat, and
oxygen, but also by specimen 'geometry'. The specimens are thin
films: this makes for a high surface-to-volume ratio, so that a large
proportion of the total material of each specimen is immediately and
directly accessible to the degradative influences. The films are
mounted on the other wall of a cooling tube, of Duran SO glass, which
surrounds an inner tube housing a high-pressure mercury lamp
(TQ-1S0, Quartzlampen GmbH, Hanau, FRG). The cooling tube also
acts as a UV filter, absorbing wavelengths below about 300 nm. The
assembly is contained in a cylindrical glass vessel, jacketed for
temperature control by water circulation: the test temperature is
maintained by regulating the temperatures of the cooling tube and the
glass vessel. Test temperatures up to about 90°C can be used, with UV
radiation intensities between about 200 and 1100 W m -2. The progress
of photo-oxidation of the specimens is followed by continuous
measurement of the uptake of oxygen from a nitrogen/oxygen
mixture filling the glass vessel. The concentration in this mixture may
174 PVC Plastics-Properties, Processing, and Applications

be used as a test variable to examine its effect on the degradation of


the material tested. In tests on PVC, the HCl evolved is also
continuously determined by absorption in water and conductivity
measurement.
Determinations of stability to photo-oxidative degradation of plas-
tics by the TNO test can be up to ten times faster than those in some
types of standard equipment (e.g. the Xenotest). They have also been
claimed to correlate well with Xenotest results, as well as with those of
long-term outdoor exposure.
The effects of the test treatments in ordinary light-stability tests (as
distinct from more fundamental research investigations) are assessed
in ways similar to those employed in heat-stability determinations.
However, because, in general, these effects take longer to appear,
evaluation by before-and-after determination of selected physical
properties (most often tensile strength and elongation; with uPVC also
impact resistance) is more conveniently applicable and common than in
heat-stability tests. Also as-in consequence of the mode of
exposure-the surface of the material is the most directly and strongly
effected, inspection for manifestations of degradation such as surface
cracks, discolouration, and development of tackiness, almost in-
variably forms part of the assessment procedure. Determination of
changes in surface contour on the micro scale* is a useful technique, as
is scanning electron microscopy (SEM) in some cases.

REFERENCES

1. Rice, P. & Adam, H. In Developments in PVC Production and


Processing-i, ed. A. Whelan & J. L. Craft, Applied Science Publishers,
London, 1977, Ch. 5.
2. Chauffoureaux, J. c., Dehennau, C. & van Rijckevorsel, J., 1. Rheology,
23(1) (1979) 1-24.
3. Abu-Isa, I. A., Polym. Engng Sci., 15(4) (1975) 299-307.
4. Sosa, J. M., 1. Polym. Sci., Polym. Chem. Ed., 13(10) (1975) 2397-405.
5. Titow, V. W. PVC Technology, 4th edn Elsevier Applied Science
Publishers, London and New York, 1984.
6. Starnes, W. H. & Edelson, D. (1976). Am. Chem. Soc. Div. Org. Coat.
Plast. Chem. Pap., 41, 505-16. And Starnes, W. H. In Developments in
Polymer Degradation-3, ed. N. Grassie, Applied Science Publishers,
London, 1981, p. 135.

* With computerised equipment such as, for example, the Hommel Tester
TIO. (Hommelwerke GmbH, FRG, and Osterwalder Werkzeugmaschinen
AG, Switzerland). Compare also Section 24.3.1(b) of Chapter 24.
4 Stabilisers 175

7. Starnes, W. H. & Edelson, D., Marcromolecules, U (1979) 797.


8. Starnes, W. H. In Developments in Polymer Degradation-3, ed. N.
Grassie. Applied Science Publishers, London, 1981, p. 135.
9. Hjertberg, T. & Sorvik, E. M. In Degradation and Stabilisation of PVC,
ed. E. D. Owen. Elsevier Applied Science Publishers, London and New
York, 1984, Ch. 2.
10. Manual of PVC: Additives (1971). Ciba-Geigy Marienberg GmbH,
Section 2.
11. Schlimper, R., Plaste u. Kautschuk, 13(4) (1966) 196-207.
12. Schlimper, R., Plaste u. Kautschuk, 14(5) (1967) 657-60.
13. Berens, A. R., Polym. Engng Sci., 14 (1974) 318-28.
14. Pukanszky, B., Nagy, T. T., Kelen, T. & Tiidos, F., l. Appl. Polym. Sci.,
27 (1982) 2615-21.
15. Decker, C. In Degradation and Stabilisation of PVC, ed. E. D. Owen.
Elsevier Applied Science Publishers, London and New York, 1984, Ch. 3.
16. Gerrard, D. L., Bowley, H. J., Biggin, I. S. & Williams, G. E., Plast.
Rubb. Mat. Appl., 6(2) (1986) 97-100.
17. Gooden, R. & Hellman, Y., 28th Macro. IUPAC Symposium
Proceedings, Amherst, 1982, p. 303.
18. Marks, G. C. & Butters, G. J., l. Macromol. Sci. Chem., AU (1978)
569-74.
19. Braun, D. In Degradation and Stabilisation of Polymers, ed. G. Geuskens.
Applied Science Publishers, London, 1975, Ch. 2.
20. Summers, J. W., 34th ANTEC SPE Proceedings, 1976, pp. 333-5.
21. Suzuki, T. & Nakumura, M., lap. Plast., 4 (1970) 16-18.
22. Kennedy, J. P. (1972) & Ichikawa, M. (1974), Polym. Engng Sci. 14,
322-6.
23. Thame, N. G., Lundberg, R. D. & Kennedy, J. P., l. Polym. Sci., AI, 10
(1972) 2507-11.
24. Mitani, K., Ogata, T., Nakatsukasa, M. & Mizutani, Y., Polymer, 21
(1980) 1463-66.
25. Allara, D. L., 34th ANTEC SPE Proceedings, 1976 pp. 245-7.
26. Starnes, W. H. & PIitz, I. M., Macromolecules, 9(4) (1976) 633-9.
27. Suzuki, T. Pure Appl. Chem., 49 (1977) 539-4l.
28. Braun, D., Kunststoffe, 54(3) (1964) 147-52.
29. The Safe Handling of Lead Chemicals, Associated Lead Manufacturers
(now Chemson), 1979.
30. Wypych, J., l. Appl. Polym. Sci., 20(2) (1976) 557-60.
31. Abed-Ali, S. S., Polym. Degrad. Stabil., 21(3) (1988) 211-25.
32. Yassin, A. A. & Sabaa, M. W., l. Polym. Sci., Polym. Chem. Ed., 18
(1980) 2513-21 and 2523-33.
33. Wilkinson, G. (Ed.), Comprehensive Organometallic Chemistry,
Pergamon Press, New York, 1982.
34. Ayrey, G. & Poller, R. C. In Developments in Polymer Stabilisation-2
ed. G. Scott, Applied Science Publishers, London, 1980, Ch. l.
35. Owen, E. D. In Degradation and Stabilisation of PVC, ed. E. D. Owen.
Elsevier Applied Science Publishers, London and New York, 1984, Ch. 5.
36. Dieckmann, D. 34th ANTEC SPE Proceedings, 1976, pp. 507-1l.
37. Hartung, M., Plast. Technol. 25(8) (1979) 67-70.
176 PVC Plastics-Properties, Processing, and Applications

38. Dunne, J., Plast. Rubb. Process. Applns 3(4) (1983) 337-42.
39. Guyot, A. & Michel, A. In Developments in Polymer Stabilisation-2,
Ed. G. Scott. Applied Science Publishers, London, 1980, p. 89.
40. Wypych, J., J. Appl. Polym. Sci., 19(12) (1975) 3387-9.
41. Mascia, L., The Role of Additives in Plastics. Edward Arnold (Publishers)
London, 1974.
42. Hybart, F. J. & Rowley, G. N., J. Appl. Polym. Sci., 16 (1972) 715-23.
43. Scott, G., Chemistry in Britain, 21(7) (1985) 648-53.
44. Hageman, H. J. & De Jonge, C. R. H. I., Kunststojfe, 62(10) (1972)
681-3.
45. Bailey, D., Tirrell, D. Pinazzi, C. & Vogl, 0., Macromolecules, 11(2)
(1978) 312-20.
46. Anon., Eur. Plast. News. 3(3) (1976) 28.
47. Szabo, E. & Lally, R. E., Polym. Engng Sci., 15(4) 277-84 (1975).
48. Katz, M., Shkolnik, S. & Ron, I., 34th ANTEC SPE Proceedings, 1976,
pp.511-12.
49. Lippoldt, R. F., 36th ANTEC SPE Proceedings, 1978 pp. 737-9.
50. Lippoldt, R. F., Plast. Engng, 34(9) (1978) 37-9.
51. Gleissner, A., Kunststojfe-Plastics, 22(1) (1975) 11-12.
52. Gerrard, D. L., Biggin, I. S. & Bowley, H. J. PRI Conference PVC '87,
1987, Paper No.3.
53. Wilson, A. S., Bowley, H. J. & Gerrard, D. L., Plast. Rubb. Int., 13(1)
(1988) 23-6.
54. Menzel, G. & Polte, A., Kunststojfe, 65(3) (1975) 149-55.
55. Collins, E. A., Metzger, A. P. & Furgason, R. R., Polym. Engng Sci.,
16(4) (1976) 240-5.
56. Fougea, D., Cahiers Centre Sci. Tech. Biltiment, 124 (1971) p. 1070.
57. Nelson, J. H., A novel method of assessing heat stability. Paper presented
at the PRI International Conference on PVC Processing, Egham Hill,
Surrey, UK, 6-7 April 1978.
58. Casel, B. & Gray, A. P., Plast. Engng 33(5) (1977) 56-8.
CHAPTER 5

Plasticisers

5.1 GENERAL DEFINITION AND NATURE


OF PLASTICISERS

The current formal definitions of a plasticiser (those of IUPAC 1,* and


the ISO,2 ASTM,3 and BS4 terminology standards) are neither
mutually identical nor fully comprehensive. Their essential elements
may be combined and augmented to formulate the following general
working definition relevant in the PVC context.
A plasticiser is a substance of low or negligible volatility, suitably
compatible with the polymer in which it is incorporated. Whilst it
improves the processability of the resulting composition, its principal
role is to impart to the ultimate product-in degrees dependent upon
the plasticiser's nature and proportion-the properties of flexibility,
extensibility and softness. Among the usual, technically significant
concomitants of plasticisation are the lowering of the glass-transition
temperature (and softening temperature generally), reduction of
strength, and increased impact resistance.
In the practical context, a distinction is commonly made (although it
does not constitute a rigid, well defined classification) between primary
and secondary plasticisers. The former are those which are highly
compatible with PVC polymers (up to at least 150 phr) , whilst the
latter, less compatible, are generally used in mixtures with primary
plasticisers to confer some special balance of properties on the PVC
composition. The extenders, a group of least compatible secondary
plasticisers, are used in some compositions as cheaper part-
replacements for other plasticisers.

* International Union of Pure and Applied Chemistry.


177
178 PVC Plastics-Properties, Processing, and Applications

Some of the effects resulting from the introduction of certain


co-monomer units (e.g. vinyl acetate, vinylidene chloride, propylene,
alkyl vinyl esters) into the vinyl chloride polymer chain-and thus
imparting more flexibility to the chains, as well as creating a less
morphologically uniform and hence less cohesive structure-are simi-
lar to those produced by admixing external plasticisers to the polymer.
These effects (and the incorporation of the co-monomers that produce
them) are commonly termed internal plasticisation. The ISO and BS
vocabulary standards2 •4 go so far as to define 'internal plasticiser' as 'a
chemical group incorporated by chemical reaction in a polymer to
plasticise it'. The principal technological advantage of internally
plasticised systems is a reduction in the processing temperature of the
polymer, and the main functional benefit is that such systems cannot
suffer loss of plasticiser. However, resins plasticised internally by
copolymerisation are generally inferior to externally plasticised sys-
tems in strength and low-temperature properties.
PVC plasticisers are mainly organic esters with high boiling points.
About two-thirds of the plasticisers in general use are diesters of
phthalic anhydride with Ce C8 alcohols. The C8 alcohols offer the best
balance of properties for general-purpose plasticisers. The other
classes of more specialised plasticisers are triaryl phosphates, alkyl
esters of dibasic alkyl acids, alkyl trimellitate esters, high-molecular-
weight polyesters and epoxies. The majority of the extender plas-
ticisers in common use are chlorinated paraffins, or hydrocarbons.
The expressions 'monomeric plasticiser' and 'polymeric plasticiser'
are commonly and widely used. Although their meaning is well
understood in the art, and rarely causes confusion, it should be
remembered that neither term is strictly accurate.
Monomeric plasticisers are not monomers in the accepted sense of
polymerisable compounds. The word 'monomeric' was originally, and
in this context incorrectly, used as the opposite of 'polymeric' to
distinguish between high-molecular-weight plasticisers, many of which
were indeed polymers, and compounds of considerably lower molecu-
lar weight. The latter might perhaps be better described as simple
ester plasticisers or low-molecular-weight plasticisers, since in most
cases their molecular weights lie between 300 and 500.
The term 'polymeric plasticiser' is less of a misnomer in that
plasticisers produced by polymerisation (e.g. the polyesters with
molecular weights up to 8000) are certainly included under this
heading. However, the designation is sometimes also applied to
5 Plasticisers 179

plasticisers of high molecular weight which are not polymers, e.g.


some complex esters, or epoxidised oils.

5.2 PLASTICISATION MECHANISM, AND SOME


RELEVANT FEATURES OF PLASTICISER STRUCTURE

Two major basic explanations of the mode of action of external


plasticisers in PVC are embodied in the alternative theories of
plasticisation usually referred to as the Lubricity Theory and the Gel
Theory.
In the former, older theory, originated by Kirkpatrick,S Clark,6 and
Barron, 7 the plasticiser is thought to act as a lubricant reducing
intermolecular friction of the polymer chains between which it is
interposed, and thus making the bulk material less resistant to
deformation.
The Gel Theory, developed through the work of Doolittle ,8,9 ascribes
the deformation resistance of amorphous polymers to the existence of
a quasi cross-linked structure, likened to a loose, three-dimensional
honeycomb, with the cross-links operating between 'active centres'
along the polymer chains. The structure is envisaged as not static, but
existing in a state of an aggregation-disaggregation equilibrium, with
the cross-links continually breaking down and re-forming. When a
plasticiser is introduced into the polymer, it takes part in the
interactions within the resulting two-component system, so that
temporary links are now formed also between the plasticiser molecules
and the polymer's 'active centres'. In consequence, at any given time,
a proportion of the centres is engaged ('masked' or 'solvated') by the
plasticiser (i.e. a solvation-desolvation equilibrium is set up) and
hence it is not available for polymer-to-polymer linking, the polymer
structure being correspondingly loosened. The suggestion that in PVC
the 'active centres' are dipoles in the polymer chain has been coupled,
in a paper by Leuchs,lO with one that they can be masked by plasticiser
via either a 'screen' or a 'hinge' action (cf. Fig. 5.1), hinge-type
plasticisers being represented by the readily polarisable aromatic
compounds, and the screen types by polar, aliphatic esters.
In the light of more recent work it would appear! that the role of the
quasi cross-links is in fact played by areas of ordered structure
(micro-aggregates or crystallites) in the polymer, and that aggregation
of polymer chains (possibly along lengths of some 11-20 repeat units)
180 PVC Plastics-Properties, Processing, and Applications

Screen type Hinge type

Fig. 5.1 Screen and hinge mechanisms of piasticiser action (after Leuchs). 10

is promoted by the presence of plasticisers and solvents, resulting in


the formation of polymer/plasticiser on polymer/solvent gels. Such
gels appear to have a significant part in determining the physical
properties of plasticised PVC, which can however also exhibit other
structural regularities not directly related to crystalline order. 1 As
remarked by Buszard, 1 it would appear that the mechanism of
polymer-plasticiser interaction in pPVC is complex and that it
operates at a number of levels, involving energy and entropy factors
resulting from the redistribution of polymer chains, an atomic-level
interaction of dipoles, and interaction within crystallite, or possibly
larger, structures.
Certain regularities have been noted by several workers, which may
be considered to amount to significant correlations, between the
chemical structure of plasticisers and their plasticising properties in
PVC. The following features of this kind may be mentioned. 1

Molecular weight: Volatility, migration and softening efficiency all


decrease with increasing molecular weight of the plasticiser.

Polarity: Increasing polarity by incorporating extra polar groups


(such as ether groups in diesters), substituting halogens into the
benzene ring of phthalates, or substituting aryl groups for alkyl ones,
reduces softening efficiency, worsens low-temperature properties of
the plasticised compounds, improves solvation, and reduces extrac-
tability by aliphatic solvents.
5 Plasticisers 181

Alkyl chain length: Increasing alkyl chain length improves the


efficiency of aliphatic and phthalic diesters at equimolar concentra-
tions. Efficiency at equal weight concentration is largely independent
of chain length.

Alkyl chain linearity: Increasing linearity improves the efficiency of


the plasticiser and low-temperature flexibility of the plasticised com-
pound, but tends to reduce its electrical resistivity.

Separation of ester grouping: Increasing the distance between ester


groups at a constant Ap/Po ratio [see Section 5.4.1(e)] increases
solvation, softening efficiency, and effectiveness.

I
,.1
'00

..0
100

~~- r--- --'~-"~,.-t--


--t--
.0 ~
,DpP\
~\ ~ TTP "',t--
~-f-\.~~-
U
~
>0

O~CIYIIPOXY • ,,,,,<J.r.
~Q ~
f/1;,.,.~ ~ ...
'"

"'(l~lri\. \
N

~p t~
slearale

~
~

0 \
u 30 Ifo..,
Di n heplyl lOIS."
."
~
DOS phthalate \.
t-

~' \
• Octyl diphonyl PhD'Phltel
"PIS,of. DBP
<-~" it,,,,... I

,----
ri oClyl phosphate
0· -I-- - --

.
:nR.~.' ~~
---~~4"
~
t-
~~
- ------- f-

..~.;-~ ,"" ~
. .~~ ....~{ ...~...
, 1-------- ----'\: ~ 1\ \'I.~ ~
of! ~ "i,,'. ~"c. ,.\.\($ t,'

..
"'b- ..0", ~ ..~-~~l>'4e\ o~..~'I.e~
"'o~"?~;. '1' ' ' ' ~~~..e~
, ~.~
~
~
~i,
,'()

40. ",.

" ;P-:f,

I
I"
0-85 0-9 0-95 1-0 1-05 1-15 1-20
Relative densily 25/25'C

Fig. 5.2 Relationships between the viscosity and relative density of plas-
ticisers in bulk and their plasticising properties in PVc. 1
182 PVC Plastics-Properties, Processing, and Applications

Reversal of ester grouping: A change from a dibasic acid ester to a


dihydric alcohol ester of similar chain length leads to a decrease in
solvation, compatibility and efficiency (e.g. di-n-octyl adipate is a
better plasticiser than 1,4-butylene glycol dipelargonate).

The above parameters also influence the relative density and viscosity
of plasticisers: thus a plot on this basis segregates plasticisers into
groups which are related to their plasticising properties: see Fig. 5.2.

5.3 MAIN OUTWARD MANIFESTATIONS


OF PLASTICISATION

5.3.1 Eft'ects of the Level of Plasticisation

The incorporation of a small proportion of plasticiser (up to about


10-17% depending on its nature) in a PVC compound leads to an
increase in modulus and tensile strength and a reduction in impact
strength (i.e. embrittlement) and in elongation at break (cf. Figs 5.3
and 5.4). This is the opposite behaviour to what might be expected,
and the phenomenon has been termed 'antiplasticisation'. Although its
manifestations are well known, the mechanism of antiplasticisation is
not yet fully understood. Some tentative explanations have been put

3'0 ~-
:;

f
80 "0
'"E 0",
2·5 E ~
Z i: Z
~ 60 2.0 g, (9
c
~
400
o
o
c -
200 :3ro
01
c
.Q
+--""'T'""-----r---r---+ O w
o 10 20 30 40
PlasticislZr conc. 010

Fig. 5.3 Some effects of low concentrations of DOP on the physical


properties of PVC (after Ghersa).l1
5 Plasticisers 183

120

110
DBS

100 DOA
u
0 90
~

-
:5OJ50
c
...en~40
... 30
u

E20
I1J

10

o 10 20 30
PlasticislZr contlZnt) phr
Fig. 5.4 Effect of some plasticisers, at low content levels, on the impact
strength of a PVC composition.

forward by various investigators in terms of the following: structural


ordering12 (not necessarily amounting to development of
crystallinity 13.14) made possible by increased freedom of movement of
the molecular chains in the presence of the relatively small amount of
plasticiser; the almost diametrically opposed suggestion that-in the
limited quantity present-the plasticiser just fills the original free
volume in the polymer and thus restricts the motion of the molecular
chains;15.16 phenomena associated with suppression of the viscoelastic
beta-relaxation process. 17-21
Because of the antiplasticisation effects (and in particular that of
embrittlement), PVC compositions containing less than about 20 phr
plasticiser are rarely encountered. It is also for this reason that
copolymers, or polymeric modifiers with homopolymer, are used
rather than low concentrations of conventional plasticisers in rigid
PVC formulations. For optimum physical properties, levels of liquid
epoxy and phosphite stabilisers, and pigment dispersion aids, should
be kept to an absolute minimum in rigid PVC formulations.
Plasticisation at a moderately higher level, typically about 20-33 phr
184 PVC Plastics-Properties, Processing, and Applications

(17-25%) with primary plasticisers, produces semi-rigid PVC com-


positions. In these, whilst the normal softening and flexibilising effects
of the plasticiser become perceptible (cf. Section 1.1.2 of Chapter 1),
the relationships between plasticiser content and degree of modifica-
tion of mechanical properties are often relatively complex and
non-linear. An early discussion of some of these effects was published
by Jacobson.14
At further increasing levels of plasticisation the PVC materials
become progressively softer, more flexible and extensible. These and
other effects are discussed in Section 5.6 below.

5.3.2 Stages of Plasticiser-Polymer Interaction

Various sequential interactions take place between a plasticiser and


PVC polymer from the time of first contact to the formation of the
ultimate, homogeneous, completely fused material: some mutual
effects can also continue for some time thereafter (see Section 5.3.3
below). The exact form of the interactions, and the steps that may be
distinguished in their progress, depend to some extent upon the nature
of the polymer/plasticiser system concerned, i.e. whether it is a paste,
or a composition undergoing dry blending, or one being melt-
compounded. However, the following summary of the main stages of
plasticisation (after Sears, Darby and Touchette22 ,23) is generally
applicable.
(i) Irreversible uptake of plasticiser into the PVC resin particles.
(ii) Absorption of the plasticiser, during which the total
resin/plasticiser volume may decrease although the resin par-
ticles swell slowly on the outside.
(iii) Diffusion of the plasticiser within the particles with little or no
volume change, but involving high activation energies. At this
stage the plasticiser is probably present as clusters of molecules
between bundles of polymer segments or molecules.
(iv) The final stage of plasticisation when the plasticiser molecules
penetrate the bundles of polymer molecules so that they are no
longer rigidly held together but behave as a polymer in its
rubbery rather than glassy state.
In some processes these four steps may not be clearly defined and
may overlap. With the usual plasticisers for PVC, of moderate
molecular weight, plasticisation can proceed through only the first two
5 Plasticisers 185

steps at room temperature. Steps (iii) and (iv) have high activation
energies, thus requiring a threshold temperature to be reached.
The plasticiser-polymer interactions during powder blending are
mentioned in Section 11.4.2(b) of Chapter 11. Interactions in the
course of melt-compounding are referred to in Section 13.4 of Chapter
13, and those during the gelation and fusion of a PVC paste are
discussed in Section 18.4 of Chapter 18.
Van Veersen & Dijkers24 compared published data from different
sources,25-29 and demonstrated that different methods involving
different processing techniques still show a comparable trend for the
solvation process of PVC when mixed with plasticisers (Table 5.1).

5.3.3 Ageing of Plasticised PVC after Processing

As has been well known for a long time,I,30 the modulus and hardness
of a plasticised PVC compound increase measurably during the period
immediately following processing. For this reason pPVC test speci-
mens are usually kept at room temperature for approximately seven
days before physical properties are determined. In the past, when
lower-molecular-weight plasticisers were used, this effect was often
attributed to plasticiser volatility. However, this is impossible since the
effect is reversible. Reheating to the processing temperature and
subsequent cooling causes the modulus and hardness to revert to their
initial values.
TABLE 5.1
Comparison of Plasticiser Absorption of PVC by DitJerent Methods

Plasticiser Dry point25 Solvation Solid-gel Maximum Relative


eC) point26 transition swelling melting
eC) temperature1:7 temperature 28 temperature 29
eC) (0C) eC)

Diethyl 56 92 88 65 58
phthalate
Dibutyl 60 97 86 75 62
phthalate
Dihexyl 72 104 75 84
phthalate
Dioctyl 80 127 118 80 84
phthalate
Di-isodecyl 86 138 132 85 94
phthalate
186 PVC Plastics-Properties, Processing, and Applications

Several workers31 •32 have followed the changes in elastic modulus


and density with storage time and temperature, and it has been
proposed that the stiffening is due to crystallisation of the PVC on
storage. This has been confirmed by DSC measurements which show
the development of endothermic peaks accompanying the stiffening. It
is suggested that the crystallites can be melted on reheating to the
processing temperature and re-form again slowly on cooling.

5.4 PRINCIPAL FUNCTIONAL PARAMETERS


OF PLASTICISER ACTION
These parameters are the main criteria on the basis of which a
plasticiser may be classified as 'good' (or otherwise). They are:
(i) compatibility and ease of mixing with the PVC polymer;
(ii) effectivity in imparting a desirable property or properties
(usually softness and flexibility) to the plasticised polymer;
(iii) permanence.
Unfortunately, some properties of a plasticiser that make for ex-
cellence in one of the above respects may also reduce performance in
another. For example, a plasticiser which by virtue of its molecular
structure and chemical make-up is easily miscible and highly com-
patible with the polymer will also, due to the same factors, normally
tend to diffuse easily through the plasticised material, with resulting
easier loss and hence not very high permanence. A good plasticiser is
therefore one which meets simultaneously all the above three main
criteria (and any others that may be relevant) to the extent necessary
in a particular application. In practice, the choice is generally a
compromise, governed by the processing technique to be used, the
end-application of the plasticised material, and economic considera-
tions. Combinations of two or more plasticisers are often used for the
best overall result in particular cases. However, it is obviously
desirable to be able to assess and compare the merits of plasticisers,
especially in relation to the above three criteria. The methods of
interest in this connection are outlined in Sections 5.4.1 to 5.4.3
below.
5.4.1 Compatibility and Miscibility
Several theoretical treatments and more practical technological tests
are available, whereby a plasticiser may be assessed for compatibility
and/or miscibility with PVC.
5 Plasticisers 187

(a) The I-l Value


This is a numerical index of the degree of interaction between polymer
and plasticiser, and can be determined from the swelling equilibria of
lightly cross-linked polymer immersed in the plasticiser. The relation-
ship used to calculate I-l from such data is
TT 113
2 P2 YI V2
I-lV2 = -In (1- V2) - V2 - .:......::....~'-
Me
where Me is the average molecular weight of the polymer segment
between cross-links, P2 is the density of the polymer, V2 is the volume
fraction of the polymer and VI is the molar volume of the solvent. The
method, developed by Gee,33 was used by Doty & Zable34 to evaluate
the miscibility of dialkyl phthalate plasticisers with PVc. Values of I-l
below O· 55 indicate high miscibility, and those above O· 55 limited
miscibility, reducing with increasing I-l value. The I-l values obtained by
Doty & Zable for some of the phthalate plasticisers were: dihexyl
phthalate -0.14; dibutyl phthalate and dioctyl phthalate -0.07;
diethyl phthalate +0.38; dilauryl phthalate + 1· 79.

(b) Solubility Parameter tJ


The Hildebrand solubility parameter tJ is related directly to a
compound's cohesive energy density, and is a constant for any given
compound. It can be shown35 ,36 that, given certain not unduly
restrictive conditions, the miscibility of a solvent and solute (or PVC
polymer and plasticiser) will in general be greater, the smaller the
difference between their solubility parameters. These values are
therefore a guide to compatibility and miscibility. 37
The solubility parameter can be calculated from the structural
formula and density of the compound involved36 ,38--40 or determined
experimentally. Table 5.2 lists the solubility parameters of some
common plasticisers, calculated by the method of Small. 38
The solubility parameter is generally a useful guide to the probable
compatibility of plasticisers with a particular polymer, providing a
number of factors are taken into consideration:
(i) the degree of hydrogen bonding power, and whether the
polymer is a proton donor or acceptor;
(ii) the degree of crystallinity of the polymer;
(iii) possible steric effects in the polymer.
The importance of the last of these, which is often disregarded, is
highlighted by the plasticising effect of pure isomers of TXP (trixylyl
188 PVC Plastics-Properties, Processing, and Applications

TABLE 5.2
Solubility Parameters of Common Plasticisers
Plasticiser Molecular weight Solubility parameter
~(calll2ml-ll2)

Dimethyl phthalate 194 10.5


Dibutyl phthalate 278 9.4
Di-isobutyl phthalate 278 9.2
Dihexyl phthalate 362 9.0
Dioctyl phthalate 390 8.85
Di-iso-octyl phthalate 390 8.85
Dinonyl phthalate 418 8.5
Di-isodecyl phthalate 446 8.5
Benzyl butyl phthalate 312 9.9
Tritolyl phosphate 326 9.8
Trixylyl phosphate 410 9.75
Dioctyl sebacate 426 8.4
Ceredor S52 (ICI) 9.3

Polyvinyl chloridea 9.7

a Solubility parameter given for PVC for comparison.

phosphate), all of which have the same calculated solubility parameter


of 9.75 1 but widely differing compatibility and plasticising effects
(Table 5.3).
The solubility parameter of the chlorinated paraffin, Ceredor S52,
suggests that it should be much more compatible than is found in
practice.

TABLE 5.3
Compatibility and Plasticising Effect of Isomers of TXP

Xylenol isomer Melting point of Plasticising effect


TXP CC)

2,6 137 Stiffest composition


2,5 78 Most incompatible
3,4 71 Not compatible
2,3 58 Borderline compatibility
3,5 40 Compatible
2,4 Liquid at room Compatible
temperature
5 Plasticisers 189

(c) Clear-Point Temperature (Solid-Gel Transition Temperature)


This has been variously termed 'clear point', 'solid-gel transition',
'fusion point', 'solution temperature' and 'apparent melting tempera-
ture', but basically it is the temperature at which a mixture of PVC
and plasticiser becomes clear or undergoes an apparent phase
change. 26-28,4t-43 It gives an indication of the compatibility and solvent
power of a plasticiser, both of which are greater the lower the
clear-point temperature. Test techniques vary considerably-from the
use of fairly concentrated suspensions to that of 4% suspensions as
described by Van Veersen & Meulenberg,27 or 5% suspensions as in
the German Standard,44 or even of virtually single particles in excess
plasticiser. 43 ,45
Although there is a variation in the values published, no doubt
because of the wide differences in experimental technique and
variations in polymer and plasticiser samples, the relative ordering of
plasticisers is fairly consistent.
Typical clear-point values for common plasticisers are shown in
Table 5.4.

(d) Interaction Parameters: Flory-Huggins (X), and 'Bigg (a)'


It has been shown that the Flory theory of melting in the presence of a
diluent could be applied to PVC-plasticiser interaction,43,46 and that
the X values correlated well with observed compatibilities.
Anagnostopoulos et al. 43 ,46 correlated the values of X with the clear
point, using the equation
1
- = 0·002226 + 0,3151«1 - X)/Vt ) (1)
Tm
where Yt is the molar volume of the plasticiser at the clear point
temperature, Tm.
Plasticisers with X values of 0·55 or above are generally regarded as
incompatible, values between 0·55 and 0·3 show moderate to poor
compatibility, and values below O· 3 good compatibility. It is interesting
to note that arranging plasticisers by X values gives a different order
from that suggested by other methods, for example solubility para-
meter, and that (particularly in the case of Ceredor S52) the value
bears more relation to the observed compatibility (Table 5.5).
Unfortunately, the molar volume of the plasticiser at the clear-point
temperature is not a readily determinable factor. Bigg45 proposed that
since 1/Tm is proportional to (1- X)/Vt in eqn (1), Vt could be
190 PVC Plastics-Properties, Processing, and Applications

TABLE 5.4
Clear-Point Temperatures of Commercial PIasticisers
Plasticiser Clear-point
temperature
CC)

Phthalates Dioctyl phthalate 117


Di-iso-octyl phthalate 116
Di-Linevol 79 phthalate 114
Di-isodecyl phthalate 139
Ditridecyl phthalate 150
Benzyl butyl phthalate 102
Low-temperature Dioctyl adipate 138
plasticisers Di-isodecyl adipate 156
Dioctyl azelate 154
Dioctyl sebacate 151
Phosphates Tritolyl phosphate 98
Trixylyl phosphate 101
Reofos 50 (Ciba-Geigy) 100
Santiciser 148 (Monsanto) 98
Trioctyl phosphate 118
Trimellitates Trioctyl trimellitate 142
Reomol LTM (Ciba-Geigy) 132
Morflex 525 (Pfizer) 147
Polymerics Crestapol 538 (Scott Bader) 138
Diolpate 150 (Briggs & Townsend) 164
Diolpate 171 137
Palamoll 644 (BASF) 155
Plastolein 9503 (Unilever-Emery) 141
Plastolein 9506 144
Plastolein 9765 151
Reopfex 430 (Ciba-Geigy) 163
Reoplex GL 123
Reoplex 903 153
Ultramoll I (Bayer) 155
Ultramoll II 165

replaced by the molecular weight, MW, of the plasticiser to give an


interaction parameter, £1', as defined in eqn (2):
(1- X) x 103
£1'= (2)
MW
The values of £1' are also shown in Table 5.5. These correlate
reasonably well with Flory-Huggins X values calculated by both
Anagnostopoulos43 ,46 and Bigg,45 as well as with observed com-
5 Plasticisers 191

TABLE 5.5
Flory-Huggins and Bigg Interaction Parameters
(X and «)

Plasticiser Xa Xb erc

Dioctyl sebacate 0.53 0.62 0.8


Ceredor S52 (ICI) 0.52 1.0
Dioctyl adipate 0.28 0.48 1.4
Trioctyl trimellitate 0.32 1.2
Benzyl butyl phthalate 0.10 0.17 2.6
Masamoll (Bayer) 0.07 2.5
Dioctyl phthalate -0.03 0.05 2.4
Dibutyl phthalate -0.05 0.04 3.4
Dctyl diphenyl phopshate -0.35 -0.02 3.3

aCalculated by Anagnostopoulos. 43 ,45


b Calculated by Bigg,45
CCalculated by Bigg45 from eqn (2).

patibility of plasticisers. Bigg and Hill47 also demonstrated that the


interaction parameter, cr, related well to the viscosity ageing charac-
teristics of PVC plastisols.

(e) Api Po Ratio


This was devised by Van Veersen & Meulenberg27 ,48,49 as a very
simplistic w~y of representing the polar-non-polar balance of a
plasticiser by a single figure. It is calculated by dividing the numbers of
C atoms in aliphatic chains in a plasticiser molecule by the number of
ester groups present. Aromatic or carboxylic C atoms are not counted.
For example, dioctyl azelate has two chains containing eight C
atoms and one chain with seven C atoms (the dibasic acid). The Api Po
ratio is therefore

(2 x 8) + 7 = 11.5
2
Similarly, the dioctyl phthalates have an Api Po ratio of 8 since
aromatic C atoms are ignored.
The Api Po ratio of a wide range of plasticisers correlates well with a
number of properties, including melting point, specific gravity, mod-
ulus, water absorption, etc.
The Api Po ratio also correlates well with the clear-point tempera-
ture, termed 'solid-gel transition temperature' by Van Veersen &
192 PVC Plastics-Properties, Processing, and Applications

Meulenberi7 (Table 5.6). In the same paper they also show clear
relationships with the data of Anagnostopoulos et aI., 43 Graham &
Darby,26 Wiirstlin & Klein,50 Jasse,51 and Doty & Zable,34 as well as
very distinct trends relating to efficiency (by 100% modulus), low-
temperature properties of compounds (Clash and Berg), extraction
resistance, volatility, and plastisol ageing characteristics. 1

(f) Loop and Roll Compatibility Tests


These are extremely simple but very useful tests for assessing the
compatibilities of plasticisers or plasticiser mixtures in a given PVC
formulation.
A test strip is cut from a sheet compression-moulded from the
compound concerned [cf. Section 17.1.3(b) of Chapter 17], and rolled
into a fairly tight ro1l27 or bent into a loop,52 which is then stored
under controlled conditions for a specified time. Absence of any
evidence of plasticiser exudation after this treatment confirms
compatibility.
One version of the loop tese2 is run as follows. A strip of the PVC
material 1 in x 6 in, and 0·05 in thick, is bent through 180° into a loop
and fastened with a strong bulldog clip at a distance of 0·75 in from
the top of the loop. The test is passed if after 24 h at 25°C and

TABLE 5.6
Parallel Trends in the Solid-Gel Transition Temperatures and
ApiPo Ratios of Some Plasticisers

Plasticiser SGTTeC) AplPo ratio


Dimethyl phthalate 93 1
Diethyl phthalate 88 2
Dibutyl phthalate 86 4
Dibutyl succinate 96 5
Dihexyl phthalate 104 6
Dibutyl adipate 98 6
Dioctyl adipate 118 8
Dibutyl sebacate 117 8
Trioctyl phosphate 121 8
Dihexyl azelate 127 9·5
Dioctyl adipate 137 10
Di-isodecyl phthalate 139 10
Dioctyl azelate 142 11·5
Dioctyl sebacate 150 12
Ditridecyl phthalate 151 13
5 Plasticisers 193

60% RH the inside of the loop bend shows no droplets of exuded


plasticiser; and is not oily or sticky.
(g) Maximum-Torque Temperature (Fusion Point) in Controlled
Mixing
This is one of the significant points on the torque-versus-time curve
obtained in the course of an assessment of plasticiser/PVC polymer
interaction in a Brabender Plasti-Corder or Plastograph [see also
Chapter 11, Section 11.4.2(b)). Early descriptions of the determination
of this value have been published by Touchette et al. 29 and
McKinney53 (see also Section 5.3.2 above).
Generally, either time to maximum torque at a fixed temperature or
temperature of maximum torque (with an increasing chamber tem-
perature at, for example, 2°C min-i) is taken as an indication of fusion
rate or relative interaction. This appears to relate reasonably well to
other methods of assessing interaction.
However, the temperature of maximum torque cannot be taken as
an indication that fusion is complete, as has been suggested by
McKinney,53 since samples of PVC removed from the chamber after
the peak has occurred may still be incompletely gelled or fused, as
shown by an acetone disintegration test. 54 An extensive, regularly
updated bibliography of papers relating to this test method is available
from Brabender. 55
5.4.2 Effectivity (Efficiency) of Plasticisers
In fundamental studies, the extent to which the glass transition
temperature (Tg) of the polymer is lowered by the introduction of a
given amount of plasticiser is frequently used as a criterion of
effectivity, since the effect can be related to the magnitude and mode
of changes in polymer chain mobility. 56 Changes in certain dynamic
mechanical properties (modulus and damping) are also used. 23 ,56
In the technological context, plasticiser effectivity is usually ex-
pressed and compared in terms of the amount of plasticiser required to
achieve a stated value of some selected property, generally of direct
practical interest. Comparisons have been made on the basis of
elongation, torsional modulus, resilience, 100% tensile modulus, and
hardness. Jones et al. 57 calculated composite or average effective
quantity values for several plasticisers from room-temperature flexibi-
lity, 100% modulus, hardness, and tensile creep determinations. The
results are given in Table 5.7.
194 PVC Plastics-Properties, Processing, and Applications

TABLE 5.7
Effectivity Quantities and Efficiencies (Relative to DOP) of Some
Common Plasticisers

Plasticiser A verage effectivity Efficiency


quantity 57 relative to
Dop1,a

Tritolyl phosphate 35·0 1-13


(ordinary commercial)
Tri-ortho-tolyl phosphate 37·2
Tri-meta-tolyl phosphate 34·4
Tri-para-tolyl phosphate 38·1
Trixylyl phosphate 36·6 1·20
Dibutyl phthalate 27·7 0·86
Di-isobutyl phthalate 29·7 1·00
Dioctyl phthalate 34·0 1·00
Di-isooctyl phthalate 35·3 1·02
Di-Alphanol-79 phthalate 0·94
Diheptyl phthalate 34·9
Dinonyl phthalate 37·5 1-10
Di-isodecyl phthalate 1·06
Ditridecyl phthalate 1-18
Dibutyl sebacate 27·5 0·72
Di-isobutyl sebacate 28·9
Dioctyl sebacate 33·7
Dicyclohexyl sebacate 33·2-
Di-iso-octyl adipate 0·84
Di-iso-octyl azelate 0·89
Paraplex G25b 39·2
Paraplex G 50b 38·7

a phr of the plasticiser required to give a compound with a 100%


modulus (at 23°C) of 1100 lbf in- 2 (7·6MPa), divided by 62·8-the
corresponding value for dioctyl phthalate.
b Rohm & Haas, USA and Europe; UK distributors Croxton & Garry
Ltd.

Many plasticiser manufacturers now include performance data on


their products not only at equal plasticiser content, but also at equal
efficiency as judged by hardness or 100% modulus. Alternatively, an
efficiency factor may be given for a plasticiser, again judged by hard-
ness or modulus and perhaps related to the performance of a common
plasticisersuch as dioctyl phthalate (DOP~f. Table 5.7.
It may be thought that high effectivity is desirable in a plasticiser
and in many cases this is so. However, on occasion the converse is
5 Plasticisers 195

true. For example, if plasticiser is appreciably cheaper than the PVC


resin, the lower its effectivity the more will be required to reach a
given modulus or hardness and hence the compound cost will be
lower. In plastisol formulations, lower plastisol viscosities and usually
better ageing characteristics may be obtained by using larger quantities
of less efficient plasticiser. (Dinonyl phthalate is particularly useful in
this type of formulation.)

5.4.3 Permanence of Plasticisers

It is obviously desirable that once the plasticiser is compounded with


the PVC resin it should be permanently retained. Its loss would not
only cause changes in the properties of the system, but may also have
undesirable external side-effects. For example, plasticised PVC floor
tiles bedded with a bitumen adhesive may blister or lift as a result of
migration of plasticiser from the tile into the adhesive. Permanence is
therefore a necessary property of a good plasticiser.
In practice there are three specific modes of loss of plasticiser from a
plasticised PVC material. These are:
(i) volatilisation, in which plasticiser is lost at a surface into air;
(ii) extraction, in which plasticiser is lost at a surface into a liquid;
(iii) migration, in which plasticiser is lost by transference into a solid
or semi-solid material in intimate surface contact with the
pPVC material.
Practical examples of applications for plasticised PVC where these
modes of loss are important are, respectively, high-temperature
cable, PVC tubing, and refrigerator gaskets.
A fourth mode of loss which is rarely encountered in practical
circumstances is exudation under pressure. 58 However, it is the critical
stage of this phenomenon which is utilised in the loop and roll
compatibility tests [see Section 5.4.1(f)).
It has been suggested by Reed59 that, for a plasticiser to be
satisfactory in general use, it should have a boiling point of at least
225°C at 4 torr, so that no appreciable volatility losses occur under
room-temperature conditions.
Studies of factors affecting loss by volatility of the plasticiser from
PVC compositions have shown that it is proportional to surface area,59
sample thickness59 time, 60,61 and increasing air flow 62 ,63 [see also
Section 24.3.2(b) on heat resistance in Chapter 24].
196 PVC Plastics-Properties, Processing, and Applications

Losses by extraction are generally more complex. In a simple case,


where the extractant, for example a 5% soap solution, merely removes
plasticiser from the surface, the process is controlled by the solid-
phase diffusion of plasticiser through the PVC compound. 61 However,
a number of extractants such as petrol, alcohol, etc., are absorbed and
swell the PVC matrix, thus increasing rates of diffusion.
Plasticiser migration is a diffusion process in which the plasticiser
from one material with a high concentration diffuses into another with
a lower concentration. A considerable amount of work has been
carried out by Knappe64--66 on diffusion of plasticisers in PVC and
their migration to other substrates. The logarithms of diffusion
coefficient values obtained by Knappe for a number of plasticisers
have been shown to decrease linearly with increasing bulk viscosities
of the plasticisers. 67

5.5 PLASTICISER TYPES, THEIR


CHARACTERISTICS AND COMMERCIAL VERSIONS

5.5.1 General Type Classification

There is no standard classification scheme for plasticisers used in PVC.


The one adopted in this chapter, which is based mainly on chemical
nature, is more convenient and systematic than most other possible
schemes. It divides the plasticisers into the following six general
groups.

(a) Phthalate plasticisers.


(b) Phosphate plasticisers.
(c) Trimellitate plasticisers.
(d) 'Low-temperature' plasticisers, i.e. those used 10 PVC com-
pounds for low-temperature applications.
(e) Polymeric plasticisers.
(f) Miscellaneous other plasticisers: (i) epoxy plasticisers; (ii)
chlorinated paraffins; (iii) monoesters; (iv) glycol esters; (v)
hydrocarbons; (vi) others.

The principal applicational features of the major types of plasticiser


are indicated in Table 5.8.
TABLE 5.8
Characteristics of the Major Types of Plasticisers

Plasticiser type Particular advantages or areas of usage Disadvantages

C4 phthalates Rapid gelation, ease of processing Very high volatility normally limits their
application
C g phthalates Used in the majority of applications not
requiring special properties
Linear phthalates Improved low-temperature properties Poorer electrical properties
DNP, DIDP Lower volatility, improved aqueous extraction Less efficient-but may be an advantage in
resistance some applications
DTDP Very low volatility Poor efficiency, expensive
BBP Rapid gelation, stain resistance
Triaryl phosphates Excellent flame retardant and gelation Poor low-temperature properties V.
properties, good resistance to microbial '1:1
attack ~
Alkyl diaryl Moderate flame retardancy with improved Expensive ~.
E:;'
phosphates low-temperature properties
Trialkyl phosphates Good low-temperature properties Poor compatibility and processing '"t:l
Trimellitates Very low volatility, excellent resistance to
aqueous extractants
Adipates Good low-temperature properties Generally poorer volatility and extraction
resistance
Azelates and sebacates Very good low-temperature properties and Expensive
permanence
AGS acid esters Good low-temperature properties---cheaper Generally poor volatility and efficiency
than other low-temperature plasticisers
Polymeric plasticisers Good extraction and migration resistance, low May exhibit poor compatibility and poor low-
volatility temperature properties, high viscosity
Epoxy esters and oils Improved heat stability, oils have reasonable Can have compatibility problems, particularly
extraction resistance on ageing
Chlorinated paraffins Low cost, reduced flammability Poor efficiency and compatibility; care needed
on stabilisation ~
-
198 PVC Plastics-Properties, Processing, and Applications

5.5.2 Plasticiser Nomenclature: Names, Synonyms, and


Abbreviations

With the very large number of plasticisers available, confusion can


sometimes arise due to the use of different synonyms for one and the
same plasticiser, or of abbreviations whose meaning may not be
directly apparent. The list in Table 5.9 may be useful as a reference in
this connection. The preferred names and abbreviations included in

TABLE 5.9
Plasticiser Names, Abbreviations, and Synonyms

Preferred chemical name" Pr.eferred Other names and abbreviations


abbreviations"

AGS esters Mixed esters of adipic, glutaric and


succinic acids also known as
nylonates
Alkyl sulphonic ester ASE n-Alkyl sulphonate
Butyl-o-acetylricinolate BAR
Benzyl butyl phthalate BBP Butyl benzyl phthalate
Butyl cyclohexyl phthalate BCHP
Butyl isodecyl phthalate BIDP
Butyl nonyl phthalate BNP
Butyl octyl phthalate BOP Butyl 2-ethylhexyl phthalate
Benzyl octyl adipate BOA Benzyl 2-ethylhexyl adipate
Dialkyl (~-~) adipate DA79A Di-Alphanolb adipate, D79A
Dialkyl (~-~) phthalate DA79P DAP, di-Alphanol b phthalate,
D 79P
Dialkyl (~-~) sebacate DA79S Di-Alphanol b sebacate, D79S
Dialkyl (~-~) azelate DA79Z Di-Alphanolb azelate
Dibutyl phthalate DBP
Dibutyl sebacate DBS
Dicapryl phthalate DCP
Dicyclohexyl phthalate DCHP
Didecyl phthalate DDP
Diethyl phthalate DEP Diethylene glycol dibenzoate
Digol benzoate DGDP
Diheptyl phthalate DHP
Dihexyl phthalate DHXP
Di-isobutyl adipate DIBA
Oi-isobutyl phthalate OIBP
Di-isodecyl adipate OIDA
Di-isodecyl phthalate DIDP
Di-Linevot< 79 phthalate D~9P
5 Plasticisers 199

TABLE 5.9-contd.

Preferred chemical name" Preferred Other names and abbreviations


abbreviations"

Di-Linevolc 911 phthalate D~llP


Di-isoheptyl phthalate DIHP
Di-isohexyl phthalate DIHXP
Di-isononyl adipate DINA
Di-isononyl phthalate DINP
Di-iso-octyl adipate DIOA
Di-iso-octyl azelate DIOZ
Di-iso-octyl phthalate DIOP
Di-iso-octyl sebacate DIOS
Di-isotridecyl phthalate DITDP DITP, ditridecyl phthalate
DTDP
Di(2-methoxyethyl)phthalate DMEP Di( ethylene glycol monomethyl
ether) phthalate
Dimethyl phthalate DMP
Dibutyl adipate DNBA
Di-n-decyl phthalate DNDP
Di-n-octyl adipate DNOA
Di-n-octyl phthalate DNOP
Dinonyl phthalate DNP Di(3,5,5-trimethylhexyl)
phthalate
Dinonyl sebacate DNS Di(3,5,5-trimethylhexyl)
sebacate
Dioctyl adipate DOA DEHA, di(2-ethylhexyl)
adipate
Dioctyl isophthalate DOIP
Dioctyl maleate DOM
Dioctyl phthalate DOP D EHP, di(2-ethylhexyl)
phthalate
Dioctyl sebacate DOS:DEHS Di(2-ethylhexyl) sebacate
Dioctyl terephthalate DOTP Di(2-ethylhexyl) terephthalate
Dioctyl azelate DOZ Di(2-ethylhexyl) azelate
Diphenyl cresyl phosphate DPCP CDP, cresyl diphenyl
DPCF phosphate; tolyl diphenyl
phosphate
Dipropylene glycol dibenzoate DPDB
Diphenyl octyl phosphate DPOP ODP, octyl diphenyl
DPOF phosphate
Diundecyl phthalate DUP
Epoxidised linseed oil ELO
Epoxidised soyabean oil ESO ESBO
Octyl decyl phthalate ODP Di-Alfold BJOphthalate
Poly(propylene adipate) PPA
Poly(propylene sebacate) PPS (continued)
200 PVC Plastics-Properties, Processing, and Applications

TABLE 5.9--contd.

Preferred chemical name a Preferred Other names and abbreviations


abbreviations a

Tributyl a-acetyl citrate TBAC


Tri(2-butoxyethyi) TBEP
phosphate
Tibutyl phosphate TBP
Tri(2-chlorethyl) phosphate TCEP
Tricresyl phosphate TCP, TCF, Tritolyl phosphate (particularly
TIP in UK)
Tri(2,3-dibromopropyl) TDBP 'Tris', T23P
phosphate
Tri(2,3-dichloropropyl) TDCP
phosphate
Triethyl o-acetylcitrate TEAC
Tri-isononyl trimellitate TINTM
Tri-iso-octyl trimellitate TIOTM
Trioctyl phosphate TOF Tri(2-ethylhexyl) phosphate
Trioctyl trimellitate TOTM Tri(2-ethylhexyl) trimellitate
Triphenyl phosphate TPF
Tetraoctyl pyromellitate TOPM Tetra(2-ethylhexyl) pyromellitate
Trixylyl phosphate TXP, TXF Trixylenyl phosphate
3,3,5-Trimethylpentane-l,4- TXIB e Texanolf isobutyrate
diol di-isobutyrate
Undecyl dodecyl phthalate UDP

a The preferred chemical names and abbreviations are those recommended in ISO
1043-1988(E) or BS 4589: 1970, or those widely accepted in the PVC industry.
b Trade name of ICI-branched chain ~-~ alcohols.
C Trade name of Shell Chemicals-predominantly linear ~-~ and ~-Cl1 alcohols.

d Trade name of Continental Oil Co.-Mixture of linear Cs and C IO alcohols.


e The same abbreviation also for 2,2,4-trimethylpentane-l,3-diol di-isobutyrate.
f Trade name of Eastman Kodak.

the list are those recommended by ISO 1043-1988 (E) or, if not
covered by this standard, by BS 4589: 1970. It should, however, be
noted that in some cases the preferred names or abbreviations differ
between the two standards: in particular, the prefix 'mixo' used by
BS 4589: 1970 to denote commercial mixtures of primary branched-
chain alcohols and ester plasticisers derived therefrom (as in for
example dimixodecyl adipate for di-iso-decyl adipate), has never been
adopted by the ISO standard (nor by anyone concerned with the use
or technology of plasticisers).
5 Plasticisers 201

Note: The following mixed-ester plasticisers are not included in


Table 5.9:
heptyl nonyl undecyl phthalate and adipate-HNUP and
HNUA (=711 P and 711 A);
hexyl octyl decyl phthalate and adipate-HXODP and
HXODA (=610 P and 610 A);
nonyl undecyl phthalate and adipate-NUP and NUA (=911
P and 911 A).
The majority of the more common monomeric plasticisers are now
marketed by most manufacturers under their chemical name or
abbreviation, usually with a trade name prefix. The same products
from different manufacturers would be expected to give similar
performance, although there might be minor differences in raw
materials, process, purity, and specification.

5.5.3 Properties of Individual Plasticiser Types, and Their Main


Effects in PVC

(a) Phthalate Plasticisers


These are compounds of the general formula
o
II
C-O-R

0::e--O-RII
o
where R is the esterifying alcohol residue. The phthalates constitute
the biggest and the most widely used single chemical group of
plasticisers, the majority being general-purpose Cg phthalates, of
which DOP is particularly important. However, numerous other
phthalates are available, with properties of interest in particular
formulations.
Phthalate plasticisers can conveniently be divided into the following
groups: lower phthalates; general-purpose phthalates; linear phtha-
lates. A comparison of the properties of PVC compounds plasticised
with 54 phr (35%) of the more important phthalates is shown in Table
5.10. Most of the alcohols used in the production of phthalates and
s

r:s
~
TABLE 5.10 Sll::".
Properties of Phthalate Plasticisers in PVC Compounds at 54 phr !;;

Name Abbrevi- Liquid properties IRHD a BSS no. Cold Vola- Extraction resistance (% mass loss) ~
.g
ation at 25°C flex tile ~

eC) loss 3-.


Visco- Density (%) Petrol Min- Olive Soap Deter- .~
sity (gmrl) eral oil gent ~
(cSt) oil '"~
~.
Dibutyl phthalate DBP 16 1·035 72 48 -19 17 23 18 19 18 15
;:,
Di-isobutyl ;::0
;:,.
phthalate DIBP 29 1·042 74 45 -5 13 20 12 12 11 14
~
Dioctyl phthalate DOP 56 0·980 78 37 -19 1·0 24 19 18 4 3 :g
Di-iso-octyl ;::.,

phthalate DIOP 53 0·981 77 39 -16 1·0 24 17 17 4 3 £


g.
Di-Alphanol 1;;
79 phthalate DA79P 48 0·983 80 36 -18 1·0 23 18 17 4 4
Dicapryl
phthalate DCP 55 0·968 79 36 -17 1·3 23 16 15 2·5 2·4
Di-n-octyl
phthalate DNOP 31 0·975 77 38 -25 0·7 25 19 23 2·1 2·0
Dinonyl phthalate DNP 80 0·970 86 26 -8 0·2 24 17 18 2·0 2·0
Oi-isononyl
phthalate DINP 0-976 80 35 -14 0-3 16 16 15 0-6 0-9
Oi-Linevol
79 phthalate O~9P 33 0-985 76 42 -26 0-8 24 21 21 6 3
Oi-Linevol
911 phthalate OL.,llP 49 0-962 87 27 -27 0-1 26 23 30 1-7 +0-8
Oi-Alfol610
phthalate (OHOP) 33 0-971 77 38 -27 0-7 21 20 19 3 1-8
Oi-Alfol 810
phthalate OOP 37 0-964 81 34 -25 0-2 20 18 18 1-2 0-8
Oi-isodecyl
phthalate DIOP 85 0-962 84 26 -16 0-1 25 22 25 0-3 0-1
Oiundecyl
phthalate OUP 54 0-947 91 20 -26 0-2 21 18 22 0 +0-2 v,
Oi-isotridecyl
~
phthalate OTDP 243 0-950 95 13 -16 0 26 25 25 +1 +0-2 El
Benzyl butyl ~.
!:;-
phthalate BBP 45 1-124 79 35 -7 3-8 12 16 18 14 8
Oi(2-meth-
'"<::l
oxyethyl)
phthalate OMEP 32 1-167 76 40 -12 10 8 14 15 16 17

a International Rubber Hardness degrees_

8
204 PVC Plastics-Properties, Processing, and Applications

other alkyl-alcohol diesters are manufactured by the 'OXO process'


or carbonylation reaction. 1

LOWER PHTHALATES
The two members of this group most significant in the PVC context
are DBP and DIBP. Originally widely used (in the early 1950s) for
their good efficiency and rapid gelation in pPVC, they are now
restricted to compositions where these properties are particularly
important, whilst their high volatility and poor aqueous extraction
resistance can be tolerated. Otherwise they have been replaced by
phthalates of higher molecular weight. Like other high-volatility
plasticisers, DBP and DIBP can adversely affect the growth of plants. 1
It is particularly important, therefore, that they should not be used in
compositions for films, hoses, glazing strips, etc., for glasshouses, or
other horticultural applications.

GENERAL-PURPOSE PHTHALATES
The Cs phthalates are the largest class of plasticisers in use today. The
most important are DOP (based on 2-ethylhexanol), and DIOP (based
on iso-octanol). DA79P, which was based on mixed ~, Cs and C9
branched-chain alchols is no longer manufactured. DOP, DIOP and
DA79P have very similar properties and are generally regarded as
interchangeable, the choice being dependent on the current supply
position.
More recently, DINP, di-isononyl phthalate, based predominantly
on dimethyl-1-heptanols, has become available, giving generally lower
volatilities and lower plastisol viscosities than the Cs phthalates. The
other ~ phthalate, DNP, based on 3,5,5-trimethylheptanol, is mark-
edly less efficient and finds particular application where low plastisol
viscosities are desirable--especially for semi-rigid dip coatings, slush
mouldings, and rotational castings (cf. Section 5.4.2).

LINEAR PHTHALATES
One of the more important developments in the use of phthalates as
plasticisers was the introduction and extensive use of linear or
predominantly linear dialkyl phthalates to improve low-temperature
performance. Since these products are available at little or no
premium over the general-purpose Cs phthalates, they have replaced a
large proportion of the more expensive diester market. The original
linear alcohols were by-products from the manufacture of detergent
5 Plasticisers 205

alcohols by fat hydrogenation, e.g. straight-chain C6-C lO alcohols from


coconut oil. The majority are now manufactured from synthetic
hydrocarbon feedstocks. 1
Linear alcohols may of course be used in the manufacture of other
non-phthalate esters. It is however in phthalates that they have had
the most impact.
In addition to their improved low-temperature properties, linear
phthalates have considerably lower volatile losses than their branched-
chain counterparts at elevated temperatures: the differences can be
particularly pronounced on prolonged processing at temperatures of
190°C and above, l and are also reflected in loss of low-temperature
flexibility on ageing at 90°C (see Fig. 5.5).
However, compounds plasticised with linear phthalates do exhibit
poorer electrical properties (i.e. lower volume resistivities), which are
undesirable in cable insulation compositions.

DOP/DOA
to 50:50
DOP/DOA

Ij 60:40

Ij
f
-10
DOP/DOA
70:30
U
e....
~
1i
'j( (I
f,//
:l DOP
!
.a
..
-20

1",/
I!
Q.
E
.!
~
610P
°

---.--
..J
_ _ _ 810P
t -3D
2 3 4 5 6
- Time [days]

Fig. 5.5 Change of low-temperature flexibility of pPVC compounds on


ageing at 90°C. 1 The compounds were formulated to give equal Clash & Berg
temperatures (341Okgfcm- 2 ) of -30°C.
206 PVC Plastics-Properties, Processing, and Applications

HIGHER PHTHALATES
In general, these are less efficient than DOP and other Cs phthalates,
but also less volatile and more resistant to aqueous extraction: see the
relevant data for DIDP, DTDP and DUP in Table 5.10, in comparison
with those for DOP, DIOP and DNOP. Before the advent of
trimellitate plasticisers, DTDP (di-isotridecyl phthalate) was widely
used in applications requiring low volatility, e.g. high-temperature
cable coverings, low-fogging leathercloth. DUP (diundecyl phthalate)
and UDP (undecyl dodecyl phthalate) are also used for low-volatility
applications, sometimes in blends with a trimellitate, but more
commonly in North America than in Europe.

MISCELLANEOUS PHTHALATES
Benzyl butyl phthalate is widely used where ease and rapidity of fusion
of the pPVC composition is important. Due to these properties it
allows regular production rates at lower temperatures or increased
rates at normal processing temperatures. It also imparts good resis-
tance to staining to pPVC films and sheeting, and hence is frequently
used in clear wear-layer compositions for vinyl flooring.
Dioctyl terephthalate (DOTP), originally introduced commercially
in the USA by Eastman Kodak, is claimed to offer reduced volatility
and generally better permanence, as well as greater lacquer mar
resistance, in comparison with DOP.
Modified phthalates, such as Hexaplas OPN (ICI), are also available
from some companies. These have similar low-temperature properties
to the straight-chain phthalates, but greater volatility. However, their
plastisol rheology and storage stability are superior, and they are
claimed to promote volume cost savings over most other phthalates.

(b) Phosphate Plasticisers


RJ
I
o
I
R 2 -O-P=O
I
o
I
R3
[R = alkyl, aryl, or substituted aryl group]
Phosphate plasticisers may be divided into four classes: triaryl phos-
phates; trialkyl phosphates; mixed alkyl aryl phosphates; and halogen-
ated alkyl phosphates.
5 Plasticisers 207

The triaryl phosphates as a group are by far the most important,


accounting for some 80-90% of the total phosphate plasticiser usage in
PVC. A detailed comparison of the phosphate plasticisers has been
published by Buszard. 68

TRIARYL PHOSPHATES
The original triaryl phosphate plasticisers were TIP (tritolyl or
tricresyl phosphate) and TXP (trixylyl phosphate). However, in the
mid-1960s, the shortage and variable quality of the coal-tar cresols and
xylenols, from which they were derived, led to the increasing
popularity of cresol diphenyl phosphate, and later to the development
of the Re%s range of synthetic triaryl phosphates based on isopropy-
lated phenol and introduced by Geigy (now Ciba-Geigy) in 1968.
The isopropylated phenyl phosphates are applicational equivalents
to the older TIP (TCP) , TXP and COP, but offer more consistent
quality, much improved light-fastness, better colour, lower odour and
lower toxicity. These products are now available in Europe and
elsewhere from Ciba-Geigy as Re%s 95, Re%s 65, and Re%s 50,
and from Albright and Wilson Ltd as Pliabrac 524, Pliabrac 521, and
Pliabrac 519. They are also available in the United States from FMC
as Kronitex 100 and Kronitex 50.
A comparison of these phosphates is shown in Table 5.11. As a

TABLE 5.11
Comparative Perfonnance of Triaryl Phosphates
(Formulation: PVC 100, plasticiser 54, white lead paste 4, calcium stearate 1.)

Re%s TXP Re%s TTP Re%s


95 65 50
Viscosity at 25°C, cSt 95 95 60 60 50
Density at 25°C, g ml- I 1·131 1·134 1·161 1·158 1·170
IRHD, Shore A 87 87 85 82 83
BS softness no. 25 24 27 31 30
Cold-flex temperature
(BS 2782 method
104B),OC +5 +8 +4 +6 +3
Volatile loss, % 0·5 0·3 0·5 0·6 1·0
Extraction resistance
weight loss, %
Petrol 15 15 15 15 15
Mineral oil 11 11 13 11 13
Olive oil 11 11 12 12 13
Soap 9 9 11 11 12
208 PVC Plastics-Properties, Processing, and Applications

group, triaryl phosphates offer excellent flame retardancy, good


gelation properties, very good high-frequency welding characteristics,
good microbial resistance, high extender tolerance and excellent
compatibility even at high humidities. They do however suffer from
poor low-temperature properties but, since they are seldom used as
sole plasticisers, this may be offset by a careful selection of other
plasticisers.
The superior flame-retardant properties of triaryl phosphates in
comparison with the alkyl diaryl and the trialkyl phosphates are
illustrated in Fig. 5.6.

Oxygen index (%)


46

Fig. 5.6 Effect of phosphate plasticisers at various concentrations on the


Oxygen Index of pPVC. 69
5 Plasticisers 209

TRIALKYL PHOSPHATES
Trioctyl phosphate (e.g. Disflamoll TOF; Mobay Chemical Corp.,
USA) is the most popular of this group for PVC formulations (e.g. for
industrial-fabric coatings; wall-coverings), but in general trialkyl
phosphates are relatively little used in PVC today. They have poor
compatibility and, although somewhat flame-retardant, they offer only
moderate advantage over phthalates in this respect. However, they do
confer excellent low-temperature properties, this being the main
reason for their use in those PVC formulations in which they are
incorporated.
MIXED ALKYL ARYL PHOSPHATES
Octyl diphenyl phosphate (e.g. Santicizer 141-Monsanto; Disflamoll
DPO-Mobay Chemical Corp.) and isodecyl diphenyl phosphate (e.g.
Santicizer 148) are two mixed alkyl aryl phosphates available commer-
cially. Three other commercial alkyl diaryl phosphates are Phosflex
362, 370 and 390 (Stauffer Chemical Co., USA). The properties
imparted to pPVC by these mixed-ester phosphate plasticisers are
intermediate between those conferred by trialkyl and triaryl phos-
phates, thus offering a compromise in flame retardance and low-
temperature properties. The physical and flammability properties
imparted by octyl diphenyl phosphate and isodecyl diphenyl phosphate
are comparable with those produced by a blend of 60% triaryl
phosphate and 40% dioctyl adipate (Table 5.12).
HALOGENATED ALKYL PHOSPHATES
These additives, for example tri(2-chloroethyl) phosphate (TCEP) and
tri(monochloropropyl) phosphate, are effective flame retardants but
exhibit poor compatibility with PVC. They are more of interest as
flame retardants in other polymers (e.g. polyurethanes), and are only
occasionally used as supplementary flame-retardant additives in PVc.
(c) Trimellitate Plasticisers
o
II
C-O-R

R-O-C
II
U C-O-R
II
o 0
Esters based on trimellitic anhydride have become very popular
primary plasticisers for PVC compounds, for use at high temperatures
N
0
-
TABLE 5.12
Performance of Dift'erent Phosphate Plasticiser Types in PVC Compounds at 54 phr
"'tl
Re%s 50 TOF Santicizer Santicizer Phosphate DOP ri
(isopropylated (trioctyl 141 148 blend (dioctyl "'tl
phenyl phosphate) (octyl (isodecyl (60% Re%s 50/ phthalate) [
::to
phosphate) diphenyl diphenyl 40% DOA) f:l
phosphate) phosphate)
.,~
{5
IRHD 83 78 76 78 76 78
BS softness no. 30 38 41 37 41 37 '"3-.
Cold-flex temperature ~
"'tl
(BS 2782 method 2l
l04B),OC 3 -50 -19 -17 -18 -19 lil
Volatile loss at 82°C, % 1·0 1·7 1·7 0·7 2·0 1·1 !:l
~.
Extraction resistance
weight loss, % ;:s
Petrol 15 17 22 20 20 24
""
""-
~
Mineral oil 13 16 21 17 17 19 :g
Olive oil 13 18 21 16 18 18
Soap 12 12 19 17 12 4 e
5'
Oxygen index, % 34 27 29 29 29 24 ~
5 Plasticisers 211

or for applications requiring excellent resistance to aqueous extrac-


tants, e.g. washing machine parts. Table 5.13 gives a comparison of
the properties of various trimellitate plasticisers available
commercially.
Since trimellitates are normally incorporated into pvc formulations
for high-temperature performance, most plasticiser manufacturers
supply them containing an antioxidant. Whether any additional
antioxidant is required will depend on the particular grade selected
and the ageing conditions to be encountered.
Branched-chain trimellitates, such as Reomol ATM (Ciba-Geigy),
generally give better electrical properties, which are required for some
cable applications, whilst straight-chain trimellitates, as with phtha-
lates, give better low-temperature properties.

(d) Aliphatic Diester Plasticisers


The aliphatic diesters are generally known as the low-temperature
plasticisers since this is their prime advantage. They are secondary
plasticisers, made from a number of linear dibasic acids with the
general structural formula ROOQCH2)n COOR.
The most popular dibasic acids are adipic (n = 4), azelaic (n = 7)
and sebacic acid (n = 8). A mixture of acids, known as AGS or 'nylon
acids' since they are a by-product of nylon production, and consisting
of adipic, glutaric and succinic acids, is also popular. Esters have also
been made from succinic acid (n = 2), e.g. Reomol SD, and glutaric
acid (n = 3), e.g. Plasthall DIDG (C. P. Hall), when they are
commercially attractive.
The majority of aliphatic diesters are manufactured from branched-
chain alcohols, such as iso-octanol, 2-ethylhexanol or isodecanol, the
latter being popular with the lower-molecular-weight acids. Linear
alcohols are generally avoided since their esters tend to crystallise at
relatively high temperatures, thus giving storage and handling
difficulties.
A comparison of the performance in PVC of the more important
linear diesters is given in Table 5.14.

(e) Polymeric plasticisers


The majority of commercial polymeric plasticisers are saturated
polyesters resulting from the reaction of a diol with a dicarboxylic
acid. They differ basically from monomeric plasticisers such as DOP in
that their molecular structure contains repeat units and their molecular
N
N
-
."
TABLE 5.13 ~
Properties of Trimellitate Plasticisers in PVC Compounds at 54 phr
[
Plasticiser Viscosity Density IRHD BSS Clash Volatile Extraction resistance (% mass loss) ~.
at 25°C at 25°C no. and loss
(cSt) (gmrl) Berg (%) Petrol Mineral Olive Soap Deter-
eC) oil oil gent
.g~
::1-.
.,'"
Tri-Alphanol 79 ~
trimellitate 181 0·995 84 30 -10 0·1 21 14 14 +0·1 +0·3 ::p
Tri-Linevol 79 c(")
trimellitate 107 0·993 83 30 -15 0·1 21 14 15 +0·2 +0·3 ~
Tri-iso-octyl ~.
trimellitate 250 0·988 91 20 -7 0·2 22 19 14 +0·4 +0·7 ;:,
;:,
Tri(2-ethylhexyl) ;:,..
trimellitate 205 0·985 88 24 -10 0·2 22 ~
12 14 +0·4 +0·8
Tri-Alfol 810 ~
trimellitate 92·5 0·971 93 17 -20 0·1 26 26 22 +1 +0·8 £

i:l
TABLE 5.14
Properties of Linear Diester Plasticisers in PVC Compounds at 54 pbr

Plasticisers Viscosity Density IRHD BSS Clash Volatile Extraction (%)


at 25°C at 25°C no. and loss
(cSt) (gmrl) Berg (%) Petrol Mineral Olive Soap Deter-
("C) oil oil gent

Di-isodecyl succinate 22·4 0·919 85 26 -38 1·8 25 24 24 4·5 1·9 v.


Iso-octyl ester ~
of AGS acids 13·5 0·928 79 37 -47 7·5 26 23 24 15 8 ~
Isodecyl ester i';.
1;;.
of AGS acids 23·3 0·917 86 25 -38 1·0 23 23 24 3·5 1
Dioctyl adipate 12·3 0·924 74 46 -45 2·4 26 22 26 7·5 4·5
'"t:!
Di-iso-octyl adipate 13·5 0·926 81 33 -48 1·7 25 21 21 8 4
Di-isodecyl adipate 22 0·912 85 27 -39 0·4 27 26 25 1·3 0·8
Benzyl octyl adipate 14·2 0·916 74 45 -36 3·2 23 23 23 17 7·5
Di-iso-octyl azelate 18 0·913 78 37 -47 0·6 24 22 25 1·4 1·0
Dibutyl sebacate 8·7 0·933 72 48 -52 9 26 26 27 18 6
Dioctyl sebacate 19·5 0·911 80 35 -51 0·5 24 24 25 0·4 0
Di-iso-octyl sebacate 22·4 0·911 80 34 -46 0·4 26 27 26 1 1

tv
V>
-
214 PVC Plastics-Properties, Processing, and Applications

weight is higher and can be varied. It is normal practice to include a


third reactant in a polyester to 'modify' or 'endstop' the product. This
is commonly either a monohydric alcohol or a monocarboxylic acid,
although isocyanates and even diazomethane have been used to
modify terminal hydroxyl and acid groups.
Thus there are three possible general structures for polymeric
plasticisers:

H-oiR-O-C-RI-C-otH non-terminated
II II
o 0 n

RII-c-iR-O-C-RI_C-iR-O-C-RII acid-terminated
II II II II
o 0 0 n 0

RII-O-C-RI_C-iR-O-C-RI_C-iRII alcohol-
II II II" terminated
o 0 0 0 n

There are therefore two main parameters which can be varied in


polymeric plasticisers-their constituents, including chain stoppers,
and their degree of polymerisation, i.e. molecular weight-and since
both these factors are important in determining the resultant pro-
perties, it can be seen that there is considerable scope for variation. It
also follows that polymeric plasticisers are not simple, readily de-
finable chemicals, as are the majority of monomeric plasticisers, and
hence they are invariably marketed under trade names rather than the
chemical names which indicate their constitution.
The most common raw materials are as follows:

dicarboxylic acids-adipic, phthalic, azelaic, sebacic;


diols-l,2-propanediol, 1,3-butanediol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol, diethylene glycol;
monocarboxylic acids-acetic, caproic, caprylic, lauric,
myristic, palmitic, stearic, pelargonic, benzoic;
monohydric alcohols-iso-octanol, 2 ethylhexanol, isodecanol,
Linevol 79 and 911 (Shell Chemicals)
The effect of molecular weight on the properties of a non-
ends topped polypropylene adipate has been demonstrated by Moseley
& DawkinslO-Table 5.15. From these results it can be seen that
5 Plasticisers 215

TABLE 5.15
The Effect of Molecular Weight on the Properties of Polypropylene
Adipate

Molecular weight 2000 3000 4000 9000


Viscosity at 25°C, P 150 250 350 850
Hydroxyl value, mg KOH g-l 55 45 30 25
Compound properties
BS softness no. 27 24 23 20
Cold-flex temperature, °C -1·7 -1·5 +2 +5·8
Volatile loss, % 3·2 2·7 2·4 2·3
Tensile strength, MN m- 2 17·8 19·8 19·9 20·8
Extraction loss, %
Hexane 0·4 0·3 0·1 0·1
Mineral oil 1·0 0·4 0·1 0
Soap solution (1 %) 9·0 6·8 4·7 3·8

increasing molecular weight gives advantages of improved permanence


and lower volatility, but disadvantages. of increasing viscosity, lower
plasticising efficiency and poorer low-temperature properties. In addi-
tion, higher-molecular-weight products are more difficult to process
and often exhibit reduced compatibility with pvc.
Moseley & Dawkins also demonstrated the effect of varying the
reactants as well as molecular weight in typical commercially available
polymeric plasticisers (Table 5.16).
Endstopping will reduce the liquid viscosity of a polymeric plas-
ticiser of given molecular weight by reducing the hydrogen-bonding
capability of the terminal hydroxyl or acid groups. Similarly, this will
increase the high humidity compatibility and improve the extraction
resistance to aqueous media. It does, however, have an adverse effect
on the extraction resistance to non-polar media such as oils and fats.
This is demonstrated in Table 5.16 by comparing polymeric plasticisers
4 and 5, which are non-endstopped, with 1 and 2, which are
alcohol-endstopped.
Mixed diols or dicarboxylic acids are frequently used to obtain a
desired balance of properties, as shown by examples 6 and 7. Example
8 may be regarded as a complex ester rather than a true polymeric
since essentially n = 1 and there are no repeat units.
An interesting, fairly recent development in polymeric plasticisers is
the use of a lactone in place of a proportion of the dibasic acid and
diol. 1 These modified polyester plasticisers have the idealised
tv
0 -.
TABLE 5.16
The Etrect of Composition on the Properties of Commercially Available Polymeric Plasticisers
-
1 2 3 4 5 6 7 8 9 10
"1::1
Acid Adipic Adipic Adipic Adipic Adipic Adipic/ Adipic/ Phthalic Phthalic mop
phthalic phthalic anhydride anhydride ~
anhydride anhydride ~
El
:::-.
Diola 1,2-Pr 1,3-Bu Ne 1,3-Bu 1,2-Pr 1,2-Pr 1,2-Pr Dieth 1,2-Pr
!:l
glycol glycol glycol glycol glycol glycol glycol glycol glycol
Chain-stopper Alcohol Alcohol Alcohol None None Alcohol Alcohol Alcohol Alcohol ~
~
Viscosity at 25°C, ~

cP 2300 3400 5500 22000 24000 800 32000 700 900 72 ....
'"
BS softness no. 32 34 30 25 24 36 29 33 34 45 ~.
Cold flex, °C -6 -7·5 0 -0·5 -1·5 -5 2 -2 1·5 -20
Tensile strength, ~
kgfcm- 2 205 211 198 210 202 210 223 191 210 147 '"~
Volatile loss, % 4·1 3·7 3·9 2·9 3·2 4·0 2·9 6·7 12·0 22·4 ""
~.
Volume resistance,
;:s
Qcm- I 1 x 1012 8 X 1011 6 X 1013 1 X 1012 5 X 1012 2 X 1013 5 X 1013 3 X 1012 6 X 1013 2 X 1013 '"
I:>..
Extraction loss, % ~
Hexane 4·2 3·9 2·7 0·7 0·7 5·7 2·8 10·1 15·1 35·0 ~
Mineral oil 3·9 3·1 1·8 0·1 0·7 5·5 3·4 6·0 4·3 16·0 [
Water 0·2 0·3 0·1 2·1 2·3 0·6 0·6 1·2 0·3 0
g.
~
Soap solution
1% 6·1 5·4 4·7 3·7 4·8 9·3 6·9 11·6 11·4 13·0
Humidity (com- Moder- Moder- Moder-
patibility) ate ate ate Poor Poor Very good Moderate Excellent Very good Excellent

a Abbreviations: Pr, propylene; Bu, butylene; Ne, neopentyl; Diet, diethylene.


5 Plasticisers 217

structure:

The commercially available examples of this type of structure, based


on caprolactone, give plasticisers which have excellent compatibility
with PVC, and extraction and migration-resistant properties which are
comparable with those of the medium-molecular-weight polyesters
endstopped with an alcohol. The caprolactone-based plasticisers,
however, have lower viscosities and much faster gelation properties.
They are therefore of particular interest in plastisols.
Most manufacturers of polymeric plasticisers offer a range of
products, from the low-molecular-weight complex ester types, such as
Uraplast W2 (Urachem) and Reoplex GL (Ciba-Geigy), to the
high-molecular-weight, harder-to-process products, such as Diolpate
150 (Briggs and Townsend), Reoplex 430 and Plastolein 9789
(Unilever-Emery).
A further group of products which may be mentioned under the
classification of polymeric plasticisers is the 'solid polymerics'. These
are much higher-molecular-weight elastomeric polymers which may be
more truly regarded as blending resins (polymeric modifiers) rather
than as plasticisers (see Chapter 8).
However, they have recently penetrated areas previously considered
to be the preserve of more conventional polymeric plasticisers and
blending grades of nitrile rubber by offering improved permanence in
addition to other advantageous properties such as improved abrasion
resistance and traction in shoe soles, etc. Typical of these products are
Elvaloy (Du Pont) ethylene interpolymer resins; polyurethane elas-
tomers such as Baymod PU* (Bayer, and Mobay in the USA) and
Durelast 100 (Briggs and Townsend); appropriate grades of Baymond
EVA; and Uresin B (Hoechst), a carbamate resin for blending with
PVC.

* Formerly Ultramoll PU.


218 PVC Plastics-Properties, Processing, and Applications

(f) Miscellaneous Plasticisers

EPOXY PLASTICISERS
The characteristic functional group of these compounds is the epoxy
group (oxirane ring)
o
1\
-C-C-

They are usually derived from the reaction of unsaturated compounds


with peracids. The unsaturated compounds used are generally natu-
rally occurring oils or the alkyl esters of natural unsaturated fatty
acids, although some 'synthetic' trigy1cerides and esters are manufac-
tured. The resulting commercial epoxy products are primary or
secondary plasticisers for PVC and also exhibit an effective stabilising
action (see also Chapters 2 and 4).
The epoxy oils are generally derived from soyabean oil (the most
popular) and linseed oil, both of which are triglycerides of unsaturated
fatty acids. They exhibit a good plasticising and stabilising action, and,
as suggested by molecular weights in excess of 900, their extraction
and migration resistance are comparable with many of the lower-
molecular-weight polymeric plasticisers. A disadvantage of the purer
epoxy oils is their high viscosity and their tendency to crystallise out at
lower temperatures, which can lead to storage difficulties. However,
any precipitation rapidly redissolves on heating to 30-40°C for a short
period, with no detrimental effect on the plasticising or stabilising
properties.
Alkyl epoxy esters are generally manufactured from tall-oil acids (a
by-product of paper manufacture), which contain a significant propor-
tion of unsaturated oleic and linoleic acids, or from purified oleic acid.
The most popular are the butyl and,2-ethylhexyl esters of these acids,
which are then epoxidised. The epoxy esters are characterised by their
good plasticising and low-temperature properties, as well as their
stabilising action. The compatibility of epoxy plasticisers with PVC is
surprisingly good in comparison with the non-epoxidised equivalents.
However, once the epoxy groupings are destroyed by undergoing a
stabilising reaction, their compatibility is greatly reduced. Care should
therefore be taken to ensure that the appropriate ultimate com-
patibility limits are not exceeded.
5 Plasticisers 219

Typical commercial products are:


Epoxidised soyabean oil: Edenol D81 (Henkel)
Lankroftex GE (Lankro Chemicals)
Paraplex G62 (Rohm & Haas)
Reoplast 39 (Ciba-Geigy)
Epoxy-alkyl esters: Edenol D72, B74, B35, HS235
Lankroftex ED3, ED6
Monoplex S-71 (Rohm & Haas)
Reoplast 38, 42

CHLORINATED PARAFFINS AND OLEFINS


The effects of chlorinated paraffins, when used within their com-
patibility limits in PVC compositions, are comparable with those of the
octylphthalates. The modern versions-produced by chlorination of
straight-chain liquid paraffin feedstocks-no longer suffer from the
poor colour and thermal stability problems which were experienced in
the early days.
Modern chlorinated paraffin plasticisers are exemplified by the
well-known Clereclor (ICI) range. Withing this range, two grades
(Cereclor S52 and S45) are specifically recommended for PVC
applications. These grades can be used as sole plasticisers in relatively
hard products, such as flooring compounds, but they are more usually
employed as partial replacements for phthalate or phosphate primary
plasticisers. Their use in PVC compounds gives significant savings in
raw material costs. The properties of the finished compound are not
impaired and the flame retardance may be improved when Ceredor is
included in a vinyl composition.
The important properties of these Ceredor grades are given in Table
5.17. Ceredor S52 is the general-purpose grade, suitable for most
applications, while the 45% chlorinate, Ceredor S45, was specifically
developed for use in PVC plastisols, where its lower viscosity is an
advantage, and for compounds having good low-temperature pro-
perties. The slightly higher volatility of Ceredor S45 still allows
compounds containing this grade to pass most international ageing loss
specifications.
The use of chlorinated paraffin secondary plasticisers is straightfor-
ward and, provided that compatibility limits are not exceeded, no
exudation occurs. The compatibility limit is of the order of 25-30 phr
in compounds of BS softness 40 (Shore A 75) based on octyl
phthalates.
220 PVC Plastics-Properties, Processing, and Applications

TABLE 5.17
Properties of tbe Cereclor Grades

Cereclor S45 Cereclor S52


Chlorine content, % 43-45 50-52
Average chain length C I5 C I5
Density, gml- 1 at 25°C 1·16 1·25
Viscosity, Pa s 0·15-0·25 1-2
Volatility, % weight loss on
heating 4 h at 180°C 2·8 1·4
Thermal stability, % HCl after
4h at 175°C 0·06-0·1 0·07-0·12
Toxicity Very low Very low

It is recommended, however, to refer always to the chlorinated


paraffin manufacturer's literature when reformulating. Normally PVC
compounds are reformulated to the same hardness. The lower
plasticising efficiency of the chlorinated paraffins and their higher
density mean, however, that phthalates are not replaced part for part.
Typically, 1·5 phr of Ceredor have to be included for each part of the
replaced octyl phthalate. Table 5.18 shows that the physical properties
are relatively unaffected in compounds reformulated to contain either
Ceredor S45 or S52.
In addition to leI, chlorinated products are also available from,
amongst others, the following manufacturers: Hoechst, Hiils, Dynamit
Nobel, and Caffaro in Europe; Diamond Shamrock, Keil, Dover, and
Witco (Pearsall Div.) in the USA; and Toya Soda, Asahi Denka, and
Ajinomoto in Japan.
The Witco Pearsall Div. Flexchlor products exemplify chlorinated
olefins, offered as alternatives to chlorinated paraffins. Derived from
straight-chain alpha-ole fins , they are claimed to be more stable to
dehydrochlorination in processing at elevated temperatures. Several
grades are available, with different viscosities and chlorine contents.

MONOESTERS
This group comprises a wide number of different plasticisers, the
majority of which are only of interest in certain specialist formulations.
Examples of these are butyl oleate, phenoxyethyl oleate and tetrahy-
drofurfuryl oleate. They are claimed to be good low-temperature
secondary plasticisers with advantages in some plastisol applications.
Two sulphonic acid esters may be included as a sub-group under the
TABLE 5.18
Properties of Compounds4 Containing Cereclor

Plasticiser
DIOP 54 38 35
DIDP 62 51 48
Reofos 95 66 30
Cereclor S45 25 15 35
Cereclor S52 30 20
v.
BS Softness no. 40 40 40 40 40 40 40 40 "tl
Shore A 75 75 75 75 75 75 75 75 ~
Tensile strength, ~.
c;.
MNm- 2 17·3 17·8 17.2 15·6 17·6 16·2 20·1 19·3
Elongation at break, % 300 315 320 315 325 330 245 290 '"<:!
Cold flex, DC -16 -20 -16 -16 -18 -16 -6 -10
Ageing loss (24 h
at lOODq, % 0·75 0·95 0·85 0·36 0·74 0·52 0·15 0·6
Volume resistivity,
Qcm x 1013 2 2 2 0·6 0·5 0·6 6 3
aFormulated for constant BS softness by varying the plasticisers (amounts given in phr) in otherwise
the same formulation.

~
-
222 PVC Plastics-Properties, Processing, and Applications

present heading: Mesamoll (an alkyl sulphonic acid ester) and the
newer Mesamoll II (an alkyl sulphonic acid/phenol ester), both
manufactured by Bayer. Mesamoll has for some time been popular in
Germany as a good primary plasticiser resembling the general-purpose
phthalates in its effects.
GLYCOL AND POLYGLYCOL ESTERS
Like most of the monoesters, the glycol esters are also of relatively
limited interest and application. They include aromatic esters of
glycol, such as diethylene glycol dibenzoate (BenzoJlex 2-45; Velsicol
Chemical Corp.), propylene glycol dibenzoate (BenzoJlex 284), and
dipropylene glycol dibenzoate (BenzoJlex 9-88): these are popular in
the United States. They are rapidly solvating plasticisers, which also
offer low fusion temperatures and good resistance to staining and oil
and solvent extraction (compared with many other monomeric plas-
ticisers). Polypropylene glycol benzoate (BenzoJlex 4(0) is offered as a
low-volatility, high-solvating, moderate-cost alternative to alkyl benzyl
phthalates.
The unsaturated acrylic and methacrylic esters of glycols, such as
diethylene glycol dimethacrylate, may also be included in this general
group. These esters, together with other cross-linkable plasticising
additives, are of interest for the speciality uses discussed in Section
22.4.2 of Chapter 22. Other applications include addition to plastisols
and rigisols as adhesion promoters for coatings, e.g. on steel.
OTHER MISCELLANEOUS PLASTICISERS
Citrate plasticisers, such as triethyl citrate (CitroJlex C-2; Morflex
Chemical Co.), acetyltriethyl citrate (CitroJlex A-2), tri-n-butyl citrate
(CitroJlex C-4) and acetyl-n-butyl citrate (CitroJlex A-4) are primary
plasticisers with good low-temperature properties and a low order of
toxicity, but not particularly good resistance to extraction by aqueous
extractants, especially soapy water. They are of particular interest in
products for food contact and medical use: a discussion of the
application of these plasticisers in medical-grade PVC has been
published by Hull & Mathur. 71
A plasticiser of international importance not readily classifiable into
the previous categories is Texanol isobutyrate (KodaJlex TX/B),
manufactured by Eastman Chemicals Inc. This product is the di-
isobutyrate of 2,2,4-trimethyl-l,3-pentanediol. It is of a particular
interest in non-stain flooring and plastisol applications such as rota-
tional casting, where low plastisol viscosities and good viscosity
5 Plasticisers 223

stability are required. The high volatility of TXIB limits its use in some
applications. Other esters of Texanol (e.g. Nuoplaz 1406; Tenneco)
are available but are much less popular.

HYDROCARBON EXTENDERS
A variety of hydrocarbon extenders and oils are available from a
number of manufacturers, including:
Dutrex (Shell);
Enerflex (BP);
Electrofine (D'Electro-Chemie);
Lipinol (Hiils);
Mobisol (Mobil);
Ravolen (Manchester Oil);
Kenplast (Kenrich Petrochemicals, USA).
These oils are used as cheap extenders in certain PVC compounds and
plastisols. They are true extenders and have very limited compatibility
with PVC.

5.5.4 Transport, Handling, and Storage of Plasticisers

This topic is considered in Section 11.2.1(a) of Chapter 11. However,


it may be additionally mentioned here that storage tanks and transfer
lines for plasticisers can be of mild- or stainless-steel construction and
suitable epoxy finishes can be applied if necessary. Cast-iron or
stainless-steel gear pumps are normally preferred, although centrifugal
pumps can be used for low-viscosity or preheated plasticisers. Positive
shut-off valves such as ball valves or plug valves should be used.
Care should be taken in the selection of polymeric and elastomeric
materials for use in contact with plasticisers, e.g. in hoses, flexible
couplings, O-rings and seals. Table 5.19 summarises the effect of liquid
plasticisers on many materials from which such products are made.
Note: In this context the term 'compatibility' is often employed in
the sense of suitability for use (satisfactory resistance on
contact) with the liquid in question. As can be seen, in this
particular application of the term its meaning is almost
directly opposite to that discussed in Section 5.4.1 above.
If any doubt exists regarding the suitability of a material for contact
with plasticisers, advice should be sought from the manufacturer of the
material or the plasticiser (and preferably both).
224 PVC Plastics-Properties, Processing, and Applications

TABLE 5.19
Suitability of Polymeric Materials for Use as
Flexible Seals, etc., in Contact with Plasticisers

Material Rating a
Butyl rubber 1
Ethylene propylene rubber 2
Chlorosulphonated polyethylene 4
Natural rubber 4
Nitrile rubber 3
Polyamide 1
Polychloroprene 4
Polyethylene 2
Polypropylene 2
Polytetrafiuoroethylene 1
Polyurethane 3
Silicone 2
Viton 2
a Rating: 1 = generally recommended; 2 =
acceptable; 3 = possibly suitable under certain
conditions; 4 = unsuitable.

5.5.5 Some Commercial Sources and Trade Names of Plasticisers

The listing in Table 5.20 is not meant to be comprehensive, but it


should provide a reasonable indication of the major Western manufac-
turers and their products.

5.6 PLASTICISER-INFLUENCED PROPERTIES OF PVC

5.6.1 Formulating Considerations-General Points

The general principles of formulating PVC compositions indicated in


Chapter 2 apply fully to plasticiser selection: that is, for each particular
formulation the selection should be made to suit the requirements
imposed by the processing method, the end-use performance, and cost
economy. The following points are also applicable specifically to
choosing plasticisers for a formulation.
It is often advantageous on technical grounds (and can actually be
cheaper in some cases) to use more than one plasticiser-i.e. to
formulate a plasticiser system-to secure the optimum balance of
5 Plasticisers 225

TABLE 5.20
Commercial Plasticisers: Some Western Manufacturers
and Trade Names
Company Classes manufactureda Trade names

United Kingdom
Albright & Wilson 1,2,4 Pliabrac
B. P. Chemicals 1,3,4,6E Bisoftex, Enerftex
Briggs & Townsend Diolpate, Dolplas
Ciba-Geigy 1,2,3,4,5, 6A, 6F Reofos, Reomol,
Reoplast, Reoplex
Courtaulds 2
Lankro Chemicals 1,3,4,6A Lankroftex
ICI 1,4,6B Cerecior, Hexaplas
Robinson Bros 5 Arbeflex
Scott Bader 1,3,5 Crestapol
Shell Chemicals 1,6E Linevol, Dobane,
Dutrex
Tenneco 2
Victor Wolf 5,6C Wolftex

Austria
Chemie Linz 1 Mollan

Belgium
Argus Chemicals 6A Drapex
Essochem Europe 1 layftex
Monsanto Europe 1,2,4,5,6F Santicizer
UCB-FfAL 1,3,4,6F

Denmark
Scandiftex 1,3,4 Scandinol

France
CdF Chemie 1 Gedeflex
D'Electrofine-Chemie 6E
ICI Europa 1,3,4 Hexaplas
Nyco S.A. 6D,6F Nycoftex
Produits Chemie Ugine
Kuhlman Plastifiant K
Rhone-Poulenc Polymeres 1,2,4,5,6B Garbeflex, Garbefos,
Alaiftex

Italy
Akzo Italia 4,5,6C,6F Estaftex
Distillerie Italiane 1,4,5, 6A, 6F Diplast, Diepox,
Staftex (continued)
226 PVC Plastics-Properties, Processing, and Applications

TABLE 5.2O--contd.

Company Classes manufactureda Trade names

Montedison 1,4 Sicol


Sisas 1
Sprea 5 Spreaflex

The Netherlands
Akzo Chemie 6A Estabex
Unilever-Emery 4,5, 6A, 6C, 6F Emery, Plastolein,
Unem
Uraplast 1,4,5 Uraplast (formerly
Scadoplast)
Sweden
Berol Kerni 1,4

Switzerland
Reichhold Chemie 1,4,5, 6A, 6E, 6F Ricatyl, Contrastat

USA
ACS Technical Products 6A Epoxol
Armak 4, 6C,6F Kesscoftex
Ashland Chemicals 5
BASF Wyandotte 1,3 Plastomoll, Palatinol
Continental Oil 1
Crowley Chemical Co. 6E Viplex
Diamond Shamrock 6B Chlorowax
Dover Chemical 6B Chlorez
Eastman Chemical
International 1,3,4,5,6F Kodaftex, Texanol
Emery Industries 4,5, 6A, 6C, 6F Emery, Plastolein
Exxon Chemical 1,3 layftex
FMC 2, 6A, 6C Kronitex
C. P. Hall Co. 4,5,6F Paraplex, Plasthall
Harwick 1,4,6F Polycizer
Hercules 1,5, 6B, 6F Clorajin, Hercoftex,
Hercolyn
ICI Americas 6B,6F Cerecior, Hexplas
Keil 6B,6D
Mobay Corp. 2 Disftamoll
Monsanto 12,3,4,5, Arocior, Santicizer
6A, 6D, 6E, 6F
Morflex Chemical Co. 1,3,4,6F Citroftex, Morftex
Nuodex Inc. 1,3,4,6F Nuoplaz
Reichold 1,3,4,5, 6A, 6C, 6F Peroxidol, Staftex
Rohm & Haas 4,5, 6A, 6C, 6F Monoplex, Paraplex
Sherex 5,6A Admex b
5 Plasticisers 227

TABLE 5.2O-contd.

Company Classes manufactureda Trade names


Stauffer Chemical Co. 2 Phosjiex
Swift 6A Epoxol
Tenneco 1,2,3,4,5 Nuoplaz
Union Carbide 2, 6A,6D F1exol
Union Camp 1,3,4,5,6C Unijiex
USS 1,3,4, 6A, 6C PX
Velsicol 6D Benzojiex
Witco Corp
Argus Chemical Div. 6A Drapex
Pearsall Chemical Div. 6B Flexchlor

West Germany
BASF 1,4,5,6F Palatinol, Plastomoll,
Palamoll
Bayer 1,2,4,5, 6E, 6F Adimoll, Disjiamoll.
Mesamoll, Vltra-
moll, Unimoll
Chemische Werke Hills 1,4, 6B, 6C, 6E Vestinol, Lipinol
Deutsche Texaco 1,3 Reproxal
Dynamit Nobel 1,3,4,5,6B,6C Witamol, Witador
Henkel & Cie 1,4,5, 6A, 6C Edenol
Hoechst 1,6B
Wacker-Chemie 1,4 Wacker

a 1, Phthalates; 2 phosphates; 3, trimellitates; 4, low-temperature plasticisers; 5,


polymerics; 6A, epoxies; 6B, chlorinated paraffins; 6C, monoesters; 6D, glycol esters;
6E, hydrocarbons; 6F, others.
b This plasticiser line bought by Nuodex Inc. in 1985.

processability, service performance and cost in a particular PVC


composition. The processing aspect is especially important in plas-
ticiser selection for PVC paste formulations, where the formulator
must take account of the need for suitable paste rheology, for a certain
(fairly high) minimum plasticiser content (dictated by the liquid nature
of the composition), and-in many cases--also for particular gelation
and fusion characteristics: these requirements will be evident from the
relevant discussion in Chapter 18. With other kinds of PVC composi-
tion, special considerations may include for example possible
difficulties presented by highly viscous polymeric plasticisers in powder
blending, or volatility of some plasticisers in calendering, where, for a
substantial portion of the processing time, the material is in the form
of a relatively thin, hot sheet.
The end-use criterion usually applied first in formulating is the
228 PVC Plastics-Properties, Processing, and Applications

required softness and/or 100% modulus of the product, and the


overall plasticiser content is decided in relation to that, commonly
initially in terms of a general-purpose Cs phthalate. Partial substitution
or addition of any speciality plasticisers that may be needed for such
properties as improved low- or high-temperature performance, flame
retardance, stain resistance, rapid gelation, migration resistance, etc.,
is then planned, and the amounts calculated on the basis of equivalent
efficiency factors (cf. Section 5.4.2, and below). The properties of
various plasticiser types relevant to such further adjustment of a
formulation are indicated in Table 5.8. Depending on the nature of the
product, it may not be necessary to use a speciality plasticiser, but
merely to 'shade' the properties a little by using a related phthalate
from a different alcohol.
The desirability of a plasticiser extender (a chlorinated paraffin or a
hydrocarbon) and/or a filler would normally be considered next.
Once the above general points have been settled, more detailed
consideration must be given to the required balance of the various
relevant properties, so that the actual plasticiser levels and ratios can
be finalised. In general, the properties imparted to a pPVC composi-
tion by a mixed plasticiser system will normally tend to represent a
combination of the individual contributions by the system's com-
ponents in accordance with the proportions present. For highest
accuracy, the plasticiser ratios in a composite system should be
determined by volume (not weight).
As has been mentioned, comparisons of the effects of different
plasticisers in a formulation, and hence also decisions regarding
plasticiser replacement or part-substitution, are commonly made on
the basis of appropriate efficiency (effectivity) quantities (see Section
5.4.2 and Tables 5.7 and 5.21). The corollary, which should not be
overlooked, is that comparisons of different plasticisers at equal
efficiencies may yield results considerably different from those ob-
tained at equal plasticisation levels. This is illustrated by the data of
Table 5.21. Compare particularly DA79 P and DNP: at equal levels
(60 phr) the former plasticiser appears to provide much better low-
temperature properties; but at equal efficiency quantities the
difference is minimal.
The efficiency factor can be very useful in calculating the ratios and
concentrations of plasticisers necessary to replace one with another.
For example, if it is desirable to improve the low-temperature
properties of a compound containing 50 phr of TIP by replacing
5 Plasticisers 229

TABLE 5.21
Comparison of Plasticisers at Equal Concentration and Equal Efficiency
Plasticiser Efficiency Efficiency Properties at Properties at
concen- factor b 60phr efficiency
tration a concentration

Tensile Cold Tensile Cold


strength flex strength flex
(MNm-~ eC) (MNm-~ eC)

Dibutyl phthalate 54·0 0·85 17·0 -25 17·9 -21


Dioctyl phthalate 63·5 1·0 17-4 -23 15-9 -27·5
Di-iso-octyl phthalate 65·5 1-03 18·4 -22 17·1 -30
Di-Alphanol 79
phthalate 61·2 0·97 16·5 -25 15-9 -28
Dinonyl phthalate 74·2 1·17 19-4 -12·5 16·0 -24·5
Tritolyl phosphate 79·3 1·25 23-1 -1·5 17-6 -13
Trixylyl phosphate 83-1 1·31 23·5 +1 17·2 -12·5
Dibutyl sebacate 49·5 0·78 14·7 -56 16·9 -39
Dioctyl sebacate 58·8 0·93 16·1 -47 16·3 -46
Dioctyl adipate 59·9 0·94 16·6 -49 16·5 -49

a phr to give a 100% modulus of 6·9 MN m- 2 (1000 Ibfin- 2).


b Efficiency concentration divided by the efficiency concentration of DOP (63·5).

20 phr of it with DOA and yet retain the same modulus, then the
20 phr of TIP should be replaced by (see Table 5.21):

0·94
20 x - = 15·0 phr DOA
1·25

Even for the experienced PVC formulator the design of a compound


to perform a critical task can be difficult, because of the conflict in the
necessary properties that so often occurs. For example, plasticisers
which impart good low-temperature properties' will inevitably have
inferior oil-extraction resistance, and will lower the volume resistivity
of the composition: this obviously complicates the formulation of an
oil-resistant cable covering for use at low temperatures. Some 'theor-
etical' aids to formulating have been mentioned in Section 2.2.3 of
Chapter 2.
230 PVC Plastics-Properties, Processing, and Applications

5.6.2 Softness and Tensile Properties

As has been mentioned the softness of a pPVC composition is an


important criterion in assessing plasticiser efficiency. The tensile
modulus at 100% elongation is also widely used in such assessments.
The tensile strength and elongation at break are sensitive to plasticiser
content (the first reducing and the second increasing with increasing
plasticisation) and-at equal plasticisation levels-also in some degree
to the nature of the plasticiser.

(a) Softness
In the rubber industry it is the hardness of a material that has been
traditionally measured, either on the BS scale (in the UK) or the
Shore Durometer scales* (especially in the USA), or more recently in
terms of the International Rubber Hardness scale (Method N of BS
903, Part A26: 1969, in technical agreement with ISO 48-1979; ASTM
D 1415-83). Each of these scales ranges from 0 to 100: the harder the
material the higher the number. However, in the case of PVC,
particularly in the UK, it is normal to employ the BS softness (BSS)
number scale, where the higher numbers represent greater softness
(cf. BS 2782, Part 3, Method 365A:1983-formerly Method 307A of
BS 2782: 1970). In practice the BS softness number may be deter-
mined either with a standard 'dead-load' precision laboratory instru-
ment (as in BS 2782, Method 365A: 1983) or with a spring-loaded
pocket instrument. The use, calibration, and limitations of pocket-type
instruments (BSS, IRH and Shore durometer) are covered by BS
2719: 1975. Such instruments, if properly used, are suitable for routine
checks of BS softness values of PVC materials, but not for standard
tests or strict laboratory or quality control.
At present, both the Shore hardness and the BS softness systems are
in use, and since a certain amount of confusion can arise, a conversion
graph is given in Fig. 5.7.

* ISO 868-1985 (identical with BS 2782: Part 3: Method 365 B:1981); ASTM
D 2240-85.
Two Shore durometer scales, are in use, A and D (respectively for softer and
harder materials), associated with two durometers of the same designations.
Scale A is applicable to most of the flexible PVC materials. Measurements
with Type D durometer should be made where values above 90 are obtained
with the Type A durometer, and Type A should be used for materials that
register less than 20 with the Type D instrument.
5 Plasticisers 231

50

40

30

BS softness number
(Depth of indentation'D' in Table 3 of BS903: part A26: 1969)

Fig.5.7 International Rubber Hardness and Shore A hardness at 20°C versus


BS softness number. e, International rubber hardness degrees (IRHD~BS
903: PART A26: 1969 (Table 3); x, Shore A duro meter hardness at 20°C.

Note: In the standard determinations of IRH, the relationship


between the depth of indentor penetration (P, mm) and the
Young's modulus of the material (M, MPa) is represented by
the expression (precise for substantially elastic, isotropic
materials):72,73
F/M = 1·9R 2 (P/R)1.35
where F is the indenting force in newtons and R the indentor
radius in mm.
Figures 5.8 and 5.9 show the variation of softness at room temperature
(23°C) with plasticiser level for nine common plasticisers, in terms of
BS softness number and Shore A hardness value respectively. As
232 PVC Plastics-Properties, Processing, and Applications

100 4

80

'-
CI
.c 3
E
::l
60
C
I/)
I/)
CI
.5 40
g
III
III 20

0 20 40 60 80 100
Plasticis~r l~vQI, phr

100

80

'-
CI
.c
E 60
::l
C
I/)
I/)
CI 8
....c 40
'0
I/)

III
III 20

o 20 40 60 80 100
Plasticis~r l~v~l, phr

Fig. 5.8 Effect of plasticiser level on BS softness number. 1, DOP; 2, DIDP;


3, DTDP; 4, DOA: 5, Re%s 65 (Ciba-Geigy); 6, TOTM; 7, ESO; 8, PPA; 9,
PPA alcohol-endstopped.
5 Plasticisers 233

100

90

« 80
l:!0
.s::
III 70

3
60

2
50
0 20 40 60 80
Plasticis~r l~v~l, phr

100

90

« 80
ClI
'-
0
.s::
III 70

60
9

50
0 20 40 60 80 100
Plasticis~r I~V~I, phr

Fig.5.9 Effect of plasticiser level on Shore A hardness. 1, DOP; 2, DIDP; 3,


DTDP; 4, DOA; 5, Re%s 65; 6, TOTM; 7, ESO; 8, PPA; 9, PPA
alcohol-endstopped.
234 PVC Plastics-Properties, Processing, and Applications

softness varies considerably with temperature, the degree of variation


depending on the plasticiser type and content, it is possible to
formulate for a desired softness at a particular temperature. Figure
5.10 shows the effect of increasing temperature on the softness of a
PVC composition plasticised with DOP at three concentrations.
Compounds based on different plasticisers, if formulated for equal
softness at one temperature, may differ at another.

(b) Tensile Strength and Elongation at Break


The effects of plasticiser type and concentration on tensile strength
and elongation at break are shown in Figs 5.11 and 5.12 respectively.
These properties also vary with temperature.

IS

130

120

110

100

L
Of
.0
E

...
z"
Of
70l
I
5
0
U)
60~
I
I
U)

ID I
SO:

40j
i
I
30~

201

10
1
, I I ,
20 30 40 SO 60 70 80
Temp«raturc. °c

Fig. 5.10 BS softness of a PVC composition versus temperature, at three


DOP content levels.
5 Plasticisers 235

25

20

-
N
E
z
l:
15
....01
.c
c:
CI
!..
'lii 10
~
'iii
c:
{!.
5

o 20 40 60 BO 100
Plasticiser level, phr

25

20

-
N
E
z
~
~15
....
.s::
01
c:
~
'lii 10
~
'iii
c:
{!.
5

o 20 40 60 BO 100
Plasticiser level, phr

Fig. 5.11 Effect of plasticiser level on tensile strength. 1, DOP; 2, mDP; 3,


DTDP; 4, DOA; 5, Reolos 65; 6, TOTM; 7, ESO; 8, PPA; 9, PPA
alcohol-endstopped.
236 PVC Plastics-Properties, Processing, and Applications

500

4
1

.-
.,e
400 2
3
.>L.
ra
~ 300
.0

1ii
c
0
~200
01
c
.2
w
100

o 20 40 60 80 100
Plasticisar laval, phr

500

400

.>L.
ra
~ 300
.0 5
1ii 6

~~
c
o
:;:; 200
ra
01
c 8
o
W
100

o 20 40 60 80 100
Plasticisar laval» phr

Fig. 5.12 Effect of plasticiser level on elongation at break. 1, DOP; 2, DIDP;


3, DTDP; 4, DOA; 5, Re%s 65; 6, TOTM; 7, ESO; 8, PPA; 9, PPA
alcohol-endstopped.
5 Plasticisers 237

5.6.3 Low-Temperature Properties


Plasticisation improves the low-temperature performance of PVC, but
the degree of improvement depends on both the concentration and the
nature of the plasticiser (cf. Fig. 5.13 and Table 5.22). As an example
of the concentration effect, if the level of plasticisation of the
compositions represented in Fig. 5.13 was increased, the curves would
be displaced to the left without substantial change in their shapes and
gradients (the latter two features being governed primarily by the
nature of the plasticisers).
It follows that a particular low-temperature performance of a pPVC
material can be formulated for by appropriately selecting, and where
necessary combining, the plasticisers (cf. for example Table 5.22). The
low-temperature properties of pPVC are very often assessed by tests
which essentially determine the stiffness in torsion at low (and usually
progressively reducing) temperatures. A test widely used in the UK is
the cold-flex test (Clash and Berg) of BS 2782: Method 150B: 1796. * In

,,
..... ......

- 50 -~o -30 - 20 -10 o 10 20 30 ~o so


TEMPERA TURE (·el
Fig. 5.13 Log rigidity modulus versus temperature for pPVC compositions
containing four common plasticisers at 54 phr. 1

* A revised version of the original specification BS 2782: 1970 Method 104B.


In the original method the deflection through 200 was regarded as equivalent
0

to a modulus of rigidity of 1655 kgf cm- 2 •


~
00

~
~
TABLE 5.22
Effect of Linevol Phthalates and Adipates on Low-Temperature Properties of Identical PVC Formulations4 ~.
Linevol 79 adipate/ Linevol 911 adipate/ 2-EH-adipate/ ~
Linevol 79 phthalate Linevol 911 phthalate 2-EH -phthalate .g
(phr) (phr) (phr) '"
::!-.
.~
50/0 30/20 20/30 0/50 50/0 30/20 20/30 0/50 50/0 30/20 20/30 0/50
Cold-flex temperature g~
(BS 2782: 1970 M 104 B), °C -44 -36 -31 -21 -23 -34 -30 -22 -35 -32 -24 -14 ~
Cold-flex temperature ~.
after 7 days at 100°C §
(BS 2782: 1970 M 104 B), °C -16 -15 -16 -13 -23 -30 -29 -22 +13 +9 -8 -5 ~
)..

a Extract from technical literature of Shell Chemicals International Ltd, reproduced with their permission.
:g

r
5 Plasticisers 239

terms of this test, the cold-flex temperature is that temperature at


which, under a specified torque, the test specimen is deflected through
an arc of 200°. The closely related test of Method 150A is also in use.
These, and other relevant test methods are discussed in Section 24.3
of Chapter 24. Figure 5.14 illustrates the effects of plasticiser nature
and concentration upon the results of the cold-flex test.
5.6.4 Electrical Properties
The electrical properties of greatest interest in flexible PVC are the
volume and surface resistivity, and the dielectric properties. Volume
resistivity and dielectric strength are naturally very important in wire
and cable insulation; high values in these properties enable thinner
coatings to be used. The effect of plasticiser type and concentration on
the volume resistivity of a PVC compound is summarised in Fig. 5.15.
Since,as is apparent from its molecular structure, PVC exhibits a
high dipole polarisation, the dielectric constant and power factor of its
compounds are very frequency- and temperature-dependent. This
limits the use of flexible PVC insulation to lower voltage and
low-frequency applications. However, the power losses at high fre-
quencies are successfully utilised in the high-frequency welding of PVC
sheet (see Chapter 21, Section 21.2.6).
Outside the area of electrical insulation, low values of resistivity,
particularly surface resistivity, are often beneficial in reducing prob-
lems of static build-up (cf. Chapter 9, Section 9.2.3). A good review of
the electrical properties of polymers and the effect of plasticisers has
been made by Coulson. 74
5.6.5 Flammmmabitity
Many plasticisers (e.g. phthalates, trimellitates, polymerics, and
others) increase the flammability of the pPVC compounds by
effectively diluting the PVC polymer, which is inherently not readily
flammable. Others, like phosphates and chlorinated paraffins and
olefins, do not have this effect. This subject is covered-among other
related topics-in the discussions of flammability of PVC materials in
Chapters 9 and 24.
5.6.6 Permmanence Properties
Plasticiser(s) of unsatisfactory permanence may be lost in substantial
amounts from a pPVC material-to the detriment of its properties-
through volatilisation (volatile loss), extraction, or migration.
240 PVC Plastics-Properties, Processing, and Applications

20

10

.
lJ
t:J~
0

...ro
'-
::J -10
'-
t:J
a. -20
E
...
t:J

x -30
.£!
....
"U -40 3
"0 2
lJ
-50

-60
0 20
Plasticiser level,

20

10

.
lJ
~
o
~ -10
...ro
::J

; -20
a.
E
2 -30
x
t:J
;;:: -40
"U
"0
lJ -50

-60~----~----.-----.-----r----'
o 20 40 60 80 100
Plasticisllr level, phr

Fig. 5.14 Effect of plasticiser level on 'Clash and Berg' low-temperature


flexibility (BS 2782: 1970, Method 104B: N. B. Current revised version, BS
2782, Method 150B: 1976). 1, DOP; 2, mDP; 3, DTDP; 4, DOA; 5, Re%s
65; 6, TOTM; 7, ESO; 8, PPA alcohol-endstopped; 10, ~9P,
5 Plasticisers 241

E
u
a
;: 10'3
>
....
I/)

I/)

~
~ 10'2
;:)
-'
~

10'O .......~_ _--L_ _ _- ' -_ _ _..L..._


40 50 60 70
PLASTICISER CONTENT (phr)

Fig. 5.15 Effect of plasticiser type and level on volume resistivity at 23°C. 1

(a) Volatile Loss


The rate of plasticiser loss by volatilisatioJ,1 is controlled by its rate of
evaporation at the surface, which normally leads (i.e. is faster than)
the rate of diffusion through the solid material to reach the surface.
Although at room temperature the volatilisation of even the general-
purpose plasticisers is relatively slow, over long periods of service their
volatile loss from, for example, PVC upholstery or other kinds of
leathercloth (which, by their nature have a high surface-to-volume
ratio) can be quite high, leading to such undesirable manifestations of
'ageing' as hardening and cracking. For best results, low-volatility
plasticisers should be used in formulations that are to be resistant to
volatile loss: such plasticisers are the polymerics, trimellitates, and
pentaerythritol esters.
Figure 5.16 illustrates the well-known fact that with monomeric
plasticisers volatile loss tends to be reasonably linear with time up to
fairly high loss levels, whereas with polymeric plasticisers the tendency
242 PVC Plastics-Properties, Processing, and Applications

40

30

200 400 600 800 1000


Hours at 100 0

Fig. 5.16 Volatile loss of some monomeric and polymeric plasticisers from
pPVC compositions.

is for the loss to stabilise at a relatively low value (after the


low-molecular-weight 'tails' have been lost) and remain at this level for
an extended period.
Laboratory determinations of volatile losses by oven tests at
elevated temperatures, and their assessment by determination of the
resultant physical property changes (ageing), are discussed in Chapter
24.

Note: The apparently characteristic changes in physical properties


may not necessarily indicate just loss of plasticiser; particu-
larly when the ageing tests are carried out at high tempera-
tures, oxidation of plasticiser and cross-linking and/or chain
scission of the polymer molecules can also be involved. In
such cases, the inclusion of an antioxidant in the composition
may appear to reduce plasticiser volatility.

Two important practical cases exemplifying some consequences of


volatile loss of plasticisers are automotive fogging and the ageing of
cable coverings.
5 Plasticisers 243

AUTOMOTIVE FOGGING
This is the build-up of an oily condensation or fog on car windscreens
and other parts of the car interior. The problem was originally
attributed entirely to volatile plasticisers, but later numerous analyses
of the deposits by a number of laboratories implicated substances of
other origin, in addition to plasticisers from PVC crash-pads and
leathercloth. These include plasticisers from adhesives, certain
pigment-dispersing media, catalyst residues and other components of
polyurethanes, some antioxidants, components of some stabiliser
systems, * and even airborne hydrocarbons, as well as minor impurities
such as residual emulsifiers in the polymer, or free-alcohol residues in
plasticisers.
There are several fogging tests in use, and a number of different test
temperatures, e.g. 60, 75 and 90°C, depending on the car
manufacturer's quality control policy and on the part of the car and
the conditions for which the material's are destined. t The test
requirements are normally in terms of a stated, high light reflectance
from a surface exposed to possible fogging in the test treatment (a
fogging deposit reduces reflectance).
The most stringent tests-as carried out for example on crash-pad
and window-visor components-involve temperatures as high as 90°C,
with a minimum reflectance requirement of 90%. To pass these tests
the PVC composition must be formulated with plasticisers such as
trimellitates, high-molecular-weight phthalates or other high-
molecular-weight plasticisers, as well as a carefully chosen polymer
and stabiliser system. Ordinary polymeric plasticisers are not generally
suitable since the low-molecular weight 'tails' can fog severely.
Trimellitates are technically preferable to high-molecular-weight
phthalates, since it is far easier to strip Cs alcohol from the finished
product than C lO-C 14 alcohols.
Some typical basic formulations designed to pass the Volvo fogging
test at 60, 75 and 90°C have been cited by Buszard. 1

* Some manufacturers offer special grades of low-fogging stabilisers. For


example, Sicostab B241 (BASF) liquid barium/zinc stabiliser is claimed to
meet all test requirements, even at 90°C.
t For example, the so-called 'Arizona Parking Lot Test' is intended to simulate
conditions inside a closed car in a sunny car park, with interior temperature
reaching 60°C.
244 PVC Plastics-Properties, Processing, and Applications

PLASTICISATION OF CABLE COVERINGS


The choice of plasticiser for cable coverings is dependent upon the
service conditions to be catered for. General-purpose insulation and
sheathing compounds based on Cs phthalates, often with chlorinated
paraffin extenders, are normally limited to a maximum continuous
service temperature of 60-65°C. For continuous operation at higher
temperatures, low-volatility plasticisers must be used, e.g. DIDP or
perhaps a selected phosphate plasticiser for a maximum rating of 75°C.
For 90°C cables DTDP is preferred. Trimellitates, polymerics, or
pentaerythritol esters are required for 105°C rated cables. The tem-
perature resistance of cable coverings and some of the tests for its
determination are discussed further in Chapter 24.

(b) Extraction Resistance


This is possessed in the highest degree by polymeric plasticisers (whose
efficiency is, however, generally somewhat lower than that of the
monometrics). Some of the most relevant points are brought out by
the data of Table 5.23. Inter alia, the figures illustrate the particularly
good resistance to non-polar extractants (hexane and oils) of a
high-molecular-weight, non-endstopped polymeric plasticiser (Diolpate
150). The endstopped polymerics Diolpate 214 and 217 show less
resistance to non-polar solvents, but better resistance to aqueous
extractants and also superior compatibility, especially at high humi-
dity, and greater efficiency. The endstopped, mixed adipate/phthalate
polymeric Diolpate 171 exhibits reasonable extraction resistance and
improved processing behaviour, both with respect to lower plastisol
viscosities and faster gelation.
It should be noted that complete gelation (fusion) of the PVC
composition in processing is essential to securing the good resistance
to extraction and migration of which polymeric plasticisers are
capable. The high-molecular-weight non-endstopped products are
particularly dependent on completeness of fusion in this respect: if the
achievement of full gelation cannot be guaranteed in a particular
compounding/processing operation, then it is preferable either to use
an endstopped polymeric plasticiser of lower molecular weight, or to
include in the formulation a proportion of a rapid-gelling plasticiser,
such as triaryl phosphate. As can be seen from Table 5.23, the
replacement of an alkyl by an aryl group in a dialkyl phthalate reduces
the non-polar extraction resistance of the plasticiser. Triaryl phos-
phates and epoxidised soya bean oil exhibit extraction resistance
TABLE 5.23
Properties and Extraction Resistance of Plasticisers at 60 phr
DOP BBP TXP ESO Diolpate Diolpate Diolpate Diolpate
150 171 214 917

Viscosity at 25°C, St 0·5 0·6 0·9 5 130 9 35 41 v.


BS softness no. 45 43 41 41 28 42 41 44 "tj
Cold-flex temperature, °C -20 -12 +2 -12 -3 -6 -7 -4
Tensile strength, MN m- 2 11·5 20·3 16·5 18·0 17·4
If
1';.
17·8 18·7 16·9
!.O.
Elongation at break, % 335 195 280 365 320 315 330 350
Volatile loss, % 22·5 16·3 6·9 9·0 2·9 3·6 3·4 3·3
'"t:I
Extraction loss, %
Hexane 35 14·0 15·5 18·6 1·2 7·6 2·9 2·4
Mineral oil 15·8 12·4 6·7 10·7 +0·5 7·3 2·1 1·9
Olive oil 23·5 15·4 9·6 14·5 3·1 9·8 5·8 3·8
Water 0·1 0·5 +0·3 0·1 1·6 0·4 0·3 0·1
Soap (1%) 12·8 19·6 21·2 4·1 7·2 8·2 2·7 2·9

~
246 PVC Plastics-Properties, Processing, and Applications

phates and epoxidised soyabean oil exhibit extraction resistance


intermediate between the dialkyl phthalates and the polymeric
plasticisers.
Solid polymeric modifiers can successfully replace high-molecular-
weight polymeric plasticisers in some applications for maximum
extraction resistance, but it should be remembered that their efficiency
is considerably lower (cf. Table 5.24).
Specimen thickness is a factor significantly influencing the results of
extraction tests: the results are higher with (i.e. more plasticiser is
extracted from) thick specimens than thin ones. This effect is
associated with the way diffusion proceeds under the concentration
gradient set up in the specimen undergoing extraction (in a thick
specimen the gradient is relatively steep, with a greater reservoir of
plasticiser in the interior). Where test results are expressed in terms of
weight of plasticiser extracted per area of specimen, with related
maximum requirements formulated on this basis, * a particular PVC

TABLE 5.24
Physical Properties of a PVC Compound Con-
taining a Solid Polyurethane Elastomer-
Durelast l00a

BS softness no. 45
Cold-flex temperature, °C -22·5
100% modulus, MN m- 2 5·6
Tensile strength, MN m- 2 15
Elongation at break, % 530
Tear strength, kN m- 1 59
Volatile loss, % 0;2
Extraction loss, %
Hexane +0·3
Mineral oil +0·1
Olive oil -0·1
Water +0·7
Soap (1%) +0·4
Formulation: PVC 100
Durelast 100 100
ESO 10
Cd stearate 6
a Trade name of Briggs & Townsend.
* Compare for example the upper limit of 10 mg dm -2 in the original EEC
Draft Directive75 on overall migration of additives from plastics food-
packaging materials when tested in contact with the range of food simulants
(distilled water, aqueous citric acid, aqueous alcohol, and olive oil).
5 Plasticisers 247

composition may meet the requirements when tested in one thickness,


but may fail at a higher specimen thickness.

Note: In practice it may be necessary to reformulate if the


practicable material thickness is limited, as was done in the
case of a thin PVC cling film which-before the introduction
of a polymeric plasticiser on reformulation (see Table 5.25)--
failed the EEC test in respect of extractability with olive oil.

(c) Migration Resistance


Migration is the transfer of plasticiser from a PVC material into
another material (which may occasionally also be PVC, of a different
composition) when the two materials are in surface contact. The
transfer takes place by diffusion, and thus the main factors governing
its rate and final extent will be the chemical make-up and molecular
size and shape of the plasticiser, its concentration gradient, the
temperature, the chemical nature and morphology of the recipient
material, and the intimacy of its surface contact with the PVC donor
material. The effects of some of these factors are illustrated by the
data of Table 5.26.
In many applications of pPVC materials, the migration resistance of
their constituent plasticisers is an important consideration. For ex-
ample, migration of plasticiser from a PVC refrigerator gasket into a
high-impact polystyrene (HIPS) refrigerator liner can lead to cracking
of the HIPS in high-stress areas or even softening of the HIPS
resulting in its adhering to the gasket. Other examples include PVC

TABLE 5.25
Reformulation of Stretch Wrap PVC Food-Packaging Films to Include a
Polymeric Plasticiser
Old New
formulation formulation

PVC suspension polymer 100 100


DOA 25 10
Reoplex 430 (Ciba-Geigy) 20
ESO 5 5
Ca/Zn stabiliser 3 3
Antifogging agents 1 1
Overall migration resistance into
olive oil (10 days at 40°C), mg dm- 2 32 9
248 PVC Plastics-Properties, Processing, and Applications

TABLE 5.26
Migration Resistance of Plasticisers"

Cellulose Natural Polyethylene


nitrate rubber

PPS 2·7 2·9 0·1


PPA 2·2 1·0 0·34
PPS/ acid-endstopped 9·1 o 0·3
PPA/ acid-endstopped 10·7 2·5 0·7
PPA/ alcohol-endstopped 6·4 0·7 0·1
Epoxidised oil 9·1 1·3 0·25
DOP 14·1 11·0 2·2
a Method according to DIN 53 405-1981.

cables in contact with plastics electrical appliance cases, self-adhesive


PVC films, insulation tapes and the adhesion of print and lacquer to
PVC films.
For practical test purposes, migration resistance is usually deter-
mined by the method of DIN 53405-1981 or the closely similar ISO
177-1976. In both methods, pre-weighed discs of the pPVC composi-
tion to be tested are sandwiched between similar discs of the relevant
plastics material, and the sandwich-placed between glass plates with
a weight on top-is heated for a prescribed period in an oven at 70°C
(the revision document for the ISO specification-ISO/DIS 177·2-
currently in train allows two other temperatures if relevant: viz. 50°C
or 85°C). The loss of weight by the PVC discs and the gain by the
recipient material are then determined.

(d) High-Humidity Compatibility


Many plasticisers which have good compatibility under normal condi-
tions of usage can exhibit severe incompatibility under conditions of
high humidity, e.g. in refrigerators or in tropical climates. Non-
ends topped polymeric plasticisers such as polypropylene adipate are
particularly bad in this respect. Phosphate plasticisers exhibit very
good compatibility at high humidity.

5.6.7 Stain Resistance

Flexible PVC is susceptible to staining by many different substances


and compositions, but particularly those that are based on oils or
oleophilic solvents (e.g. ball-point pen ink, shoe polish, tar, etc.). It
5 Plasticisers 249

has been shown that the degree of staining increases with the
plasticiser content, and that at equal levels of softness the type of
plasticiser is also important. 1 Plasticisers which give reduced levels of
staining are 2,2,4-trimethyl-l,3-pentanediol di-isobutyrate (e.g.
Kodafiex TXIB; Eastman Chemicals), the monoisobutyrate monoben-
zoate ester of the above diol (e.g. Nuoplaz 1046; Tenneco), benzyl-
butyl phthalate (e.g. Santicizer 160; Monsanto), and triaryl phosphates
(e.g. Reofos 50). The major applications where stain resistance is
important are in PVC flooring, and, to a lesser extent, in wall
coverings and claddings.

5.6.8 Resistance to Weathering and Photodegradation

Although these properties of PVC materials depend primarily upon


the stabiliser system (see Chapter 4), they are also influenced by the
plasticisers in pPVc. The following are among the manifestations of
weathering in which plasticisers playa part.
(i) Discolouration (which may be accelerated by photo-oxidation
of a plasticiser).
(ii) Loss of fiexibility-due to loss of plasticiser by volatilisation,
extraction or photo-oxidation.
(iii) Surface tackiness. This is usually due to plasticiser exuding to
the surface, frequently as a result of its partial exclusion from
the polymer undergoing some cross-linking in the course of
photodegradation-see Section 4.1.3 of Chapter 4. The exuda-
tion is most frequent with plasticisers containing carbon-carbon
double bonds, chlorinated paraffins or high levels of epoxy
compounds [which may also partly lose their compatibility with
PVC as their oxirane groups are used up while discharging the
stabilising action of which they are capable: see Chapter 4,
Section 4.3.5(c)].
(iv) Dirt pick-up. This is often promoted by (iii), and is particularly
a problem with PVC-coated steel used in outdoor cladding.
(v) Sensitisation of the PVC polymer and promotion of its
dehydrochlorination, by transfer to the polymer of free radicals
first formed in the plasticiser. 76 For compositions plasticised
with DOP, DOA and BBP it has been confirmed77 that this
promotion of dehydrochlorination depends on the extent of
sorption of solar-radiation photons by the plasticiser (and hence
on the nature and amount of plasticiser present).
250 PVC Plastics-Properties, Processing, and Applications

In general, aliphatic diesters impart good light stability, providing


they are within their compatibility limits. Straight-chain phthalates are
superior to their branched-chain counterparts, although the high linear
phthalates exhibit poorer compatibility. Phosphates are poorer than
phthalates, except when included in phthalate-plasticised compositions
at low concentrations, when they apparently stabilise the formulations.
Aromatic phthalates such as BBP have markedly poorer light stability
than dialkyl phthalates.
Some aspects of the weathering resistance of PVC, and its evalua-
tion, are also discussed in Chapter 24.

5.6.9 Resistance to Biological Attack

The resistance of PVC materials, including plasticised compositions, to


microbiological attack (by fungi and bacteria) and to insect and animal
depredations is discussed in Chapter 24.

5.7 TOXICITY AND HEALTH ASPECTS

5.7.1 Plasticisers in Food-Contact and Medical Applications

It is particularly important that all formulation constituents used in


PVC materials for these applications should be non-toxic and non-
carcinogenic. Regulatory measures exist in most countries, but they
are by no means identical. In the USA, for example, only those
additives may be used which are specifically permitted by the Food
and Drugs Administration (FDA). In the UK and West Germany
there is currently no list of specifically, legally approved materials, but
voluntary observance is assumed of recommendations issued by the
British Plastics Federation (BPF) and the Kunststoff-Kommission des
Bundesgesundheitsamtes (BGA) respectively. These recommenda-
tions are in line with the relevant Council of Europe or EEC directives
that are coming into being. It is essential that, for detailed up-to-date
relevant information, the user of plasticisers should consult the
plasticiser manufacturer or the national or international organisation
concerned.
The possible carcinogenic effects of the most common plasticisers
5 Plasticisers 251

have been the subject of several investigations. 1 Whilst the question is


not yet completely settled, the balance of all currently available
evidence strongly supports the conclusion that the two plasticisers-
DOP and DOA-most closely investigated because of their wide use,
present no demonstrable direct carcinogenic or toxic risk to man in the
quantities in which they are likely to migrate into foodstuffs packed in
pPVC materials. This view is embodied also in the informed response
by the BPF78 and the UK Ministry of Agriculture, Fisheries and Food79
to certain fairly recent sensationalist claims about the alleged cancer or
toxic risks supposedly presented by the migration of plasticisers-
especially DOA-from PVC cling film into foods.

5.7.2 Plasticiser Handling and Processing

The majority of plasticisers manufactured today are of a low order of


toxicity and constitute little hazard in use either from direct toxic
effects or dermatitic effects on handling. However, as with all organic
materials, good working practice should be employed. Adequate
ventilation should be ensured in the vicinity of heated equipment
where plasticiser fumes may be produced. Table 5.27 indicates the
concentration of plasticiser vapour which could occur in saturated air
at 160°C. Laboratory experiments80 and actual measurements on
industrial plastisol coating plants indicate that 25-50 kg h- 1 of plas-
ticiser could be lost by volatilisation alone. This indicates the need for
good ventilation if the threshold limit value (TL V) of 5 mg m -3 is to be
met; this is considered to be the safe maximum concentration by the
American Conference of Governmental Industrial Hygienists81 and
adopted by the US Health and Safety Administration (OHSA).

TABLE 5.27
Vapour Pressure of Dialkyl Phthalates

Plasticiser Molecular Vapour Concentration in


weight pressure saturated air
(mmHg) at 160°C (g m- 3 )

DBP 278 1·2 12


DOP 390 0·121 1·75
DIDP 447 0·029 0·48
252 PVC Plastics-Properties, Processing, and Applications

TABLE 5.28
Standards Relevant to the Properties and Testing of Plasticisers and Their
Etfects in PVC

Entry Standard specification


no.
Designation Subject (not necessarily
the official title)
Bulk properties
1 ISO 1385-1977 Parts 1-5 Phthalate esters for industrial use
Method of test: (1) general; (2)
colour after heating; (3) ash
determination; (4)
determination of acidity; (5)
determination of ester content.
2 ISO 2520-1974 Tritolyl Phosphate for Industrial
Use-List of test methods
3 ISO 2521-1974 Tritolyl Phosphate for Industrial
Use-Determination of acidity
4 ISO 2522-1974 Tritolyl Phosphate for Industrial
Use-Determination of
apparent free phenol content
5 ISO 2523-1974 Adipate Esters for Industrial
use-Methods of test
6 ISO 2524-1974 Adipate Esters for Industrial
Use-Measurement of colour
after heating
7 ISO 2525-1974 Adipate Esters for Industrial
Use-Determination of acidity
8 ISO 2526-1974 Adipate Esters for Industrial
Use-Determination of ash
9 ISO 2527-1974 Adipate Esters for Industrial
Use-Determination of ester
content
10 BS 573: 1973 (1987) Dibutyl phthalate
11 BS 574: 1973 (1987) Diethyl phthalate
12 BS 1995: 1973 (1987) Di-(2-ethylhexyl) phthalate
13 BS 1996: 1973 (1987) Dimethyl phthalate
14 BS 1997: 1973 (1987) Glycerol triacetate (triacetin)
15 BS 1998: 1970 (1987) Triphenyl phosphate
16 BS 1999: 1964 Tritolyl phosphate
(±ISO 2520/2)
17 BS 2535: 1973 (1987) Dibutyl sebacate
18 BS 2536: 1973 (1987) Di-(2-ethylphenyl) sebacate
19 BS 3647: 1973 (1987) Dimethoxyethyl phthalate
20 BS 4835: 1973 (1987) Methods of Test for Plasticiser
Esters (±ISO 1385 and 2524)
5 Plasticisers 253

TABLE 5.28--contd.

Entry Standard specification


no.
Designation Subject (not necessarily
the official title)

21 BS 4968: 1973 Di-isobutyl phthalate, di-iso-octyl


phthalate and di-iso-octyl
sebacate
22 ASTM D 1045-86 Sampling and Testing Plasticisers
Used in Plastics
23 ASTM D 1249-81 Specification for Octyl
Orthophthalate Plasticisers
24 ASTM D 2288-69 (1980) Test for Weight Loss of
Plasticisers on Heating
25 DIN 53 400 (1970) Testing of Plasticisers:
(under revision since 1985) Determination of Density,
Refractive Index, Flash Point
and Viscosity
26 DIN 53 401 (1985) Plasticisers: Determination of
saponification value
27 DIN 53 402 (1985) Plasticisers: Determination of
acid value
28 DIN 53 404 (1952) Plasticisers: Determination of
saponification rate (Withdrawn
in 1984)
29 DIN 53 409 (1967) Plasticisers and Solvents:
Determination of Hazen colour
(platinum cobalt colour,
APHA method)

Properties in association with PVC (Compatibility; Volatility; Migration)


30 ISO 176-1976 Plasticiser Loss from Plastics
(Activated Carbon Method)
31 ISO 177-1977 Plastics-Determination of
migration of plasticisers
32 BS 2782: Part 4 Plasticiser Loss (Activated
Methods 465 A Carbon Method) (=ISO 176)
and B: 1979 (1986)
33 BS 2782: Part 5 Effect of PVC Compound on the
Method 511 A: 1970 Loss Tangent of Polyethylene
34 ASTM D 1203-67 (1981) Volatile Loss of Plasticisers from
Plastics (Activated Carbon
Methods)

(continued)
254 PVC Plastics-Properties, Processing, and Applications

TABLE 5.28-contd.

Entry Standard specification


no.
Designation Subject (not necessarily
the official title)

35 ASTM D 2134-66 (1980) Test for Softening of Organic


Coatings by Plastic
Compositions (e.g. effect of
plasticisers from pPVC on
nitrocellulose lacquers)
36 ASTM D 2383 88 Standard Practice for Testing
Plasticiser Compatibility in
pPVC under Humid Conditions
37 ASTM D 3291-74 (1980) Test for Compatibility of
Plasticisers in PVC Plastics
under Compression
38 ASTM D 3421-75 Extraction and Analysis of
Plasticiser Mixtures from Vinyl
Chloride Plastics
39 DIN 53 405 (1981) Determination of Migration of
Plasticisers
40 DIN 53 407 (1971) Determination of Loss of Weight
of Plasticised Plastics by the
Activated Carbon Method
41 DIN 53 408 (1967) Determination of Solubility
Temperature of PVC in
Plasticisers
Effects on PVC
42 ISO 4574-1978 PVC Resins-Determination of
Hot Plasticiser Absorption
43 ISO 4608-1084 Vinyl Chloride Homopolymers
and Copolymers: Determination
of Plasticiser Absorption at
Room Temperature
44 BS 2782: Part 4 Determination of Plasticiser
Method 454 E: Absorption at Room
1978 (1984) Temperature by PVC Resins
(""ISO 4608)
45 ASTM D 2396-79 (1985) Powder-Mix Test for PVC Resins
in a Torque Rheometer
46 ASTM D 3367-75 (1986) Test for Plasticiser Sorption by
PVC Resins under Applied
Centrifugal Force
47 DIN 53408 (1967) Determination of the Solubility
Temperature of PVC in
Plasticisers
5 Plasticisers 2'55

5.8 STANDARDS RELEVANT TO PLASTICISERS

The standards (some of which have already been mentioned in this


chapter) are listed in Table 5.28. The extraction of plasticisers from
PVC compositions, and their determination, are dealt with in Section
2.4 of Chapter 2.

REFERENCES

1. Buszard, D. L. In PVC Technology, 4th edn, W. V. Titow. Elsevier


Applied Science Publishers, London and New York, 1984, Ch. 5, 6 and 7.
2. ISO 472-1979. Plastics-Vocabulary.
3. ASTM D 883-86b. Standard Terms and Definitions Relating to Plastics.
4. BS 1755. Glossary of Terms Used in the Plastics Industry. Part I: 1982,
Polymer and Plastics Technology.
5. Kirkpatrick, A., J. Appl. Phys., 11 (1940) 255.
6. Clark, F. W., Chem. Ind., 60 (1941) 255.
7. Barron, H., Plastics (London), 7 (1943) 449.
8. Doolittle, A. K., The Technology of Solvents and Plasticisers. John Wiley,
New York, 1954, Ch. 14 and 15.
9. Doolittle, A. K., Plasticiser Technology, ed. P. F. Bruins. Reinhold, New
York, 1965, Ch. 1.
10. Leuchs, D., Kunststoffe, 46 (1956) 547.
11. Ghersa, P., Mod Plast. 36(2) (1958) 135.
12. Horsley, R. A. In Progress in Plastics, ed. P. Morgan. Iliffe, London,
1957, p. 77.
13. Tabb, D. L. & Koenig, J. L., Macromolecules, 8 (1975) 929.
14. Jacobson, U., Brit. Plast., 32(4) (1959) 152.
15. Robeson, L. M., Polym. Engng Sci., 9 (1969) 277.
16. Robeson, L. M. & Faucher, J. A., J. Polym. Sci. B, 7 (1969) 59.
17. Bohn, L., Kunststoffe, S3 (1963) 826.
18. Nakamura, K., Hashimoto, F., Nakanishi, M., Kinjo, N., Komatsu, T. &
Nakagawa, T., Proc. 5th Int. Congo Rheol., 1970, p. 409.
19. Kinjo, N. & Nakagawa, T., Polym. J. 4(2) (1973) 143.
20. Pezzin, G., Ajroldi, G. & Garbuglio, D. M., J. Appl. Polym. Sci., 11
(1967) 2553.
21. Pezzin, G., Ajroldi, G., Casiraghi, T., Garbuglio, C. & Vittadini, J., J.
Appl. Polym. Sci., 16 (1972) 1839.
22. Sears, J. K., Darby, J. R. & Touchette, N. W. Paper presented at the
12th Ann. It. Tech. Meeting of Sabine Area AICHE and the Texas-
Louisiana Gulf ACs, Orange, Texas, 1965.
23: Darby, J. R. & Sears, J. K. In Encyclopedia of Polymer Science and
Technology, Vol. 10, ed. H. F. Mark et al. Interscience, New York, 1969.
24. Van Veersen, G. J. & Dijkers, J. L. c., Kunststoffe, 64 (1974) 292.
25. Mazzur, R. P., SPE Tech. Papers, 13 (1967) 177.
256 PVC Plastics-Properties, Processing, and Applications

26. Graham, P. R & Darby, J. R, SPE J., 17 (1961) 91.


27. Van Veersen, G. J. & Meulenberg, A. J., SPE Tech. Papers, 18 (1972)
314.
28. Luther, H., Glander, F. O. & Schleese, E., Kunststojfe, 29 (1963) 409.
29. Touchette, N. W., Seppala, H. J. & Darby, J. R, SPE 20th Ann. Tech.
Con/., January 1964.
30. Bessant, K. H. c., Dilke, M. G., Hollis, C. E. & Millane, J. J., J. Appl.
Chem., 2(9) (1952) 501.
31. Juijn, J. A., Crystallinity in Atactic Polyvinyl Chloride. J. A. Pasmans,
s'Gravenhage, 1972, Ch. 4, p. 42.
32. Lehame, S. A., Park, G. S. & Norman, R. H., Brit. Polym. J., 11 (March
1979) 7.
33. Gee, G., Trans. Faraday Soc., 42B (1946) 33; 42 (1946) 585.
34. Doty, P. & Zable, H. S., J. Polym. Sci., 1 (1946) 90.
35. Burrell, H., Interchem. Rev., (Spring 1955) 3.
36. Brydson, J. A., Plastics, 26 (1961) 107.
37. Gardon, J. L. In Encyclopedia of Polymer Science and Technology,
Volume 3, ed. H. F. Mark et al. Interscience, New York, 1969, p. 833.
38. Small, P. A., J. Appl. Chem., 3 (1953) 71.
39. Fedors, R F., Polym. Engng Sci., 14 (1974) 147.
40. Koenhen, D. M. & Smoulders, C. A., J. Appl. Polym. Sci., 19 (1975)
1163.
41. Severs, F. T. & Smitmans, G., Paint Varnish Prod., 47 (1957) 54.
42. Thinius, K., Plaste u. Kaut., 5 (1958) 52.
43. Anagnostopoulos, C. E., Coran, A. Y. & Gamrath, H. R. J. Appl.
Polym. Sci., 4(11) (1960) 181.
44. DIN 53408-1967 Determination of solubility temperature of polyvinyl
chloride (PVC) in plasticisers.
45. Bigg, D. C. H., J. Appl. Polym. Sci., 19 (1975) 3119.
46. Anagnostopoulos, C. E., Coran, A. Y. & Gamrath, H. R., Mod. Plast.,
43 (1965) 141.
47. Bigg, D. C. H. & Hill, R. J., J. Appl. Polym. Sci., 20 (1976) 565.
48. Van Veersen, G. J. & Meulenberg, A. J., Kunststojfe, 57 (1967) 561.
49. Van Veersen, G. J. & Meulenberg, A. J., Kunststojfe, 56 (1966) 23.
50. Wiirstlin, F. & Klein, H., Kunststojfe, 46 (1956) 23.
51. Jasse, B., RGCP Plastiques, 5(6) (1968) 393.
52. Bell, K. M. & McAdam, B. W., Kunststojfe, 57 (1967) 26.
53. McKinney, P. V., J. Appl. Polym. Sci., 9 (1965) 3359.
54. Paul, K. T., RAPRA Members J., (November 1973) 273.
55. Chemical Industry Bibliography. Published annually by Brabender OHG,
Duisburg, FRG.
56. Immergut, E. H. & Mark, H. F., ACS Adv. Chem. Series, 48 (1965)
Ch. 1.
57. Jones, H., Hill, A. & Williamson, I., Plast. Inst. Trans., (1950) 18.
58. Frey, H. E., Kunststojfe, 46 (1956) 81.
59. Reed, M. c., J. Polym. Sci., 2 (1947) 115.
60. Reed, M. C. & Connor, L., Ind. Engng Chem., 40 (1948) 1414.
61. Quackenbos, H. M., Ind. Engng Chem., 46 (1954) 1335.
5 Plasticisers 257

62. Small, P. A., J. Soc. Chern. Ind. Lond., 66 (1947) 17.


63. Royen, M., Bull. Am. Soc. Test. Mat., 243 (1960) 43.
64. Knappe, W., Kunststoffe, 52 (1962) 387.
65. Knappe, W., Z. Angew. Phys., 6 (1954) 97.
66. Hellwege, K. H., Knappe, W. & Lohe, P., Koll. Zeit., 179(1) (1961)
40-9.
67. Titow, W. V. In Penn's PVC Technology, 3rd edn, ed. W. V. Titow & B.
J. Lanham. Applied Science Publishers, London, 1971, pp. 85-8.
68. Buszard, D. L., Chern. Ind., 16 (1978) 610.
69. Sherwood, M., Chern. Ind., 24 (1982) 994.
70. Moseley, J. & Dawkins, P., Chern. Ind., 16 (1978) 620.
71. Hull, E. H. & Mathur, K. K., Mod. Plast. Int., 14(6) (1984) 42-5.
72. ASTM D 1415-83, Standard test method for rubber property-
International hardness.
73. BS 903 (Methods of testing vulcanised rubber): Part A26 (Determination
of hardness): 1969, Appendix A (Relation between IRHD and Young's
modulus).
74. Coulson, S. H. In Plasticisers, Stabilisers and Fillers, ed. P. Ritchie.
Iliffe/PRI, London, 1972, Ch. 8.
75. EEC Draft Directive on the overall migration limit for the constituents of
plastics materials and articles intended to come into contact with
foodstuffs. Ref.: R/1444/78.
76. Biggin, I. S., Gerrard, D. L. & Williams, G. E., J. Vinyl Tech. 4 (1982)
150-6.
77. Gerrard, D. L., Bowley, H. J., Biggin, I. S. Williams, G. E. Plast. Rubb.
Process. Applns, 6(2) (1986) 97-100.
78. Your Questions Answered About Plasticised PVC Cling Film, British
Plastics Federation, 1986.
79. Surveillance Report on Plasticiser Levels in Food Contact Materials and
Foods, UK Ministry of Agriculture Fisheries and Food, 1987.
80. Poppe, A. C., Kunststo!fe, 70(1) (1980) 38-40.
81. Threshold Limit Values for Chemical Substances in Workroom Air for
1978, American Conf. of Govt. Ind. Hygienists, Cincinnati, Ohio.
82. Threshold Limit Values 1980 Health and Safety Executive, Guidance Note
EH15/80.
CHAPTER 6

Fillers

6.1 DEFINITION AND GENERAL


FUNCTIONS OF FILLERS

Fillers may be broadly defined as solid particulate or fibrous


materials, substantially inert chemically, incorporated in plastics com-
positions (including PVC) to modify the properties or to reduce
material cost. Cost reduction is often the primary reason for the use of
a filler, and because of this the term is occasionally treated
(incorrectly) as if it was synonymous with 'cheapening extender'. In
fact all fillers, when present in the significant quantities in which they
are normally used affect in some measure the material and/or
processing properties of the plastic: some-which may be termed
'functional fillers'-are indeed used, often at increased cost, expressly
as property modifiers, e.g. glass fibres as reinforcing filler in uPVC
compositions, antimony trioxide or alumina trihydrate as flame
retardants in pPVc. It may be noted that the functional aspect is
emphasised in the standard definitions of a filler (cf. for example, ISO
472-1979; BS 1755: Part 1:1967; ASTM D 883-83).
In the ideal case, the incorporation of a filler might confer the-
combined benefits of some technical advantages in the properties and
service performance of the product, possibly improvement in ap-
pearance, product cost reduction, and improved or easier processing
at no higher cost. In practice usually only one, or some, of these
features can be secured, often at the expense of the others, and the
selection of a filler or a filler system in any particular case is usually a
compromise dictated by the balance of technical requirements and cost
considerations. For example, whilst such low-cost fillers as ground
limestone and coarse ground whitings offer the highest material cost
258
6 Fillers 259

savings in many flexible PVC compositions, they can also adversely


affect the processing, and some physical properties of the end-product;
incorporation of glass-fibre reinforcement in uPVC upgrades mechani-
cal properties but increases the cost and affects the processing
behaviour of the material.
Whilst many fillers find application in PVC, the greatest industrial
and commercial importance has been attained by calcium carbonate,
chrysotile (white) asbestos, and certain types of clay.

6.2 PARTICULATE MINERAL FILLERS

On the basis of their chemical structure these fillers may be classified


into three broad groups: silicates and silicas; sulphates of the alkaline-
earth metals; and various kinds of calcium carbonate.

6.2.1 Silicates and Silicas

The silicate mineral fillers most widely used in PVC are clay and
asbestos. Others, with a relatively minor scale of application, are talc,
wollastonite, and mica; slate flour has occasionally been used as a
cheapening extender (slate is a complex of muscovite mica, chlorite,
and quartz, i.e. a composite hydrated potassium/magnesium/
aluminium silicate combined with silica); a proprietary form of
magnesium silicate has been evaluated as a lubricant additive
(i.e. not as a filler) in some uPVC compositions (see Chapter 7,
Section 7.1).
The common mineral silica fillers (sand, diatomaceoQ.s silica, quartz)
are of little interest for PVC compositions. Some special froms of
fine-particle silica are used, not as fillers but-at relatively low levels
of addition-as matting or anti-blocking agents in some pPVC
compositions, and as thickening agents in pastes (see the appropriate
chapters via the Index).
Some material property data for silicate fillers are given in Table
6.1.

(a) Clay
There are several varieties of clay, all essentially forms of complex,
hydrated alumino-silicates, with varying amounts of other, minor,
constituents (including oxides of iron, potassium, and titanium). Of
~

TABLE 6.1
Some Material Properties of Silicate Fillers Used in PVC·
."
Filler material Specific Refractive Oil Mohs Particle Remarks
gravity index absorption a hardness shape ~
."
~
Clay ~.
Kaolinite 2·60 1·56 36 2·5 Platelets Speswhite: b pH 5·0; brightness (ISO)
85·5; particle size 80% below 21lm ~
Hexafil: pH 9·0; brightness (ISO) 65; i::l
~
particle size 80% below 2 Ilm ...'"
Calcined 2·63 1·62 25 2·5 Platelets (some Pole Star 501: b pH 5·0; brightness ~.
fused into (ISO) 84·5; particle size 50% below
aggregates) 2 Ilm, 10% about 10 Ilm c~
Asbestos (chrysotile) 2·55 1·55 34 2·5-4·0 Fibres "~
Talc (Carotalc C ) 2·80 1·59 27-40 1·0-1·5 Platy '"
~.
Calcium silicate
;:
Wollastonite 2·90 1·59 26 5·0 Crystalline '"'-"
Precipitated 2·23 1·40 160 5·0 Crystalline Average particle size <lllm ).

Mica (muscovite) 2·75 1·59 47 3·0 Platelets ~


Nepheline syenite 2·60 1·60 20 6·0 Crystalline [
g.
a Most of the data relate to the rub-out test of ASTM D281-31 (1974). ill
b English China Clays International (data from Plast. Rubb. Int., 10(1) (Feb. 1985), 17).
C Croxton & Garry Ltd, UK (subsidiary of Pliiss-Staufer AG, Switzerland).
6 Fillers 261

the various clays only kaolinite ('kaolin', 'china clay'*) is significant as


a filler for PVC, used either directly (after grinding and some
purification) or in the calcined form (in which it is usually known as
calcined clay). Calcination refines the clay (by removing some im-
purities, including iron compounds, which significantly improves
electrical resistivity and enhances whiteness), removes the water of
hydration, and improves the processing performance. The main uses
of china clay in PVC are as a filler in some plasticised compositions for
extrusion and calendering, and in pastes (especially for certain coating

TABLE 6.2
Effects of Some men at Increasing Loading Levels upon Three Properties of a
Simple pPVC Compound"
Filler Properties of compound

Nature Content Tensile strength Cold flex temp. Water absorption


(phr) (lbfin- 2) eC) (% wt increase
ASTM D638 BS 2782 after 48 h immersion
at 60°c)

None 0 1700 -21 0·6


Hard china 20 1700 -18 2·8
clay 30 1400 3·7
40 1210 -15 4·9
50 890 5·1
60 1090 -9 6·5
Precipitated 20 1300 -20 1·5
calcium 30 1210 1·5
carbonate 40 920 -19 1·5
50 750 1·2
60 500 -18 1·2
Wollastonite 20 1450 -17 11·3
30 1150 8·3
40 780 -16·5 6·8
50 820 6·5
60 1100 -16 7·1
Carbon black 20 1920 -14·5 1·2
(MPC) 30 1710 -11 0·9
40 1760 -7 0·9

a PVC polymer 100 pbw; DOP 50 phr; basic lead carbonate 7 phr; filler as shown.

* Strictly speaking, although kaolinite-AI2(Si20s)(OH)4-is the principal


component of china clay, the two are not entirely identical.
262 PVC Plastics-Properties, Processing, and Applications

applications). It is also used in some formulations for pPVC hose,


wellington boots, floor tiles, and rigid PVC pipes and fittings.
Note: Bentonite clay has also been used (as well as china clay) in
some carpet-backing compositions based on PVC latices.!
In all its applications in PVC, china clay has been yielding ground to
calcium carbonate fillers, which are normally cheaper grade-for-grade
whilst otherwise fairly comparable in their effects (except for their
somewhat greater opacifying action, and some of the differences
brought out in Table 6.2 and Fig. 6.1). Calcined clay is used mainly in
pPVC cable insulation compounds where-although calcium carbonate
fillers (notably ground whiting) also compete-it is superior by virtue
of its better electrical properties; in some cases it is used in addition to

300

c 200
.2
1G Carbon black ,/.
'"o
C

100

o 10 20 30 40 50 60 70
./. By WQight of filler

Fig. 6.1 Effect of some fillers on the elongation of a pPVC compound (PCC,
precipitated calcium carbonate).
6 Fillers 263

a calcium carbonate filler, to improve insulation resistance (especially


in high-temperature insulation). Some effects of a calcined clay filler in
a pPVC composition are shown in Table 6.3. Much industrial
information on china clay is contained in a publication by Highley. 2

(b) Asbestos
The only form of asbestos used as a filler in PVC is chrysotile (white
asbestos). Chemically this is a hydrated magnesium silicate
(3MgO·2SiO·2H20). It is a fibrous material (fibre length 1-40mm,
fibre diameter 0·01-1 ,urn) with a very high fusion point (1500°C) and
100% strength retention at temperatures up to 400°C. 3 Its main
applications in PVC are in flooring compositions (where a short-fibre
grade is used, improving melt cohesion in processing and providing
some reinforcement in the product, including improved hardness and
denting resistance), and as reinforcement in pressed sheet (e.g.
Dura/orm; Turner Brothers Asbestos, UK); a longer-fibre grade is
used in the sheet, which finds application as internal and external
cladding material for buildings (especially industrial buildings),
corrosion-resistant trunking and ducting, and the like. Despite the
increasing stranglehold on the use of asbestos by restrictive and
prohibitory regulations, its safe handling and incorporation in plastics

TABLE 6.3
Some Eft'ects of a Calcined Clay Filler" in a pPVC Compositionb

Filler content, phr 0 5 10 15 20 30 40 50


Composition
propertyc

Tensile strength, Ibf in- 2 2500 2500 2500 2500 2400 2500 2400 2400
Elongation at break, % 300 280 270 250 230 170 170 120
Modulus at 100% extension, Ibf 1500 1700 1800 1900 2000 2200 2300 2400
. -2
In
Tear strength, Ib in -1 1200 1300 1400 1400 1400 1400 1500 1500
BS softness no. 38 32 32 30 29 28 26 23
Volume resistivity, ohm em x 1014
After conditioning at 23°C, 0·3 11 13 15 13 12 8 6
65%RH
After immersion in water for 0·2 3 6 7 7 6 4 2
24h at 6O"C 0·006 0·5 0·9 1-1 9 7 6

• Pole Star 501, English China Clays International.


b PVC polymer 100 pbw; DOP 50 phr; triabasic lead sulphate 7 phr; paraffin wax 1 phr; filler as
shown.
C Compounding and testing in accordance with BS 2571:1955.
264 PVC Plastics-Properties, Processing, and Applications

is technically practicable, if appropriate precautions are observed. 4 For


several years past much effort has been devoted to developing
mineral-fibre replacements for asbestos, so far without real success,
although optimistic claims in that regard have been made from time to
time. The possibility that the stability and colour of asbestos-
containing PVC compositions may be affected by the iron compounds
present as minor chemical constituents in chrysotile, is a factor in their
formulation in processing [ef. entry for lead salicilate in Table 4.1 in
Chapter 4, and Chapter 2, Section 2.2.6(d)].

(c) Talc
This material also consists of hydrated magnesium and silicon oxides
(with admixtures of other minerals and impurities, never completely
removed in preliminary processing). The chemical composition and
the particle shape of talc vary somewhat according to the source; the
shape may also be influenced by the grinding process: the particles
may be granular, plate-like ('platy' or 'scaly'), or needle-shaped, with
sizes in the range 1-50 .um.3 Talc is used in some calendered PVC
floor-tile compounds to increase melt cohesion and the stiffness and
hardness of the finished product: its low tinctorial power and its
refractive index (which is close to that of PVC resin) also make it of
interest as a filler for translucent compositions.

(d) Other Silicate Fillers

WOLLASTONITE
This is a calcium metasilicate/ sometimes employed as a filler in floor
tiles and plastisol products.

MICA
The name is a general one for a group of complex
potassium/aluminium silicates with plate-like particles. Mica is of
some interest in certain electrical insulation formulations. Fibrous
calcium silicate has been suggested as a low-cost alternative to both
mica and wollastonite.

NEPHELINE SYENITE
This is a form of anhydrous sodium/potassium/aluminium silicate. It
has been used in some semi-transparent PVC compositions (e.g. for
filled sheet) because of its low opacifying effect.
6 Fillers 265

6.2.2 Alkaline-Earth Metal Sulphates

Only two of these have some relevance as fillers for PVC, viz. barium
sulphate and anhydrous calcium sulphate.

(a) Barium Sulphate


The two grades of barium sulphate (BaS04) in use as fillers are both
produced from its naturally occurring form, the mineral barytes. The
grades are: the mineral itself, ground and purified; and precipitated
BaS04, known as 'blanc fixe'. Except where a high-density filled
compound may be required for some special reason (as for example in
backings for heavy floor coverings), the high specific gravity of BaS04
(4·5 in the crystalline form) is a disadvantage as it makes the filler
expensive on a volume cost basis. Its advantages are high brightness
(up to 99·5% reflectance) and low oil absorption (9-14gg- 1). Flexible
PVC compositions incorporating this filler find use in specialised
applications where high resistance to acids or opacity to X-rays is
required.

Note: A·typical basic formulation for an X-ray opaque film-coating


solution for surface application to PVC articles would be:
PVC polymer 100 pbw; cyclohexanone 63 phr; tetrahydrofu-
ran 63 phr; BaS04 40 phr.

(b) Anhydrous Calcium Sulphate


Anhydrous calcium sulphate (CaS04) is commercially available as a
filler in two forms: particulate and fibrous. An example of the former
is Snow White (US Gypsum Co.) a filler of 7 J.lm average particle size
now offered for PVC pastes and some solid pPVC compositions, inter
alia; other relevant grades are CS20 (for pastes) and CA-5 for PVC
pipes, conduit, and cladding. The commercial fibrous CaS0 4 (from the
same producer) is Franklin Fiber. This filler consists of single-crystal
fibres (in which the calcium sulphate is said to be in the hemihydrate
form*) of 60 J.lm average length and 2 J.lm average diameter. 5 It is
among those that have been suggested as possible substitutes for
asbestos. 6

* Truly anhydrous fibres are also available for plastics compositions for
high-temperature applications.
266 PVC Plastics-Properties, Processing, and Applications

6.2.3 Calcium Carbonate FUlers

(a) General: Types and Characteristics


The calcium carbonate (CaC03) fillers may be classified into the
following general types.

Mineral CaCOJ fillers: Whiting; ground limestone, marble and


calcite; ground dolomite.

Precipitated CaCOJ : The mineral calcium carbonates are available


at relatively low cost and in large quantities from abundant natural
sources. The energy required for their processing (grinding and
classification) is comparatively low. Their characteristics, desirable in
fillers, include low plasticiser absorption, absence of water of crystal-
lisation, and generally good resistance to thermal decomposition
during processing of the plastics compositions in which they are
incorporated, relative softness, good white colour, and purity. The
precipitated grades share these properties (although their oil and
plasticiser absorption is comparatively high); they are commonly used
for specialised applications, notably in rigid PVC compositions.

Many grades of the various types of calcium carbonate fillers are


available in surface-coated versions (see Section 6.4).

(b) Whiting
This is a fine, white powder, produced by grinding and classifying
chalk,7 which is fairly pure natural calcium carbonate found in the
form of deposits of aggregated, fossilised skeletons of microscopic
marine organisms collectively known as nanofossils, and comprising
mainly the groups foraminifera and coccoliths. The deposits were
produced, in the course of tens of millions of years, in the Cretaceous
period of the Mesozoic era (Latin creta = chalk). Apart from its
whiteness, the most characteristic features of whiting are its particle
size and shape. The particles are small-typically below 10 Ilm in size:
under suitable magnification some can be seen to have a fine granular
structure, with the granules (in most cases about 0·2-0·6Ilm) recog-
nisable as elements of a coccolith skeleton; some of the particles are
actually complete, ring-shaped skeletons roughly 4-8 Ilm in diameter,
or parts of such rings.
6 Fillers 267

Basic dry grinding of chalk leads to an end-product with the


majority of particles between 1 and 5 J.tm in size; this range is very well
suited to the material's application as a filler for PVC. Of particular
interest are whitings from Northern European chalks which are noted
for their purity (especially the almost complete absence of silicates,
and freedom from iron compounds).

(c) Ground Limestone, Marble, and Calcite


Limestone is a very widely occurring natural calcium carbonate formed
from deposits of calcified foraminifera, originally sedimented and later
consolidated by heat and pressure. Marble and calcite are hard,
compact crystalline varieties of limestone. 7 ,8 There are only a few
areas where the deposits of limestone, marble or calcite are pure
enough for grinding and processing into fillers for PVc. Of the ground
end-products, limestone fillers are the coarsest (and hence have the
lowest oil and plasticiser absorption) and of, relatively, the poorest
colour. The colour (whiteness) of ground marble and calcite is very
good; their oil absorption is lower than that of whiting. The filler
grades available are produced by either wet or dry processing. The
wet-ground materials are of higher quality, with finer particle size and
more uniform size distribution, but they are more expensive.

(d) Ground Dolomite


Limestones containing about 45% magnesium carbonate, i.e. 55: 45
CaC03 /MgC0 3 , are called dolomites (those with lower MgC0 3
contents are known as magnesian limestones). The filler grades of
ground dolomite have very good colour, and plasticiser absorptions
higher than those of their ground marble counterparts. Scandinavia
has the best deposits of dolomite.

(e) Precipitated Calcium Carbonates


These are available in two versions: as powders specially manufactured
by controlled precipitation from solutions of calcium salts, and as a
by-product from water-softening plants. Both sources provide powders
of fine particle size; few particles exceed 1 J.tm, and the average size
is well below this level. * For this reason the precipitated calcium

* For example the typical primary particle size of Winnofil (leI) precipitated
calcium carbonate (calcium-stearate-coated) is 0·06-0·09 ,urn. Although there
is some aggregation into larger secondary particles, the aggregates tend to
disperse in plastics compositions on incorporation and in processing.
268 PVC Plastics-Properties, Processing, and Applications

carbonates are normally supplied in the coated form (see Section 6.4
below) to counteract agglomeration and aid dispersion in polymer
compositions: it is an advantage of the precipitation processes that
particle-coating treatments can be applied in the course of manufac-
ture (and not as an additional processing step). The process also
affords good control over the quality, particle size, and purity of the
product, and the colour (whiteness) is normally very good. However,
the production cost of precipitated calcium carbonate fillers is in
general considerably higher than that of their ground counterparts.
Precipitated calcium carbonates are sometimes referred to as
'precipitated whiting' (especially in sales literature). This nomencla-
ture is incorrect (see the description of whiting above).
(f) Filler Properties and Selection Criteria
The features especially important in the selection of CaC03 (and
other) fillers for particular applications are: (i) maximum particle size;
(ii) particle size distribution and mean particle size; (iii) colour
(whiteness)-dry brightness; (iv) refractive index (important to opac-
ifying effects); (v) oil (plasticiser) absorption; (vi) dispersion charac-
teristics; (vii) cost.
MAXIMUM PARTICLE SIZE
Coarse filler particles can spoil the surface appearance of the product,
and impair mechanical properties (by providing points of local stress
concentration). For most pPVC compositions for extrusion, fine-gauge
calendering, and injection moulding, a maximum particle size of
10 J.lm is normally acceptable. In plastisols for spread-coating still
larger particles can be tolerated due to a higher plasticiser content and
less need for particularly good mechanical properties (but in low-
viscosity plastisols coarse filler particles may tend to sediment-out).
For rigid PVC compositions it had long been accepted that the
maximum filler particle size should be under 1 J.lm for the desirable
level of mechanical properties and surface appearance. This effectively
restricted this usage area to precipitated calcium carbonates. However,
ground natural CaC0 3 fillers-which are cheaper~an now be used
(with maximum particle size of about 5 J.lm), thanks to improvements
in selection and milling techniques, compounding equipment, and
formulations.
PARTICLE SIZE DISTRIBUTION AND MEAN PARTICLE SIZE
The particle size distribution influences the way in which the filler
particles pack together. This in turn affects the highest tolerable filler
6 Fillers 269

loading that is still compatible with acceptable rheological properties


of heavily filled PVC melts and pastes. For example, with PVC pastes
for car-body undersealing, the use as filler of a blend of fine-ground
whiting and a coarser-ground calcite permits high loading levels, whilst
the paste is still sufficiently fluid for spray application, and the sprayed
coating has good non-sag characteristics.
In general, the finer the mean particle size, the better the physical
properties and surface appearance of the filled material (for the same
content and size of the coarsest particles). In PVC pastes for slush or
rotational moulding, fillers of mean particle size no greater than
1-31lm should be used to avoid filler settlement problems in
processing.
A standard method suitable for the determination of the particle
size distribution in the sub-sieve range of such fillers as clay, talc,
mica, and the calcium carbonates (as well as titanium dioxide and
other mineral pigments) is the sedimentation method of ASTM D
3360. 9

DRY BRIGlITNESS
This is normally measured and expressed in terms of percentage of
light of a stated wavelength reflected from the smoothed surface of the
white filler powder specimen in comparison with a stated standard
material.
Note: The method of ISO 2470 10 (originally established for white
paper and board) is commonly used, with a magnesium oxide
powder standard, or an absolute standard. 10

REFRACTIVE INDEX (OPACIFYING EFFECT)


The main factor governing the opacifying effect ('hiding power') of a
white filler or pigment in a given medium is the extent to which incident
light is refracted and reflected (scattered) by the particles. * Both the
refraction and reflection depend on the refractive indext of the filler or
pigment material in the medium (reflection also to some extent on the

* In a dispersion of filler particles in a medium the incident light will undergo


multiple refractions and reflections.
t For practical purposes the refractive index of a filler material may be
regarded as constant: however, as with any other material, it normally
increases somewhat with decreasing wavelength of the incident light ('normal
dispersion'). For materials that actually absorb light in any part of the
wavelength region concerned, the refractive index also changes within the
absorption band ('anomalous dispersion,).12
270 PVC Plastics-Properties, Processing, and Applications

particle configuration and size), and both increase with its value.
Thus---other factors (such as particle size and shape, size distribution,
level of loading, and dispersion) being equal-the higher its refractive
index, the greater the opacifying effect of a filler or pigment in a given
plastics composition.
Note: For light incident normally (i.e. at zero angle of incidence) on
the surface of a substantially transparent dielectric material
(such as that of one of the fillers discussed in this section) of
refractive index n, the proportion reflected is given by the
Fresnel relationshipll r = (n - 1)2/(n + 1)2. This proportion
increases with increasing angle of incidence (i.e. as the light
strikes the surface more obliquely) in accordance with a
function more complex than the simple Fresnel equation. At
grazing incidence a phase change also occurs.
The opacifying capabilities of a few common fillers-in comparison
with that of titanium dioxide-in air, PVC polymer, and a common
general-purpose plasticiser (DOP), are illustrated by the data of Table
6.4. As can be seen, all the filler materials listed are strongly opaque in
air, as their refractive indices are much higher than unity and the
proportions of light reflected (even in the ideal, lower-limit case of
normal incidence to which the Fresnel relationship applies) are quite
substantial, ranging from 4·8% for kaolinite to 6% for barium
sulphate. However, the table also brings out clearly the difference in
opacifying power in PVC and DOP between white fillers on one hand
and a true pigment like titanium dioxide on the other. Thus, the
refractive indices of even anatase (the less opaque of the two Ti0 2
pigments) in the two media are comparable with that of barium
sulphate (the most opaque of the fillers) in air, as are the percentages
of light reflected. At the same time, the refractive indices of barium
sulphate in PVC and DOP are both near unity (indicating relatively
little opacification by refraction) and the corresponding light reflection
values are only 0·096% and 0·26% respectively.
Note: Thus if reflection was due only to normally incident light the
filler would appear almost transparent even in DOP. In
practice various degrees of optical translucence are achiev-
able in PVC compositions.
Another point brought out by the data of Table 6.4 is that whilst the
refractive indices of two fillers in a medium may differ by a factor of
TABLE 6.4
Refractive Indices of Some White Fillers, and Proportions of Light Re8ected at Normal Incidence in
Three Media, in Comparison with Titanium Dioxide Pigments
Refractive index values Fraction of light reflected
at normal incidenceo
In air, In PVC polymer InDOP In air In PVC polymer In DOP
n. np = n./npb n. = n./n L c ra rp r.
0\
Kaolinite 1·56 1·006 1·047 0·048 0·000009 0·00053 :!l
Whiting 1·57 1·013 1·054 0·049 0·000042 0·00069 ~
-
Talc 1·59 1·026 1·067 0·052 0·00016 0·0011 t:!
Calcined clay 1·62 1·045 1·087 0·056 0·00048 0·0017
Precipitated CaC03 1·63 1·052 1·094 0·057 0·00064 0·0020
Barium sulphate 1·65 1·064 1·107 0·060 0·00096 0·0026
Titanium dioxide
Anatase 2·52 1·626 1·691 0·186 0·057 0·066
Rutile 2·76 1·781 1·852 0·219 0·079 0·089
r r. = (n. -1)2/(n. + 1)2; rp = (np -l?l(n p + 1)2; rl = (n. -l?/(n. + 1f.
b np = refractive index of PVC polymer: taken as 1·55 for the purpose of the calculation.
C nL = refractive index of DOP: taken as 1·49 for the purpose of the calculation.

!:j
....
272 PVC Plastics-Properties, Processing, and Applications

only 1·057, the fractions of normally incident light they will respec-
tively reflect can differ by a factor of nearly 5 (compare the relevant
data for kaolinite and barium sulphate in DOP).
Differences between the refractive indices of a filler in air and in a
PVC composition play a cardinal role in the phenomenon of 'stress
whitening' ('crease whitening'). This can be brought about by strong
local stressing (as for example by sharp bending or creasing) of a filled
PVC material in which the interfacial adhesion between the filler
particles and the polymer matrix is relatively poor (e.g. as a result of
incomplete 'wetting-out' of the former by the latter in compounding
and processing). The 'whitening' is strong local opacification caused by
the formation of microvoids between the filler particles and the PVC
matrix: in these voids the local refraction and reflection of light by the
particles is governed by their refractive index relative to air (or even
partial vacuum), which is much higher than that relative to the PVC
composition (with or without plasticisers-cf. Table 6.4).

OIL (PLASTICISER) ABSORPTION


The standard tests for this property originally evolved for use with
pigments for paints, and many specify the use of an oil (commonly
linseed oil). However, they are also applicable to pigments and fillers
for plastics: in the context of PVC this kind of test is normally run with
DOP (or sometimes with another plasticiser that is relevant to a
particular formulation). In terms of the standard tests, oil (or
plasticiser) absorption is defined as the weight in grams of the
appropriate oil (or plasticiser) required to 'wet-out' completely (so
that a paste of stipulated consistency is formed) 100 g of the pigment
or filler. The main relevant standard specifications are: ISO 787:Part
5-1980 (palette-knife rub-out on a glass plate of 100 g of pigment or
filler with oil added dropwise) identical with BS 3483:Part 7:1982;
ASTM D 281-84 (spatula rub-out of 100 g of pigment with linseed oil
or another liquid, to a stiff, putty-like paste); ASTM D 1483-84
(Gardner-Coleman method, involving dropwise addition, with gentle
stirring, of specified linseed oil to 100 g of pigment).
Note: DIN 53199 originally operated in Germany has been aban-
doned in favour of ISO 787 Part 5.
The plasticiser absorption of pigments and fillers for PVC composi-
tions is related to, but is not a direct measure of, the actual 'plasticiser
demand', i.e. the extent to which the filler will absorb plasticiser when
6 Fillers 273

incorporated in a plasticised composition. It is an important considera-


tion in deciding on fillers for such compositions, including pastes.
The plasticiser demand and oil absorption both tend to increase with
the surface area of the filler, and hence to decrease with increasing
particle size. Fillers with good particle packing characteristics exhibit
lower oil absorptions, and the more crystalline the particles the less
they absorb internally. The presence of a coating on a filler (see
Section 6.4) reduces oil absorption in tests and the actual plasticiser
demand in PVC compositions. Thus the use of coated fillers can save
costs by permitting either increased filler loading for the same amount
of plasticiser, or a reduction in plasticiser for the same filler loading.
The filler's plasticiser absorption can be related to the softness of a
filled flexible compound, and the viscosity of a filled plastisol. Fillers
with high oil absorptions (over 20 g per 100 g) will normally necessitate
the use of substantially more plasticiser when formulating for a
particular BS softness, than will low-absorption fillers. In a plastisol
the oil absorption of the filler is directly related to its effect on
viscosity, whilst-in general-increased filler loadings result in an
increase in viscosity. If high viscosity is required but-to limit the
effect on final properties-only a relatively low filler loading can be
tolerated, then a filler with high oil absorption may usefully be chosen
to increase the viscosity to the required level. However, it is more
common to find examples where the upper viscosity limit is reached
before the limiting effect on physical properties. In such cases,
low-absorption fillers will effectively mean that higher loadings can be
achieved, with corresponding reductions in overall formulation cost.

DISPERSION CHARACrERISTICS
It is important that any filler used should be thoroughly and uniformly
dispersed in the PVC composition. Non-uniform dispersion can
adversely affect the physical properties, whilst undispersed aggregates
have the same effect as large particles (see above). Different kinds of
filler can differ in ease of dispersion in a given composition;
fine-particle versions of a filler are generally more difficult to disperse
than coarse ones. The presence of a stearate coating on a filler
facilitates and speeds up dispersion in PVC compositions.

COST
With the partial exception of some functional fillers, filler addition is
commonly a means of reducing formulation cost. However, it is always
274 PVC Plastics-Properties, Processing, and Applications

important to consider in this context not just the price of the filler, but
also its nett cost-effectiveness in the composition and in processing.
A substantial loading of a low-price filler may appear attractive, but
the apparent price advantage could easily be offset by a consequent
reduction in processing rate (with lower output), cost of any extra
pigment that might be required to improve whiteness, increased
plasticiser level, poorer physical properties and/or surface finish. For
example, whilst the cheapest CaC03 fillers-ground coarse whitings
and limestone-are widely used, at high loadings, in low-cost flooring
compositions, they are not normally suitable for applications in which
good physical properties and appearance of the product are important.
Moreover, their high plasticiser demand, relatively poor whiteness and
dispersibility will-in comparison with a finer, more uniform CaC0 3
filler grade-necessitate more plasticiser and pigment, with longer and
harder mixing. Fusion times in melt-processing could also be longer. A
coated filler, although more expensive than an uncoated grade, can
give up to 50% higher extrusion outputs, as well as allowing reductions
in the lubricant and/or plasticiser contents. Fine fillers can be used at a
higher loading for the same physical property level as that given by
coarser fillers at lower loading, so that where special specifications
have to be met, the higher loading of a fine filler will help to reduce
the cost further. This is frequently the case with whitings in cable
compounds, where a fine-grade filler costs only marginally more than
a coarser grade, but can be used at much higher loadings, giving
greater savings on polymer and plasticiser.
The relatively highly-priced precipitated, surface-coated calcium
carbonate fillers can-by virtue of their very small particle size,
uniformity and good dispersibility~ffer advantages that favourably
affect the ultimate product cost and quality. The advantages are:
shorter fusion times and the counteraction of plate-out in processing,
and (in the product) improved surface smoothness and gloss, and
prevention of such surface defects as 'sharkskin' that can sometimes
arise under high shear gradients in processing (e.g. in some injection
mOUldings). Impact resistance improvements are also effected [see
Section 6.3.1(e)iii].
In considering the effective cost of a filler for a formulation, an
important element is the volume cost (cf. Section 2.3 of Chapter 2).
The relative densities (SG) of mineral fillers are considerably higher
than those of the resin/plasticiser mix, and their cost per unit volume
is the product of unit weight cost and density in each case. Thus, for
6 Fillers 275

example, for calcium carbonate, with a relative density of 2·7, the cost
of 1 ml will be 2·7 times the cost of 1 g; for barium sulphate the factor
is about 4·5, and so on.
(g) Applications, and Some Effects of Filler Loading
The main applications of CaC0 3 fillers are indicated in Table 6.5. The
following points may be mentioned by way of amplification.
FLOORING
This is a big usage area for fillers, especially asbestos and CaC03 in
PVC. Calcium carbonate fillers are incorporated in flooring composi-
tions not merely to save cost, but also because substantial filler
loadings increase weight, reduce shrinkage, and improve impact
identation resistance. Crystalline types (calcite) and finely ground
limestone are widely used in plastisol compositions for backed
flooring, produced by spreading the plastisol on a substrate (fabric or
paper). Filler loadings may range between 200 and 500phr, subject to
considerations of the required plastisol rheology. Figure 6.2 presents
some relevant data l for a plastisol composition highly filled with
Calibrite (special ground calcite grade; Pliiss-Staufer AG). As indi-
cated by the figure, it is possible, by running the spreading process at
suitably high shear rates (i.e. high spreading speeds, which also result
in high output), to operate at very high loadings of this particular filler
whilst keeping the viscosity reasonably low.
PLASTICISED COMPOUNDS
Fine-ground whitings and calcites are the most suitable CaC0 3 fillers
for extrusion compounds. Filler loadings in the range 20-100 phr are
normal. Some typical effects of increasing filler loading are shown in
Table 6.6. As can be seen, the effect of a fine whiting (in loadings up
to 40 phr) on some physical characteristics of the compound is not very
great. Table 6.7 shows the effects of increasing loading level of a
coated whiting (Omya BSH). The coated whitings have good disper-
sion characteristics and improve the process ability of the compound.
They suffer little agglomeration and, being hydrophobic, resist
moisture pick-up in storage. The coating also improves the free-
flowing characteristics of the filler, making it particularly suitable for
bulk-handling systems. In cable compounds, coated whiting offers
some advantages (including lower plasticiser demand) over cor-
responding uncoated grades, even at relatively low loading levels-d.
Table 6.8.
TABLE 6.5
Applications of CaC03 Fillers in PVC

Application Relevant filler Filler features and advantages / Examples


Remarks of
Type a Typical particle commercial
size (1'"1) products

Mean Nominal
maximum

1. Plastisols
Fabric coatings; foams Ground calcite 13-15 60-75 Low plasticiser demand, good Calibrite b
rheological properties (for
fast spreading)
Ground calcite (s) 3-5 10-20 The finer filler gives good sur- Millicarb;b Omya
face finish; obviates possible BLHb
settlement problems
Spread-coated flooring Ground calcite (some 30 200 Good physical properties are Omya D40b
(base coats) grades of ground lime- not normally critical in this
stone also suitable) application, hence relatively
coarse filler can be used for
high loading and fast
spreading rates
Rotational moulding; dip- Ground calcite (s) 3 10 Filler fineness and crystalline Millicarb;b Omya
coating structure (and coating if pre- D2b
sent) give, respectively free-
dom from settlement and re-
latively moderate thickening
2. Extrusion compounds
(a) flexible:
General Ground whiting, s 2 10 Fine particle size gives good Britomya BSH;b
Ground calcite 3 10 surface finish and physical Millicarb b
properties
Dry blends Precipitated, s <1 <4 Good dispersion, low equip- Day/Cal;C
ment abrasion, good flow, Hakuenka b
relatively low plasticiser
demand
Ground calcite 1-3 7-10 Good dispersion and physical Millicarb ;b
properties Hydrocarb b
Cable sheathing and Ground whiting (s) Up to 2 10 Good physical properties and Britomya M or
insulation fast output promoted by BSHb
filler fineness (fastest pro-
duction with coated grades).
Special 'electrical' grades
available
(b) Rigid:
Pipe, cladding, profiles Precipitated, s <5 About 7 Small particle size and good Super-Pflex 200;d
Ground whiting, s 1-2 5 dispersion are particularly Omyalite 9srb
important (for good physical
properties and processability,
respectively)
Soil pipe, rainwater goods Ground whiting, s 2 10 Somewhat coarser particles ac- Britomya BSHb
ceptable here
3. Injection-moulding compounds
(a) Flexible:
General Ground calcite 3 These fine-particle grades give Millicarb b
10} good balance of physical
Ground whiting, s 2 10 properties, ease of dispersion Britomya BSHb
and pro<:e~sability
Shoe-sole compounds Ground calcite Finest particle grades required for good wear Hydrocarb b
Ground whiting (s) properties, resistance to flex cracking, cut growth Omyalite b
Precipitated, s and other effects of damage in service
(b) Rigid:
Pipe fittings Generally similar to those for rigid extrusion compounds, but fine particle size
(especially low maximum size) even more important (because of need to ensure
good physical properties of compounds based on polymer of low K value) (continued)
TABLE 6.5-contd. ~
Application Relevant filler Filler features and advantages / Examples
Remarks of
Type" Typical particle commercial
size (11m) products
"tI
Mean Nominal ~
"tI
maximum
~

General Generally as for extruded soil pipe and rain-water goods


4. Calendering compounds t
~
(a) Flexible: ~
Thin sheeting Ground calcite (s) 3 10 Good dispersion, physical pro- Millicarb;b Pfinyl ~.
Ground limestone (s) <5 10 perties, surface finish, and 402;d Britomya ....
Ground whiting, s 2 10 low plasticiser demand are BSH·, b ~
<::>
the main requirements to be
met
"~
'"
~.
Thick sheeting Ground whiting (s) 2-3 10- Physical properties usually less MordenR;b
100 critical, hence less refined Britomya
filler may be used. Coarse V/L;b ~
).
ground calcite may be in- Britomya
~
cluded in some compositions BSHb ~
I:>
to counteract blister 5'.
formation !:l
(b) Rigid sheeting Ground whiting, s 1-2 5-10 Fine grades (coated for good Britomya BSH;b
dispersion) required, to give Omyalite 95Tb
good physical properties.
Finest particle size for high
impact strength sheeting

"s = Stearate or other suitable surface treatment (desirable but optional if shown in brackets).
b Croxton & Garry Ltd, UK.
C H"rnsnn Fnternnses_ lJSA_
6 Fillers 279

10 4
9
B
c.. 7
u
6
>:
..... 5
'iii
0 4
U
III
:> 3

103
300 400 500 600
Calibrite loading, phr

Fig. 6.2 Viscosity of a Calibrite-filled plastisol composition for spread-coating


as a function of filler loading and shear rate.

RIGID COMPOUNDS
In these, the more expensive CaC0 3 fillers are used-viz. surface-
treated precipitated grades and ultrafine ground, surface-treated chalk
whitings-not as cheapening extenders but, at relatively low loading
levels, to improve processing and/or product properties. In the
whitings, even a small proportion of particles coarser than about 2 Ilm
can have a detrimental effect on the mechanical properties of the
compound.
Even when present in a relatively low proportion, fine CaC0 3 filler
can increase the internal friction in the stock during, compounding and
TABLE 6.6
Some Elfects of FiBer (3 pm Whiting) Loading on Plasticised Compound"

Filler, phr 0 10 20 30 40
Tensile strength, lbf in- 2 2585 2605 2500 2465 2410
Elongation at break, % 325 335 325 315 305
Hardness, Shore A 79 80 81 82 83
Relative density 1·234 1·271 1·312 1·350 1·384
Brittle temperature, °C -50 -40 -35 -30 -30

aPVC resin 100 phr; plasticiser (DOP) 55 phr; stabiliser (Ba/Cd) 2 phr; lubricant (stearic
acid) 0·5 phr; filler 0-40 phr.
280 PVC Plastics-Properties, Processing, and Applications

TABLE 6.7
Some Effects of Increased Loadings of a Coated Whiting (Omya BSH) on a
Plasticised Compound"

Filler, phr 0 10 12 15 20 35 50 150


Tensile strength, lbf in- 2 2700 2500 2475 2425 2425 2225 2035 1925
Modulus at 100%
elongation, lbf in - 2 2225 1985 1970 1965 1925 1850 1775 1950
Elongation at break, % 200 210 215 210 210 200 185 125
Tear resistance, lb in- 1 81 81 80 78 76 75 67 47
Brittle temperature, °C -20 -19 -19 -18 -18 -17 -14 -5

a PVC resin 100 phr; plasticiser (DOP) 50 phr; stabiliser (dibasic lead phthalate) 3 phr;
lubricant (dibasic lead stearate) 1 phr; filler 0-150 phr.

processing: this improves the dispersion of the other additives (pig-


ments, lubricants, stabilisers, etc.).
With precipitated, surface-treated calcium carbonates-typically
characterised by very fine particle size (about O·lllm) and narrow size
distribution-the filler's own dispersibility, and its effect on that of
other additives in the uPVC compound, are very good at the usual
relatively low incorporation levels (up to about 10 phr); the dispersed
filler also promotes uniform frictional heating and shear throughout
the stock, and thus reduces fusion time. In some formulations it is
possible to reduce or even eliminate the polymeric processing-aid
additive by substituting an only slightly higher proportion (in terms of
phr) of precipitated CaC0 3 filler. At loadings significantly above
TABLE 6.8
Effect of Surface-Treated Whiting on Some Pro-
perties of a Cable Compound

PVC resin 100 100


nop 45 43·3
Lead stabiliser 3 3
Lubricant 1 o
Uncoated whiting 15 o
Coated whiting o 15
Tensile strength, kg cm- 2 190 195
Elongation at break, % 200 210
Brittle temperature, °C -17 -18
Relative density 1·33 1·33
Volume resistivity 1.7 x 1014 5·5 x 1014
at 20°C, Oem
6 Fillers 281

10 phr, the internal shear increase in the stock can become excessive,
due to the thickening effect of the very fine filler particles.
These effects are much less drastic with the so-called ultra-fine
ground whitings which-despite the name-are coarser by an order of
magnitude than the precipitated CaC03 grades. Because of this, even
at loadings substantially in excess of 10 phr, the number of particles
present in the melt and the total particle surface are much less, and
hence the rise in internal shear remains within acceptable limits.
Modern compounding machinery makes it possible to produce rigid
compounds (e.g. for extrusion) containing up to 100 phr of such fillers.
Whilst at such loading levels the use of the filler in a rigid compound
can bring significant cost saving, the increased density and the possible
reduction of some physical properties (especially impact strength)
must be considered.
In any particular case the choice of type of CaC0 3 filler and the
loading level will depend on the nature of the process and the end-use
of the product: it will be made in the light of experience and/or advice
from a reputable supplier of the filler. Final optimisation is a matter
for laboratory production trials.

6.3 FUNCTIONAL FILLERS

These are the fillers that impart or modify a particular property or


group of properties in a PVC composition: their presence most often
increases the formulation cost, and may also make processing more
difficult or expensive.

6.3.1 Reinforcing F~ers

Most of these are fibrous, although glass spheres (and even precipi-
tated CaC03 when used in uPVC at low levels of loading) may be
included under this heading. With the partial exception of chrysotile
asbestos, none is in particularly wide industrial use in PVC: however,
several merit a mention for the sake of their general technological
interest.

(a) Asbestos (Chrysotile) Fibres


The application of chrysotile asbestos as a reinforcing filler for PVC
has already been mentioned [in Section 6.2.1(b)]. It may be noted
282 PVC Plastics-Properties, Processing, and Applications

additionally that, as in the case of most reinforcing fillers, good


interfacial contact (with the right degree of adhesion) between the
fibre and the polymer matrix improves the initial dispersion and the
reinforcing effect. Some surface treatments (notably with a poly-
ethylene glycol) applied to the asbestos fibre were found 13 to improve
the impact strength and flexural modulus of the filled PVC compound.
The practical and commercial repercussions of the concern about
health hazards believed to be associated with the handling of asbestos
in processes and products have made themselves strongly felt on both
sides of the Atlantic.

(b) Miscellaneous Inorganic Microfibres


None of these is of major current importance as a reinforcement for
PVC. However, the following materials may be briefly mentioned to
illustrate what is generally available in the way of possible asbestos
substitutes.
(i) Hydrated sodium/aluminium fibre (Dawsonite; ALCOA). *
(ii) Potassium titanate fibre (Tismo;t developed by the Otsuka
Chemical Co., Japan, and marketed by the Biddle Sawyer
Corp., USA).
(iii) 'Processed Mineral Fibre' (PMF; Jim Walter Resources Inc.,
USA), produced from blast-furnace slag.
(iv) Polymeric calcium sodium metaphosphate fibre (Phosphate
Fiber; Monsanto). This high-strength fibre is claimed to de-
grade naturally (by hydrolysis to orthophosphate ions) if
ingested, inhaled, or exposed for prolonged periods to the
environment.
(v) A low-cost slag fibre (Thermafiber FRF; USG Acoustical
Products, USA). This is offered mainly as a cheaper alternative
to milled glass.

(c) Glass Fibres


As in the case of other thermoplastics, the incorporation of glass fibres
in a rigid PVC compound can substantially upgrade some mechanical

* Aluminium Company of America.


t This fibre may be regarded as the technical successor to the Du Pont Fybex
potassium titanate fibre, which was discontinued in 1974. Until that time some
Fybex-reinforced rigid PVC compositions were also available from certain
suppliers. 1,3,4
6 Fillers 283

properties (especially the flexural modulus and tensile strength), as


well as resistance to creep and fatigue. As with other thermoplastics
reinforced with short glass fibres, the degree of improvement in these
properties depends on the orientation of the fibres in relation to the
direction of imposed stress, and-given that-also on the fibre length,
amount present, and the interfacial adhesion between the fibres and
the PVC matrix. The temperature of deflection under load is also
normally increased by glass-fibre reinforcement of uPVC, but the
increase is only relatively moderate (cf. Tables 6.9 and 6.10 and
Appendix 1).
After their original introduction, towards the end of the 1960s/ the
industrial demand for glass-fibre-reinforced uPVC compositions was
not particularly high. In the late 1970s it declined further, to the point
where the compositions ceased to be produced, partly as a result of
two unfavourable features of these materials: the adverse effect of
moisture on their mechanical properties (attributable to disruption by
moisture of the matrix-glass interfacial bond), and the further
complication by the presence of the glass fibres of the melt rheology in
processing (already fairly difficult due to the high melt viscosity of
uPVC and its susceptibility to thermal degradation). In 1986, the
second generation of glass-fibre-reinforced uPVC compositions for
injection moulding and extrusion was launched by B. F. Goodrich in
the shape of the various grades* of their Fiberloc compounds. These
incorporate a specially developed surface treatment for the glass fibres
to promote effective adhesion to the PVC matrix. The easy-flow
grades also benefit from the know-how accumulated by B. F.
Goodrich in this area. All grades are said to be produced by a special
compounding procedure. Some properties of one original producer's
first-generation reinforced uPVC compounds (as moulded, i.e. not
after prolonged exposure to moisture), and those of some Fiberloc
grades are shown, respectively, in Tables 6.9 and 6.10.

(d) Microspheres
Hollow microspheres (glass or ceramic) are occasionally used in some
PVC pastes, where they increase viscosity in processing, as well as the
hardness and abrasion resistance of the products, with less effect upon
the density than would be exerted by solid microspheres. Slag

* Over 20 basic grades are available, plus special additional grades repre-
senting variants adjusted for particular purposes.
TABLE 6.9
Effect of Glass-Fibre Reinforcement on Some Properties of Rigid PVC

Property Method Units Unreinforced Reinforced


of (Ethyl 7042 (Ethyl 7042 compoundt
determination compoundt

10% glass 20% glass 30% glass

Specific gravity ASTM 0 792 1·40 ± 0·02 1·45 1·53 1·61


. -1
Mould shrinkage in In
or
-1
mmmm 0·003-0·004 0·002 0·001 0·001
Tensile strength ASTM 0·638 lbf in -2 (MN m -2) 6400(44·1) 9000 (62·0) 14000 (96·5) 16000 (110·3)
Tensile modulus ASTM 0 638 lbf in -2 (MN m -2) 420000 (2 896) 650000 (4481) 1200 000 (8273) 1300000 (8963)
flexural modulus ASTM 0 790 lbf in -2 (MN m -2) 375 000 (2 585) 600 000 (4 136) 950000 (6550) 1100 000 (7584)
~ in (3·175 mm) bar ASTM 0 256 ft lbf in -1 (J m -1) 15 (800·20) 6 (320·08) 3·5 (186·71) 2 (106·69)
Heat distortion at
264 lbf in -2 (1.82 MN m -2) ASTM 0 648 °C 70·6 81·7 86·7 87·8

• Ethyl Corporation, USA (the PVC business of this company was taken over in the early 1980s by Georgia-Pacific Chemicals Inc., which in tum was
incorporated in the Georgia Gulf Corp. in 1985: ct. Table 3.8 in Chapter 3).
TABLE 6.10
Some Properties of New-Generation Glass-Fibre-Reinforced UPVC Compounds"
(Table based on manufacturer's published data)
Extrusion Injection moulding
b b
Single- Twin· Nomrol High·fIow, Nomrol High-jlow, b Nomrol High·fIow, High-flow
screw screw flow high-Dr' flow high-DT flow high-DT high-impact
Glass fibre content % by weight 10 10 10 10 20 20 30 30 30
Specific gravity 1·39 1-40 1·43 1·37 1·50 1-43 1·57 1·53
Tensile properties
Strength lit x (lbf in -2) 7-8 g·3 10·5 g·O 12·g 10·0 13·9 11·5 15·0
Elongation at break % 7·2 5·0 6·0 6·6 2·7 4·4 2·0 3·5
Flexural properties
Strength lit x (Ibf in -2) 11·7 12·6 17·6 12·2 22·5 15·g 22·g 17·9 21·0
Modulus 1(i' x (Ibf in -2) 4·5 5·1 6·4 4·6 9·7 6·g 11·9 9·5 12·0
Impact resistance (Izod) ft-Ib in-I
Notched 1-6 l·g O·g l·g 1·0 1·9 1-1 l·g O·g
Unnotched g·5 9·0 6·0 g.g g·O 9·3 g·4 g.g 9·0
Deflection temperature under load OC 77 7g 75 73 75 74 76 75 76
(264lbf in - 2)
Coefficient of linear thermal 10- 5 x (OC)-1
4-1 4·3 3·6 3·g 2·3 3·6 2·2 2·5 2·0
expansion
Flow in