Polymer Chemistry

: Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999)
POLYMER CHEMISTRY

CONTENTS
PART POLYMER STRUCTURE AND PROPERTIES

1. Basic principles 2. Molecular weight and polymer solutions 3. Chemical structure and polymer morphology 4. Chemical structure and polymer properties 5. Evaluation, characterization, and analysis of polymers

POLYMER CHEMISTRY

CONTENTS
PART VINYL POLYMERS

6. Free radical polymerization 7. Ionic polymerization 8. Vinyl polymerization with complex coordination catalysts 9. Reactions of vinyl polymers

POLYMER CHEMISTRY

CONTENTS
PART NONVINYL POLYMERS 10. Step-reaction and ring-opening polymerization 11. Polyethers, polysulfides, and related polymers 12. Polyesters 13. Polyamides and related polymers 14. Phenol-, urea-, and melamine-formaldehyde polymers 15. Heterocyclic polymers 16. Inorganic and partially inorganic polymers 17. Miscellaneous organic polymers 18. Natural polymers
POLYMER CHEMISTRY

Chapter 1. Basic principles

1.1 Introduction and Historical Development 1.2 Definitions 1.3 Polymerization Processes 1.4 Step-reaction Polymerization 1.5 Chain-reaction Polymerization 1.6 Step-reaction Addition and Chain-reaction Condensation 1.7 Nomenclature 1.8 Industrial Polymers 1.9 Polymer Recycling
POLYMER CHEMISTRY

1.1 Introduction and Historical Development

A. Development of civilization Stone age Bronze age Iron age Polymer age B. Application of polymeric materials
PE milk bottles Polyamide bulletproof vests Polyurethane artificial heart Fluorinated environments phosphazene elastomer for arctic

POLYMER CHEMISTRY

C. The purpose of this book

1. Property difference between polymer and low molecular weight compound 2. Chemistry of polymer synthesis 3. Chemistry of polymer modification

POLYMER CHEMISTRY

D. Development of polymer chemistry

1833 : Berzelius, the first use of terminology, polymer 1839 : Synthesis of polystyrene 1860s : Poly(ethylene glycol), Poly(ethylene succinate) 1900s : Leo Baekeland, synthesis of phenol formaldehyde resin 1920s : Hermann staudinger Structure of polymer(long-chain molecules), Novel Prize(1953 ) 1939 : W.H. Carothers, Nylon synthesis (Du Pont) 1963 : Ziegler-Natta, stereoregular polymerization 1974 : Paul Flory, polymer solution property 1984 : Bruce Merrifield, solid-phase protein process
POLYMER CHEMISTRY

E. Examples of monomers and polymers

Monomer
CH2 CH2 CH2 CHCl

Polymer

CH2CH2

CH2CH2 Cl

O H2C CH2

CH2CH2O
CH2CH2O O

HOCH2CH2OH

HO

CO2H

POLYMER CHEMISTRY

1.2 Definitions
A. Acoording to the amount of repeating units
monomer : one unit oligomer : few polymer : many (poly many, mer part) telechelic polymer : polymer containing reactive end group (tele = far, chele = claw) telechelic oligomer : oligomer containing reactive end group macromer(=macro monomer) : monomer containing long chain

POLYMER CHEMISTRY

1.2 Definitions
B. DP : Degree of polymerization

The total number of repeating units contained terminal group

C. The kinds of applied monomers One kind : Homopolymer Two kinds : Copolymer Three kinds : Terpolymer

POLYMER CHEMISTRY

D. Types of copolymer

Homopolymer : -A-A-A-A-A-A-A-ARandom copolymer : -A-B-B-A-B-A-A-B-

Alternating copolymer : -A-B-A-B-A-B-A-BBlock copolymer : Graft copolymer : -A-A-A-A-B-B-B-B-A-A-A-A-A-A-A-A-

B-B-B-B-B-

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E. Representation of polymer types

(a) linear(b)branch

(c)network

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F. Representation of polymer architectures

(a) star polymer

(b) comb polymer

(c)ladder polymer

(d) semi- ladder (or stepladder) polymer

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F. Representation of polymer architectures

(e) polyrotaxane

(f) polycatenane

(g) dendrimer
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G. Thermoplastic and thermoset (reaction to temperature)

Thermoplastic : Linear or branched polymer

Thermoset : Network polymer

POLYMER CHEMISTRY

1.3 Polymerization Processes

A. Classification of polymers to be suggested by Carothers

Addition polymers : repeating units and monomers are same

Condensation polymers : repeating units and monomers are not equal, to be split out small molecule

POLYMER CHEMISTRY

Other examples 1. Polyester from lactone (1.7) &

from -hydroxycarboxylic acid (1.8)

O O C
O R O C

(1.7)

O OH R CO2H O R C + H 2O

(1.8)

POLYMER CHEMISTRY

Other examples 2. Polyamide from lactam (1.9), and from -aminocarboxylic acid (1.10)

O NH R C NH R

O C

(1.9)

O H 2N R CO2H NH R C + H2O

(1.10)

POLYMER CHEMISTRY

Other examples 3. Polyurethane from diisocyanate and dialcohol(1.11) and from diamine and bischloroformate(1.12):
OCN R NCO + HO R' OH
O O

CNH

NHCO

R'

(1.11)

H2N

NH2 + ClCO
O

R'

OCCl
O

(1.12)
R' O + 2HCl

CNH

NHCO

POLYMER CHEMISTRY

Other examples 4. Hydrocarbon polymer from ethylene (1.13), and from ,-dibromide (1.14)

CH2

CH2

initiator

CH2CH2

(1.13)

BrCH2(CH2)8CH2Br

2Na

CH2CH2

2NaBr (1.14)

FUNCTIONALCHEMISTRY POLYMER POLYMERS LAB

1.3 Polymerization Processes

B. Modern classification of polymerization according to polymerization mechanism Step growth polymerization : Polymers build up stepwise

Chain growth polymerization : Addition polymerization molecular weights increase successively, one by one monomer Ring-opening polymerization may be either step or chain reaction
POLYMER CHEMISTRY

1.4 Step-reaction Polymerization

A. Monomer to have difunctional group
1. One having both reactive functional groups in one molecule

R
O

HO

CO2H

+ H 2O

(1.8)

O H 2N R CO2H NH R C + H 2O

(1.10)
POLYMER CHEMISTRY

2. Other having two difunctional monomers

A
OCN

R
R

A + B
NCO + HO

R'
R'

R'

OH
O O

CNH

NHCO

R'

(1.11)

H 2N

NH2 + ClCO
O

R'

OCCl
O

(1.12)
R' O + 2HCl

CNH

NHCO

POLYMER CHEMISTRY

B. Reaction : Condensation reaction using functional group

Example - Polyesterification
O n HO CO2H O C
n

nH2O

(1.3)

nHO2C

CO2H O C

nHOCH2CH2OH O COCH2CH2O
n

(1.4)

2nH2O

POLYMER CHEMISTRY

C. Carothers equation
( NO : number of molecules N : total molecules after a given reaction period. NON : The amount reacted P : The reaction conversion ) NON P= NO Or

N=NO(1P)

( DP is the average number of repeating units of all molecules present) DP=NO/N DP= 1 1-P DP = 1 1- 0.98

Forexample At98%conversion

POLYMER CHEMISTRY

(A) Unreacted monomer

A (a)
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

(B) 50% reacted, DP = 1.3

(b) A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

(C) 75% reacted, DP = 1.7

(c) A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

(D) 100% reacted, DP = 3

A (d)
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

A
B

1.5 Chain-reaction Polymerization

A. Monomer : vinyl monomer CH2=CH2 B. Reaction : Addition reaction initiated by active species C. Mechanism : Initiation R + CH2=CH2 RCH2CH2

. .
POLYMER CHEMISTRY

Propagation RCH2CH2 + CH2=CH2 RCH2CH2CH2CH2

TABLE 1.1 Comparison of Step-Reaction and Chain-Reaction Polymerization

StepReaction
Growth occurs throughout matrix by reaction between monomers, oligomers, and polymers DP low to moderate
a

ChainReaction
Growth occurs by successive addition of monomer units to limited number of growing chains DP can be very high Monomer consumed relatively slowly, but molecular weight increases rapidly Initiation and propagation mechanisms different Usually chain-terminating step involved Polymerizaion rate increases initially as initiator units generated; remains relatively constant until monomer depleted

Monomer consumed rapidly while molecular weight increases slowly No initiator needed; same reaction mechanism throughout No termination step; end groups still reactive Polymerization rate decreases steadily as functional groups consumed
a

DP, average degree of polymerization.

1.6 Step-reaction Addition and Chain-reaction Condensation

A. Step-reaction Addition.
O

(CH 2)6

O O

(CH 2)6

(1.15)

O
POLYMER CHEMISTRY

1.6 Step-reaction Addition and Chain-reaction Condensation

B. Chain-reaction Condensation

CH2N2

BF3

CH2

N2

(1.16)

POLYMER CHEMISTRY

1.7 Nomenclature
A. Types of Nomenclature

a. Source name : to be based on names of corresponding monomer Polyethylene, Poly(vinyl chloride), Poly(ethylene oxide) b. IUPAC name : to be based on CRU, systematic name Poly(methylene), Poly(1-chloroethylene), Poly(oxyethylene) c. Functional group name : Acoording to name of functional group in the polymer backbone Polyamide, Polyester
POLYMER CHEMISTRY

1.7 Nomenclature

d. Trade name : The commercial names by manufacturer Teflon, Nylon

e. Abbreviation name : PVC, PET

f. Complex and Network polymer : Phenol-formaldehyde polymer

g. Vinyl polymer : Polyolefin

POLYMER CHEMISTRY

1.7.1 Vinyl polymers

A. Vinyl polymers
a. Source name : Polystyrene, Poly(acrylic acid), Poly(-methyl styrene), Poly(1-pentene) b. IUPAC name : Poly(1-phenylethylene), Poly(1-carboxylatoethylene) Poly(1-methyl-1-phenylethylene), Poly(1-propylethylene) Polystyrene Poly(acrylic acid)
CH2CH

CH2CH CO2H

Poly(-methylstyrene)
CH3 CH2C

Poly(1-pentene)
CH2CH CH2CH2CH3
POLYMER CHEMISTRY

1.7.1 Vinyl polymers

B. Diene monomers
CH2CH HC CH2
CH2CH CHCH 2

1,2-addition Source name : 1,2-Poly(1,3-butadiene)

1,4-addition 1,4-Poly(1,3-butadiene)

IUPAC name : Poly(1-vinylethylene)

Poly(1-butene-1,4-diyl)

cf) Table 1.2

POLYMER CHEMISTRY

1.7.2 Vinyl copolymer

Systematic
Poly[styrene-co-(methyl methacrylate)] Poly[styrene-alt-(methyl methacrylate)] Polystyrene-block-poly(methyl methacrylate) Polystyrene-graft-poly(methyl methacrylate)

Concise
Copoly(styrene/methyl methacrylate) Alt-copoly(styrene/methyl methacrylate) Block-copoly(styrene/methyl methacrylate) Graft-copoly(styrene/methyl methacrylate)

POLYMER CHEMISTRY

1.7.3 Nonvinyl Polymers

O O CCH 2CH2

oxy 1-oxopropane-1,3-diyl

CH2CH2

oxy ethylene oxy

terephthaloyl
POLYMER CHEMISTRY

* Representative Nomenclature of Nonvinyl Polymers

Monomer structure
O H2C CH2
CH2CH2O

Polymer repeating unit

Source or Common Name

IUPAC name

Poly(ethylene oxide)

Poly(oxyethylene)

HOCH2CH2OH

CH2CH2O
O

Poly(ethylene glycol)
O

Poly(oxyethylene)

H2N(CH2)6NH2
HO2C(CH2)8CO2H

NH(CH2)6NHC(CH 2)8C

Poly(hexamethylene Poly(iminohexanesebacamide) or Nylon6,10 1,6-diyliminosebacoyl)

cf) Table 1.3

POLYMER CHEMISTRY

1.7.4 Nonvinyl copolymers

a. Poly(ethylene terephthalate-co-ethylene isophthalate)

O OCH 2CH2O C

C OCH 2CH2OC C O

b. Poly[(6-aminohexanoic acid)-co-(11-aminoundecanoic acid)]

O NH CH2
5

O NH CH2
10

C
POLYMER CHEMISTRY

1.7.5 End Group

OCH2CH2

OH

-Hydro--hydroxypoly(oxyethylene)

POLYMER CHEMISTRY

1.7.6 Abbreviations

PVC

Poly(vinyl chloride)

HDPE High-density polyethylene LDPE Low-density polyethylene PET Poly(ethylene terephthalate)

POLYMER CHEMISTRY

1.8 Industrial Polymers

a. The world consumption of synthetic polymers : 150 million metric tons per year.
1) Plastics : 56% 2) Fibers : 18% 3) Synthetic rubber : 11% 4) Coating and Adhesives : 15%

b.Styrene-butadiene copolymer
Synthetic rubber, PET
Latex paint

Fiber (polyester) Plastic

POLYMER CHEMISTRY

(bottle)

1.8.1 Plastics
1) Commodity plastics LDPE, HDPE, PP, PVC, PS cf) Table 1.4 2) Engineering plastics Acetal, Polyamide, Polyamideimide, Polyarylate, Polybenzimidazole, etc. cf) Table 1.5 3) Thermosetting plastics Phenol-formaldehyde, Urea-formaldehyde, Unsaturated polyester, Epoxy, Melamine-formaldehyde cf) Table 1.6 4) Functional plastics Optics, Biomaterial, etc.
POLYMER CHEMISTRY

TABLE 1.4 Commodity Plastic

Type

Abbreviation

MajorUses Packaging film, wire and cable insulation, toys, flexible bottles housewares, coatings Bottles, drums, pipe, conduit, sheet, film, wire and cable insulation Automobile and appliance parts, furniture, cordage, webbing, carpeting, film packaging Construction, rigid pipe, flooring, wire and cable insulation, film and sheet Packaging (foam and film), foam insulation appliances, housewares, toys

Low-density polyethylene LDPE High-density Polyethylene Polypropylene Poly(vinyl chloride) Polystyrene HDPE PP PVC PS

POLYMER CHEMISTRY

TABLE 1.5 Principal Engineering Plastics Type Acetala Polyamideb Polyamideimide Polyarylate Polybenzimidazole Poltcarbonate Polyeseterc Polyetheretherketone Polyetherimide Polyimide Poly(phenylene oxide) Poly(phenylene sulfide) Polysulfoned Abbreviation POM PAI PBI PC PEEK PEI PI PPO PPS ChapterWhereDiscussed C 11 13 13 12 17 12 12 11 11 13 11 11 11
POLYMER CHEMISTRY

TABLE 1.6 Principal Thermosetting Plastics Type Abbreviation TypicalUses ChapterWhere Discussed 14

PF Electrical and electronic equipment, automobile parts, utensil handles, plywood adhesives, particle board binder Urea-formaldehyde UF Similar to PF polymer; also treatment of textiles, coatings Unsaturated polyester UP Construction, automobile parts, boat hulls, marine accessories, corrosion-resistant ducting, pipe, tanks, etc., business equipment Epoxy - Protective coatings, adhesives, electrical and electronics applications, industrial flooring highway paving materials, composites Melamine-formaldehyde MF Similar to UF polymers; decorative panels, counter and table tops, dinnerware

Phenol-formaldehyde

14 12

11

14

1.8.2 Fibers
1) Cellulosic : Acetate rayon, Viscose rayon 2) Noncellulosic : Polyester, Nylon(Nylon6,6, Nylon6, etc) Olefin (PP, Copolymer(PVC 85%+PAN and others 15%; vinyon)) 3) Acrylic : Contain at least 80% acrylonitrile (PAN 80% + PVC and others 20%)
POLYMER CHEMISTRY

1.8.3 Rubber (Elastomers)

1) Natural rubber : cis-polyisoprene 2) Synthetic rubber : Styrene-butadiene, Polybutadiene, Ethylene-propylene(EPDM), Polychloroprene, Polyisoprene, Nitrile, Butyl, Silicone, Urethane 3) Thermoplastic elastomer : Styrene-butadiene block copolymer (SB or SBS)
POLYMER CHEMISTRY

TABLE 1.7 Principal Synthetic Fibers Type Cellulosic Acetate rayon Viscose rayon Noncellulosic Polyester Nylon Olefin Description Cellulose acetate Regenerated cellulose Principally poly(ethylene terephthalate) Includes nylon 66, nylon 6, and a variety of other aliphatic and aromatic polyamides Includes polypropylene and copolymers of vinyl chloride, with lesser amounts of acrylonitrile, vinyl acetate, or vinylidene chloride (copolymers consisting of more than 85% vinyl chloride are called vinyon fibers) Contain at least 80% acrylonitrile; included are modacrylic fibers comprising acrylonitrile and about 20% vinyl chloride or vinylidene chloride

Acrylic

1.8.4 Coating and Adhesives

1) Coating : Lacquer, Vanishes, Paint (Oil or Latex), Latex 2) Adhesives : Solvent based, Hot melt, Pressure sensitive, etc. Acrylate, Epoxy, Urethane, Cyanoacrylate

POLYMER CHEMISTRY

TABLE 1.8 Principal Types of Synthetic Rubber Type

Styrene-butadiene Polybutadiene Ethylenepropylene Polychloroprene Polyisoprene Nitrile Butyl Silicone Urethane

Description
Copolymer of the two monomers in various proportions depending on properties desired; called SBR for styrene-butadiene rubber Consists almost entirely of the cis-1,4 polymer Often abbreviated EPDM for ethylene-propylene-diene monomer; made up principally of ethylene and propylene units with small amounts of a diene to provide unsaturation Principally the trans-1,4polymer, but also some cis-1,4 and 1,2 polymer; also known as neoprene rubber Mainly the cis-1,4 polymer; sometimes called synthetic natural rubber Copolymer of acrylonitrile and butadiene, mainly the latter Copolyner of isobutylene and isoprene, with only small amounts of the Latter Contains inorganic backbone of alternating oxygen and methylated silicon atoms; also called polysiloxane (Chap. 15) Elastomers prepared by linking polyethers through urethane groups (Chap. 13)

1.9 Polymer Recycling

a. Durability of polymer property
1) Advantage : Good materials for use 2) Disadvantage : Environmental problem

b. Treatment of waste polymer : Incinerate, Landfill, Recycling

ex) Waste Tire : Paving materials Waste PET : To make monomer ( hydrolysis ) To make polyol ( glycolysis )

POLYMER CHEMISTRY

TABLE 1.9 Plastics Recycling Codea

Number
1 2 3 4 5 6 7
a

Letters
PETEb HDPE V or PVC LDPE PP PS OTHER

Plastic
Poly(ethylene terephthalate) High-density polyethylene Poly(vinyl chloride) Low-density polyethylene Polypropylene Polystyrene Others or mixed plastics

Adopted by the Society of the Plastics lndustry (SPI). b PET is the more widely accepted abbreviation.
POLYMER CHEMISTRY