Polymer Degradation and Stability 12 (1985) 229-240

Effect of Lubricants on the Photo-oxidative Degradation

of Solid Poly(Vinyl Chloride)

T. A. Skowronski, J. F. R a b e k & B. R ~ n b y

Department of Polymer Technology,The Royal Institute of Technology,

Stockholm, Sweden

(Received: 25 September, 1984)

ABSTRACT

Various commercially employed lubricants, such as low molecular weight

polyethylene (Type PA-520 Wax), hydroxystearic acid (Loxiol G-21),
buty l stearate (Lo xiol G-32) and di-st eary l pht halate (Lo xiol G-60 ), have
been examined for their active r6le in the photo-oxidative degradation of
poly(vinyl chloride) (PVC). The results show that low molecular weight
polyethylene has an obvious accelerating effect on the photo-oxidative
degradation of PVC, whereas other lubricants reduce the effect of photo-
oxidation. None of the lubricants used has an obvious rdle in the chain
scission and crosslinking of PVC.

INTRODUCTION

Poly(vinyl chloride) (PVC) is unsuitable for processing into useful articles

in its pure unmodified form. This hard horny material is difficult to
process and extremely susceptible to rapid degradation at the
temperatures necessary for processing. However, the addition of suitable
thermal- and light-stabilizers, lubricants, plasticizers, fillers and other
additives can transform it either into a soft flexible material with
pronounced rubbery characteristics, or, alternatively, into a tough rigid
material suitable for water pipes, roofs, sheeting and a host of other
applications.
Lubricants, although used at relatively low concentration, are essential
229
Polymer Degradation and Stability 0141-3910/85/$03.30 Elsevier Applied Science
Publishers Ltd, England, 1985. Printed in Great Britain
230 T. A. Skowronski, J. F. Rabek, B. Rdnby

additives for PVC plastics. Lubricants are needed to promote controlled

release from mill or calender rolls, from injection, compression or
plastisol moulds and from the injection press and extruder screws and
cylinders, and also in forming dies.
Addition of different additives may, however, have an unexpected
effect on PVC photo-stability. In a systematic approach to this problem,
we have examined the effects of some commercial additives, such as
thermal stabilizers,l'2 fillers and pigments 3 and modifiers, 4 on the photo-
chemical stability of PVC. A limited examination of only one commercial
lubricant (Hoechst Wax type E--low molecular weight polyethylene) has
been published previously. 5 In this paper we present a much broader
study of the effects of commercially employed lubricants on the photo-
oxidative degradation of PVC.

EXPERIMENTAL

Suspension-polymerized PVC (Pevikon S-658)was obtained from Kema-

Nord AB (Sweden) in the form of a white powder. The manufacturer's
data are: Fikentscher K value, 66; Mn=56000; Mw=145000, i.e.
polydispersity factor, 2.58.
The following lubricants have been examined:
--(CH2~CH 2~-- (I)
Low molecular weight polyethylene wax (M= 2000) Type PA-520 (Hoechst AG,
Germany).
CH3CH(OH)(CH2) 15COOH (II)
Hydroxystearic acid (Loxiol G-21) (Neynaber Chem GmbH, Germany).

CH3(CH2) 16COO(CH2)3CH 3 (III)

Butyl stearate (Loxiol G-31) (Neynaber Chem GmbH, Germany).

C6H4(COO(CH2) 17CH3)2 (IV)

Di-stearyl phthalate (Loxiol G-60) (Neynaber Chem GmbH, Germany).
The composition of the PVC compounds was as follows: 100 parts of
PVC, 1 part of lubricant (I-IV) and 2 parts oflrgastab 17M (dibutyl-S,S'-
di(isooctylthioglycolate) (from Ciba-Geigy, Switzerland). This compound
was homogenized for 7 min on a laboratory two-roll mill at 170-175 C.
Rolled foils (skin) (0.8 mm thick) were further pressed at 200 kg/cm z for
 Effect of lubricants on the photo-oxidative degradation of solid PVC 231

3 min to an even thickness of 0.8 mm. Dumb-bell shaped specimens,

80mm long, 10mm wide and 0.8mm thick, for tensile strength and
elongation tests were cut from pressed sheets.
The followinglight sources were used for irradiation of PVC samples:
(1) A high pressure lamp, Type HPM-15 (1000W), supplied by
Philips, The Netherlands, at a distance of 50cm was used for
kinetics of photolysis (ultraviolet spectra, ESR measurements and
oxygen uptake).
(2) A low pressure lamp, Type RUL 3500A (120W, eight lamps),
supplied by the Southern New England Ultraviolet Company,
USA, at distance of 50 cm from irradiated samples was used in a
specially constructed photo-reactor in which samples were
irradiated from both sides. This was used for infra-red spectra, gel
formation and mechanical testing measurements.
The choice of lamps has been dictated by the design of the experimental
equipment and the requirements for irradiation in the spectral range
similar to that emitted by the sun.
The photolysis of lubricants was measured by the changes in their
ultraviolet absorption spectra which were recorded using a Perkin-Elmer
575 UV/VIS spectrometer.
The hydroperoxy hydroxyl (OOH/OH) (3450cm -1) and carbonyl
(CO) (1720cm -1) groups were determined from infra-red spectra
measured by an MIR accessory, Type 186-0382, with the computerized
Perkin-Elmer Model 580B Infrared Spectrometer.
ESR spectra were determined with a Bruker ER-420 ESR spectrometer
using accessories for solid samples, low temperature ultraviolet
irradiation and controlled temperatures.
The oxygen uptake was measured by a specially constructed oxygen
pressure monitor with a pressure transducer (Vallidyne Type P10)
mounted in a metal cell at 20 to 60 + 0.01 C. PVC film samples of 3 cm
diameter were first prevacuated at 10- 5 torr and the cell was filled with
pure oxygen at I atm. The oxygen uptake was monitored with a CD 12
transducer and an XY recorder.
The gel content of the PVC samples was measured by extracting 0.5 g
(W1) with THF for 24h in a Soxhlet apparatus equipped with Swedish
cellulose thimbles No. 401 (from Grycksbo Pappersbruk AB, Sweden).
The insoluble portion (W2) was weighed after drying to constant weight.
The gel content (in wt ~o) was calculated as 100 (W2/W 0.
232 T. A. Skowronski, J. F. Rabek, B. RtJnby

The tensile strength and elongation of the PVC samples were measured
using an Instron testing instrument (Model 1122), strained at the rate of
10mm/min (F--- 5000 N). The results from mechanical testing are
presented as average values of twenty measurements for each type of
sample and for each time period of ultraviolet irradiation.

RESULTS AND DISCUSSION

The lubricants used in the experiments differ greatly chemically. In group
A (external lubricants) are paraffinic waxes and low molecular weight
polyolefins, whereas, group B (internal lubricants) comprises esters of
fatty acids. The chemical structure of the lubricants has an effect on the
rheological properties of PVC materials. It is now generally accepted that
PVC requires two types of lubricant---external and internal--but there is
no clear line of demarcation between substances which act as one or the
other.6-lo External lubricants promote slippage between resin particles.
This reduces frictional heat build-up and delays fusion. Internal
lubricants reduce melt viscosity and the consequent frictional heat build-
up whichresults in thermal degradation of PVC. These lubricants are
generally more compatible with the PVC than those acting externally.
During ultraviolet irradiation of these two types of lubricant
completely different photo-chemical processes occur. In the case of low
molecular weight polyethylene (I) (Type A), photo-oxidation processes

0.~

0 l6 ~ (timnl)
20
0
0./~ , , ~ ~ ~ l ~ r , ,

220 21,0 260 280 300 320 (rim)

Fig. 1. Change in ultraviolet absorption spectrum of low molecular weight polyethylene
Wax Type PA-520 (melt film ~ 20 m#) during ultraviolet irradiation in air.
 Effect of lubricants on the photo-oxidative degradation of solid PVC 233

0.3- . o--

02-

01-

0 1~0 I i i i J
20 /~0 BO 80 100 {hr)

Fig. 2. Kinetics of formation of carbonyl groups (CO) from infra-red absorption

spectra of low molecular weight polyethylene Wax Type PA-250 (melt film ~ 50 m~)
during ultraviolet irradiation in air.

predominate. Ultraviolet (Fig. 1) and infra-red (Fig. 2) absorption

spectra show the formation of carbonyl groups. In this study the
formation of hydroperoxy hydroxyl groups (OOH/OH) has not been
observed, although the occurrence of absorption at 3370cm -1 (OH)
in oxidized high molecular weight polyethylene samples has been
described. 1~'12 When (I) is irradiated with uv at a low temperature
( - 1 9 6 C ) in air, an unsymmetric single line ESR spectrum (Fig. 3) is

. . . . , . ..

, 50G \
Fig. 3. ESR spectrum of POO. radical formed during ultraviolet irradiation of low
molecular weight polyethylene Wax Type PA-250 in air: ( - - ) at - 196C; ( - - - - ) at
- 7 0 C ; and ( . . . . . . ) at room temperature.
234 T. A. Skowronski, J. F. Rabek, B. R~nby

observed, and attributed to the formation of polyethylene peroxy radicals

(POO.).13 On warming the sample to room temperature, the observed
ESR spectrum slowly disappears. At low temperatures the POO. radicals
are well separated in a rigid molecular framework, whereas, at higher
temperature, cross-termination and/or hydrogen abstraction reactions
decrease the radical concentration.
During ultraviolet irradiation of group B (II-IV) lubricants fast
photolysis occurs (Figs 4-6). The radicals formed seem to recombine,
even at low temperature, because they are not detected even in low
temperature ultraviolet irradiations.
Addition of lubricants of groups A and B to a PVC sample influences
its photo-oxidative degradation. In the case of lubricant (I) (group A) the
formation of hydroperoxy/hydroxyl (OOH/OH) (Fig. 7) and carbonyl

0.8 0.8

0.6
0.6 ~ t,(rnin)
0

0.4 0.4

20
40
0.2 0.2

0 I I I I o
240 260 280 300 320(nrn) 240 260 280 300 320 (nm)

Fig. 4. Change in ultraviolet absorption Fig. 5. Change in ultraviolet absorption

spectra of hydroxystearic acid (Loxiol G- spectra of butyl stearate (Loxiol G-31) in
21) in ethanol (l 10-1M) during ultra- ethanol (2x 10-1M) during ultraviolet
violet irradiation in air. irradiation in air.
 Effect of lubricants on the photo-oxidative degradation of solid PVC 235

Ai
0.5- ti(mm)

O,Z, 60

0.3

0.2 I I I I
2z,0 260 280 300 320(nm)
Fig. 6. Change in ultraviolet absorption spectra of di-stearyl phthalate (Loiol G-60)
(melt film ~ 20 m#) during ultraviolet irradiation in air.

(CO) (Fig. 8) groups increases compared with the pure PVC sample. A
similar effect has been observed during the measurement of oxygen
uptake by a PVC sample (Fig. 9) where lubricant (I) evidently accelerates
the photo-oxidation of the sample. In the case of lubricants of group B
(II-IV) the amount of OOH/OH (Fig. 7) and CO (Fig. 8) groups formed
is smaller than in a pure PVC sample. The oxygen uptake is also lower
(Fig. 9) when lubricants of group B are present. These results indicate
that free radicals formed by photolysis of different types of lubricants
participate in secondary reactions with free radicals formed from the
photolysis of PVC. Lubricants of group B, which are compatible with
PVC, act as effective scavengers of free radicals formed from PVC. It is
practically impossible (because of difficulties in component separation) to
determine whether the increased amount of OOH/OH and CO groups
formed in the case of the PVC-lubricant I mixture belong to the PVC
and/or to (I). The lubricants of group A have limited compatibility with
PVC. The 1500 mol. wt (I), being slightly more compatible with PVC than
2000 tool. wt, probably influences the oxidative degradation of PVC more
than the higher molecular weight material, which was examined here. It
seems likely that the photo-oxidation of lubricant (I) occurs separately
and independently of the photo-oxidation of PVC. The results shown in
Figs 7-9 are probably due to addition of the effects of photo-oxidation of
both components separately. This suggestion is supported experimentally
by measurements of gel content (Fig. 10) and the mechanical properties,
tensile strength (Fig. l l) and elongation (Fig. 12), which show that
 to

0.2~;
d o0.6]
)-4
020 0.5
-r

o
o

0.16 0.4-
:x

0.12 0.3- /
0.08. 0.2-
/
/
004 0.1- J
~
0 r I
o 1o'oo 2o'00 3ooo' ~(hrl 1000 2000 3000 t(hr)

Fig. 7. Kinetics of formation of hydroperoxy/hydroxyl
(OOH/OH) groups from infra-red absorption spectra in: ( x )
pure PVC and PVC with: (A) low molecular weight polyethylene
Wax Type PA-250; ( 0 ) hydroxystearic acid (Loxiol G-21); (A)
butyl stearate (Loxiol G-31) and (O) di-stearyl phthalate (Loxiol
G-60) during ultraviolet irradiation in air.
Fig. 8. Kinetics of formation of carbonyl (CO) groups from
infra-red absorption spectra in: ( x ) pure PVC and PVC with:
(/k) low molecular weight polyethylene Wax Type PA-250; ( 0 )
hydroxystearic acid (Loxiol G-21); (A) butyl stearate (Loxiol G-
31) and (O) di-stearyl phthalate (Loxiol G-60) during ultraviolet
irradiation in air.
 Effect of lubricants on the photo-oxidative degradation of solid PVC 237

20-
g

'~ 15-

~o
>-

'-I //A

0 I" I I I
0 1000 2000 3000 t (hr)

Fig. 9. Oxygen uptake by: (x) pure PVC and PVC with: (A) low molecular weight
polyethylene Wax Type PA-250; (O) hydroxystearic acid (Loxiol G-21); (A) butyl
stearate (Loxiol G-31) and (O) di-stearyl phthalate (Loxiol G-60) during ultraviolet
irradiation in air.

addition of one part of lubricant (I-IV) to a hundred parts of PVC has

practically no influence on the measured values. In general, lubricants
(I-IV) do not change the observed chain scission and crosslinking
processes but they can evidently have an influence on the retardation of
photo-oxidation of PVC samples (lubricants II-IV). These results have
some relevance to the application of lubricants in products from PVC
which will be exposed outdoors to the sun's radiation. In this case it is
recommended that lubricants of group B be used rather than group A if
long-term properties are important.
In conclusion, we would emphasize that lubricant selection in industry
is presently more an art than a science. It must be recognized that there is
no additive which is inert photo-chemically during the photo-degradation
of PVC. If lubricants of group A and B are used together, synergistic
and/or antagonistic effects, not only on rheological, but also on photo-
chemical behaviour, can be observed. This problem requires more
extended research.
 ~.0-
A A
J
Ill
t.9

3,0 -

2.0-

1.0- /."

0
0 10~30 2()00 3000 t(hr)
Fig. 10. Kinetics of gel formation in ( x ) pure PVC and PVC with: (/k) low molecular
weight polyethylene Wax Type PA-250; (O) hydroxystearic acid (Loxiol G-21); (A) butyl
stearate (Loxiol G-31) and (O) di-stearyl phthalate (Loxiol G-60) during ultraviolet
irradiation in air.

60-
E

50-

40

30 [ I I
0 I000 2000 3000 t (hr)
Fig. I I. Changes of tensile strength of( x ) pure PVC and PVC with: (A) low molecular
weight polyethylene Wax Type PA-250; (O) hydroxystearic acid (Loxiol G-21); (A) butyl
stearate (Loxiol G-31) and (O) di-stearyl phthalate (Loxiol G-60) during ultraviolet
irradiation in air.
 Effect of lubricants on the photo-oxidative degradation of solid PVC 239

J
100 z

80

60

40
"o.\
2O
x\

0 1

0 1000 20too 30100 t(hr)

Fig. 12. Changes of elongation at break of () pure PVC and PVC with: (A) low
molecular weight polyethylene Wax Type PA-250; (Q) hydroxystearic acid (Loxiol G-
21): (A) butyl stearate (Loxiol G-31) and (O) di-stearyl phthalate (Loxiol G-60) during
ultraviolet irradiation in air.

ACKNOWLEDGEMENT

These investigations are part of a research programme on the r61e of

commercial additives in the photo-degradation of PVC supported by the
Swedish National Board for Technical Development (STU), which the
authors gratefully acknowledge.

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240 T. A. Skowronski, J. F. Rabek, B. R,inby

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