European PolymerJournal, 1967,Vol. 3, pp. 267-281. Perpmon Prt~ Ltd.

Printed in England

THE THERMAL DECOMPOSITION OF POLYVINYLCHLORIDE~I. KINETICS OF DEHYDROCHLORINATION

W. C. GEm)v.s
Rubber and Plastics Research Association of Great Britain, Shawbury, Shrewsbury, Shropshire

(Received 17 October 1966)

Almract---Optimum conditions have beem established for a study of the early stages (0-005-5 per cent)
of the thermal dehydrochlorination of unplasticized, tmstab'dized PVC; the catalytic effects of both
oxygen and hydrogen chloride have been demonstrated. Results obtained at 150 and 182 in nitrogen
show that the stability of PVC depends to a certain extent on polymerization conditions. Of a number
of possible sm3ctmal abnormalities controlled by polymerization conditions, eAix~tneous impurities
make only a small contribution to initiation of thermal dehydrochlorination but chain-4mds, measured
as inverse molecular weight, appear to have a greater effect. These results are discussed in the context
of both molecular-elimination and radical-chain mechanisms for dehydrochlorination.

INTRODUCTION
WnL~ exposed to various forms of energy polyvinylchloride (PVC) liberates hydrogen
chloride to leave a highly coloured product. In certain circumstances cross-linking
and chain-scission reactions can also occur with corresponding changes in the mechanical properties of the polymer but the word "degradation" tends to be confined to the
dehydrochlorination reaction. The problem of PVC degradation has been tackled by
many workers and has been the subject of several reviews(t-6) but there remains
considerable controversy over the basic dehydrochlorination mechanism quite apart
from the details of subsidiary reactions.
Even at very low extents of reaction 0ess than 0.01 per cent loss of hydrogen chloride)
the colour of the degraded polymer suggests that polyenes with over ten double bonds
in conjugation are established almost immediately. Random elimination of hydrogen
chloride would produce such lengths of conjugation only in the later stages of reaction
and it appears that some form of chain reaction is operating whereby hydrogen chloride
is lost from successive units in the polymer chain.
--CH2---CHC1----C'H2---CHCl---CHe--CHC1----CH ==CH---CH = C H - - C H - - C H - -

Despite the diversity of proposed mechanisms, there is common agreement that the
idealized structure of PVC, --(CH2--CHC1)n--, is intrinsically stable at temperatures
below 200 , as confirmed by the thermal stability of model compounds such as 2,4dichloropentane <7) and 1,3,5-trichlorohexane. s'9) Thus instability in PVC must be
caused by the structural abnormalities which are present to varying extents in all types
of PVC. Polymerization conditions, isolation and storage all contribute to irregularities
such as chain-end groups, branch points, random unsaturation, oxidation structures
267

268

w . C . GEDDES

and extraneous impurities is' 10,11) but as yet little advance has been made in correlating
dehydrochlorination with these structural irregularities, mainly because of difficulties
associated with complete characterization of PVC samples, a prerequisite for direct
comparison of results from different laboratories.
The difficulty of comparison is not confined to polymer characterization; techniques
employed to follow the reaction and assess stability can also be criticized. Thermal
dehydrochlorination can be measured in a number of ways with varying degrees of
accuracy and sensitivity. Thermogravimetry, the traditional method of investigating
polymer degradation, is most insensitive for PVC dehydrochlorination C12-15) and the
measurement of volatiles by pressure, another standard technique for degradation in
vacuo, is only a slight improvement. C16-21) In order to study the very early stages one
must turn to more sensitive methods, all of which involve absorption of volatiles
in solution. Simple acid-base titration ~22-26) is probably the most reliable and
reproducible method used so far although conductimetry~27-3~> and absolute pH
measurement C32,33) have the greatest potential.
Potentiometric t15,34-37) and
argentimetric (13,14,18, 3a-43) titrations are less sensitive but the latter have the
advantage of estimating chloride ion as distinct from total acid, which is the measurement in most other methods.
The question of the extent to which structural irregularities are involved in the
dehydrochlorination of PVC would best be answered by a study of the kinetics of
dehydrochlorination of model compounds, i.e. compounds containing one possible
irregularity together with a short chain of PVC. Failing this, the problem becomes
one of characterization of laboratory or commercial polymer and its subsequent
chemical modification in a controlled manner; the effect of a particular abnormal
grouping on dehydrochlorination can then be investigated.
The variable which can be dealt with most readily is extraneous impurity but before
embarking on such a kinetic study one must establish reliable and reproducible dehydrochlorination conditions and techniques.
EXPERIMENTAL
Materials

Polyvinylchlorid samples were kindly supplied by British Geon Ltd., and I.C.I. Ltd. (Plastics
Division). A sample of low molecular-weight PVC prepared by Dr. J. M. Pearson, University of
Aberdeen, was also used. Oxygen-freenitrogen from the British Oxygen Company was used without
further purification. All reagents and solvents were Analar grade unless otherwise stated.
Apparatus

A silicone oil thermostat bath was constructed to give a control of better than _+ 0.1 in the range up
to 200.
In view of the adverse effectof metals on PVC degradation,~44-47)the dehydrochlorination apparatus
was constructed entirely from glass. The reaction vessel consisted of a conical flask with an elongated
neck, the flat bottom being retained to give uniform heating of powders and films. An inlet at 1 cm
above the bottom of the flask was so angled that gas, pre-heated in a glass spiral, swept the surface
and carried any volatiles into the titration cell. The hydrogen chloride absorption cell consisted of a
500-ml round-bottomed flanged flask with a multi-socket lid fitted with glass electrode, calomel
electrode, dreschel bubbler and burette containing N/100 sodium hydroxide solution. The bubbler
was connected to the reaction vessel by ball and socket joints for flexibility and the electrodes were in
circuit with a Cambridge pH meter
Procedure

With a gas flowof 25-30 ml/min, the pH of the solution in the absorption cell (1~. potassium chloride
solution) reached a constant value between pH 7.0 and 8.0 after 4 hr. During PVC dehydrochlorina-

The Thermal Decomposition of Polyvinylchloride--I

269

tions, hydrogen chloride evolution was measured by adding aliquots of NIl00 sodium hydroxide to the
solution and noting the time taken for the pH to return to the original value. It was possible to measure
10-7 moles of hydrogen chloride with reasonable accuracy while a further qualitative check was obtained
from pH readings between additions.
The reaction vessel was loaded by disconnecting the apparatus and dropping in pieces of PVC films
or spraying PVC powder from a weighing stick over the bottom of the reaction vessel in a uniform
layer. This operation interrupted the gas flow for only 90 sec at the most but carbon dioxide in the air
admitted to the apparatus could be detected by titration in the first 15 cain. This blank, amounting to
10-~ moles, was reproducible and allowances were made in dehydrochlorination calculations. It was
found that PVC samples took 10 rain to get within 5 of the bath temperature and, with the low gas
flow rate, a delay of 5-10 rain can be expected for hydrogen chloride to reach the absorption cell;
readings in the first 20 min therefore may not be very significant.

Viscosity
Intrinsic viscosities of PVC samples dissolved in freshly distilled cyclohexanone were determined at
25 using an Ubbelohde suspended-level dilution viscometer. Humber-average molecular weights
were obtained from Danusso's relatiunship:(4s)
[1] (dl/g) = 2-4 x 10-4. Mn0' 77.

PVC films
Transparent films of PVC were prepared by heating PVC powder between aluminium plates at 110
for 2 rain and then subjecting the powder to pressures of 10,000-15,000 p.s.i, with cooling.

RESULTS
Figure l, which refers to a sample of suspension-polymerized PVC, demonstrates
the characteristic dehydrochlorination curve in which the rate gradually increases over
the first 3 or 4 hr and eventually settles down to a constant value. This induction or

3o[
20

o.,o!

ioo

200

Tirol,,

300

mtn

F[o. 1. The dehydrochlorination of 316 powder in nitrogen at 150 .

settling period covers only the first 0.1 per cent reaction at 150 (hydrogen chloride
evolution will be given mainly in/~moles hydrogen chloride/g polymer and 160/~ tool
HC1/gPVCis equivalent to 1 per cent loss of available hydrogen chloride). It is possible
that the settling period is associated with the diffusion and solubility of hydrogen
chloride in the polymer and does not have any chemical significance.
Polymerization conditions
If it is assumed that dehydrochlorination in PVC is initiated by structural abnormalities, one would expect some correlation between rate of dehydrochlorination and
polymerization conditions. Table 1 contains rates of dehydrochlorination in nitrogen

270

W.C. GEDDES
TAme 1. Em~CTOFPOLYMERIZATIONCONDITIONSONDEHYDROCHI.DRINATION
OF PVC 1'OWDEgIN mTROOr,~AT 182"5 AND 150
Rate of

Polymerization conditions
Code

Source

316
429
448
222
2111
427
237

A
A
A
A
B
A
A

P34
1

B
C

ALD

System
suspension
suspension
suspension
suspension
suspension
emulsion
low temp.
emulsion
bulk; - 50
solution
(n-propionaldehyde)

Initiator

Intrinsic
viscosity

dehydrocldorination
(pmol H C I ] g
PVC/min)

(dl/g)

182.5

150

1.40
1.55
1.60
1-78
1.04
1-22
1.32

0.095
0.108
0.125
0-119

redox

1.09
1.04
0.93
0.72
0.75
1.16
1.34

B(C2H4)2/O2

0.93

0-35

AZBN

0.07

--

peroxide
peroxide
peroxide
peroxide
peroxide

0-5~*

* Value at 8 per cent loss of HC1.

at 150 and 182.5 for various samples of PVC. The five-fold range of values obtained
at 182.5 seems to substantiate the above assumption but one or two points are worthy
of note. Within one supplier's range (A's suspension polymers) an inverse relationship was found between rate of dehydrochlorination and molecular weight but samples
o f suspension PVC from different sources, with roughly the same intrinsic viscosity,
had widely different rates. Also PVC prepared by emulsion polymerization did not
behave Hke the corresponding suspension polymer. The sample, P34, with the highest
thermal stability (see Table 1) was prepared at - 5 0 by bulk polymerization using
boron triethyl and oxygen as catalyst, whereas a sample o f PVC prepared in n-propionaldehyde with azobisisobutyronitrile as initiator gave a very high rate o f dehydrochlorination at 150 under nitrogen. Initially the rate was as high as 20/zmol/g PVC/
rain but dropped rapidly to a value of 0-50 at 8 per cent loss o f hydrogen chloride.
Unpurified polymer was used for the latter experiment and it is possible that unreacted
azobisisobutyronitrile together with n-propionaldehyde and its peroxide, which may
have been present in substantial quantities, were responsible for the high rate; the very
low molecular weight may, however, have a direct bearing on the relative instability.
It is apparent that polymerization conditions play a major part in deciding the thermal
stability of a PVC sample but details of commercial polymerization processes are not
normally fully disclosed and hence the significance o f the data in Table 1 is limited.
However, other parameters must be checked and standardized before a detailed
investigation of structural abnormalities and their effect on dehydrochlorination is
possible.

Effect of atmosphere
Most fundamental studies of PVC degradation have been carried out under inert
conditions, e.g. in nitrogen, argon or vacuum, but in practice other environments, which
cause dramatic changes in degradation processes, are encountered.

The ThermalDecompositionof Polyvinylchloride---I

271

Oxygen
Oxygen is always present to a certain extent during processing and its effect on
degradation processes is of particular interest. The increased dehydrochlorination has
been observed on many occasions(22'25,26'28'29'35'37'44'45) and Fig. 2 demonstrates
that not only is there an increase in rate but also the evolution becomes accelerating.
Initially the rate in oxygen was 1.7 times that in nitrogen but after 5 per cent loss of
hydrogen chloride this factor had increased to 2-7. Dehydrocldorination of PVC in
oxygen is an exothermic reaction(1s) in comparison to the slightly endothermic behaviour
in nitrogen(49) but the reaction conditions in Fig. 2 were essentially isothermal and
autocatalysis in oxygen must be an inherent feature of the reaction mechanism; this is
an important consideration in the formulation of an overall mechanism.
I000

"

80C

:L

G
a. 600!

_o
c 400

200

I00

200
Time,

300

rain

Fzo. 2. The dehydrochlorination of 448 powder at 182.5 in nitrogen (l) and oxygen (2).

It has been suggested that oxygen causes an increase in the concentration of initiation
sites(2S, 44, 50) and reactivates termination sites (45) to produce an increase in dehydrochlorination. This theory can be tested by providing alternating atmospheres of oxygen
and nitrogen while the PVC is heated. If oxygen does, in fact, increase the concentration
of initiation sites the rate of dehydrochlorination may be expected to remain at a high
level even after the oxygen is taken away. Figure 3 shows that the initial linear evolution
in nitrogen was immediately transformed into the accelerating evolution characteristic
of oxygen; the first 120 rain of dehydrochlorination in oxygen is shown for comparison.
However, when nitrogen was restored the rate dropped very quickly to a value of the
same order as the rate during the first nitrogen period. Thus it can be concluded that
the presence of oxygen during dehydrochlorination has no permanent effect on the rate.

272

;j

W.C. GEDDES

6O

Nitrogen

Oxygen

40

"8
g
-r

2o

I00

I
200
Time,

I
500

I
400

min

Fie. 3. The effectof alternatingatmospheresof nitrogenand oxygenon the dehydrochlorination of 448 powder at 182.5. The first 120 min of dehydrochlorinationin oxygen are
includedas comparison.

Hydrogen chloride
From the very early days of PVC there has been a widespread belief that one of the
degradation products, hydrogen chloride, acts as a catalyst; this view was supported
to a certain extent by the stabilization imparted by acid accepters such as basic lead
sulphate and basic lead carbonate and recently several workers have demonstrated the
phenomenon of hydrogen chloride catalysis.(is, 19,21,2s)
A study of autocatalysis was not the intention of the present investigations but several
results have been obtained which illustrate the effect of hydrogen chloride on the thermal
dehydrochlorination in nitrogen. In the routine preliminaries to the kinetic study,
different amounts of PVC powder were tested to find the optimum sample size for the
dehydrochlorination apparatus. Linear evolutions of hydrogen chloride were obtained
with samples of less than 400 mg but when the charge exceeded this figure the evolution
became accelerating (Fig. 4). The immediate conclusion from these experiments is that
the optimum sample size for this particular apparatus is less than 400 mg but, in addition,
the acceleration observed with large samples of PVC can be attributed to catalysis by
the hydrogen chloride which remains in the vicinity of the polymer as a result of inefficient removal by the carrier gas.
This hypothesis was tested by heating large granules or agglomerates, about 1 mm
dia., sieved from a batch of suspension PVC. Although only 200 mg were used the
large granules might be expected to simulate conditions in thick layers of PVC powder,
by retaining a high concentration of hydrogen chloride. As can be seen in Fig. 5, the
large granules did, in fact, give an accelerating evolution of hydrogen chloride compared
to the linear evolution from the sample with average granule size (0.15 ram). The fact
that acceleration was reduced when the large granules were ground up seems to confirm
the catalytic effect of hydrogen chloride which is not removed immediately from the
reaction site.

The ThermalDecompositionof Polyvinylchloride---I

273

15

400

E
~L

300

'3

-5
200

I00

I00

200
Time,

300

rain

FIG. 4. The effectof samplesize on the dehydrocldorinationof 448 powderat 182.5

in nitrogen. (1)--~200g; (2)-0.316 g; (3)-0.504 g; (4)-0.665 g; (5)-1.016 g.
The use of unplasticized PVC films reveals the additional problem of hydrogen
chloride diffusion as well as providing another itlustradon of catalysis. Figure 6 shows
that, as the film thickness increased, there was a corresponding time-lag before hydrogen
chloride was detected. Such behaviour is controlled by the diffusion of hydrogen
chloride from the PVC film and is not a serious problem in that allowances can be made
for the delay while the actual rate ofdehydrochlorinationremains unaltered. However,
the thicker films exhibited an accelerating evolution of hydrogen chloride, the extent of
acceleration being roughly proportional to the thickness of the film so that eventually
the order of curves 2, 3 and 4 in Fig. 6 was reversed. Thus it appears that hydrogen
chloride unable to diffuse from the polymer film is capable of catalysing the dehydrochlorination reaction.
To avoid unnecessary side-reactions resulting from the presence of oxygen and
hydrogen chloride, a standard procedure was adopted whereby PVC powder (200 rag),
spread in a uniform layer on the bottom of the reaction vessel, was heated in a stream
of nitrogen.
Extraction of extraneous material
It is not possible to obtain PVC as a pure compound in the sense.of a completely
homogeneous structure but the polymer can be purified by removal of extraneous
material incorporated during polymerization and isolation. A solution-precipitation
18

274

W.C. GEDDES
500
D2

_e 400

o"
300

200

"I"

I00

tOO

200

Time,

300

min

FIG. 5. The effect of agglomerates on the dehydrochlorinationof 2111 powderin

nitrogen at 182.5% (1) averageparticlesize; (2) largeagglomerates.
procedure is the normally accepted method of purifying polymer but in the case of
PVC, where the usual solvents are cyclohexanone and tetrahydrofuran, such treatment
may result in the retention of small amounts of solvent in the polymer even after many
hours of vacuum drying. It is well known that these two solvents peroxidise easily and
it has been shown that peroxides can induce thermal dehydrochlorination in PVC. (25' 27)
Thus solution-precipitation cycles may not result in a purer polymer as far as dehydrochlorination kinetics are concerned.
Reagents chosen for Soxhlet extraction work had to satisfy the requirements of being
non-solvents for PVC and having boiling points below 100--in order to minimize
degradation during extraction. Methanol, ether, n-heptane and water were chosen to
give a range of polar and non-polar solvents but n-heptane and water did not satisfy
the second requirement fully because after 50 hr the polymer was slightly pink in colour.
Water removed up to 20 mg siliceous material from the filter tube but this figure was
considerably reduced when the tubes were pre-treated with acid. Unsatisfactory
results were obtained with ether and n-heptane due to the retention in the polymer of
0.2 and 1-5 per cent respectively, even after 72 hr at 10 - 4 ~
Hg. Extraction figures
for sample 448, based on the weights of residues obtained on evaporation of the solvent,
were found to be 0.6 per cent for ether, 0.2 per cent for n-heptane, 0.2 per cent for
methanol and 0.1 per cent for water but the methanol figure is the only really reliable
one. Preliminary experiments showed that over 80 per cent of extraction occurred in
the first 20 hr but 50 hr gave more reproducible results.
To avoid thermal dehydrochlorination during extraction, the polymer was cold
extracted and Table 2 shows that cold extraction removed less material than normal

The Thermal Decomposition of Polyvinylchloride--I

275

,2

200

150

I00

-3o
"r"
50

50

I00

150

Time;

rain

FIG. 6. The effect of film thickness on the dehydrochlorination of pressed films of 448
in nitrogen at 182.5. (1) powder; (2) film, 0-20 ram; (3) film, 0.35 ram; (4) film 0.90 mm.
extraction, the difference in the case o f methanol being due to the increasing solubility
o f low molecular-weight polymer with temperature. F o r water, which is unlikely to
dissolve PVC itself, the residue was the same in both cases, suggesting that the substantial loss in weight in a normal extraction was actually loss of hydrogen chloride
TASLE 2. EXTRACTIONOF 10g 448 SUSPEN~ONPVC

Water

Methanol

Loss (rag)
Residue (rag)

Normal

Cold'

Normal

Cold

28"0
10-3

11.9
10.8

22.2
20.2

8.0
6.8

which would not of course be included in the res/due.It is significant that the extract was
always less than the loss in weight o f the polymer but it was noted that for polymer 448
0-015 per cent was lost after high vacuum treatment and the discrepancies in extraction
figures can be attributed to volat/les in the crude polymer.

W.C. GEDDES

276

Normal methanol extraction gave the most reliable results and various polymers were
submitted to this procedure, Table 3. In general the level of extractable material in the
A suspension PVC range is less than the B suspension polymer, the A emulsion
TABLE 3.

METHANOL EXTRACTION OF P V C SAMPLES AND DEHYDROCHLORINATION OF CRUDE

AND EXTRACTED P V C IN NITROGEN AT 1 5 0

Extraction
Polymer
316
429
448
585
222
586
CST 2111
427
P33
P34

Intrinsic
viscosity
(dl/g)
1.09
1.04
0.93
0.85
0"72
0.61
0.75
1"16
1"62
0"93

Rate of
dehydrochlorination
(/~mol/g PVC/min)
^

Mn

Loss
weight
per cent

Residue
weight
per cent

Crude

Extracted

54,000
51,700
45,600
40,800
32,000
25,800
33,600
60,800
92,000
45,000

0.20
0.24
0.22
0.12
0"30
1"32
1-16
2"52
0-50
0-87

0.10
0-17
0.20
0.10
0'27
1"02
0"82
1"72
0.50
0-77

0.095
0.108
0.125
0.124
0-119
------

0.074
0.078
0.107
0.103
0"097
0.109
-----

polymer (427) and the experimental samples. The normal procedure was not possible
with the emulsion polymer because of its very small particle size and the polymer
was shaken with methanol and filtered on a No. 4 porosity sintered-glass crucible. It
is possible that the high extract weight may be due in part to some polymer permeating
the filter but a high value might be expected in any case from polymers prepared in the
presence of emulsifying agents.
Infra-red spectra showed that extracts consisted mainly of PVC, presumably in the
form of very low molecular-weight polymer. In addition, sharp peaks in the region of
1720-1735 cm -1 suggested a carbonyl function which may possibly arise from initiator
residues, emulsifiers or suspension stabilizers, or even oxidized PVC but there was
insufficient material to permit isolation and identification of any specific compound.
Without further knowledge of polymerization systems one can only speculate on the
nature of extractable materials in PVC.
Dehydrochlorination studies on extracted polymers gave the overall picture o f a
slight reduction in rate of dehydrochlorination without any alteration in the shape of
the dehydrochlorination curve (Fig. 7). In some instances, after ether extraction for
example, a very slight increase was observed, which may be due to the small quantity
of ether, and its peroxide, retained in the polymer. N o r m a l extraction with water
produced the biggest decrease in rate but degradation during extraction was thought to
be responsible for this change in rate and, in fact, cold extraction resulted in a much
smaller reduction. Some results of dehydrochlorination in nitrogen at 150 for crude
and extracted polymers in the suspension PVC range (Table 3) show that the
decrease in rate is always less than 30 per cent, implying that extraneous impurities do
not play a big part in determining the thermal stability of PVC.

The ThermalDecompositionof Polyvinylchloride---I

277

g
3

-r~

10

I00

200
Time,

300
mln

FIG. 7. The effect of methanol extraction on the dehydrochlorinationof 316 in

nitrogen at 150. (1) crude; (2) methanolextracted.
Inspection of the data in Tables 1 and 3 reveals that, in both crude and extracted
samples of the family of suspension polymers, there is an inverse relationship
between rate of dehydrochlorination and intrinsic viscosity. Polymers 585 and 586 are
not original members of this group and may not fit the pattern set by 316, 429 and 448.
Sample 222 may also be anomalous because it is believed that its low molecular weight
was achieved by the use of chain-transfer agents, a point which may be important if the
inverse relationship is interpreted as a direct relationship between rate of dehydrochlorination and concentration of a particular end group.
DISCUSSION
From dehydrochlorination results reported in the literature, it is not yet possible to
make a choice between a molecular-elimination reaction and a radical-chain process
for PVC degradation, both being plausible from a theoretical standpoint; both mechanisms will therefore be discussed.
The former mechanism is said to involve an aUylic-activated elimination of hydrogen
chloride operating once the first molecule of hydrogen chloride is lost from a polymer
chain and eventually leading to long conjugated unsaturated sequences. (22,28, 44. 51)
The radical-chain mechanism has several variations but Winkler's scheme(52) is a good
example. The propagation steps consist of rearrangement of PVC macroradical (I)
to give a carbon-carbon double bond and a free chlorine atom which then abstracts the
nearest hydrogen atom, normally on the adjacent methylenic carbon atom and consequently activated by the unsaturation, to give hydrogen chloride and a second macroradical (II) capable of repetition of steps (i) and (ii) until a long polyene chain is formed.
---CHCI--~H--CHCI--CHe--CHCI---CH2--

(I)

(i)

--CHC1--CH = CH--CH2--CHCI---CH2~ + CI"

C~

--CHC1---CH= CH~ H--CHCI---CH2--+HCI

(n)

(ii)

278

W.C. GEDDES

Alternative schemes have reactions (i) and (ii) interchanged12)and some suggestions
embody a hybrid of unimolecular and radical schemes with molecular elimination
activated by an adjacent macroradical.26'27)
Although data concerning the basic mechanism of PVC dehydrochlorination are
meagre, there is considerable experimental evidence involving subsidiary reactions,
particularly reactions controlled by the nature of the atmosphere. Under inert conditions, such as nitrogen, argon and vacuum, thermal dehydrochlorination proceeds at
a constant rate; it is known that oxygen induces increased dehydrochlorination and
more precise studies have revealed an accelerating evolution of hydrogen chloride under
oxidative conditions.22'25.45) In thermal oxidation of hydrocarbon polymers, radical
mechanisms are postulated to explain autoxidation and hence similar mechanisms have
been applied to the thermal degradation of PVC in the presence of oxygen. As Rieche
has pointed out, it does not necessarily follow that dehydrochlorination in inert atmospheres is also a radical reaction25) but Winkler's radical-chain mechanism52)can be
extended to explain experimental evidence concerning oxidative degradation in PVC.
The propagating macroradical (I) captures a molecule of oxygen and the resulting
peroxy radical then abstracts a methylenic hydrogen atom from another polymer chain
to provide a second macroradical capable of continuing the dehydrochlorination chain.
This constitutes a simple transfer step and should not disturb the kinetics unduly but
there is also formed a hydroperoxide which may decompose to give two radicals, both
of which, by suitable hydrogen abstraction, are potential initiators for further dehydrochlorination. Thus a branching chain reaction is established and hydrogen chloride
evolution becomes accelerating. Of course the intermediate radicals may also abstract
other hydrogen atoms to give radicals which are inactive in dehydrochlorination and
the branching efficiency may be reduced; for example, when PVC is heated in the
presence of hydroquinone, dehydrochlorination in oxygen and air is reduced to the
level attained in nitrogen. 1s'25)
In some dehydrochlorination schemes, where radical reactions are not considered, the
catalytic effect of oxygen is attributed to an increase in labile oxidation structures which
somehow act as initiation sites for molecular elimination of hydrogen chloride. 2s'44.50)
Figure 3 shows that oxygen has no permanent effect on dehydrochlorination and hence
any labile structures formed during degradation in oxygen bear no resemblance, as
regards reactivity, to labile structures already in the polymer. Talamini1s) found that
the extent of acceleration of dehydrochlorination in oxygen is proportional to the
amount of unsaturation in the PVC and it is possible that short-lived aUylic peroxides
contribute to initiation of dehydrochlorination under oxidative conditions.
Whichever mechanism is favoured the question of initiation remains unanswered.
Alkyl or alkoxy radicals, which are usually preferred in initiation of radical-chain
dehydrochlorination, may be derived from extraneous impurities in the polymer but
results in Table 3 show that the contribution from this type of irregularity is small.
Talamini demonstrated that purification of samples of PVC prepared in a variety of
polymerization systems had a normalizing effect; in other words, the rates of dehydrochlorination, which covered a thirty-fold range in the crude polymers, were reduced
after extraction and also brought closer together to give only a two-fold range. Talamini's interpretation of these results involves initiation by extraneous impurities, but
it is worth considering the effect of loss of low molecular-weight polymer during
purification.

The Thermal Decompositionof Polyvinylchloride--I

279

Extraction of 0.2 per cent by weight from Breon 111 is accompanied by a small ( < 2
per cent) increase in molecular weight, partly due to the removal of low molecularweight PVC. If this material has a molecular weight of 500, extraction is equivalent to
reducing the number of chain ends in the system by 15 per cent. A corresponding
reduction in rate of dehydrochlorination implies that the reaction is controlled by
chain-ends and linear relationships between rate of dehydrochlorination and inverse
molecular weight, which is proportional to chain-end concentration, have been
demonstrated.~27, 29) It is interesting to note that in both cases extrapolation to infinite
molecular weight, or zero chain-end concentration, gave a non-zero rate which suggests
that only part of the dehydrochlorination is controlled by chain-ends. A study of
fractionated PVC gave a different picture with the inverse relationship being obeyed
for low molecular-weight fractions while high fractions had rates which were independent of molecular weight. (17'26) These results may still conform with the chain-end
hypothesis if one assumes that certain end groups are not distributed uniformly among
the fractions. In fact Bengough Cs3)has shown that fractionation leads to a preponderance of allylic groups in low molecular-weight fractions.
Both mechanisms make use of unsaturation in the polymer, in the form of activated
allylic elimination in non-radical mechanisms and to provide a chlorine atom by
homolysis of allylic carbon--chlorine bonds in radical mechanisms. Although certain
chain-end groups may also give rise to alkyl or alkoxy radicals, it is possible that
unsaturated chain-end groups, formed by termination and transfer reactions during
polymerization, hold the key to data relating dehydrochlorination to molecular weight
and extractable material. Molecular weight, or more precisely intrinsic viscosity, may
however involve parameters other than chain-end concentrations and it would be
dangerous to draw conclusions correlating dehydrochlorination with certain chain-end
groups without further evidence.
Recent evidence is overwhelmingly in favour of catalysis of dehydrochlorination by
hydrogen chloride ~1s,19,21'25) but this autocatalysis can obscure the fundamental
kinetics if insufficient attention is paid to experimental conditions. Figures 4-6 illustrate
how thick powder layers, large agglomerates and thick films all contribute to autocatalysis and Luther has recently shown how dehydrochlorination is related to the size
of granules in suspension PVC. (21) However, the phenomenon of hydrogen chloride
catalysis becomes an embarrassment when considered in terms of dehydrochlorination
mechanisms. In molecular elimination reactions, the dehydrochlorination chain is
probably terminated by some irregularity in the polymer chain. It is possible that
reversible addition of hydrogen chloride in a different orientation may in fact produce
a structure capable of further chain dehydrochlorination. In the radical-chain picture,
homolysis of hydrogen chloride would produce a free chlorine atom and constitute
catalysis but such dissociation normally occurs at higher temperatures. On the other
hand, the known catalytic homolysis of peroxides in the presence of hydrogen chloride 54)
can be used to explain autocatalysis in PVC, provided that peroxides are acting as
initiators.
In the light of these results it would appear that, although acid acceptors contribute
to stabilization, a true stabilizer for PVC must accomplish much more than prevention
of hydrogen chloride catalysis.

280

W . C . GEDDES

REFERENCES
(1) F. Chovassus and R. De Broutelles, The stabilization of polyvinyl chloride, Arnold, London
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(2) S.L. Madorsky, Thermaldegradation o f Organic Polymers, I.nterscience, London (1964).
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R6sum6--Des conditions optima ont 6t6 6tablies pour une 6tude des premiers stades (0.005-5 ~o) de
la d6shydrochloruration thermique du Chlorure de Polyvinyle non plastifi6 et non stabilis6; les effets

The Thermal Decomposition of Polyvinylchloride--I

281

catalytiques de l'oxyg/me et de l'acide chlorhydrique tousles deux ont ~t6 d~.montr~. Les r6sultats
obtenns b 150 et ~ 182 d~nq l'azote montrent que la stabilit6 du Chlorure de Polyvinyle d6pend darts
une certaine mesure des conditions de polym~risation. Parmi un certain hombre d'anomalies de
structure possibles contr61/~s par les conditions de polym~'isation, les impuret~s ~
ne prennent
qu'un petite part ~ l'initiation de la d/~thydrochloruration thermique mais les fins de chaine, mesurOys
comme poids mol~nflaires i n v z r s ~ paraissent avoir un etfet plus prononc6. Ces r~ultats sent
discut6s clans le contexte des m~x~mismes autant d'~limination molb~ulaire que des chaines de radicaux
pour la d~hydrochloruration.
Semmm'io---Sono state determinate le migliori condizioni per lo studio dei primi stadi (0.005-5 ~ )
deft" eliminazione di acido cloridrico dal PVC non plastificato e non stabilizzato~ ad opel a della
temperatura; ~ state dimostrato che sia l'acido cloridrico che l'ossigeno esercitano un' azione catalitica.
I dati ottenuti a 150 e 182 in azoto dimostrano c h e l a stabflitb del PVC dipende, entre certi limiti,
dalle condizioni di p o l i m e r i ~ d o n e . Tra le varie possibili anomalie strutturali determinate dalle
condizioni di p o l i m e r / ~ d o n e , le impurezze estranee danno solo un piccolo contribute all'inlzi~zione
dell' "hminazione termica di acido cloridrico mentre i terminafi delle catene, misurati come l'inverso
del peso molecolare, sembrano avere un effetto pih vistoso. I risultati sono discussi per reliminazione
di acido cloridrico sia in termini del meccanismo di eliminazione molecolare che di quello radicalecatena.
Z~mmmmMsM~g--Es wurden die optimalen Bedingungen festgestellt, um die ersten Stufen (0-005
bis 5Yo) der thermischen Abspaltung yon Chlorwasserstoff aus nicht plastiziertem, unstabilisiertem
PVC zu untersuchen. Die katalytischen Effekte yon sowohl Saut~toffals auch Chlorwasserstoff wurden
nach gewiesen. Die unter Stickstoffbei 150 und 182 erhaltenen Ergebnisse zeigen, dab die Stabilitat
yon PVC bis zu einvm gewissen Grad yon den Polymerisationsbedingungen abhangt. Aus der Zahl
der m6glichen strukturellen Abnormitaten, die von den Polymerisationsbedinmmgen abhangig sind,
spielen for die Initierung der thermischen Chlorwasserstpffabspaltung Verunreinigungen nur eine
geringe Rolle, wghrend die Zahl der Kettenenden, gemessen also reziproker Wert des Molekulargewichts, einen grSflcren EinfluB zu haben scheinen. Dime Resultate werden in Verbindung mit sowohi
der molekularen Eliminierung als auch Radikalkettenmechanismen flir die Chlorwasserst offabspalt ung
diskutiert.