Polymer Degradation and Stability 38 (1992) 255-259

Kinetics of polymer degradation involving the

splitting off of small molecules: Part 8.
Thermal degradation of polyvinyl esters
Peter ~imon & Milan Ryb~ir
Department of Physical Chemistry, Faculty of Chemical Technology, Slovak Technical University, Radlinsk~ho 9,
812 37 Bratislava, Czechoslovakia

(Received 18 September 1991; accepted 4 October 1991)

High conversion kinetic runs of the thermal degradation of polyvinyl esters

have been treated using the theory developed previously. For polyvinyl
acetate, polyvinyl propionate, polyvinyl butyrate and polyvinyl valerate,
excellent agreement has been obtained between theory and experiment for the
model of gradual zip propagation. In the case of polyvinyl caproate, better
agreement has been reached for the model of immediate zip growth. The
results obtained suggest that the pre-exponential factor and activation energy
for random elimination of acetic acid from polyvinyl acetate increase with
increasing molecular weight and the extrapolation to infinite chain length gives
the values log(A/s -1) = 14-0 and Ea = 192 kJ mol -I. In all cases, the initiation
step of the zip reaction is not autocatalytic. The pre-exponential factors and
activation energies for random elimination of acids are arranged in a zig-zag
fashion, but the rate constants of random elimination increase with increasing
length of the acyl substituent. The ratio of the rate constants for zip
propagation and random elimination exhibits a minimum at polyvinyl butyr-
ate. The content of structural irregularities causing premature zip termination
is rather high.

INTRODUCTION attributed to the action of acetic acid which

The thermal degradation of polyvinyl esters
occurs by the zip elimination of acids, polyene
sequences being formed along the polymer
backbone. Only a few detailed studies on this
subject have been reported, the greatest
attention having been paid to the degradation of
polyvinyl acetate (PVAc).
Decomposition of PVAc begins at about
190°C. 1 Acetic acid is the main component
(90-98%) of the volatile products in the
degradation up to 300°C. 1-3 The process is
non-radical L3 and acceleration of the degradation
by acids 3'4 indicates that ionic elimination takes
place. The kinetic curves have a distinct
autocatalytic character; ~-3,5-8 some authors sug-
gest that the autocatalytic behaviour may be
Polymer Degradation and Stability 0141-3910/92/$05.00
© 1992 Elsevier Science Publishers Ltd.
255
accumulates in the sample due to hindered
diffusion. 3'7 The question of where the initiating
step of the zip reaction occurs is not fully
resolved. Grassie ~ has concluded that the
initiation cannot be at random along the polymer
chain but must take place at the chain ends. The
idea is supported by experiments in which
dependence of the degradation rate upon the
relative molecular weight of the polymer has
been found. 4'5 Barrales-Rienda e t al. 7 have
observed a very moderate influence of the
molecular weight of PVAc on the rate of
elimination of acetic acid, however, and have
ascribed the variation in rate rather to different
contents of isotactic triads than to a true
molecular weight effect. On the contrary, other
authors believe that the initiation occurs at
random 3'6'9'1° and this suggestion is also sup-
ported experimentally. In some cases no
difference in rate for samples with different
256 Peter ~imon, Milan Rybdr
molecular weight has been observed 2,3 and,
moreover, Minsker et al. have found that in the
early stages of degradation only stochastic
elimination of acetic acid takes place. 9 Once the
initiation has given rise to a double bond, there is
a methylene group in the a~-position and adjacent
to an acetyl group. This structure is highly
reactive, and another molecule of acetic acid is
produced leaving a double bond again with an
a-methylene group adjacent to an acetyl group. 1
The allylic activation in PVAc thus leads to a
one-sided zip propagation in the direction of the
methylene group. In the early stages of
degradation, polyenes with a smaller number of
double bonds are predominant. 4 The average
polyene length is 1-2-1.5, which is much less
than in PVC. 11 These findings give support to the
assumption that the zip propagation proceeds at
a low rate I and the zip termination is practically
absent. 12
Degradation studies for polyvinyl esters other
than PVAc are rare. 8,13 Barrales-Rienda et al.
have dealt with five members of the homologous
series of polyvinyl-n-alkyl esters, namely PVAc,
polyvinyl propionate (PVPr), polyvinyl butyrate
(PVBu), polyvinyl valerate (PVVa) and polyvinyl
caproate (PVCa). 8 They have eliminated mole-
cular weight as a variable by using the same
backbone for the synthesis of all the polymers.
They have found that PVPr, like PVAc, degrades
by an autocatalytic mechanism. Increasing the
length of the n-acyl portion leads to a decrease in
the participation of the autocatalytic mechanism.
The last member of the series, PVCa, degrades
by first-order kinetics. The kinetic runs have
been treated using a simple autocatalytic
equation and the energy of activation for the
initation reaction has been found to decrease as
the length of the n-acyl substituent increases.
The decrease is not constant or regular, but takes
place in a zig-zag fashion, suggesting an
odd-even effect.
In Parts 1, 2 and 3 of this series of papers, the
dehydrochlorination of PVC in an inert atmos-
phere has been studied. 14q6 Autocatalytic mech-
anisms of polymer degradation occurring via
elimination of low molecular weight compounds
have been analyzed 17a8 in Parts 4 and 5 and the
theory has been applied to the study of the
thermal degradation of PVC in HCI and
oxidative atmospheres. 19'2° The mechanism de-
scribed in Part 5 involves random initiation and
gradual slow zip propagation without termina-
tion. The facts mentioned above for PVAc
degradation suggest that this is the mechanism
which takes place in the degradation of polyvinyl
esters. The aim of this paper is to employ the
theory for the treatment of experimental data
described by Barrales-Rienda et al. 7"8
SIMULATION OF THE KINETIC CURVES
For the simulation of the kinetic curves we use
the same procedure as in Parts 3, 6 and 7,16'19'2°
i.e. the whole set of kinetic runs obtained for
various temperatures is treated simultaneously.
As in previous cases, 19'2° the sum of the squares
of the differences between the experimental and
theoretical values of conversion is rather rich in
minima. Preliminary calculations have shown
that the minima corresponding to the zip
mechanism are found solely for the value fl ~ 0,
which means that the initiation reaction is not
autocatalytic. Equations (13) and (14) from Part
5 for the time dependence of the conversion x
and the probability p are thus reduced to the
form
dx
dt = B(xm x)[1 + (1 - za/z)yp]
- - (1)
dP= B ( 1 - p ) (2)
dt
The solution of eqn (2) is given by eqn (20) Part
1, and the ratio z J z is expressed by eqn (21) Part
5. After combining it with these equations, eqn
(1) is integrated numerically by the fourth-order
Runge-Kutta method. The rate constant of
random elimination, B, is expressed by eqn (1)
Part 3 and the ratio of rate contants, y, is
supposed to obey the Arrhenius relation given by
eqn (2) Part 6. Then the parameters for the
minimization of the sum of the squares are A,
Ea, zkAy, AE~, Po and Xm. The values of Ay and
E~ are calculated by eqns (3) and (4) Part 6.
RESULTS A N D DISCUSSION
In the calculations, the agreement between the
theoretical and experimental kinetic curves is
excellent in all cases except PVCa. The standard
deviation per mesh point lies within the values
0-008 (PVAc NM-14) to 0.031 (PVAC GL-03).
Figure 1 shows that the deviations between
experimental and calculated values of conversion
 Kinetics of polymer degradation: Part 8 257

parameter P0 in the minimization loses any

.04 meaning. Agreement between theory and experi-
ment is worse; this is indicated not only by the
standard deviation per mesh point, which is
.Or
0.054, but also by the occurrence of systematic
• e
#oe + +
• • O &~O
deviations between the experimental and theore-
10+ I +eChOO0 0 ~ ++
0 K 0% q &~. + . ~ . t xet p
tical kinetic runs. The kinetic runs for PVCa
.x degradation resemble those for the de-
x A/~ A
• •
hydrochlorination of PVC in an inert
- .02 atmosphere. 16 Hence, we have tried to treat these
data using the model of immediate zip growth
without considering autocatalysis of the
- .04
initiation. 15'16 This calculation has given a high
value for the parameter P0 and values of
Fig. 1. Deviation diagram for PVAc NM-14. Temperatures, parameters A log A and AEa, leading to high
°C; O, 261-6; O, 271-4; +, 281-1; x, 291.2; &, 300.7; A, values of the zip length m. In this case, eqn (20)
310.5; ~, 320-2.
Part 2 converts to eqn (14) Part 1, i.e. into the
kinetic equation of the degradation of a priori
for PVAc NM-14 do not exhibit any regularity, given sequences. Taking into account the
which indicates that the theory adequately presence of impurities, integration of eqn (14)
describes the experimental data. Similar devia- Part 1 yields
tion diagrams have been obtained for the other 1 - e -~'
polyvinyl esters (except PVCa). The results of X = Xm (3)
1 - (1 - p0)e -n`
the calculations are listed in Tables 1 and 2.
For PVCa, only the minimum corresponding to The values of kinetic parameters for this model
first-order kinetics has been found with a are given in Table 2. The standard deviation is
combination of A~ and E~ leading to the value 0-048, which indicates that this model describes
~/--~ 0. This minimum does not correspond to a the degradation of PVCa better than the one for
zip reaction. For this case, the introduction of the gradual zip growth. The model of the degrada-

Table 1. Kinetic parameters for the degradation of PVAc

Polymer ~ M, x 10 4 a log (A/s ~) Ea log (AT/s t) Ey P0 Xm

(kJ mol ]) (kJ mol -])

AH-22 20 13.75 188.9 12.75 166.8 0.257 1-000

NM-14 12 13.76 188.9 7.40 106-5 0.318 1-000
NL-05 4.2 12.48 173-7 14.04 179.2 0.302 1.000
GL-03 3-0 12-67 175-0 10.80 145-7 0.234 1.000

a Denotation of polymers and molecular weights taken from Barrales-Rienda et al. 7

Table 2. Kinetic parameters for the degradation of polyvinyi esters

Polymer log(A/s -1) Ea log(Ay/s -~) E~ A logAy AEy p, X m

(kJ mol -l ) (kJ mol -t) (kJ mol -l)

PVAc 12.48 173-7 14.04 179-2 1.56 5-5 0.302 1.000

PVPr 12-75 176.3 11-51 155.0 -1.24 -21-4 0.140 0.965
PVBu 12-11 168.6 12-20 162.0 0-09 -6.6 0.510 0.946
PVVa 13.37 182-4 12.90 167.2 -0.47 -15.2 0.356 0.963
PVCa 11.53 157-3 . . . . . 0.928
gradual
zip growth
PVCa 11.95 157.3 0.299 1.000
immediate
zip growth
258
tion of a priori given sequences does not involve
zip termination as a chemical reaction. The zip
growth ceases only at the ends of the sequences
or at the monomeric units which have already
been degraded. 14 The same assumption is
adopted for the model of gradual zip growth. The
principal difference between the models is that in
the model of a priori given sequences the zip
growth occurs at a very high propagation rate; ~4
in the model of gradual growth the rates of the
initiation and propagation are comparable.18 We
have thus come to the conclusion that in the
degradation of PVCa the propagation rate is
much higher than the initiation rate. However, as
Fig. 2 shows, for the model of degradation of a
priori given sequences, the deviations between
the experimental and kinetic runs also exhibit
regular trends up to x ~<0-25. The regularity in
the deviations indicates that neither in this case is
the description of the experimental data by the
theory fully adequate. At the beginning, the
degradation of PVCa is very fast, 8 which could be
caused, for example, by a high content of defect
structures causing accelerated elimination or by
deceleration of the zip propagation with increas-
ing zip length. None of these effects is taken into
account in our kinetic models; of course, it could
be done, but the construction of a model taking
these subtler effects into account would require
complementary experimental support for the
mechanism of PVCa degradation.
It can be seen from Table 1 that the
parameters of random elimination of acetic acid
from PVAc depend upon the molecular weight of
the polymer. Linear extrapolation to the value
.08 ~ o
~0
+ ~o
.04 x
o
N
.2 -~0 A~.4 £,6
i x + @
-.o4 t x ++
x+XXxx x ~ ×
- .08
Fig. 2. Deviation diagram for PVCa for the model of a
priori given sequences. Temperatures, °C; 0 , 246.4; C),
261.3; +, 271.2; x, 280.8; A, 290.3; &, 299.9; ~ , 309.2.
Peter ~imon, Milan Rybdr
1/Mn--~O gives the values log(A/s -1) = 14.0 and
Ea = 192 kJ mo1-1, with corresponding correla-
tion coefficients 0.915 and 0-935. The values of
kinetic parameters for an infinite polymer chain
suggest that the hypothesis about the independ-
ence of these parameters of the type of PVAc
used by some authors 2'3 is acceptable only for
polymers with molecular weight M, > 105.
Table 2 shows that the parameters of random
elimination of acids from polyvinyl esters are
arranged in a zig-zag fashion which is in accord
with Barrales-Rienda et al. s However, the rate
constants of random elimination calculated from
the data of Table 2 by eqn (1) Part 3 for a chosen
temperature, B, increase almost linearly with
increasing length of the acyl substituent (Fig. 3).
This result indicates that increasing the length of
the acyl subsitutent leads to decreasing stability
of polyvinyl esters. This conclusion is in accord
with the experimental findings.8 As far as PVCa
is concerned, from Fig. 3 it is obvious that the
rate constant B for the immediate zip growth
model follows the trend of the points illustrated
much better than B for the model of gradual zip
growth.
Table 1 shows that there is no regularity in the
values A~ and E~ for PVAcs with various
molecular weights. As these parameters are
associated with zip propagation, they probably
depend upon the morphology of the polymer
chain like the zip length in the case of PVC
dehydrochlorination.16The activation energy, Er,
L °l
t5
@
@ •
m
I XOx p
i i i i
Fig. 3. Dependence of the rate constant at 300°C of random
elimination (B) on the length of the acyl substituent, o, the
rate constant for the random elimination of PVCa.
 Kinetics of polymer degradation: Part 8
12
lO
I
l~/Ae
I
PVI~r
I
PVBu
I
l~/Va
I
II~C&
Fig. 4. Depenoence of Y at 300°C on the length ot the acyl
substituent.
is mostly less than Ea; consequently, according to
eqn (2) Part 6, y decreases with increasing
temperature. F r o m Table 2 it can be seen that
the values of AAy and AEy are again arranged in
a zig-zag fashion as the length of acyl substituents
in polyvinyl esters increases. The values of y
calculated using eqn (2) Part 6 for a chosen
t e m p e r a t u r e show a m i n i m u m at P V B u (Fig. 4).
For the degradation of P V C a , the value of y is
very high (infinite).
The probability of the presence of an
irregularity preventing the zip propagation, Po, is
rather high for all polyvinyl esters, much higher
than for P V C . 16'19,20 High values o f p o should lead
to the formation of shorter p o l y e n e s e q u e n c e s
during degradation in comparision with P V C , as
has been o b s e r v e d e x p e r i m e n t a l l y . " As well as
the lower initiation and propagation rates, this
259
can be another reason for the higher thermal
stability of polyvinyl esters c o m p a r e d with P V C .
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