Polymer Degradation and Stability 71 (2001) 299304

www.elsevier.nl/locate/polydegstab

Thermal degradation of blends of PVAC with polysiloxane II

S. Zulqar *, S. Ahmad
Chemistry Department, Quaid-i-Azam University, Islamabad 45320, Pakistan
Received 28 June 2000; accepted 22 August 2000

Abstract
Thermal degradation of blends of poly(vinyl acetate) (PVAC) with polysiloxane; poly(dimethyl siloxane) (PDMS), poly(diphenyl
siloxane) (PDPS), and poly(dimethyldiphenyl siloxane) (PDMDPS) has been investigated for comparison with the behaviour
already reported for PVCpolysiloxane blends, using thermogravimetry (TG), dierential thermogravimetry (DTG) and dierential
thermal analysis (DTA). The presence of PVAC has an eect very similar to that of PVC on the degradation of polysiloxane. Acetic
acid/acetate radical production is accelerated in the blends compared to PVAC alone at the low loading of polysiloxane, which
causes some destabilisation. However in blends containing 50% and more siloxane, both polymers are stabilized, particularly the
PDMS blends which show much slower weight loss. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Polymer blends; PVAC; Polysiloxane; Thermal degradation; Thermogravimetery; Dierential thermal analysis

1. Introduction
Blending has been reported to have a great inuence
on thermal stability of individual polymers [1,2]. In the
previous paper of this series [3], we have reported the
degradation behaviour of PVC blended with PDPS and
PDMDPS. Earlier investigation in this series includes
PVCPDMS [4], PVCpoly (ethylene adipate) [5] and
PVCbisphenol A polycarbonate [6] blends. In view of
the similarities between the degradation behaviour of
PVC and PVAC, we felt it to be useful to examine the
corresponding blends of PVAC with polysiloxane (PDPS,
PDMDPS and PDMS). The present communication
deals with aspects of the degradation of PVACpolysiloxane blends, examined by a broadly similar experimental approach to that for PVCpolysiloxane systems
[3].

UK) was distilled twice under vacuum to remove any

nal traces of inhibitors and dried over anhydrous Calcium chloride (CaCl2). Tetrahydrofuran (THF) was
distilled and dried over sodium wire before use.
2.2. Preparation of polymers and polyblends
Polysiloxanes (PDPS, PDMS and PDMDPS) were
prepared from their respective hydroxysiloxanes as
reported earlier [7]. PVAC was synthesized by bulk
polymerization using AIBN (0.05%) as free radical
initiator. Blends of PVAC with PDPS, PDMS and
PDMDPS were prepared at dierent ratios of (3:1,
1:1,1:3) using a common solvent (THF). Films of the
samples were cast by evaporating the common solvent.
These lms were then placed in a vacuum oven at 40 C
for 24 h to remove the solvent and stored in a vacuum
desiccator.

2. Experimental

2.3. Thermal analysis

2.1. Materials

Thermogravimetric analysis (TGA), dierential thermogravimetry (DTG) and dierential thermal analysis
(DTA) were performed on NETZSCH simultaneous
thermal analyzer (STA-429). Samples weighing 5.0 mg
were heated under a dynamic nitrogen atmosphere from
20800 C at a heating rate of 10 C/min. The Horowitz
method was applied for the determination of activation

a,a-Azobisisobutyronitrile (AIBN) (E. Merck) was

recrystallised from methanol. Vinyl acetate (BDH, Poole,
* Corresponding author. Tel.: +92-0-51829167; fax: +92-0821397.

0141-3910/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(00)00179-8

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S. Zulqar, S. Ahmad / Polymer Degradation and Stability 71 (2001) 299304

energies and order of reaction using thermogravimetric

data.
3. Results and discussion
3.1. Poly (vinyl acetate)poly (diphenyl siloxane)
blends
Thermogravimetric (TG) traces for PVAC, PVAC
PDPS blends and PDPS are given in Fig. 1. Thermal
degradation of PVAC proceeds in two steps similar to
that of PVC. In the rst step elimination of acetic acid
at 250 C leads to the formation of polyene sequences
[8]. These sequences then re-arrange and decompose to
aromatic and aliphatic hydrocarbon at 460 C. In the
case of PDPS, thermal degradation starts at 287 C and
weight loss is only 15% compared to 75% of PVAC up
to 400 C. The observed weight losses at 300 C for
PVAC, PVACPDPS (3:1), PVACPDPS (1:1), PVAC
PDPS (1:3) and PDPS are 61, 37, 31, 20 and 4%
respectively.
Plots of T0, T5, T50 and Tmax are shown in Fig. 2. T0
values indicate that degradation in the blends starts at
the deacetylation temperature of PVAC. PDPS starts
degradation at the highest temperature relative to
PVAC and the blends. T5 indicates that blends containing 75% PVAC are slightly destabilized after the
threshold of deacetylation. T50 and Tmax show a linear
increase in thermal degradation temperature of blends
with increase in the siloxane concentrations.
The DTG traces for the blends are given in Fig. 3.
PVAC exhibits two peaks with rate maxima at 300 and
450 C, corresponding to the elimination of acetic acid
and decomposition of polyene sequences respectively,
formed in the rst step. Grassie [9] found that while acetic acid accounts for up to 95% of the evolved volatiles in

Fig. 1. TG curves (dynamic nitrogen, heating rate 10 C/min) for

PDPSPVAC blends: 100% PDPS (1), 75% PDPS (2), 50% PDPS (3),
25% PDPS (4) and 0% PDPS (5).

the degradation range of the rst step, about 5% consisted of carbon dioxide, water, methane and ketene, all
of which were suggested to arise from the decomposition of acetic acid. PDPS exhibits only one peak with
Dmax at 475 C. DTG curves for blends show an intermediate behaviour of rate maxima relative to the component polymers. The rst peak of PVAC is only
slightly shifted to high temperature with increases in the
siloxane concentrations. The second peak, an overlap of

Fig. 2. Eect of blend composition on T0, T5, T50 and Tmax values of
PDPSPVAC blends.

Fig. 3. DTG curves (dynamic nitrogen, heating rate 10 C/min) for
PDPSPVAC blends: 0% PDPS (1), 25% PDPS (2), 50% PDPS (3),
75% PDPS (4) and 100% PDPS (5).

S. Zulqar, S. Ahmad / Polymer Degradation and Stability 71 (2001) 299304

polyene and PDPS decomposition, shows a very slow

increase in the Dmax values due to the increase in the
siloxane concentrations.
The DTA traces for the blends are given in Fig. 4.
PVAC shows an endotherm at 300 C due to the evolution of acetic acid and an exotherm (480 C) on account
of decomposition of the polyene to volatile products.
PDPS gives an exotherm at 530 C because of deterioration of the main chain [7]. In the blends the rst
endotherm of PVAC is slightly shifted to a high temperature with an increase in the siloxane concentration
and the second peak overlaps with exotherm of PDPS
as found in the PVCsiloxane blends [3,4].
3.2. Poly (vinyl acetate)poly (dimethyl siloxane)
blends
Thermogravimetric (TG) traces are given in Fig. 5. In
case of PDMS thermal degradation starts at 310 C and
weight loss is 0% compared to 61% of PVAC up to
300 C. The observed weight loss at 400 C for PVAC,
PVACPDMS (3:1), PVACPDMS (1:1), PVACPDMS
(1:3) and PDMS is 75, 65, 50, 38 and 10% respectively.
Plots of T0, T5, T50 and Tmax calculated from TG
curves vs blend composition are shown in Fig. 6. T0
indicates that the initial thermal degradation temperatures for PVAC and the blends is the same. T0 for
PMDS is highest when compared to PVAC and the
blends. T5 indicates that the blend containing 75%
PVAC is slightly destabilized in the beginning similar to
the PVCPDMS blends [4]. Tmax shows a linear increase

301

in degradation temperatures of the blends with an

increase in the siloxane concentrations.
DTG curves for the blends are given in Fig. 7. PDMS
exhibits only one peak at 510 C due to degradation to
low molecular weight cyclic products [7]. In the blends
the rst peak of PVAC exhibits no detectable change in
the temperature while the second peak, an overlap of
PVAC (polyenes) and PDMS degradation, is shifted to
higher temperatures consistent with the behaviour of
PVC-PDMS blends [4].
The DTA traces are given in Fig. 8. In the blends the
rst peak of PVAC (endotherm) exhibits no detectable
dierence in temperature, however the second one
(broad exotherm) is shifted to higher temperature with
an increase in the siloxane concentration.
3.3. Poly (vinyl acetate)poly (dimethyldiphenyl
siloxane) blends
Thermogravimetric (TG) traces are given in Fig. 9.
the case of PDMDPS thermal degradation starts
310 C and weight loss is 0% compared to 61%
PVAC up to 300 C. The observed weight losses

In
at
of
at

Fig. 5. TG curves (dynamic nitrogen, heating rate 10 C/min) for

PDMSPVAC blends: 100% PDMS (1), 75% PDMS (2), 50% PDMS
(3), 25% PDMS (4) and 0% PDMS (5).

Fig. 4. DTA curves (dynamic nitrogen, heating rate 10 C/min) for
PDPSPVAC blends: 0% PDPS (1), 25% PDPS (2), 50% PDPS (3),
75% PDPS (4) and 100% PDPS (5).

Fig. 6. Eect of blend composition on T0, T5, T50 and Tmax values of
PDMSPVAC blends.

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S. Zulqar, S. Ahmad / Polymer Degradation and Stability 71 (2001) 299304

Fig. 9. TG curves (dynamic nitrogen, heating rate 10 C/min) for

PDMDPSPVAC blends: 100% PDMDPS (1), 75% PDMDPS (2),
50% PDMDPS (3), 25% PDMDPS (4) and 0% PDMDPS (5).

Fig. 7. DTG curves (dynamic nitrogen, heating rate 10 C/min) for
PDMSPVAC blends: 25% PDMS (1), 50% PDMS (2), 75% PDMS
(3) and 100% PDMS (4).

Fig. 10. Eect of blend composition on T0, T5, T50 and Tmax values of
PDMDPSPVAC blends.

Fig. 8. DTA curves (dynamic nitrogen, heating rate 10 C/min) for
PDMSPVAC blends: 0% PDMS (1), 25% PDMS (2), 50% PDMS
(3), 75% PDMS (4) and 100% PDMS (5).

400 C for PVAC, PVACPDMDPS (3:1), PVAC

PDMDPS (1:1), PVACPDMDPS (1:3) and PDMDPS
are 75, 56, 48, 44 and 25% respectively.
Plots of T0, T5, T50 and Tmax obtained from the TG
data are shown in Fig. 10. T0 indicates that in PVAC
and blends degradation starts at a temperature similar to
that of PDPS and PDMS blends. T0 for PDMDPS is
higher as compared to PVAC and the blends. T5 indicates

that the blend containing 75% PVAC is slightly destabilized in the beginning similar to PVCPDMDPS
blends [3]. T50 and Tmax indicate a linear increase in the
degradation temperatures with an increase in the siloxane concentrations.
DTG traces for the blends and component systems
are given in Fig. 11. PDMDPS exhibits only one peak
with Dmax at 510 C. In blends, the rst peak of PVAC is
slightly shifted to a higher temperature, while the second peak, which is an overlap of polyene and PDMDPS
degradation, moves towards a higher temperature with
an increase in PDMDPS concentrations.
DTA results (Fig. 12) are also consistent with the TG
and DTG observations. In the blends the rst peak
(endotherm) of PVAC is slightly shifted to a higher
temperature, showing an overall decrease in the rate of
evolution of acetic acid with an increase in the siloxane
concentration. The second peak (a broad exotherm)
which is an overlap of PVAC (polyene degradation) and
PDMDPS decompositions are also shifted to higher
temperatures with an increase in the siloxane concentrations.
Activation energy and order of reactions were calculated for the component polymers and their blends by

S. Zulqar, S. Ahmad / Polymer Degradation and Stability 71 (2001) 299304

303

Fig. 12. DTA curves (dynamic nitrogen, heating rate 10 C/ min) for
PDMDPSPVAC blends: 25% PDMDPS (1), 50% PDMDPS (2),
75% PDMDPS (3) and 100% PDMDPS (4).
Fig. 11. DTG curves (dynamic nitrogen, heating rate 10 C/ min) for
PDMDPSPVAC blends: 25% PDMDPS (1), 50% PDMDPS (2),
75% PDMDPS (3) and 100% PDMDPS (4).

using the method of Horowitz and Gehson [10]. These

calculations are based on the weight loss and not on the
individual products. Activation energy data (Table 1) of
the blends also show an overall increase, with an
increase in the siloxane concentrations.
4. Discussion
TG, DTG, DTA and activation energy data are very
consistent towards the overall thermal stability of polymer blends. Since the blends are immiscible the agents
responsible for the changing behaviour must be capable
of diusion across the boundaries. The eects observed
in the previous studies of PVAC polyblends suggest that
either acetic acid or acetate radicals must be involved.
TG results show a slight destabilization at the beginning
of degradation (up to a weight loss of 510%), especially at the low concentration of polysiloxane (PDMS,
PDPS and PDMDPS). This destabilization may be due
to delay in the release of chain carriers (acetic acid or
acetate radicals) from the blends containing an excess of
PVAC in the presence of siloxane. Similar eects were
reported in the case of PVCPDMS [4], PVCPDPS
and PVCPDMDPS [3] blends due to delay in the
release of chloride radicals. Blends containing 50% and
more siloxane show stability throughout the decomposition range, which increases with the siloxane concentrations. This can be explained on the basis of the

diusion theory in heterogeneous systems as expected in

the PVCsiloxane [3,4] blends, where the increased
amount of siloxane (PDPS, PDMS, and PDMDPS)
results in the accumulation of CH3COOH or acetate
radicals, consequently decreasing the release of these
catalysing agents.
Polysiloxanes are substantially more stable than
PVAC, so that increasing the quantity of polysiloxane
in the blends, gradually increases the stability. Blends of
PVAC containing 50% and more PDMS and PDMDPS
concentrations are more stable than the pure siloxane.
This behaviour can be explained on the basis of crosslinking induced by the presence of PVAC. This crosslinking in PDMS and PDMDPS (20% phenyl
concentration) can be induced by free radicals (acetate
radicals or its products), diusing from the PVAC
phase, which are responsible for abstraction of hydrogen atoms from methyl groups in PDMS and
PDMDPS; pairs of such macro radicals crosslink
(Scheme 1). This crosslinking cannot be induced in
PDPS blends because hydrogen abstraction is not possible due to the absence of methyl groups in the chains,
as suggested in PVCPDPS blends [3].
Previous instances of acetate radical migration and
hydrogen abstraction in the thermal degradation of
PVAC polyblends are, for example, the case of PVAC
PMMA [11], where monomer production in the PMMA
is induced at the deacetylation temperatures, which are
much lower than those normally required to secure
depolymerisation. Another example is PVACPS [12]
where polystyrene under goes increased chain scission at
the deacetylation temperature of PVAC. These eects
cannot be explained by the attack of CH3COOH (which

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S. Zulqar, S. Ahmad / Polymer Degradation and Stability 71 (2001) 299304

Table 1
Comparative TG, DTG, DTA and activation energies data for PVACsiloxane blends
TG ( C)

DTG ( C)

DTA ( C)

Eact (kcal/mol)

Blend Composition (%)

T0

T50

T100

II

Peaks

Thermal eect

PVA-PDPS
1000
7525
5050
2575
0100

250
250
250
250
287

310
372
450
464
500

505
510
530
545
540

300
335
337
350
475

450
458
494
540

300

480

480
530
530

Endoa

PVAPDMS
7525
5050
2575
0100

250
250
250
310

337
412
430
492

600
605
610
600

315
325
345
510

475
505
560

300
300
315

425
537
599
520

Endo
Endo
Endo

PVAPDMDPS
7525
5050
2575
0100

250
250
250
310

361
412
430
450

570
580
580
550

312
335
349
510

462
485
535

300
300
324
525

537
550
560

Endo
Endo
Endo

a
b

300
300

Endo
Endo

II

II

Exob

45
41.4
40.5
39.8
43.34

36
34
33
40

Exo
Exo
Exo
Exo

43
31

Exo
Exo
Exo
Exo

42.6
36.5
43.5
42

Exo
Exo
Exo

35.4

Reaction order

2
1.5
1.5
1.5
0.5

1
2
1.5
1

34.8
31.5

1.5
1.5

1.5
1

28
33
49

2
1.5
1.5
1.5

0.5

1
1

Endotherm.
Exotherm.

Scheme 2. Free radical mechanism for degradation in PVAC.

References

Scheme 1. Cross-linking in PDMS induced by acetate radicals.

in fact tends to stabilize PMMA). It is only the radical

mechanism of PVAC polyblends degradation, which
provides a ready explanation.
Jammison and McNeill [11] suggested the formation
of acetate radicals in PVACPMMA blends by the following mechanism. Further this mechanism gives a
ready explanation for the production of side volatiles
(CO2, H2O, methane and ketene) in the degradation of
PVAC (Scheme 2).

[1] Rincon A, McNeill IC. Polym Degrad Stab 1993;40:125.

[2] Kovacic T, Klaric I, Nardelli A, Baric B. Polym Degrad Stab
1993;40:91.
[3] Zulqar S, Ahmad S. Polym Degrad Stab 1999;65:243.
[4] McNeill IC, Basan S. Polym Degrad Stab 1993;39:139.
[5] McNeill IC, Basan S. Polym Degrad Stab 1993;43:311.
[6] McNeill IC, Basan S. Polym Degrad Stab 1993;39:145.
[7] Mazher M, Zulqar M, Piracha A, Ali S, Ahmad A. J Chem Soc
Pak 1990;12:225.
[8] Gadner DL, McNeill IC. J Thermal Anal 1969;1:389.
[9] Grassie N. Trans Faraday Soc 1952;48:379, ibid 1953;49:1953.
[10] Horowitz HH, Gehson M. Anal Chem 1963;35:1464.
[11] Gamieson A, McNeill IC. J Polym Sci Polym Chem Ed
1976;14:1839.
[12] Gamieson A, McNeill IC. J Polym Sci Polym Chem Ed
1976;14:603.