Polymer Degradation and Stability 85 (2004) 1035e1039

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Epoxidation of thermally degraded poly(vinyl chloride)*

Tibor Szakács, Béla Iván)
Department of Polymer Chemistry and Material Science, Institute of Materials and Environmental Chemistry, Chemical
Research Center, Hungarian Academy of Sciences, Pusztaszeri u. 59-67, P.O. Box 17, H-1525 Budapest, Hungary
Received 21 December 2002; accepted 22 April 2003

Abstract

Epoxidation of conjugated polyenes formed by thermal degradation of poly(vinyl chloride) (PVC) was carried out in
cyclohexanone and tetrahydrofuran solution with m-chloroperoxybenzoic acid (mCPBA). PVC was thermally degraded in the solid
state under continuous nitrogen flow at 200 (C for 30 min leading to 0.6 mol% double bonds in the polymer chain as determined
from the UV-visible spectrum of the degraded polymer. Cyclohexanone proved to be an inappropriate solvent for the epoxidation
reaction probably due to its competitive reaction with the peroxide. UV-visible and FTIR spectroscopic analyses indicate that the
epoxidation of polyenes by mCPBA in THF occurs in high yields leading to polyepoxy sequences in the PVC chain, and there are no
signs of side reactions, such as oxidation of double bonds in polyenes to carbonyl groups. To our knowledge this is the first report on
epoxidation of polymers containing conjugated double bond sequences. The resulting new epoxidised PVC might be useful in
a variety of applications, such as fully miscible secondary epoxy stabiliser for PVC itself without plasticising effect, starting material
for epoxy curing and co-curing for reactive blends, etc.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Poly(vinyl chloride); PVC; Thermal degradation; Epoxidation; m-Chloroperoxybenzoic acid

1. Introduction reactive polyene structures in the chain may provide

Poly(vinyl chloride) (PVC) is one of the most versatile
commodity polymers which can be used for a large
variety of applications. However, it is well known that
PVC has poor thermal, thermo-oxidative and light
stability during processing and use [1]. In all cases the
primary chain degradation process of PVC is the zip-
elimination of HCl and the simultaneous formation of
conjugated sequences of double bonds ( polyenes) in the
polymer chain [1e7]. This process is shown in Scheme 1.
Polyenes formed inevitably during PVC degradation, i.e.
during processing, are highly reactive species and easily
react with oxidising agents, such as oxygen and ozone
(see [1] and references therein). The existence of such
*
Based on a paper presented at the 2nd International Conference on
Modification, Degradation and Stabilisation of Polymers (MoDeSt),
Budapest, 30 Junee4 July, 2002.
) Corresponding author.
E-mail address: bi@chemres.hu (B. Iván).
several chemical modification processes for obtaining
PVCs with useful pendant groups during or after
processing, or by recyclisation of PVC products.
Epoxidation of double bonds with peroxides, such
as H2O2 or peroxy acids, is a versatile method for
obtaining epoxidised compounds, monomers and poly-
mers. Among others, b-carotene with 11 double bonds,
which can be considered as a model for polyenes in PVC,
has been the subject of epoxidation studies in recent years
[8,9]. The epoxidation of non-conjugated terminal [10,11]
and in-chain unsaturations [12e14] has already been
reported for a variety of polymers. This reaction was also
used for the quantitative determination of double bonds
in copolymers with low olefin contents [12]. Surprisingly,
epoxidation of polymers containing conjugated double
bond sequences has not been reported yet.
Epoxidised poly(vinyl chloride) is a potentially useful
material for the polymer industry because its use as
a secondary stabiliser (costabiliser) or as a photocurable
resin is feasible. Several studies have recently dealt with
investigating the stabilising effect of epoxidised

0141-3910/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2003.04.003
1036 T. Szakács, B. Iván / Polymer Degradation and Stability 85 (2004) 1035e1039

CH C H2 C H2 30 min. The amount of double bonds was determined

CH CH CH CH from the UV-visible spectrum of the degraded polymer.

Cl Cl Cl 2.3. Epoxidation

H Cl Epoxidation of degraded poly(vinyl chloride) with

mCPBA was carried out in solution (1% w/v PVC in
cyclohexanone or tetrahydrofuran) at room temperature
CH CH CH2
or at 40 (C for different times. The reaction products
CH CH CH CH were precipitated into methanol, and then the samples
were dried under vacuum at room temperature.
Cl Cl

2.4. Characterisation
HCl

UV-visible spectroscopy: A UV-VIS spectrophotom-

CH CH CH eter (HP8452) was used for determining the concentra-
CH CH CH CH tion and lengths of polyene sequences. Freshly distilled
peroxide-free THF was used as solvent and reference.
Cl The following relationship between the absorption
H Cl coefficients (3) and the length of polyenes (i) for PVC
solution in tetrahydrofuran was used [19]:
Scheme 1. Zip-elimination of HCl during degradation of PVC.
3i;THF ¼ 10000C27700
ði  1Þ ½dm3 mol 1 cm1 
polymers and oils in PVC recipes [15e17]. The most The concentration ( pi) of polyenes containing i conju-
common costabilisers based on epoxy compounds are gated double bonds can be calculated with the following
epoxidised soybean oil, esters of oleic acid, sunflower oil equation:
and linseed oil. Epoxidised polystyrene-b-polybutadi-
ene-b-polystyrene triblock copolymers were also in- A)i M
pi ¼
vestigated as PVC costabilisers [18]. 3)i c) d
In this study, for the first time we report on the
chemical modification of thermally degraded PVCs with where Ai is the measured absorbance, M is the molecular
m-chloroperoxybenzoic acid (mCPBA) to form poly- weight of the vinyl chloride monomer (62.5), 3i is the
epoxy sequences in the main chain of this polymer. absorption coefficient, c is the polymer concentration (in
g/dm3) and d is the optical path length.
In carrying out Fourier transform infrared (FTIR)
spectroscopy, the FTIR spectra were recorded with solid
2. Experimental samples using a Nicolet Magna 750 FTIR spectropho-
tometer.
2.1. Materials

A suspension PVC (Ongrovil S5070) from Borsod- 3. Results and discussion

chem Ltd. (Hungary) was used (Mn ¼ 60 000, Mw =
Mn ¼ 1:96). m-Chloroperoxybenzoic acid (mCPBA)
(Aldrich, 77%) was purified by washing it with a phos-
phate buffer ( pHZ7) prepared from KH2PO4 and
K2HPO4. It was then washed with distilled water, and
the solid material was dried in vacuum. Cyclohexanone
(Aldrich 99.8%) was passed through a chromatography
column filled with neutral aluminium oxide. Tetrahy-
drofuran (Chemolab, Hungary) was freshly distilled
before use.
2.2. Degradation
Thermal degradation of PVC was carried out in the
solid state under continuous nitrogen flow at 200 (C for
The aim of this study was to explore epoxidation of
polyenes in thermally degraded PVC in order to obtain
a modified polymer with polyepoxy sequences. With the
epoxidation of conjugated double bonds in degraded
PVC it is possible to introduce epoxy groups in the PVC
chain. This new material possesses the same structure as
the original PVC but it contains epoxy groups which are
suitable functional groups for several subsequent trans-
formations.
After the degradation of PVC in inert atmosphere for
30 min, the resulting red coloured polymer was dissolved
in freshly distilled THF and its UV-visible spectrum was
recorded. Fig. 1 shows the UV-visible spectra of the
untreated and the thermally degraded PVC. From
 T. Szakács, B. Iván / Polymer Degradation and Stability 85 (2004) 1035e1039 1037

1.0 1.0

0.8 0.8

0.6 0.6
2 1
A

A
0.4 0.4 2

3
0.2 1
0.2

0.0
200 300 400 500
λ [nm]
Fig. 1. UV-visible spectra of virgin (1) and the degraded (2) PVC.
previous studies [1,19e28] it is known that each
absorbance maximum in the spectra of degraded PVCs
corresponds to one polyene sequence with a given
length. With the equation described in the Experimental
section, we calculated the amount of double bonds in
the degraded PVC. Thermal degradation for 30 min
resulted in 0.6 mol% double bonds in the polymer chain.
The expected modification reaction by mCPBA is
shown in Scheme 2. This process leads to PVCs
containing polyepoxy sequences. Fig. 2 shows the UV
and visible spectra of the degraded PVC, the epoxidised
PVC and the control sample after 2.5 h reaction time in
cyclohexanone solution with 20-fold excess of mCPBA
at room temperature. The control sample underwent all
the treatments but in the absence of m-chloroperox-
ybenzoic acid. As shown in this Figure, the absorption
CH2 CH ( CH CH ) n CH2 CH
Cl
O
C 0.8
OOH
0.0
600 200 300 400 500 600
λ [nm]
Fig. 2. UV-visible spectra of the degraded (1), the control (2) and
epoxidised (3) PVC samples (reaction conditions: 20! mCPBA excess
in cyclohexanone, 2.5 h, room temperature).
of the epoxidised polymer is lower than that of the
starting material, i.e. the degraded PVC, and the control
sample in the spectral region above 400 nm. This region
corresponds to polyenes with more than eight double
bonds. These results indicate that in spite of their lower
concentration, longer polyenes are more reactive with
mCPBA than shorter ones. The spectra in Fig. 2 also
show that the reaction is incomplete under the in-
vestigated conditions in cyclohexanone.
In order to increase the extent of epoxidation, the
reaction temperature was raised in another experiment
to 40 (C. Fig. 3 displays UV-visible spectra of the
degraded PVC and samples epoxidised at 25 and 40 (C.
Other reaction conditions were the same as for the
reaction with 2.5 h reaction time in cyclohexanone. It
can be concluded from this figure that the increase
of the temperature does not influence the yield of the
epoxidation reaction. Therefore, the reaction time was
Cl
1.0
0.6 1
A

0.4 2
Cl
3
0.2

CH2 CH ( CH CH ) n CH2 CH 0.0

200 300 400 500 600

Cl O Cl
λ [nm]

Fig. 3. UV-visible spectra of the degraded PVC (1), and samples

Scheme 2. Epoxidation of thermally degraded poly(vinyl chloride) with epoxidised at 25 (C (2) and at 40 (C (3) for 2.5 h with 20! excess of
m-chloroperoxybenzoic acid. mCPBA in cyclohexanone solution.
1038 T. Szakács, B. Iván / Polymer Degradation and Stability 85 (2004) 1035e1039

1.0

0.8 9 8.5 (A)

9 8.0
0.6
9 7.5
A

% Transmittance
1
0.4 9 7.0
2
3
9 6.5
0.2
9 6.0

0.0 9 5.5
200 300 400 500 600
λ [nm] 9 5.0

Fig. 4. UV-visible spectra of the degraded PVC (1), and samples 9 4.5
epoxidised for 2.5 h (2) and 21 h (3) at room temperature with 20! 2 00 0 1900 1800 1 70 0 1 60 0 1500
excess of mCPBA in cyclohexanone solution.
Waven u mb e rs [cm-1]

significantly increased. In the next experiment the 9 6.0

epoxidation was carried out for 21 h. Fig. 4 shows (B)
UV-visible spectra of the degraded PVC, the sample 9 5.5
which was epoxidised for 2.5 h and the polymer reacted
for 21 h. It can be seen that there is no significant
% Transmittance

9 5.0
differences between the absorption spectra of samples
epoxidised for 2.5 h and 21 h in cyclohexanone. These 9 4.5
results indicate that the extent of epoxidation is quite
limited by using cyclohexanone as the reaction medium.
9 4.0
According to literature reports [29], the low epoxidation
yields in cyclohexanone might be due to the fact that
9 3.5
mCPBA can oxidise ketones into orthocarbonates
thereby consuming the oxidising agent.
Tetrahydrofuran (THF) another good solvent for 9 3.0
2 00 0 1900 1800 1 70 0 1 60 0 1500
PVC, was also tested as reaction medium aiming at
increasing the epoxidation yield. Fig. 5 shows the Waven u mb e rs [cm-1]
differences between the UV-visible spectra of samples

1.0 98 (C)
% Transmittance

97

96
0.5
A

5 1
2
3 95
4

94
2 00 0 1900 1800 1 70 0 1 60 0 1500
0.0
200 300 400 500 600 Waven u mb e rs [cm-1]
λ [nm]
Fig. 6. FTIR spectra of virgin (A), degraded (B) and epoxidised (C)
Fig. 5. UV-visible spectra of the degraded PVC (1), control in PVC samples (epoxidation conditions: THF solution, 20 h, room
tetrahydrofuran (2), control in cyclohexanone (3), a sample epoxidised temperature).
in cyclohexanone (4) and PVC epoxidised in tetrahydrofuran (5)
(reaction conditions: 20 h, room temperature).
 T. Szakács, B. Iván / Polymer Degradation and Stability 85 (2004) 1035e1039
epoxidised with mCPBA in THF and cyclohexanone.
These polymers were obtained by epoxidation with 40-
fold excess of mCPBA for 20 h at room temperature. In
contrast to the control sample in cyclohexanone, the
UV-visible spectra of degraded PVC and the control in
THF are the same. After the epoxidation in THF only
small absorbances of the epoxidised sample can be
observed below 400 nm, i.e. a colourless product is
formed. Thus, it can be concluded that solvents like
THF are better choices for this reaction as is proved by
these experiments.
Fig. 6 shows FTIR spectra of the starting PVC, and
the degraded and epoxidised samples between 1500 and
2000 cm1. A characteristic band of conjugated polyenes
appears at 1670 cm1 after degradation. This IR signal
disappears on epoxidation, indicating high extent of the
formation of polyepoxy segments in the polymer. It can
also be seen that the carbonyl bands did not change
during epoxidation. This means that epoxidation of
polyenes by mCPBA in THF occurs in high yields, and
there are no signs of side reactions, such as oxidation of
double bonds in polyenes into carbonyl groups.
4. Conclusions
In summary, a new chemical modification reaction
for PVC, epoxidation of conjugated double bond-
containing sequences (polyenes) formed by thermal
degradation in the polymer chains was attempted for
the first time. The epoxidation of degraded PVCs was
carried out with m-chloroperoxybenzoic acid (mCPBA)
in different solutions under various conditions. It was
found that this reaction in cyclohexanone leads only to
low extent of epoxidation. Conversion of polyenes to
polyepoxy sequences in the PVC chain was achieved by
using tetrahydrofuran as the reaction medium. The
resulting colourless PVCs with polyepoxy sequences are
suitable for completely compatible secondary PVC
stabiliser without plasticising effect and starting materi-
als for photocurable resins and a variety of other
subsequent modifications reactions.
1039
Acknowledgements
Partial support of this work by the National Scientific
Research Fund (OTKA T023423) and technical assis-
tance by Mrs. E. Tyroler are gratefully acknowledged.
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