Eur. Polym. J. Vol. 30, No. I, pp. 17-23, 1994 0014-3057/94 $6.00 + 0.

00
Printed in Great Britain. All rights reserved Copyright © 1994 Pergamon Press Ltd

FTIR STUDY OF THERMAL OXIDATION OF ENR

B. T. POll a n d K. S. LEE
School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia

(Received 26 January 1993; accepted 17 March 1993)

Abstract--Thermal oxidation of two grades of purified epoxidized natural rubber (ENR 25 and ENR 50)
and one grade of unmodified natural rubber (purified SMR L grade) were studied using Fourier Transform
Infrared Spectroscopy (FTIR). Changes in the characteristic absorption band, particularly the hydroxyl
and carbonyl peaks of the degraded rubbers are carefully monitored. Results indicate that thermal
oxidation occurs in the double bond region for SMR L to form oxidative products which mainly consist
of hydroperoxide, hydroxyl and carbonyl compounds. In the case of ENR, thermal oxidation occurs not
only in the double bond region, but also involves epoxide ring-opening reaction to yield oxidative products
having similar functional groups as that of SMR L. For the three rubbers studied, increasing temperature
of thermal oxidation increases the rate of oxidation. From a time-dependent study, it suggests that thermal
oxidation of ENR is an autocatalytic process. No attempt, however, is made to ascertain the exact
chemical structures of the oxidative products formed in this study.

INTRODUCTION and methanol. The precipitated rubbers were then dried in

a vacuum oven.
Epoxidized n a t u r a l r u b b e r ( E N R ) is a chemically
modified n a t u r a l rubber. M a n y studies o n the physi-
cal properties o f E N R have been reported recently.
These include mechanical [1, 2], blending [3-5] a n d
scorch property [6] of E N R . The optimization study
o f sodium c a r b o n a t e a n d sulphur c o n c e n t r a t i o n in
order to increase the ageing performance of E N R 50
vulcanizate was also reported by A b u et al. [7]. O n the
other h a n d , Gelling a n d M o r r i s o n [8] concluded t h a t
the p o o r ageing b e h a v i o u r of sulphur vulcanizate of
E N R is due to acid-catalysed ring-opening reactions
o f the epoxide groups with the f o r m a t i o n of ether
crosslinks. However, study o n the thermal oxidative
b e h a v i o u r of unvulcanized E N R seems scarce. In
view o f the increasing interest in the rubber, it is thus
the aim of this p a p e r to describe some of our findings
on the t h e r m a l ageing of the unvulcanized E N R using
Fourier T r a n s f o r m Infrared ( F T I R ) spectroscopic
technique.
EXPERIMENTAL PROCEDURES
Materials
SMR L, ENR 25 and ENR 50 having respectively 0, 25
and 50 mol% of epoxidation were used. The rubbers were
freshly supplied by Rubber Research Institute of Malaysia
and their respective technical specification is shown in
Table 1.
Purification of rubbers were carried out before testing.
For ENR, the rubber was precipitated from tetrahydrofuran
solution and in the case of SMR L, it was precipitated from
toluene solution. The respective precipitants are n-heptane
Table 1. Technical specification of SMR L and ENR
SMR L EMR 25 ENR 50
Tg(°C) -72 -45 -20
Specific gravity 0.92 0.97 1.03
Mooney viscosity, 78 110 140
ML, 1 +4(100 °)
Sample preparation and testing
The purified rubbers were dissolved in their respective
solvents to give a solution of 4% w/v concentration. To
facilitate easy dissolution of rubbers, the rubber sample was
cut into small chips and dissolved in the solvent with
constant stirring. The solution was then casted onto a glass
mould and dried in a vacuum oven at room temperature
until a film of uniform thickness with constant weight was
obtained. The rubber film was carefully mounted onto the
window (2 x 1.5 cm) of a film homer which was made of
manila card having a dimension of 8 x 5 cm. Thickness of
the film was between 0.15 and 0.18 mm. The rubber films
were then aged in air ovens at 90°, 120° and 160°C for 2 hr.
In order to study the effect of oxidation times on the thermal
oxidation of ENR, one sample of ENR 25 was also aged at
140° for 30, 60, 90 and 180 min. Fourier Transform Infrared
(FTIR) spectrometer (Perkin-Elmer 1600 Series model) was
used to obtain the i.r. spectra because of its sensitivity and
ability to detect weak signals. The equipment was operated
with a resolution of 4cm -I and scanning range from
4400-450 cm- t For the oxidation times study, the scanning
range was from 1900-1600 cm -t with the aim of focussing
the study on the carbonyl group absorption region. Pro-
gressive spectral changes as a result of thermal oxidation can
be obtained by subtraction of the spectra of the unoxidized
material from those of the oxidized one to give the difference
spectra as shown below:
Difference spectra = ko x (oxidized spectrum)
- ku x (unoxidized spectrum)
where k o and k u are variables which can be used to
compensate for differences in film thickness. In this study,
ko/k u is 1 because identical area of the same sample was
scanned each time. Any increase in absorption above the
base line is a result of an increment of new species whereas
any decrease in absorption below the base line indicates a
decrement of existing species.
RESULTS AND DISCUSSION
F T I R spectra for unoxidized a n d oxidized rubbers
were o b t a i n e d a n d discussed as follows:

17
18 B.T. POH and K. S. LEE

4.0

835
J,

3.0 J

J
e,)
1660
~ 2.o -~

<

1,0 I

A
I I ! I I I i I I ! I
4000 3000 2000 1600 1200 800 450
W a v e n u m b e r (cm -1)

Fig. I. FTIR spectrum of unoxidized SMR L.

4.0

835

3.0
870

ee
2.o 1065
o
e~
<

1660

1.0

I ] ~ I I ~ | | | I I I m
4000 3000 2000 1600 1200 800 450
W a v e n u m b e r (cm -1)

Fig. 2. FTIR spectrum of unoxidizedENR 25.

 FTIR study of thermal oxidation of ENR
4.0
3.0
o
e.2
2.0
o
<
1.0 ¸
\
0 I ~ I ! !
4000 3000 2000
Wavenumber (cm -l)
Fig. 3. FTIR spectrum of unoxidized ENR 50.
FTIR spectra of unoxidized rubbers
Figures 1, 2 and 3 show respectively the F T I R
absorption spectra for SMR L, ENR 25 and ENR 50.
Differences between SMR L and ENR are observed
but the most obvious difference occurs in the "finger
print" region, i.e. 1500-700 crn -t. In the case of
ENR, a new absorption band is observed at 870 cm-
which is associated with the presence of epoxide
group [9]. As the degree of epoxidation is increased,
the absorbance of 870 crn- ~ is increased correspond-
ingly. A weak absorption is also detected at
1065 cm -~ for ENR spectra. This is attributed to the
presence of tetrahydrofuran ring, a secondary
product derived from the epoxide ring-opening reac-
tion which occurs during the preparation of ENR
[10]. The reduction in the number of double bonds in
ENR is reflected from the decrease in the absorption
band at 1660cm -~ and 835cm -1 as shown in the
ENR spectra. On the other hand, the broad absorp-
tion in the region between 3600-3200 crn-~ in ENR
is associated with the presence of hydroxyl groups
(e.g. glycol and hydroxyl formate) resulting from the
acid catalysed reaction on the epoxide ring during
ENR preparation [10].
FTIR spectra of oxidized rubbers
In order to facilitate the analysis for the oxidized
rubbers, the results are presented in the form of
difference spectra as shown in Figs 4, 5 and 6
respectively for SMR L, ENR 25 and E N R 50.
Changes in the chemical structure of the rubbers
upon thermal oxidation can be monitored by the
difference spectra technique. In the case of SMR L,
19
870
1065
1660
I I I I I I I
1600 1200 800 450
a new broad absorption peak at 3450 cm -1 is ob-
served and this is associated with the presence of
hydroperoxide and alcohol. The presence of carbonyl
groups in the rubber after thermal ageing is indicated
by the appearance of absorption peaks at 1770 cm-
and 1720cm-'. The 1770cm -~ peak is associated
with the presence of ester complexes (e.g. lactone)
[l 1], whereas the peak at 1720cm -t is attributed to
the presence of aldehyde, ketones and carboxylic
acids. With the formation of the oxidative products,
a reduction in double bonds is observed as shown by
the decrease in the absorption bands at 1660 cm-
and 835 cm -~. In addition to the above absorption
bands, a series of new absorption in the
1300-900 cm -1 region is also observed. This region of
absorption is assigned to the presence of C - - O - - C
group due to the formation of esters. The intensity of
the absorption in this region is increased with the
increase in the temperature of ageing indicating the
presence of more ester compounds.
In the case of ENR, thermal oxidation occurs in
the double bond and the epoxide group regions as
demonstrated by the decrease in absorption bands at
1660 and 835 cm -1 (for double bond) and 870 cm -~
(for epoxide) in Figs 5 and 6 for ENR 25 and E N R
50 respectively. The functional group of the oxidative
products are similar to those observed for SMR L as
indicated by the similar new absorption band at
3450 cm -1, 1770 cm -t, 1720 cm -l and 1300--900 cm -I
regions for ENR. Table 2 shows a comparison in
absorbance between the various rubbers at three
characteristic absorption peaks.
The result indicates that a similar quantity of oxi-
dative products are formed during thermal oxidation
20 B.T. Port and K. S. Ll~

of SMR L and ENR 25. In the case of SMR L,
thermal oxidation occurs in the double bond as
shown by the decrease in the absorption bands at
1660 cm -1 and 835 cm -] whereas in ENR 25, thermal
oxidation occurs not only in the double bond region
but also involves the epoxide group as shown by the
drop in absorption band at 870cm-L The lower
number of double bond in ENR 25 is compensated
by the presence of epoxide group, thus the amount
of oxidative products formed is similar to that of
SMR L.
In the case of ENR 50, due to the presence of
50 mol% of epoxide group compared to 25 mol% in
ENR 25, the oxidation products obtained in the
former is about twice the amount observed for the
latter as indicated in Table 2. The result is further
confirmed by the drop in absorbance at 870 crn -J
( - 1.25 and - 2 . 1 3 for ENR 25 and ENR 50 respect-
ively at 160 ° of oxidation) where epoxide ring-open-
ing reaction occurs when ENR is aged. This
observation is consistent with our previous DSC
study on ENR where epoxide ring-opening reaction
was detected at about 155 ° [6]. Since epoxide ring-
opening reaction occurs in the bulk state, we believe
that the reaction involves a homolytic process, thus
giving rise to free radicals as shown below:

90°C

-1 I I I I I I I I '= i I I i

120°C

-1

m
~-2
m
m
! ! ! i I t 1 i i i i i-!
1770 ~.. 1720
160°C
3450 1080
1

-1

-2

835~
-3 I I I 'i I I i I i i t
40100 3000 2000 1600 1200 800 450
Wavenumber (cm -])
Fig. 4. Difference spectra of oxidized SMR L at various temperatures of oxidation for 2 hr.
 FTIR study of thermal oxidation of ENR 21

1""
a
90°C

0-

-l I I I | I I I I 'l I I I

1w 120°C

O"

--1 ~

¢l

~O - 2 -
m

I i'' i I I I w I t I

.~ 1720

°t 3450~
1080

160°C

0 -

1660

-I --
/,
870
i
?
835

-3 I a I I I I i I I I I I
4000 3000 2000 1600 1200 800 450
Wavenumber (cm -l)

Fig. 5. Difference spectra of oxidized ENR 25 at various temperatures of oxidation for 2 hr.

CH 3 would increase the amount of oxidative products.

---CH2--~.-'-C.H---CH2-- CH;
--CH~. ---CH--CH2--
A B
The radicals of A and B will react with the adjacent
rubber molecules to form hydroperoxide, alcohols
and ester as detected by FTIR spectra. For all the
rubbers studied, increasing temperature of oxidation
This is due to the increase in thermal energy and thus
the rate of reaction is increased correspondingly.
Figure 7 shows the difference spectra of ENR 25 at
various oxidation times at 140° which is the tempera-
ture normally used for accelerated sulphur vulcaniza-
tion of natural rubber [12]. The scanning range is
from 1900-1600cm -~ i.e. in the carbonyl group
absorption region. From the spectra, it is obvious
that at short oxidation times (< 60 min for ENR 25),
little thermal oxidation is observed. However, if the
oxidation time is further increased, thermal oxidation
becomes very significant as exhibited by the marked
increase in the difference absorbance at 1720 cra-L
22 B.T. Port and K. S. LEE

-1 I , I , I
2

120°C

m -2 I ! i I | ! ! I I I ! I
8
= 3
1770 r1720
1080
2 4
160°C

3450
4,

-I

-2
t
870
-3 I I I I [ I I | ! I I I
4000 3000 2000 1600 1200 800 450
Wavenumber (cm -1)

Fig. 6. Difference spectra of oxidized ENR 50 at various temperatures of oxidation for 2 hr.

The time-dependent behaviour of thermal oxidation CONCLUSION

of ENR 25 at 140 ° is illustrated in Fig. 8. It shows
that the oxidative rate increases with increasing oxi- From the study, the following conclusions can be
dation time. This observation leads us to believe that drawn:
thermal oxidation of ENR is an autocatalytic pro- (1) Thermal oxidation of SMR L occurs in the
cess, a phenomenon similar to that of unmodified double bond region to form oxidative products
natural rubber [13]. which consist mainly of hydroperoxide, car-
boxylic acids, alcohols, ester and other carbonyl
compounds. In the case of ENR, the reaction
Table 2. Absorbanee at 1080¢m -I, 1720era -R a n d
occurs not only in the double bond region, but
3450em -I for the various rubbers oxidized at 160° for also involves epoxide ring-opening to form oxi-
2 hr dative products having similar functional groups
Absorbanee at: as that of SMR L.
(2) Oxidative rate in ENR increases with an increase
Rubber 1080 em - t 1720 em -t 3450 em -t in the degree of cpoxidation. Also, it inereases
SMR L 0.82 1.36 0.66 with increasing oxidation time suggesting that
ENR 25 0.81 1.39 0.63 thermal oxidation of ENR is an autocatalytic
ENR 50 1.85 2.60 0.80
process.
 FTIR study of thermal oxidation of ENR 23

140°C

o
0~
e~

t~
e~

B A

-1
1900 1840 1780 1720 1660 1600
W a v e n u m b e r (cm -1)

Fig. 7. Difference spectra of oxidized ENR 25 at various oxidation times at 140". (A) 30 min; (B) 60 rain;
(C) 90 rain; (D) 180 min.
/

1.5

t~
1.0

0.5 ×

×ix
f
I 1 I 1 I I
30 60 90 120 150 180
Time (rain)
Fig. 8. Variation of difference absorbance at 1720 crn- with oxidation time for ENR 25 aged at 140°.

REFERENCES 7. A. Ainu, K. A. R. Ku Ismail and S. Dulngali. Preprint

1. M. Nasir, B. T. Poh and P. S. Ng. Eur, Polym. J. 25,
267 (1989).
2. M. Nasir and C. H. Choo. Eur. Polym. J. 25, 355 (1989).
3. S. C. Ng and K. K. Chee. Rubb. Chem. Techn. 62, 585
(1989).
4. K. T. Varughese, P. P. De, S. K. Sanyal and S. K. De.
J. appl. Polym. Sci. 37, 2537 (1989).
5. Z. A. Nasir and C. T. Ratnam. J. appl. Polym. Sci. 38,
1219 (1989).
6. B. T. Poh and B. K. Tan. J. appl. Polym. Sci. 42, 1407
0990.
of International Rubber Conference, Kuala Lumpur,
Malaysia, 1985.
8. I. R. Gelling and N. J. Morrison. Rubb. Chem. Techn.
58, 243 (1985).
9. I. R. Gelling. Rubb. Chem. Techn. 58, 86 (1985).
10. S. C. Ng and L. H. Gan. Eur. Polym. J. 17, 1073 (1981).
II. R. L. Pecsok, P. C. Painter, J. R. Shelton and J. L.
Koenig. Rub& Chem. Techn. 49, 1010 (1976).
12. L. Bateman (Ed.) The Chemistry and Physics of Rubber-
like Substances, p. 513. Applied Science, London,
(1963).
13. J. I. Cunneen. Rub& Chem. Techn. 41, 182 0968).