KINETIC MODEL FOR THERMAL DEHYDROCHLORINATION OF

CHLORINATED NATURAL RUBBER WITH DIFFERENT CHLORINE

CONTENT

JING CHEN,1,* LANZHEN HE,2 YASHENG CHEN,2 JIEPING ZHONG,2 CANZHONG HE,3 LINXUE KONG4
1
CHEMISTRY SCIENCE AND TECHNOLOGY SCHOOL, INSTITUTE OF PHYSICAL CHEMISTRY,
ZHANJIANG NORMAL UNIVERSITY, ZHANJIANG 524048, P.R. CHINA
2
GUANGDONG OCEAN UNIVERSITY, COLLEGE OF SCIENCE, GUANGDONG, ZHANJIANG 524088, P.R. CHINA
3
AGRICULTURE MINISTRY KEY LABORATORY OF NATURAL RUBBER PROCESSING, AGRICULTURAL PRODUCTS
PROCESSING RESEARCH INSTITUTE, CHINESE ACADEMY OF TROPICAL AGRICULTURAL SCIENCES,
GUANGDONG, ZHANJIANG 524001, P.R. CHINA
4
CENTRE FOR MATERIAL AND FIBRE INNOVATION, INSTITUTE FOR TECHNOLOGY RESEARCH INNOVATION,
DEAKIN UNIVERSITY, GEELONG VIC, AUSTRALIA

RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 87, No. 2, pp. 370–382 (2014)

ABSTRACT
A novel model for calculating dehydrochlorination kinetics at a lower temperature of chlorinated natural rubber
(CNR) is presented. It has been observed that dehydrochlorination is complex and involves three different stages. A
model that accounts for dehydrochlorination at lower temperature is proposed. The kinetic parameters are obtained
from dehydrochlorination experiments at 60–90 8C. The results of the kinetic calculation show that the apparent
activation energy decreases with an increment of chlorine content. Higher chlorine content CNR makes it easier to
remove hydrochloric acid when heated, but its dehydrochlorination rate affected by temperature is significantly less
than that of the sample with a lower chlorine content. The thermogravimetric/derivative thermogravimetry results show
that the beginning temperature of thermo-oxidative degradation rises with the increment of chlorine content. During
the heating process, the higher chlorine content CNR is more stable than the lower one. The results suggest the storage
conditions and basis for selection of appropriate temperature for the preparation of CNR from latex. [doi:10.5254/
rct.13.86940]

INTRODUCTION
Chlorinated natural rubber (CNR) is made from natural rubber (NR) by chlorination
modification and obtained nontoxic and tasteless, white or creamy yellow powder NR
derivatives. It is used as an additive to adhesive compositions around chloroprene rubber,
which, in turn, are widely used in industry for bonding vulcanized rubber with various metals
or with each other.1,2 There are two main kinds of methods for the production of CNR. In the
traditional solution process, chlorination is carried out by passing chlorine gas into the NR,
which is first dissolved in CCl4. In contrast, in the new latex process, the stabilized NR latex
is chlorinated directly with chlorine gas.3–6 The fine structures of CNR prepared from latex
and solution processes are different, whereas their basic structures are similar. The 1H- and
13
C-NMR of CNR from solution suggest that five (not six) membered cycles are formed
during chlorination of NR, and with the increase in the chlorination degree, signals in the
olefinic region of spectra appear, which indicate the formation of exo- and internal C¼C
double bonds, differing from analogous fragments that form in the first stage of the reaction.7
It is well known that the thermal stability of chlorinated polymers has an important effect on
their preparation, storage, processing, and performance.8 There are numerous C–Cl bonds in CNR
molecular chains, and the nonregularity between CNR molecular chains and -Cl cause them to be
vulnerable to the effect of light, heat, oxygen, and acid and may give rise to the variation of CNR
structure and properties. There are some reports related to the thermal stability of CNR, attempts to

*Corresponding author. Email: chchjing@163.com

370
THERMAL DEHYDROCHLORINATION OF CHLORINATED NATURAL RUBBER 371

delay the dehydrochlorination reaction, and improvement in the thermal stability of CNR.9–11
Studies of the thermo-oxidative degradation of CNR from latex by the use of thermogravimetric
(TG) analysis, coupled with Fourier transform infrared spectra (FTIR) spectroscopy, ultraviolet-
visible spectroscopy, and difference FTIR, have indicated that the thermal degradation of CNR is
mainly a dehydrochlorination reaction with a little oxidative scission of the molecular backbones,
and the conjugated polyenes are formed on the molecules of CNR. During the early stage of the
thermal degradation of CNR, only hydrochloric acid (HCl) is released, and this leads to severe
discoloration.12–14
The objective of the present work is to study the thermal dehydrochlorination of CNR samples
with different chlorine content and the proposal of a kinetic mechanism that accounts for the entire
complex process. Kinetic parameters will be obtained from dehydrochlorination experiments, and a
conductive detection method was used to determine the HCl amount and dehydrochlorination rate
from CNR during the heating process.

EXPERIMENTAL SECTION
CNR SAMPLE PREPARATION
A total of 66.7 g of NR latex (total solid content 60%) was added to 313 mL distilled water, and
then 20.0 g fatty alcohol polyoxyethylene ether (Peregal O, mass percentage 10%) was added as a
stabilizer. The mixture was then subjected to stirring for 1 h to produce stabilized NR latex. A
solution of 400 mL of HCl (mass percentage 30%) was added to a 1500 mL three- necked quartz
bottle, and the reaction temperature was adjusted using a water bath. Protective gas nitrogen was
then infused to discharge the air from the reaction system. Then, chlorine (Cl2) was infused. After
the reaction system became saturated with chlorine, the stabilized NR latex was coagulated slowly
with continuous stirring, until the dry rubber content of NR latex in this reaction system was about
5%. During the reaction, the CNR samples with a different degree of chlorination were removed
from the reaction system at regular intervals. After the reaction, nitrogen gas was infused again to
discharge chlorine. The reaction mixture was filtrated, washed, and neutralized with 5% sodium
carbonate (Na2CO3), and then it was washed by distilled water to pH » 7. No precipitates were
observed when the filtrate was tested using 0.1 mol/L silver nitrate (AgNO3). To avoid CNR
decomposition during the drying process, the wet CNR samples were dried in a vacuum dryer filled
with some silica gel for 120 h.

DETERMINATION OF CHLORINE CONTENT

A sample of CNR (0.05~0.10 g) was packed in a ashless filter and fixed onto the spiral wire of an
oxygen combustion flask in advance in accordance with ANSI Standard GB/T9872-1998. Sodium
hydroxide solution (2%, 100 mL) was added into the combustion flask, and the oxygen was infused to
replace the air inside. Then, the end of the filter paper was lit up and put promptly into the combustion
flask; the flask cap was sealed firmly. After the complete combustion of the CNR and the complete
absorption of the gas produced, nitric acid solution (1:1) was added to the solution to regulate the
systematic pH to between 1 and 0. Finally, after the introduction of AgNO3 standard solution (0.05
mol/L, 30–50 mL), ferriammonium sulfate–saturated solution (1–2 mL), and CCl4 (1–2 mL) to the
sample solution, ammonium thiocyanate (NH4SCN) standard solution (0.05 mol/L) was added
slowly to titrate until the end point was reached. Chlorine content (Cl%)15 is calculated as follows:
½cðAgNO3 Þ 3 V0  cðNH4 SCNÞ 3 V1  3 103 3 35:45
3 100% ð1Þ
ms
372 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 87, No. 2, pp. 370–382 (2014)

FIG. 1. — (a) Schematic diagram. (b) Reactor diagram. 1. Conductivity meter. 2. Absorption cell. 3. Constant-temperature
water bath. 4. Thermostatic bath. 5. Reactor.

where V0 and V1 are the volume of AgNO3 and NH4SCN standard solution, respectively, and Ms is
the quality (in grams) of the CNR sample. The titration was performed three times for each sample,
and the mean was used as the final results.

DETERMINATION OF HCL LOSS AMOUNT

A sample of 8.0 g CNR was put into a 250 mL three-necked bottle. Nitrogen, preheated in the
pipeline placed in a thermostatic bath, was purged consecutively to a three-necked bottle to carry off
dehydrochlorinated HCl from CNR.16 The double-distilled water was used to absorb HCl; the ionic
conductivity was detected by a conductivity meter at regular intervals.7 The experimental apparatus
of dehydrochlorination is shown in Figure 1. As there is a very good linear correlation between HCl
concentration and conductivity, the molar number of HCl can be calculated by Eq. 2:
ct 3 500
y¼ nmol  g1 ð2Þ
mg
where ct is the molar concentration of HCl at time t and mg is the weight of dried CNR sample.

THERMOGRAVIMETRIC/DERIVATIVE THERMOGRAVIMETRY AND FTIR ANALYSIS

The thermal analysis was carried out by use of a PerkinElmer Thermal Gravity Analyzer in the
air. The temperature rose from room temperature to 700 8C at the heating rate of 10 8C/min. The
FTIR was recorded on an IR-6700 (Nicolet, Thermo Fisher Scientific, Madison, WI) spectrometer
in the region 400–4000 cm1 by KBr method.

RESULTS AND DISCUSSION

CHLORINATION PROCESS

The chlorine content of CNR at a different reaction time when the experiment was carried out at
25 8C is shown in Figure 2.
It can be seen from Figure 2 that the reaction process can be divided into three stages. During
the initial stage, chlorine content rises dramatically with increasing reaction time. But when the
chlorine content reaches about 60%, it is difficult to raise the chlorination rate. Many research
results have been reported on the chlorination mechanism and structure of CNR. The chlorination
THERMAL DEHYDROCHLORINATION OF CHLORINATED NATURAL RUBBER 373

FIG. 2. — The change of chlorine content with reaction time (25 8C).

reaction scheme (Scheme 1) of NR in latex and the possible structure of CNR have been
suggested.13
From Scheme 1, the chlorine content of (C), (D), and (E) could be calculated as 34.6%, 57.2%,
and 65.5%, respectively, so we can speculate that stage I of chlorination should be the reaction
ABC, and stage II should be process CD; process DE can be regarded as stage III. During
the preparation process of CNR from solution, NR dissolved in CCl4 was in the stretching state; in
this way, NR molecules easily interact with Cl2, and the reaction temperature is lower and the
reaction time shorter. While in latex, NR molecules are compacted in the colloidal particle in the
water phase, and Cl2 should go through the outer layer of the NR particles so as to contact with the
NR molecules and react. When the degree of chlorination becomes higher, the volume of CNR
would be larger, the available space in the particles becomes smaller and smaller, and the molecular
motion tends to be slower. Thus, the reaction rate decreases in the late stage of chlorination.3 To
speed up the chlorination, the reaction temperature should be lifted, but the oxidation of polymers
would be difficult to avoid, so there are some carboxyl compounds in the products. Cl2 dissolved in
water easily produces hypochlorous acid with a strong oxidizing property, which is one of the
causes of the production of carboxyl groups in CNR from latex.4 On the other hand, the lower
chlorination rate may be due to the occurrence of the dehydrochlorination reaction in the process of

SCHEME. 1. — Chlorination process of NR.

374 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 87, No. 2, pp. 370–382 (2014)

FIG. 3. — FTIR spectra of CNR of chlorine content (%): (A) 45.3; (B) 50.5; (C) 53.5; (D) 65.3.

chlorination. Therefore, exploration of the dehydrochlorination law of different chlorine contents

of CNR focuses on the effect on the chlorination reaction rate and mechanism to help improve the
reaction rate.

FTIR ANALYSIS
The structure of CNR remains widely unknown, and several studies have concluded that CNR
contains mainly cyclized units. Thus, the following chlorination reaction scheme of NR in latex and
the possible structure of CNR have been suggested.13,17 The FTIR spectra of CNR of different
chlorine contents are shown in Figure 3.
It can be seen that the wave numbers of IR absorption peaks for CNR A–D are similar,
except for the difference in absorption intensities. The absorption peaks at 930 to 670 cm1 are
attributed to the stretching vibrations of the C–Cl bond, the strong absorption peaks at 1270
cm1 are attributed to the wagging vibration of C–H in –CHCl–, and the absorption at 1430
cm1 is attributed to the asymmetric wagging vibration of C–H in methylene with adjacent
chlorine atom (–CH2–(–CHCl)–); these peaks become stronger from A to D. The absorption
intensity at 1380 cm1 is attributed to the symmetric wagging vibration of C–H in CH3, and the
peak at 2800–3000 cm1 is due to the stretching vibration of saturated C–H. At the same time,
the intensities of absorbance at 1630 cm1, which is assigned to the stretching vibration of C¼C
THERMAL DEHYDROCHLORINATION OF CHLORINATED NATURAL RUBBER 375

FIG. 4. — HCl loss amount with heating time in different temperature (Cl% ¼ 50.3%).

of conjugated polyene sequences, decreased gradually from A to D. The appearance of a strong

absorption peak at 1738 cm1 together with the absorption peak at 3500 cm1 indicates there are
some carboxyl and carbonyl groups on the molecular chain of CNR. During the chlorination
process, some C¼C bonds in NR have been oxidized to carboxyl and carbonyl groups in the
presence of hypochloric acid.5

HCL LOSS AMOUNT AT DIFFERENT TEMPERATURES

According to Figures 4–6, heating temperature and chlorine content have a significant effect on
HCl amount and the dehydrochlorination rate. The dehydrochlorination process can be divided into
three stages: induced stage, auto-accelerated stage, and auto-retardated stage. During the induced
stage, there is almost no release of HCl. In the auto-accelerated stage, the HCl amount rises quickly,
and the corresponding slope rises with increment of temperature. However, in the auto-retardated
stage, the curve becomes more flat. During the heating process, when the heating temperature is 70
8C and 80 8C with the heating time prolonged, the sample color was nearly unchanged, whereas
when the heating temperature reached 90 8C with heating time extended, the sample color gradually
turned yellow.
The starting times of dehydrochlorination at different conditions are shown in Table I.
We can see from Table I that the induction period is shortened when the heating temperature is
elevated. The CNR samples with higher chlorine content are more likely to release HCl at the
experimental temperature. It can be explained, on the other hand, that the chlorine content reaches to
about 60%; it is difficult to raise the chlorination rate. During the chlorination of NR, the
dehydrochlorination of CNR occurs at the same time.
The time of the first stage is obviously shorter than the other two stages, so to simplify, we take
them as one stage for the kinetics calculation. Using different models to fit the dehydrochlorination
process, a model of y¼kln tþB better fitted the experimental results. The dehydrochlorination rate
constant (k) and the coefficients (a) of the model for all the experiments as well the calculated
statistical coefficients R are tabulated in Tables II, III, and IV. The results show that the value of R of
376 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 87, No. 2, pp. 370–382 (2014)

FIG. 5. — HCl loss amount with heating time in different temperature (Cl% ¼ 53.5%).

nearly all groups of experiment data is larger than 0.99, which suggests that the model can express
the dehydrochlorination process of CNR of different chlorine content.
To determine the apparent activation energy starting with the Arrhenius equationk ¼
Aexp[Ea/(RT)], we take the logarithm of both sides and derive

FIG. 6. — HCl loss amount with heating time in different temperature (Cl% ¼ 65.4%).
THERMAL DEHYDROCHLORINATION OF CHLORINATED NATURAL RUBBER 377

TABLE I
STARTING TIME OF DEHYDROCHLORINATION AT DIFFERENT CONDITIONS
(MIN )

Temperature

Chlorine content 70 8C 80 8C 90 8C 100 8C

50.3% 80 60 55 32
53.5% 30 17 12 7
65.3% 22 14 10 5

TABLE II
KINETIC PARAMETERS OF CNR (50.3%)

Heating temperature/8C Equation Correlation coefficient (R)

70 y ¼ 0.0057 ln t – 0.0253 0.9910

80 y ¼ 0.0119 ln t – 0.0506 0.9873
90 y ¼ 0.027 ln t – 0.1052 0.9929
100 y ¼ 0.0311 ln t – 0.1006 0.9916

TABLE III
KINETIC PARAMETERS OF CNR (53.5%)

Heating temperature/8C Equation Correlation coefficient (R)

70 y ¼ 0.0071 ln t – 0.0239 0.9963

80 y ¼ 0.0135 ln t – 0.0383 0.9936
90 y ¼ 0.0231 ln t – 0.0619 0.9869
100 y ¼ 0.0309 ln t – 0.0683 0.9910

TABLE IV
KINETIC PARAMETERS OF CNR (65.3%)

Heating temperature/8C Equation Correlation coefficient (R)

70 y ¼ 0.0217 ln t – 0.0629 0.9982

80 y ¼ 0.027 ln t – 0.0685 0.9984
90 y ¼ 0.03271 ln t – 0.0729 0.9966
100 y ¼ 0.0354 ln t – 0.0635 0.9926

Ea
lnk ¼ lnA  ð3Þ
RT
When we then graph lnk against 1/T (Figure 7), the apparent activation energy (Ea) can be
obtained from the slope of the resulting straight line and can be calculated as 17.7 kJ/mol (Cl% ¼
65.3), 52.8 kJ/mol (Cl% ¼ 53.5), and 63.2 kJ/mol (Cl% ¼ 50.3), respectively. The value of Ea
increases with the decrease of chlorine content.
It is interesting to find that when Ea is graphed against chlorine content (x, %), a straight line
can be obtained, and the equation can be expressed as Ea ¼ 214.65  3.0174x. The correlation
378 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 87, No. 2, pp. 370–382 (2014)

FIG. 7. — Calculation of kinetic parameters.

coefficient R is 0.99987, and the results are shown in Figure 8. The results suggest that the higher the
chlorine content, the easier to remove HCl, but its dehydrochlorination rate is less sensitive to
heating temperature. Therefore, at low temperature, the dehydrochlorination rate of high chlorine
content CNR is greater, but at high temperature, the rate tends to be equal. When the temperature is
greater than 100 8C, the dehydrochlorination rate of lower chlorine content CNR would be faster
than that of higher chlorine content CNR. The level of chlorine content below which there is no
dehydrochlorination should be further verified by experiments.
Theoretically, CNR produced from latex is C10H11Cl7, containing 65.48% chlorine.5 That is to
say, all adjacent carbon atoms bond chlorine atoms. Besides, there are many unstable groups in
molecular chains. Therefore, CNR produced from latex more easily releases HCl and produces a

FIG. 8. — The relationship between Ea and chlorine content.

THERMAL DEHYDROCHLORINATION OF CHLORINATED NATURAL RUBBER 379

SCHEME 2. — Possible scheme of cyclic conjugated dienes formed on CNR molecular chains.

new conjugated double bond formed by three or four carbon-carbon double bonds.6 Yu10,11
reported that transition-metal ions can accelerate the dehydrochlorination process of CNR.
Meanwhile, alkaline earth metals and long-chain fatty salts of rare earth metals can stabilize
poly(vinyl chloride) (PVC) significantly but pose unnoticeable effects on CNR. This indicated that
the stabilization of CNR and PVC may have a different mechanism. The mechanism of CNR
dehydrochlorination, perhaps being the process of free radical reactions, is evidently distinguished
from the thermal degradation of PVC. The dehydrochlorination process of CNR produced from
latex can not only happen intramolecularly and form double bonds or rings but can also occur
extramolecularly and form a cross-link structure, which should be further verified by experiments.
From the studies of some researchers,8,13,18 a chlorination reaction scheme of NR in latex and
possible structure of CNR have been suggested (Scheme 2). During the degradation of CNR, HCl is
eliminated from CNR molecular chains, and the conjugated polyene sequences are formed.

TG/DERIVATIVE THERMOGRAVIMETRY ANALYSIS OF CNR

The TG analysis and derivative thermogravimetry (DTG) methods were adopted to study the
stability of prepared CNR. The TG and DTG curves of degradation of CNR in air are shown in
Figures 9–11.
Two peaks appear on the DTG curve, which indicates that the thermo-oxidative degradation of
CNR is a multistep reaction. The first peak may be caused by the dehydrochlorination of CNR

FIG. 9. — TG/DTG curve of CNR (Cl% ¼ 50.3%).

380 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 87, No. 2, pp. 370–382 (2014)

FIG. 10. — TG/DTG curve of CNR (Cl% ¼ 53.5%).

molecular chains. The chain of CNR C–Cl and C–H breaking occurs in the dehydrochlorination
reaction; the gas produced in the second step is mainly carbon dioxide, which results in CNR
backbone oxidation fracture.13 The first step ranging from 160 8C to 390 8C is mainly a
dehydrochlorination reaction with a little oxidative scission of molecular backbones to release
carbon dioxide, and the conjugated polyene sequences (–[C¼C]–)n¼3,4 are formed on the molecules

FIG. 11. — TG/DTG curve of CNR (Cl% ¼ 65.3%).

THERMAL DEHYDROCHLORINATION OF CHLORINATED NATURAL RUBBER 381

of CNR. The second step ranging from 390 8C to 585 8C is an oxidative degradation reaction of the
molecular backbones of CNR, and the evolved gas is only carbon dioxide. The beginning
temperature of thermo-oxidative degradation of CNR with different chlorine content calculated
from the TG curve is 207 8C, 227 8C, and 258 8C, respectively, which rise with the increase of
chlorine content of CNR. It shows that at the heating process, the higher the chlorine content, the
better thermal stability of CNR.

CONCLUSION
The dehydrochlorination process of CNR heating in lower temperature can be distinguished by
three stages: induced stage, auto-accelerated stage, and auto-retardated stage when heating at a
constant temperature. Along with the increment of temperature and chlorine content, the induction
period is shortened, and the higher chlorine content of CNR samples is more likely to release HCl at
the experimental temperature.
A formula y ¼ kln t þ A was the better-fitted model to the dehydrochlorination process. The
results of the kinetic calculation show that the apparent activation energy (Ea) increases with the
decrease of chlorine content. The higher the chlorine content, the easier to remove HCl, but the
dehydrochlorination rate of lower chlorine content samples is affected more remarkably by
temperature, so when the reaction temperature is higher, low chlorine content CNR makes
removing HCl easier.
The beginning temperature of thermo-oxidative degradation of CNR rises with the increase of
chlorine content of CNR. During the heating process, the greater the amount of chlorine content, the
more stable the CNR.

ACKNOWLEDGEMENTS
This work was supported financially by the National Natural Science Foundation of China
(No. 50873031) and Guangdong Provincial Natural Science Foundation of China
(9152402301000021).

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[Received September 2013, Revised November 2013]