POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 2007; 18: 822–828

Published online 6 June 2007 in Wiley InterScience (www.interscience.wiley.com) DOI: 10.1002/pat.941

A novel approach to synthesis of functional CPVC

and CPE or graft copolymers—in situ chlorinating graft
Jiruo Zhao1,2*, Junyuan Li2, Ying Feng2 and Jinghua Yin1
1
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun
130022, People’s Republic of China
2
Key Laboratory of Rubber-Plastics, Ministry of Education, Qingdao University of Science Technology, Qingdao 266042, People’s Republic of
China
Received 21 September 2006; Revised 10 April 2007; Accepted 10 April 2007

A new process of graft copolymerization of poly(vinyl chloride) (PVC) and polyethylene (PE) with
other monomers was developed. The grafted chlorinated poly(vinyl chloride) (CPVC) and chlori-
nated polyethylene (CPE) were synthesized by in situ chlorinating graft copolymerization (ISCGC)
and were characterized. Convincing evidence for grafting and the structure of graft copolymers was
obtained using FT-IR, 1H-NMR, gel permeation chromatography (GPC), and the vulcanized curves.
Their mechanical properties were also measured. The results show that the products have different
molecular structure from those prepared by other conventional graft processes. Their graft chains are
short, being highly branched and chlorinated. The graft copolymers have no crosslinking structure.
The unique molecular structure will make the materials equipped with special properties. Copyright
# 2007 John Wiley & Sons, Ltd.

KEYWORDS: graft copolymers; in situ chlorinating graft copolymerization; polyethylene; poly(vinyl chloride); structure

INTRODUCTION One step reaction: Both chlorination and graft copolymeriza-

Graft copolymerization is one of the most important methods
to synthesize graft polymer materials. As chlorine-containing
polymers, poly(vinyl chloride) (PVC) and chlorinated
polyethylene (CPE), were used as backbone molecules of
graft copolymers a graft reaction may be initiated in different
ways such as cationic,1,2 anionic,3 radical,4–6 radiation7,8, and
recently atom transfer radical polymerization (ATRP).9,10
Generally, a graft copolymer is synthesized by several steps:
(1) choosing or preparing a backbone polymer; (2) if
necessary, creating active sites on backbone polymer, such
as dehydrochlorination11 or introducing functional groups12
in PVC; (3) grafting monomers onto the molecules of
backbone polymers. These processes cannot be followed
easily or in an economically feasible fashion to synthesize
graft copolymers for industrialization because of organic
solvents or water used as reaction medium.1,13
Here we present a new process to prepare graft
copolymers, named in situ chlorinating graft copolymeriza-
tion (ISCGC). It means that the chlorination and graft
copolymerization of the polymer happed at the same time. It
has the following advantages:
tion of backbone polymers are completed simultaneously by
one reaction step.
Easy to obtain new polymers with improved properties: Different
polymers with desired functional groups and molecular
structures could be prepared by changing the backbone
and grafting monomers, chlorine contents, and reaction
conditions.
An environmental-friendly process: The new method is a gas–
solid state reaction adding neither organic solvent nor
initiator, and adopts a closed-circle process generating
almost no waste. Chlorine is utilized circularly and, as a
by-product, hydrochloride gas is absorbed by water to pro-
duce hydrochloric acid with the concentration up to 30%. It
can be utilized to avoid draining of the acid solution.
The foundation of this new process is that chlorination of
organic polymer is a radical reaction and there exist
backbone polymer radicals in the reaction system. The graft
reactions may be initiated by the reaction of monomer with
backbone polymer radicals. This process is suitable especi-
ally for bulk reaction. According to the reaction mechanism,
the backbone polymers for ISCGC may be all chlorinatable

*Correspondence to: J. Zhao, State Key Laboratory of Polymer

Physics and Chemistry, Changchun Institute of Applied Chem-
istry, Chinese Academy of Sciences, Changchun 130022,
People’s Republic of China.
E-mail: jiruozhao@qust.edu.cn
Contract/grant sponsor: National Natural Science Foundation of
China; contract/grant number: 50373042, 50390090.

Copyright # 2007 John Wiley & Sons, Ltd.


polymers [e.g. high density polyethylene (HDPE), low
density polyethylene (LDPE), polypropylene (PP), poly-
styrene (PS), poly(vinyl chloride) (PVC), polybutylene (PB),
ethylene-vinyl acetate copolymer (EVA), natural rubber
(NR), chloroprene (CR), etc.] and the graft monomers may be
any radical polymerizable vinyl monomer, especially, (meth)
acrylic monomers and their derivatives with HO– and epoxy
groups, styrene, acrylonitrile, etc. If necessary, more than one
monomer can be used.
EXPERIMENTAL
Materials
Most of the reagents and all of the solvents were obtained
from commercial suppliers. Methyl methacrylate (MMA),
butyl acrylate (BA), crylic acid (AA), and 2-hydroxy
ethylacrylate (HEA) were purified by vacuum distillation,
and maleic anhydride (MAH) is purified by recrystallization.
Polyethylene (PE), L0555P, MI ¼ 0.5 (1908C, 2.16 kg), was
provided by Liaoyang Petrochemical & Fiber Corp., China.
PVC (PD ¼ 700) and chlorine (Cl2) were provided by Haijing
Chemical Ltd., Qingdao, Shandong, China.
Reaction procedure
The typical reaction procedure of ISCGC is illuminated
below by the reaction of MAH and PE:
A round-bottom three-necked flask equipped with a vane
stirrer, thermometer, and gas delivery tube was charged with
a definite amounts of MAH dissolved in acetone (MAH:
acetone ¼ 1:3 g/ml) and PE power, and the contents of the
flask are stirred to make the solution of MAH well absorbed
by PE. Then a proper amount of specific isolator6 was added
to avoid the agglomeration of PE. The reaction mixture was
deaerated by nitrogen gas (N2) at about 408C for 15 min to
eliminate the acetone and the oxygen gas (O2). As the
chlorine gas was introduced instead of N2, the reaction
would be initiated. The reaction temperature would ascend
gradually as the reaction heat was released and it was well
maintained at a target temperature by a water-bath or air
with an accuracy of
28C. The reaction process was indicated
by the amount of hydrogen chloride (HCl) released from the
reaction system. The reaction temperature was elevated as
the reaction proceeded and was under 1108C, before the
chlorine content reached 17%, and then at 136
28C through
the reaction process. When the desired chlorine content was
reached, the chlorine gas was stopped and the reaction was
terminated. The system was cooled down to below 1008C.
The chlorine gas in the reactor was drawn out by vacuum
and then air was let into the reactor. The vacuum and air
influx operations were performed alternately some times to
ensure the residual chlorine cleaned out completely. CPE
and chlorinated poly(vinyl chloride) (CPVC) were prepared
by the same program without the monomer.
Similar processes were used in the graft copolymerization
of MMA, AA, HEA, and BA onto PE or PVC.
The procedure with the chlorinated polymerization of
monomers is as follows:
Copyright # 2007 John Wiley & Sons, Ltd.
Synthesis of graft CPVC and CPE 823
Table 1. The solvents and precipitators used for different
types of products
Systems Solvents Precipitators
PE/MAH Toluene Acetone
PE/MMA Toluene Acetone
PVC/BA THF Methanol/acetone (1:1 by vol.)
PVC/MAH THF Methanol
A certain amount of HEA or BA is added into a
round-bottom three-necked flask mentioned above, and
then the reaction system was deaerated by N2 at room
temperature for 15 min to eliminate O2. According to the
reactive conditions of PE and PVC with HEA and BA,
respectively, such as the temperature, chlorine content, etc.,
the chlorinated polymerization of HEA or BA takes place
through chlorine.
Purification of the products
All of the crude products of ISCGC were purified by
reprecipitation. The solvents and precipitators used for
different products are listed in Table 1.
The crude product of ISCGC was dissolved in the
corresponding solvent and heated (if necessary). The
solution was poured into a great volume of the correspond-
ing precipitator to let the graft copolymer precipitate and the
precipitate was filtered and dried in an oven. The process
was repeated three times and the final product was dried in a
vacuum oven at 50608C for 24 hr.
Characterization
FT-IR spectra were measured by Nicolet Magna-IR 750
spectrophotometer (KBr).1H-NMR spectra were recorded at
1208C in 1,2-dichlorobenzene-d by AV400 (TMS), Bruker,
Switzerland. GPC was performed using Waters 410 GPC
with THF as solvent. The vulcanized curves were measured
by EK-2000P vulcanizing apparatus (Taiwan Industrial
Finite, China). Tensile strength, extensibility at break, and
300% tensile strength were tested with a tensile testing
machine at 258C and at a tensile rate of 10 or 500 mm/min.
Brinell hardness was tested by a Brinell durometer.
Measurements of graft degree (GD) and the
number of grafted branches
GD of PE/MMA and PVC/BA systems
GD of PE/MMA system was determined by gravimetric
analysis. For Sohxlet extraction, a weighed amount of the
product was taken and extracted with acetone for 48 hr until
constant weight to remove the homopolymer. The product
containing graft copolymers, after extraction, were dried in a
vacuum oven at 50608C for 24 hr to a constant weight and
then GD was calculated. GD of PE/HEA and PVC/BA
systems is determined by 1H-NMR spectroscopy.
Polym. Adv. Technol. 2007; 18: 822–828
DOI: 10.1002/pat
824 J. Zhao et al.

The number of grafted branches was estimated by
molecular weight analysis. Thus, assuming that the mol-
ecular weight of the branches is equal to that of the extracted
homopolymer, the number of grafted branches is calculated
as follows:1
Mn;graft  Mn;CPVC
Branch number ¼
Mn;homopolymer
Gel content measurements
The samples were soaked in a special solvent for 48 hr and
then dried in a vacuum oven until it attains a constant weight
and quantified. The gel content in the solvent was calculated
as follows:
Ws
Gel content % ¼  100 %
Wo
where Ws and Wo represent the weight after soaking and
the initial weight, respectively.
RESULTS AND DISCUSSION
Reaction mechanism
As is well known, chlorine molecules can split into chlorine
radicals by heat or irradiation. Radical is a chemical species
with high chemical reactivity. In chlorinization of PE or PVC,
chlorine radicals substitute H atoms on polymer chains to
produce chlorinated polymers. In the presence of a monomer
with radical polymerization, there is another important
reaction, a free radical polymerization between the mono-
mers and the macromolecular radical, and the reaction is
accompanied by the chlorinated reaction. It can be specu-
lated that the graft copolymers will be produced by the
polymerization of monomers initiated with backbone
macroradicals and the chlorination of polymer and the graft
of monomers will take place at the same time in the process.
Scheme 1 shows the process of ISCGC by an example of the
reaction of HEA and PE.
The new process (ISCGC) is developed on the basis of
chlorination of polymer.14 Similar to the technology of
solid-state chlorination of PE,6 it is an environmental-
friendly process due to it being a closed-circle process
without any organic solvent, initiator, and producing few
(1)
wastes. Almost 100% of chlorine is utilized in circulation and
the concentration of hydrochloric acid, as a by-product, was
up to 30%. It can be speculated that ISCGC on the basis of
solid-state chlorination of polymer is an environmental-
friendly process too.
Mechanical properties
We first mixed a few of the monomers with PVC or PE in a
reactor and then the reaction was carried out through the
(2)
gas–solid state. The mechanical properties of the process are
given in Table 2.
Table 2 shows a variety of new materials exhibiting a
combination of useful properties or a notable change in the
mechanical properties. By carrying out the reaction with one
or several monomers having the special properties of the
material, the modified material is obtained. The procedure is
simple and cheap due to a slight improvement in the inherent
technology.6 This technique could be developed to modify a
commercially available polymer and to prepare some very
interesting polymers, such as graft copolymers or functio-
nalized polymers.
The existence of graft copolymer
The existence of graft copolymers in the reaction products
was proved from the illustrations of BA/PVC and MAH/PE
by IR and 1H-NMR, respectively.
The reaction of BA/PVC and MAH/PE was carried out
and the products were purified. The IR spectra and 1H-NMR
spectra of CPVC, CPE, and the products of BA/PVC and
MAH/PE are presented in Fig. 1 and Fig. 2, respectively.

.
CH 2 CH CH2 CH 2 + CH2 CH CH2 CH CH 2 CH2
COOCH 2CH 2 OH
CH 2
. CH COOCH 2 CH 2OH
n CH 2 CH

CO OCH 2 CH 2 OH CH 2 CH CH2 CH2

.
CH 2 CH CH 2 CH
n
HOCH 2CH 2 OOC COOCH 2CH 2OH

Cl . CH 2 CH CH 2 CH 2
CH 2 CH CH2 CHCl
n
HOCH 2CH 2OOC COOCH 2CH 2OH

Cl2
CH2 CH CH2 CH 2 + Cl.
CH2 CH CH 2 CHCl
n
HOCH 2 CH 2OOC COOCH 2CH 2 OH

Scheme 1. The reactive process between macroradicals and monomers.

Copyright # 2007 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2007; 18: 822–828
DOI: 10.1002/pat
 Synthesis of graft CPVC and CPE 825

Table 2. The mechanical properties of some modified systems

Chloride Tensile strength Extensibility Hardness (A) or
Systemsa content (Wt%) at break (MPa) at break (%) Brinell (B) hardness

PVC/BA 60.2 23.7 267 93 (B)

CPVC 61.6 23.3 200 95 (B)
PE/HEA 36.3 6.33 972 70 (A)
PE/AA 35.5 10.3 739 74 (A)
PE/MMA 35.0 13.5 896 80 (A)
PE/MAH 35.0 10.1 839 73 (A)
PE/(MMA/MAH) 34.6 15.1 690 78 (A)
CPE 36.1 9.49 590 88 (A)
a
(1) PVC/BA, PE/monomer, etc. are representative of the reactive system, that PVC and PE react with BA or some monomers by ISCGC. (2) The
quantity of BA is 4 parts in the reactive system, MMA/MAH is 4 and 3 parts, others (HEA, AA, MMA, MAH) are 5 parts. (3) 40 parts of DOP is
added into the product of CPVC series in the measurement of properties.

The IR spectrum of the products of BA/PVC showed an
obvious absorption peak at 1752 cm1, attributed to the
carbonyl group of the ester group of grafted BA. No such
peak was observed in CPVC. Comparing the two IR spectra
at 920 and 960 cm1, it is found that the peak of 960 cm1 is
lower than the peak of 920 cm1 in CPVC and it is opposite to
CPVC in BA/PVC. These show a distinct evidence of
grafting. The 1H-NMR spectra of the products of BA/PVC
show several new chemical shifts at 1.02.0 ppm, and no
such chemical shifts were observed in CPVC. The signals at
1.0, 1.27, and 1.60 ppm are connected respectively
to CH3–CH2–, –CH2–, and –CH2–CH2Cl of grafted BA,
confirming the occurrence of the grafting reaction. Thus
1
H-NMR analysis also indicates the grafting of BA monomer
onto CPVC, complementary to IR analysis.
Similarly, Fig. 1 compares IR spectra of the products of
MAH/PE and CPE. In Fig. 1, a new absorption band centered
at 17101880 cm1 in MAH/PE, compared with CPE. The
frequency of carbonyl vibrational stretching is shifted from
low wave number to a high wave number due to inducing
and conjugating effect of Cl atoms in the chain, i.e. the peak of
C–– O by ISCGC has shifted to the left. An absorption peak at
1711 cm1 corresponds to association of hydrogen bond from
the adjacent carboxyl, which was produced by the reaction of
MAH and methanol7 with separation, at 1750 cm1,
1794 cm1, and 1879 cm1, corresponding to C – – O vibrational
stretching with MAH. In ISCGC, some reactions occur
simultaneously resulting in a few constructions with
differential wave numbers in IR spectra. It showed a distinct
evidence of grafting too. The 1H-NMR spectrum of the

Figure 1. FT-IR spectra of CPE, CPVC, and the products from PE/MAH and
PVC/BA.
Copyright # 2007 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2007; 18: 822–828
DOI: 10.1002/pat
826 J. Zhao et al.
Figure 2. 1H-NMR spectra of CPE, CPVC, and the products from PE/MAH and
PVC/BA.
products of MAH/PE shows a chemical shift of 5.02 ppm
pointing to the existence of MAN graft chains in the
macromolecules. There is reason to consider that the
construction is,
H*
H C C Cl
O C C O
O in a graft copolymers
grafted onto a block chain. Because of high Cl radical
concentration in the reactive system, the MAH radical is
terminated easily resulting in the construction.15 The
chemical shift of –CH2– is at 1.21.43 ppm, but the chemical
shift of –CHCl– is at 3.353.57 ppm due to substitution of H
for Cl. At 2.022.39 ppm it belonged to –CH2–COR.
According to the above analysis, it is concluded that the
chemical shift 5.02 ppm of MAH by ISCGC is from the
influence of an electron-attracting group of –Cl and –COR.
The success of the grafting by ISCGC was clearly visible in
the above analysis of the resulting polymers. There are the
graft copolymers too in the systems of PE/MMA, PE/HEA,
and PVC/MAH by IR and 1H-NMR.
In addition, the vulcanization curve of the PE/MAH
product blended with PP-diamino-diphenyl-methane was
measured and compared with CPEs. The difference in the
torque of the grafting system was 7.75 kgcm and there was
no difference in the torque for CPE. The result shows that the
reactive product of PE/MAH was crosslinkable owing to the
MAH onto the backbone.
Copyright # 2007 John Wiley & Sons, Ltd.
The reactions of the macroradical with chlorine radical and
the vinyl monomer are a pair of competing reactions. Though
the chlorinating reaction is dominant, the graft reaction will
take place inevitably. This is the basis of the ISCGC.
Structure of graft copolymers by ISCGC
In the course of these investigations, we became interested in
exploring the structure of graft copolymers. We think that a
polymer with special molecular structure could be produced
in ISCGC.
Molecular weight of branch chains
In a process of ISCGC, the initiation, propagation, and
termination of graft chains occur at the same time. Because of
the high chlorine radical concentration, the termination
between macroradicals and chlorine radicals takes place
frequently. So it is necessary for ISCGC to produce shorter
branch chains than other graft methods.16
Thus, a molecular weight equal to that of the extracted
homopolymer is assumed. By determining the molecular
weights of homopolymers separated from reaction mixtures,
we could get the information about the branch chains in the
graft copolymers. In addition, the monomers BA and HEA
were polymerized in chlorine for indicating the role of
chlorine radicals in the process of terminating macroradicals.
By GPC, Mw, Mn, and Mw/Mn of the homopolymer fractions
isolated from PVC/BA, PE/MMA, and PE/HEA reaction
mixture and the chlorinated polymer with BA and HEA are
given in Fig. 3 and Table 3.
Table 3 and Fig. 3 show indirectly that branch chains were
relatively short by ISCGC. If there are shorter branch chains,
it implies that ISCGC can produce more graft chains than
other methods with the same amount of graft monomer and
Polym. Adv. Technol. 2007; 18: 822–828
DOI: 10.1002/pat
 Synthesis of graft CPVC and CPE 827

Figure 4. GPC curves of some graft copolymers, CPE and

CPVC.

Figure 3. GPC curves of some homopolymers separated The data in Table 4 indicate that there is no crosslinking in
from reaction mixtures, chloro-HEA and chloro-BA. graft copolymers prepared by ISCGC.

have a better modifying effect. In fact, the mechanical
properties of some modified systems too (Table 2) show a
notable modifying effect.
Molecular structure of graft copolymer
without crosslink
The course of ISCGC is very complicated. The imaginable
reactions include graft copolymerization and homopolymer-
ization of monomers, chlorination of backbone polymers,
branch chains, etc. Whether crosslinking reactions occur is
one of the most significant questions. The gel contents of
some grafting systems are tabulated in Table 4 for an
indication of the graft copolymer structure.
Number of branch chains in graft copolymers
As mentioned above, there is very much opportunity for
grafting branch chains onto the backbone polymers due to a
number of radical sites in the polymer chain, which were
produced by the initiation of many chlorine radicals with the
polymer. The results of the analysis from Figs 4 and 5 are
presented in Table 5.
There are lots of deviations in Table 5 (or in Figs 4 and 5),
such as Ng of PVC/BA system more than PE/HEA and PE/
MMA systems. It is in contradiction to the comparison of
PVC with PE because the occurring graft reaction with PE is
more easy than with PVC in the process of ISCGC. It is due to
solubility of the polymers in the solvent with GPC producing

Table 3. GPC analysis of homopolymers isolated from the

reaction systems
Systems Homopolymers Mw Mn Mw/Mn Mh
PVC/BA PBA 1403 681 2.06 —
PE/MMA PMMA 821 803 1.02 —
PE/HEA PHEA 741 730 1.02 —
CPE/MMA16 PMMA — — — 1.6  105
5.0  105
Chloro-PHEAa Chloro-PHEA 741 733 1.01 —
Chloro-PBAa Chloro-PBA 1651 1074 1.54 —
a
PHEA and PBA were obtained by chlorinated polymerization of
HEA and BA in chlorine.

Table 4. Gel content with some graft systems

Systems Gel content (%) Solvents

PVC/MAH All dissolving THF

PVC/BA All dissolving THF
PE/MAH 0.0446 Xylene Figure 5. GPC curves of some homopolymers separated
PE/HEA All dissolving THF
from reaction mixtures.
Copyright # 2007 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2007; 18: 822–828
DOI: 10.1002/pat
828 J. Zhao et al.

Table 5. Number of the graft chain with some graft systems

Measurement
Systems GD (%) Ng Mn procedure for GD (%)a

PE/MMA 2.75 6.27 95,126 Weighing

CPE — — 90,089 —
PMMAb — — 803 —
1
PE/HEA 1.98 6.4 94,847 H-NMR
PHEAb — — 730 —
1
PVC/BA 1.52 29.4 111,927 H-NMR
CPVC — — 91,852 —
PBAb — — 681 —
Cationic grafting of olefins from PVC1 — 0.71.8 — —
CPE/MMAc 2.8 1.68 — —
a
That MAH do not homopolymerize in the course is considered both in this work and Deng et al.17
b
The homopolymers are from the graft systems.
c
MMA is grafted onto CPE with BPO in water suspension.15

the deviations of Mn, the solubility of the graft copolymer of
PVC being much better than that of the graft copolymer of PE
in THF. But compared with References [1, 16] it may be
inferred from GD and Mn or Ng that there are many branch
chains in graft copolymers synthesized by ISCGC. When
chlorine is introduced continuously into the reaction system,
chlorine radicals are formed and attack the backbone
polymers to produce a large number of backbone macro-
radicals, then a portion of the backbone macroradicals will
act with monomers to form branch chains. So the number of
branch chains is more than that of graft copolymers
synthesized by other graft processes.1,16 The special proper-
ties of the products with ISCGC depend on the construction
of the graft copolymers.
CONCLUSIONS
ISCGC is a new, simple, and convenient process to
synthesize graft copolymers. Compared to other graft
processes, the products of ISCGC have their structure
characteristics: more branch points, relatively short branch
chains, no crosslink and being totally different physical-
mechanical properties compared with the backbone poly-
mer. By a careful choice of the backbone polymers, graft
monomers, chlorine contents, and reaction conditions, it will
be very convenient to prepare graft copolymers with
different physical and chemical properties.
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Copyright # 2007 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2007; 18: 822–828
DOI: 10.1002/pat