Polymer 48 (2007) 2496e2502

www.elsevier.com/locate/polymer

Synthesis of novel functional polyolefin containing carboxylic

acid via FriedeleCrafts acylation reaction
Yi Zheng a,b, Yanguo Li a, Li Pan a,b, Yuesheng Li a,*
a

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
5625 Renmin Street, Changchun 130022, China
b
Graduate School of the Chinese Academy of Sciences, Changchun 130022, China
Received 19 July 2006; received in revised form 17 September 2006; accepted 14 February 2007
Available online 16 February 2007
Dedicated to the memory of Professor Baotong Huang on the first anniversary of his death.

Abstract
The strong polar group, carboxylic acid, has triumphantly been introduced into ethylene and allylbenzene copolymers without obvious degradation or crosslinking via FriedeleCrafts (FeC) acylation reaction with glutaric anhydride (GA), succinic anhydride (SA) and phthalic anhydride (PA) in the presence of anhydrous aluminum chloride in carbon disulfide. Some important reaction parameters were examined in
order to optimize the acylation process. In the optimum reaction conditions, almost all of the phenyls can be acylated with any anhydride.
The microstructure of acylated copolymer was characterized by FT-IR, 1H NMR and 1He1H COSY. All the peaks of acylated copolymers
can be accurately attributed, which indicates that all the acylation reactions occur only at the para-positions of the substituent of the aromatic
rings. The thermal behavior was studied by differential scanning calorimetry (DSC), showing that the melting temperatures (Tms) of acylated
copolymers with GA firstly decrease slowly and then increase significantly with the increase of the amount of carboxyl acid groups.
2007 Elsevier Ltd. All rights reserved.
Keywords: Functionalization of polymers; Polyolefins; FriedeleCrafts acylation reaction

1. Introduction
Chemical and physical properties of polyolefins like adhesion, dyeability and compatibility with additives or polar polymers can be improved by incorporation of functional groups [1].
However, direct insertion-type copolymerization using polar
comonomers is very difficult due to the Lewis acidity of heterogeneous ZieglereNatta and homogeneous metallocene/aluminoxane catalysts [2]. Latest developments of late transition
metal catalysts show much more improved tolerance against polar functionality due to the typically lower Lewis acidity, but
they also suffer from the significantl decrease of catalyst activity and polymer molecular weight because of the heteroatom
(O, N, etc.)-containing functional groups [3]. As an alternative
approach, by designing and synthesizing polyolefins containing
* Corresponding author. Tel.: 86 431 5695272; fax: 86 431 5685653.
E-mail address: ysli@ciac.jl.cn (Y. Li).
0032-3861/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2007.02.036

reactive groups that are free of catalyst-deactivating heteroatoms but very facile in functional transformation reactions,
the functionalization of polyolefins by the reactive polyolefin
intermediate is able to effectively avoid catalyst deactivation
and produce functional polyolefins with well-defined molecular
structures. To date, numerous studies have been carried out to
introduce polar groups into nonpolar polyolefin by chemical
modification such as a variety of functionalization reactions
via dienes or borane comonomers with pendent double bonds
[4]. Despite introducing polar groups, these modification reactions also have several drawbacks such as high cost, low conversion and multistep organic synthesis.
In contrast to the aliphatic hydrocarbons, which are inert to
most chemical modifications, the activated aromatic units can
undergo various electrophilic substitution reactions, such as
nitration, sulfonation, halogenation, alkylation and so on [5].
So if phenyls are introduced into nonpolar polyolefins, a variety of modification reactions can be carried out. However, there

Y. Zheng et al. / Polymer 48 (2007) 2496e2502

are only a few catalysts being capable of copolymerizing ethylene and styrene [6]. Some works have been done on chemical modification of olefin and substituent styrene copolymer
[7]. However, in these works the pristine copolymers before
modification are difficult to obtain with high molecular
weight, and also the substituent styrenes commonly lie on
the end of the copolymers for the chain transfer reaction in
the copolymerization of ethylene and substituent styrene [8].
Therefore, we chose allylbenzene or 4-phenyl-1-butene instead of substituent styrenes as comonomer because they
have outstanding virtues lie in the copolymerization is facile
and common catalysts such as metallocenes and post-metallocenes can accomplish the copolymerization [9]. Metallocene
and post-metallocene catalysts can play a great role in producing the reactive polyolefin intermediate with even distribution, high comonomer content and narrow molecular weight
distributions [10]. In this article, we obtained the polyolefin
intermediate containing reactive pendant phenyls by the
copolymerization of ethylene and allylbenzene/4-phenyl-1butene using rac-ethylenebis(indenyl)zirconium dichloride
(rac-Et(Ind)2ZrCl2) as catalyst [11]. Then, carboxyl groups
were introduced into pendant phenyls of the copolymers
through a convenient yet highly efficient FeC acylation
reaction (Scheme 1) [12]. This method not only overcomes
the negative influence of using polar commoners in direct insertion-type copolymerization such as significantly reduced
catalyst activity but also can be designed as new platforms
for successive reactions [13]. The modified polyolefins bearing
carboxyl and/or carbonyl groups have been widely applied in
many fields. For example, they can be used as polar pigments
and additives due to the compatibility with oxygen- and nitrogen-containing polymers. In addition, they can also be used to
prepare macromoleculeemetal complexes [14] and remove
toxic metal ions from industrial effluent water supplies to
avoid one of the major causes of water and soil pollutions because of the existence of coordination groups [15]. Hence, the
polyolefins modified by acylation might also be used in the
fields mentioned above. Unfortunately, there is only limited information about introducing carboxyls into aromatic rings and
most of them are polystyrene polymers which are usually insoluble, so a precise characterization is difficult [16]. The
modified copolymers we report here using different kinds of
cyclic-anhydride are soluble, so the structure is unambiguously revealed by 1H NMR and 1He1H COSY spectral analyses. At the same time, a variety of reactive conditions have
been investigated, if desired, almost all of the benzene groups
can be acylated.

O
n

m
x

+ R

O
O
R=

x = 1,2

Scheme 1. FeC acylation reaction with different anhydride.

CO2H

2497

2. Experimental part
2.1. Materials
Ethylene and allylbenzene/4-phenyl-1-butene copolymers
(3.85 and 6.45 pendant aromatic nuclei per 100 carbon atoms
in the backbone, respectively) were prepared according to the
procedures described in Ref. [9a] with minor modification. GA
was distilled under vacuum, and carbon disulfide was dried
overnight with calcium chloride, filtered and distilled prior
to use. Anhydrous aluminum trichloride, SA and PA were purified by sublimation before use. All other chemicals were
commercially available and used without further purification.
2.2. Acylation reaction
A typical reaction (entry 8 in Table 1) was carried out in a
250 ml three-necked round-bottom flask equipped with a condenser, a nitrogen inlet and a magnetic stirrer. After the flask
was degassed and purged with nitrogen, carbon disulfide
(40 ml) was added into the mixture of copolymer (0.5 g,
1.1 mmol pendant aromatic nuclei) and finely powdered anhydrous aluminum chloride (0.59 g, 4.4 mmol) in a water bath at
50  C. The mixture was stirred for 10 min then GA (0.12 g,
1.1 mmol), which was sonicated in carbon disulfide (20 ml)
to give a uniform suspension solution, was added to the mixture in a portion over 55 min, and the solution turned to dark
red gradually. After the addition of GA solution in carbon disulfide was finished, the mixture was stirred for another 5 min.
The reaction was quenched by the addition of ice water followed by dilute hydrochloric acid and then the product was
thoroughly washed with water to remove any residual free acid.
The concentrated organic phase was precipitated into ethanol,
filtered and subsequently dried overnight under vacuum at
70  C.
2.3. Characterization
1

H NMR and two-dimensional 1He1H COSY spectra were

recorded on a Varian Unity 400 MHz spectrometer at 100  C
using standard parameters. In both cases, 1,1,2,2-tetrachloroethane-d2 was used as solvent and all chemical shifts were referred to the solvent shift at 5.94 ppm. The polymer films
(0.5 mm) for the Fourier transform infrared (FT-IR) spectral
analyses were prepared by melt pressing at 140  C and the
spectra were measured with a Bio-Red FTS-135 spectrophotometer. The melting temperatures (Tms) of acylated copolymers were obtained by means of DSC with a PerkineElmer
Pyris 1 Differential Scanning Calorimeter at a rate of 10  C/
min. Tm values reported in Table 1 were obtained from the
second heating curve. The molecular weights and molecular
weight distributions of the copolymers were determined at
150  C by a PL-GPC 220 type high-temperature chromatograph equipped with three PLgel 10 mm Mixed-B LS type columns. 1,2,4-Trichlorobenzene (TCB) was employed as solvent
at a flow rate of 1.0 ml/min. The calibration was made with
polystyrene standard EasiCal PS-1 (PL Ltd).

Y. Zheng et al. / Polymer 48 (2007) 2496e2502

2498
Table 1
Acylation of copolymers with anhydridesa
Entry
b

1
2b
3b
4b
5c
6c
7c
8c
9c
10c
11c
12c
13c
14c
15c
a
b
c
d
e
f
g

Acylating agent

AlCl3d

Temp ( C)

Time (h)

Yield (g)

Aromatic nucleie

Carboxyl groupe

Mwf (kg/mol)

Mw/Mnf

Tmg ( C)

e
GA
GA
GA
e
GA
GA
GA
GA
GA
GA
SA
SA
PA
PA

e
4
4
4
e
4
4
4
2
6
4
4
4
4
4

e
10
30
50
e
10
30
50
50
50
50
50
50
50
50

e
1
1
1
e
1
1
1
1
1
2
1
2
1
2

e
0.50
0.45
0.42
e
0.49
0.53
0.57
0.53
0.59
0.60
0.57
0.58
0.60
0.64

6.45
6.35
3.43
0.85
3.85
3.76
3.75
3.57
3.55
3.53
3.38
3.70
3.65
3.80
3.78

e
0.24
1.46
0.76
e
0.18
1.23
2.96
1.54
3.07
3.16
3.42
3.60
2.52
3.56

58.7
55.3
47.6
50.2
34.1
32.8
29.5
27.6
28.8
27.4
26.8
29.5
28.1
30.5
26.7

3.25
2.99
2.78
2.86
2.78
2.24
2.39
2.59
2.48
2.52
2.25
2.37
2.42
2.52
2.43

126.6
127.0
128.0
128.4
89.1
88.8
86.9
91.7
85.7
93.7
92.1
93.4
94.5
88.9
89.3

Reaction conditions: copolymer, 0.5 g; solvent, CS2; total volume, 60 ml; [acylating agent]/[aromatic nuclei], 1/1 (molar ratio).
Ethylene and 4-phenyl-1-butene copolymers.
Ethylene and allylbenzene copolymers.
[AlCl3]/[aromatic nuclei] (molar ratio).
Results from 1H NMR analysis, given per 100 carbon atoms in the copolymer backbone.
Weight-average molecular weight and polydispersity index determined by GPC.
Melting temperature determined by DSC.

3. Results and discussion

3.1. Synthesis of functional polyolefins
For the sake of overcoming the shortcoming that the polar
comonomers significantly reduce catalyst activity in direct
insertion-type copolymerization, we chose allylbenzene and
4-phenyl-1-butene as reactive comonomers which are free of
catalyst-deactivating heteroatoms but facile in functional
transformation reactions. When the copolymers as reactive
intermediate were prepared by the copolymerization of ethylene with allylbenzene or 4-phenyl-1-butene, the pendent
phenyls of them can serve as reactive sites to bring carboxylic
acid as strong polar groups into the polymer chains by FeC
acylation reactions.
FeC acylation reactions are aromatic substitution reactions
in which benzene (or substituted benzene) undergoes acylation
when treated with carboxylic acid derivatives (usually acyl
halide or anhydride) and a Lewis acid catalyst, such as
AlCl3 [17]. They have often been used as the initial reaction
in a number of methods for the preparation of functionalized
polystyrenes because they are mild and easily operated, and no
toxic problems are involved, as well. However, there is only
limited information about acylation of ethylene rich copolymers because it is not convenient to introduce phenyl groups
into polyethylene. The FeC acylation reactions are applied
to polystyrene widely. However, the crosslinking reaction of
acylated macromolecules usually occurs in FeC acylation
process of polystyrene, which leads to changes in the molecular mass and the solubility of the modified polymers. In order
to overcome these problems, Hird and Eisenberg reported a
simple method that aluminum chloride and acetyl chloride are
allowed to react together prior to addition to the substrate for
the preparation of partial p-carboxylation of linear polystyrene

without degradation or crosslinking [16b]. However, when we

try the way, we only obtained ethylene rich copolymer with
very low acylation rate. It is well established that the ratio
of catalyst to acyl component and the sequence in which the
reactants are mixed can be of great importance in FeC acylation reactions. So we try to challenge the subject by changing
the reaction conditions and sequence to get high acylation rate
copolymer without degradation or crosslinking.
In this study, there are few residual double bonds in the ethylene and allylbenzene/4-phenyl-1-butene copolymers, so to
great extent that it avoids the crosslinking in acylation reaction. The ordinary acylation solvents could be carbon disulfide, nitrobenzene, dichloromethane and tetrachloroethane.
The two copolymers can dissolve in high-boiling chlorinated
solvents and nitrobenzene only at elevated temperature, but
we cannot obtain satisfying results. Thus, we chose carbon disulfide as acylation solvent, which can dissolve the copolymer
sufficiently at lower temperature and also be a good carrier for
FeC catalyst. The other factor that controls the nature of acylated copolymer is the sequence in which the reactants are
mixed. It is noteworthy that if the anhydrides were added at
the primary stage, it would lead to crosslinking, furthermore
the gelatin also occurred if the anhydrides were added fast
at the last stage. In order to obtain the copolymers without
crosslinking, we must add the anhydrides in batches and
slowly. Other parameters such as the amount of AlCl3, reaction temperature and reaction time were also examined so as
to optimize the process. The degree of acylation corresponding
to carboxylic acid value of the copolymers and the residual
pendant aromatic groups was determined by 1H NMR and
the data are presented in Table 1.
When acylating the ethylene and 4-phenyl-1-butene copolymers, there is a considerable shedding of phenyls with the increase of temperature. At the same time, the rate of acylation

Y. Zheng et al. / Polymer 48 (2007) 2496e2502

3.2. Characterization of functional polymers

FT-IR was the first spectroscopic tool we used to identify
our successful acylation of the ethylene and allylbenzene copolymers. The FT-IR spectra of the pristine copolymer and
the acylated copolymers with GA, SA and PA in the range
3500e600 cm1 are given in Fig. 1aed, respectively, corresponding to the product coming from entries 5, 11, 13 and
15 in Table 1. By comparing the above four spectra, it is clear
that in the spectra of the acylated copolymers (traces b, c and
d) new peaks, which are absent in the spectrum of the pristine
copolymer (trace a), can be ascertained. The new peaks at
1684 and 1708 cm1 in Fig. 1b are ascribable, respectively,
to different carbonyl functional groups of individual ketone and
acid carbonyl groups. The new peaks at 1685 and 1711 cm1
in Fig. 1c are similarly ascribable, respectively, to individual
ketone and acid carbonyl groups. The new peaks at 1674
and 1695 cm1 in Fig. 1d can be assigned to the diaryl ketone
and isolated aromatic carboxylic acid carbonyl groups,

Absorbance

increases and the melting temperature (Tm) also increases

somewhat. This can be explained by considering that the Fe
C alkylation and FeC acylation have similar reaction conditions. So as the FeC acylation happens, the FeC alkylation
can also take place. However, the FeC alkylation is sufficiently reversible, which ultimately leads to the thermodynamically most stable product by alkylationedealkylation. As for
ethylene and 4-phenyl-1-butene copolymers, there is larger
steric bulk between the benzene rings and the copolymer backbone, so the dealkylation will happen more easily. The considerable shedding of benzene rings heightens the extent of
crystallization of the copolymer, which causes the increase
of Tm. In order to obtain acylated copolymer without crosslinking and degradation, we select ethylene and allylbenzene
copolymers to investigate further.
As show in Table 1, when the temperature was raised from
10 to 50  C (entries 6e8), the amount of carboxyl groups increased noticeably, while the phenyls pendant on the polymer
backbone only slightly diminished. As well, the molar ratio of
[AlCl3]/[GA] plays an important role on the degree of acylation in the FeC acylation reactions. As the ratio of [AlCl3]/
[GA] was systematically varied from 2:1 to 6:1 (entries 8e
10 in Table 1), the carboxyl groups also increased significantly, meanwhile the benzene ring content did not really
change obviously. To further investigate the effect of reaction
time on the degree of acylation, we prolonged the reaction
time to 2 h and found that almost all the residual benzene rings
acylated at the cost of slight brushing aromatic nuclei off. In
the optimal reaction conditions, we conducted the similar acylation reactions with SA and PA, and got resemblant trend.
When using PA as acylating agent, the degree of acylation is
more sensitive to reaction time than GA and SA. One plausible
explanation for the observed result is that the steric bulk of PA
affects the access to aromatic nuclei, so accomplishing acylation reaction needs more reaction time for PA. All the acylated
copolymers are soluble and sufficiently characterized.

2499

3500

3000

2500

2000

1500

1000

Wavenumber (cm-1)
Fig. 1. FT-IR spectra of pristine copolymer (a) and the acylated copolymers
with GA (b), SA (c) and PA (d) in the range 3500e600 cm1.

respectively. When carbonyl groups conjugate with more aromatic groups, the wavenumber of carbonyl groups will be
lower.
1
H NMR and two-dimensional 1He1H COSY spectral analyses unambiguously reveal the microstructure of the acylated
copolymers. Because of the homogeneity of the reaction, the
distribution of the acylate groups is believed to be random
along the polymer chains. Fig. 2 shows the 1H NMR spectra of
starting copolymer (A) and acylated copolymers with SA (B),
GA (C) and PA (D). Fig. 2A displays typical 1H NMR spectrum of the starting copolymer with five peaks (d 1.25, 1.60,
2.51, 7.11 and 7.22 ppm). When acylation with SA, two new
characteristic signals (d 2.74 and 3.23 ppm) were observed
for the methylene protons of eCOCH2CH2COOH moiety, corresponding to the product coming from entry 12 in Table 1.
Also when acylation reaction with GA, three new characteristic signals (d 2.05, 2.46 and 3.00 ppm) were observed for the
methylene protons of eCOCH2CH2CH2COOH moiety, corresponding to the product coming from entry 8 in Table 1. When
acylation with PA, four new characteristic signals (d 7.33,
7.52, 7.57 and 8.01 ppm) were detected for dicarbonyl aromatic protons, corresponding to the product coming from entry 14 in Table 1. These new peaks sufficiently prove that the
pendant benzene rings have been acylated.
To further reveal the slight influence of the acylation reaction upon the chemical shifts of starting copolymer, 1He1H
COSY was performed as shown in Figs. 3 and 4, corresponding to Fig. 2C and D, respectively. All the peaks of acylated
copolymers can be accurately attributed. It is noteworthy
that the acylation reaction by anhydrides occurred exclusively
at the para-position with respect to the substituent of the aromatic ring. It is rational because acylation is an electrophilic
reaction, and there is no enough steric bulk to insert the complexes of anhydrides and AlCl3 between the copolymer backbone and the ortho-position of phenyls. The chemical shifts of
all the peaks are shown in Fig. 5.

Y. Zheng et al. / Polymer 48 (2007) 2496e2502

2500

Fig. 2. 1H NMR spectra of pristine copolymer (A) and the acylated copolymers with SA (B), GA (C) and PA (D).

The amount of phenyls in starting copolymers (Ns) and

acylated copolymers (Na) can be calculated by Eqs. (1) and (2).




Ns Id =2= If =2 Ie  100
1



Na Id I3 =2= If =2 Ie I4  100

Here, the symbol I represents the resonance integrals and the

subscripted numbers refer to the peak numbers, as shown in
Fig. 2. Ns and Na refer to the total number of pendant aromatic
groups given per 100 carbon atoms in the backbone. It should
be noted that the aromatic nuclei pendant on the backbone

Fig. 3. 1He1H COSY spectrum of acylated copolymer with GA.

only slightly diminish, so we can conclude that neither crosslinking nor degradation occurs to a significant extent during
the acylation reaction of the copolymer.
The amount of carboxyl groups of acylated copolymers
with GA (NGA), SA (NSA) and PA (NPA), respectively, can be
estimated from the relative intensities of the respective signals
in 1H NMR spectra according to the following Eqs. (3)e(5):



NSA I5 I6 =4= If =2 Ie I4  100




NGA I5 I6 =4= If =2 Ie I4  100

Fig. 4. 1He1H COSY spectrum of acylated copolymer with PA.

Y. Zheng et al. / Polymer 48 (2007) 2496e2502

f

a:
b:
c:
d:
e:
f:

e
d
c

a
b

7.11
7.22
7.11
2.51
1.60
1.25

HO

5
2
1

1:
2:
3:
O 4:
5:
7
6:
7:

4
3

5
2
1

7.82
7.22
2.57
1.60
3.00
2.05
2.46

OH

7.82
7.22
2.55
1.60
3.23
2.74

1:
2:
3:
4:
5:
6:
7:
8:

7.57
7.22
2.57
1.60
8.01
7.52
7.57
7.33

6
5

7
8

O
HO

Fig. 5. 1H data for acylated copolymers.

 

NPA I5 = If =2 Ie I4  100

acylation increasing due to the large size of the aromatic group

linking carboxyl group which hinders the interactions among
the acid groups.
4. Conclusions

1:
2:
3:
4:
5:
6:

2501

where NSA, NGA and NPA refer to the total number of pendant
carboxyl groups given per 100 carbon atoms in the backbone.
By comparing the data of NSA, NGA, NPA and Na, the most interesting feature we observe is that almost all the aromatic
groups (more than 90%) are acylated with any anhydride in
the optimum reaction conditions. Overall, the FeC acylation
is very effective to introduce carboxylic acid units into the
starting nonpolar copolymer.
GPC results show that the molecular weight of the acylated
copolymer with GA decreases somewhat with the increasing
degree of acylation (entries 5e11 in Table 1). The similar results were obtained when we use SA (entries 12 and 13 in Table
1) and PA (entries 14 and 15 in Table 1) instead of GA. This
was not expected because the incorporation of the carboxyl
acid groups should have increased the molecular weight of
the ethylene and allylbenzene copolymers. The somewhat
decrease in molecular weight may indicate that some acylated
copolymer conglomerate is more compact than the parent
copolymer molecule due to the formation of hydrophilic domains. A similar result was observed for the published sulfonation polymer [18]. More importantly, one can conclude that
neither crosslinking nor degradation occurred to a significant
extent during the acylation reaction of the copolymer because
the Mw =Mn of acylated copolymers did not increase.
DSC results show that the Tms of acylated copolymers with
GA decrease slowly as the amount of carboxyl acid groups is
raised from 0 to 1.54 (entries 5e7 and 9 in Table 1) but then
increase significantly as the degree of acylation is raised further. The phenomenon can be explained as follows: when
a small quantity of noncrystallizable comonomer units is randomly incorporated into the backbone of a crystallizable polymer, the degree of crystallinity of the polymer will decrease.
Therefore, the melting temperature also decreases. However,
with the degree of acylation increasing further, the interactions
among the acid groups, e.g. hydrogen bonding, become the
main factor affecting the Tm. Thus, the Tm of acylated copolymer increases obviously as the carboxyl groups in the copolymer reach some degree. The acylated copolymers with SA
have the similar trend, however, when the acylating agent is
PA, there is no obvious effect on Tm with the degree of

Carboxyls as strong polar groups were introduced effectively into nonpolar ethylene and allylbenzene copolymers
without obvious degradation or crosslinking by convenient
FeC acylation reaction, avoiding the shortcomings of direct
insertion-type copolymerization of ethylene and polar comonomers. FT-IR, 1H NMR and 1He1H COSY spectroscopic
analyses unambiguously reveal the microstructure of the acylated copolymers. NMR has been shown to be, once again,
a very powerful tool and the only technique that permits elucidation of, with some accuracy, the polymer microstructure
study. The functionalized polyolefin offers possibility for the
development of novel ethylene rich copolymer blends and
composites, thus extending the application field of nonpolar
polyolefin.
Acknowledgements
The authors are grateful for subsidy provided by the National Natural Science Foundation of China (nos. 20334030
and 50525312) and by the National Basic Research Program
of China (no. 2005CB623800).
References
[1] For reviews of functionalized polyolefins, see:
(a) Padwa AR. Prog Polym Sci 1989;14:811e33;
(b) Dong JY, Hu YL. Coord Chem Rev 2006;250:47e65;
(c) Boaen NK, Hillmyer MA. Chem Soc Rev 2005;34:267e75.
[2] Boffa LS, Novak BM. Chem Rev 2002;100:1479e93.
[3] (a) Mecking S, Johnson LK, Wang L, Brookhart M. J Am Chem Soc
1998;120:888e99;
(b) Heinemann J, Muhaupt R, Brinkmann P, Luinstra G. Macromol Chem
Phys 1999;200:384e9;
(c) Meneghetti SP, Kress J, Lutz PJ. Macromol Chem Phys 2000;201:
1823e32;
(d) Boone HW, Athey PA, Mullins MJ, Philipp D, Muller R,
Goddard WA. J Am Chem Soc 2002;124:8790e1;
(e) Britovsek GJP, Gibson VC, Spitzmesser SK, Tellmann KP,
White AJP, Williams DJ. J Chem Soc Dalton Trans 2002;1159e71;
(f) Liu JY, Zheng Y, Li YS. Polymer 2004;45:2297e301.
[4] (a) Chung TC, Rhubright D. J Polym Sci Part A Polym Chem 1993;31:
2759e63;
(b) Marathe S, Sivaram S. Macromolecules 1994;27:1083e6;
(c) Lipponen S, Seppala J. J Polym Sci Part A Polym Chem 2004;42:
1461e7;
(d) Chung TC, Rhubright D. Macromolecules 1993;26:3019e25;
(e) Cao CG, Zou JF, Dong JY, Hu YL, Chung TC. J Polym Sci Part A
Polym Chem 2005;43:429e37;
(f) Nam YG, Shiono T, Ikeda T. Macromolecules 2002;35:6760e2;
(g) Dong JY, Hong H, Chung TC. Macromolecules 2003;36:6000e9;
(h) Chung TC, Dong JY. Macromolecules 2002;35:2868e70;
(i) Fan GQ, Dong JY, Wang ZQ, Chung TC. J Polym Sci Part A Polym
Chem 2006;44:429e37;
(j) Zhang YC, Chen JY, Li HL. Polymer 2006;47:4750e9.

2502

Y. Zheng et al. / Polymer 48 (2007) 2496e2502

[5] (a) Wang L, Meng YZ, Wang SJ, Li XH, Xiao M. J Polym Sci Part A
Polym Chem 2005;43:6411e8;
(b) Yang JE, Lee JS. Electrochim Acta 2004;50:617e20;
(c) Jang BB, Lee K, Kwon WJ, Suh J. J Polym Sci Part A Polym Chem
1999;37:3169e77;
(d) Roscoe SB, Gong CG, Frechet JMJ, Walzer JF. J Polym Sci Part A
Polym Chem 2000;38:2979e92;
(e) Fernyhough CM, Young RN, Ryan AJ, Hutchings LR. Polymer 2006;
47:3455e63.
[6] (a) Hou ZM, Luo YJ, Li XF. J Organomet Chem 2006;691:3114e21;
(b) Lahitte JF, Plentz-Meneghetti S, Peruch F, Muller R, Lutz PJ.
Polymer 2006;47:1063e72;
(c) Craymer JF, Kas RM, Coughlin EB. Polyhedron 2005;24:1347e55;
(d) Ishiyama T, Miyoshi K, Nakazawa H. J Mol Catal A Chem 2004;221:
41e5;
(e) Gentil S, Pirio N, Meunier P, Gallou F, Paquette LA. Eur Polym J
2004;40:2241e6.
[7] (a) Lu B, Chung TC. J Polym Sci Part A Polym Chem 2000;38:1337e43;
(b) Sangeetha D. Eur Polym J 2005;41:2644e52;
(c) Shim SY, Weiss RA. Polym Int 2005;54:1220e3;
(d) Zhang GI, Liu L, Wang HM, Jiang M. Eur Polym J 2000;36:61e8;
(e) Zou JF, Cao CG, Dong JY, Hu YL, Chung TC. Macromol Rapid
Commun 2004;25:1797e804;
(f) Dong JY, Manias E, Chung TC. Macromolecules 2002;35:3439e47.
[8] (a) Dong JY, Chung TC. Macromolecules 2002;35:1622e31;
(b) Chung TC, Dong JY. J Am Chem Soc 2001;123:4871e6;
(c) Dong JY, Wang ZM, Hong H, Chung TC. Macromolecules 2002;35:
9352e9;
(d) Kandil U, Chung TC. J Polym Sci Part A Polym Chem 2005;43:
1858e72;
(e) Liu YY, Hu YL, Mike Chung TC. Polymer 2005;46:10585e91.
[9] (a) Byun DJ, Shin DK, Kim Y. Macromol Rapid Commun 1999;20:
419e22;
(b) Kumar KR, Sivaram S. Polym Int 2001;50:367e74;
(c) Byun DJ, Choi KY, Kim SY. Macromol Chem Phys 2001;202:
992e7.
[10] (a) Reybuck S, Waymouth RM. J Polym Sci Part A Polym Chem 2004;
42:3323e31;

[11]

[12]

[13]
[14]

[15]

[16]

[17]
[18]

(b) Byun DJ, Kim SY. Macromolecules 2000;33:1921e3;

(c) Tang LM, Hu T, Pan L, Li YS. J Polym Sci Part A Polym Chem 2005;
43:6323e30;
(d) Naga N, Toyota A. Polymer 2004;45:7513e7;
(e) Paavola S, Saarinen T, Lofgren B, Pitanen P. Polymer 2004;45:
2099e110;
(f) Pan L, Liu YG, Zhang KY, Bo SQ, Li YS. Polymer 2006;47:
1465e72;
(g) De Rosa C, Auriemma F. Polymer 2006;47:2179e88;
(h) Uotila R, Hippi U, Paavola S, Seppala J. Polymer 2005;46:
7923e30;
(i) Grisi F, Pragliola S, Costabile C, Longo P. Polymer 2006;47:1930e4.
(a) Hakala K, Helaja T, Lofgren B. J Polym Sci Part A Polym Chem
2000;38:1966e71;
(b) Lehmus P, Kokko E, Harkki O, Leino R, Luttikhedde HJG,
Nasman JH, et al. Macromolecules 1999;32:3547e52;
(c) Britto ML, Galland GB, dos Santos JHZ, Forte MC. Polymer 2001;
42:6355e61.
(a) Xu H, Hu XZ. J Polym Sci Part A Polym Chem 1998;36:2151e4;
(b) Tabak G, Pham TN, Levesque G, Haraoubia R. J Polym Sci Part A
Polym Chem 1998;36:117e27.
Cheng SK, Wang CC, Chen CY. Mater Chem Phys 2003;78:581e90.
(a) Pesonen H, Sillanpaa A, Aksela R, Laasonen K. Polymer 2005;46:
12641e52;
(b) Pesonen H, Sillanpaa A, Aksela R, Laasonen K. Polymer 2005;46:
12653e61;
(c) Zhang GZ, Jiang M, Zhu L, Wu C. Polymer 2001;42:151e9.
(a) Bazunova MV, Kolesov SV, Korsakov AV. Russ J Appl Chem+ 2006;
79:853e5;
(b) Combellas C, Fuchs A, Kanoufi F, Mazouzi D, Nunige S. Polymer
2004;45:4669e75;
(c) Polyakova IV, Pisarev OA. J Chromatogr A 2005;1092:135e41.
(a) Liu L, Jiang M. Macromolecules 1995;28:8702e4;
(b) Hird B, Eisenberg A. J Polym Sci Part A Polym Chem 1993;31:
1377e81.
Andrew SJ. Introduction to organic chemistry. New York: Wiley; 1971.
Wang SH, Zeng ZH, Yang SH, Weng LT, Wong PCL, Ho K. Macromolecules 2000;33:3232e6.