European Polymer Journal 38 (2002) 1275–1279

www.elsevier.com/locate/europolj

Copolymerization of N-phenylmaleimide with styrene by

rare earth coordination catalyst
Yanbing Lu, Weilin Sun *, Zhiquan Shen
Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
Received 23 October 2001; received in revised form 7 December 2001; accepted 10 December 2001

Abstract
The copolymerization of N-phenylmaleimide (NPMI) with styrene (St) was studied with a rare earth coordination
catalyst NdðnaphÞ3 –AlEt3 in toluene at 50 °C. The compositions of the two monomers in copolymers were close to 1:1
even at a high monomer conversion of about 60%, and did not change as the NPMI feed mole fraction varied from 10%
to 90%. The copolymer was characterized by 13 C nuclear magnetic resonance spectroscopy, showing that the copolymer
possessed a nearly alternating structure. The thermal properties of the copolymers were also investigated. It was
presumed that a charge transfer complex of NPMI and St participated in the polymerization process. Ó 2002 Elsevier
Science Ltd. All rights reserved.

Keywords: Copolymerization; N-phenylmaleimide; Rare earth coordination catalyst

1. Introduction NPMI catalyzed by a rare earth catalyst composed of

Copolymerizations of N-phenylmaleimide (NPMI)
with common monomers have stimulated great interest
because such copolymers contain five-member planar
rings in the chain, which hinder the rotation of the
imides residues around the backbone chain of the mac-
romolecules, resulting in a greater structural stiffness
and a higher thermal stability [1]. Free radical copoly-
merization of NPMI with St has been studied and is
dominated by alternating copolymerization with the
participation of a monomer charge transfer complex
(CTC) in both initiation and chain propagation [2,3].
However, the copolymerization of NPMI with St by
coordination catalysts has never been reported.
Rare earth coordination catalysts have been devel-
oped as effective catalysts for the polymerizations of
conjugated dienes, alkynes, cyclic monomers, and so
forth [4,5]. Jiang et al. reported the polymerization of
*
Corresponding author. Tel.: +86-571-795-1059; fax: +86-
571-795-1773.
E-mail address: opl_sunwl@emb.zju.edu.cn (W. Sun).
0014-3057/02/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 4 - 3 0 5 7 ( 0 2 ) 0 0 0 1 3 - 7
neodymium acetylacetonate (NdðacacÞ3  3H2 O), dibu-
tylmagnesium ðMgðn-BuÞ2 Þ, and hexamethylphosphor-
amide (HMPA) in tetrahydrofuran and toluene [6]. The
resulting polymer has high molecular weight ð 9:0 
104 Þ and shows excellent thermal stability.
This paper reports the copolymerization of NPMI
with St by a rare earth coordination catalyst Nd-
ðnaphÞ3 –AlEt3 in toluene at 50 °C. Characterization
showed that the copolymers possessed a nearly alter-
nating structure, which could be the result of the par-
ticipation of a CTC of the two monomers in the
polymerization process.
2. Experimental
2.1. Materials
Neodymium naphthenate [NdðnaphÞ3 ] was prepared
from neodymium oxide as described previously [4].
Triethyl aluminum AlEt3 was used as purchased. The
binary catalysts were obtained by adding triethyl alu-
minum into the toluene solution of NdðnaphÞ3 and
ageing for 30 min at 50 °C.
1276 Y. Lu et al. / European Polymer Journal 38 (2002) 1275–1279
St was distilled under reduced pressure prior to use.
NPMI was prepared from maleic anhydride and aniline
according to the method described in the literature [7]
and recrystallized from cyclohexane three times. It was
further characterized by nuclear magnetic resonance
(NMR) and infrared spectra (IR) in order to make sure
that it was free from uncyclized maleamic acid and un-
reacted maleic anhydride. The purity of NPMI was
measured by elemental analysis.
Anal. calcd. for C10 H7 O7 N (173.17): C, 69.36%; H,
4.07%; N, 8.09%. Found: C, 69.32%; H, 4.06%; N, 8.04%.
IR spectrum (KBr), 3091, 1708, 1594, 1507, 1396, 1144,
831, 757, and 696 cm1 . 1 H NMR spectrum (d), CDCl3 ,
6.84 ppm (2H, –C@C–), 7.39 ppm (5H, aromatics).
Toluene was purified according to the usual method
and distilled prior to use.
2.2. Copolymerization
The catalyst and a toluene solution of St and NPMI
were introduced into ampoules which were heated,
evacuated and filled with nitrogen several times, and the
ampoules were put into a thermostat at 50 °C. After a
fixed time, the polymerization was terminated by adding
ethanol with 10% HCl to destroy the trapped catalyst.
The resultant copolymer was filtered off, washed several
times with pure ethanol, and dried under vacuum to
constant weight.
2.3. Characterization
The compositions of copolymer were calculated on
the basis of the nitrogen content in the copolymer, which
was determined by an EA-1110 elemental analyzer.
The 1 H NMR and 13 C NMR spectra were recorded
on a Bruker Avance AMX-500 NMR spectrometer for
solutions in CDCl3 with TMS as internal standard. A
FT-IR (KBr pellets) spectrum was measured on a Bru-
ker Vector 22 spectrometer. Gel permeation chromato-
graphy (GPC) was carried out on a Waters 150 C GPC
instrument at 25 °C using THF as eluent. Molecular
weights were calibrated with mono-disperse polystyrene
standards. The glass transition temperature (Tg ) was
measured on a Pyris-1 DSC in a nitrogen stream at a
heating rate of 10 °C min1 . Thermogravimetric analysis
(TGA) was obtained on a STA409PC thermogravimet-
ric analyzer at a heating rate of 10 °C min1 under a
nitrogen atmosphere.
3. Results and discussion
3.1. Copolymerization features
When St or NPMI was added solely into the catalyst
NdðnaphÞ3 –AlEt3 , no polymer was obtained. However,
copolymers were obtained when the mixture of St and
NPMI was added into the catalyst. It is well known that
St is an electron donor monomer and NPMI is an
electron acceptor monomer, and they form a CTC in
solution. The complex has a significantly higher reac-
tivity than that of either St or NPMI. The rare earth
catalyst initiates the complex ‘‘monomer’’ to produce
the copolymer. The possible copolymerization process is
illustrated in Scheme 1.
The yield and the composition of the NPMI–St co-
polymers obtained at a wide range of monomer feed
ratios are summarized in Table 1. It can be seen that the
yield of the copolymers reaches a maximum at a 1:1
monomer feed ratio under a certain total concentration
of the two monomers. Such a dependence on the
monomer feed could be attributed to the formation of a
1:1 donor–acceptor CTC between the monomer NPMI
and St. The mole ratio of NPMI and St incorporated in
the copolymers was always nearly close to 1 while the
NPMI feed mole content varies from 10% to 90% even
at such a high conversion, which also confirmed that a
CTC was participating in the copolymerization. This is
quite unique on comparing results with those of free
radical systems [8,9].
The molar ratio of AlEt3 to NdðnaphÞ3 is one of the
important factors influencing the yield of the copolymer.
The effect of the Al/Nd ratio on the yield of copolymer
at different polymerization times is shown in Fig. 1. The
maximum yield under the conditions tested was ob-
tained at an Al/Nd value in the range 7–11.
Fig. 2 illustrates the time dependence of the yield and
the number average molecular weight of the copolymer.
It can be seen from Fig. 2 that the yield of the copolymer
increased with an increase of the polymerization time,
but the number average molecular weight decreased
slightly, which is probably due to the copolymerization
of NPMI and St behaving as a precipitation polymer-
ization.
The effects of the initial concentration of the catalyst
and the monomer on copolymerization are shown in
Figs. 3 and 4. It is seen from Figs. 3 and 4 that the yield
of the copolymer increased with increasing initial con-
centrations of the catalyst and the monomer.
Scheme 1.
 Y. Lu et al. / European Polymer Journal 38 (2002) 1275–1279 1277

Table 1
Composition of St–NPMI copolymers prepared by NdðnaphÞ3 –AlEt3 catalysta
NPMI in monomer (mol.%) Yield (%) Nitrogen content (%)b NPMI in copolymer (mol.%)c
1 10 22.27 4.30 40.6
2 20 39.30 4.58 44.0
3 40 58.25 4.74 46.0
4 50 63.12 4.79 46.7
5 60 52.57 4.93 48.5
6 80 30.28 5.36 54.2
7 90 14.87 5.71 59.2
a
½NdðnaphÞ3 ¼ 5:0  103 mol L1 , ½AlEt3 ¼ 4:5  102 mol L1 , ½St þ ½NPMI ¼ 8:0  101 mol L1 , 50 °C, 6 h, toluene.
b
Measured by elemental analysis.
c
Calculated based on the nitrogen content from the elemental analysis.

Fig. 1. Effect of the Al/Nd ratio on the yield of NPMI–St co-

Fig. 2. Time dependence of the yield and the number aver-
polymer. Conditions: ½NdðnaphÞ3 ¼ 5:0  103 mol L1 , ½St ¼
age molecular weight of NPMI–St copolymer. Conditions:
½NPMI ¼ 4:0  101 mol L1 , 50 °C, toluene, 6 h.
½AlEt3 ¼ 4:5  102 mol L1 , other conditions are the same as
in Fig. 1.

3.2. Copolymer characterization

The FT-IR spectrum of the resultant copolymer is

illustrated in Fig. 5, which is very similar to the alter-
nating copolymers produced by a free radical process.
Fig. 6 shows the 13 C NMR spectrum of the prepared
copolymer in CDCl3 . The peak at d ¼ 178:0 ppm is as-
signed to the carbonyl groups in imides from NPMI,
and the bands at 126–133 ppm are assigned to the
phenyl rings from both monomers. The broad band
from 34 to 53 ppm is associated with the substituted
methylene of the backbone of the copolymer. The peak
at d ¼ 138:40 ppm is assigned to the NPMI–St–NPMI
triad according to the chemical shift assignment of the
13
C NMR spectrum for St–NPMI copolymer triads
[10,11]. This justifies that an alternating copolymer of
NPMI and St was obtained.
Fig. 3. Effect of the concentration of the catalyst on the yield of
The DSC thermogram of the copolymer is illustrated
NPMI–St copolymer. Conditions: Al=Nd ¼ 9, other conditions
in Fig. 7. It is seen from Fig. 7 that a glass transition are the same as in Fig. 1.
temperature of 230 °C was observed. The glass transi-
tion temperatures of polystyrene (about 100 °C) [12] and
poly(NPMI) (over 300 °C) are not seen. The single glass there is only a relatively homogeneous structure of units
transition temperature of the copolymer indicated that in the chain of the copolymer. It is in agreement with the
1278 Y. Lu et al. / European Polymer Journal 38 (2002) 1275–1279

result from the 13 C NMR spectrum that the copolymer is

alternating. The Tg value was similar to that of alter-
nating copolymers of St and NPMI prepared via free
radical polymerization [8]. The high Tg of the copolymer
is due to the incorporation of NPMI into the polymer
backbone. The rigid imide rings significantly hinder
segmental rotation and thus stiffen the chain. The in-
corporation of NPMI also significantly improved the
thermal stability of the copolymer. Under a nitrogen
atmosphere, the copolymer is stable up to 400 °C, as
illustrated in the TGA thermogram of Fig. 8. After that,
the weight loss of the copolymer is very fast. The im-
provement in the thermal properties as compared to
polystyrene also suggests that a large proportion of
NPMI is incorporated into the copolymer.
Fig. 4. Effect of initial concentration of NPMI on the yield of
NPMI–St copolymer. Conditions: ½St ¼ ½NPMI , other condi-
tions are the same as in Fig. 1.

Fig. 5. FT-IR spectrum of NPMI–St copolymer. Fig. 7. DSC thermogram of NPMI–St copolymer.

13
Fig. 6. C NMR spectrum of NPMI–St copolymer.
 Y. Lu et al. / European Polymer Journal 38 (2002) 1275–1279
Fig. 8. TGA thermogram of NPMI–St copolymer.
4. Conclusion
Copolymers of NPMI with St were prepared using
a rare earth coordination catalyst NdðnaphÞ3 –AlEt3 in
toluene at 50 °C. A CTC of NPMI and St participated in
the copolymerization process, which was further dem-
onstrated by elemental analysis, 13 C NMR spectroscopy
and DSC. The compositions of the copolymers are al-
ways close to 1:1 in comonomer feed even at a high
monomer conversion no matter how the mole content of
the NPMI feed varies from 10 to 90%. The thermal
property of the copolymer is much improved as com-
pared to polystyrene.
Acknowledgements
Financial supports of this project by the special
funds for Major State Basic Research Projects (No.
1999064801) and National Natural Science Foundation
1279
of China (No. 29974024 and 59873018) are greatly ap-
preciated.
References
[1] Rzaev ZMO. Complex-radical alternating copolymeriza-
tion. Prog Polym Sci 2000;25:163–217.
[2] Cheng HT, Zhao GQ, Yan DY. Free-radical copolymer-
ization of styrene with N-phenylmaleimide initiated by
thiol. J Polym Sci Polym Chem Ed 1992;30:2181–5.
[3] Mohamed AA, Jebrael FH, Elsabee MZ. Copolymeriza-
tion of styrene with N-arylmaleimides. Macromolecules
1986;19:32–7.
[4] Ouyang J, Shen ZQ. Collection of synthetic rubber
catalyzed by rare earth catalysts. Beijing: Science Press;
1980.
[5] Shen ZQ, Zhang YF. Polymer synthesis by rare earth
coordination catalysts. Prog Natural Sci 1995;5:641–7.
[6] Jiang LM, Zhang YF, Shen ZQ, Shen LF, Yuan HZ.
Polymerization of N-phenylmaleimide with rare earth
coordination catalysts. Macromol Rapid Commun 1996;
17:427–31.
[7] Cava MP, Deada AA, Muth K, Mitchell MJ. Org Synth
Coll 1973;V:944–6.
[8] Rienda JMB, Campa JIGDL, Ramos JG. Free-radical
copolymerization of N-phenylmaleimide. J Macromol Sci
Chem 1977;A11:267–86.
[9] Shan GR, Weng ZX, Huang ZM, Pan ZR. Free radical
copolymerization and kinetic treatment of styrene with
N-phenylmaleimide. J Appl Polym Sci 1997;63:1535–42.
[10] Shan GR, Weng ZX, Huang ZM, Pan ZR. Studies on the
microstructure of vinyl/N-phenylmaleimide copolymers by
NMR and their applications. J Appl Polym Sci 2000;77:
2581–7.
[11] Nguyen T, Hieu H. Determination of triad sequence
distribution of copolymers of maleic anhydride and its
derivates with donor monomers by 13 C NMR spectro-
scopy. Polymer 1999;40:1081–6.
[12] Brandrup J, Immergut EH. Polymer handbook. 3rd ed.
New York: Wiley; 1989.