Polymer International 41 (1996)93-96

Photoinduced Charge-Transfer
Polymerization of Acrylonitrile Initiated
by N -Substituted Phenothiazines
Dong-yi Wang, Wei-xiao Cao & Xin-de Feng*

Department of Chemistry, Peking University, Beijing 100871,Peoples Republic of China

(Received 22 March 1996;accepted 22 April 1996)

Abstract: The polymerization of acrylonitrile (AN) initiated with phenothiazine

(PTZ) and its derivatives has been studied. It is found that N-alkyl- substituted
phenothiazines possess greater ability to initiate the polymerization of AN under
UV irradiation. The initiation mechanism proposed is that the exciplex formed
between N-substituted PTZ and AN plays a key role in the initiation process.
The kinetic equation for N-methyl phenothiazine (NMP) was determined to be
rate of polymerization, R , = KmMP]0.46[AN]144.

Key words: charge-transfer complex, exciplex, photopolymerization.

INTRODU CTlO N EXPERIMENTAL

Polymerization in which a charge-transfer process is Materials

involved in the initiation or propagation step has been
extensively investigated.v2 Polymerization initiated
with electron acceptors, or electron donors, usually
follows such a charge-transfer mechanism,334either
through the formation of an exciplex between the
excited state of the initiator and the ground state of the
monomer, or through the excitation of a charge-transfer
complex (CTC) formed by the ground states of initiator
and monomer.
In previous we have reported the photo-
polymerization of acrylonitrile, or methyl acrylate,
via charge-transfer mechanism in the presence of aro-
matic amines as an electron donor. Phenothiazine
(thiodiphenylamine) is an electron donor, but whether it
can initiate the photopolymerization of acrylonitrile has
not yet been reported. Recently, we found that pheno-
thiazine and its derivatives can initiate photo-
polymerization of acrylonitrile effectively. In this article
we report this polymerization and discuss the initiation
mechanism.
* To whom all correspondence should be addressed.
93
0 1996 SCI. Printed in Great Britain
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Acrylonitrile was distilled over CaH, before use (b.p.
77-78C; nio = 1.3815). Phenothiazine from Fluka was
purified by recrystallization twice from petroleum ether
(60-90C); m.p. 183-184C. 2-Acetyl phenothiazine
from Aldrich was purified by recrystallization from
ethyl acetate; m.p. 192-193C. The other phenothiazine
derivatives were synthesized according to Refs 9-1 1.
Their structures and melting points are shown on the
next page.
Polymerization
The polymerization was carried out in a dilatometer in
a thermostat at 25.0 k 0.1C with a 300W medium
pressure Hg lamp as light source at a distance of 7-Ocm
from the dilatometer, and using l c m thick saturated
CuSO, solution (aq.) as filter. The absorbance of the
polymerization system at 365 nm was controlled to be
0-10. The molecular weight was determined viscometri-
cally and calculated according to the equation : I 2
[q] = 0.92 x (DMF, 25C)
10-4M05
94
P system were controlled to give the same absorbance at
R = -CH3 (NMP); m.p. 98-99C
-CH=CH, (NEP),; m.p. 102-104C
-CH(CH,), (NIPP); m.p. 59-60C
-CH2CH=CH2 (NAP); b.p.169-17l0C/0.7mmHg
-COCH, (NACP); m.p. 204-205C
R, = H, R, = -CH(OH)CH3(2HEP); m.p.145-147C
R, = H, R, = -CH=CH, (2VP); m.p. 178-180C
R, = R, = -COCH3 (DACP); m.p. 251-252C
Spectral analysis
The absorption spectra and fluorescence spectra were
recorded on a Shimadzu UV-250 spectrophotometer
and an Hitachi-850 fluorescence spectrophotometer,
respectively.
RESULTS AND DISCUSSION
In order to compare the initiation abilities of the
various phenothiazine derivatives, which were used as
initiators, their concentrations in the polymerization
A F
1.2
0.6
0.0
210 32-0 370
Fig. 1. UV spectra of NMP in AN or in CH,CN. 1,
~ AN; 2, P M P ] = 2 x 1 0 - 4 ~in
[NMP] = 2 x l O W 4 in
CH,CN.
D-Y. Wang, W-X. Cao, X-D. Feng
365nm, i.e. about 0.1. The rate of polymerization (R,)
and molecular weights ( M W ) of polymers were deter-
mined in AN/DMSO (1 : 1vol.) at 25"C, and are listed
in Table 1.
From Table 1 we can see that N-alkyl-substituted
phenothiazines are much better than PTZ, or its 2-
substituted compounds, when used as initiator in the
polymerization of AN under irradiation. This result is
in accordance with the initiation mechanism in which
phenothiazine, or its derivatives, plays the role of elec-
tron donor in the formation of an exciplex with AN.
The molecular weight ( M W ) of the polymers decreases
with increase of R,. The initiation mechanism should
be similar to that which we previously proposed for the
aromatic amine and AN system;13 NMP is shown in
Scheme 1 as an example.
The CTC formation has been verified by determi-
nation of the UV spectra of NMP. The NMP spectrum
in AN is obviously broadened compared with that in
acetonitrile (Fig. l), because of the CTC formation
between NMP and AN. The exciplex forms through
CTC excitation (route l), or NMP excitation (route 2).
Free radicals NMP' and AN' were formed through the
exciplex, an intimate ion pair, via H + transfer of NMP
to AN. The exciplex formation in the AN/NMP system
was verified by the determination of the fluorescence of
NMP. The fluorescence peak of NMP at 450nm is
quenched systematically by the addition of AN. At the
same time a new peak from the exciplex appears at
550nm (Fig. 2). Similar results for NEP, NIPP and
60
a0
20
0
400 500 600 nnr
Fig. 2. The fluorescence spectra of NMP with different [AN].
[MP] = 1.0 x lo-, M in CH,CI,. [AN][M]: 1, 0; 2, 0.12; 3,
0.24; 4,0*35;5,0*58; 6, 1.01; 7, 1.52; 8, 2.92.
POLYMER INTERNATIONAL VOL. 41, NO. 1, 1996
Photoinduced charge-transfer polymerization 95

CH3 CH;

I
CH3

I H+ transfer

H&CN
H H

Scheme 1

NAP were obtained with corresponding peak wave-
lengths of 550, 550 and 545 nm, respectively.
The free radical nature of the initiation was verified
by the fact that 2,2'-diphenylpicryl hydrazyl (DPPH) or
2,2,6,6-tetramethylpiperidinoxyfree radicals (TMPNO'),
inhibit the polymerization significantly. The results are
shown in Table 2.
From the relations of R,-[initiation] and Rp-
[monomer], the power dependence on initiator and
monomer for the NMP-AN system were determined to

TABLE 1. R , and M W in photopolymerization of AN with dif-

ferent phenothiazine derivatives as initiator

Initiator Conc. x IO4 ASe6nm R, x 105 MW x 10-4

(mol I-') (mol I-' s-')

PTZ 1.03 0.102 5.34 37.20

NlPP 2.97 0.103 22.40 4.8
NEP 1.97 0.108 20.90 5.1 6
NMP 3.42 0.097 19.60 6.57
NAP 2.00 0.101 19.10 5.05
2HEP 0.82 0.105 6.54 22.30
2VP 0.49 0.108 6.61 22.20
NACP' - 3.88 35.40
DACP 0.39 0.1 06 4.56 37.50
Blank - 0.00 0.07 -

a Saturated solution in AN/DMSO (1 : 1 vol.).

POLYMER INTERNATIONAL VOL. 41, NO. 1, 1996

96 D-Y. Wang, W-X.Cao, X-D. Feng

be 0.46 and 1.44, respectively. So the rate equation of ACKNOWLEDGEMENT

polymerization is derived as :
The authors are grateful to the National Natural
R, = K[NMP]0'46[AN]1.44
Science Foundation of China for financial support of
From the relation of R, and polymerization tem- this work.
perature, the apparent activation energy of poly-
merization, E, was determined to be 29.7kJmol-l. The
power dependence on initiator and monomer and E are REFERENCES
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POLYMER INTERNATIONAL VOL. 41, NO. 1, 1996