Synthetic Metals, 1 7 (1987) 247 -252 2/47

M O R P H O L O G Y AND C H A R A C T E R I Z A T I O N OF P O L Y A C E T Y L E N E FILMS S Y N T H E S I Z E D IN A LIQUID

CRYSTAL SOLVENT

K. ARAYA

Advanced Research Laboratory, Hitachi, Ltd., Kokubunji, Tokyo 185 (Japan)

A. MUKOH and T. N A R A H A R A

Hitachi R e s e a r c h Laboratory, Hitachi, Ltd., Hitachi, Ibaraki 319-12 (Japan)

K. AKAGI and H. SHIRAKAWA

Institute of Materials Science, University of Tsukuba, Sakura-mura,

Ibaraki 305 (Japan)

ABSTRACT
The synthesis of oriented p o l y a c e t y l e n e films was investigated by using a
nematic liquid crystal as a p o l y m e r i z a t i o n solvent. As a result, when p o l y m e r -
ization was carried out on a quiesent surface of the nematic catalyst solution,
partially oriented polyacetylene films were obtained. On the other hand, in the
p o l y m e r i z a t i o n under a flow of the nematic catalyst solution, highly oriented
films were obtained.
The order parameter of the o r i e n t e d sample, estimated from polarized absorp-
tion spectra, was about 0.57. The m a x i m u m value of parallel electrical conduc-
tivity of the films doped with iodine was 4600 S/cm, while that of the films
doped with arsenic p e n t a f l u o r i d e was ii000 S/cm.

INTRODUCTION

The o r i e n t a t i o n of p o l y a c e t y l e n e (PA) films has attracted much interest from

the viewpoint of the estimation of anisotropic properties that must be associ-

ated with one-dimensional conjugated systems. Moreover, considerable enhance-

ment of electrical conductivity might be expected for the doped samples. There-
fore, several syntheses of o r i e n t e d PA films have been reported so far [1-6].
Recently, we also found that highly oriented PA films could be obtained under a
flow of the nematic catalyst solution [7,8]. In this paper, we report the
morphology of the PA films synthesized in a nematic liquid crystal, and also

the optical properties and electrical c o n d u c t i v i t i e s of the oriented PA films.

0379-6779/87/$3.50 © Elsevier Sequoia/Printed in The Netherlands

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EXPERIMENTAL

The nematic liquid crystal used was a m i x t u r e of 4 - ( t r a n s - 4 - n - p r o p y l c y c l o -

h e x y l ) - e t h o x y b e n z e n e and 4 - ( t r a n s - 4 - n - p r o p y l c y c l o h e x y l ) - b u t o x y b e n z e n e . This mix-

ture was chosen for chemical stability in the presence of Ziegler-Natta catalyst
[8]. The phase d i a g r a m of this binary system is presented in Fig. i. Both compo-
nent compounds are m o n o t r o p i c a l l y mesomophic, but the nematic liquid crystal is
stable within the middle composition region. Actually, an equimolar m i x t u r e of
these compounds was used as a p o l y m e r i z a t i o n solvent. The solid-nematic liquid
crystal transition temperature is 20 °C and the nematic liquid c r y s t a l - i s o t r o p i c

liquid transition temperature is 34 °C. However, due to supercooling, solidifi-

cation was not observed down to 0 °C. Therefore,.we were able to use this
mixture in a temperature range of 0 to 34 °C.

The catalyst systems used were Ti(OBu)4-AIEt3, TiCI4-AIEt3, TiO(acac 2-AIEt3,

and V O ( a c a c ) 2 - A i E t 3. The c o m p o s i t i o n ratio of the catalyst system (M/A1) was
3.0, where M denotes a transition metal. The catalyst components were d i s s o l v e d

in a nematic liquid crystal solvent both d i r e c t l y and indirectly. In the latter

case, the conventional catalyst solution ( toluene ) was added to the solid of
the above mixture at -78 °C, and then toluene was removed by pumping. This

method is almost the same as that reported by T. Woerner et al. [3]. A small amount
o f toluene d i s s o l v e d in the m i x t u r e did not cause phase separation, but only

d e p r e s s e d the transition t e m p e r a t u r e [9]. The other p o l y m e r i z a t i o n procedure

was d e s c r i b e d in a previous paper [8].

40

C
10- A'C~HT~ OC2Hs

00 i I , I I I I I I
B'C3HT~OC4H9
20 40 60 80 100
Mol% of B
Fig. I. Phase d i a g r a m of 4 - ( t r a n s - 4 - n - p r o p y l c y c l o h e x y l ) - e t h o x y b e n z e n e [A] /
4 - ( t r a n s - 4 - n - p r o p y l c y c l o h e x y l ) - b u t o x y b e n z e n e [B] system.
C : Solid phase, N : Nematic liquid crystal phase, I : Isotropic liquid phase.
 249

R E S U L T S AND D I S C U S S I O N

Morphology
When p o l y m e r i z a t i o n was carried out on a q u i e s c e n t surface of a nematic cata-
lyst solution, each of the four catalyst systems presented similar m i c r o s c o p i c
morphology. First, the o r i e n t a t i o n of fibrils was o b s e r v e d locally. Second, the

fibrils in the film were larger than for films p r e p a r e d in toluene. Their dia-
meter was about i00 nm and their length was over i0 ~m. Generally, polymeri-
zation in a liquid crystal is characterized by a considerable increase of the
p o l y m e r i z a t i o n rate and the polymer m o l e c u l a r weight. [10-12]. Therefore, it
can be considered that m o l e c u l a r weights of PA obtained in a liquid crystal
are higher than those o b t a i n e d by the Shirakawa method. This may reflect the
m o r p h o l o g y change.
Among the four catalysts, T i ( O B u ) 4 - A I E t 3 and V O ( a c a c ) 2 - A i E t 3 presented uni-
form PA film. The former is especially good. This result is consistent with a
conventional synthesis that uses toluene as a p o l y m e r i z a t i o n solvent [13]. In
the V O ( a c a c ) 2 - A i E t 3 system (50 mmol/l), the m a c r o s c o p i c m o r p h o l o g y of PA
o b t a i n e d in a nematic phase (20 °C) is in the form of film, w h i l e PA obtained
in an isotropic phase (50 °C) is in the form of powder. It is known that
m a c r o s c o p i c m o r p h o l o g y is a function of catalyst concentration. In this case,
m o r p h o l o g y changes depend on the phase state. In the T i ( O B u ) 4 - A I E t 3 system, such
a m a c r c o s c o p i c m o r p h o l o g y change is not observed.
The synthesis of o r i e n t e d PA film was examined only in the T i ( O B u ) 4 - A I E t 3
system suitable for acetylene polymerization. The typical SEM p h o t o g r a p h of
o r i e n t e d PA film is presented in Fig. 2. This o r i e n t a t i o n is due to m a c r o s c o p i c
alignment of nematic liquid crystals under a flow. The o r i e n t a t i o n of fibrils
c o r r e s p o n d e d to the flow direction. In the present method, the area of o r i e n t e d
film can be controlled by changing the size of the reaction flask. The thickness
can be controlled by adjusting p o l y m e r i z a t i o n temperature and time. The rela-

t i o n s h i p between the p o l y m e r i z a t i o n conditions and the film thickness is

summarized in Table i. Samples A,B,C were used for m e a s u r e m e n t s of ultraviolet-
visible (UV) a b s o r p t i o n spectra, infrared (IR) absorption spectra, and electri-
cal conductivity, respectively.

Table 1

The d e p e n d e n c e of film thickness on p o l y m e r i z a t i o n conditions

Samples Temperature(°C) Time(min.) Pressure(torr) Thickness(~m)

A 19 0.2 456 <i

B 13 I0 464 1 - i0
C i0 120 467 i0 - 30
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Fig. 2. Scanning electron micrograph of oriented polyacetylene film obtained

by flowing the nematic catalyst solution.

Optical anisotropies
The polarized absorption spectra in the UV region were measured on thin film.
In this section, we refer only to optical anisotropy. Detailed results will be
reported separately [14]. The optical anisotropy (R) of the absorption peak
(around 2 eV) is about 5. As the order parameter is defined by (R-I)/(R+2) [15],
the order parameter of fibrils in the film is calculated to be 0.57. This value
is approximately equal to the values of the nematic liquid crystals [16].
In the IR spectra measurement, thick film was used. As is well known that
in-plane and out-of-plane vibrations of PA correspond to the parallel and per-
 25]

pendicular d i r e c t i o n s of p o l a r i z e d light [17,18]. Therefore, optical a n i s o t r o p y

can be readily estimated. The absorption peaks at 450, 1330, and 3045 cm -I are
a t t r i b u t e d to the in-plane v i b r a t i o n of the cis-form; so those at 740 and 1015
cm -I are the o u t - o f - p l a n e v i b r a t i o n s of the c i s - f o r m and the trans-form, respec-
tively. The optical a n i s o t r o p i e s from these peaks were 2.0 - 3.0. This clearly
shows the o r i e n t a t i o n of PA, but is lower than that estimated with UV spectra.
From these optical observations, only at the nascent stage of polymerization,
the o r i e n t a t i o n of fibrils seems to be affected by the alignment effect of
liquid crystal molecules. Consequently, as the PA film get thicker, the orienta-

tion seems to get worse.

Electrical c o n d u c t i v i t y
We report only p r e l i m i n a r y results on room t e m p e r a t u r e electrical conductivi-
ties of PA films doped with 12 and AsF 5 . Detailed results and d i s c u s s i o n will
be reported in a separate paper [19]. In 12 doping, the m a x i m u m values of paral-
lel and p e r p e n d i c u l a r c o n d u c t i v i t i e s were 4600 S/cm and 390 S/cm, respectively.

With AsF 5 doping, the parallel and p e r p e n d i c u l a r conductivities were ii000 S/cm
and 2400 S/cm, respectively. Each m a x i m u m value of parallel c o n d u c t i v i t i e s
attained through 12 and AsF 5 doping is the highest value among those reported
so far [20]. These are higher by 3 times and 8 times than those of stretched
aligned films and randomly oriented films, respectively [21]. Since the electri-
cal anisotropy of 12 o b t a i n e d for the 12 doped film is comparable to values

o b t a i n e d for 12 d o p e d stretched films with an elongation of 2.9 [1,21], the

present film apparently has the same degree of fibril alignment as the stretched
film. However, the conductivity of the former is 3 times higher than that of the
latter. Mechanical e l o n g a t i o n often results in the cleavage of fibrils. There-
fore, such a structural d i f f e r e n c e may affect the conductivity. Moreover, the
d i f f e r e n c e in conductivities may be affected by the d i f f e r e n c e in m o l e c u l a r

weight of PA as mentioned in the m o r p h o l o g y section.

ACKNOWLEDGEMENTS
The authors thank Mr. Kitamura for helpful d i s c u s s i o n s on liquid crystals.

REFERENCES

1 H. Shirakawa and S. Ikeda, Synth. Met. t 1 (1979/80) 175.

2 W.H. Meyer, Mol. Cryst. Liq. Cryst., 77 (1981) 137.

3 T. Woerner, A.G. M a c D i a r m i d and A.J. Heeger, J. Polym. Sci. Polym. Lett. Ed.,
20 (1982) 305.
4 M. Ozaki, Y. Ikeda and T. Arakawa, J. Polym. Sci. Polym. Lett. Ed., 21 (1983)
989.
252

5 G. Leising, Polym. Bull., ii (1984) 401.

6 G. Lugli, V. Pedretti and G. Perego, J. Polym. Sci. Polym. Lett. Ed.,
23 (1985) 129.
7 K. Araya, A. Mukoh, T. Narahara and H. Shirakawa, Chem. Lett., (1984) 1141.
8 K. Araya, A. Mukoh, T. Narahara and H. Shirakawa, Synth. Met., 14 (1986) 1 9 9
9 J.S. Dave and M.J.S. Dewar, J. Chem. Soc., (1954) 4616.
I0 Y.B. Amerik, I.I. Konstantinov and B.A. Krentsel, J. Polym. Sci, C23 (1968)
231.
ii W.E. Bacon, J. Phys., 36 (1975) CI-409.
12 B. Samori and L. Fiocco, J. Am. Chem. Soc., 104 (1982) 2634.
13 T. Ito, H. Shirakawa and S. Ikeda, J. Polym. Sci. Polym. Chem. Ed., 12
(1974) ii.

14 Y. Kaneko, Y. Tokura, H. Okamoto, T. Koda, H. Shirakawa and K. Araya,

to be published.
15 W. Haase and H. Wedel, Mol. Cryst. Liq. Cryst., 38 (1977) 61.
16 W. Maiser and A. Saupe, Z. Naturforsch., 16a (1961) 816.
17 H. Shirakawa and S. Ikeda., Polym. J., 2 (1971) 231.
18 M. Galtier, M. Charbonnel, A. Montaner and J.L. Ribet, Polymer, 12 (1984)
1253.
19 K. Akagi, H. Shirakawa, K.Araya, A. Mukoh and T. Narahara, to be p u b l i s h e d
20 Y.W. Park, A.J. Heeger, M.A. Druy and A.G. MacDiarmid, J. Chem. Phys.,

73 (1980) 946.

21 Y.W. Park, M.A. Druy, C.K. Chiang, A.G. MacDiarmid, A.J. Heeger,
H. Shirakawa and S. Ikeda, J. Polym. Sci. Polym. Lett. Ed., 17 (1979) 195.