Synthesis and Properties of Silicon-Containing Polyacetylenes

35

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Synthesis and Properties of SiliconContaining Polyacetylenes Toshio Masuda and Toshinobu Higashimura Department of Polymer Chemistry, Kyoto University, Kyoto 606, Japan

The synthesis, structure, properties, and applications of Si-containing polyacetylenes are reviewed. Various Si-containing acetylenes were polymerized, namely, HC=CCH[Si(CH ) ](n-C H ) (2c), HC=C[[o-Si(CH ) ]C H ] (3), and CH C=CSi(CH ) (4a). Compounds 2c and 3 polymerize in high yields with Mo and W catalysts, whereas 4a produces a polymer with Nb and Ta catalysts. The molecular weights of the polymers are in the range 10 -10 . The polymers possess the structure -(CR=CR') -. Poly(2c), poly(3), and poly(4a) are yellow, purple, and colorless solids, respectively. Unlike polyacetylene, these polymers are stable in air and soluble in many organic solvents. Poly(4a) shows extremely high oxygen permeability and ethanol permselectivity during ethanol-water pervaporation. 3 3

3 3

6

4

3

5

11

3 3

5

6

n

THE METHODS FOR PREPARN IG POLYACETYLENE

are well established, and the applications of polyacetylene are the subject of intensive research at present (J, 2). In contrast, the study of substituted polyacetylenes has not advanced so much (3-6), probably because the preparation of high-molecular-weight polymers from substituted acetylenes has been difficult. In addition, relatively few studies have been made about Si-containing polyacetylenes, and no review article has been published. Transition metal catalysts are useful for the polymerization of acetylenes. Ti catalysts are known to polymerize acetylene. Catalysts containing group V and VI transition metals (i.e., Nb, Ta, Mo, and W) polymerize substituted acetylenes (3, 4). The group V and VI transition metal catalysts can be classified into three groups: (1) chlorides of Nb, Ta, Mo, and W; (2) 1:1 mixtures of the metal chlorides with organometallic cocatalysts (e.g., 0065-2393/90/0224-0641$06.25/0 © 1990 American Chemical Society

In Silicon-Based Polymer Science; Zeigler, J., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1989.


642

SILICON-BASED POLYMER SCIENCE: A COMPREHENSIVE RESOURCE

(C 6 H 5 ) 4 Sn); and (3) catalysts obtained by UV irradiation of the CC1 4 solution of Mo(CO)6 and W(CO) 6 . The following relationships between the structure of acetylenic mono mers and the activity of catalysts are observed usually: Ziegler catalysts can give rise to polymers from acetylene and monosubstituted acetylenes without bulky substituents. In contrast, Mo and W catalysts are very effective for monosubstituted acetylenes with bulky substituents and disubstituted acet ylenes with less bulky substituents. Further, Nb and Ta catalysts are useful for various disubstituted acetylenes, including those with bulky substituents. We have been interested in the synthesis of high-molecular-weight poly mers from substituted acetylenes by use of group V and VI transition metal catalysts (3, 4). Such monomers include H C = C ( £ e r f - C 4 H 9 ) , HC=C[(oC F 3 ) C 6 H 4 ] , CH3C^C(n-C 5 H n ), C H 3 C ^ C C 6 H 5 , ClC^C(n-C 6 H 1 3 ), and C1C=CC 6 H 5 . All these monomers are sterically fairly crowded. When suit able catalysts and solvents are chosen for the individual monomers, the polymer yields can become as high as 80-100%. The molecular weights of those polymers are in the range 5 Χ 105-2 Χ 106. In contrast, acetylenes that are sterically not so crowded, such as HC=C(n-C 6 H 1 3 ) and H C = C C 6 H 5 , give polymers with lower molecular weight, probably because of side re actions like cyclization. Many properties of polyacetylenes with bulky substituents are substan tially different from those of polyacetylene. For example, the substituted polyacetylenes are soluble because of the interaction between the substit uents and solvent. Furthermore, such polymers are usually only lightly colored and are stable in air at room temperature. These properties arise from twisted conformations assumed by the main chain because of the pres ence of substituents. The electrically insulating and nonparamagnetic prop erties of substituted polyacetylenes are attributable also to the same cause.

Polymerization of Si-Containing Monosubstituted Acetylenes Among Si-containing acetylene monomers, only (trimethylsilyl)acetylene (HC=CSi(CH 3 ) 3 ; la) has appeared in the literature, if our studies are ex cepted. CHa HC=CSi-R CH3 1 R: la, C H 3 ; lb, C 6 H 5 ; lc, fert-butyl; Id, n-C 6 H 1 3 ; le, - C H 2 C H 2 C 6 H 5 ; If, - C H 2 C 6 H 5



35.

MASUDA & HIGASHIMURA

Silicon-Containing Polyacetylenes

643

Russian researchers (7) have reported that MoCl 5 polymerizes this mon omer to give a yellow polymer. Zeigler (8) has synthesized a totally soluble polymer by using a mixture of WC1 6 and methylmagnesium bromide. A French group (9) has used a metal carbene complex, (CO) 5 W = C R ^ , as initiator. However, the polymers of la [poly(la)] so produced usually have low molecular weights, around 104, and are often partly insoluble in all known solvents. The polymerization of la and its homologues (lb—If) was studied first (10, 11). Polymerizations were carried out with WC1 6 as catalyst in toluene at 30 or 80 ° C for 24 h. All the monomers in Table I produce methanolinsoluble polymers in moderate to good yields. Table I. Polymerization of H O=CSi(CH3)2R by WC16 R CU3b

C 6 Hs teri-CiHg n-C 6 H Β

C H 2 C H 2 C eHs CH2C6H5

Yield (%)

M /

47 44 87 21 33 38

partly insoluble partly insoluble partly insoluble 9800 9000 7100

NOTE: The reactions were carried out in toluene at 80 °C for 24 h ([M]o = 0.50 M; [catalyst] = 10 mM). Practically no or very little polymers were formed with Mo, Nb, or Ta catalysts. fl Values of M n were measured by gel permeation chromatography. The reaction was carried out at 30 °C. b

Poly(la), poly(lb), and poly(lc), which possess inflexible R groups, are partly insoluble in all known solvents. In contrast, poly(ld), poly(le), and poly(lf), whose R groups are flexible, dissolve completely in toluene. The molecular weights of these polymers, however, are not more than 104. All the poly(l)s are yellow. Whereas poly(ld) is rubbery, other poly(l)s are powdery. Because the type 1 monomers do not give rise to high-molecular-weight polymers, we next considered 3-(trimethylsilyl)-l-alkynes (2) as monomers (12). HC^CCHR Si(CH3)3 2 R: 2a, C H 3 ; 2b, n-C 3 H 7 ; 2c, n - C 5 H n ; 2d, n-C v H 1 5 In these monomers, the silyl group is not directly bonded to the acetylenic carbon. Although linear 1-alkynes produce oligomeric products only,


644



the type 2 monomers are expected to form high-molecular-weight polymers because of steric crowding. These monomers are prepared from the corresponding 1-alkynes by dilithiation followed by silylation at C-3. When the type 2 monomers are polymerized with MoCl 5 and WC1 6 in toluene at 30 ° C for 24 h, the yields of methanol-insoluble polymers become as high as 70-80% (Table II). For the polymerization of 2c, use of (C 2 H 5 ) 3 SiH as cocatalyst enhances both the yield and the molecular weight of the polymer. The Mo(CO)6- and W(CO)6-based catalysts are also effective.

Table II. Polymerization of HC=CCH[Si(CH3)3]R by Mo and W Catalysts R M , ( X io ) Catalyst Yield (% ; CH3 partly insoluble 80 M0CI5 WC1 6 70 partly insoluble n-C3H7 M0CI5 82 partly insoluble WC1 6 74 partly insoluble B-C5H11 M 0 C I 5 77 98 WC1 6 72 42 n - C 7 H 1 5 M0CI5 82 170 WC1 6 80 55 n-CMn MoCl 5 -(C 2 H 5 )3SiH 90 320 WCl 6 -(C 2 H 5 ) 3 SiH 88 300 Mo(CO) -hv 75 100 W(CO)6-/ivfc 81 160 3

6

a

b

NOTE: The reactions were carried out in toluene at 3 0 ° C for 24 h ([M]o = 0 . 5 0 M; [catalyst] = [cocatalyst] = 10 mM). Practically no or very little polymers were formed with Nb or Ta catalysts. "Values of M w were measured by gel permeation chromatography. fe The reaction was carried out in C C 1 4 .

Poly(2a) and poly(2b) are partly insoluble in toluene. In contrast, poly(2c) and poly(2d) are totally soluble in toluene, because they have a long, flexible alkyl chain. The molecular weights of these polymers are fairly high, 5 X 104-3 x 105. Free-standing films can be obtained from poly(2c) and poly(2d) by solution casting (usually, a molecular weight of over 105 is necessary for the formation of free-standing film from a substituted polyacetylene). All the poly(2)s are yellow solids. The third type of monomer among Si-containing monosubstituted acetylenes is o-(trimethylsilyl)phenylacetylene (3).

(CH3)3Si 3



35.


Silicon-Containing

645

Polyacetylenes

Because phenylaeetylene is not very crowded sterically, the molecular weight of the polymer is usually in the 104 range only (3, 4). o-Methylphenylacetylene, which has a somewhat larger steric crowding, produces a polymer with higher molecular weight. In this respect, we determined how high the molecular weight of poly(3) can be. The monomer is prepared from phenylaeetylene by metallation at the terminal and ortho positions, silylation at both positions, and partial desilylation (13). Table III shows results of the polymerization of 3 by various catalysts (14). Poly(3) is obtained almost quantitatively in the presence of W and Mo catalysts. Nb and Ta catalysts also give the polymer, although the yields are not high. The molecular weight of poly(3) exceeds 106 in many cases. Poly(3) is dark purple, in striking contrast with the whiteness or paleness of most disubstituted acetylene polymers. A tough film can be prepared by casting from the polymer solution. Table IH. Polymerization of HC=C[[o-Si(CH3)3]C6H4] by Various Catalysts Catalyst

WC1 6

W(CO) -hv M0CI5 6

b

Mo(CO) 6 -/iv & WCl 6 -(C 2 H 5 ) 3 SiH MoCl5-(C 2 H 5)3SiH NbCl 5 -(C 2 H 5 ) 3 SiH TaCl 5 -(C 2 H 5 ) 3 SiH

Yield (%)

Μ«,(Χ 10 )

91 94 86 0 100 100 35 15

1500 1400 1700

3

a

1600 1100 1300 180

NOTE: The reactions were carried out in toluene at 30 °C for 24 h ([M]o = 1.0 M; [catalyst] = [cocatalyst] = 10 mM). e Values of M w were determined by GPC. fc The reaction was carried out in CC14.

Living polymerization is a polymerization in which neither termination nor chain transfer occurs. Certain Mo catalysts effect the living polymeri zation of 3 (15). The molecular weight distribution (MWD) of the polymer formed with MoCl 5 alone is broad (Figure 1). The MoCl 5 -(n-C 4 H 9 ) 4 Sn cat alyst narrows the M W D significantly, but it is yet imperfect. In contrast, when a three-component catalyst, MoCl5-(n-C 4 H 9 ) 4 Sn-C2H 5 OH is used, the M W D becomes very narrow, with the polydispersity ratio (MJ M J being close to unity. For MoOCl4-based catalysts as well, a three-component cat alyst, M o O C l 4 - ( n - C 4 H 9 ) 4 S n - C 2 H 5 O H produces poly(3) with a narrow MWD.

Polymerization of Si-Containing Disubstituted Acetylenes l-(Trimethylsilyl)-l-propyne (CH 3 C=CSi(CH 3 ) 3 ; 4a) is a representative Sicontaining disubstituted monomer (16, 17).



35

10 s

1 ,0* MW(PSt) 5Ό EV(ml) 4

10

'

10

s

40 4

9 4

10*

?0 2

5

10

3

EV(ml)

MW(PSt)

0

3

Figure 1. Living polymerization of HC=C[[o-Si(CH )3]C6H ] by MoCh or MoOCl4-(n-C H ) Sn-C H OH (1:1:0.5) in toluene at 30 °C. [M] = 1.0 or 0.10 M; conversion = 100%. Abbreviations are defined as follows: PSt, polystyrene; EV, elution volume.

6

1Ο UÔ


35.


Silicon-Containing

647

Polyacetylenes

ÇH3

CH 3 C=CSi-R CH3 4 R: 4a, C H 3 ; 4b, n-C 6 H 1 3 ; 4c, C 6 H 5 ;


4d, -CH 2 Si(CH 3 ) 3 ; 4e, -CH 2 -CH 2 Si(CH 3 ) 3 Because 4a is remarkably hindered sterically, it does not polymerize at all with Mo or W catalysts. On the contrary, the chlorides and bromides of Nb and Ta give a soluble polymer virtually quantitatively (Table IV). The molecular weights of the polymer are in the 105-106 range. Table IV. Polymerization of CH3C=^CSi(CH3)3 by NbX5 and TaX5 Catalyst Mj(x 10 ) Yield (Ψο) insoluble 94 NbF5 310 100 NbCls 280 100 NbBr5 0 Nbl 5 0 TaF5 730 100 TaCl5 410 95 TaBr5 0 Tal5 3

a

NOTE; The reactions were carried out in toluene at 80 °C for 24 h ([M]o = 1.0 M; [catalyst] = 20 mM). No polymer was formed with Mo or W catalysts. "Values of M w were determined by GPC.

Figure 2 illustrates the effects of cocatalysts on the polymerization of 4a by TaCl 5 (18). The polymerization by TaCl 5 alone is virtually completed after 1 h under the conditions shown in Figure 2. The molecular weight of the polymer is about 106 regardless of polymer yield. When (C 6 H 5 ) 3 Bi is added as cocatalyst, polymerization is much faster than that by TaCl 5 alone. The polymer formed has a superhigh molecular weight of up to 4 X 106, the highest molecular weight among those of all the substituted polyacetylenes. The living polymerization of 4a is possible by using NbCl 5 as catalyst and eyclohexane as solvent (19). In this polymerization, the molecular weight increases in direct proportion to conversion (Figure 3). The M J M n ratio is as small as 1.2 regardless of conversion. Figure 3 (right) shows that the MWD is narrow and that the peak shifts toward the high-molecular-weight side with increasing conversion. The polymerization of several homologues of 4a (4b-4e) has also been examined (20, 21). All these monomers are polymerizable (Table V). As for



648


Tim* . min

Tim*, min

Figure 2. Effect of cocatalyst on the polymerization of CH3C=CSi(CH3)3 by TaCl5 in toluene at 80 °C. [M]0 = 1.0 M ; [catalyst] = 20 mM. (Reproduced from reference 18. Copyright 1986 American Chemical Society.)

Convn,% Figure 3. Living polymerization of CH3C=CSi(CH3)3 by NbCh in eyclohexane at 25 °C for 24 h. [M]0 = 1.0 M; [catalyst] = 20 mM. (Reproduced with permission from reference 19. Copyright 1988.)

Table V. Polymerization of CH3C=CSi(CH3)2R R n-CeH i 3 C6H5

-CH 2 Si(CH 3 ) 3 —CH2CH2Si(CH3)3

Catalyst

Yield (%)

TaCl5-(C6H5)3Bi TaCl5-(C6H5)4Sn TaCl5 TaCl5-(C6H5)4Sn

75 15 100 58

Mw(Xl03)a 1400 460 1500 400

NOTE: The reactions were carried out in toluene at 80 °C for 24 h ([M]0 = 1.0 M; [catalyst] = [cocatalyst] = 20 mM). "Values of M w were measured by GPC.



35.



649

the catalysts, either TaCl 5 alone or its mixtures with cocatalysts are effective. The polymer yields range from 15 to 100% depending on the kind of mon omers, whereas the molecular weights of all the polymers are in the 105-106 range. The poly(4)s are all white solids that are soluble in low-polarity sol vents. Free-standing films can be obtained by solution casting. A relationship between the structure and polymerizability of sterically crowded acetylenes can be deduced as follows: C H 3 C = C S i ( C H 3 ) 3 , CH 3 C=CSi(CH 3 ) 2 (n-C 6 H 1 3 ), CH 3 C=CSi(CH 3 ) 2 (C 6 H 5 ), and HC=C(terfC4H9) are polymerizable, whereas C 2 H 5 C = CSi(CH3)3, CH3C-CSi(CH3)2(5ec-C3H7), C H 3 C = C S i ( C H 3 ) 2 ( i e r f - C 4 H 9 ) , and C H 3 C=C(tert-C 4 H 9) are not polymerizable. The polymer molecular weight generally tends to increase with increasing steric crowding of the monomer. However, if the steric crowding exceeds a certain limit, the monomer will not polymerize. For instance, 4a is polymerizable, whereas C 2 H 5 C=CSi(CH 3 ) 3 is not polymerizable; 4b and 4c are polymerizable, whereas sec-C H - and tert-C 4 H 9-substituted analogues are not polymer izable. HC=C(tert-C 4 H 9 ) is polymerizable, whereas C H 3 C = C ( t e r £ - C 4 H 9 ) is not. 3

7

Structure and Properties of Polymers Poly(2c), poly(3), and poly(4a) are interesting and representative Si-contain ing polyacetylenes in the sense that they are high-molecular-weight, totally soluble,film-formingpolymers. The IR, * H , and 1 3 C NMR spectra of poly(2c) are shown in Figure 4a. The C = C stretching, deformation of the C H adjacent to Si, and Si-C stretch ing are seen in the IR spectrum. The olefinic, alkyl, and (CH 3 ) 3 Si protons are all evident in the *H NMR spectrum. In the 1 3 C NMR spectrum, the olefinic, alkyl, and (CH 3 ) 3 Si carbons can be seen. Figure 4b is the corre sponding set of spectra for poly(3). The IR spectrum confirms the presence of Si atoms. In the 1 3 C NMR spectrum, olefinic and phenyl carbons are detected in the region δ 150-120, whereas the (CH 3 ) 3 Si carbons are at δ 0. The IR spectrum of poly(4a) (Figure 4c) clearly shows the C = C stretching. The two broad peaks in the * H NMR spectrum of poly(4a) are assignable to two kinds of methyl protons. In the 1 3 C NMR spectrum, all of the two olefinic carbons and two kinds of methyl carbons appear at reasonable po sitions. All the spectra in Figure 4 are consistent with the presence of the C = C bond in the polymers. No signals attributable to the C=C bond are observed in any spectra. Data from elemental analysis of these polymers agree well with the theoretical values for the polymerization products. These results indicate that the polymers have the alternating double bond structure -(CR = C R ' ) „ - . Figure 5 presents the UV-visible spectra of the three Si-containing


650


f

c=c

1


>T^SiM#3 nC

5 11 H

SiC-H .

1 *

-1.

3000 2000

H NMR

* nI

,1 i

.

1 .

1500

Si-C .

.

1

.

. 1

500 cm-1

K>00

-fCH=Cfe b I c d H-Ç^CH^ICHa b,c d

7

1 3

6

5

a

C NMR

A 8,ppm

3

2

b

•iC=Çh

c CDCt 3 f

160

140

120

100

CDCI 3

80 60 δ, ppm

40

20

0

Figure 4a. IR, J H , and 13C NMR spectra of -[CH = CCH[Si(CH3)3] (n-CsHii)]n-(Reproduced from reference 12. Copyright 1987 American Chemical Society.)




3000 2000


1500

1000

651

500cm"

Figure 4b. IR, Ή, and 13C spectra of-[CH = C[[o-Si(CH3)3]C6H4]]n-. (Re produced from reference 14. Copyright 1989 American Chemical Society.)



652


13,t

NMR CDCI3

a b

160

140

120

100

80

60

40

20

0

Figure 4c. IR, Ή, and 13C NMR spectra of-[CH3C = CSi(CH3)3]n-. (Repro duced from reference 17. Copyright 1985 American Chemical Society.)


35.


Silicon-Containing

653

Polyacetylenes

-n

1

R

ο ·

10

R

Poly (dimethyl siloxane)

_#

ooCM 1 LUX

R'

1: Me,

Si M e

2: H,

t-Bu

3: Me,

D 5 11 ÇH-n-CgH,,

A: H,

3

_ C

5: Cellulose acetate

CI,

3

H

SiMe

*1 10

R'

3

0-CeHi3

6: Me,

Ph

7: CI,

Ph

e

Cellulose triacetate

I 10"

10"

10'

Q ι

10"

R g-m-nrf #

Figure 11. Flot of a versus R in ethanol-water pervaporation through -(CR = CR')n- membranes (ethanol, 10 wt %; 133 Fa). (Reproduced with per mission from reference 3. Copyright 1986 Springer-Verlag.)

Figure 12 shows examples of the potential applications of substituted polyacetylenes studied, especially poly(4a). Oxygen enrichment (26-28, 31-33) is applicable to combustion furnaces, car engines, and respirationaiding apparatus. The transport of oxygen dissolved in water (33, 34) can be applied to contact lenses and artificial lungs. Liquid-mixture separation (30,


In Silicon-Based Polymer Science; Zeigler, J., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1989. 3

Figure 12. Potential applications of -[CH C

=

3

3

n

CSi(CH ) ] ~.

Isomer separation

Car engine

Photoresist

E-beam resist

Ethanol concn.

Combustion furnace

Enrichment

Polymer Degradation

Transport of Dissolved 0~

Liquid Separation

3

-4GMe=CSille f£


660


35) can be applied to the concentration of ethanol from fermented biomass. Polymer degradation (36-38) has relevance to resist materials for micro lithography. In relation to such applications of substituted polyacetylenes, some 25 papers in academic meetings, as well as about 75 Japanese patents, have appeared so far.

Acknowledgment


We thank E.-T. Kang of the National University of Singapore and K. Tamao of Kyoto University for many helpful suggestions.

References 1. 2. 3. 4.

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5. Gibson, H . W.; Porchan, J. M . In Encyclopedia

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lenes; Elsevier: Amsterdam, 1981; ρ 85. 14. Masuda, T.; Hamano, T.; Tsuchihara, R.; Higashimura, T. Macromolecules 1989, 22, 1036. 15. Masuda, T.; Yoshimura, T.; Fujimori, J.; Higashimura, T. J. Chem. Soc., Chem. Commun. 1987, 1805.

16. Masuda, T.; Isobe, E . ; Higashimura, T.; Takada, K. J. Am. Chem. Soc. 1983, 105, 7473. 17. Masuda, T.; Isobe, E.; Higashimura, T. Macromolecules 1985, 18, 841. 18. Masuda, T.; Isobe, E.; Hamano, T.; Higashimura, T. Macromolecules 1986, 19, 2448. 19. Fujimori, J.; Masuda, T.; Higashimura, T. Polym. Rull. 1988, 20, 1. 20. Masuda, T.; Isobe, E.; Hamano, T.; Higashimura, T. J. Polym. Sci., Polym. Chem. Ed. 1987, 25, 1353.

21. Isobe, E.; Masuda, T.; Higashimura, T.; Yamamoto, A. J. Polym. Sci., Polym. Chem. Ed. 1986, 24, 1839.

22. Masuda, T.; Tang, B.-Z.; Higashimura, T.; Yamaoka, H . Macromolecules 1985, 18, 2369.


35.


Silicon-Containing

661

Polyacetylenes

23. Masuda, T.; Tang, B.-Z.; Tanaka, Α.; Higashimura, T. Macromolecules 1986, 19, 1459. 24. Masuda, T.; Tang, B.-Z.; Matsumoto, T.; Higashimura, T., to be published. 25. Industrial Gas Separations; Whyte, T. E., Jr.; Yon, C.M., Wagener, Ε. H., Eds.; ACS Symposium Series 223; American Chemical Society: Washington, DC, 1983. 26. Takada, K.; Matsuya, H . ; Masuda, T.; Higashimura, T.J. Appl. Polym. Sci. 1985, 30, 1605. 27. Masuda, T.; Iguchi, Y.; Tang, B.-Z.; Higashimura, T. Polymer 1988, 29, 2041. 28. Shimomura, H.; Nakanishi, K.; Odani, H . ; Kurata, M . ; Masuda, T.; Higashi


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RECEIVED

29. Frennesson, I.; Tragardh, G.; Hahn-Hagerdal, B. Chem. Eng. Commun. 1986, 45, 277. 30. Masuda, T.; Tang, B.-Z.; Higashimura, T. Polym. J. (Tokyo) 1986, 18, 565. 31. Ichiraku, Y.; Stern, S. Α.; Nakagawa, T. J. Membr. Sci. 1987, 34, 5. 32. Langsam, M.; Robeson, L. M . Polym. Prepr. (Am. Chem. Soc., Div. Polym.

Chem.) 1988, 29(1), 112. 33. Masuda, T. Maku 1988, 13, 195. 34. Tang, B.-Z.; Masuda, T.; Higashimura, T. J. Polym. Sci., Polym. Phys. Ed. 1989, 27, 1261. 35. Ishihara, K.; Nagase, Y.; Matsui, K. Makromol. Chem., Rapid Commun. 1986,

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for

review

1988.

May

27,

1988.

ACCEPTED

revised

manuscript

December


7,

Synthesis and Properties of Silicon-Containing Polyacetylenes

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