폴리(1-비닐-2-트리메틸실릴아세틸렌)의 합성과 특성

갈영순; 정발; 최삼권

Polymer(Korea), Vol.14, No.4, 361-370, August, 1990

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폴리(1-비닐-2-트리메틸실릴아세틸렌)의 합성과 특성

Synthesis and Properties of Poly(1-phenyl-2-trimethyl-silylacetylene)

갈영순, 정발, 최삼권

초록

여러가지 전이금속 촉매에 의해서 1-페닐-2-트리메틸실릴아세틸렌을 중합시킨 결과 WCl₆에 대한 단량체의 몰비와 WCl₆에 대한 Me₄Sn의 몰비가 각각 50과 1일때 가장 좋은 중합수율을 보였다. NMR, IR, UV-Visible 스펙트라등을 분석한 결과 합성한 중합체는 어느 정도 트리메틸실릴 기가 떨어진 부분을 포함하는 선형 공액구조의 중합체임을 알 수 있었다. 이 중합체는 클로로포름, 벤젠, 사염화탄소와 같은 방향성 혹은 할로겐화 탄화수소 용매에 완전히 용해하였다. THF 용매에서 (n-Bu)₄N⁺F^-에 의한 폴리 (1-페닐-2-트리메틸실리아세틸렌)의 디실릴레이션 반응결과 실릴기가 없는 폴리(페닐아세틸렌)을 합성할 수 있있다.

The polymerization of 1-phenyl-2-trimethylsilylacetylene was carried out using various transition metal catalysts. The best result was obtained when the mole ratios of monomer to WCl₆ and Me₄Sn to WCl₆ were 50 and 1, respectively. WCl₆-based catalysts were more effective than MoCl₅-based catalysts. The NMR, IR, and UV-visible spectra indicated that the resulting polymer has a linear conjugated polyene containing some desily1ated portion. This polymer is completely soluble in aromatic and halogenated hydrocarbons such as chloroform, benzene. CCl₄, etc. The desilylation reaction of poly(1-phenol-2-trimethylsilylacetylene) by (n-Bu)₄N⁺F^- in THF give a completely desilylated one, i. e. poly(phenylacetylene).

[References]

Simionescu CI, Pearce V, Dumitrescu S, J. Polym. Sci. A: Polym. Chem., 16, 2497 (1977)
Watson WH, McMordie WC, Lands LG, J. Polym. Sci., 55, 137 (1961)
Chiang AC, Waters PF, Aldridge MH, J. Polym. Sci. A: Polym. Chem., 20, 1807 (1982)
Akopyan LA, Ambartsumyan GV, Ovakimyan EV, Matsoyan SG, Vysokomol. Soyed., A19, 271 (1977)
Chauser MG, Rodionov YM, Misin VM, Cherkashin MI, Russ. Chem. Rev., 45, 348 (1976)
Dandliker G, Helv. Chim. Acta, 52, 1482 (1969)
Masuda T, Mouri T, Higashimura T, Bull. Chem. Soc. Jpn., 53, 1152 (1980)
Masuda T, Takahashi T, Higashimura T, J. Chem. Soc.-Chem. Commun., 1297 (1982)
Gal YS, Cho HN, Choi SK, Polym.(Korea), 9(5), 361 (1985)
Gal YS, Choi SK, Polym.(Korea), 11(6), 563 (1987)
Gal YS, Choi SK, J. Polym. Sci. C: Polym. Lett., 26, 115 (1988)
Kim YH, Gal YS, Kim UY, Choi SK, Macromolecules, 21, 1991 (1988)
Kim YH, Choi KY, Choi SK, J. Polym. Sci. C: Polym. Lett., 27, 443 (1989)
Cho OK, Kim YH, Choi KY, Choi SK, Macromolecules, 23, 12 (1990)
Masuda T, Isobe E, Higashimura T, Takada K, J. Am. Chem. Soc., 105, 7473 (1983)
Takada K, Matsuya H, Masuda T, Higashimura T, J. Appl. Polym. Sci., 30, 1605 (1985)
Kita H, Sakamoto T, Tanaka K, Okamoto K, Polym. Bull., 20, 349 (1988)
Shimomura H, Nakanishi K, Odani H, Kurata M, Masuda T, Higashimura T, Kobunshi Ronbunshu, 43, 747 (1986)
Nagase Y, Mori S, Matsui K, J. Appl. Polym. Sci., 37, 1259 (1989)
Gal YS, Choi SK, J. Polym. Sci. A: Polym. Chem., 25, 2323 (1987)
Seyferth D, Vaughan LG, Suzuki R, J. Org. Chem., 1, 437 (1964)
Gal YS, Cho HN, Choi SK, J. Polym. Sci. A: Polym. Chem., 24, 2021 (1986)
Gal YS, Cho HN, Choi SK, Polym.(Korea), 10(7), 688 (1986)
Gal YS, Cho HN, Kwon SK, Choi SK, Polym.(Korea), 12(1), 30 (1988)
Fleming I, "Comprensive Organic Chemistry," Vol. 3, pp. 541-686, Pergamon, Oxford (1979)
Ziegler JM, Polym. Prepr., 25, 223 (1984)
Okano Y, Masuda T, Higashimura T, J. Polym. Sci. A: Polym. Chem., 22, 1603 (1984)
Gal YS, Choi SK, unpublished results

[Referenced By]

[1] Simionescu CI, Pearce V, Dumitrescu S, J. Polym. Sci. A: Polym. Chem., 16, 2497 (1977)

[2] Watson WH, McMordie WC, Lands LG, J. Polym. Sci., 55, 137 (1961)

[3] Chiang AC, Waters PF, Aldridge MH, J. Polym. Sci. A: Polym. Chem., 20, 1807 (1982)

[4] Akopyan LA, Ambartsumyan GV, Ovakimyan EV, Matsoyan SG, Vysokomol. Soyed., A19, 271 (1977)

[5] Chauser MG, Rodionov YM, Misin VM, Cherkashin MI, Russ. Chem. Rev., 45, 348 (1976)

[6] Dandliker G, Helv. Chim. Acta, 52, 1482 (1969)

[7] Masuda T, Mouri T, Higashimura T, Bull. Chem. Soc. Jpn., 53, 1152 (1980)

[8] Masuda T, Takahashi T, Higashimura T, J. Chem. Soc.-Chem. Commun., 1297 (1982)

[9] Gal YS, Cho HN, Choi SK, Polym.(Korea), 9(5), 361 (1985)

[10] Gal YS, Choi SK, Polym.(Korea), 11(6), 563 (1987)

[11] Gal YS, Choi SK, J. Polym. Sci. C: Polym. Lett., 26, 115 (1988)

[12] Kim YH, Gal YS, Kim UY, Choi SK, Macromolecules, 21, 1991 (1988)

[13] Kim YH, Choi KY, Choi SK, J. Polym. Sci. C: Polym. Lett., 27, 443 (1989)

[14] Cho OK, Kim YH, Choi KY, Choi SK, Macromolecules, 23, 12 (1990)

[15] Masuda T, Isobe E, Higashimura T, Takada K, J. Am. Chem. Soc., 105, 7473 (1983)

[16] Takada K, Matsuya H, Masuda T, Higashimura T, J. Appl. Polym. Sci., 30, 1605 (1985)

[17] Kita H, Sakamoto T, Tanaka K, Okamoto K, Polym. Bull., 20, 349 (1988)

[18] Shimomura H, Nakanishi K, Odani H, Kurata M, Masuda T, Higashimura T, Kobunshi Ronbunshu, 43, 747 (1986)

[19] Nagase Y, Mori S, Matsui K, J. Appl. Polym. Sci., 37, 1259 (1989)

[20] Gal YS, Choi SK, J. Polym. Sci. A: Polym. Chem., 25, 2323 (1987)

[21] Seyferth D, Vaughan LG, Suzuki R, J. Org. Chem., 1, 437 (1964)

[22] Gal YS, Cho HN, Choi SK, J. Polym. Sci. A: Polym. Chem., 24, 2021 (1986)

[23] Gal YS, Cho HN, Choi SK, Polym.(Korea), 10(7), 688 (1986)

[24] Gal YS, Cho HN, Kwon SK, Choi SK, Polym.(Korea), 12(1), 30 (1988)

[25] Fleming I, "Comprensive Organic Chemistry," Vol. 3, pp. 541-686, Pergamon, Oxford (1979)

[26] Ziegler JM, Polym. Prepr., 25, 223 (1984)

[27] Okano Y, Masuda T, Higashimura T, J. Polym. Sci. A: Polym. Chem., 22, 1603 (1984)

[28] Gal YS, Choi SK, unpublished results