규소를 포함하는 사다리형 중합체의 합성 및 특성

김선일; 이봉우; 나재운; 송연호; 정일남

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.3, 369-376, June, 1995

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규소를 포함하는 사다리형 중합체의 합성 및 특성

Synthesis and Properties of Ladder Polymers Containing Silicon Atom

김선일, 이봉우, 나재운, 송연호, 정일남

초록

유기실리콘 중합체의 원료인 allyldichlorosilane(yield; 37.7%)을 구리촉매하에 alkyl chloride와 염화수소를 260℃에서 금속규소와 직접합성하는 방법을 연구 검토하였다. 0℃ 또는 실온에서 염화알루미늄 촉매하에서 여러 가지 치환기를 갖는 벤젠화합물과 allyldichlorosilane을 Friedel-Crafts 알킬화 반응시켜 3-Phenyl-1,1-dichloro-1-silabutane을 좋은 수율(78.2%)로 얻었다. 여러종의 단위체들(yield : 52∼78%)을 염화백금산 촉매하에서 3-phenyl-1,1-dichloro-1-silabutane과 olefins을 수소규소화 반응시켜 합성하였다. 단위체를 가수분해시켜 실리콘을 포함하는 사다리형 중합체의 최적반응조건은 0℃에서 THF와 물의 비를 5:2, 단위체의량을 0.05mo1e 비로 유지하면서 3시간 동안 격렬하게 교반하면서 반응시킨 경우 75∼93%의 좋은 수율로 얻었다. 중합체의 고온에 대한 열적특성은 실리콘에 두 개의 phenyl기가 치환된 중합체가 490℃로 가장 높았으며, 유리전이온도는 가교그룹의 길이가 길수록 Tg값이 낮아지는 경향성(-38∼-69℃)을 보였다.

Direct synthesis of allyldichlorosilane(yield; 37.7%) was investigated by reaction of elemental silicon simultaneously with allyl chloride and hydrogen chloride in the presence of copper catalyst at 260℃. 3-Phenyl-1,1-dichloro-1-silabutane was obtained in good yield(78.2%) by the Friedel-Crafts alkylation of the substituted benzenes with allyldichlorosilane in the presence of aluminum chloride at 0℃ or room temperature. Various monomers(yield : 52∼78%) were synthesized by hydrosilylation of 3-phenol-1,1-dichloro-1-silabutane with olefins in the presence of hexachloroplatinic acid catalyst. Synthesis and characterization of ladder polymers(yield : 75∼93%) containing silicon atom were investigated.

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[1] Hurd DT, J. Am. Chem. Soc., 67, 1813 (1945)

[2] Mironov VM, Zelinskii DN, Izv. Akad. Nauk. SSSR Otd. Khim., 8, 383 (1957)

[3] Yeon SH, Lee BW, Kim SI, Jung IN, Organometallics, 12, 4887 (1993)

[4] Balson M, Bull. Soc. Chim. France, 2, 539 (1897)

[5] Wagner GH, Bailey DL, Pines AN, Dunham ML, Mcinite DB, Ind. Eng. Chem., 45, 367 (1953)

[6] Nametkin NS, Vdovin VM, Finkel ES, Oppengeim VD, Chekalina NA, Izv. Akad. Nauk. SSSR. Ser. Khim., 11, 1998 (1966)

[7] Lee BW, Yoo BR, Kim SI, Jung IN, Organometallics, 13, 1312 (1994)

[8] Marcinied B, "Comprehensive Handbook on Hydrosilylation," Pergamon Press, Oxford (1982)

[9] Gordon F, Stone A, "Comprehensive Organometallic Chemistry," Pergamon Press, Oxford (1982)

[10] Farmer EM, J. Soc. Chem. Ind., 66, 86 (1947)

[11] Cundy CS, Kingston LA, Adv. Organometal. Chem. Acad., 12, 297 (1973)

[12] Speier JL, Webster JA, Bames GH, J. Am. Chem. Soc., 79, 974 (1957)

[13] Dohmaru T, Nagata Y, Tsurugi J, J. Am. Chem. Soc., 101, 1031 (1973)

[14] Eabon C, "Organosilicon Compounds," Butterworth, London (1960)

[15] Bazant V, Chvalovsky V, Ratousky J, Chemistry of organosilicon Compounds, Acad. Press, 1, 139, New York (1965)

[16] Freidlina RK, Tsao I, Chukovskaya ET, Dokl. Akad. Nauk. SSSR, 132, 149 (1960)

[17] Eabon C, Bott RW, "In the Bond to Carbon," Marcel Dekker, 1, 213, New York (1968)

[18] Speier JL, U.S. Patent, 2,971,864 (1961)

[19] Randolph CL, Wrighton MS, J. Am. Chem. Soc., 108, 3366 (1986)