알코올-활성화된 MgCl<sub>2</sub>담지 TiCl<sub>4</sub>촉매에 의한 프로필렌의 중합 ; 촉매제조 조건

이동호; 이주홍; 노석균; 정영태

Polymer(Korea), Vol.18, No.4, 439-447, July, 1994

Export Citation

알코올-활성화된 MgCl₂담지 TiCl₄촉매에 의한 프로필렌의 중합 ; 촉매제조 조건

Propylene Polymerization with Alcohol-activated MgCl₂-supported TiCl₄ Catalyst Preparation

이동호, 이주홍, 노석균, 정영태

초록

Ethanol(EtOH), 2-methyl-1-propanol(i-BuOH), 2-ethyl-1-hexanol(EHA) 등을 Mgcl₂의 용매로 사용하고 용액상 또는 침전상으로 담지 TiCl₄중합촉매를 제조하여 프로필렌을 중합할 때에, 촉매제조 조건 즉 알코올의 종류, 용제인 xylene과 n-hexane, 반응온도, TiC1₄ 재처리, 촉매세척 등이 촉매의 활성과 입체규칙성에 미치는 영향을 조사하였다. MgCl₂용매로 EHA를 사용하였을 경우에 가장 큰 촉매활성을 나타내었으며, n-hexane으로 MgCl₂용액을 묽혀 주는 것이 촉매제조상의 용이함 뿐만 아니라 활성증가의 면에서 유리하였다. EtOH에 용해된 MgCl₂는 n-hexane으로 침전되고 재침전된 MgCl₂에서 얻은 촉매의 활성과 입체규칙성이 향상되었으며, 용제로 xylene을 사용하는 것이 촉매제조에 편리하였다. MgCl₂를 용액상으로 TiCl₄와 반응시켜 촉매를 제조할 경우에 저온에서 얻은 촉매의 활성과 입체규칙성이 우세하였으나, 침전상으로 반응하여 얻은 촉매의 거동은 반응온도에 거의 무관하였다. 제조한 촉매를 TiCl로 재처리하면 활성과 입체 규칙성이 향상되었으면, 촉매의 세척제로 1,2-dichloroehane을 사용하면 입체규칙성이 증가되었다.

For the preparation of supported TiCl₄ catalysts, MgCl₂ was dissolved in ethanol, i-butanol or 2-ethyl-1-hexanol(EHA) and used as solution pr after precipitaion. The effects of various preparation conditions on catalyst behaviors have been studied for propylene polymerization. EHA solvent gave highesl. activity and n-hexane diluent showed advantages for not only easy handing but high activity. MgC1₂ dissolved in ethanol could be precipitated with n-hexane and the catalyst prepared from reprecipitated MgCl₂ improved its activity and isospecificity. Retreatment of prepared catalyst with TiCl₄ resutlted in high activity as well as stereoregularity and 1,2-dichloroethane was a suitble washing medium for high stereogularity

[References]

Japanese Kokai 78,118,290 (1978)
Chem. Abs., 90(104), 663 (1978)
German Offen 2,638,429 (1977)
Chem. Abs., 86(107), 244 (1977)
Kashiwa N, Mizuno A, Minami S, Polym. Bull., 12, 105 (1984)
Yano T, Ikai S, Shimazu M, J. Polym. Sci. A: Polym. Chem., 23, 1455 (1985)
Burkhardt TJ, Langer AW, Barist A, Funk WG, "Transition Metal Catalyzed POlymerization," ed. by R.P. Quirk, p. 227, Harwood Academic Publishers, New York (1983)
Lee DH, Min KE, Ha KR, Jo WH, Polym.(Korea), 11(3), 278 (1987)
Do JG, Jeong YT, Lee DH, Polym.(Korea), 14(3), 240 (1990)
Lee DH, Song KC, Jeong YT, Ha KR, Polym.(Korea), 16(1), 61 (1992)
Jeong YT, Lee DH, Makromol. Chem., 191, 1487 (1990)
Hu Y, Chien JCW, J. Polym. Sci. A: Polym. Chem., 26, 2003 (1988)
Hu Y, Vizzini JC, Chien JCW, J. Polym. Sci. A: Polym. Chem., 28, 273 (1990)
Jeong YT, Lee DH, Soga K, Makromol. Chem. Rapid Commun., 12, 5 (1991)
Ittel SD, Mulhaupt R, Klabunde U, J. Polym. Sci. A: Polym. Chem., 24, 3447 (1986)
Lee DH, Kim JT, Jeong YT, Polym.(Korea), 16(4), 451 (1992)
Hogan JP, J. Polym. Sci. A: Polym. Chem., 6, 2637 (1970)
Karol FJ, Karapinka GL, J. Polym. Sci. A: Polym. Chem., 10, 2621 (1972)
Japanese Kokai 82,170,907 (1982)
Chem. Abs., 98(126), 816 (1983)
Japanese Kokai 82,158,204 (1982)
Chem. Abs., 98(107), 954 (1983)
Spitz R, Bobichon C, Daranel L, Guyot A, "Catalytic Olefin Polymerization," ed. by T. Keii and K. Soga, p. 107, Kodansha-Elsevier, Tokyo (1990)
Busico V, Corradini P, Makromol. Chem., 186, 1279 (1986)

[Referenced By]

[1] Japanese Kokai 78,118,290 (1978)

[2] Chem. Abs., 90(104), 663 (1978)

[3] German Offen 2,638,429 (1977)

[4] Chem. Abs., 86(107), 244 (1977)

[5] Kashiwa N, Mizuno A, Minami S, Polym. Bull., 12, 105 (1984)

[6] Yano T, Ikai S, Shimazu M, J. Polym. Sci. A: Polym. Chem., 23, 1455 (1985)

[7] Burkhardt TJ, Langer AW, Barist A, Funk WG, "Transition Metal Catalyzed POlymerization," ed. by R.P. Quirk, p. 227, Harwood Academic Publishers, New York (1983)

[8] Lee DH, Min KE, Ha KR, Jo WH, Polym.(Korea), 11(3), 278 (1987)

[9] Do JG, Jeong YT, Lee DH, Polym.(Korea), 14(3), 240 (1990)

[10] Lee DH, Song KC, Jeong YT, Ha KR, Polym.(Korea), 16(1), 61 (1992)

[11] Jeong YT, Lee DH, Makromol. Chem., 191, 1487 (1990)

[12] Hu Y, Chien JCW, J. Polym. Sci. A: Polym. Chem., 26, 2003 (1988)

[13] Hu Y, Vizzini JC, Chien JCW, J. Polym. Sci. A: Polym. Chem., 28, 273 (1990)

[14] Jeong YT, Lee DH, Soga K, Makromol. Chem. Rapid Commun., 12, 5 (1991)

[15] Ittel SD, Mulhaupt R, Klabunde U, J. Polym. Sci. A: Polym. Chem., 24, 3447 (1986)

[16] Lee DH, Kim JT, Jeong YT, Polym.(Korea), 16(4), 451 (1992)

[17] Hogan JP, J. Polym. Sci. A: Polym. Chem., 6, 2637 (1970)

[18] Karol FJ, Karapinka GL, J. Polym. Sci. A: Polym. Chem., 10, 2621 (1972)

[19] Japanese Kokai 82,170,907 (1982)

[20] Chem. Abs., 98(126), 816 (1983)

[21] Japanese Kokai 82,158,204 (1982)

[22] Chem. Abs., 98(107), 954 (1983)

[23] Spitz R, Bobichon C, Daranel L, Guyot A, "Catalytic Olefin Polymerization," ed. by T. Keii and K. Soga, p. 107, Kodansha-Elsevier, Tokyo (1990)

[24] Busico V, Corradini P, Makromol. Chem., 186, 1279 (1986)