SiO2Mg(OEt)2/Ethyl Benzoate/TiCl4촉매에 의한 프로필렌 중합특성연구

정동욱; 최홍기; 한택규; 우성일; 성준용; 노중석

HWAHAK KONGHAK, Vol.31, No.5, 556-562, October, 1993

Export Citation

SiO₂Mg(OEt)₂/Ethyl Benzoate/TiCl₄촉매에 의한 프로필렌 중합특성연구

A Study on Propylene Polymerization with SiO₂/Mg(OEt)₂/Ethyl Benzoate/TiCl₄ Catalysts

정동욱, 최홍기, 한택규, 우성일, 성준용, 노중석

초록

구형의 모양이고, 입자크기 분포가 고른 실리카(Davison-952)에 담지된 폴리프로필렌 중합용 촉매 SiO₂/Mg-(OEt)₂/ethyl benzoate/TiCl₄를 합성하였다. 외부전자공여체인 p-ethoxy ethyl benzoate(PEEB)와 공촉매인 tri-ethylaluminum(TEA)의 양의 변화에 따라, 8atm의 고압, 헵탄 슬러리상으로 프로필렌을 중합하여, 활성과 입체규칙성에 대한 TEA, PEEB의 영향을 고찰하였다. 또한 온도변화에 따른 활성과 입체규칙성의 변화를 고찰하였다. TEA/Ti 몰비가 200이고, 온도가 70℃에서 1시간 동안의 평균 최대 활성을 가지며, TEA의 양이 증가함에 따라 I.I.(isotactic index)값이 감소하며, 온도변화에 따른 I.I. 변화는 없었다. [TEA]/[Ti]=200, 온도 70℃로 하였을 때 1시간 동안의 평균 중합속도는 16.2kg-PP/g-Tiㆍhrㆍatm이고, I.I.는 84%였다. 그런데 같은 온도, 같은 TEA 양의조건에서 외부전자공여체인 PEEB를 [PEEB]/[Al]=0.17로 첨가하여 중합하였을 때, 활성은 12.4kg-PP/g-Tiㆍhrㆍatm으로 감소하였으나, 입체규칙성을 93%로 향상되었다. 또한 [PEEB]/[Al]=0.25일 때 활성은 5.2kg-PP/g-Tiㆍhrㆍatm로 감소하고 입체규칙성은 96%로 증가하였다.

SiO₂/Mg(OEt)₂/ethyl benzoate/TiCl₄ catalysts need for propylene polymerization were prepared by using silica(Davison-952) as a support, which is known to produce polypropylene with spherical shape and narrow particle size distribution. Propylene polymerization was carried out with the silica supported catalyst cocatalyzed with triethylaluminum(TEA) in the presence of an external electron donor(EED), p-ethoxy ethyl benzoate(PEEB) at 8atm. The effect of TEA, PEEB concentration and polymerization temperature on activity as well as stereospecificity was investigated. The maximum average polymerization rate during the initial first hour of polymerization was obtained at the mole ratio of [TEA]/[Ti]=200 and 70℃. The increase of TEA concentration decreased stereospecificity. As the polvmerization temperature increased, the stereo-specificity did not change. The polymerization activity in the absence of PEEB was 16.2kg-PP/g Ti-hrㆍatm and the isotactic indox was 84% at the molar ratio of TEA to Ti of 200 and 70℃. However, the activity decreased to 12.4kg-PP/g-Tiㆍhrㆍatm and isotactic index increased to 93% at the same polymerization condi-tion except for the addition of PEEB of which amount is 17% of [TEA]. Further addition of PEEB([PEEB]/[Al]=0.25) decreased the activity to 5.2kg-PP/g-Tiㆍhrㆍatm and increased isotactic index to 96%.

[References]

Michael S, Volker D, Ger. Offen. DE 3,819,577 (1988)
Galli P, Luciani L, Cecchini C, Makromol. Chem., 94, 63 (1981)
Hussein FD, Gaines DM, Liu HT, Miller DJ, Eur. Patent, Appl. EP 251,100 (1988)
Ebara T, Sasaki T, Kawai K, Eur. Patent, Appl. EP 376,084 (1990)
Kelland JW, Eur. Patent, Appl. EP 371,644 (1990)
Terano M, Soga H, Inoue M, Jpn Kakai Tokyo Koho JP 63,185,007 (1988)
Matsuura M, Fujita T, Eur. Patent, Appl. EP 299,712 (1989)
Nestierode SM, Eur. Patent, Appl. EP 0,236,082 (1987)
Kim I, Woo SI, Polym.(Korea), 15(4), 417 (1991)
Kim I, Woo SI, Polym.(Korea), 16(5), 570 (1992)
Chiang R, J. Polym. Sci. A: Polym. Chem., 35, 235 (1958)
Tait PJT, Watkins ND, "Comprehensive Polymer Science," ed. Allen, G., 533 (1989)
Zahkarov VA, Burkatov GD, Chumaevskii NB, Yermakov YI, Makromol. Chem., 178, 967 (1977)
Pusico U, Corradini P, Proto A, Makromol. Chem., 187, 1125 (1986)
Kashiwa N, Yoshitake J, Tsutsui T, "Transition Metal and organometallics as Catalysts for Olefin Polymerization," ed., Kaminsky, W. and Sinn, H., 33 (1988)
Tait PJT, Jaber IA, "Catalytic Olefin Polymerization," ed., Keii, T. and Soga, K., 11 (1989)
Keii T, Suzuki E, Tamura M, Murata M, Doi Y, Makromol. Chem., 183, 2285 (1982)
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Han JD, Kim I, Woo SI, Polym.(Korea), 13(2), 147 (1989)
Keii T, Soga K, Saiki N, J. Polym. Sci. C: Polym. Lett., 16, 1507 (1967)
Spitz R, Lacombe JL, Guyot A, J. Polym. Sci. A: Polym. Chem., 22, 2625 (1984)
Han JD, Kim JH, Kim I, Woo SI, HWAHAK KONGHAK, 27(2), 206 (1989)
Spitz R, Lacombe JL, Primet M, Guyot A, "Transition Metal Catalyzed Polymerization: Alkens and Diens, Part A," ed., Quirk, R., Harwood Academic Pub. New York, 389 (1983)
Keii T, Suzuki E, Tamura M, Doi Y, "Transition Metal Catalyzed Polymerization: Alkens and Diens, Part A," ed., Quirk, R., Harwood Academic Pub. New York, 97 (1983)
Sacchi MC, Tritto I, Locatelli P, Eur. Polym. J., 24, 137 (1988)
Barbe PC, Noristi L, Schexnayder MA, "Advances in Polyolefins," ed., Seymour, R.B. and Cheng, T., Plenum Press, New York, 2285 (1987)
Goodall BL, MMI. Int. Symp. "Transition Metal Catalyzed Polymerization: Unsolved Problem," Midland (1981)
Coutinho FMB, Maria LS, Polym. Bull., 26, 535 (1991)
Soga K, Park JR, "Catalytic Olefin Polymerization," 131 (1989)
Kashiwa N, Yoshitake J, Polym. Bull., 12, 99 (1984)

[Referenced By]

[1] Michael S, Volker D, Ger. Offen. DE 3,819,577 (1988)

[2] Galli P, Luciani L, Cecchini C, Makromol. Chem., 94, 63 (1981)

[3] Hussein FD, Gaines DM, Liu HT, Miller DJ, Eur. Patent, Appl. EP 251,100 (1988)

[4] Ebara T, Sasaki T, Kawai K, Eur. Patent, Appl. EP 376,084 (1990)

[5] Kelland JW, Eur. Patent, Appl. EP 371,644 (1990)

[6] Terano M, Soga H, Inoue M, Jpn Kakai Tokyo Koho JP 63,185,007 (1988)

[7] Matsuura M, Fujita T, Eur. Patent, Appl. EP 299,712 (1989)

[8] Nestierode SM, Eur. Patent, Appl. EP 0,236,082 (1987)

[9] Kim I, Woo SI, Polym.(Korea), 15(4), 417 (1991)

[10] Kim I, Woo SI, Polym.(Korea), 16(5), 570 (1992)

[11] Chiang R, J. Polym. Sci. A: Polym. Chem., 35, 235 (1958)

[12] Tait PJT, Watkins ND, "Comprehensive Polymer Science," ed. Allen, G., 533 (1989)

[13] Zahkarov VA, Burkatov GD, Chumaevskii NB, Yermakov YI, Makromol. Chem., 178, 967 (1977)

[14] Pusico U, Corradini P, Proto A, Makromol. Chem., 187, 1125 (1986)

[15] Kashiwa N, Yoshitake J, Tsutsui T, "Transition Metal and organometallics as Catalysts for Olefin Polymerization," ed., Kaminsky, W. and Sinn, H., 33 (1988)

[16] Tait PJT, Jaber IA, "Catalytic Olefin Polymerization," ed., Keii, T. and Soga, K., 11 (1989)

[17] Keii T, Suzuki E, Tamura M, Murata M, Doi Y, Makromol. Chem., 183, 2285 (1982)

[18] Burfield DR, McKenzie ID, Tait PJT, Polymer, 13, 302 (1972)

[19] Han JD, Kim I, Woo SI, Polym.(Korea), 13(2), 147 (1989)

[20] Keii T, Soga K, Saiki N, J. Polym. Sci. C: Polym. Lett., 16, 1507 (1967)

[21] Spitz R, Lacombe JL, Guyot A, J. Polym. Sci. A: Polym. Chem., 22, 2625 (1984)

[22] Han JD, Kim JH, Kim I, Woo SI, HWAHAK KONGHAK, 27(2), 206 (1989)

[23] Spitz R, Lacombe JL, Primet M, Guyot A, "Transition Metal Catalyzed Polymerization: Alkens and Diens, Part A," ed., Quirk, R., Harwood Academic Pub. New York, 389 (1983)

[24] Keii T, Suzuki E, Tamura M, Doi Y, "Transition Metal Catalyzed Polymerization: Alkens and Diens, Part A," ed., Quirk, R., Harwood Academic Pub. New York, 97 (1983)

[25] Sacchi MC, Tritto I, Locatelli P, Eur. Polym. J., 24, 137 (1988)

[26] Barbe PC, Noristi L, Schexnayder MA, "Advances in Polyolefins," ed., Seymour, R.B. and Cheng, T., Plenum Press, New York, 2285 (1987)

[27] Goodall BL, MMI. Int. Symp. "Transition Metal Catalyzed Polymerization: Unsolved Problem," Midland (1981)

[28] Coutinho FMB, Maria LS, Polym. Bull., 26, 535 (1991)

[29] Soga K, Park JR, "Catalytic Olefin Polymerization," 131 (1989)

[30] Kashiwa N, Yoshitake J, Polym. Bull., 12, 99 (1984)