입체규칙도가 우수한 고활성 이에스테르 촉매에 의한 프로필렌중합에서 외부 전자공여체의 영향

김일; 우성일

Polymer(Korea), Vol.15, No.4, 417-424, August, 1991

The Effect of External Electron Donors on the Polymerization of Propylene over a Highly Isospecific and Active Diester Catalyst

김일, 우성일

초록

이에톡시마그네슘을 사부톡시티탄, 무수프탈산 및 염화티탄과 반응시켜 내부전자공여체로서 이에스터르가 포함된 새로운 염화마그넥슘 담지 염화티탄촉매를 제조하였다. 이 촉매를 삼에틸알루미늄을 공촉매로하여 프로필렌중합에 이용할 경우 활성이 대단히 높고 입체규칙도가 뛰어났다. 외부전자공여체가 촉매의 촬성 및 입체규칙도에 미치는 영향을 조사하기 위하여 삼에톡시페닐실란(PTES). 에릴벤조이트(EB), 테트라히드로푸란(THF)과 같은 외부전자공여체(ED)를 촉매에 첨가하여 프로필렌 중합을 수행하였다. 또한 이들 전자공여체를 첨가하지 않았을 때와 첨가하였을 때의 활성점의 수를 일산화탄소 흡착법을 이용하여 측정하였다. 실험격과 PTES를 외부전자공여체로 사용하였을 때 입체규칙도가 우수할 뿐만 아니라 높은 활성도를 보였다. PTES를 공촉매용액에 첨가함으로써 입체적으로 불규칙한 활활성점들이 입체규칙 활성점으로 전환되었으며 중합활성점들이 안정화되었다.

A new MgCl₂-supported TiC1₂ catalyst with a diester as an internal donor was prepared from the reactions of Mg(OEt)₂ a with Ti(OBu)₄, phthalic anhydride. and TiCl₄. The catalyst combined with AlEt₃ showed very high activity and isospecificity for the propylene polymerizations. In order to investigate the effects of external donor (ED) on the productivity and the isospecificity of the catalyst, the polymerization of propylene was carried out by modifying this catalyst with various external donors such as phenytriethoxy silane (PTES), ethyl benzoate(EB), and tetrahydrofuran (THF) The number of active sites was also determined by the CO inhibition method in the absence and presence of external donors. The results showed that PTES is the best external donor in that it produced highly isotactic polypropylene, in association with high activity of the rata]pest. The addition of PTES to the coatalyst solution not only transformed atactic sites to isotactic ones, but stabilized polymerization centers so that the active sites deactivated less sharply.

[References]

U.S. Patent, 4,107,413
Ger. Patent, 2,029,992, Montedison
Japan Patent, 75-126,590
Japan Patent, 77-151-691, Mitsui Petrochem.
Pino P, Mulhaupt R, Angew. Chem.-Int. Edit., 19, 857 (1980)
Soga K, Sano T, Yamamoto K, Shiono T, Chem. Lett., 425 (1982)
Hu Y, Chien JCW, J. Polym. Sci. A: Polym. Chem., 26, 2003 (1988)
Kissin YV, Sivak AJ, J. Polym. Sci. A: Polym. Chem., 22, 3747 (1984)
Kim I, Woo SI, Polym. Bull., 23, 35 (1990)
Jeong YT, Lee DH, Makromol. Chem., 191, 1487 (1990)
Karol FJ, Catal. Rev.-Sci. Eng., 26, 557 (1984)
Parodi S, Nocci R, Giannini U, barbe PK, Sacata U, Japan Patent, 57-63310 (1982)
Kioka M, Kashiwa N, Japan Patent, 58-83006 (1983)
Terano M, Soga H, Kimura K, inoue M, Miyosh K, Japan Patent, 60-23404 (1985)
Busico V, Corradini P, Proto A, Savino V, Makromol. Chem., 186, 1279 (1985)
Seppala JV, Harkonen M, Luciani L, Makromol. Chem., 190, 2535 (1989)
Kashiwa N, Yoshitake J, Toyota A, Polym. Bull., 19, 333 (1988)
Kim I, Kim JH, Woo SI, J. Appl. Polym. Sci., 39, 837 (1990)
Caunt AD, Br. Polym. J., 13, 22 (1981)
Kim I, Woo SI, Makromol. Chem., in press
Soga K, Shiono T, "Transition Metal Caalyzed Polymerization," R.P. Quirk, Ed., Cambridge University Press, New York (1988)
Bradley DC, Mehrotra RC, Gaur DP, "Metal Alkoxides," Academic Press, London (1978)
Wang H, Jiang R, Fu Z, Zhang S, Gao B, "Transition Metal Catalyzed Polymerization," R.P. Quirk, Ed., Cmabridge University Press, New York (1988)
Keii T, Suzuki E, Tamura M, Murata M, Doi Y, Makromol. Chem., 183, 2285 (1982)
Sormunen P, Pakkanen TT, Vahasarja E, Iiskola E, "Catalytic Olefin Polymerization," T. Keii and K. Soga, Ed., Elsevier, Amsterdam (1990)
Spitz R, Lacombe JL, Primet M, J. Polym. Sci. A: Polym. Chem., 22, 2611 (1984)
Kim I, Chung MC, Choi HK, Kim JH, Woo SI, "Catalytic Olefin Polymerization," T. Keii and K. Soga, Ed., Elsevier, Amsterdam (1990)
Chien JCW, Bres P, J. Polym. Sci. A: Polym. Chem., 24, 1967 (1986)

[Referenced By]

[1] U.S. Patent, 4,107,413

[2] Ger. Patent, 2,029,992, Montedison

[3] Japan Patent, 75-126,590

[4] Japan Patent, 77-151-691, Mitsui Petrochem.

[5] Pino P, Mulhaupt R, Angew. Chem.-Int. Edit., 19, 857 (1980)

[6] Soga K, Sano T, Yamamoto K, Shiono T, Chem. Lett., 425 (1982)

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

[8] Kissin YV, Sivak AJ, J. Polym. Sci. A: Polym. Chem., 22, 3747 (1984)

[9] Kim I, Woo SI, Polym. Bull., 23, 35 (1990)

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

[11] Karol FJ, Catal. Rev.-Sci. Eng., 26, 557 (1984)

[12] Parodi S, Nocci R, Giannini U, barbe PK, Sacata U, Japan Patent, 57-63310 (1982)

[13] Kioka M, Kashiwa N, Japan Patent, 58-83006 (1983)

[14] Terano M, Soga H, Kimura K, inoue M, Miyosh K, Japan Patent, 60-23404 (1985)

[15] Busico V, Corradini P, Proto A, Savino V, Makromol. Chem., 186, 1279 (1985)

[16] Seppala JV, Harkonen M, Luciani L, Makromol. Chem., 190, 2535 (1989)

[17] Kashiwa N, Yoshitake J, Toyota A, Polym. Bull., 19, 333 (1988)

[18] Kim I, Kim JH, Woo SI, J. Appl. Polym. Sci., 39, 837 (1990)

[19] Caunt AD, Br. Polym. J., 13, 22 (1981)

[20] Kim I, Woo SI, Makromol. Chem., in press

[21] Soga K, Shiono T, "Transition Metal Caalyzed Polymerization," R.P. Quirk, Ed., Cambridge University Press, New York (1988)

[22] Bradley DC, Mehrotra RC, Gaur DP, "Metal Alkoxides," Academic Press, London (1978)

[23] Wang H, Jiang R, Fu Z, Zhang S, Gao B, "Transition Metal Catalyzed Polymerization," R.P. Quirk, Ed., Cmabridge University Press, New York (1988)

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

[25] Sormunen P, Pakkanen TT, Vahasarja E, Iiskola E, "Catalytic Olefin Polymerization," T. Keii and K. Soga, Ed., Elsevier, Amsterdam (1990)

[26] Spitz R, Lacombe JL, Primet M, J. Polym. Sci. A: Polym. Chem., 22, 2611 (1984)

[27] Kim I, Chung MC, Choi HK, Kim JH, Woo SI, "Catalytic Olefin Polymerization," T. Keii and K. Soga, Ed., Elsevier, Amsterdam (1990)

[28] Chien JCW, Bres P, J. Polym. Sci. A: Polym. Chem., 24, 1967 (1986)