고활성 염화마그네슘 담지 티탄촉매에 의한 에틸렌, 프로필렌, 1-부텐 및 스티렌 중합의 비교 연구

김일; 우성일

Polymer(Korea), Vol.15, No.3, 348-355, June, 1991

A Comparative Study on the Polymerization of Ethylene, Propylene, 1-Butene and Styrene over a Highly active MgCl₂-Supported Ticl₄ Catalyst

김일, 우성일

초록

Mg(OEt)₂를 Ti(OBu)₄, 무수프탈산 및 사염화티탄과 반응시켜 합성한 새로운 염화마그네슘 담지 염화티탄촉매를 AlEt₃/삼에톡시페닐실란(PTES)으로 활성화시켜 에틸렌, 프로필렌, 1-부텐 및 스티렌 중합거동에 대한 비교연구를 행하였다. 또한 슬러리상 중합에서 더욱 정확하게 활성을 비교하고 성장속도 상수(k_p)를 계산하기 위하여 용매 (노르말헵탄)에 대한 단량체들의 용해도를 측정하였다. 올레핀중합에 대한 활성도는 노르말헵탄에 용해된 단량체농도에 입각하여 보정하기 전후에 그 순서가 달라졌다. 폴리프로필렌(PP)과 폴리(1-부텐) (PB)의 입체규칙도(I.I.)는 PTES의 첨가로 크게 개선되었고 프로필렌과 1-부텐중합에 대한 속도-시간 곡선의 유사함으로 미루어 보아 프로필렌과 1-부텐에 대한 활성점의 성질이 서로 비슷한 것으로 짐작되었다. 활성점농도(C^*)의 측정결과 C^*와 k_p의 크기 순서는 에틸렌>프로필렌>1-부텐이었다. PTES의 첨가여부에 따른 스티렌중합의 거동(활성도 및 입체규칙도)으로부터 스티렌에 대한 입체규칙중합은 프로필렌 중합에서의 입체규칙도와는 상관없이 비균질 지글러-나타 촉매의 반응기구에 의해 진행됨을 알 수 있었다.

A comparative study has been made on the behaviors of ethylene, propylene, 1-butene and styrene polymerizations using a new MgCl₂-supported TiCl₄ catalyst prepared by the reaction of Mg(OEt)₂ with Ti(OBu)₄, phthalic anhydride and TiCl₄, in conjunction with AlEt₃ and phenyltriethoxy silane (PTES). Solubilities of monomers to a solvent (n-heptane) were also measured with a view to comparing the productivity of catalyst for each monomer and calculating the propagation rate constant (k_p) more exactly in slurry-phase polymerizations. The order of activity for olefin polymerizations was changed before and after normalization based on the concentration of monomer in n-heptane. The isotacticity (I.I.) of polypropylene (PP) and poly(1-butene) (PB) was remakably improved by PTES and simlar rate-time profiles were observed for propylene and 1-butene polymerizations, suggesting that the nature of active sites for both monomers is similar to each other. From the measurement of the number of active sites (C^*), it was clear that both C^* and k_p were in the order of ethylene > propylene > 1-butene. The results on styrene polymerizations (activity and isospecificity) in the absence and presence of PTES suggested that isotactic polymerization of styrene proceeds via heterogeneous Ziegler-Natta catalysts without regard to the I.I. in propylene polymerizations.

[References]

Zambelli A, Locatelli P, Sacchi MC, Rigamonti E, Macromolecules, 13, 798 (1980)
Zambelli A, Locatelli P, Sacchi MC, Tritto I, Macromolecules, 15, 831 (1982)
Busico V, Corradini P, "Transition Metal Catalyzed Polymerizations," R.P. Quirk, ed., Cambridge Univ. Press, New York, 551 (1988)
Pino P, Mulhaupt R, Angew. Makromol. Chem., 19, 857 (1980)
Barbe PC, Cecchin G, Noristi L, Adv. Polym. Sci., 81, 1 (1987)
Soga K, Shiono T, Doi Y, Makromol. Chem., 189, 1531 (1988)
Chien JCW, Hu Y, J. Polym. Sci. A: Polym. Chem., 26, 2003 (1988)
Chien JCW, Hu Y, J. Polym. Sci. A: Polym. Chem., 26, 2973 (1988)
Chien JCW, Hu Y, J. Polym. Sci. A: Polym. Chem., 27, 897 (1989)
Kim I, Woo SI, Polym.(Korea), to submitted (1988)
Kim I, Woo SI, Catalyst Prepared Based on Ger. Offen. DE 3,629,932 (1988)
Kashiwa N, Yoshitake J, Mizuno A, Polymer, 28, 1227 (1987)
Natta G, Makromol. Chem., 16, 213 (1955)
Starling KE, "Fluid Thermodynamic Properties for Light Petroleum Systems," Gulf Pub. Co., Houston, 139 (1973)
Natta G, Danusso F, Sianesi D, Makromol. Chem., 30, 238 (1959)
Zakharov VA, Buktov GD, Yermakov YI, Adv. Polym. Sci., 51, 61 (1983)
Busico V, Corradini P, DeMartino L, Albizzati E, Makromol. Chem., 183, 2285 (1982)
Keii T, Suzuki E, Tamura M, Murata M, Doi Y, Makromol. Chem., 183, 2285 (1982)
Galli P, Luciani L, Cecchin G, Angew. Makromol. Chem., 94, 63 (1981)
Chien JCW, Wu JC, Kuo CI, J. Polym. Sci. A: Polym. Chem., 20, 2019 (1982)
Kashiwa N, Yoshitake J, Makromol. Chem., 185, 1133 (1984)
Zakharov VA, Makhtarulin SI, Anufrienk VA, Makromol. Chem., 185, 1781 (1984)
Soga K, Sano T, Ohnishi R, Polym. Bull., 4, 157 (1981)
Longo P, Grassi A, Oliva L, Ammendola P, Makromol. Chem., 191, 237 (1990)
Shelden RA, Fueno T, Furukawa J, J. Polym. Sci. A: Polym. Chem., 3, 23 (1965)
Ammendola P, Tanoredi T, Zambelli A, Macromolecules, 19, 307 (1986)
Kashiwa N, "Transition Metal Catalyzed Polymerizations," R.P. Quirk, ed., Harwood Academic Pub., New York, 379 (1983)
Saegusa T, Imai K, Uezima T, Furukawa J, Shokubai, 7, 43 (1965)
Soga K, Uozumi T, Yanagihara H, Siono T, Makromol. Chem. Rapid Commun., 11, 229 (1990)

[Referenced By]

[1] Zambelli A, Locatelli P, Sacchi MC, Rigamonti E, Macromolecules, 13, 798 (1980)

[2] Zambelli A, Locatelli P, Sacchi MC, Tritto I, Macromolecules, 15, 831 (1982)

[3] Busico V, Corradini P, "Transition Metal Catalyzed Polymerizations," R.P. Quirk, ed., Cambridge Univ. Press, New York, 551 (1988)

[4] Pino P, Mulhaupt R, Angew. Makromol. Chem., 19, 857 (1980)

[5] Barbe PC, Cecchin G, Noristi L, Adv. Polym. Sci., 81, 1 (1987)

[6] Soga K, Shiono T, Doi Y, Makromol. Chem., 189, 1531 (1988)

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

[8] Chien JCW, Hu Y, J. Polym. Sci. A: Polym. Chem., 26, 2973 (1988)

[9] Chien JCW, Hu Y, J. Polym. Sci. A: Polym. Chem., 27, 897 (1989)

[10] Kim I, Woo SI, Polym.(Korea), to submitted (1988)

[11] Kim I, Woo SI, Catalyst Prepared Based on Ger. Offen. DE 3,629,932 (1988)

[12] Kashiwa N, Yoshitake J, Mizuno A, Polymer, 28, 1227 (1987)

[13] Natta G, Makromol. Chem., 16, 213 (1955)

[14] Starling KE, "Fluid Thermodynamic Properties for Light Petroleum Systems," Gulf Pub. Co., Houston, 139 (1973)

[15] Natta G, Danusso F, Sianesi D, Makromol. Chem., 30, 238 (1959)

[16] Zakharov VA, Buktov GD, Yermakov YI, Adv. Polym. Sci., 51, 61 (1983)

[17] Busico V, Corradini P, DeMartino L, Albizzati E, Makromol. Chem., 183, 2285 (1982)

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

[19] Galli P, Luciani L, Cecchin G, Angew. Makromol. Chem., 94, 63 (1981)

[20] Chien JCW, Wu JC, Kuo CI, J. Polym. Sci. A: Polym. Chem., 20, 2019 (1982)

[21] Kashiwa N, Yoshitake J, Makromol. Chem., 185, 1133 (1984)

[22] Zakharov VA, Makhtarulin SI, Anufrienk VA, Makromol. Chem., 185, 1781 (1984)

[23] Soga K, Sano T, Ohnishi R, Polym. Bull., 4, 157 (1981)

[24] Longo P, Grassi A, Oliva L, Ammendola P, Makromol. Chem., 191, 237 (1990)

[25] Shelden RA, Fueno T, Furukawa J, J. Polym. Sci. A: Polym. Chem., 3, 23 (1965)

[26] Ammendola P, Tanoredi T, Zambelli A, Macromolecules, 19, 307 (1986)

[27] Kashiwa N, "Transition Metal Catalyzed Polymerizations," R.P. Quirk, ed., Harwood Academic Pub., New York, 379 (1983)

[28] Saegusa T, Imai K, Uezima T, Furukawa J, Shokubai, 7, 43 (1965)

[29] Soga K, Uozumi T, Yanagihara H, Siono T, Makromol. Chem. Rapid Commun., 11, 229 (1990)