Effects of molecular dispersion state of surface Ti species on ethylene-propylene copolymerization with TiCl3-based Ziegler-Natta model catalyst

Toshiaki Taniike; Shougo Takahashi; Toru Wada; Iku Kouzai; Minoru Terano

Macromolecular Research, Vol.18, No.9, 834-838, September, 2010

DOI10.1007/s13233-010-0904-3 Export Citation

Effects of molecular dispersion state of surface Ti species on ethylene-propylene copolymerization with TiCl3-based Ziegler-Natta model catalyst

Toshiaki Taniike, Shougo Takahashi, Toru Wada, Iku Kouzai, and Minoru Terano^†

School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa, 923-1292, Japan

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The dispersion state of surface Ti species is one of the most important factors affecting the polymerization properties of MgCl2-supported heterogeneous Ziegler-Natta catalysts. In this paper, ethylene-propylene copolymerization was carried out using a novel Ziegler-Natta model catalyst with "isolated" and "clustered" TiCl3 molecules on MgCl2. At a lower ethylene/propylene feed ratio, the dispersion state of the Ti species strongly affected both the composition and sequence distribution of the copolymers. The "isolated" Ti species gave a relatively random copolymer, and clustering of Ti species enhanced the bulkiness. The addition of an external donor basically deteriorated the random copolymerization character of the "isolated Ti species but the degree of deterioration depended on the type of donors. On the other hand, the balance between the monomer feed and consumption dominated the copolymerization performance at a higher ethylene/propylene feed ratio to obscure the effects of the dispersion state.

Keywords:Ti dispersion state of surface;E-P copolymerization;TiCl3-based Ziegler-Natta model catalyst

[References]

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Cheng HN, Kakugo M, Macromolecules, 24, 1724 (1991)
Cecchin G, Morini G, Pelliconi A, Macromol. Symp., 173, 195 (2001)
Albizzati E, Giannini U, Collina G, Noristi L, Resconi L, Propylene Handbook, Moore EP, Ed., Hanser, New York 1996, Chapter 2.
Taniike T, Terano M, Macromol. Rapid Commun., 29(17), 1472 (2008)
Wada T, Taniike T, Kouzai I, Takahashi S, Terano M, Macromol. Rapid Commun., 30(11), 887 (2009)
Kouzai I, Liu B, Wada T, Terano M, Macromol. React. Eng., 1, 160 (2007)
Soga K, Terano M, Makromol. Chem., 182, 2439 (1981)
Shiono T, Uchino H, Soga K, Polym. Bull., 21, 19 (1989)
Soga K, Terano M, Polym. Bull., 1, 849 (1979)
Kashiwa N, Yoshitake J, Makromol. Chem., 185, 1133 (1984)
Soga K, Yanagihara H, Lee D, Makromol. Chem., 190, 995 (1989)
Busico V, Corradini P, Ferraro A, Proto A, Makromol. Chem., 187, 1125 (1986)
Kravchenko R, Waymouth RM, Macromolecules, 31(1), 1 (1998)
Kissin YV, Rishina LA, J. Polym. Sci. A: Polym. Chem., 40(9), 1353 (2002)
Busico V, Cipullo R, Chadwick JC, Modder JF, Sudmeijer O, Macromolecules, 27(26), 7538 (1994)
Pasquet V, Spitz R, Makromol. Chem., 194, 451 (1993)
Tait PJT, Berry IG, Catalyst Design for Tailor-Made Polyolefins, Soga K, Terano M, Eds., Elsevier-Kodansha, Tokyo, 1994, p. 55.
Spitz R, Masson R, Bobichon C, Guyot A, Makromol. Chem., 189, 1043 (1988)
Chien JCW, Nozaki T, J. Polym. Sci. A: Polym. Chem., 31, 227 (1993)
Kim I, Kim JH, Choi HK, Chung MC, Woo SI, J. Appl. Polym. Sci., 48, 721 (1993)
Awudza JAM, Tait PJT, J. Polym. Sci. A: Polym. Chem., 46, 267 (2007)
Takahashi S, Taniike T, Wada T, Kouzai I, Terano M, inpreparation.
Soga K, Uozumi T, Park J, Makromol. Chem., 191, 2853 (1990)

[Referenced By]

[1] Kakugo M, Naito Y, Mizunuma K, Miyatake T, Macromolecules, 15, 1150 (1982)

[2] Cheng HN, Kakugo M, Macromolecules, 24, 1724 (1991)

[3] Cecchin G, Morini G, Pelliconi A, Macromol. Symp., 173, 195 (2001)

[4] Albizzati E, Giannini U, Collina G, Noristi L, Resconi L, Propylene Handbook, Moore EP, Ed., Hanser, New York 1996, Chapter 2.

[5] Taniike T, Terano M, Macromol. Rapid Commun., 29(17), 1472 (2008)

[6] Wada T, Taniike T, Kouzai I, Takahashi S, Terano M, Macromol. Rapid Commun., 30(11), 887 (2009)

[7] Kouzai I, Liu B, Wada T, Terano M, Macromol. React. Eng., 1, 160 (2007)

[8] Soga K, Terano M, Makromol. Chem., 182, 2439 (1981)

[9] Shiono T, Uchino H, Soga K, Polym. Bull., 21, 19 (1989)

[10] Soga K, Terano M, Polym. Bull., 1, 849 (1979)

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

[12] Soga K, Yanagihara H, Lee D, Makromol. Chem., 190, 995 (1989)

[13] Busico V, Corradini P, Ferraro A, Proto A, Makromol. Chem., 187, 1125 (1986)

[14] Kravchenko R, Waymouth RM, Macromolecules, 31(1), 1 (1998)

[15] Kissin YV, Rishina LA, J. Polym. Sci. A: Polym. Chem., 40(9), 1353 (2002)

[16] Busico V, Cipullo R, Chadwick JC, Modder JF, Sudmeijer O, Macromolecules, 27(26), 7538 (1994)

[17] Pasquet V, Spitz R, Makromol. Chem., 194, 451 (1993)

[18] Tait PJT, Berry IG, Catalyst Design for Tailor-Made Polyolefins, Soga K, Terano M, Eds., Elsevier-Kodansha, Tokyo, 1994, p. 55.

[19] Spitz R, Masson R, Bobichon C, Guyot A, Makromol. Chem., 189, 1043 (1988)

[20] Chien JCW, Nozaki T, J. Polym. Sci. A: Polym. Chem., 31, 227 (1993)

[21] Kim I, Kim JH, Choi HK, Chung MC, Woo SI, J. Appl. Polym. Sci., 48, 721 (1993)

[22] Awudza JAM, Tait PJT, J. Polym. Sci. A: Polym. Chem., 46, 267 (2007)

[23] Takahashi S, Taniike T, Wada T, Kouzai I, Terano M, inpreparation.

[24] Soga K, Uozumi T, Park J, Makromol. Chem., 191, 2853 (1990)