Polymerization of Highly Isotactic Polypropylene with Mg(OEt)2/DNBP/TiCl4-AlEt3/External Donor Catalyst Systems: Effects of Alkoxy Monosilanes as External Donors

Kang KK; Shiono T; Jeong YT; Lee DH

Korea Polymer Journal, Vol.6, No.2, 167-173, June, 1998

Polymerization of Highly Isotactic Polypropylene with Mg(OEt)₂/DNBP/TiCl₄-AlEt₃/External Donor Catalyst Systems: Effects of Alkoxy Monosilanes as External Donors

Kang KK, Shiono T, Jeong YT, Lee DH

From propylene polymerization using Mg(OEt)₂/di-butylphthalate/TiCl₄ catalyst and various monosilane compounds (R¹R¹Si(OMe)₂) as an external donor, it has been found that the stereoregularity of the isotactic polymer fraction was increased with the decrease of carbon chains of alkyl groups R² when R¹ was the bulky cyclohexyl group, and the degree of isotacticity of the polymer was highest in the case of n-propyl group. When R¹ was the bulky 2-phenylpropyl group instead of the cyclohexyl group, the stereoregularity of the formed polymer showed similar trend as the case of the cyclohexyl group. Cyclohexyl and 2-phenylpropyl group in monosilane compounds used as an external donor led to higher polymer yield and better stereoregularity in the isotactic fraction of the polymer. This result indicates that cyclohexyl and 2-phenylpropyl group in monosilane compound used as an external donor was actively involved in the generation of isospecific sites in propylene polymerization with Mg(OEt)₂/야-butylphthalate/TiCl₄ catalyst. The molecular weight of the polymer also showed an increasing trend in the case of alkoxy monosilanes as an external donor along with high isospecificity.

[References]

Soga K, Shiono T, Doi Y, Makromol. Chem., 189, 1531 (1988)
Shiono T, Soga K, Transition Method Catalyzed Polymerizations, Ziegler-Natta and Metathesis Polymerizations, Ed. by R.P. Quirk, Cambridge University Press, Cambridge, pp. 266-279 (1988)
Lee DH, Jeong YT, Soga K, Shiono T, J. Appl. Polym. Sci., 47, 1449 (1993)
Jeong YT, Lee DH, Makromol. Chem., 191, 1487 (1990)
Harkonen M, Kuutti L, Seppala JV, Makromol. Chem., 193, 1413 (1992)
Harkonen M, Seppala JV, Vaananen T, Catalytic Olefin Polymerization, Studies in Surface and Catalysis, Ed. by K. Soga, Elsevier, Tokyo, vol. 56, pp. 87-107 (1990)
Proto A, Oliva L, Sivak AJ, Cullo LA, Macromolecules, 23, 2904 (1990)
Okano T, chida K, Furuhashi H, Nakano A, Ueki S, Catalytic Olefin Polymerization, Studies in Surface and Catalysis, Ed. by K. Soga, Elsevier, Tokyo, vol. 56, pp. 177-183 (1990)
Seppala JV, Harkonen M, Luciani L, Makromol. Chem., 190, 2535 (1989)
Harkonen M, Seppala JV, Vaananen T, Makromol. Chem., 192, 721 (1991)
Chadwick JC, Kessel GMMV, Sudmeijer O, Macromol. Chem. Phys., 196, 1431 (1995)
Iiskola E, Sormunen P, Graroff T, Vahasarja E, Pakkanen TT, Pakkanen TA, Transition Metals and Organometallics as Catalysts for Olefin Polymerization, Eds. by W. Kaminsky and H. Shin, Springer-Verlag. Berlin, pp. 113-122 (1988)
Sacchi MC, Forlini F, Tritto I, Mendichi R, Zannoni G, Macromolecules, 25, 5914 (1992)
Guyot A, Spitz R, Journaud C, Eisenstein O, Macromol. Symp., 89, 39 (1995)
Eur. Patent, 276576 (1987)
Barb PC, Albizzati E, Giannini U, Baruzzi G, Noristi L, Chem. Abstr., 109, 150246 (1988)
Eur. Patent, 261961, Mitsubishi Petrochem. Corp., Inv.: M. Matsuura, T. Fujita and K. Hirakawa, Chem. Abstr., 109, 93831 (1988)
Eur. Patent, 250229, Amoco Corp., Inv.: C.R. Hoppin and B.S.Tovrog. Chem. Abstr., 109, 7118 (1988)
Lee BW, Yoo BR, Kim SI, Jung IN, Organometallics, 13, 1312 (1994)
Yeon SH, Lee BW, Kim SI, Jung IN, Organometallics, 12, 4887 (1993)
Korea Patent, 96-10695
Jung IN, Han JS, Cho EJ, Yeon SH, Korea Institute of Science and Technology, Inv. (1996)
Jung IN, Yeon SH, Han JS, Chem. Abstr., U.S. Patent, 5,233,069, Korea Institute of Science and Technology, Inv., 119, 226189 (1993)

[Referenced By]

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

[2] Shiono T, Soga K, Transition Method Catalyzed Polymerizations, Ziegler-Natta and Metathesis Polymerizations, Ed. by R.P. Quirk, Cambridge University Press, Cambridge, pp. 266-279 (1988)

[3] Lee DH, Jeong YT, Soga K, Shiono T, J. Appl. Polym. Sci., 47, 1449 (1993)

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

[5] Harkonen M, Kuutti L, Seppala JV, Makromol. Chem., 193, 1413 (1992)

[6] Harkonen M, Seppala JV, Vaananen T, Catalytic Olefin Polymerization, Studies in Surface and Catalysis, Ed. by K. Soga, Elsevier, Tokyo, vol. 56, pp. 87-107 (1990)

[7] Proto A, Oliva L, Sivak AJ, Cullo LA, Macromolecules, 23, 2904 (1990)

[8] Okano T, chida K, Furuhashi H, Nakano A, Ueki S, Catalytic Olefin Polymerization, Studies in Surface and Catalysis, Ed. by K. Soga, Elsevier, Tokyo, vol. 56, pp. 177-183 (1990)

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

[10] Harkonen M, Seppala JV, Vaananen T, Makromol. Chem., 192, 721 (1991)

[11] Chadwick JC, Kessel GMMV, Sudmeijer O, Macromol. Chem. Phys., 196, 1431 (1995)

[12] Iiskola E, Sormunen P, Graroff T, Vahasarja E, Pakkanen TT, Pakkanen TA, Transition Metals and Organometallics as Catalysts for Olefin Polymerization, Eds. by W. Kaminsky and H. Shin, Springer-Verlag. Berlin, pp. 113-122 (1988)

[13] Sacchi MC, Forlini F, Tritto I, Mendichi R, Zannoni G, Macromolecules, 25, 5914 (1992)

[14] Guyot A, Spitz R, Journaud C, Eisenstein O, Macromol. Symp., 89, 39 (1995)

[15] Eur. Patent, 276576 (1987)

[16] Barb PC, Albizzati E, Giannini U, Baruzzi G, Noristi L, Chem. Abstr., 109, 150246 (1988)

[17] Eur. Patent, 261961, Mitsubishi Petrochem. Corp., Inv.: M. Matsuura, T. Fujita and K. Hirakawa, Chem. Abstr., 109, 93831 (1988)

[18] Eur. Patent, 250229, Amoco Corp., Inv.: C.R. Hoppin and B.S.Tovrog. Chem. Abstr., 109, 7118 (1988)

[19] Lee BW, Yoo BR, Kim SI, Jung IN, Organometallics, 13, 1312 (1994)

[20] Yeon SH, Lee BW, Kim SI, Jung IN, Organometallics, 12, 4887 (1993)

[21] Korea Patent, 96-10695

[22] Jung IN, Han JS, Cho EJ, Yeon SH, Korea Institute of Science and Technology, Inv. (1996)

[23] Jung IN, Yeon SH, Han JS, Chem. Abstr., U.S. Patent, 5,233,069, Korea Institute of Science and Technology, Inv., 119, 226189 (1993)