Polymerizations of Ethylene with Dinuclear Hexamethyltrisiloxanediylbis-(cyclopentadienylindenylzirconium dichloride)

Lee DH; Yoon KB; Lee HB; Noh SK; Shim JY

Korea Polymer Journal, Vol.4, No.2, 107-111, October, 1996

Lee DH, Yoon KB, Lee HB, Noh SK, Shim JY

With a new trisiloxane-bridged dinuclear zirconocene, hexamethyltrisiloxanediylbis (cyclopentadienylindenylzirconium dichloride) (TSDZ) CI₂IndZr-CpSi(CH₃)₂-O-Si-(CH_/3-O-Si(CH_/3)_/2Cp-ZrIndCI_/2, the polymerizations of ethylene were carried out in the presence of modified MAO(MMAO) as a cocatalyst. The effects of MMAO amount and polymerization temperature (T_p) on polymerization behaviours of TSDZ were examined and compared with those of monouclear zirconocenes such as cyclopentadienylindenylzirconium dichloride, biscyclopentadienylzirconium dichloride and bisindenylzirconium dichloride. The catalytic activity of TSDZ was comparable to that of mononuclear zirconocenes, while the weight-average molecular weight (M_w) and polydispersity index (M_w/M_w) of polyethylene (PE) prepared with the former were much higher than those of PE with the latter. With increasing MMAO concentration, the catalytic activity increased but M_w decreased for TSDZ, as well as monouclear zirconocenes. With increasing T_p, the catalytic activity of TSDZ was a maximum at 40 ℃ while that of mononuclear zirconocenes increased steadily. For increased T_p, the decrease of M_w and M_w/M_n, for TSDZ was extraordinary compared to that for mononuclear zirconocenes.

[References]

Sinn H, Kaminsky W, Vollmer HJ, Woldt R, Angew. Chem.-Int. Edit., 92, 396 (1980)
Brintzinger HH, Fisher D, Mulhaupt R, Rieger B, Waymouth RM, Angew. Chem.-Int. Edit., 34, 1143 (1995)
Arnt M, Kaminsky W, Schipfner GU, Proceedings of Metallocene '95, Schotland Business Research Inc., Skillman, New Jersey, pp. 403 (1995)
Reddy KD, Petersen JL, Organometallics, 8, 2107 (1989)
Cunenca T, Flores JC, Gomez-Sal R, Parra-Hake M, Royo P, Inorg. Chem., 32, 3608 (1993)
Cuneca T, Padilla A, Royo P, Parra-Hake M, Pellinghelli MA, Tripicchio A, Organometallics, 14, 848 (1995)
Jungling S, Mulhaupt R, Plenio H, J. Org. Chem., 460, 191 (1993)
Lee DH, Yoon KB, Lee EH, Noh SK, Lee CS, Huh WS, Macromol. Rapid Commun., 17, 325 (1996)
Lee DH, yoon KB, Lee EH, Noh SK, Byun GG, Lee CS, Macromol. Rapid Commun., 16, 265 (1995)
Noh SK, Byun GG, Lee CS, Lee DH, Yoon KB, Kang KS, J. Org. Chem., 518, 1 (1996)
Morris RJ, J. Org. Chem., 489, C4 (1995)
Giannetti E, Nicoletti GM, Mazzochi R, J. Polym. Sci. A: Polym. Chem., 23, 2117 (1985)
Mallin DT, Rausch MD, Mintz EA, Rheinggold AL, J. Org. Chem., 381, 35 (1990)
Lee IM, Gauthier J, Ball JM, Iyengar B, Collins S, Organometallics, 11, 2115 (1992)
Mohring PC, Coville NJ, J. Mol. Catal., 77, 41 (1992)
Mohring PC, Coville NJ, J. Org. Chem., 479, 1 (1994)
Chien JCW, Razavi A, J. Polym. Sci. A: Polym. Chem., 26, 2369 (1988)
Chien JCW, Wang BP, J. Polym. Sci. A: Polym. Chem., 28, 15 (1990)
Resconi L, Bossi S, Abis L, Macromolecules, 23, 4489 (1990)
Kaminsky W, Ahlers A, Lindenhof NM, Angew. Chem.-Int. Edit., 28, 1216 (1989)

[Referenced By]

[1] Sinn H, Kaminsky W, Vollmer HJ, Woldt R, Angew. Chem.-Int. Edit., 92, 396 (1980)

[2] Brintzinger HH, Fisher D, Mulhaupt R, Rieger B, Waymouth RM, Angew. Chem.-Int. Edit., 34, 1143 (1995)

[3] Arnt M, Kaminsky W, Schipfner GU, Proceedings of Metallocene '95, Schotland Business Research Inc., Skillman, New Jersey, pp. 403 (1995)

[4] Reddy KD, Petersen JL, Organometallics, 8, 2107 (1989)

[5] Cunenca T, Flores JC, Gomez-Sal R, Parra-Hake M, Royo P, Inorg. Chem., 32, 3608 (1993)

[6] Cuneca T, Padilla A, Royo P, Parra-Hake M, Pellinghelli MA, Tripicchio A, Organometallics, 14, 848 (1995)

[7] Jungling S, Mulhaupt R, Plenio H, J. Org. Chem., 460, 191 (1993)

[8] Lee DH, Yoon KB, Lee EH, Noh SK, Lee CS, Huh WS, Macromol. Rapid Commun., 17, 325 (1996)

[9] Lee DH, yoon KB, Lee EH, Noh SK, Byun GG, Lee CS, Macromol. Rapid Commun., 16, 265 (1995)

[10] Noh SK, Byun GG, Lee CS, Lee DH, Yoon KB, Kang KS, J. Org. Chem., 518, 1 (1996)

[11] Morris RJ, J. Org. Chem., 489, C4 (1995)

[12] Giannetti E, Nicoletti GM, Mazzochi R, J. Polym. Sci. A: Polym. Chem., 23, 2117 (1985)

[13] Mallin DT, Rausch MD, Mintz EA, Rheinggold AL, J. Org. Chem., 381, 35 (1990)

[14] Lee IM, Gauthier J, Ball JM, Iyengar B, Collins S, Organometallics, 11, 2115 (1992)

[15] Mohring PC, Coville NJ, J. Mol. Catal., 77, 41 (1992)

[16] Mohring PC, Coville NJ, J. Org. Chem., 479, 1 (1994)

[17] Chien JCW, Razavi A, J. Polym. Sci. A: Polym. Chem., 26, 2369 (1988)

[18] Chien JCW, Wang BP, J. Polym. Sci. A: Polym. Chem., 28, 15 (1990)

[19] Resconi L, Bossi S, Abis L, Macromolecules, 23, 4489 (1990)

[20] Kaminsky W, Ahlers A, Lindenhof NM, Angew. Chem.-Int. Edit., 28, 1216 (1989)