Synthesis and Application in Ethylene Polymerization of p-Biphenylene-bridged Dinuclear Zirconocenes

Chem. J. Chinese Universities ›› 2002, Vol. 23 ›› Issue (11): 2089.

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Synthesis and Application in Ethylene Polymerization of p-Biphenylene-bridged Dinuclear Zirconocenes

DENG Xiao-Bin¹, XU Shan-Sheng¹, WANG Bai-Quan^1,2, ZHOU Xiu-Zhong¹, YANG Ling³, LI Yu-Fei³, HU You-Liang³

1. Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China;
2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;
3. Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China

Received:2001-09-11 Online:2002-11-24 Published:2002-11-24

Abstract

Abstract: ?Dibromobiphenyl reacted with n-BuLi to form 4,4′-dilithiobiphenyl, which further reacted with 2,3,4,5-tetramethylcyclopent-2-enone following the elimination of water to give the ligand 4-(C₅Me₄H)C₆H₄—C₆H₄(C₅Me₄H)-4(1). Ligand 1 reacted with n-BuLi and ZrCl₄ to form the p-biphenylene-bridged dinuclear tetramethylcyclopentadienyl zirconium trichlorides 4-(C₅Me₄ZrCl₃)·C₆H₄—C₆H₄(C₅Me₄ZrCl₃)-4, which reacted in situ with cyclopentadienyl lithium(CpLi) or indenyl lithium(IndLi) to give the corresponding p-biphenylene-bridged dinuclear zirconocenes 4-(C₅Me₄ZrCl₂Cp′)C₆H₄-C₆H₄(C₅Me₄ZrCl₂Cp′)-4 [Cp′= Cp(2), Ind(3)]. The zirconocenes 2 and 3 were characterized by ¹H NMR, MS spectra and elemental analysis, and were studied for ethylene polymerization with methyl aluminoxane(MAO) as cocatalyst. Both 3 and 4 show very high activities and reach the maximum at a higher temperature, indicating that the introduction of the p-biphenylene-bridge increased the catalytic activity and thermal stability of the dinuclear zirconocene catalysts.

Key words: Metallocene, Dinuclear, Zirconium, Indenyl

CLC Number:

O627

TrendMD:

DENG Xiao-Bin, XU Shan-Sheng, WANG Bai-Quan, ZHOU Xiu-Zhong, YANG Ling, LI Yu-Fei, HU You-Liang . Synthesis and Application in Ethylene Polymerization of p-Biphenylene-bridged Dinuclear Zirconocenes[J]. Chem. J. Chinese Universities, 2002, 23(11): 2089.

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Synthesis and Application in Ethylene Polymerization of p-Biphenylene-bridged Dinuclear Zirconocenes

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