Chinese Journal of Organic Chemistry >
Study on the Influence of the Weak Effect of Benzyl Benzene Ring on the Polymerization Behavior of Ethylene
Received date: 2017-01-27
Revised date: 2017-03-27
Online published: 2017-04-21
Supported by
Project supported by the National Natural Science Foundation of China (No. U1362111).
In order to study the effect of the benzyl benzene ring on the catalytic behavior of binuclear metallocene, the binuclear metallocene [μ,μ-1,4-(CH2)2(C6H4)] [(η5-C5H5)TiCl2(η5-(C6H5)C(Me)2(C5H3)]2 [(TiBz)2] is synthesized and characterized by 1H NMR, 13C NMR, mass spectra and elemental analysis. When combined with methylaluminoxane (MAO), the (TiBz)2/MAO system catalyzed ethylene polymerization and the polymer with C(4) branch were obtained. It is suggested that the C(4) branch is from the ethylene trimerization by the weak effect between the benzyl and center metal. The (TiBz)2/MAO system also showed great ability for ethylene copolymerization with 1-hexene and the incorporation of 1-hexene in polymer reached up to 13.7 mol%. The 13C NMR result of polymer showed that the polymer contained alternatively copolymerized HEHE fragment and the possible mechanism is presented for explaining the special catalytic behavior. It is the weak effect between the benzyl and center metal that led to the alternative insertion of ethylene and 1-hexene, and the narrow molecular weight distribution (PDI=2.23) meant that there could be a great synergistic effect between the two activate center metals in the polymerization process, which greatly increased the copolymerization capability.
Key words： benzyl; binuclear metallocene; weak effect; copolymerization ability; mechanism
Xu Sheng, Liang Chunchao, Lü Zhongwen, Zhu Yuling, Zhang Cui, Mi Puke . Study on the Influence of the Weak Effect of Benzyl Benzene Ring on the Polymerization Behavior of Ethylene[J]. Chinese Journal of Organic Chemistry, 2017 , 37(5) : 1284 -1289 . DOI: 10.6023/cjoc201701052
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