Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C₁-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes

苯基取代基对丙烯与C₁对称桥联硅烯(芴基)(酰胺基)二甲基钛配合物立体选择性聚合中硅烯桥的影响

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Abstract

A C₁-symmetric (methylphenyl)silylene-bridged (fluorenyl)(naphthylamido) titanium complex (1) and (diphenyl)silylene-bridged (fluorenyl)(naphthylamido) titanium complex (2) were synthesized and characterized by ¹H NMR, element analysis, and X-ray crystal analysis. The coordination mode of the fluorenyl ligand to the titanium metal is an η³ manner in each complex. These complexes were applied for propylene polymerization using dried modified methyaluminoxane (dMMAO) as a cocatalyst under different propylene pressures in a semi batch-type method. The catalytic activity was strongly dependent on the structure of the complex and the propylene pressure, where complex 1 exhibited the highest activity (600 kg mol(-1)·h(-1)) under a propylene pressure of 8.0 atm to produce high molecular weight polypropylene. The polypropylenes obtained were syndiotactic-rich with an rr value of 0.50, indicating that the silylene bridge was not efficient for the isospecificity of a constrained geometry catalyst (CGC). The mechanical properties of the resulting polymers depended on their microstructure.

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