桥联稀土异双核Mt-Sm(Mt=Zr,Ti)茂金属配合物催化乙烯聚合研究  被引量:4

Study on the polymerization of ethylene with carbon bridged dinuclear metallocene of Ti-Sm and Zr-Sm

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作  者:孙俊全[1] 班青[1] 徐永进[1] 

机构地区:[1]浙江大学化学工程学系,浙江杭州310027

出  处:《浙江大学学报(工学版)》2004年第8期1061-1066,共6页Journal of Zhejiang University:Engineering Science

基  金:国家自然科学基金资助项目(20074028);中国石油化工股份有限公司资助项目(X500030).

摘  要:在合成新型的碳桥联前过渡金属稀土异核茂金属化合物[(C5H5)MtCl2][(C5H4)CMe2(C9H6)][(C5H5)Sm Cl][Mt=Zr(5),Ti(7)]之后,经甲基铝氧烷活化催化乙烯聚合,考察了催化剂浓度、[Al]/[Cat]、温度、聚合时间对聚合反应的影响.与相应的单核茂金属相比,发现TiSm体系(7)的催化活性升高,而ZrSm体系(5)的活性有所下降;然而,随着时间的延长,前者所得的聚乙烯分子质量逐步下降,而后者所得的聚乙烯分子质量逐步上升.TiSm体系(7)与ZrSm体系(5)不同的催化性能也许与Sm和不同的前过渡金属间的组合有关.所得聚乙烯的GPC分析呈双峰,相对分子质量分布较宽(>3 00).It has been synthesized two dinuclear metallocene complexes [(C5H5)MtCl2] [(C5H4)CMe2 (C9H6)] [(C5H5)SmCl][Mt=Zr(5), Ti(7)], which were used for ethylene polymerization with MAO as cocatalyst. Detailed study on the effect of polymerization caused by catalyst concentration, molar ratio of [Al]/[Cat], temperature and time shows that the catalytic activity of complex 7 is higher than that of the corresponding mononuclear metallocene of Cp2 TiQ2, while the catalytic activity of complex 5 is lower than that of the corresponding mononuclear met allocene of Cp2ZrCl2; The molecular weight of polyethylene produced by above two catalyst systems is somewhat decreased, and the molecular weight distribution becomes broader. With prolongation of time, the molecular weight of polyethylene obtained by complex 7 decreases, while the molecular weight of polyethylene obtained by complex 5 increases.

关 键 词:异核茂金属 茂锆 茂钛 乙烯聚合 

分 类 号:O627[理学—有机化学]

 

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