双核茂金属催化剂的合成、表征与应用  

Synthesis of Methylene-bridged Binuclear Metallocene Complexes and Application for Propylene Syndiospecific Polymerization

作　　者：邵炉 梁春超 许胜[1] 米普科[1] 王婷兰[1] 义建军 SHAO Lu;LIANG Chunchao;XU Sheng;MI Puke;WANG Tinglan;YI Jianjun(School of Materials Science and Engineering,School of Chemistry and Engineering,Shanghai Key Laboratory of Advance Materials,Key Laboratory for Ultrafine Materials of Ministry of Education,East China University of Science and Technology,Shanghai 200237,China;Petrochemical Research Institute,PetroChina,Beijing 102206,China)

机构地区：[1]上海先进聚合物材料重点实验室,超细材料制备与应用教育部重点实验室,华东理工大学材料科学与工程学院,化学与分子工程学院,上海200237 [2]中国石油,石油化工研究院,北京102206

出　　处：《高等学校化学学报》2019年第6期1324-1332,共9页Chemical Journal of Chinese Universities

基　　金：国家重点研发计划项目(批准号:2017YFB0306701);中石油创新基金(批准号:2017D-007-0501);国家自然科学基金(批准号:L11362111)资助~~

摘　　要：使用桥连配体锂盐与MCl4络合,合成了4个不同结构的双核茂金属化合物[μ,μ-(CH2)3]{[C(H)·(η5-C5H4)(η^5-C13H8)](MCl2)}2[M=Zr or Ti](4,5)和[μ,μ-(CH2)3]{[C(H)(η^5-C5H4)(η^5-C9H6)]·(MCl2)}2[M=Zr or Ti](6,7),配体和化合物都经过核磁氢谱(1HNMR)、碳谱(13CNMR)、红外光谱(IR)及元素分析等表征,确认了化学结构.以甲基铝氧烷(MAO)为助催化剂,化合物4~7为催化剂催化丙烯聚合,考察了聚合温度、乙烯压力、铝钛或铝锆比对催化剂活性及聚合物分子量的影响.结果表明,多亚甲基桥连双核茂金属是高活性乙烯和丙烯聚合催化剂,乙烯聚合活性最高达到7.5×10^6gPE/(molZr·h)(化合物6),丙烯聚合活性达10×10^5gsPP/(molZr·h)(化合物4).所得间规聚丙烯(sPP)的间规度指数(SI,r)达到90%.在同样条件下,双核化合物的催化活性、聚合物分子量Mw(>100000)以及分子量分布(MWD>2.5)均比相应的单核化合物高(Mw<70000,MWD≤2),表明该体系中存在较强的核效应.In order to investigate the differences between binuclear metallocene catalysts and mononuclear catalysts for propylene syndiotactic polymerization, binuclear metallocene complexes [μ,μ-(CH2)3]·{[C(H)(η^5 -C5H4)(η^5 -C13H8 )](MCl2)} 2[M=Zr or Ti]( 4 , 5 ), and [μ,μ-(CH2)3]·{[C(H)(η^5 -C5H4)·(η^5 -C9H6)](MCl2)} 2[M=Zr or Ti]( 6 , 7 ) were synthesized and characterized by 1 H NMR, 13 C NMR, mass spectra and elemental analysis. When combined with methylaluminoxane(MAO), these metallocene complexes shown high catalytic activity for the polymerization of ethylene and propylene, the activity of \{polyethylene\}(PE) reaches up to 7.5×10^6 g PE/(mol Zr·h)(complex 6 ) and 10×10^5 g sPP/\{(mol Zr·h)\}(complex 4 ) for polypropylene(PP). The syndiotacticity index(SI) of polypropylene(sPP) by \{complex\} 4 was more than 90%. It is found that, under the same conditions, binuclear complexes’ catalytic activity, Mw (>100000) and molecular weight distribution(MWD>2.5) are higher than that of corresponding mononuclear metallocene complexes(Mw <70000, MWD≤2), which suggests that there are cooperation effect in binuclear system.

关 键 词：双核茂金属催化剂 间规聚丙烯 核效应 

分 类 号：O631[理学—高分子化学] O614.8[理学—化学]