Polymerizable group 4 ansa-cyclopentadienyl-amido catalysts for the copolymerization of ethylene with 1-octene
作者:Wendy Rusli、Boon-Ying Tay、Ludger P. Stubbs、Martin van Meurs、Jozel Tan、Chacko Jacob、Sze-Chen Chia、Yuan-Ling Woo、Cun Wang
DOI:10.1016/j.jorganchem.2011.03.007
日期:2011.6
6a and 6b. A polystyrene-immobilized constrained-geometry catalyst 8 was formed by the radical copolymerization of 7a with styrene using AIBN as the initiator. The complexes 6a, 6b, 7a and 8 gave active homogeneous catalysts for the copolymerization of ethylene with 1-octene when treated with excess methylalumoxane (MAO). The polymerization results showed that 7a was highly active and effective for
苯乙烯单元已被成功地结合到半茂金属限制几何构型框架为[(η 5 -C 5我4)森达2(η 1 -NC 6 H ^ 4 CH CH 2)] MX 2(中号 =的Ti,X = NME 2,图6a ;中号 =锆,X = NME 2,图6b ;中号 =的Ti,X =氯,图7a ;中号 =锆,X =氯,7b)。这些配合物已通过1 H NMR,13 C NMR光谱以及6a和6b的单晶X射线衍射研究进行了表征。使用AIBN作为引发剂,通过7a与苯乙烯的自由基共聚来形成聚苯乙烯固定的约束几何催化剂8。当用过量的甲基铝氧烷(MAO)处理时,配合物6a,6b,7a和8提供了活性均相催化剂,用于乙烯与1-辛烯的共聚。聚合结果表明7a具有很高的活性和对共聚单体1-辛烯的结合有效,而锆配合物6b和固定化催化剂8的活性低,且1-辛烯在分子量分布较宽的产物中的掺入率低。