有机镍均相催化剂固相化研究  

Studies on the Heterogenization of the Homogeneous Organic Nickel Catalyst

作　　者：栾家国[1] 钱君律[1] 李森[1] 

机构地区：[1]同济大学化学系

出　　处：《同济大学学报（自然科学版）》1994年第3期365-370,共6页Journal of Tongji University:Natural Science

摘　　要：将聚苯乙烯用乙酰氨酰化成聚乙酰基苯乙烯（Ⅴ），（Ⅴ）溴化为聚溴乙酰基苯乙烯（Ⅵ），（Ⅵ）与三苯膦成聚溴化三苯膦乙酰基苯乙烯（Ⅶ），（Ⅶ）脱溴化氢成聚三苯膦亚甲基甲酰苯乙烯（Ⅷ），（Ⅷ）在三苯膦存在下与双（１，５－环辛二烯）合镍配位，将（苯甲酰亚甲基二苯膦基）（苯基）（三苯膦基）合镍（１）这一结构以双基配位方式固载到聚苯乙烯上，得到聚（苯甲酰亚甲基二苯膦代乙烯基）（苯基）（三苯膦基）合镍（Ⅸ）．经对１，５－己二烯异构化为甲叉环成烷的催化性能观察，表明固载催化剂（Ⅸ）活性不劣于相应的均相催化剂，并可重复使用．The structure of { α- [(diphenylphosphino) methylene] benzene- methanolato- O.P} (Phenyl)(triphenylph-osphine)nickel is bound over OP-chelate ligand to polystyrene by a five-step process, that is acetylation of polystyrene to form poly (4-acetylstyrene)(Ⅴ); bromination of Ⅴ to give poly (4 - bromoacetylstyrene)(Ⅵ); reaction of Ⅵ with triphenylphosphine to form poly (vinyphenacyl triphenylphosphonium bromide)(Ⅶ); dehydrobromination of Ⅶ to give poly (vinyltriphenyl - phosphine benzoylmethylene) (Ⅷ); finally, reaction of Ⅷ in the presence of triphenylphosphine with his - (1,5 - cyclooctadiene)nickel to give the target compound poly (vinylphenacyldiphen ylphosphine)(phenyl) (triphenylpho sphine)nickel(Ⅸ). For the catalysis of the 1,5-hexadiene to form methylene cyclopentane as main product, the activity of polymer-immobilized complex observed is as good as that of the homogeneous species and it can be reused. The effects of solvent, the diene-catalyst ratio and the reaction take for the isomerization are also studied.

关 键 词：有机镍 催化剂 固相化 聚苯乙烯 

分 类 号：TQ426.8[化学工程]