双吡唑亚胺镍/甲基铝氧烷催化降冰片烯的聚合  

Norbornene Polymerization Catalyzed by Bispyrazolylimineylimine Nickel(Ⅱ)/MAO Catalytic Systems

作　　者：王媛媛[1] 祝方明[1] 林尚安[1] 

机构地区：[1]中山大学化学与化学工程学院高分子科学研究所,广州510275

出　　处：《高等学校化学学报》2008年第8期1684-1688,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20734004;20674097);广东省自然科学基金(批准号:039184)资助

摘　　要：合成了两种双吡唑亚胺镍配合物:双-N-(苯基-1-3,5-二甲基吡唑基亚甲基)苯基亚胺二溴化镍(Cat.1)和双-4-甲氧基-N-(苯基-1-3,5-二甲基吡唑基亚甲基)苯基亚胺二溴化镍(Cat.2).研究了Cat.1/MAO和Cat.2/MAO催化体系对降冰片烯(NBE)单体聚合的催化性能,考察了各种聚合条件,如温度、Al/Ni摩尔比及催化剂浓度对降冰片烯的催化效率、单体转化率、聚合物分子量及分子量分布的影响.研究结果表明,Cat.1/MAO和Cat.2/MAO催化体系对降冰片烯聚合具有较高的催化效率,可达到105g PNBE/(molNi)数量级,所得聚降冰片烯(PNBE)的重均分子量在105以上,分子量分布指数在2左右.聚合产物的1H NMR和FTIR谱分析结果表明,该聚合反应是以单体的乙烯基加成聚合机理进行的.Two bispyrazolylimine nickel complexes [ bis-N- （phenyl-1,3,5-dimethylpyrazolylmethylene） pheny- limine nickel dibromide] （Cat. 1） and [ bis-4-methoxy-N-（phenyl-1,3,5-dimethylpyrazolylmethylene） phenylimine nickel dibromide ] （Cat. 2） were synthesized. Norbornene polymerization catalyzed by Cat. 1/MAO and Cat. 2/MAO systems was investigated. The catalytic efficiency, molecular weight and molecular weight distribution were influenced by the polymerization conditions, such as the polymerization temperature, Al/Ni molar ratio and catalyst concentration. The results show that Cat. 1/MAO and Cat. 2/MAO systems displayed a high catalytic efficiency with 10^5 g PNBE/（ mol Ni） magnitude order. The molecular weights of PNBE were higher than 10^5 and the molecular weight distributions were around 2. According to ^1H NMR and the FTIR spectra, the mechanism of the norbornene polymerization is vinyl-addition type polymerization.

关 键 词：双吡唑亚胺镍配合物 聚降冰片烯聚合 乙烯基加成聚合 

分 类 号：O631[理学—高分子化学]