文献类型：期刊文献

中文题名：水杨醛亚胺镍配合物催化乙烯与甲基丙烯酸甲酯的共聚反应

英文题名：Copolymerization of Ethylene and Methyl Methacrylate with Salicylaldiminate Nickel(Ⅱ)Complexes

作者：张丹枫[1];张玉军[1];喻国聪[1];高文豪[1]

机构：[1]华东理工大学材料科学与工程学院,上海市先进聚合物材料重点实验室,上海200237

年份：2017

卷号：38

期号：11

起止页码：2082

中文期刊名：高等学校化学学报

外文期刊名：Chemical Journal of Chinese Universities

收录：CSTPCD;;Scopus;北大核心:【北大核心2014】；CSCD:【CSCD2017_2018】；

基金：上海市重点学科和重点实验室项目(批准号:B502)资助

语种：中文

中文关键词：水杨醛亚胺镍配合物;聚烯烃;乙烯-甲基丙烯酸甲酯共聚;催化活性

外文关键词：Salicylaldiminate-based nickel(Ⅱ)complex;Polyolefin;Copolymerization of ethylene andmethyl methacrylate;Catalytic activity

摘要：以4种基于水杨醛亚胺配体的镍配合物bis[N-(2,6-diisopropylphenyl)salicylaldiminate]-nickel(Ⅱ)(C1),bis[N-(2,6-diisopropylphenyl)-3-methylsalicylaldiminate]-nickel(Ⅱ)(C2),bis[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ⅱ)(C3)和[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ph)(PPh3)(C4)为催化剂,在甲基铝氧烷(MAO)作用下,对乙烯与甲基丙烯酸甲酯(MMA)进行催化共聚.以C3为模型催化剂,研究了Al/Ni摩尔比、聚合温度、聚合时间等对共聚反应的影响.在最佳的聚合条件下,探索了不同的催化剂结构对共聚反应的影响.结果表明,对于双(水杨醛亚胺)镍配合物,C2的活性高于C1和C3,为13.1 kg/(mol Ni·h),而C3的插入率最低,为14.1%.对于具有相同配体不同结构的配合物C3和C4,含双水杨醛亚胺配体的C3的催化活性高于含单水杨醛亚胺配体的C4,而两者在共聚单体MMA的插入率方面差别不大.对所得共聚物微观结构和热性能进行了表征.
Four salicylaldiminate-based nickel(Ⅱ)complexes:bis[N-(2,6-diisopropylphenyl)salicylaldiminate]-nickel(Ⅱ)(C1),bis[N-(2,6-diisopropylphenyl)-3-methylsalicylaldiminate]-nickel(Ⅱ)(C2),bis[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ⅱ)(C3)and[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ph)(PPh3)(C4),in the presence of methylaluminoxane(MAO),were applied in copolymerization of ethylene and methyl methacrylate(MMA).The influences of polymerization parameters,such as molar ratio of Al/Ni,polymerization temperature and time,on the copolymerization were studied with complex C3 as a model catalyst.Based on these results,the effect of the structure of the nickel complexes on the copolymerization was explored under optimized polymerization conditions.Complex C2 exhibits higher catalytic activity of 13.1 kg/(mol Ni·h)than C1 and C3,while C3 gives the lowest comonomer MMA incorporation of 14.1%in the obtained copolymers.For complexes C3 and C4,with the same ligand but different structures,C3 displays better catalytic activity than C4,but their comonomer MMA incorporations are similar.The microstructures and thermo-properties of the obtained copolymers were characterized by means of FTIR,1 H NMR,13 C NMR,GPC and DSC.