不饱和取代水杨醛亚胺镍的合成及其对乙烯聚合的催化性能  

Synthesis of Unsaturated Substituted Salicylaldiminato Nickel(Ⅱ) Complexes and Their Catalytic Performance for Ethylene Polymerization

作　　者：徐永进[1] 孙俊全[1] 单玉华[1] 王临才[1] 

机构地区：[1]浙江大学联合化学反应工程研究所,浙江杭州310027

出　　处：《催化学报》2004年第7期518-522,共5页

基　　金：国家自然科学基金 ( 2 0 0 740 2 8);中国石油化工股份有限公司 (X5 0 0 0 3 0 )资助项目

摘　　要：合成了烯丙基对甲基水杨醛亚胺和环戊烯基对甲基水杨醛亚胺配体 ,并与trans [NiCl(Ph) (PPh3 ) 2 ]反应合成了配合物[O (3 allyl) (5 CH3 )C6H2 o C(H)∶N 2 ,6 C6H3 (i Pr) 2 ]Ni(PPh3 ) (Ph)和 [O (3 cyclopentenyl) (5 CH3 )C6H2 o C(H)∶N 2 ,6 C6H3 (i Pr) 2 ]Ni(PPh3 ) (Ph) ,以MS ,1 HNMR和元素分析对配体及配合物进行了表征 .在Ni(COD) 2 (COD环辛二烯 )助催化下成功地催化乙烯聚合 ,在 80 8kPa的压力下 ,前者配合物的最高活性可达 2 6 5kg/ (mol·h) ,聚乙烯的粘均分子量在 (0 95～ 3 85 )× 1 0 4间 ;后者配合物的最高活性可达 4 34kg/ (mol·h) ,聚乙烯的粘均分子量在 (0 87～ 5 81 )× 1 0 4间 .添加THF ,CH3 COOEt和EtOEt对催化聚合性能无显著影响 ,添加甲基丙烯酸甲醇则不仅不发生共聚 。Allyl substituted salicylaldimine and cyclopentenyl substituted salicylaldimine were prepared and reacted with trans [NiCl(Ph)(PPh 3)] to complexes [ O (3 allyl)(5 CH 3)C 6H 2 o C(H)∶N 2,6 C 6H 3( i Pr) 2]Ni (PPh 3)(Ph) and [ O (3 cyclopentenyl)(5 CH 3)C 6H 2 o C(H)∶N 2,6 C 6H 3( i Pr) 2]Ni(PPh 3)(Ph). These complexes activated by Ni(COD) 2 (COD1,5 cyclooctadiene) could catalyze ethylene polymerization effectively. At p =808 kPa, the activity of the first complex reached 265 kg/(mol·h) , and the M η of the polymer product ranged in 0 95×10 4～3 85×10 4; the activity of the second complex reached 434 kg/(mol·h) , and the M η of the polymer product ranged in 0 87×10 4～5 81×10 4. Addition of THF, CH 3COOEt and EtOEt had no evident effects on the polymerization, but addition of methyl methacrylate reduced the polymerization reactivity markedly.

关 键 词：水杨醛亚胺 镍配合物 合成 乙烯聚合 催化性能 聚乙烯 环戊烯基取代 烯丙基取代 催化剂 

分 类 号：O643[理学—物理化学] O631.3[理学—化学]