新型Cp'Ti(O-C_6H_4-X)_3茂钛催化剂的苯乙烯间规本体聚合研究  

NEW HIGHLY ACTIVE CATALYSTS Cp'Ti(O-C_6H_4-X)_3 FOR BULK SYNDIOSPECIFIC POLYMERIZATION OF STYRENE

作　　者：沈志刚[1] 周文乐[1] 祝方明[2] 林尚安[2] 

机构地区：[1]上海石油化工研究院,上海201208 [2]中山大学高分子研究所,广州510275

出　　处：《高分子学报》2004年第1期45-49,共5页Acta Polymerica Sinica

基　　金：国家科技部"九五"攻关 (批准号 96 A12 0 2 0 5);国家自然科学基金项目 (基金号 2 0 1740 50 );中石化重点资助课题

摘　　要：对位卤代的苯酚与五甲基茂三氯化钛在三乙胺存在下进行酯化反应 ,制得五甲基茂基三 (对 卤代苯氧基 )钛的 4种新型化合物Cp Ti(O C6 H4 X) 3(X =F ,Cl,Br,I) .用作主催化剂经甲基铝氧烷 (MAO)和三异丁基铝 (TIBA)活化 ,对苯乙烯间规聚合显示出极高的催化活性 ,催化剂热稳定性好 ,制得的聚苯乙烯间规度、分子量和熔点均高 ,在MAO TIBA Ti =4 0 0 2 0 0 1(摩尔比 ) ,温度 6 0℃时 ,10min催化效率可达 3 4 7× 10 6gPS mol·Ti,MAO TIBA Ti=4 0 0 2 0 0 1时茂钛化合物的催化活性几乎是MAO Ti=6 0 0时的 10倍以上 ;4种茂钛催化剂的活性次序Cp Ti(O C6 H4 F) 3 >Cp Ti(O C6 H4 Cl) 3 >Cp Ti(O C6 H4 Br) 3 >Cp Ti(O C6 H4 I) 3 .Four kinds of ancillary ligands O C 6H 4 X \[ X(p)=F, Cl,Br,I\] were introduced in the design of novel monotitanocene catalysts,Cp * Ti (O C 6H 4 X) 3 .All of the new catalysts show high activity for styrene sy ndiotact ic polymerization.The catalytic activity of the four monotitanocene increase d in the order:Cp *Ti(O C 6H 4 I) 3 <Cp * Ti (O C 6H 4 Br) 3 <Cp * Ti(O C 6H 4 Cl) 3 <Cp *Ti(O C 6H 4 F) 3.The addition of triisobutylaluminium(TIBA) to the catalyst syst em cause d a dramatic increase of s PS yield .At 90℃,MAO/TIBA/Ti=400/200/1(molar ra t io),the catalytic efficiency of Cp *Ti(O C 6H 4 F) 3 is up to 3.46×10 6 g polymer/m ol·Ti·10 min.The polymerization activity of Cp *Ti(O C 6H 4 X) 3 at MAO/ TIBA/Ti=400/ 200/1(molar ratio) is about 10 times higher than that at MAO/Ti=600(in the absen ce of TIBA).The catalytic efficiency of the catalyst and the molecular weight were affected by catalyst composition,monomer concentration and polymerizatio n temperature.The kinetics of styrene syndiotactic polymerization in toluene was also studied.

关 键 词：苯乙烯 间规聚合 工程塑料 茂钛催化剂 甲基铝氧烷 三异丁基铝 催化活性 对位卤代 酚氧基辅配体 

分 类 号：O631.5[理学—高分子化学]