制备间规聚苯乙烯的新型催化剂的研究  

Study on novel titanocene complexes for preparing syndiotactic polystyrene

作　　者：沈志刚[1] 赵微微[1] 祝方明[2] 林尚安[2] 

机构地区：[1]中国石油化工股份有限公司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：《合成树脂及塑料》2003年第5期5-7,32,共4页China Synthetic Resin and Plastics

基　　金：国家自然科学基金(20174050);中国石油化工集团公司重点资助课题

摘　　要：对位卤索取代的苯酚与五甲基三氯单茂钛在三乙胺存在下进行酯化反应,制得4种五甲基茂基三(对-卤代苯氧基)钛的新型茂钛化合物[Cp*Ti(O-C6H4-X)3,(X为F、Cl、Br、I)].经元素分析、质谱、核磁共振谱证实了上述结构.在甲基铝氧烷和三异丁基铝活化下,4种茂钛化合物对苯乙烯间规聚合显示出极高的催化活性,制得的间规聚合物间规度(大于96%)和熔点(大于270℃)高.4种茂钛化合物的活性从大到小依次为:五甲基茂基三(对-氟苯氧基)钛、五甲基茂基三(对-氯苯氧基)钛、五甲基茂基三(对-溴苯氧基)钛、五甲基茂基三(对-碘苯氧基)钛.Four kinds of novel monotitanocenes [Cp*Ti(0-C6H4-X)3, (X=F, Cl, Br, I)] were synthesized by esterifica-tion reaction of Cp*Tid3 with HO-C6H4-X at the presence of triethylamine. Their structures were characterized by means of element analysis (EA), nuclear magnetic resonance hydrogen spectrometry (1H-NMR) and mass spectrometry (MS). At the activation with methylaluminoxane (MAO) and triisobutylaluminium (TIBA), the monotitanocene catalysts showed very high catalytic activity, in an escalating order of Cp*Ti(0-C6H4-I)3 < Cp*Ti(O-C6H4-Br)3 <Cp*Ti(0-C6H4-Cl)3 <CP*Ti(O-C6H4-F)3. The syndiotactic polystyrene (sPS) so prepared with the catalysts possess a syndiotacticity over 96% and a melt point of 270 ℃.

关 键 词：制备 聚苯乙烯 催化剂 间规聚合 茂钛化合物 

分 类 号：TQ325[化学工程—合成树脂塑料工业]