降冰片烯二羧酸二乙酯内给电子体构型对Ziegler-Natta催化剂催化丙烯聚合的研究  

THE EFFECT OF CONFIGURATION STRUCTURE OF 5-NORBORNENE-2,3-DICARBOXYLIC ACID DIETHYL ESTER AS INRERNAL ELECTRON DONOR ON ZIEGLER-NATTA CATALYST FOR PROPYLENE BULK POLYMERIZATION

作　　者：董小芳[1] 崔晓鹏[1] 杨敏[1] 刘宾元[1] 

机构地区：[1]河北工业大学化工学院高分子材料科学与工程系,天津300130

出　　处：《精细石油化工》2016年第1期42-46,共5页Speciality Petrochemicals

基　　金：河北省自然科学基金(B2015202049);国家自然科学基金(21004017)

摘　　要：合成了3种不同构型的内给电子体化合物:顺-5-降冰片烯-内型-2,3-二羧酸二乙酯(endo-NDDE),顺-5-降冰片烯-外型-2,3-二羧酸二乙酯(exo-NDDE)和反-5-降冰片烯-2,3-二羧酸二乙酯(trans-NDDE),并且制备了相应的催化剂。研究了内给电子体构型的变化对丙烯聚合Ziegler-Natta催化剂活性,聚合物等规度、相对分子质量及其分布的影响。实验结果表明,以exo-NDDE为内给电子体的丙烯聚合Ziegler-Natta催化剂活性最高,以trans-NDDE为内给电子体的丙烯聚合Ziegler-Natta催化剂活性最低,但是后者催化得到的聚丙烯相对分子质量最大(其中重均相对分子质量27.1×104 g/mol),相对分子质量分布最宽为5.5。对比丙烯聚合和1-丁烯聚合实验数据,对于同一催化体系,催化剂活性不仅受内给电子体的影响,同时α烯烃支链的长度也会对催化剂活性有一定的影响。The 5-norbornene-2,3-dicarboxylic acid diethyl ester（NDDE）compounds with different configuration：endo,exo,and trans were systematically synthesized and investigated for use as an in ternal donor（ID）on the preference of Ziegler-Natta catalyst activity,stereospecificity,molecularweight and the molecular weight distribution（PDI）.The catalysts employing NDDE cis-5-Norbornene-exo-2,3-dicarboxylic acid diethyl ester and trans-5-Norbornene-2,3-dicarboxylic acid diethyl ester as IED show the highest and lowest result in catalyst activity,but the PP synthesized by the later shows the highest molecular weight（Mw=27.1×104g/mol）and the most broad molecular weight distribution（PDI=5.5）.It is concluded that the catalyst activity depend on not only the ID,but also on the branch ofα-olefins by comparing propylene polymerization and 1-butene polymerization for the same system.

关 键 词：ZIEGLER-NATTA催化剂 丙烯聚合 内给电子体 

分 类 号：TQ325.14[化学工程—合成树脂塑料工业]