π-烯烃配体钯配合物的制备及催化降冰片烯衍生物聚合研究.pdf

π-烯烃配体钯配合物的制备及催化降冰片烯衍生物聚合研究.pdf分类号:密级:U D C:编号:河北工业大学硕士学位论文π-烯烃配体钯配合物的制备及催化降冰片烯衍生物聚合研究论文作者:郭婧学生类别:全日制学科门类:理科学科专业:高分子化学与物理指导教师:刘宾元职称:教授Thesis Submitted toHebei University of TechnologyforThe Master Degree ofChemistry and Physics ofPolymersπ-PLEXESSYNTHESISANDITSAPPLICATIONINTHENORBORNENEDERIVATIVESPOLYMERIZATIONbyGuo JingSupervisor: Prof. Liu BinyuanMay 2013河北工业大学硕士学位论文I摘要本文合成了一种双环戊二烯型π-烯烃金属钯配合物,该类配合物为催化剂前驱物与六氟化锑银原位反应后的产物,成功实现了降冰片烯衍生物1,4-二氢-1,4-甲桥萘(BNB)、exo-双环戊二烯(exo-DCPD) 和5-乙叉基-2-降冰片烯(ENB)的乙烯加成聚合物。并以乙烯为链转移剂获得了端基功能化的聚降冰片烯。同时研究了聚合物的溶解性、热稳定性等性能,主要内容如下:1. 合成三种带有不同烷氧基团的后过渡金属钯催化剂,该催化剂对空气、水不敏感。2. 成功制备1,4-二氢-1,4-甲桥萘和exo-双环戊二烯单体。利用IR、1H NMR等手段进行了表征。,单体与催化剂摩尔比,温度,溶剂量等条件对降冰片烯、1,4-二氢-1,4-甲桥萘、exo-双环戊二烯单体和5-乙叉基-2-降冰片烯聚合活性的影响。通过对聚合物的IR、1H NMR等分析,证明得到了乙烯加成聚合物。4. 分别研究了1,4-二氢-1,4-甲桥萘、exo-双环戊二烯单体和5-乙叉基-2-降冰片烯聚合物的溶解性、热稳定性,结果表明1,4-二氢-1,4-甲桥萘、exo-双环戊二烯单体和5-乙叉基-2-降冰片烯聚合物的溶解性比PNB有所改善。5. 通过IR、1H NMR和GPC的测试分析,初步探究了PENB的交联原因。关键词:钯催化剂,降冰片烯,1,4-二氢-1,4-甲桥萘,exo-双环戊二烯,5-乙叉基-2-降冰片烯,乙烯加成聚合π-烯烃配体钯配合物的制备及降冰片烯衍生物聚合研究IIABSTRACTThreekinds of palladium(II) complexes with alkoxy substituted dicyclopentadiene were essfully synthesized and its application in the norbornene derivatives: benzonorbornadiene, exo-dicyclopentadiene and 5-vinyl-2-norbornenevinylic addition functionalized polynorbornene was also synthesized in the presence of ethylene as chain , the solubility and thermal properties of resulting polymerswere also investigated, andthe results were summarized as follows: of palladium(II) complexes were essfully prepared, which were stable to the air and some heat-. Benzonorbornadiene and exo-dicyclopentadiene were synthesized according to the literature reported,and the structure of benzonorbornadiene and exo-dicyclopentadienewere characterized by IR and 1H NMR . The effects of reaction conditionsinvolvingreaction time,molar ratio of monomer to catalyst, temperature,and solvent on the polymerization we