7-氧杂降冰片烯的官能化及其开环易位聚合

FUNCTIONALIZATION OF 7-OXANORBORNENE AND ITS RING-OPENING METATHESIS POLYMERIZATION

设计合成了含氧化乙烯重复单元和咪唑盐侧基的降冰片烯类单体,用Grubbs催化剂(PCy3)2Ru(CHPh)Cl2(1)和(SIMes)(PCy3)Ru(CHPh)Cl2(2)对单体进行了开环易位聚合(ROMP).考察了单体在不同条件下(溶剂、温度等)的聚合反应,尤其是在离子液体中ROMP的聚合特征.结果表明,2的催化活性比1的高;2催化单体在有机溶剂中聚合所得聚合物的分子量不可控,而在离子液体[BMIm]PF6中能够顺利进行均相聚合反应,且对聚合物的分子量可控性较好.用核磁共振谱(NMR)对合成的单体及聚合物的结构进行了表征.用差示扫描量热法(DSC)测定聚合物的玻璃化转变温度为-17.34℃,采用循环伏安法测得聚合物的电化学稳定窗口为3.0V.

A novel norbornene derivative containing oxyethylene repeating unit and imidazolium ionic moiety was designed and synthesized. The monomer was polymerized via ring-opening metathesis polymerization initiated by Grubbs catalysts （PCy3）2Ru（CHPh）Cl2 （ 1 ） and （SIMes）（PCy3）Ru（CHPh）Cl2（2）. The polymerization reactions were conducted in organic solvents as well as in ionic liquid [ BMIm] PF6 under various conditions. The results demonstrated that complex 2 possessed higher catalytic activity than complex 1. The ROMP using 2 as catalyst in organic solvents was not controlled and the resulting molecular weights were much higher than the calculated values, while the polymerization in ionic liquid was homogeneous and the molecular weights of polymers could be preferably controled. The monomer and the polymers were characterized with NMR spectroscopy, DSC and cyclic voltammetry, respectively. The polymer has a glass transition temperature of - 17.34℃ and an electrochemical stability window of 3.0V.