二苯基碘鎓盐引发氨酯型乙烯基醚热聚合  

Thermal Polymerization of Urethane Vinyl Ethers Initiated by Diaryldiodonium Salt

作　　者：庞来兴[1] 曾兆华[1] 杨建文[1] 陈用烈[1] 

机构地区：[1]中山大学化学与化学工程学院,广州510275

出　　处：《高等学校化学学报》2004年第11期2153-2156,共4页Chemical Journal of Chinese Universities

基　　金：广东省科委重大科技专项 (批准号 :粤财企 [2 0 0 1] 3 67号 );广东省自然科学基金 (批准号 :0 1110 4)资助

摘　　要：合成了 2种固态氨酯型乙烯基醚 PUE1和 PUE2 ,并对其结构和性能进行了表征 .研究发现 ,二芳基碘六氟磷酸盐 ( PI81 0 )能引发 PUE1和 PUE2发生阳离子热聚合 ,热聚合温度远低于 PI81 0的纯态热分解温度 ,且聚合转化率很高 .初步认为热聚合机理是富电子的乙烯基醚双键和缺电子的二苯基碘盐阳离子之间形成中间态电荷转移复合物 ,降低了二苯基碘盐的热分解温度 ,进而生成引发活性种乙烯基醚阳离子自由基或质子酸 。Two solid vinyl ether terminated aliphatic urethanes, named PUE1 and PUE2, were synthesized and characterized. PUE1 is a crystalline compound with a melting point of 101 ℃; PUE2 is a prepolymer with glass transition temperatures of 30.8 and 17.2 ℃. Both compounds undergo rapid thermal polymerization in the presence of diphenyliodonium hexafluorophosphate(PI810) at different temperatures. The thermal polymerization temperatures for these systems are much lower than the thermal decomposition temperature of neat PI810. The initiation mechanism is presumably based on the electron transfer from electron-rich vinyl ether to electron-dificient diphenyliodonium salt, forming an intermediate charge transfer complex, which can undergo rapid electron transfer or decompose to give radical-cationic vinyl ether or protonic acid, both of which are responsible for the initiation of vinyl ether cationic polymerization.

关 键 词：氨酯型乙烯基醚 二苯基碘鎓六氟磷酸盐 热聚合 阳离子聚合 

分 类 号：O657[理学—分析化学]