氧杂环丁烷开环聚合  

Cationic Ring-opening Polymerization of Substituted Oxetane Monomers

作　　者：叶霖[1] 高鹏[1] 张晓雯[1] 冯增国[1] 吴锋[2] 陈实[2] 王国庆[2] 

机构地区：[1]北京理工大学材料科学与工程学院,北京100081 [2]北京理工大学化工与环境学院

出　　处：《功能高分子学报》2005年第4期651-659,共9页Journal of Functional Polymers

基　　金：国家"973"计划(批准号2002CB211800)资助

摘　　要：合成了以丙腈基和三甘醇单甲醚为侧基的两类聚氧杂环丁烷POE与POA。用GPC测定了其分子量和分子量分布,用1H-NMR和13C-NMR谱表征了聚合物的结构。认为活性链端机理和活性单体机理两种机理的相互竞争、相互转换可解释氧杂环丁烷阳离子开环聚合反应中无法通过单体与引发剂的摩尔浓度比来调节聚合物分子量,分子量分布宽,并伴有大量齐聚物生成的现象。采用逐滴进样可使AM机理占据主导地位,从而得到分子量可控的较窄分布的聚氧杂环丁烷。测试了聚合物与高氯酸锂复配后的电导率,结果表明:氧/锂摩尔比为20/1时,POE的室温电导率为10-4.43S/cm,80℃时为10-3.44S/cm。Two polyoxetanes, poly 3-（2-cyano ethoxy）methyl-3＇-methyloxetane（POA） and poly 3-（methoxy（triethyl- enoxy）） methyl-3＇-methyloxetane （POE） were synthesized by the cationic ring-opening polymerization（CROP）. In order to investigate the reaction mechanism of CROP, four groups of polymerization experiments were carried out under various reaction conditions, and GPC was used to measure the molecular weight and its distributions. The structure o polymers was characterized by ^1H-NMR and ^13C-NMR. The observations such as molecular weight hardly relying on the ratio of monomer to initiator（M/I）, broad molecular weight distribution and the formation of oligomers are explained by the competition and transformation of two chain propagation mechanisms, i.e. active chain end （ACE）mechanism and active monomer （AM）mechanism. The polymerization can be controlled to predominately follow up AM mechanism by adding monomer dropwise so that the narrow distribution polymer whose molecular weight depended on M/I is obtained without oligomer. And ion conductivity of polymers complexed with LiClO4 was measured. POE electrolyte with a ratio of no / nLi = 20/1 has the highest ion conductivity which reached 10^-4.43 S/cm at room temperature and 10^-3.44 S/cm at 80℃.

关 键 词：氧杂环丁烷 阳离子开环聚合 活性链端机理 活性单体机理 电导率 

分 类 号：O631[理学—高分子化学]