摘要
合成了一种新型的二氟烷基磺酰氟单体2-(双环[2.2.1]庚-5-烯-2)-1,1-二氟-2-甲氧基丙基-1-磺酰氟.首先利用二氟甲基2-吡啶基砜和2-乙酰基-5-降冰片烯发生亲核加成反应,在低温下用三氟甲磺酸甲酯保护加成产物中的羟基,之后在KOH/MeOH的条件下脱去吡啶基,得到的二氟亚磺酸盐和Slectfluor试剂反应制得想要的二氟烷基磺酰氟单体.这种新型的二氟烷基磺酰氟单体和不同比例的降冰片烯单体在Grubbs第二代催化剂存在条件下进行开环烯烃复分解聚合(ROMP),所得的聚合物在碱性条件下水解,再用稀盐酸处理最终制得新型的含有二氟烷基磺酸的聚合物电解质膜.这些新型的聚合物电解质膜具有中等的室温质子电导(12～49mS/cm).
A novel difluoroalkanesulfonyl fluoride monomer,2-（bicyclo[2.2.1]hept-5-en-2-yl）-1,1-difluoro-2-methoxypropane-1-sulfonyl fluoride,was synthesized in two steps.Nucleophilic addition of 2-acetyl-5-norbornene with difluoromethyl 2-pyridyl sulfone,followed by methylation with methyl trifluoromethanesulfonate produced substituted difluoromethyl 2-pyridyl sulfone.Removal of the pyridyl group with KOH/MeOH,and fluorination with Selectfluor afforded the desired monomer.Novel poly（norbornene）s containing pendent difluoroalkanesulfonic acids were synthesized by copolymerization of varying molar ratios of norbornene with difluoroalkanesulfonyl fluoride monomer by ring opening metathesis polymerization（ROMP） using Grubbs second-generation catalyst,followed by hydrolyzing under basic condition and treatment with aqueous HCl.Room temperature proton conductivity（12-49 mS/cm） was observed with these new type of membranes.
出处
《中国科学：化学》
CAS
CSCD
北大核心
2011年第12期1833-1839,共7页
SCIENTIA SINICA Chimica
基金
国家自然科学基金(20825209,20832008和20772144)
中国科学院知识创新工程重要方向性项目资助
关键词
聚合物电解质膜
亲核二氟甲基化
二氟烷基磺酰氟
开环烯烃复分解聚合
polymer electrolyte membranes
nucleophilic difluoromethylation
difluoroalkanesulfonyl fluoride
ring opening metathesis polymerization
