聚偏氟乙烯-b-聚甲氧基聚乙二醇甲基丙烯酸酯共聚物的合成和凝聚态结构  

Synthesis and condensed matter structure of poly(vinylidene fluoride)-b-poly(poly(ethylene glycol)methyl ether methacrylate)copolymer

作　　者：高珊珊[1,2] 王文硕[1] 包永忠 GAO Shanshan;WANG Wenshuo;BAO Yongzhong(State Key Laboratory of Chemical Engineering,College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310058,China;College of Chemistry and Chemical Engineering,Guizhou University,Guiyang 550025,China)

机构地区：[1]化学工程联合国家重点实验室(浙江大学),浙江大学化学工程与生物工程学院,浙江杭州310058 [2]贵州大学化学与化工学院,贵州贵阳550025

出　　处：《高校化学工程学报》2023年第4期560-566,共7页Journal of Chemical Engineering of Chinese Universities

摘　　要：为了制备综合性能优异的固态聚合物电解质基材,通过碘转移活性自由基聚合(ITP)合成聚偏氟乙烯-b-聚甲氧基聚乙二醇甲基丙烯酸酯(PVDF-b-PPEGMA)共聚物。通过1H-核磁共振和凝胶渗透色谱证明了共聚物分子的合成,采用红外光谱和透射电子显微镜分析共聚物的凝聚态结构,并测试共聚物/双三氟甲基磺酰亚胺锂(LiTFSi)固态聚合物电解质的电导率。结果表明:聚甲氧基聚乙二醇甲基丙烯酸酯(PPEGMA)链段的嵌段引入可促进β相聚偏氟乙烯(PVDF)结晶的形成;PVDF和PPEGMA链段热力学不相容,嵌段共聚物存在微相分离,随着PPEGMA嵌段比增加,共聚物由“海-岛”相结构向双连续相结构转变。PPEGMA质量分数为25.5%的嵌段共聚物与锂盐混合(氧化乙烯与Li^(+)物质的量比n(EO):n(Li^(+))为10:1)能达到9.4×10^(-5)S·cm^(−1)的室温离子电导率。In order to obtain solid polymer electrolyte matrices with good comprehensive properties,poly(vinylidene fluoride)and poly(ethylene glycol)methyl ether methacrylate block copolymers(PVDF-b-PPEGMA)were synthesized by iodine transfer polymerization(ITP).The molecular structure of synthesized block copolymer were confirmed by 1H nuclear magnetic resonance and gel permeation chromatography.The condense matter structures were characterized by Flourier transform infrared and transmission electron microscopy,and the conductivity of copolymer/bis(trifluoromethane sulfonimide)(LiTFSi)solid polymer electrolyte was measured.The results indicate that the introduction of PPEGMA promotes formation ofβ-phase PVDF crystalline.The block copolymers exhibited micro-phase separation behavior due to the thermodynamics incompatibility of PVDF and PPEGMA.Micro-phase structure varied from‘sea-island’to bicontinuous with the increase of PPEGMA block ratios.The ionic conductivity was 9.4×10^(-5)S·cm^(-1)at ambient temperature when the block copolymer containing 25.5%PPEGMA was composited with bis(trifluoromethanesulfonyl)imide(the molar ratio of ethylene oxide to Li+is 10:1).

关 键 词：偏氟乙烯 甲氧基聚乙二醇甲基丙烯酸酯 嵌段共聚物 结晶 相结构 

分 类 号：TQ317.5[化学工程—高聚物工业]