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作 者:冯增国
出 处:《Chinese Journal of Polymer Science》2006年第5期503-513,共11页高分子科学(英文版)
基 金:This research work was funded by National Key Projects on Basic Research and Development (The "973" Project, No. 2002CB211800).
摘 要:Two oxetane-derived monomers, 3-(2-cyano-ethoxy)methyl- and 3-(methoxy-(triethylenoxy))methyl-3'- methyloxetane (COX and MTOX), were prepared from 3-hydroxymethyl-3'-methyloxetane. Their homo- and copolymerization in solution were carried out by the cationic ring-opening polymerization with BF3 · Et2O and 1,4-butanediol as co-initiator. The molecular weight and molecular weight distribution were determined using GPC so as to reveal the competition and interchange between active chain end (ACE) and activated monomer (AM) mechanism in the process. The reactivity ratios of the two monomers were calculated according to Kelen-Tudos using ^1H-NMR analysis. The influence of functional side chains in the monomers on the copolymerization behaviors was discussed in virtue of the reactivity ratio data. When doped with lithium salt LiTFSI, the ion conductivity of the homopolymer of MTOX reached 10^-3.58 S/cm at 30℃ and 10^-2.73 S/cm at 80℃, respectively, showing its potential to be used as polymer electrolyte for lithium ion battery.Two oxetane-derived monomers, 3-(2-cyano-ethoxy)methyl- and 3-(methoxy-(triethylenoxy))methyl-3'- methyloxetane (COX and MTOX), were prepared from 3-hydroxymethyl-3'-methyloxetane. Their homo- and copolymerization in solution were carried out by the cationic ring-opening polymerization with BF3 · Et2O and 1,4-butanediol as co-initiator. The molecular weight and molecular weight distribution were determined using GPC so as to reveal the competition and interchange between active chain end (ACE) and activated monomer (AM) mechanism in the process. The reactivity ratios of the two monomers were calculated according to Kelen-Tudos using ^1H-NMR analysis. The influence of functional side chains in the monomers on the copolymerization behaviors was discussed in virtue of the reactivity ratio data. When doped with lithium salt LiTFSI, the ion conductivity of the homopolymer of MTOX reached 10^-3.58 S/cm at 30℃ and 10^-2.73 S/cm at 80℃, respectively, showing its potential to be used as polymer electrolyte for lithium ion battery.
关 键 词:Oxetane-derived monomer Cationic ring-opening polymerization AM mechanism ACE mechanism Reactivity ratio Ion conductivity.
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