高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (10): 1946-1951.

• 研究论文 • 上一篇    下一篇

3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3'-甲基氧杂环丁烷的合成及其共聚体研究

叶霖1, 冯增国1, 李世亭1, 吴锋2,3, 陈实2,3, 王国庆2,3   

  1. 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,北京100081;
    3. 国家高技术绿色材料发展中心,北京100081
  • 收稿日期:2004-11-03 出版日期:2005-10-10 发布日期:2005-10-10
  • 基金资助:

    国家“九七三”计划(批准号:2002CB211800)资助.

Studies on Synthesis of 3-(2-Cyano ethoxy)methyl- and 3-[triethylenoxy)]methyl-3'-methyloxetane and Their Copolymers

YE Lin1, FENG Zeng-Guo1, LI Shi-Ting1, WU Feng2,3, CHEN Shi2,3, WANG Guo-Qing2,3   

  1. 1. School of Materials Science & Engineering,
    2. School of Chemical Engineering & Environment,
    3. Laboratory of National Development Center of Hi-Tech Green Materials,Beijing Institute of Technology,Beijing 100081,China
  • Received:2004-11-03 Online:2005-10-10 Published:2005-10-10

摘要: 以三羟甲基乙烷为原料,通过脱水反应首先制得3-羟甲基-3'-甲基氧杂环丁烷(HMO).HMO再分别与丙烯腈和二缩三乙二醇单甲醚反应得到两个取代氧杂环丁烷单体3-(2-氰基乙氧基)甲基-和3-[甲氧基(三乙氧基)]甲基-3'-甲基氧杂环丁烷(HMOAN和HMOPEO).再用阳离子开环聚合方法,以BF3.乙醚作催化剂,丁二醇为引发剂,将两类单体共聚即可得到一系列不同组成的共聚物(PAP).利用1H NMR谱图计算了该共聚物中两种不同结构单元的比,结果表明,其与投料比基本吻合.GPC测得该共聚物的数均分子量范围为2 756-5 342,分子量分布为1.26-1.83.DSC测试结果发现,除在225-246 K之间有一个玻璃化转变温度之外,在305-348 K之间还存在一个热转变温度.TGA测得共聚物的分解温度为573 K,远高于目前广泛使用的液体电解质.电导率测试结果表明,AN20的室温电导率可达到1.07×10-5S/cm,353 K时电导率可达到2.79×10-4S/cm,接近实用要求.

关键词: 氧杂环丁烷单体, 阳离子开环聚合, 共聚反应, 离子电导率

Abstract: The two monomers 3-(2-cyano ethoxy)methyl- and 3-[-methyl-triethyloxetane were prepared from the reaction of 3-methyl-3'-hydroxylmethyl oxetane(HMO) with acrylonitrile and triethylene glycol monomethyl ether,respectively.A novel series of copolymers were synthesized by starting from these two monomers along with BF3·ether as the catalyst and BDO as the initiator via a cationic ring-opening copolymerization.The GPC analysis presents the number average molecular weight of the copolymers ranging from 2 756 to 5 342,and polydispersity from 1.26 to 1.83.Regarding the glass transition temperature(Tg),the DSC results imply that these copolymers would have a higher ion inductivity than pure PEO.And the TGA measurements reveal that the copolymers possess a very high heat decomposition temperature.The conductivity of the AN20 at room temperature is about 1.07×10-5 S/cm,while at 353 K is 2.79×10-4(S/cm),approaching the practical requirement of polymer electrolytes for lithium ion batteries.

Key words: Oxetane-derived monomer, Cationic ring-opening polymerization, Copolymerization, Ion conductivity

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