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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (07): 697-702. 上一篇    下一篇

研究论文

镍催化转移缩聚合成全氟环丁基芳基醚聚合物

吕绪良*,1，何超1，李垚功2，贾其1，宫长青1   

  1. (1解放军理工大学工程兵工程学院 南京 210007)
    (2中国科学院上海有机化学研究所 上海 200032)
  • 投稿日期:2010-01-28 修回日期:2010-03-02 发布日期:2010-04-14
  • 通讯作者: 吕绪良 E-mail:xllu1957@126.com

Synthesis of Perfluorocyclobutyl Aryl Ether-Containing Polymers via Kumada Catalyst-Tranfer Polycondensation

Lü Xuliang*,1 He Chao1 Li Yaogong2 Jia Qi1 Gong Changqing1   

  1. (1 Engineering Institute of Corps of Engineer, PLA University of Science and Technology, Nanjing 210007)
    (2 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032)
  • Received:2010-01-28 Revised:2010-03-02 Published:2010-04-14

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被引次数

12 | 1

研究了通过镍催化转移缩聚的方法来合成全氟环丁基芳基醚聚合物. 首先, 我们以对溴苯酚和1,2-二溴四氟乙烷为起始原料, 通过两步反应得到对溴三氟乙烯基芳基醚, 进一步加热环化二聚得到单体1,2-二(4-溴苯氧基)六氟环丁烷. 该二聚物再与异丙基格氏试剂发生镁交换反应, 生成格氏试剂中间体, 在催化剂Ni(dppe)Cl2的存在下发生镍催化转移缩聚生成聚合物. 研究了反应时间、温度和单体投料比对催化缩聚反应的影响.

关键词: 全氟环丁基芳基醚, 镍催化转移缩聚, 含氟聚合物

The synthesis of perfluorocyclobutyl aryl ether-based polymers via Kumada catalyst-tranfer polycondensation was studied. Firstly, 1-bromo-4-(1,2,2-trifluorovinyloxy)benzene was prepared through two-step reaction using 4-bromophenol and 1,2-dibromo-1,1,2,2-tetrafluoroethane as starting materials. Then, [2π＋2π] cycloaddition of 1-bromo-4-(1,2,2-trifluorovinyloxy)benzene yielded the dimer 4,4 -(perfluorocyclobutane-1,2-diyl)bis(oxy)bis(bromobenzene). Treatment of this dimer with i-PrMgCl gave an intermediate via a magnesium-bromine exchange reaction. Finally, polymerization of the intermediate was carried out using Ni(dppe)Cl2 as catalyst to yield polymer. Effect of reaction time and temperature as well as the feed ratio of the monomer to the catalyst on the polycondensation was also investigated.

Key words: perfluorocyclobutyl aryl ether, kumada catalyst-tranfer polycondensation, fluoropolymer