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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (22): 2629-2634. 上一篇    下一篇

研究论文

1,3-二(炔丙基氧)苯与4,4'-二叠氮甲基联苯的聚合反应及聚合物性能的研究

黄建智1，万里强1，田建军1，赵占峰1，王晓飞1，扈艳红1，黄发荣*,1，杜磊2   

  1. (1华东理工大学材料科学与工程学院 超细材料制备与应用教育部重点实验室 上海 200237)
    (2上海航天科技集团第八研究院 上海 200233)
  • 投稿日期:2006-12-31 修回日期:2007-06-24 发布日期:2007-11-28
  • 通讯作者: 黄发荣

Polymerization of 1,3-Di(propargyloxy)benzene with 4,4'-Diazido- methylbiphenyl and Properties of the Formed Polytriazole

HUANG Jian-Zhi1; WAN Li-Qiang1; TIAN Jian-Jun1; ZHAO Zhan-Feng1; WANG Xiao-Fei1; HU Yan-Hong1; HUANG Fa-Rong*1; DU Lei2   

  1. (1 Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237)
    (2 The Eighth Academy of China Aerospace Corporation, Shanghai 200233)
  • Received:2006-12-31 Revised:2007-06-24 Published:2007-11-28
  • Contact: HUANG Fa-Rong

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研究了1,3-二(炔丙基氧)苯(BPOB)与4,4'-二叠氮甲基联苯(DAMBP)的本体聚合行为. 核磁共振氢谱(1H NMR)表征了聚合物的结构, 通过傅立叶红外技术(FT-IR)观察了反应过程中的基团变化情况, 采用差示扫描量热技术(DSC)研究了聚合反应动力学, 在较低温度(80 ℃)下二元叠氮与二元炔发生了1,3-偶极环加成聚合反应, 生成了主链含三唑环的聚合物; 利用Kissinger法和Crane法处理得到了反应的动力学参数: 反应级数为0.92, 反应活化能Ea为79.8 kJ• mol－1, 频率因子A为1.26×1010 min－1. 利用凝胶渗透色谱(GPC)、动态热机械分析(DMA)和热重分析方法(TGA)研究了聚合产物的性能. 结果表明, 聚合物的数均分子量达4.22×104, 聚合物有较高的玻璃化转变温度和良好的热稳定性, 玻璃化转变温度达到131 ℃, 热分解温度(Td5)达355 ℃

关键词: 1,3-偶极环加成反应, 聚合反应动力学, 线型聚三唑, 二元叠氮, 二元炔化合物

The bulk polymerization of two monomers, 1,3-di(propargyloxy)benzene and 4,4'-diazidomethylbiphenyl, was conducted and a polytriazole was obtained by 1,3-dipolar cycloaddition between these monomers. The structure of the polytriazole was determined by hydrogen nuclear magnetic resonance (1H NMR). The variation of the functional groups during the polymerization was analyzed by FT-IR. The polymerization kinetics was investigated by differential scanning calorimetry at different heating rates, and the kinetic parameters were obtained by Kissinger and Crane methods: the reaction order 0.92, the apparent activation energy Ea＝79.8 kJ•mol－1, and the frequency factor A＝1.26×1010 min－1. The results showed that the two monomers were easy to form the polytriazole at 80 ℃, which was characterized by gel permeation chromatography (GPC), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). The number average molecular weight of the polytriazole was 4.22×104. The polymer showed good thermal stability. The glass transition temperature of the polymer arrived at 131 ℃. The decomposition temperature (Td5) of the polymer reached 355 ℃.

Key words: 1,3-dipolar cycloaddition, polymerization kinetics, linear polytrizaole, diazide, dipropargyl compound