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

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E_a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(T_d5)达355 ℃

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

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 E_a＝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 (T_d5) of the polymer reached 355 ℃.