己二胺四亚甲基膦酸掺杂聚苯胺的制备与结构表征

Preparation,and characterization of HDTMPA-PANI

为制备较好阻燃性、导电性能和热稳定性的功能化聚苯胺,以苯胺为单体,己二胺四亚甲基膦酸(HDTMPA)为掺杂剂,过硫酸铵为氧化剂,通过化学氧化聚合法合成本征态和掺杂态聚苯胺。采用单因素试验方法,探讨原料配比、反应温度和反应时间等因素对己二胺四亚甲基膦酸掺杂聚苯胺(HDTMPA-PANI)电阻率和产量的影响,考察热处理温度对其电阻率的影响。运用红外光谱和透射电镜测试技术,研究HDTMPA-PANI的分子结构和聚集态微观结构。结果表明,制备HDTMPA-PANI的最佳工艺条件为:过硫酸铵、HDTMPA和苯胺的摩尔比为1.1∶1.6∶1,反应时间1.0 h,反应温度5℃,HDTMPA-PANI的粉末电阻率约30.80Ω·cm,热分解温度大于150℃。HDTMPA-PANI分子中苯胺单体以头尾形式相连,大分子间通过分子间作用力结合形成不规则的、较致密的块状结构。

In order to prepare functional polyaniline with better flame retardant,electrical conductivity and thermal stability,undoped and doped polyaniline were synthesized by chemical oxidative polymerization method,using aniline as the reactive monomer,HDTMPA as the dopant and ammonium peroxydisulfate as the oxidant. The effects of raw material ratio,reaction temperature and time on the resistivity and yield of HDTMPA-PANI were studied using single factor experiment method.The influence of heat treatment temperature on the resistivity of HDTMPA-PANI was discussed; themolecular structure and aggregation structure of HDTMPA-PANI were measured by infrared spectroscopy and transmission electron microscopy（ TEM）. It was found that the optimal technological conditions for the preparation of HDTMPA-PANI were as below： the molar ratio of ammonium sulfate,HDTMPA and aniline was 1.1 ∶ 1.6 ∶ 1,the reaction time was 1. 0 h and the reaction temperature was5 ℃. The resistivity of HDTMPA-PANI powder was about 30. 80 Ω · cm,thermal decomposition temperature was more than 150 ℃. The aniline monomer was connected by the head and tail,and large molecules were formed by the intermolecular forces and combined the irregular and dense block structures.