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在高温下 ,二氯二茂钛受光照引发二苯乙炔聚合 ,得到结晶度为 95 %的聚二苯乙炔 .经红外、质谱、热分析、X光衍射、元素分析等方法 ,确定其结构为顺顺式螺旋刚性棒状结构 ,形成假六方晶系堆积 ,螺旋柱直径即螺旋轴间距为 1 46nm ,其特征红外吸收峰位于 1179cm-1和 115 6cm-1.在聚合引发阶段中止反应 ,分离出聚合中间体六苯基苯 .根据不同温度时聚合转化率与时间的关系曲线 ,测得聚合活化能为 2 6× 10 5J/mol.热分析表明 ,结晶聚二苯乙炔在 493K至 5 73K比较稳定 ;在 713K的吸热峰显示出破坏晶格的能量 .根据聚合反应诱导期长、中间体和聚合物的结构以及阻聚反应 ,推断聚合过程中二氯二茂钛受光照产生二氯化钛 ,催化二苯乙炔进行均相定向聚合 .结晶聚二苯乙炔电导率小于 10 -12 (Ωcm) -1.
Under high temperature, the titanocene was polymerized by light irradiation of titanocene to obtain poly (diphenylacetylene) with 95% crystallinity.The structure was determined by infrared, mass spectrometry, thermal analysis, X-ray diffraction and elemental analysis Cis-type spiral rigid rod-like structure, the formation of pseudo-hexagonal system accumulation, helical column diameter or helical axis spacing of 1 46nm, the characteristic infrared absorption peaks at 1179cm-1 and 1156cm-1 in the polymerization initiation phase of the reaction was isolated According to the curve of the polymerization conversion rate versus time at different temperatures, the activation energy of polymerization was measured to be 26 × 10 5 J / mol. The thermal analysis showed that the crystallization of poly (styrenephthalate) at 493K to 5 73K And the endothermic peak at 713K shows the energy to destroy the crystal lattice.According to the long induction period of the polymerization reaction, the structure of the intermediate and the polymer and the polymerization inhibition reaction, it is deduced that during the polymerization, the titanocene dichloride Titanium, and catalyzed stilbene for homogeneous orientation polymerization.The conductivity of the crystalline poly (diphenylacetylene) is less than 10 -12 (Ωcm) -1.