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采用Nd(P507)3 LiBu AlEt3和AlEt3 VCl3两种催化剂体系分别合成了两种分子量与反式1,4单元结构含量不同的反式1,4 聚丁二烯样品(TPBD)。用DSC方法不仅研究了两样品六方相晶体的非等温结晶过程,同时还对单斜相结晶的非等温动力学过程进行了研究。Avrami方程分析显示,在低结晶度下TPBD六方相和单斜相的结晶生长过程呈现热成核的三维球晶生长。研究表明:虽然Ozawa方程在较低温度下能描述TPBD的六方相结构的实验数据,但不能完全描述在较高温度下六方相及单斜相非等温结晶过程,而用莫志深等建议的方程则能很好地描述TPBD六方相和单斜相非等温结晶过程。由Kissinger方程得到TPBD六方相和单斜相结晶的平均结晶活化能分别为-165.8kJ/mol和-220.5kJ/mol。
Two trans-1,4-polybutadiene samples (TPBD) with different molecular weights and trans 1,4 units were synthesized by Nd (P507) 3 LiBu AlEt3 and AlEt3 VCl3 catalysts. The DSC method not only studied the non-isothermal crystallization of hexagonal samples, but also studied the non-isothermal kinetics of monoclinic crystals. Avrami equation analysis shows that the crystal growth of the hexagonal and monoclinic phases of TPBD shows a three-dimensional thermo-nucleated spherulitic growth at low crystallinity. The results show that although the Ozawa equation can describe the experimental data of the hexagonal phase structure of TPBD at lower temperature, it can not fully describe the non-isothermal crystallization process of hexagonal phase and monoclinic phase at higher temperature. However, The equation can well describe the non-isothermal crystallization process of hexagonal and monoclinic phase of TPBD. The average activation energies of the hexagonal and monoclinic phases of TPBD obtained by Kissinger equation are -165.8kJ / mol and -220.5kJ / mol, respectively.