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稳定合成高分子量聚对苯二甲酰对苯二胺(PPTA)树脂是生产高性能芳纶纤维的基础.在PPTA聚合过程中,以单体对苯二甲酰氯(TPC)/N-甲基吡咯烷酮(NMP)溶液与单体对苯二胺(PPD)/NMP溶液进行溶液缩聚反应是最理想高效的方式,但是因为TPC/NMP间未知的相互作用导致这种聚合方式难以实现.通过实验与计算模拟相结合的方式,利用红外光谱(FTIR)、核磁共振(1H NMR)、飞行时间质谱及示差扫描量热分析对TPC/NMP间的反应进行了分析,并通过分子模拟计算证明TPC与NMP会发生类似Vilsmeier-Haack反应,导致TPC上的酰氯基团失活,从而严重影响其聚合反应活性.最后,通过PPTA聚合实验验证了该结论的正确性.
Stable synthesis of high molecular weight poly (p-phenyleneterephthalamide) (PPTA) resin is the basis for the production of high-performance aramid fiber.Under the process of PPTA polymerization, the monomer of terephthalic acid (TPC) / N-methyl Polycondensation reaction of pyrrolidone (NMP) solution and monomer p-phenylenediamine (PPD) / NMP solution is the most ideal and efficient way, but this polymerization mode is difficult to realize because of the unknown interaction between TPC / NMP. The reaction between TPC / NMP was analyzed by FTIR, 1H NMR, TOFM and DSC. The results of molecular simulation showed that TPC and NMP A similar Vilsmeier-Haack reaction will occur, resulting in the inactivation of the acid chloride groups on the TPC, which will seriously affect its polymerization activity.Finally, the correctness of this conclusion is verified by PPTA polymerization experiments.