Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (6): 1132-1137.DOI: 10.6023/cjoc201312006 Previous Articles     Next Articles

Articles

对苯二甲酰氯与N-甲基吡咯烷酮反应机理以及对聚对苯二甲酰对苯二胺聚合的影响

郭澄龙a, 许甲a, 王力慧a, 庹新林a, 王罗新b   

  1. a. 清华大学化工系高分子研究所先进材料教育部重点实验室 北京 100084;
    b. 武汉纺织大学材料科学与工程学院 武汉 430200
  • 收稿日期:2013-12-06 修回日期:2014-01-17 发布日期:2014-03-03
  • 通讯作者: 庹新林 E-mail:tuoxl@mail.tsinghua.edu.cn
  • 基金资助:

    国家重点基础研究发展计划(973计划,No. 2011CB606102)资助项目.

Reaction Mechanism of Terephthaloyl Chloride/N-Methyl-2-pyrrolidone and the Effect on Poly(p-phenylene terephthalamide) Polymerization

Guo Chenglonga, Xu Jiaa, Wang Lihuia, Tuo Xinlina, Wang Luoxinb   

  1. a. Key Laboratory of Advanced Materials MOE, Institute of Polymer Science and Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084;
    b. College of Material Science and Engineering, Wuhan Textile University, Wuhan 430200
  • Received:2013-12-06 Revised:2014-01-17 Published:2014-03-03
  • Supported by:

    Project supported by the National Basic Research Program of China (973 Program, No. 2011CB606102).

Stable synthesis of high molecular weight of poly(p-phenylene terephthalamide) (PPTA) resin is the basis for the production of high-performance aramid fibers. In PPTA polymerization process, the feeding method of the monomer terephthaloyl chloride (TPC) has important influence on the molecular weight. In theory, using TPC/N-methyl-2-pyrrolidone (NMP) solution and monomer p-phenylene diamine (PPD)/NMP solution for solution polycondensation is the most ideal and effective way, but in real polymerization process, it is difficult to synthesize high molecular weight PPTA due to some unknown interaction between TPC and NMP. This article combines experiments and molecular stimulation together, using Frontier infrared spectroscopy (FTIR), 1H NMR, the time of flight mass spectrometer (TOF-MS) and differential scanning calorimetric analysis (DSC), analyzing the reaction between TPC and NMP, and verified that TPC and NMP has obvious reaction similar to Vilsmeier-Haack reaction through molecular stimulation, which may cause the chloride group on the TPC deactivating, and seriously influence its reactivity. And the conclusion is verified through PPTA polymerization experiments, and the longer TPC/NMP solution is prepared, the worse of the polymerization effect is. These observations and experiments suggest that it is not feasible to synthesize high molecular weight PPTA in industry using TPC/NMP solution feeding method.

Key words: PPTA, TPC/NMP, Vilsmeier-Haack reaction, molecular simulation