涂料工业 ›› 2010, Vol. 40 ›› Issue (2): 7-11.

• • 上一篇    下一篇

间苯二胺扩链剂酰基化合成聚脲反应动力学研究

刘宗瑜1,宋 蔚1,邓 宇2,郝静梅2   

  1. 1. 天津理工大学环境科学与安全工程学院,天津 300191;2. 天津科技大学化工学院,天津 300457
  • 出版日期:2010-02-28 发布日期:2019-05-31
  • 作者简介:刘宗瑜(1956-),男,副教授,主要从事环境工程和防腐蚀涂料的研究与应用。
  • 基金资助:
    国家自然科学基金(批准号:20676105)

Acetylating Modification Chain Extenderm-Phenylenediamine and Polyurea Reaction Kinetics

Liu Zongyu1, Song Wei1, Deng Yu2, Hao Jingmei2   

  1. 1. College of Entironmental Science and Safety Engineering, Tianjin Unirersity of Technology, Tianjin 300191,China; 2. College of Chemical Engineering, Tianjin University of Science & Technology, Tianjin 300457, China
  • Online:2010-02-28 Published:2019-05-31

摘要: 采用酰基化方法对扩链剂间苯二胺进行了改性,以减缓聚脲的高反应活性来研究合成反应的动力学方程。以间苯二胺、冰乙酸为原料,磷酸为催化剂合成了新型位阻型扩链剂二乙酰间苯二胺,并用红外光谱、高分辨质谱、凯氏定氮法和核磁共振氢谱分析确定了合成产物的化学结构。将它和端氨基聚醚、4,4’-二苯甲烷二异氰酸酯(MDI)通过两步溶液法合成了新型聚脲,考察了改性二胺扩链剂对聚脲性能的影响,并用傅里叶变换红外光谱仪(FTIR)跟踪该固化反应过程,得到了不同温度下的反应速度常数。实验结果表明,当用改性扩链剂代替原扩链剂合成聚脲时,凝胶时间大大延长。该反应体系表现为良好的一级动力学关系,并得出该反应的活化能。

关键词: 聚脲, 扩链剂, 二乙酰间苯二胺, 反应动力学

Abstract: Diacetyl m-phenylenediamine, a new hindered chain extender of polyurea, was prepared by acylation of m-phenylenediamine with glacial acetic acid at the presence of phosphoric acid as catalyst.This extender can decelerate the rate of polymerization between amines and isocyanates, easing to study the kinetics of curing of polyurea reaction. FTIR HRMS(ESI), Micro-kjeldahl method and 'H-NMR were used to determine the chemical structure of the extender. Polyureas were synthesized using methylene diphenyl-4, 4-diisocyanate and amine terminated poly oxypropylene ) by a two- step solution process.The influence of modified diamine extender on polyurea was investigated. And the curing precess was followed with FTIR to obtain the reaction constant at various temperatures. It was found that the gel time was prolonged, i. e, the reaction activity was decreased when diacetyl m-phenylenediamine was used as chain extender instead of m-phenylenediamine The results of kinetics experiments showed that the reaction belongs to a first -order reaction and give the value of Ea.

Key words: polyurea, chain extender, diacetyl m-phenylenediamine;reaction kinetics