不同结构聚三唑的固相聚合反应动力学  

Solid-Phase Polymerization Kinetics of Polytriazoles with Different Structures

作　　者：叶涛 吴雪莹 光善仪 徐洪耀 Tao Ye;XueyingWu;Shanyi Guang;Hongyao Xu(Key Laboratory of Eco-Textile Ministry of Education,School of Chemistry and Chemical Engineering,Donghua University,Shanghai 201620,China;Analytical Testing Centre and School of Materials and State Key Laboratory of Fibre Modification,Donghua University,Shanghai 201620,China)

机构地区：[1]东华大学化学与化工学院生态纺织教育部重点实验室,上海201620 [2]东华大学分析测试中心及材料学院纤维改性国家重点实验室,上海201620

出　　处：《高分子材料科学与工程》2025年第2期87-96,共10页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(52372282)。

摘　　要：以4,4'-二叠氮二苯甲烷(DAM)分别与DIAH,BPDIA,DIAO,BADIA不同酰亚胺炔在本体热聚合条件下制备了不同结构的聚三唑,利用红外和差示扫描量热法研究了其聚合反应工艺及其动力学之间的差异,通过外推法求出特征温度,用Kissinger和Ozawa法计算出相关动力学参数,并研究了催化剂对聚合反应动力学的影响。结果表明,聚合体系中含有柔性结构或者引入侧基结构会降低反应起始温度、反应峰值温度和反应所需的活化能,4种体系的反应级数均为0.95,可认为叠氮与炔基的反应是一级反应,向体系中加入催化剂可以有效地降低反应所需的活化能,不同催化剂的催化效果有着明显差异,使用Cu(PPh3)3Br作为催化剂时,体系的反应活化能为138.92 k J/mol,催化效果最好。Polytriazoles with different structures were prepared by using 4,4'-diazidodiphenylmethane(DAM)with four imide alkynes,DIAH,BPDIA,DIAO,and BADIA,respectively,under the conditions of intrinsic thermal polymerization.And the differences between their polymerization processes and their kinetics were studied by IR and differential scanning calorimetry.The characteristic temperatures were found out through extrapolation,and the relevant kinetics parameters were calculated by Kissinger and Ozawa method.And the effect of the addition of catalyst on the kinetics of the polymerization reaction was also investigated.The results show that the inclusion of flexible structure or the introduction of side group structure in the polymerization system would reduce the initial reaction temperature,peak reaction temperature and activation energy required by the reaction.The reaction level of all four systems is 0.95,which can be considered that the reaction between azide and alkyne is a first-order reaction.And the addition of catalyst to the system can effectively reduce the activation energy required for the reaction.The catalytic effect of different catalysts is obviously different.The reaction activation energy of the system when using Cu(PPh3)3Br as catalyst is 138.92 kJ/mol,which has the bettert catalytic effect.

关 键 词：聚合反应动力学 酰亚胺炔 活化能 4 4'-二叠氮二苯甲烷 

分 类 号：O631.5[理学—高分子化学]