摘要
采用非等温差示扫描量热法(DSC)研究了不同代数的超支化聚酯/聚乙二醇型聚氨酯体系的固化反应动力学,采用Kissinger法、Flynn-Wall-Ozawa法、Friedman-Reich-Levi法和Crane公式计算了各体系的表观活化能、反应级数、指前因子以及机理函数等固化反应动力学参数。结果表明,加入6%的第二、三、四代超支化聚酯后,聚氨酯反应体系的表观活化能由52.493 kJ·mol-1分别提高至100.862 kJ·mol-1、92.565 kJ·mol-1、76.315 kJ·mol-1;超支化聚酯的加入对-NCO与-OH之间的反应有一定的延缓作用,但不改变固化机理。从氢键和溶解度参数的角度浅析了超支化聚酯影响聚乙二醇型聚氨酯体系固化的原因。
Curing reaction kinetics of hyperbranched polyester（HBP）/PEG polyurethane systems were investigated by non-isothermal differential scanning calorimetry（DSC）.As for the HBP/PEG polyurethane systems containing different generations of HBP,the values of apparent activation energy,reaction order and frequency factor,and the curing reaction mechanism function were evaluated by Kissinger method,Flynn-Wall-Ozawa method,Friedman-Reich-Levi method and Crane formula,respectively.The results show that,after adding 6% hyperbranched polyester of the second,third and fourth generation,the values of apparent activation energy increase from 52.493 kJ·mol-1 to 92.565 kJ·mol-1,100.862 kJ·mol-1,76.315 kJ·mol-1,respectively.The addition of different generations of hyperbranched polyester can slow down the curing reaction between-NCO groups and-OH groups,but has no obvious effect on the curing reaction mechanism.From the point of view of hydrogen bond and solubility parameters,the sketchy analysis of the occurring reasons of above phenomena caused by the addition of different generations of HBP was conducted.
出处
《高校化学工程学报》
EI
CAS
CSCD
北大核心
2011年第3期447-452,共6页
Journal of Chemical Engineering of Chinese Universities
基金
常州大学校基金项目(ZMF08020068)
关键词
超支化聚酯
聚氨酯
固化动力学
差示扫描量热法(DSC)
氢键
溶解度参数
hyperbranched polyester
polyurethane
curing kinetics
differential scanning calorimetry（DSC）
hydrogen bond
solubility parameter
