用FTIR研究聚氨酯弹性体的固化动力学
李再峰 胥振芹 丁彩凤 高照连 李德和 杨光华
摘要:使用傅里叶变换红外光谱仪,原位跟踪了催化及未催化聚氨酯弹性体(PU)的固化反
应动力学行为。结果表明,—NCO和—OH的本体聚合在反应初期遵循二级反应和催化动
力学规律;未催化和催化的PU固化反应的活化能分别为48.0kJ/mol和38.86kJ/mol,频率因子
分别为3.01×108L/(mol.s)和1.14×108L/(mol.s)。
关键词:傅里叶变换红外光谱;聚氨酯;本体聚合;固化;动力学
中图分类号:TQ334.1文献标识码:A
文章编号:1000-1255(2000)04-0219-03
Curing kinetics of PU elastomers by FTIR
Li Zaifeng Xu Zhenqin Ding Caifeng Gao Zhaolian
and Li Dehe
(Department of Applied Chemistry,Qingdao Institute of Chemical
Technology,Qingdao,Shandong 266042)
Yang Guanghua
(Key Laboratory of State Heavy Oil Processing,University of Petroleum,Beijing 102200)
Abstract:The kinetics of curing reaction of
polyurethane elastomers was analysed by in- situ quantitive FTIR.The reactions,
uncatalyzed and catalyzed by dibutyltin dilaurate(DBTDL), followed second- order
kinetics at low conversion.At high conversion, however, the second- order rate constants
decreased with the increase of reaction extent, due to the influence of diffusion
control.The reaction kinetics parameters were given and the possible reaction mechanism
was further
offered. DBTDL was effectively positive catalyst for the reaction of — NCO with — OH.
Keywords: Fourier transfer infrared spectroscopy;polyurethane;bulk
polymerization;curing;kinetics
基金项目:国家计划经济发展委员会“八五”重点科技攻关资助项目(85-507-20)。
作者简介:李再峰,32岁,博士,讲师。已发表论文16篇。
李再峰(青岛化工学院应用化学系,山东青岛266042)
胥振芹(青岛化工学院应用化学系,山东青岛266042)
丁彩凤(青岛化工学院应用化学系,山东青岛266042)
高照连(青岛化工学院应用化学系,山东青岛266042)
李德和(石油大学重质油加工实验室,北京102200)
参考文献:
1,Ricter E B, Macosko C W.Kinetics fast(RIM) urethane
polymerization[J].Polym Eng Sci,1978,16(13): 1 013
2,Camargo R E ,Macosko C W, Tirrell M V, et al.Experimental studies of phase separation
in reaction injection
molded(RIM)polyurethanes[J]. Polym Eng Sci, 1982,22(11): 719
3,Nguyen A H , Marechal E. Infrared kinetics study of catalyzed and uncatalyzed reaction
of butanol- 1 with α - 1
naphthylisocyanate in various solvents[J]. J Macromol Sci Chem, 1981,A16(4): 88
4,邵雯,赵根所,杨惠昌.用红外光谱法研究聚氨酯生成动力学[J].光谱学与光谱分析,1985,5(3):8
5,Hsu T J,Lee L.Reaction injection molding of polyureas I.Kinetics study[J]. J Polym Eng
Sci,1988,28(25):957
6,李再峰,辛浩波,杨光华,等.RIM聚氨酯弹性体预聚物的反应动力学研究[J].青岛化工学院学报,1998,19(4):324
7,潘碧莲,徐强,姜志国.RIM聚氨酯体系锡/胺催化剂作用机理的研究[J].高分子材料科学与工程,1993,(3):17~23
8,罗善国,潭惠民,张建国,等.聚氨酯体系中的相互作用[J].北京理工大学学报,1997,17(4):426~427
收稿日期:1999-07-27
修订日期:1999-11-25 |