环氧丙烷阴离子聚合及反应动力学  

Anionic Polymerization of Propylene Oxide and Its Kinetics

作　　者：朱叙伟[1] 杨鹏飞[1,2] 李俊英[1] 李天铎[1,2] 

机构地区：[1]山东轻工业学院轻化与环境工程学院,山东济南250353 [2]江南大学化学与材料工程学院,江苏无锡214122

出　　处：《高分子材料科学与工程》2010年第3期15-18,共4页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(20676074)

摘　　要：用六甲基磷酰三胺作溶剂,叔丁醇钾作引发剂进行环氧丙烷的活性聚合反应,得到分子量分布系数为1.04的聚环氧丙烷,用红外光谱(IR)和核磁共振(1H-NMR)表征产物结构,确定了1H-NMR谱图中各峰的归属;用核磁共振法测定了产物的数均分子量,发现其存在2800的上限;同时,根据1H-NMR数据计算出反应中的链转移常数,链转移常数的迅速增大是产生分子量上限的原因之一;最后,用在线红外技术研究环氧丙烷阴离子聚合过程,根据吸光度-浓度工作曲线求得聚合反应的活化能为38.0kJ/mol,动力学方程为r=dC/dt=1.7×103exp(Ea/RT)C(mol.L-1.min-1)。The polymerization of propylene oxide in hexamethyl phosphoramide（HMPT）was investigated with potassium t-butoxide as initiator.Monodisperse poly（propylene oxide）was obtained（PDI=1.04）,then infrared spectroscopic（IR）and hydrogen nuclear magnetic resonance spectrum（1H-NMR）were used to characterize its structure,all the peaks in 1H-NMR spectra was assigned as well.Number average molecular weight was calculated by 1H-NMR and was limited to about 2800.Chain-transfer constants were calculated out and were found to increase with the molar ratio of propylene oxide to potassium t-butoxide,which may be lead to the upper limit of molecular weight.In-situ FT-IR spectroscopy was used to illustrate the anionic polymerization of propylene oxide.According to the calibration of absorbance to concentration,activation energy was worked out to be 38.0 kJ/mol and the kinetic equation was deduced to be.

关 键 词：阴离子聚合 聚环氧丙烷 动力学 在线红外 

分 类 号：TQ316.324[化学工程—高聚物工业]