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纸质出版日期:1964-8-20,
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谢洪泉, 金炳兴, 单新忠. 以乙基鋰为催化剂的丁二烯阴离子聚合动力学[J]. 高分子学报, 1964,6(4):312-316.
SHIEH HONG-CHUAN, CHIN PING-SHING, SHEN SHIN-CHUNG. KINETIC STUDY OF ANIONIC POLYMERIZATION OF BUTADIENE BY ETHYLLITHIUM[J]. Acta Polymerica Sinica, 1964,6(4):312-316.
本工作用膨胀计研究了乙基锂在苯中聚合丁二烯的动力学
指出聚合速度对单体浓度是一级关系
对催化剂浓度是1/6—1/7级关系。聚合活化能为19千卡左右。通过气体体积色谱法测定聚合过程中未参与引发的乙基锂水解后放出的乙烷量以研究引发速度。结果指出
聚合转化率达10%左右时
将近90%的乙基锂已参与引发。此外
还研究了给电子试剂对聚合速度的影响
指出四氢呋喃能大大提高聚合速度及引发速度
三乙胺或乙醚次之
乙硫醚、苯甲醚或萘则影响不大。
Kinetics of polymerization of butadiene by ethyllithium in benzene have been studied by means of dihtometer. It has been shown that the polymerization rate iS first order in monomer concentration and 1/6 th order in ethyllithium concentration,when the con-centration of ethyllithium is in the range of 0.0045—0.0215 mole/liter. within 10-30℃,the activation energy of polymerization has been determined to be 19+0.5 kcal/mole.The rate of initiation has been determined by measuring the volume of ethane evolved after hydrolyzing the ethyllithium unconsumed in polymerization.The results show that when the conversion reaches about 10%,90%of ethyllithium is consumed in initiation Molecular weight distribution of the product as determined by fractional precipitation is shown to be very narrow. Addition of small quantity of tetrahydrofuran greatly increases both the polymerization rate and the initiation rate. Ethyl ether or triethylamine likewise increases the polymerization rate but less strongly.Anisole.diethyl sulfide or naphthalene almost show no effect on the polymerization rate.
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