Abstract: Hydroxy terminated polydimethylsiloxane (PDMS)was synthesized by using the one-step process via the anionic ring-opening polymerization of octamethylcyclotetrasiloxane (D₄) catalyzed by tetramethyl ammonium hydroxide (TMAH) in the presence of a minute amount of water.Based on the conversion and molecular weight of synthesized polymer determined with gel permeation chromatography (GPC), the teminated hydroxy group concentration (［OH］) of polymer was calculated. According to the mechanism study of teminated hydroxy formation and the transformation of catalyst in the process of polymerization, a kinetic model of teminated hydroxy formation was established.The relationship between chain transfer rate constant and temperature was obtained from the experimental data.The kinetic behavior of teminated hydroxy formation could be predicted by using the kinetic model.

摘要： 微量水条件下进行环硅氧烷阴离子开环聚合，一步制备羟基聚硅氧烷.在此基础上，对端羟基的生成机理及催化剂在聚合过程中的转化关系进行分析，建立了聚合过程中端羟基生成的动力学模型.运用该模型和实验数据，可以估算链转移速率常数，并得到链转移速率常数与温度关系的阿累尼乌斯方程，求得活化能为116 kJ•mol^-1.模型可用来预测端羟基生成的动力学行为.