自由基聚合反应动力学常数测定技术

自由基聚合是一类重要的聚合反应，其反应动力学常数的获取对于聚合机理研究、聚合物链结构定制、反应过程调控都有着重要的意义。综述了自由基聚合中最重要的链增长和链终止反应速率常数的测定方法，着重介绍连续脉冲激光引发结合凝胶渗透色谱测定链增长反应速率常数、单脉冲-连续脉冲激光耦合结合近红外光谱与电子顺磁共振波谱测定链终止反应速率常数，涵盖了各方法的检测原理、要求和适用条件，讨论了增长自由基链长对链增长和链终止反应速率常数的影响。此外，对链增长和链终止反应速率常数检测方法的提升和新方法的开发进行了展望。

Characterization technique for kinetic coefficients of free radical polymerization

Free radical polymerization (FRP) is one of the key polymerization reactions, its kinetic coefficient is imperative for mechanism study, chain structure customization, and reaction process control. In this paper, we review the state-of-art characterization technique involved in determination of critical parameters in FRP, i.e., propagation rate coefficient and termination rate coefficient. A pulsed laser polymerization (PLP) in conjunction with size exclusion chromatography (SEC) is effective to determine propagation rate coefficient. A particular single pulse-pulsed laser polymerization (SP-PLP) in conjunction with near infrared (NIR) and electron paramagnetic resonance (EPR) spectroscopy is unrivaled to identify termination rate coefficient. The theory, test prerequisites, and testing conditions for each detection method are outlined, and the effects of increased radical chain length on propagation and termination rate coefficient are discussed. In addition, the potential on the improvement and development of new technique for the propagation rate coefficient and termination rate coefficient is delivered.