化工学报 ›› 2023, Vol. 74 ›› Issue (2): 559-570.DOI: 10.11949/0438-1157.20221217

• 综述与专论 • 上一篇    下一篇

自由基聚合反应动力学常数测定技术

李雨萧1,2(), 王青月2, Ho Lim Khak2(), 李晓辉3, Erlita Mastan3, 彭博3(), 王文俊1,2,4()   

  1. 1.浙江大学工程师学院衢州分院,浙江 衢州 324000
    2.浙江大学衢州研究院,浙江 衢州 324000
    3.巴斯夫新材料 有限公司,上海 200137
    4.浙江大学化学工程联合国家重点实验室,浙江 杭州 310027
  • 收稿日期:2022-09-06 修回日期:2022-11-18 出版日期:2023-02-05 发布日期:2023-03-21
  • 通讯作者: Ho Lim Khak,彭博,王文俊
  • 作者简介:李雨萧(1999 —)女,硕士研究生,liyuxiao@zju.edu.cn
  • 基金资助:
    浙江大学衢州研究院项目(IZQ2021RCZX003);巴斯夫新材料有限公司项目

Characterization technique for kinetic coefficients of free radical polymerization

Yuxiao LI1,2(), Qingyue WANG2, Khak Ho LIM2(), Xiaohui LI3, Erlita MASTAN3, Bo PENG3(), Wenjun WANG1,2,4()   

  1. 1.Polytechnic Institute of Zhejiang University, Quzhou 324000, Zhejiang, China
    2.Institute of Zhejiang University-Quzhou, Quzhou 324000, Zhejiang, China
    3.BASF Advanced Chemicals Co. Ltd. , Shanghai 200137, China
    4.State Key Laboratory of Chemical Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
  • Received:2022-09-06 Revised:2022-11-18 Online:2023-02-05 Published:2023-03-21
  • Contact: Khak Ho LIM, Bo PENG, Wenjun WANG

摘要:

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。

关键词: 自由基聚合, 链增长速率常数, 链终止速率常数, 连续脉冲激光引发聚合, 单脉冲-连续脉冲耦合

Abstract:

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.

Key words: free radical polymerization, propagation rate coefficient, termination rate coefficient, pulsed laser polymerization, single pulse-pulsed laser

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