自由基聚合反应动力学常数测定技术

doi:10.11949/0438-1157.20221217

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

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.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.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/Abstract

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

中图分类号:

TQ 028.8

李雨萧, 王青月, Ho Lim Khak, 李晓辉, Erlita Mastan, 彭博, 王文俊. 自由基聚合反应动力学常数测定技术[J]. 化工学报, 2023, 74(2): 559-570.

Yuxiao LI, Qingyue WANG, Khak Ho LIM, Xiaohui LI, Erlita MASTAN, Bo PENG, Wenjun WANG. Characterization technique for kinetic coefficients of free radical polymerization[J]. CIESC Journal, 2023, 74(2): 559-570.

图/表 4

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114	Boukaftane C, van Herk A M. PLP and MALDI-ToF determination of propagation rate coefficients of fast-polymerizing acrylates with heterocyclic side-chains: tetrahydrofurfuryl acrylate and (R)-alpha-acryloyloxy-beta, beta-dimethyl-gamma-butyrolactone[J]. Macromolecular Chemistry and Physics, 2011, 212(1): 96-101.
115	Shi Y J, Yu M X, Liu J, et al. Quantitative structure-property relationship model for predicting the propagation rate coefficient in free radical polymerization[J]. Macromolecules, 2022, 55(21): 9397-9410.

单体	本体/溶液聚合	文献
苯乙烯	本体，苯甲醇， N-甲基吡咯烷酮，苯甲醚，二甲基甲酰胺，异丁酸甲酯，甲苯，苯，二甲基亚砜，溴化苯，环己烷，均三甲基苯，二氯乙烷，乙腈，二氧化碳，丙烯腈	[6,24-27,35-36,46-47]
4-甲基苯乙烯	本体	[46]
4-氟苯乙烯	本体	[46]
4-氯苯乙烯	本体	[46]
4-溴代苯乙烯	本体	[46]
4-甲氧基苯乙烯	本体	[46]
丙烯腈	碳酸丙烯酯	[48]
甲基丙烯酸甲酯	本体, 丙烯腈，苯甲醚，苯甲醇，苯，溴化苯，二氧化碳，环己烷，二甲基亚砜，二甲基甲酰胺，甲基乙基甲酮，乙醇，甲醇，均三甲基苯，异丁酸甲酯，N-甲基吡咯烷酮，甲苯，二氯乙烷	[23-27,29,49-53]
甲基丙烯酸乙酯	本体	[23,30,37,54]
甲基丙烯酸丁酯	本体，2-庚酮	[23,30,54-57]
i-甲基丙烯酸丁酯	本体	[57]
甲基丙烯酸异辛酯	本体	[57]
i-甲基丙烯酸异癸酯	本体	[57]
甲基丙烯酸月桂酯	本体，2-庚酮，乙酸辛酯	[30,55-57]
甲基丙烯酸苄基酯	本体	[23,58]
甲基丙烯酸环己酯	本体，2-庚酮，乙酸辛酯	[58-59]
i-甲基丙烯酸冰片酯	本体	[58]
甲基丙烯酸羟乙酯	本体	[59]
甲基丙烯酸羟丙酯	本体	[58]
甲基丙烯酸缩水甘油酯	本体	[58-60]
甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷	本体	[61]
甲基丙烯腈	本体	[62]
非电离甲基丙烯酸	本体，甲醇，甲苯，四氢呋喃，乙酸，水	[32,40,51,63]
丙烯酸甲酯	本体，链长依赖性链增长反应速率常数	[63-64]
丙烯酸丁酯	本体，四氢呋喃，二氧化碳	[65-68]
丙烯酸丁酯二聚物	本体	[69]
2-乙基己基丙烯酸甲酯	本体	[35]
丙烯酸十二烷基酯	本体	[63]
N-异丙基丙烯酰胺	水	[70]
丙烯酸	水	[38]
丙烯酰胺	水	[41]
乙酸乙烯酯	本体，叔丁醇，二氧化碳	[71-73]
新癸酸乙烯基酯	本体	[74]
氯丁二烯	本体	[33]
1,3-丁二烯	氯苯	[43]
甲基丙烯酸α-羟乙酯	苯，丁酮，氯苯，氯仿，环己烷，乙醇，二氯甲烷，乙酸乙酯，四氢呋喃，1-戊醇，丙醇，甲苯，二甲苯，乙苯	[75]
N-乙烯基吡咯烷酮	水	[76]
衣康酸二甲酯	水	[77]
氨基甲酸羟丙酯丙烯酸酯	本体	[78]
甲基丙烯酸亚乙基脲乙氧基酯	本体	[78]
2-(乙基(苯基)氨基)甲基乙酸乙酯	本体	[79]
2-正吗啉丙烯酸乙酯	本体	[79]
2-（1-哌啶基）甲基丙烯酸乙酯	本体	[79]
n-戊基丙烯酸甲酯	本体，甲苯	[80]
苯乙烯和甲基丙烯酸缩水甘油酯共聚	本体	[60]
甲基丙烯酸羟乙酯和甲基丙烯酸丁酯共聚	本体，二甲苯，二甲基甲酰胺，正丁醇	[81]
丙烯酸甲酯和N-叔丁基丙烯酰胺共聚	乙醇水溶液	[82]

单体	本体/溶液聚合	文献
苯乙烯	本体，苯甲醇， N-甲基吡咯烷酮，苯甲醚，二甲基甲酰胺，异丁酸甲酯，甲苯，苯，二甲基亚砜，溴化苯，环己烷，均三甲基苯，二氯乙烷，乙腈，二氧化碳，丙烯腈	[6,24-27,35-36,46-47]
4-甲基苯乙烯	本体	[46]
4-氟苯乙烯	本体	[46]
4-氯苯乙烯	本体	[46]
4-溴代苯乙烯	本体	[46]
4-甲氧基苯乙烯	本体	[46]
丙烯腈	碳酸丙烯酯	[48]
甲基丙烯酸甲酯	本体, 丙烯腈，苯甲醚，苯甲醇，苯，溴化苯，二氧化碳，环己烷，二甲基亚砜，二甲基甲酰胺，甲基乙基甲酮，乙醇，甲醇，均三甲基苯，异丁酸甲酯，N-甲基吡咯烷酮，甲苯，二氯乙烷	[23-27,29,49-53]
甲基丙烯酸乙酯	本体	[23,30,37,54]
甲基丙烯酸丁酯	本体，2-庚酮	[23,30,54-57]
i-甲基丙烯酸丁酯	本体	[57]
甲基丙烯酸异辛酯	本体	[57]
i-甲基丙烯酸异癸酯	本体	[57]
甲基丙烯酸月桂酯	本体，2-庚酮，乙酸辛酯	[30,55-57]
甲基丙烯酸苄基酯	本体	[23,58]
甲基丙烯酸环己酯	本体，2-庚酮，乙酸辛酯	[58-59]
i-甲基丙烯酸冰片酯	本体	[58]
甲基丙烯酸羟乙酯	本体	[59]
甲基丙烯酸羟丙酯	本体	[58]
甲基丙烯酸缩水甘油酯	本体	[58-60]
甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷	本体	[61]
甲基丙烯腈	本体	[62]
非电离甲基丙烯酸	本体，甲醇，甲苯，四氢呋喃，乙酸，水	[32,40,51,63]
丙烯酸甲酯	本体，链长依赖性链增长反应速率常数	[63-64]
丙烯酸丁酯	本体，四氢呋喃，二氧化碳	[65-68]
丙烯酸丁酯二聚物	本体	[69]
2-乙基己基丙烯酸甲酯	本体	[35]
丙烯酸十二烷基酯	本体	[63]
N-异丙基丙烯酰胺	水	[70]
丙烯酸	水	[38]
丙烯酰胺	水	[41]
乙酸乙烯酯	本体，叔丁醇，二氧化碳	[71-73]
新癸酸乙烯基酯	本体	[74]
氯丁二烯	本体	[33]
1,3-丁二烯	氯苯	[43]
甲基丙烯酸α-羟乙酯	苯，丁酮，氯苯，氯仿，环己烷，乙醇，二氯甲烷，乙酸乙酯，四氢呋喃，1-戊醇，丙醇，甲苯，二甲苯，乙苯	[75]
N-乙烯基吡咯烷酮	水	[76]
衣康酸二甲酯	水	[77]
氨基甲酸羟丙酯丙烯酸酯	本体	[78]
甲基丙烯酸亚乙基脲乙氧基酯	本体	[78]
2-(乙基(苯基)氨基)甲基乙酸乙酯	本体	[79]
2-正吗啉丙烯酸乙酯	本体	[79]
2-（1-哌啶基）甲基丙烯酸乙酯	本体	[79]
n-戊基丙烯酸甲酯	本体，甲苯	[80]
苯乙烯和甲基丙烯酸缩水甘油酯共聚	本体	[60]
甲基丙烯酸羟乙酯和甲基丙烯酸丁酯共聚	本体，二甲苯，二甲基甲酰胺，正丁醇	[81]
丙烯酸甲酯和N-叔丁基丙烯酰胺共聚	乙醇水溶液	[82]

单体	本体/溶液聚合	文献
衣康酸二丁酯	本体	[87]
丙烯酸甲酯	本体，甲苯	[88]
丙烯酸十二烷基酯	本体，甲苯	[88]
甲基丙烯酸三甲氨基乙酯	本体，水	[5,99]
丙烯酸三甲氨基乙酯	水	[99]
苯乙烯	本体	[99]
丙烯酰胺	水	[99]
甲基丙烯酸钠酯	水	[99]

单体	本体/溶液聚合	文献
衣康酸二丁酯	本体	[87]
丙烯酸甲酯	本体，甲苯	[88]
丙烯酸十二烷基酯	本体，甲苯	[88]
甲基丙烯酸三甲氨基乙酯	本体，水	[5,99]
丙烯酸三甲氨基乙酯	水	[99]
苯乙烯	本体	[99]
丙烯酰胺	水	[99]
甲基丙烯酸钠酯	水	[99]

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自由基聚合反应动力学常数测定技术

Characterization technique for kinetic coefficients of free radical polymerization

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