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化学进展 2022, Vol. 34 Issue (6): 1298-1307 DOI: 10.7536/PC210736 前一篇   后一篇

• 综述与评论 •

RAFT链转移剂的选用原则及通用型RAFT链转移剂

尹航1,2, 李智1,2, 郭晓峰1,2, 冯岸超1,2,*(), 张立群1,2, 汤华燊3   

  1. 1 北京化工大学 有机无机复合材料国家重点实验室 北京 100029
    2 北京化工大学材料科学与工程学院 先进弹性体材料研究中心 北京 100029
    3 澳大利亚莫纳什大学化学学院 澳大利亚克莱顿VIC3800
  • 收稿日期:2021-07-28 修回日期:2021-12-14 出版日期:2022-04-01 发布日期:2022-04-01
  • 通讯作者: 冯岸超
  • 基金资助:
    有机-无机复合材料国家重点实验室(oic-202103015); 中国石油化工总公司(H2019485)
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Selection Principle of RAFT Chain Transfer Agents and Universal RAFT Chain Transfer Agents

Hang Yin1,2, Zhi Li1,2, Xiaofeng Guo1,2, Anchao Feng1,2(), Liqun Zhang1,2, San Hoa Thang3   

  1. 1 State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology,Beijing 100029, China
    2 Center of Advanced Elastomer Materials, College of Materials Science and Engineering, Beijing University of Chemical Technology,Beijing 100029, China
    3 School of Chemistry, Monash University, Clayton, Victoria 3800, Australia
  • Received:2021-07-28 Revised:2021-12-14 Online:2022-04-01 Published:2022-04-01
  • Contact: Anchao Feng
  • Supported by:
    Foundation of State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology(oic-202103015); China Petrochemical Corporation(H2019485)

可逆加成-断裂链转移聚合(RAFT Polymerization)是目前最为常用的活性可控自由基聚合方法之一,因其产物分子量分布较窄、适用单体范围广、反应条件温和等优势得到了不同领域科学家的广泛应用。然而,科学家们在选择RAFT链转移剂(也称RAFT试剂)时,经常会忽略RAFT链转移剂与单体活性的匹配原则,导致在制备高活单体与低活单体的嵌段共聚物方面存在产物分子量分布宽、聚合速率慢,甚至反应无法成功进行的问题。基于此,本文首先综述聚合中RAFT链转移剂的选用原则,随后介绍近几年开发的一类同时适用于高/低活性单体聚合的通用型RAFT链转移剂(Universal/Switchable RAFT agent)的作用原理及适用条件,并着重探讨了基于通用型RAFT链转移剂制备高/低活性单体的嵌段共聚物的最新进展及应用。

关键词： RAFT聚合, 通用型RAFT链转移剂, 嵌段共聚物, 自组装

Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT Polymerization) is currently one of the most common “Reversible Deactivation Radical Polymerization”, and it has been widely used by scientists in different directions because of its advantages such as narrow molecular weight distribution, wide range of applicable monomers, and mild reaction conditions. However, when scientists choose RAFT chain transfer agents (also known as RAFT agents) in polymerization, they often donot clearly understand the principle of matching the activity of RAFT chain transfer agents and monomers. Therefore, in the preparation of block copolymers of “more activated” monomers (MAMs) and “less activated” monomers (LAMs), there are problems that the product has a wide molecular weight distribution, a slow polymerization rate, and even the reaction cannot successfully continue. Based on this, we first review the selection principles of RAFT chain transfer agents in polymerization, and then introduce the principle and application conditions of a universal RAFT chain transfer agent (Universal RAFT agent) (including non switchable type and proton switchable type) developed in recent years that is suitable for the polymerization of MAMs/LAMs. Finally, the latest development and application of block copolymers with MAMs and LAMs based on Universal RAFT agents are discussed in depth.

Contents

1 Introduction

2 Structure of RAFT agents and selection principle

3 (Non Switchable) Universal RAFT agents

4 Proton Switchable RAFT agents

4.1 Chain transfer kinetics

4.2 Application of Switchable RAFT agents in aqueous solution

4.3 Effect of acids’ type and amount on Switchable RAFT agents’ activity

4.4 Removal method of end group

4.5 Block copolymer realized with Switchable RAFT agents

5 Conclusions and outlook

Key words: RAFT polymerization, universal RAFT agent, block copolymers, self-assembly
()
图1 RAFT聚合机理[2]
Fig. 1 Mechanism of RAFT polymerization[2]
图2 RAFT试剂结构
Fig. 2 Structures of RAFT agents
图3 (a)适用于聚合各种单体的RAFT试剂R基团的选用原则;(b)适用于聚合各种单体的RAFT试剂Z基团的选用原则[2]
Fig. 3 (a) Guidelines for selection of the R-group of RAFT agents for various polymerizations; (b) Guidelines for selection of the Z-group of RAFT agents for various polymerization[2]
图4 常见(无切换型)Universal RAFT试剂结构
Fig. 4 Structures of popular (Non Switchable)Universal RAFT agents
图5 Proton Switchable RAFT 试剂的作用机理与常见Proton Switchable RAFT试剂结构[50]
Fig. 5 Mechanism and structure of Proton Switchable RAFT[50]
表1 利用Switchable RAFT试剂制备的高活/低活嵌段共聚物
Table 1 MAMs-b-LAMs copolymer prepared with Switchable RAFT agent
More activated monomer Polymerization environment of more activated monomer Less activated monomer Polymerization environment of less activated monomer Year ref
St Bulk polymerization VAc Bulk polymerization 2009 49
MMA MeCN VAc EA 2009 51
MA MeCN NVC MeCN 2009 51
DMA H2O NVC 1,4-dioxane 2011 54
DMA H2O VAc DMF 2011 54
DMA H2O NVP MeCN 2011 54
MA MeCN VAc MeCN 2012 53
NIPAM MeCN NVP 1,4-dioxane 2015 48
t-BA 1,4-dioxane NVP 1,4-dioxane 2019 56
MAA 1,4-dioxane NVP 1,4-dioxane 2019 56
BzMA MeCN DEAEMA, NVP 1,4-dioxane 2020 13
图6 Switchable RAFT试剂制备pH刺激响应生物相容性嵌段共聚物[56]
Fig. 6 pH stimuli biocompatible block copolymer utilizing Switchable RAFT agents[56]
图7 利用Switchable RAFT试剂合成 CO2 响应梯度共聚物及其受控自组装[13]
Fig. 7 CO2-responsive gradient copolymers by Switchable RAFT polymerization and their controlled self-assembly
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