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Progress in Chemistry 2022, Vol. 34 Issue (6): 1298-1307 DOI: 10.7536/PC210736 Previous Articles   Next Articles

• Review •

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: Revised: Online: Published:
  • 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)
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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
Fig. 1 Mechanism of RAFT polymerization[2]
Fig. 2 Structures of RAFT agents
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]
Fig. 4 Structures of popular (Non Switchable)Universal RAFT agents
Fig. 5 Mechanism and structure of Proton Switchable RAFT[50]
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
Fig. 6 pH stimuli biocompatible block copolymer utilizing Switchable RAFT agents[56]
Fig. 7 CO2-responsive gradient copolymers by Switchable RAFT polymerization and their controlled self-assembly
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