Advances in Sulfur-centered Radical Reversible-deactivation Polymerizations

Han-chu Huang

doi:10.11777/j.issn1000-3304.2024.24211

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Advances in Sulfur-centered Radical Reversible-deactivation Polymerizations

Feature Article | 更新时间：2025-01-26

- Advances in Sulfur-centered Radical Reversible-deactivation Polymerizations
- Acta Polymerica Sinica Vol. 56, Issue 1, Pages: 79-90(2025)
- 作者机构：
  
  中山大学材料科学与工程学院聚合物复合材料及功能材料教育部重点实验室广州 510006
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24211
  CLC：
- CSTR：32057.14.GFZXB.2024.7297
- Published：20 January 2025，
  
  Published Online：25 November 2024，
  
  Received：07 August 2024，
  
  Accepted：2024-09-11
- 稿件说明：
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黄汉初. 硫自由基可逆失活聚合研究进展. 高分子学报, 2025, 56(1), 79-90

Huang, H. C. Advances in sulfur-centered radical reversible-deactivation polymerizations. Acta Polymerica Sinica, 2025, 56(1), 79-90
黄汉初. 硫自由基可逆失活聚合研究进展. 高分子学报, 2025, 56(1), 79-90 DOI： 10.11777/j.issn1000-3304.2024.24211. CSTR： 32057.14.GFZXB.2024.7297.

Huang, H. C. Advances in sulfur-centered radical reversible-deactivation polymerizations. Acta Polymerica Sinica, 2025, 56(1), 79-90 DOI： 10.11777/j.issn1000-3304.2024.24211. CSTR： 32057.14.GFZXB.2024.7297.

摘要

发展硫自由基的可逆失活聚合方法将有助于开发新的可控聚合反应，对推动功能高分子材料的发展具有重要的意义. 尽管国内外在硫自由基聚合反应的调控方面已经取得一定的研究进展，但硫自由基可逆失活聚合的研究仍然处于初级阶段，无论单体开发还是应用研究仍然存在很大的发展空间. 本文首先回顾了硫自由基聚合的发展历程，接着分别介绍了自由基脱二氧化硫和自由基脱硫两种间接调控硫自由基聚合反应的策略，然后重点阐述了硫自由基加成-断裂链转移聚合这一直接调控硫自由基的策略，最后总结和展望了该领域存在的挑战及未来发展趋势.

Abstract

Reversible-deactivation radical polymerization (RDRP) has emerged as a preeminent method for fabricating polymers with precisely controlled structures

finding applications across diverse fields. However

the existing RDRP methods have posed significant challenges in controlling sulfur-centered radicals. Therefore

the sulfur-centered radical polymerizations still suffer from poor control over molecular weight and dispersity

impeding their utility in generating polymers with well-defined architectures. In recent years

our efforts to address this issue have included desulfonylation or desulfurization to form a stabilized alkyl radical capable of being controlled by conventional RDRP methods. Furthermore

our group recently introduced an innovative thiyl radical addition-fragmentation chain transfer (SRAFT) polymerization strategy utilizing allyl sulfides as chain transfer agents for reversibly deactivating the propagating thiyl radicals. This breakthrough enables direct control over the thiyl radical polymerizations and facilitates the production of polymers with well-defined architectures. This feature article aims to describe these recent advancements and focus on SRAFT polymerization. From this article

readers should gain a comprehension of the sulfur-centered radical reversible-deactivation polymerization (SRDP)

along with the future directions of this field.

关键词

可逆失活自由基聚合硫自由基连锁聚合大环开环聚合

Keywords

Reversible-deactivation radical polymerizationSulfur-centered radicalChain-growth polymerizationMacrocyclic ring-opening polymerization

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