Synthesis of Cleavable Hyperbranched Polymers by Thiol-xanthate and Thiol-phenylsulfone Sequential Reactions

Yu-peng Liu; Han-ying Zhao

doi:10.11777/j.issn1000-3304.2026.26121

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Synthesis of Cleavable Hyperbranched Polymers by Thiol-xanthate and Thiol-phenylsulfone Sequential Reactions

更新时间：2026-07-10

- Synthesis of Cleavable Hyperbranched Polymers by Thiol-xanthate and Thiol-phenylsulfone Sequential Reactions
- Acta Polymerica Sinica Pages: 1-13(2026)
- 作者机构：
  
  南开大学化学学院功能高分子材料教育部重点实验室天津 300071
- 作者简介：
  
  Han-ying Zhao, E-mail: hyzhao@nankai.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26121
  CLC：
- CSTR：32057.14.GFZXB.2026.7625
- Received：15 April 2026，
  
  Accepted：13 May 2026，
  
  Online First：10 July 2026，
- 稿件说明：
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刘宇鹏, 赵汉英. 巯基-黄原酸酯和巯基-苯磺酰基串联反应合成可断裂超支化聚合物. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26121.

Liu, Y. P.; Zhao, H. Y. Synthesis of cleavable hyperbranched polymers by thiol-xanthate and thiol-phenylsulfone sequential reactions. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26121.
刘宇鹏, 赵汉英. 巯基-黄原酸酯和巯基-苯磺酰基串联反应合成可断裂超支化聚合物. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26121. DOI： CSTR： 32057.14.GFZXB.2026.7625.

Liu, Y. P.; Zhao, H. Y. Synthesis of cleavable hyperbranched polymers by thiol-xanthate and thiol-phenylsulfone sequential reactions. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26121. DOI： CSTR： 32057.14.GFZXB.2026.7625.

摘要

超支化聚合物是一类具有高度支化结构的三维高分子. 由于其特殊的分子结构，超支化聚合物呈现出独特的物理化学性质. 可断裂超支化聚合物能在特定条件下使聚合物链发生断裂，因此合成此类聚合物在生物医学和材料科学等领域具有重要意义和潜在应用价值. 本实验设计并合成了一种新型黄原酸酯链转移剂，可用于调控醋酸乙烯酯的RAFT聚合反应，通过聚合反应得到了AB

型扩链前体聚合物. 通过巯基-黄原酸酯和巯基-苯磺酰基串联反应，一锅法合成了超支化聚合物. 在碱催化下加入巯基化合物，聚合物链中的芳基硫醚键断裂，致聚合物结构破坏. 利用核磁共振氢谱和凝胶渗透色谱对扩链反应过程进行了研究；并探讨了反应条件(包括扩链前体聚合度、投料比、温度和扩链引发剂等)对超支化聚合物合成的影响. 结果表明，RAFT聚合技术结合巯基化学反应，为构建可断裂超支化聚合物提供了一种有效方法.

Abstract

Hyperbranched polymers are a class of important polymers with unique physicochemical properties. The synthesis of cleavable hyperbranched polymers is of great significance in the fields of biomedical and materials science. In this study

a novel xanthate chain transfer agent was designed and used to mediate the RAFT polymerization of vinyl acetate and AB

-type precursor polymers were synthesized. The precursors were subsequently used in one-pot synthesis of cleavable hyperbranched polymers

via

sequential thiol-xanthate and thiol-phenylsulfone reactions. The thioether bonds in the polymer structures can be cleaved by small molecular thiol compounds under alkaline catalysis. The chain extension process was monitored by

H-NMR and GPC. The influences of the factors

including the degree of polymerization of the precursor

feed ratio

temperature

and chain extension initiator

were investigated. The strategy based on a combination of RAFT polymerization and thiol chemistries

offers a new and effective approach to the synthesis of cleavable hyperbranched polymers.

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references

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