One-step Synthesis of Dipeptide-functionalized Polyethers through Site-selective Anionic Ring-opening Polymerization

Qi-yi Chen; Xing-pei Hong; Li-jun Liu; Jun-peng Zhao

doi:10.11777/j.issn1000-3304.2026.26095

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One-step Synthesis of Dipeptide-functionalized Polyethers through Site-selective Anionic Ring-opening Polymerization

更新时间：2026-07-06

- One-step Synthesis of Dipeptide-functionalized Polyethers through Site-selective Anionic Ring-opening Polymerization
- Acta Polymerica Sinica Pages: 1-10(2026)
- 作者机构：
  
  华南理工大学材料科学与工程学院广州 510640
- 作者简介：
  
  Jun-peng Zhao, E-mail: msjpzhao@scut.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26095
  CLC：
- CSTR：32057.14.GFZXB.2026.7641
- Received：26 March 2026，
  
  Accepted：26 May 2026，
  
  Online First：06 July 2026，
- 稿件说明：
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陈奇艺, 洪兴沛, 刘利君, 赵俊鹏. 位点选择性阴离子开环聚合一步合成二肽功能化聚醚. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26095.

Chen, Q. Y.; Hong, X. P.; Liu, L. J.; Zhao, J. P. One-step synthesis of dipeptide-functionalized polyethers through site-selective anionic ring-opening polymerization. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26095.
陈奇艺, 洪兴沛, 刘利君, 赵俊鹏. 位点选择性阴离子开环聚合一步合成二肽功能化聚醚. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26095. DOI： CSTR： 32057.14.GFZXB.2026.7641.

Chen, Q. Y.; Hong, X. P.; Liu, L. J.; Zhao, J. P. One-step synthesis of dipeptide-functionalized polyethers through site-selective anionic ring-opening polymerization. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26095. DOI： CSTR： 32057.14.GFZXB.2026.7641.

摘要

功能化引发剂是高效合成端基功能化高分子的关键策略. 含有质子型功能基团的引发剂与阴离子聚合往往不相容，导致产物结构不可控. 本研究以氨基受保护的二肽为生物质引发剂，实现了多质子体系中端基功能化聚环氧乙/丙烷的一步可控合成. 实验和计算结果共同表明，聚合仅从二肽的羧基端发生，双组分有机催化剂在增长链末端的醇羟基和引发端的肽酰胺之间产生酸性反转效应，确保聚醚具有可控的分子量、低分散度和完整保留的端基二肽结构. 该工作拓宽了酸性反转机理和位点选择性阴离子开环聚合方法的适用性，为进一步扩充生物质引发剂，构建多样化的生物质-聚醚功能材料打下了基础.

Abstract

Employing functionalized initiators is a key strategy for the efficient synthesis of end-functionalized polymers. Initiators containing protonic functional groups are often incompatible with the harsh conditions of anionic polymerization

leading to uncontrollable product structures. In this work

amino-protected dipeptides were used as biomass initiators to achieve one-step controlled synthesis of end-functionalized poly(ethylene/propylene oxide) in multiprotonic systems. Experimental results and theoretical calculations jointly demonstrated that polymerization occured exclusively from the carboxyl site of the dipeptide. The two-component Lewis pair organocatalyst exerted an acidity reversal effect between the alcohol hydroxyl group at the growing polyether chain end and the peptide amide on the initiator moiety

ensuring that the polyethers had controllable molar mass

low dispersity

and fully retained end-group dipeptide structures. This work broadens the applicability of the acidity reversal mechanism and site-selective anionic ring-opening polymerization method

laying the foundation for further expansion of biomass initiators and the construction of diverse biomass-polyether functional materials.

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references

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