Efficient Synthesis of Block Copolyesters <italic style="font-style: italic">via</italic> Ring-opening Copolymerization of Cyclic Esters Based on Ionic Urea-Base Organocatalysts

Wei-bin Pan; Xian-zhang Liu; Jie Jin; Du-bing Chen; Yi-zhou Yang; Yi Wen; Jing-shu Wu; Yong-hang Xu; Li-miao Lin; Min Zhang

doi:10.11777/j.issn1000-3304.2026.26097

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Efficient Synthesis of Block Copolyesters via Ring-opening Copolymerization of Cyclic Esters Based on Ionic Urea-Base Organocatalysts

更新时间：2026-07-24

- Efficient Synthesis of Block Copolyesters via Ring-opening Copolymerization of Cyclic Esters Based on Ionic Urea-Base Organocatalysts
- Acta Polymerica Sinica Pages: 1-12(2026)
- 作者机构：
  
  1.佛山大学，材料与能源学院，佛山 528000
  2.佛山大学，环境与化工学院，佛山 528000
- 作者简介：
  
  Yong-hang Xu, E-mail: yonghangxu@fosu.edu.cn
  Li-miao Lin, E-mail: linlimiao@fosu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26097
  CLC：
- CSTR：32057.14.GFZXB.2026.7642
- Received：27 March 2026，
  
  Accepted：26 May 2026，
  
  Online First：24 July 2026，
- 稿件说明：
移动端阅览
潘炜斌, 刘先章, 靳杰, 陈杜冰, 杨艺洲, 温仪, 吴静姝, 许泳行, 林丽苗, 张敏. 基于离子型脲-碱有机催化剂的环酯开环共聚高效合成嵌段共聚酯. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26097.

Pan, W. B.; Liu, X. Z.; Jin, J.; Chen, D. B.; Yang, Y. Z.; Wen, Y.; Wu, J. S.; Xu, Y. H.; Lin, L. M.; Zhang, M. Efficient synthesis of block copolyesters via ring-opening copolymerization of cyclic esters based on ionic urea-base organocatalysts. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26097.
潘炜斌, 刘先章, 靳杰, 陈杜冰, 杨艺洲, 温仪, 吴静姝, 许泳行, 林丽苗, 张敏. 基于离子型脲-碱有机催化剂的环酯开环共聚高效合成嵌段共聚酯. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26097. DOI： CSTR： 32057.14.GFZXB.2026.7642.

Pan, W. B.; Liu, X. Z.; Jin, J.; Chen, D. B.; Yang, Y. Z.; Wen, Y.; Wu, J. S.; Xu, Y. H.; Lin, L. M.; Zhang, M. Efficient synthesis of block copolyesters via ring-opening copolymerization of cyclic esters based on ionic urea-base organocatalysts. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26097. DOI： CSTR： 32057.14.GFZXB.2026.7642.

摘要

为实现环状单体的绿色高效开环共聚，制备可持续嵌段共聚酯，开发了一系列基于脲与有机碱构筑的双功能离子型有机催化剂，其在交酯和内酯的开环聚合中表现出优异的催化活性与可控性，特别是在催化丙交酯均聚反应中的转换频率(TOF)值高达2.341×10

-1

. 在制备的双功能离子型脲-碱有机催化剂中，由1

3-二苯基脲(U2)与四丁基氢氧化铵(BN)反应制备得到的催化剂(U2BN)对丙交酯和己内酯同时具有较高的催化活性. 利用该U2BN催化剂，通过一锅法顺序投料成功制备了以

-己内酯与

-戊内酯的共聚物(PVCL)为软段、聚乳酸(PLA)为硬段的三嵌段共聚酯，核磁共振波谱(NMR)和凝胶渗透色谱(GPC)测试结果证明了其ABA序列结构. PLA-PVCL-PLA嵌段共聚酯呈现微相分离结构，该结构特征使其表现出热塑性弹性体的特性，实现了高断裂伸长率与高弹性回复率的统一. 本工作为可降解共聚酯材料合成提供了新的催化与结构调控策略.

Abstract

To achieve green and efficient ring-opening copolymerization of cyclic monomers and prepare sustainable block copolyesters

this study developed a series of bifunctional ionic organocatalysts based on ureas and

organic bases. These catalysts exhibited excellent catalytic activity and controllability in the ring-opening polymerization of lactides and lactones

achieving a turnover frequency (TOF) as high as 2.341×10

-1

in the homopolymerization of lactide. Among the prepared bifunctional ionic urea-base organocatalysts

the catalyst U2BN

derived from the reaction of 1

3-diphenylurea (U2) and tetrabutylammonium hydroxide (BN)

exhibited high catalytic activity toward both lactide and caprolactone simultaneously. Therefore

a triblock copolyester with poly(

-caprolactone-

-valerolactone) (PCVL) as the soft segment and polylactide (PLA) as the hard segment was successfully synthesized

via

a one-pot sequential feeding strategy using U2BN. Nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) analyses confirmed the ABA sequence structure. The PLA-PVCL-PLA block copolyester exhibited a microphase-separated morphology

as evidenced by the distinct melting peaks of PVCL and PLA in the differential scanning calorimetry (DSC) analysis. This structural feature endowed the polymer with thermoplastic elastomer characteristics

achieving a combination of high elongation at break and high elastic recovery. This study provides a new strategy for the catalytic and structural regulation of biodegradable copolyesters.

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Efficient Synthesis of Block Copolyesters via Ring-opening Copolymerization of Cyclic Esters Based on Ionic Urea-Base Organocatalysts

DOI：10.11777/j.issn1000-3304.2026.26097

摘要

Abstract

关键词

Keywords

references