Fabrication and Reprocessability of Epoxidized Natural Rubber/Maleated Chitin Vitrimer

Hui-juan Lu; Bo Wu; Si-wu Wu; Shui-dong Zhang; Bao-chun Guo

doi:10.11777/j.issn1000-3304.2025.25225

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Fabrication and Reprocessability of Epoxidized Natural Rubber/Maleated Chitin Vitrimer

Research Article | 更新时间：2025-12-18

- Fabrication and Reprocessability of Epoxidized Natural Rubber/Maleated Chitin Vitrimer
- Acta Polymerica Sinica Vol. 56, Issue 12, Pages: 2430-2440(2025)
- 作者机构：
  
  1.华南理工大学前沿弹性体研究院华南理工大学机械与汽车工程学院广州 510640
  2.广东省高分子先进制造技术装备重点实验室华南理工大学广州 510640
  3.国家先进高分子材料产业创新中心广州 510632
  4.华南理工大学前沿弹性体研究院华南理工大学材料与工程学院广州 510640
- 作者简介：
  
  Shui-dong Zhang, E-mail: starch@scut.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25225
  CLC：
- CSTR：32057.14.GFZXB.2025.7471
- Received：31 August 2025，
  
  Accepted：26 September 2025，
  
  Published Online：12 November 2025，
  
  Published：20 December 2025
- 稿件说明：
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陆慧娟, 吴博, 吴思武, 张水洞, 郭宝春. 环氧化天然橡胶/马来酰化甲壳素Vitrimer的制备及可反复加工性能研究. 高分子学报, 2025, 56(12), 2430-2440

Lu, H. J.; Wu, B.; Wu, S. W.; Zhang, S. D.; Guo, B. C. Fabrication and reprocessability of epoxidized natural rubber/maleated chitin Vitrimer. Acta Polymerica Sinica, 2025, 56(12), 2430-2440
陆慧娟, 吴博, 吴思武, 张水洞, 郭宝春. 环氧化天然橡胶/马来酰化甲壳素Vitrimer的制备及可反复加工性能研究. 高分子学报, 2025, 56(12), 2430-2440 DOI： 10.11777/j.issn1000-3304.2025.25225. CSTR： 32057.14.GFZXB.2025.7471.

Lu, H. J.; Wu, B.; Wu, S. W.; Zhang, S. D.; Guo, B. C. Fabrication and reprocessability of epoxidized natural rubber/maleated chitin Vitrimer. Acta Polymerica Sinica, 2025, 56(12), 2430-2440 DOI： 10.11777/j.issn1000-3304.2025.25225. CSTR： 32057.14.GFZXB.2025.7471.

摘要

以天然多糖为大分子交联剂制备具反复加工生物基环氧化天然橡胶(ENR) Vitrimer，是解决硫化橡胶难循环加工所致的资源浪费与高碳排放问题有效策略，然而天然多糖难以与橡胶发生界面反应且相容性差. 本研究以马来酸酐改性甲壳素(MCh)作为大分子交

联剂，与ENR通过热加工界面反应构建基于

-羟基酯键的动态交联网络. 采用傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、平衡溶胀和硫化曲线测试表征其结构，通过单轴拉伸、动态热机械分析(DMA)、示差扫描量热法(DSC)以及应力松弛与应变回复测试等多种方法评价其力学、动态力学性能和再加工性能. 结果表明，MCh与ENR界面形成的

-羟基酯键交联结构，增加了界面相容性. 当MCh添加量为30 phr时，ENR Vitrimer的拉伸强度是纯ENR的8.4倍. 且其酯交换活化能仅为61.8 kJ/mol，经2次加工(180 ℃、15 MPa硫化30 min)后拉伸强度保持率均≥88%，展示动态交联网络重排而具反复加工性优点. 研究结果为制备可再加工的高性能ENR Vitrimer提供新的思路，为复合材料界面增容提供新方法.

Abstract

Preparation of a recyclable bio-based epoxidized natural rubber (ENR) Vitrimer using natural polysaccharide as a macromolecular crosslinker is an effective strategy to address resource waste and high carbon emissions caused by the difficulty in recycling vulcanized rubber. However

natural polysaccharides struggle to undergo interfacial reactions with rubber and exhibit poor compatibility. In this study

maleic anhydride-modified chitin (MCh) was used as a macromolecular crosslinker to construct a dynamic crosslinking network based on

-hydroxy ester bonds with ENR through thermal processing interfacial reactions. The structure was characterized using Fourier transform infrared spectroscopy (FTIR)

X-ray photo

electron spectroscopy (XPS)

equilibrium swelling

and vulcanization curve tests. Mechanical properties

dynamic mechanical properties

and reprocessability were evaluated through uniaxial tensile testing

dynamic mechanical analysis (DMA)

differential scanning calorimetry (DSC)

stress relaxation

and strain recovery tests. The results showed that the

-hydroxy ester bonds crosslinking structure formed at the MCh-ENR interface enhances interfacial compatibility. When 30 phr of MCh was added

the tensile strength of the ENR Vitrimer was 8.4 times that of neat ENR. Moreover

its ester exchange activation energy was only 61.8 kJ/mol

and after two processing cycles (180 ℃

15 MPa vulcanization for 30 min)

the tensile strength retention rate was ≥88%

demonstrating the advantages of the dynamic crosslinking network's rearrangement for repeated processability. These findings provide new insights for preparing high-performance

recyclable ENR Vitrimers and offer a novel approach for enhancing interfacial compatibility in composite materials.

关键词

Keywords

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