氢键网络与硫键互穿结构协同提高溶聚丁苯橡胶/环氧天然橡胶复合材料强度及延展性

袁成; 李鑫; 崔凌峰; 黄舸舸; 熊玉竹

doi:10.11777/j.issn1000-3304.2025.25162

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氢键网络与硫键互穿结构协同提高溶聚丁苯橡胶/环氧天然橡胶复合材料强度及延展性

研究论文 | 更新时间：2026-02-09

- 氢键网络与硫键互穿结构协同提高溶聚丁苯橡胶/环氧天然橡胶复合材料强度及延展性
- Synergistic Enhancement of Strength and Ductility in Solution-polymerized Styrene-butadiene Rubber/Epoxidized Natural Rubber Composites through Interpenetrating Hydrogen Bonding and Sulfur Networks
- 高分子学报 2026年57卷第2期页码：570-585
- 作者机构：
  
  1.贵州大学材料与冶金学院贵阳 550025
  2.贵州轮胎股份有限公司贵阳 550008
- 作者简介：
  
  E-mail: yzxiong@gzu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 52063006);贵州省科技成果转化项目(项目号黔科合成果〔2023〕重大003号)
- DOI：10.11777/j.issn1000-3304.2025.25162
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7458
- 收稿：2025-07-03，
  
  录用：2025-09-01，
  
  网络首发：2025-10-15，
  
  纸质出版：2026-02-20
- 稿件说明：
移动端阅览
袁成, 李鑫, 崔凌峰, 黄舸舸, 熊玉竹. 氢键网络与硫键互穿结构协同提高溶聚丁苯橡胶/环氧天然橡胶复合材料强度及延展性. 高分子学报, 2026, 57(2), 570-585.

Yuan, C.; Li, X.; Cui, L. F.; Huang, G. G.; Xiong, Y. Z. Synergistic enhancement of strength and ductility in solution-polymerized styrene-butadiene rubber/epoxidized natural rubber composites through interpenetrating hydrogen bonding and sulfur networks. Acta Polymerica Sinica (in Chinese), 2026, 57(2), 570-585.
袁成, 李鑫, 崔凌峰, 黄舸舸, 熊玉竹. 氢键网络与硫键互穿结构协同提高溶聚丁苯橡胶/环氧天然橡胶复合材料强度及延展性. 高分子学报, 2026, 57(2), 570-585. DOI： 10.11777/j.issn1000-3304.2025.25162. CSTR： 32057.14.GFZXB.2025.7458.

Yuan, C.; Li, X.; Cui, L. F.; Huang, G. G.; Xiong, Y. Z. Synergistic enhancement of strength and ductility in solution-polymerized styrene-butadiene rubber/epoxidized natural rubber composites through interpenetrating hydrogen bonding and sulfur networks. Acta Polymerica Sinica (in Chinese), 2026, 57(2), 570-585. DOI： 10.11777/j.issn1000-3304.2025.25162. CSTR： 32057.14.GFZXB.2025.7458.

摘要

针对传统橡胶复合材料中强度与延展性难以同时提升的问题，提出氢键网络与共价键网络协同作用解决这一难题. 通过氨基-环氧基团开环反应制备含八重氢键的环氧天然橡胶(ENR)，与溶聚丁苯橡胶(SSBR)共混后，利用硫键桥接构建互穿网络结构. 共价键提供刚性骨架，动态八重氢键通过断裂-重组机制耗散能量，改善局部应力集中，实现强度与延展性协同优化. 结果表明：在SSBR/ENR复合材料中引入少量氢键即可使拉伸强度从2.1 MPa增至4.88 MPa，断裂伸长率由240%提升至500%，断裂韧性从3.2 MJ/m

跃升至12.4 MJ/m

，耐磨性和耐疲劳性也显著提升. 氢键密度可通过反应条件精准调控，满足多样化需求. 该技术采用常规混炼硫化工艺，与现有橡胶工业生产可完全兼容，全有机组分设计规避了加工流动性劣化问题，为开发绿色高性能橡胶复合材料提供了创新技术路径.

Abstract

Currently

rubber composites are primarily reinforced by adding traditional fillers

but excessive filler content makes it difficult to balance both strength and elongation simultaneously. In this study

a novel filler-free reinforced rubber composite system was developed using a synergistic strategy of bioinspired hydrogen bond networks and covalent bonds. First

based on the ring-opening reaction between amino and epoxy groups

epoxidized natural rubber (ENR) with an octuple hydrogen bond structure was designed and prepared. It was then blended with non-polar rubber (solution-polymerized styrene-butadiene rubber

SSBR)

using sulfur bonds as bridges to connect the molecular chains of the two rubbers

forming a three-dimensional interpenetrating network structure. In this system

covalent bonds ensure the structural integrity and rigid support of the rubber composite

while the octuple hydrogen bonds act as sacrificial bonds. Through their reversible break-recombination behavior

they effectively enhance the mechanical properties and elongation of the rubber composite

while also imparting a certain degree of self-recovery capability. Experimental results showed that with only a small amount of the octuple hydrogen bond structure added

the tensile strength of the rubber composite increased from 2.1 MPa to 4.88 MPa

the elongation at break improved from 240% to 500%

and the fracture toughness rose from 3.2 MJ/m

to 12.4 MJ/m

. The wear resistance and fatigue resistance were also significantly enhanced. The density of the octuple hydrogen bonds could be controllably adjusted according to practical application requirements. Notably

this technology employed conventional mixing and vulcanization processes

making it compatible with existing rubber industry production lines. The all-organic component de

sign avoided the processing fluidity degradation issues caused by traditional fillers. This study provides new theoretical guidance and technical pathways for developing environmentally friendly high-performance rubber materials

holding significant importance for promoting the green upgrade of the rubber industry.

关键词

Keywords

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许婧婧 , 王君 , 罗宝玉 , 黄义钢 , 董康 , 陈亚婷 , 王鹭飞 , 刘文国 , 赵晓东 , 梁雪 , 王贵宾 . 溶聚丁苯橡胶/天然橡胶并用胶的性能研究 . 橡胶工业 , 2024 , 71 ( 10 ), 745 - 753 .

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