高强度二硫键/氢键双动态交联丁苯橡胶的设计及可回收、形状记忆性能研究

张文琪; 范雯雯; 张若涵; 彭倩倩; 李祥亮; 雷岚; 李辉

doi:10.11777/j.issn1000-3304.2024.24313

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高强度二硫键/氢键双动态交联丁苯橡胶的设计及可回收、形状记忆性能研究

研究论文 | 更新时间：2025-04-28

- 高强度二硫键/氢键双动态交联丁苯橡胶的设计及可回收、形状记忆性能研究
- Mechanical Robust Dynamic Disulfide and Hydrogen Bonded Double Crosslinking Styrene Butadiene Rubbers with Recyclability and Shape Memory Capability
- 高分子学报 2025年56卷第5期页码：845-860
- 作者机构：
  
  1.济南大学化学化工学院山东省氟化学化工材料重点实验室济南 250022
  2.山东圣泉电子材料有限公司济南 250204
- 作者简介：
  
  E-mail: chm_leil@ujn.edu.cn
  chm_lih1@ujn.edu.cn
- 基金信息：
  
  山东省自然科学基金(ZR2021ME055;ZR2022QB170);济南大学新引进人才科研项目(XBS2418);山东省科学院齐鲁工业大学生物基材料与绿色造纸国家重点实验室项目(GZKF202128)
- DOI：10.11777/j.issn1000-3304.2024.24313
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7357
- 收稿日期：2024-12-30，
  
  录用日期：2025-02-06，
  
  网络出版日期：2025-04-15，
  
  纸质出版日期：2025-05-20
- 稿件说明：
移动端阅览
张文琪, 范雯雯, 张若涵, 彭倩倩, 李祥亮, 雷岚, 李辉. 高强度二硫键/氢键双动态交联丁苯橡胶的设计及可回收、形状记忆性能研究. 高分子学报, 2025, 56(5), 845-860

Zhang, W. Q.; Fan, W. W.; Zhang, R. H.; Peng, Q. Q.; Li, X. L.; Lei, L.; Li, H. Mechanical robust dynamic disulfide and hydrogen bonded double crosslinking styrene butadiene rubbers with recyclability and shape memory capability. Acta Polymerica Sinica, 2025, 56(5), 845-860
张文琪, 范雯雯, 张若涵, 彭倩倩, 李祥亮, 雷岚, 李辉. 高强度二硫键/氢键双动态交联丁苯橡胶的设计及可回收、形状记忆性能研究. 高分子学报, 2025, 56(5), 845-860 DOI： 10.11777/j.issn1000-3304.2024.24313. CSTR： 32057.14.GFZXB.2025.7357.

Zhang, W. Q.; Fan, W. W.; Zhang, R. H.; Peng, Q. Q.; Li, X. L.; Lei, L.; Li, H. Mechanical robust dynamic disulfide and hydrogen bonded double crosslinking styrene butadiene rubbers with recyclability and shape memory capability. Acta Polymerica Sinica, 2025, 56(5), 845-860 DOI： 10.11777/j.issn1000-3304.2024.24313. CSTR： 32057.14.GFZXB.2025.7357.

摘要

传统化学键硫化的丁苯橡胶机械性能优异，但无法再加工且废料处理对环境危害极大，因此，制备兼具优异机械性能和可回收

性、形状记忆等多功能丁苯橡胶具有重要意义，但仍面临巨大挑战. 本研究通过一锅法-热压法成功制备了一种高强度、可回收和三重形状记忆的二硫键/氢键双动态交联丁苯橡胶. 以丁苯橡胶(SBR)为主链，通过1

4-双键与间氯过氧苯甲酸的环氧化反应生成环氧化丁苯橡胶(ESBR)，再分别引入二硫键交联剂4

4′-二氨基二苯二硫醚(DTDA)与氢键交联剂3-氨基-1

4-三唑(ATA)合成动态二硫键和氢键交联密度可调的双动态交联网络丁苯橡胶(ESBR-DTDA-ATA). 结果表明，动态氢键和二硫键交联网络在机械性能上呈现显著的协同增强作用. 通过优化两种交联剂的比例，获得了性能最优的ESBR-DTDA

10%

-ATA

，其断裂强度高达15.9 MPa，断裂伸长率为114.7%，杨氏模量和韧性分别高达231.3 MPa和14.4 MJ/m

. 此外，ESBR-DTDA

10%

-ATA

具有可回收性，回收材料的机械强度仍高达11.3 MPa，回收率为72%，并且动态二硫键和氢键赋予ESBR-DTDA

10%

-ATA

良好的三重形状记忆性能. 这一简单而高效的双动态网络设计理念，为开发兼具优异机械性能、可回收性及形状记忆功能的多功能先进材料提供了新的思路与启发.

Abstract

The traditional chemically vulcanized styrene-butadiene rubber possesses remarkable mechanical properties; however

it cannot be reprocessed

and its waste treatment poses significant environmental hazards. Consequently

the development of multifunctional styrene-butadiene rubber that combines superior mechanical properties with recyclability and shape memory capabilities is of substantial importance

yet remains fraught with challenges. a high-strength

recyclable

and triple-shape-memory dynamic disulfide and hydrogen-bonded double crosslink

ing styrene-butadiene rubber was successfully synthesized

via

a one-pot hot pressing method in this study. Using styrene-butadiene rubber (SBR) as the main chain

epoxidized styrene-butadiene rubber (ESBR) was produced through the epoxidation of 1

4-double bonds utilizing m-chloroperoxybenzoic acid. Subsequently

the disulfide crosslinking agent 4

4'-diaminodiphenyl disulfide (DTDA) and the hydrogen-bonding crosslinking agent 3-amino-1

‍2

‍4-triazole (ATA) were introduced to construct dynamic double crosslinking network in ESBR (ESBR-DTDA-ATA) with adjustable densities of disulfide and hydrogen bonds. The results indicated that the dynamic hydrogen-bonding and disulfide-bonding crosslinking networks exhibited remarkable synergistic enhancement of mechanical properties. By optimizing the ratios of the two crosslinking agents

ESBR-DTDA

10%

-ATA

yielded the best mechanical performance

presenting a breaking strength of 15.9 MPa

elongation at break of 114.7%

and Young's modulus and toughness of 231.3 MPa and 14.4 MJ/m³

respectively. Additionally

ESBR-DTDA

10%

-ATA

demonstrated recyclability

retaining a mechanical strength of 11.3 MPa in the recycled material with a recovery rate of 72%. The dynamic disulfide and hydrogen bonds endow ESBR-DTDA

10%

-ATA

with impressive triple shape memory property. This facile and efficient design strategy of double dynamic network offers a viable approach to replacing traditional vulcanized styrene-butadiene rubber

inspiring the development of multifunctional advanced materials with superior mechanical properties

recyclability

and shape memory functionalities.

关键词

Keywords

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