Mechanical Robust Dynamic Disulfide and Hydrogen Bonded Double Crosslinking Styrene Butadiene Rubbers with Recyclability and Shape Memory Capability

Wen-qi Zhang; Wen-wen Fan; Ruo-han Zhang; Qian-qian Peng; Xiang-liang Li; Lan Lei; Hui Li

doi:10.11777/j.issn1000-3304.2024.24313

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Mechanical Robust Dynamic Disulfide and Hydrogen Bonded Double Crosslinking Styrene Butadiene Rubbers with Recyclability and Shape Memory Capability

Research Article | 更新时间：2025-06-17

- Mechanical Robust Dynamic Disulfide and Hydrogen Bonded Double Crosslinking Styrene Butadiene Rubbers with Recyclability and Shape Memory Capability
- Acta Polymerica Sinica Vol. 56, Issue 5, Pages: 845-860(2025)
- 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：
  
  Lan Lei, E-mail: chm_leil@ujn.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24313
  CLC：
- CSTR：32057.14.GFZXB.2025.7357
- Received：30 December 2024，
  
  Accepted：06 February 2025，
  
  Published Online：15 April 2025，
  
  Published：20 May 2025
- 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

references

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