硫化天然橡胶的本征自修复与固相回收加工

向洪平; 容敏智; 章明秋

doi:10.11777/j.issn1000-3304.2017.17016

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硫化天然橡胶的本征自修复与固相回收加工

研究论文 | 更新时间：2021-01-26

- 硫化天然橡胶的本征自修复与固相回收加工
- Intrinsic Self-healing and Solid-state Recycling of Vulcanized Natural Rubber
- 高分子学报 2017年第7期页码：1130-1140
- 作者机构：
  
  1.中山大学化学学院聚合物复合材料及功能材料教育部重点实验室广州 510275
  2.广东工业大学材料与能源学院广东省功能软凝聚态物质重点实验室广州 510006
- 作者简介：
  
  容敏智, E-mail:cesrmz@mail.sysu.edu.cn Min-zhi Rong, E-mail:cesrmz@mail.sysu.edu.cn
  章明秋, E-mail:ceszmq@mail.sysu.edu.cn Ming-qiu Zhang, E-mail:ceszmq@mail.sysu.edu.cn
- 基金信息：
  
  国家自然科学基金(51333008);国家自然科学基金(51673219)
- DOI：10.11777/j.issn1000-3304.2017.17016
  中图分类号：
- 纸质出版日期：2017-7，
  
  收稿日期：2017-1-17，
  
  修回日期：2017-3-28，
扫描看全文
向洪平, 容敏智, 章明秋. 硫化天然橡胶的本征自修复与固相回收加工[J]. 高分子学报, 2017,(7):1130-1140.

Hong-ping Xiang, Min-zhi Rong, Ming-qiu Zhang. Intrinsic Self-healing and Solid-state Recycling of Vulcanized Natural Rubber[J]. Acta Polymerica Sinica, 2017,(7):1130-1140.
向洪平, 容敏智, 章明秋. 硫化天然橡胶的本征自修复与固相回收加工[J]. 高分子学报, 2017,(7):1130-1140. DOI： 10.11777/j.issn1000-3304.2017.17016.

Hong-ping Xiang, Min-zhi Rong, Ming-qiu Zhang. Intrinsic Self-healing and Solid-state Recycling of Vulcanized Natural Rubber[J]. Acta Polymerica Sinica, 2017,(7):1130-1140. DOI： 10.11777/j.issn1000-3304.2017.17016.

摘要

通过小分子模拟试验和应力松弛，发现甲基丙烯酸铜（MA-Cu）比氯化铜（CuCl

）更适合用作硫化天然橡胶中二硫键交换反应催化剂，并且硫化天然橡胶中的二硫键交换反应需要在高于120℃的温度下才能高效进行，这保障了相关制品在较低温工作时的结构与性能稳定.进一步的实验结果表明，硫化天然橡胶在MA-Cu辅助作用下获得了多次自修复与固相回收加工性能，损伤自修复后的硫化天然橡胶与固相回收加工的再生硫化天然橡胶，其拉伸强度均可恢复到原始材料强度的80%左右.

Abstract

Sulfur-vulcanized natural rubber is constructed by three-dimensional crosslinked networks containing plenty of monosulfidic

disulfide and polysulfide linkages

which is insoluble and infusible and hence difficult to be reprocessed. Considering that disulfide bonds possess dynamic reversibility under certain circumstances

however

we might impart rehabilitation power and processibility to vulcanized natural rubber if disulfide exchange among different disulfide and polysulfide bonds were activated. Model disulfide metathesis between equimolar small-molecule disulfides and stress relaxation of vulcanized natural rubber reveal that copper(Ⅱ) methacrylate (MA-Cu) is an effective catalyst of disulfide metathesis. Compared with CuCl

MA-Cu is more suitable for working with vulcanized natural rubber from the view point of environmental polarity and activation energy involved in stress relaxation. By incorporating MA-Cu during compounding of natural rubber and other ingredients as defined by industrial formulation

built-in sulfur-crosslinked networks are created after vulcanization and become dynamically reversible at or above 120℃ under the action of MA-Cu. Accordingly

rearrangement of the crosslinked networks is enabled as a result of reversible exchange of the sulfur bonds

which not only provides thermal deformability like linear polymers

but also helps to re-establish covalent bonding across cracked surfaces. Based on this finding

the vulcanized natural rubber is successfully coupled with multiple arbitrarily reshaping

intrinsic self -healing and solid-state recycling capabilities. Either the cracked or the reprocessed vulcanized natural rubber can restore mechanical properties of the original version to a great extent (~80%). Because disulfide metathesis is triggered at temperature ≥ 120℃

above the working temperatures for most natural rubber products

the materials are allowed to keep their structure and properties stability in the course of the operation. The approach proposed here has nothing to do with conventional measures of rubber reclaiming

via

de-crosslinking

and is eco-friendly and energy-saving. Moreover

the sulfur-crosslinked networks are not intentionally introduced into the vulcanized natural rubber but present following traditional technique. All these factors benefit popularization of the concept in practical applications.

关键词

硫化天然橡胶动态共价键二硫键交换反应本征型自修复固相回收

Keywords

Vulcanized natural rubberDynamic covalent bondDisulfide metathesisIntrinsic self-healingSolid-state recycling

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