新型耐迁移橡胶防老剂的研究进展

doi:10.16085/j.issn.1000-6613.2023-0520

摘要/Abstract

摘要：

首先介绍了橡胶防老剂的相关理论研究，橡胶材料老化的本质为自由基反应，其防护机理主要是抑制自由基的形成，实验研究集中于差示扫描量热、核磁、紫外分光、红外光谱等分析橡胶材料以及防老剂的结构变化，而理论研究则集中于分子模拟，包括解离能、溶解度、均方位移等参数计算。其次，通过对国内外商业化橡胶防老剂的使用现状进行追踪，分析了新型橡胶防老剂的开发与应用情况，包括胺类防老剂的改性方法、防老剂的复配研究以及具备特殊功能的新型防老剂应用等，结合几类耐迁移橡胶防老剂的结构特点和应用结果，指出具备耐迁移和低毒性等特点的新型橡胶防老剂是未来发展方向。最后，总结了新型耐迁移橡胶防老剂应集中于发挥防老剂大分子化和多官能化的协同作用，可以更好地适应橡胶工业的持续发展。

关键词: 橡胶防老剂, 老化机理, 耐迁移, 分子模拟

Abstract:

The work introduced the theoretical research on rubber antioxidants at first. The essence of rubber material aging was free radical reaction, and its protection mechanism was mainly to inhibit the formation of free radicals. Experiments of mechanism focused on differential scanning calorimeter, nuclear magnetic resonance, ultraviolet spectroscopy and infrared spectroscopy to analyze the structural changes of both rubber materials and antioxidants, while the theoretical research focused on molecular simulation including the calculation of parameters such as dissociation energy, solubility and mean square displacement. Secondly, though tracing the commercial rubber antioxidants, the development and application of novel rubber antioxidants were analyzed including the modifying of amine antioxidants, the compounding of antioxidants and the application of new antioxidants with special functions, etc. Combining with the structural features and experimental results of several types of anti-migration rubber antioxidants, it was proposed that the novel rubber antioxidants with anti-migration and low toxicity were the crucial points. Finally, it was summarized that the novel anti-migration rubber antioxidants should focus on the improvement of synergistic effect of macro-molecular and multi-functional for antioxidants, which can better adapt to the sustainable development of rubber industry.

Key words: rubber antioxidants, aging mechanism, anti-migration, molecular simulation

中图分类号:

TQ330.38

欧阳素芳, 周道伟, 黄伟, 贾凤. 新型耐迁移橡胶防老剂的研究进展[J]. 化工进展, 2023, 42(7): 3708-3719.

OUYANG Sufang, ZHOU Daowei, HUANG Wei, JIA Feng. Research progress on novel anti-migration rubber antioxidants[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3708-3719.

图/表 11

表1 中国橡胶防老剂产量与表观需求量

年份	产量/万吨	表观需求量/万吨
2014	36.91	33.59
2015	37.77	34.68
2016	37.75	33.28
2017	36.90	35.89
2018	36.50	35.33
2019	37.20	36.01
2020	36.74	35.56
2021	41.45	40.10
2022	39.42	—

图1 高分子链RH热氧老化机理及防老剂作用过程

图2 不同防老剂的防护作用机理

图3 电子与原子分子尺度的模拟流程

图4 “大马哈鱼”事件

图5 胺类防老剂改性的工艺方法

图6 RU系列防老剂的化学结构

图7 两种反应型防老剂的合成路线

图8 几种交联型橡胶防老剂

图9 几种聚合型橡胶防老剂

图10 几种负载型橡胶防老剂

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