负载-包覆-接枝三级功能化防老剂的设计及其对天然橡胶复合材料长效抗老化性能的影响

doi:10.3976/j.issn.1002-4026.20260056

山东科学 ›› 2026, Vol. 39 ›› Issue (5): 53-64.doi: 10.3976/j.issn.1002-4026.20260056

负载-包覆-接枝三级功能化防老剂的设计及其对天然橡胶复合材料长效抗老化性能的影响

郑佳旺¹(), 郭玉霞², 刘孝阳³, 程歆童¹, 刘致华¹, 李思锦¹, 赵帅¹, 李琳¹^,^*()

¹ 青岛科技大学高分子科学与工程学院山东省教育厅橡胶塑料重点实验室/山东省橡胶塑料重点实验室, 山东青岛 266042
² 山东日科化学股份有限公司, 山东潍坊 261000
³ 山东梅德业高分子材料有限公司, 山东潍坊 261000

收稿日期:2026-03-20 修回日期:2026-04-07 出版日期:2026-10-20 上线日期:2026-09-30
通信作者: *李琳,女,副教授,研究方向为石墨烯的低成本绿色宏量制备及其在功能性橡胶/弹性体材料(高阻尼、高气体阻隔、静电屏蔽、导电、导热)中的应用。E-mail:qustlilin@163.com, Tel:18553282659
作者简介:郑佳旺(2001—),男,硕士,研究方向为橡塑功能助剂。E-mail:zjw15164181831@163.com
基金资助:
国家自然科学基金(51703111);国家自然科学基金(51603111);山东省自然科学基金(ZR2021ME107);国家重点研发计划(2022YFD2301202);中国博士后科学基金(2022M721903);中国博士后科学基金(2021M700553);中国博士后科学基金(2020M672014)

Design of a load-coat-graft tri-level functionalized antioxidant and its impact on the long-term anti-aging performance of natural rubber composites

ZHENG Jiawang¹(), GUO Yuxia², LIU Xiaoyang³, CHENG Xintong¹, LIU Zhihua¹, LI Sijin¹, ZHAO Shuai¹, LI Lin¹^,^*()

¹ Shandong Provincial Key Laboratory of Rubber and Plastics/Key Laboratory of Rubber and Plastics, Department of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
² Shandong Rike Chemical Co., Ltd., Weifang 261000, China
³ Shandong Meideye Polymer Materials Co., Ltd., Weifang 261000, China

Received:2026-03-20 Revised:2026-04-07 Published:2026-10-20 Online:2026-09-30

摘要/Abstract

摘要：

为了解决天然橡胶(NR)由于分子结构中存在双键和α-H等高活性位点导致其在服役过程中易老化的问题,创新性地设计并制备了基于硅藻土(DE)的具有“负载-包覆-接枝”三级功能化结构的负载型长效缓释防老剂(4010NA@DE)。首先采用硅藻土负载防老剂N-异丙基-N’-苯基对苯二胺(4010NA),再利用聚多巴胺(PDA)进行表面包覆,最后引入柔性油胺(YA)分子接枝改性。该设计可有效抑制天然橡胶复合材料中小分子防老剂的迁移,同时改善负载型防老剂与橡胶基体的相容性,可以解决传统防老剂易喷霜失效和长效防护能力差的难题。实验结果表明,添加4010NA@DE的天然橡胶复合材料具备优异的抗老化性能:在100 ℃热氧老化672 h后,拉伸强度仍高于20 MPa,断裂伸长率在450%以上,且表面无喷霜现象,拉伸强度保持率与断裂伸长保持率分别达81%和68%,老化系数为56%。本研究为开发长效、耐迁移的橡胶防老化体系提供了新思路。

关键词: 天然橡胶, 硅藻土, 负载型防老剂, 抗老化性能

Abstract:

To address the susceptibility of natural rubber (NR) to oxidative aging arising from highly reactive sites such as double bonds and α-hydrogens in its molecular structure, this study designs and prepares a supported long-term sustained-release antioxidant system (4010NA@DE) with a three-level “load-coat-graft” functional architecture based on diatomite (DE). The antioxidant N-isopropyl-N'-phenyl-p-phenylenediamine (4010NA) is first loaded onto diatomite, followed by surface coating with polydopamine, and subsequent grafting of flexible oleylamine chains. This hierarchical design effectively suppresses migration of small-molecule antioxidants within the natural rubber matrix while improving interfacial compatibility, thereby mitigating issues of blooming and rapid depletion associated with conventional antioxidants. Experimental results show that NR composites incorporating 4010NA@DE exhibit excellent anti-aging performance. After 672 h of thermo-oxidative aging at 100 ℃, the tensile strength remains above 20 MPa and the elongation at break exceeds 450%, with no observable surface blooming. The retention rates of tensile strength and elongation at break reach 81% and 68%, respectively, with an aging coefficient of 0.56. This work provides a viable strategy for designing durable, migration-resistant antioxidant systems for long-term protection of rubber materials.

Key words: natural rubber, diatomite, supported antioxidant, anti-aging performance

中图分类号:

TQ33

郑佳旺, 郭玉霞, 刘孝阳, 程歆童, 刘致华, 李思锦, 赵帅, 李琳. 负载-包覆-接枝三级功能化防老剂的设计及其对天然橡胶复合材料长效抗老化性能的影响[J]. 山东科学, 2026, 39(5): 53-64.

ZHENG Jiawang, GUO Yuxia, LIU Xiaoyang, CHENG Xintong, LIU Zhihua, LI Sijin, ZHAO Shuai, LI Lin. Design of a load-coat-graft tri-level functionalized antioxidant and its impact on the long-term anti-aging performance of natural rubber composites[J]. Shandong Science, 2026, 39(5): 53-64.

图/表 5

参考文献 56

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负载-包覆-接枝三级功能化防老剂的设计及其对天然橡胶复合材料长效抗老化性能的影响

Design of a load-coat-graft tri-level functionalized antioxidant and its impact on the long-term anti-aging performance of natural rubber composites

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