热氧老化对基于双重动态共价键的可降解树脂性能的影响

doi:10.19595/j.cnki.1000-6753.tces.240694

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摘要

双重动态交联环氧树脂材料因其良好的动态性能在环保电工装备领域具有重要应用,但其在高温、高压、湿热环境下的长期服役可靠性仍面临挑战。该文制备了不同二硫键含量的动态酯键与二硫键的双重交联可降解树脂,系统地研究了其在不同老化阶段的微观形态、电气性能、弯曲性能、动态热力学性能以及降解性能,并基于热重点斜法建立了其快速热老化寿命评估模型。研究结果表明,二硫键的引入导致双重动态交联网络更容易受到热氧老化的影响。在220℃下老化720 h后,S—S键含量为30%的基于酯交换和二硫键的双重动态键类玻璃化环氧树脂的弯曲强度由18.41 MPa下降至5.13 MPa,断裂类型转变为脆断;击穿场强由41 kV/mm下降至39.12 kV/mm,介质损耗因数由2.98×10^-3升高至3.64×10^-3,发生明显绝缘劣化。热氧老化会影响树脂动态交联网络,导致树脂玻璃化转变温度由133.9℃升高至196.1℃,降解效率下降。该文为改善双重动态交联环氧树脂材料的性能提供了重要参考,有助于推动环保电工装备领域的进一步发展和应用。

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关键词 ：类玻璃高分子, 双重动态交联, 可降解环氧树脂, 热氧老化, 寿命评估

Abstract：

Epoxy Resin (EP) possesses advantages such as low cost, high mechanical strength, robust chemical resistance, and excellent electrical insulation properties, making it extensively utilized in various epoxy cast electrical equipment like dry transformers and reactors. Nonetheless, the three-dimensional cross-linked network of resins exhibits non-melting characteristics, posing challenges in the degradation and recycling of retired epoxy electrical equipment. Nowadays, researchers have achieved epoxy resin recycling by incorporating dynamic covalent bonds into the epoxy resin crosslinking network to develop degradable Vitrimer epoxy resin materials. However, when applied to complex environments like high temperature, humidity, and intense electric fields, the internal crosslinking network of epoxy Vitrimers material may deteriorate, impacting its operational longevity. Therefore, besides ensuring favorable electrical, mechanical, and thermal properties, the enduring reliable performance of Vitrimer resin cannot be disregarded. This paper prepared dual-dynamic bonds Vitrimer resin with varying disulfide bond contents. The micromorphology, electrical characteristics, mechanical properties, dynamic thermodynamic properties, and degradation properties of Vitrimer resin at diverse aging stages were regularly investigated and the life evaluation model is constructed at last.
Firstly, dual dynamic crosslinked Vitrimer resin basded on ester bonds and varied disulfide bonds were prepared with 3,3’-Dithiodipropionic acid (DTDPA) and Hexahydro-4-methylphthalic anhydride (MHHPA) as the curing agent, with Triethanolamine acting as the catalyst. Subsequently, the accelerated thermo-oxygen aging tests were carried out, during which the microscopic morphology, electrical properties, bending characteristics, dynamic thermodynamic attributes, and degradation properties of vitrimer resin were periodically evaluated. Experiment results revealed alterations in the resin's microstructure under hot oxygen aging, leading to random internal cross-linked network fractures that generate abundant free radicals, ultimately causing resin failure. The resin's bending strength diminishes, rigidity increases, toughness notably decreases, and the bending fracture transitions to a brittle fracture pattern. As aging progresses, a denser cross-linked network forms on the resin's surface, elevating T_g. The integration of disulfide bonds makes the resin system more susceptible to oxidation and molecular chain breakage, resulting in reduced breakdown voltage, heightened dielectric loss factor, and increased insulation deterioration. Throughout the aging process, the degradation rate of Vitrimer resin in glycol solution decreases due to surface ester bond reduction and oxide layer formation, while the destruction of the disulfide crosslinking network prevents resin degradation in dithiothreitol solution. Lastly, a life evaluation model for the dual dynamic crosslinked Vitrimer resin was formulated based on the results of bending strength and TGA tests.
The dual dynamic crosslinked Vitrimer resin has excellent comprehensive properties and can realize the recycling of decommissioned epoxy electrical equipment. In this paper, the effect of thermal oxygen aging on the properties of dual dynamic crosslinked degradable resin was studied, which laid the experimental and theoretical foundation for the long-term service of vitrification epoxy resin in electrical equipment.

Key words： Vitrimer dual-dynamic bonds degradable epoxy resins thermal oxygen aging electrical equipment

收稿日期: 2024-05-06

PACS:

TM21

基金资助:

国家自然科学基金资助项目（52377025）

通讯作者: 刘畅女,2000年生,硕士研究生,研究方向为绿色环保电工材料研发、可降解环氧树脂老化特性及回收特性。E-mail：liu6087610@163.com

作者简介: 刘贺晨男,1989年生,博士,副教授,研究方向为环保型环氧树脂及其复合材料研制、电气设备绝缘状态评估及聚合物电树枝特性研究等。E-mail：hc.liu@ncepu.edu.cn

引用本文:

刘贺晨, 刘畅, 孙章林, 刘云鹏, 江钰哲. 热氧老化对基于双重动态共价键的可降解树脂性能的影响[J]. 电工技术学报, 0, (): 2492941-2492941. Liu Hechen, Liu Chang, Sun Zhanglin, Liu Yunpeng, Jiang Yuzhe. The Effect of Thermal Oxygen Aging on the Properties of Degradable Resin Based on Dual-Dynamic Bonds. Transactions of China Electrotechnical Society, 0, (): 2492941-2492941.

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