基于亚胺键的香草醛基可降解环氧树脂综合性能研究

doi:10.19595/j.cnki.1000-6753.tces.240564

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摘要

双酚A型环氧树脂（DGEBA）因其优异的综合性能被广泛应用于环氧绝缘电工设备等领域,但由于环氧树脂固化后会形成永久性的三维交联网络,导致大量电工装备退役后无法实现高效降解和回收利用,造成严重的资源浪费。该文采用香草醛为原料,同时引入动态亚胺键制备可降解香草醛基类玻璃化环氧树脂（EDV）。将DGEBA和EDV进行共混,试验分析不同共混比例下树脂的电学、热学、力学基本服役特性,并对其降解回收利用性能进行了探索。研究结果表明：当DGEBA和EDV摩尔比例为0.75:0.25时,共混树脂具有优异的热力学性能,其中玻璃化转变温度高达159℃。含EDV的环氧树脂均表现出降解和自修复特性,最快可在10 h内完成降解,在180℃/1 h内完成自修复。EDV表现出优异的物理化学回收性能,回收树脂最大电气击穿强度保持在98%以上。含动态亚胺键的香草醛类玻璃化树脂体系有望为电工装备材料的环保升级提供新的选择方向和技术支撑。

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关键词 ： Vitrimer, 环氧树脂, 香草醛, 亚胺键, 降解回收

Abstract：

Bisphenol A-type epoxy resins are widely used in epoxy-insulated electrical equipment and other fields due to their excellent comprehensive performance, but due to the formation of permanent three-dimensional cross-linking network after curing of epoxy resins, a large number of electrical equipment can not be efficiently degraded and recycled after decommissioning, which results in a serious waste of resources. In this paper, vanillin is used as the raw material to prepare bio-based epoxy resin, and at the same time, dynamic imine bonding is introduced to prepare degradable vanillin-based glassy epoxy resin (EDV), and the traditional bisphenol A-based epoxy resin (DGEBA) and vanillin-based epoxy resin are blended with different ratios, and the high-performance, degradable and recycled epoxy resin copolymers are prepared, and the curing process is analyzed in detail, and the experiments are analyzed The basic service characteristics of the resin under different blending ratios in terms of electrical, thermal and mechanical properties, and its degradation and recycling properties were explored.
Firstly, in order to prepare vanillin-based epoxy resins based on imine bonding, vanillin and p-aminophenol were chosen as raw materials, and the syntheses were epoxidized and blended with conventional bisphenol A-type epoxy resins at different ratios, and MHHPA and EMIP were chosen as the curing agent and promoter, respectively, and were prepared in accordance with the curing mode of the probe, and at the same time, conventional bisphenol A-type epoxy resins were set up as the control group. Then, Fourier infrared spectroscopy tests were carried out and the results showed that the epoxy resin was correctly synthesized and fully cured. Finally, the data of different systems of epoxy resins were comparatively analyzed by thermogravimetric analysis, dynamic thermodynamic analysis, tensile bending test, comprehensive analysis of electrical properties, degradation recycling and self-repairing test to assess their applicability in the field of electrical engineering.
The following conclusions can be drawn from the experimental analysis: (1) The Van-0.25 system has the best heat resistance, mechanical properties, and electrical properties, but exhibits poor degradation recycling performance and low self-healing efficiency due to the low content of imine bonding, and the Van-1 all-bio-based resin has a less comprehensive performance than traditional epoxy resins, but meets the in-service requirements of electrical materials, and exhibits a better self-healing (2) With the increase of EDV content, the curing rate of the resin system is accelerated, and the samples are fully cured and crosslinked, showing excellent solvent resistance, as verified by infrared spectroscopy and gelation rate tests. It was demonstrated that the glass transition temperature, mechanical strength of the polymers were related to the cross-linking density and the rigidity of the chain segment structure, in which Van-0.25 had the highest glass transition temperature and mechanical strength, and also showed excellent thermal stability, and the introduction of the bio-based resins played a certain flame-retardant effect on the epoxy resin. The electrical properties decrease with the increase of imine bond content, and the dielectric properties are excellent, showing certain water resistance.3) The Vitrimer system constructed in the paper can be degraded and recycled and thermo-pressurized recycled due to the dynamic exchange of imine bonds at high temperatures, in which the chemical recycling effect is good, and the breakdown strength is maintained within a certain strength. In addition, the Vitrimer system also showed good self-healing performance, and all the specimens were repaired within 180 min.

Key words： Vitrimer epoxy resin vanillin imine bond degradation and recovery

收稿日期: 2024-04-10

PACS:

TM215

基金资助:

国家自然科学基金（52377025）和中央高校基本科研业务费专项资金（20226934）资助项目

通讯作者: 刘贺晨男,1989年生,副教授,硕士生导师,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

作者简介: 刘云鹏男,1976年生,博士,教授,博士生导师,研究方向为特高压输电技术、电气设备在线检测和外绝缘。E-mail：liuyunpeng@ncepu.edu.cn

引用本文:

刘云鹏, 黎馨阳, 刘贺晨, 白怡宁, 江钰哲. 基于亚胺键的香草醛基可降解环氧树脂综合性能研究[J]. 电工技术学报, 0, (): 2492934-2492934. Liu Yunpeng, Li Xinyang, Liu Hechen, Bai Yining, Jiang Yuzhe. Comprehensive Performance Study of Vanillin-Based Degradable Epoxy Resin Based on Imine Bonding. Transactions of China Electrotechnical Society, 0, (): 2492934-2492934.

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