电工技术学报  2024, Vol. 39 Issue (16): 5134-5148    DOI: 10.19595/j.cnki.1000-6753.tces.230908
高电压与放电 |
催化剂对基于动态酯交换Vitrimers材料性能的影响
刘贺晨1,2, 魏利伟1, 孙章林1, 刘畅1, 刘云鹏1,2
1.河北省绿色高效电工新材料与设备重点实验室(华北电力大学) 保定 071003;
2.新能源电力系统全国重点实验室(华北电力大学) 北京 102206
Effect of Catalysts on the Performance of Vitrimers Based on Dynamic Ester Exchange
Liu Hechen1,2, Wei Liwei1, Sun Zhanglin1, Liu Chang1, Liu Yunpeng1,2
1. Hebei Key Laboratory of Green and Efficient New Electrical Materials and Equipment North China Electric Power University Baoding 071003 China;
2. State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources North China Electric Power University Beijing 102206 China
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摘要 传统环氧树脂作为干式变压器、电压互感器和复合绝缘子等电工装备的主要原材料,有着良好的力学性能和电学性能,但是其固化后形成的交联网络难溶难熔。随着环氧树脂基电工装备运行年限的增长,大量退役设备的处理面临巨大的挑战。该文制备了基于酯交换的酸酐固化类玻璃化环氧树脂材料(Vitrimers),系统地研究了催化剂对树脂力学、电学、热学以及动态交换性能的影响规律,并使用醇类溶液探索其降解性能。研究结果显示,与传统环氧树脂相比,Vitrimers体系的断裂伸长率较高,表现出良好的韧性。在Vitrimers体系中以1,5,7-三叠氮双环(4.4.0)癸-5-烯(TBD)为催化剂的Vitrimers具有较佳的综合特性,在高温下表现出良好的应力弛豫特性,且能够在7 h(190℃)全部溶解于乙二醇(EG)溶液中。该文研究结果表明,类玻璃化环氧树脂有较综合的力-热-电特性,能够快速溶解于降解溶液,有望用作电工装备的新型环保树脂基体。
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刘贺晨
魏利伟
孙章林
刘畅
刘云鹏
关键词 类玻璃化环氧树脂材料环氧树脂催化剂降解电工装备    
Abstract:Epoxy resins are widely used in electrotechnical equipment because of their dimensional stability, resistance to cracking, and excellent electrical insulation and mechanical properties after curing. However, the irreversible crosslinking network of traditional thermosetting epoxy resins makes it difficult to degrade and recycle. As the operating life of epoxy resin-based electrotechnical equipment increases, the management of large quantities of thermoset waste faces great difficulties. Current recycling methods of resin waste are environmentally polluting, energy intensive, and do not meet the eye of sustainable development. In order to elimate thermosetting epoxy resin waste from the source, this paper investigates the effect of catalyst type on the performance of glass-like epoxy resins (Vitrimers) and explores the degradation rate of different resin systems in alcohol solutions.
Firstly, different Vitrimers systems, named V-TBD, V-TEOA, V-Sn, V-Zn, were prepared using 1,5,7-triazabicyclo(4.4.0)dec-5-ene (TBD), triethanolamine (TEOA), stannous isooctanoate (Sn(Oct)2), and zinc acetylacetonate (Zn(acac)2) as catalysts in this paper. Comparatively, we analyzed the conventional resins (T-DMP) and different Vitrimers for their mechanical, electrical and thermal properties. The results showed that compared with the conventional epoxy resin, the tensile strength, flexural strength and electrical properties of Vitrimers were reduced, but its elongation at break was higher and showed good toughness. Among them, the comprehensive mechanical properties of V-TEOA was second only to T-DMP. Its tensile strength, bending strength and elongation at break were 77.33 MPa, 23.08 MPa and 10.98%, respectively. V-TBD had high retention rate of electrical insulation properties. It had only 5.2% decrease in breakdown strength, and the leakage current and dielectric loss factor were slightly higher than those of T-DMP. Catalysts containing metal ions led to a serious degradation of the electrical properties of Vitrimers. In addition, the thermal stability of all Vitrimers systems was lower than that of conventional resin, which was caused by the weak bonding of the dynamic bonds. However, V-TBD and V-Zn had higher glass transition temperatures than the conventional resin, which were 163.89℃ and 158.65℃. Then, the stress relaxation of the conventional resin and Vitrimers was investigated. Unlike the conventional resin, Vitrimers showed good stress relaxation at high temperatures due to the activation of exchange reactions between the dynamic ester bonds contained in the crosslinked network. Among them, V-TBD had the shortest stress relaxation time at the same temperature, indicating the fastest rate of ester exchange reaction. Finally, the degradation characteristics of conventional resins and Vitrimers were studied in a solution of ethylene glycol (EG). The conventional epoxy resin could not be dissolved, while Vitrimers can be able to achieve dissolution. Among them, V-TBD showed the best dissolution effect.
In conclusion, the introduction of dynamic bonds in the cross-linking network after the curing of epoxy resins makes the degradation and recycling of resins possible, which provides a base material for new green electrotechnical equipment. Vitrimers using TBD as a catalyst has good mechanical, electrical, and thermal properties, can be fast dissolved in ethylene glycol solution, and is expected to be used as a matrix resin in the field of electrical equipment.
Key wordsVitrimers    epoxy resin    catalyst    degradation    electrotechnical equipment   
收稿日期: 2023-06-13     
PACS: TM21  
基金资助:国家自然科学基金(52007062)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、电工装备在线检测和外绝缘。E-mail:liuyunpeng@ncepu.edu.cn   
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、电工装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, 魏利伟, 孙章林, 刘畅, 刘云鹏. 催化剂对基于动态酯交换Vitrimers材料性能的影响[J]. 电工技术学报, 2024, 39(16): 5134-5148. Liu Hechen, Wei Liwei, Sun Zhanglin, Liu Chang, Liu Yunpeng. Effect of Catalysts on the Performance of Vitrimers Based on Dynamic Ester Exchange. Transactions of China Electrotechnical Society, 2024, 39(16): 5134-5148.
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