基于动态受阻硫脲键的自修复硅橡胶的绝缘性能

doi:10.19595/j.cnki.1000-6753.tces.242005

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摘要含有动态受阻硫脲键的有机硅是一种新型智能绝缘材料,可用于电力设备和电子器件。目前关于自修复材料的研究多集中于机械性能的修复效率,较少关注其绝缘性能。为研究自修复材料在电气领域应用的可行性,该文以聚二甲基硅氧烷（PDMS）为基体,通过对苯二异硫氰酸酯和氨丙基双封端聚二甲基硅氧烷合成动态硫脲键,利用无水哌嗪提供空间位阻结构,同时采用三（2-氨乙基）胺调整分子链结构,研制了一种具有修复效果和良好绝缘性能的材料。基于拉伸试验、击穿和电导试验、宽带介电谱测试及热修复试验,对比样品修复前后的机械性能、绝缘性能和介电性能,发现动态键的加入使材料具备自修复能力,且相对介电常数增加。随着交联密度的提高,样品直流击穿强度和体积电阻率上升。该文可为开发同时具有修复性和绝缘性能的材料提供一条有效的途径。

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关键词 ：自修复材料, 硫脲, 聚二甲基硅氧烷（PDMS）, 绝缘性能, 空间电荷

Abstract：Silicone rubber is a kind of insulating material widely used in power system. However, due to its poor mechanical strength, it is easy to be damaged during use, which affects its service life. Self-healing materials can repair their own minor damages under certain conditions, and then restore certain original properties. Silicone containing dynamic hindered thiourea bonds is a new type of intelligent insulation material, which can be used in power equipment and electronic devices. At present, the research on self-healing materials mainly focuses on the repair efficiency of mechanical properties, and pays less attention to their insulation properties. In order to study the feasibility of self-healing materials in electrical field, dynamic thiourea bond was synthesized by p-phenyldiisothiocyanate and aminopropyl double-ended polydimethicone. Anhydrous piperazine provided steric hindrance structure, and tri(2-aminoethyl)amine was used to adjust the molecular chain structure. A kind of material with healing property and insulating property was developed.
In this study, the crosslinking degree is variable and the cross-linking degree of PDMS-1, PDMS-2 and PDMS-3 increased. Firstly, the structure of the sample was tested, and the successful synthesis of thiourea bond was verified by Fourier transform infrared spectroscopy. The cross-linked structure was verified by swelling experiment, and the glass transition temperature was obtained by differential scanning calorimetry. It was found that the glass transition temperature of the sample increased with the increase of the cross-linking degree. The mechanical tests show that the elongation at break of the sample is close to 55%~59%, and the elastic modulus decreases from 23.535 MPa to 5.707 MPa with the increase of crosslinking degree, and the tensile strength increases first and then decreases. Due to the introduction of dynamic bond, the relative permittivity of the sample increases compared with that of ordinary silicone rubber, ranging from 2.1~4.8. It is found that the activation energy of thiourea bond is lower than that of urea bond through relaxation peak. The results of space charge show that with the increase of cross-linking degree, the homo-charge injection increases. The insulation test results show that the DC resistivity and breakdown field strength increase with the increase of crosslinking degree.
The self-healing properties of the material were verified by scratch repair experiments. Scratches were made on the surface of self-healing PDMS and ordinary commercial PDMS samples with a clean utility knife, and the wounds were fixed with a long tail clip after the wound was split. The morphology of the samples before and after the repair was observed with a microscope. After two days of treatment at 90℃, the incision of ordinary silicone rubber had a weak trend of repair, and PDMS-1 after 24 h of heat treatment, the incision became significantly smaller. The healing efficiency of the sample was evaluated by tensile strength and insulation properties. The repair efficiency of PDMS-1 with linear structure and PDMS-2 with low crosslinking degree can reach more than 60% based on mechanical properties, while the repair efficiency of PDMS-3 is low due to the high cross-linking degree, which limits the movement of chain segments. The breakdown strength of PDMS-1 and the repair efficiency of PDMS-2 can reach 84.3% and 79.1% respectively.
Through the above experiments, the following conclusions are drawn: (1) The self-healing PDMS containing the dynamic hindered thiourea bond has good repair performance, and the repair efficiency based on the breakdown strength can recover up to 84.3%. Although the resistivity decreases before and after repair, it still has good insulation effect; The repair efficiency of PDMS-1 with linear structure and PDMS-2 with low crosslinking degree can reach more than 60%. (2) The cross-linked structure can improve the insulation performance by affecting the movement of carriers, including resistivity and breakdown strength, etc., while also weakening the repair efficiency of the material by hindering the movement of the molecular chain.

Key words： Self-healing material thiourea polydimethylsiloxane (PDMS) insulating property space charge

收稿日期: 2024-11-08

PACS:

TM215.2

基金资助:国网北京市电力公司资助项目（ZYKCJS[2023]010）

通讯作者: 吕泽鹏男,1987年生,教授,博士生导师,研究方向为绝缘材料的电荷输运、电树、局部放电和老化过程。E-mail：lv.zepeng.insu@xjtu.edu.cn

作者简介: 丁一铭男,1994年生,助理工程师,研究方向为高压电缆检修和和高分子绝缘材料应用。E-mail：2386234727@qq.com

引用本文:

丁一铭, 焦宇阳, 翟涵君, 吕泽鹏, 马宪伟. 基于动态受阻硫脲键的自修复硅橡胶的绝缘性能[J]. 电工技术学报, 2024, 39(zk1): 150-158. Ding Yiming, Jiao Yuyang, Zhai Hanjun, Lü Zepeng, Ma Xianwei. Insulation Properties of Self-Healing Silicone Based on Dynamic Hindered Thiourea Bond. Transactions of China Electrotechnical Society, 2024, 39(zk1): 150-158.

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