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Article(id=1203281567989867238, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1203281560800830004, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.05.004, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1715616000000, receivedDateStr=2024-05-14, revisedDate=1722787200000, revisedDateStr=2024-08-05, acceptedDate=null, acceptedDateStr=null, onlineDate=1764814281699, onlineDateStr=2025-12-04, pubDate=1747670400000, pubDateStr=2025-05-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1764814281699, onlineIssueDateStr=2025-12-04, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1764814281699, creator=13701087609, updateTime=1764814281699, updator=13701087609, issue=Issue{id=1203281560800830004, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='5', pageStart='1', pageEnd='144', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=0, articleOrder=1, issueType=-1, specialIssue=null, createTime=1764814279985, creator=13701087609, updateTime=1764814963861, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1203284429251784784, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1203281560800830004, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1203284429251784785, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1203281560800830004, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=22, endPage=29, ext={EN=ArticleExt(id=1203281568312828667, articleId=1203281567989867238, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation and performance of healable silicone rubber insulating materials based on dynamic hindered urea bonds, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=

To achieve the healability and reprocessability of silicone rubber insulating materials, it is feasible to introduce healable functional groups into the structural network of silicone rubber to extend its service life and reduce the safety hazards of power system operation. This paper used silane coupling agents to introduce amino groups into the main chain of silicone rubber, and then introduced dynamic hindered urea bonds into the silicone rubber network through the reversible reaction of isocyanates and hindered amines. A healable silicone rubber material was prepared, and the mechanical, electrical, healable, and reprocessable properties of silicone rubber were studied. The results show that the insulation performance of silicone rubber containing dynamically hindered urea bonds meets the application standards. Under certain temperature and pressure, silicone rubber samples can heal mechanical damage and electrical breakdown damage with high healing efficiency. The sample can be reprocessed through the cutting-hot pressing process, and the reprocessed sample can still retain certain mechanical and electrical insulation properties.

, articleAbstract=

To achieve the healability and reprocessability of silicone rubber insulating materials, it is feasible to introduce healable functional groups into the structural network of silicone rubber to extend its service life and reduce the safety hazards of power system operation. This paper used silane coupling agents to introduce amino groups into the main chain of silicone rubber, and then introduced dynamic hindered urea bonds into the silicone rubber network through the reversible reaction of isocyanates and hindered amines. A healable silicone rubber material was prepared, and the mechanical, electrical, healable, and reprocessable properties of silicone rubber were studied. The results show that the insulation performance of silicone rubber containing dynamically hindered urea bonds meets the application standards. Under certain temperature and pressure, silicone rubber samples can heal mechanical damage and electrical breakdown damage with high healing efficiency. The sample can be reprocessed through the cutting-hot pressing process, and the reprocessed sample can still retain certain mechanical and electrical insulation properties.

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为实现硅橡胶绝缘材料的可修复性和再加工性，可向其结构网络中引入可修复性基团以延长材料使用寿命，减少电力系统运行安全隐患。本文使用硅烷偶联剂在硅橡胶主链上接入氨基，并利用异氰酸酯与受阻胺的可逆反应向硅橡胶网络中引入动态受阻脲键，制备得到一种具有可修复性的硅橡胶材料，然后研究硅橡胶的力学性能、电气性能、可修复性能以及可再加工性能。结果表明：含动态受阻脲键的硅橡胶绝缘性能达到应用标准；在一定温度和压力下，硅橡胶样品可以修复机械损伤和电击穿损伤，且修复效率较高；通过切块-热压工序可以将样品进行再加工，再加工后的样品仍可以保留一定的力学性能和电气绝缘性能。

, articleAbstract=

为实现硅橡胶绝缘材料的可修复性和再加工性，可向其结构网络中引入可修复性基团以延长材料使用寿命，减少电力系统运行安全隐患。本文使用硅烷偶联剂在硅橡胶主链上接入氨基，并利用异氰酸酯与受阻胺的可逆反应向硅橡胶网络中引入动态受阻脲键，制备得到一种具有可修复性的硅橡胶材料，然后研究硅橡胶的力学性能、电气性能、可修复性能以及可再加工性能。结果表明：含动态受阻脲键的硅橡胶绝缘性能达到应用标准；在一定温度和压力下，硅橡胶样品可以修复机械损伤和电击穿损伤，且修复效率较高；通过切块-热压工序可以将样品进行再加工，再加工后的样品仍可以保留一定的力学性能和电气绝缘性能。

, correspAuthors=null, authorNote=null, correspAuthorsNote=
张磊（1988-），汉族，浙江宁波人，副教授，博士，主要从事聚合物电介质的研究。
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王大为（1976-），汉族，辽宁铁岭人，高级工程师，主要从事高压电缆的研究；

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王大为（1976-），汉族，辽宁铁岭人，高级工程师，主要从事高压电缆的研究；

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王大为（1976-），汉族，辽宁铁岭人，高级工程师，主要从事高压电缆的研究；

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Effect of nanofiber doping on electrical properties of silicone rubber[J]. Insulating Materials,2023,55(12):38-45., articleTitle=Effect of nanofiber doping on electrical properties of silicone rubber, refAbstract=null), Reference(id=1203365335140376687, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281567989867238, doi=null, pmid=null, pmcid=null, year=2019, volume=26, issue=4, pageStart=1181, pageEnd=1189, url=null, language=null, rfNumber=[20], rfOrder=24, authorNames=ZHUBin, JIAZhidong, HUHao, journalName=IEEE Transactions on Dielectrics and Electrical Insulation, refType=null, unstructuredReference=ZHUBin, JIAZhidong, HUHao, et al. Interface resistivity and interfacial DC breakdown voltage of double-layer dielectrics[J]. 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基于动态受阻脲键的可修复硅橡胶绝缘材料制备与性能研究
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王大为 1 , 尚英强 1 , 刘青 1 , 郑天宇 1 , 徐毅明 2 , 吕泽鹏 2 , 张磊 2
绝缘材料 | 材料研究 2025,58(5): 22-29
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绝缘材料 | 材料研究 2025, 58(5): 22-29
基于动态受阻脲键的可修复硅橡胶绝缘材料制备与性能研究
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王大为1, 尚英强1, 刘青1, 郑天宇1, 徐毅明2, 吕泽鹏2, 张磊2
作者信息
  • 1.国网北京市电力公司，北京 100022
  • 2.西安交通大学 电工材料电气绝缘全国重点实验室，陕西 西安 710049

    • 王大为（1976-），汉族，辽宁铁岭人，高级工程师，主要从事高压电缆的研究；

通讯作者:

张磊（1988-），汉族，浙江宁波人，副教授，博士，主要从事聚合物电介质的研究。
Preparation and performance of healable silicone rubber insulating materials based on dynamic hindered urea bonds
Dawei WANG1, Yingqiang SHANG1, Qing LIU1, Tianyu ZHENG1, Yiming XU2, Zepeng LÜ2, Lei ZHANG2
Affiliations
  • 1. State Grid Beijing Electric Power Company, Beijing 100022, China
  • 2. State Key Laboratory of Electrical Insulation and Power Equipment, Xi′an Jiaotong University, Xi′an 710049, China
出版时间: 2025-05-20 doi: 10.16790/j.cnki.1009-9239.im.2025.05.004
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摘要
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为实现硅橡胶绝缘材料的可修复性和再加工性，可向其结构网络中引入可修复性基团以延长材料使用寿命，减少电力系统运行安全隐患。本文使用硅烷偶联剂在硅橡胶主链上接入氨基，并利用异氰酸酯与受阻胺的可逆反应向硅橡胶网络中引入动态受阻脲键，制备得到一种具有可修复性的硅橡胶材料，然后研究硅橡胶的力学性能、电气性能、可修复性能以及可再加工性能。结果表明：含动态受阻脲键的硅橡胶绝缘性能达到应用标准；在一定温度和压力下，硅橡胶样品可以修复机械损伤和电击穿损伤，且修复效率较高；通过切块-热压工序可以将样品进行再加工，再加工后的样品仍可以保留一定的力学性能和电气绝缘性能。

硅橡胶  /  动态受阻脲键  /  可修复

To achieve the healability and reprocessability of silicone rubber insulating materials, it is feasible to introduce healable functional groups into the structural network of silicone rubber to extend its service life and reduce the safety hazards of power system operation. This paper used silane coupling agents to introduce amino groups into the main chain of silicone rubber, and then introduced dynamic hindered urea bonds into the silicone rubber network through the reversible reaction of isocyanates and hindered amines. A healable silicone rubber material was prepared, and the mechanical, electrical, healable, and reprocessable properties of silicone rubber were studied. The results show that the insulation performance of silicone rubber containing dynamically hindered urea bonds meets the application standards. Under certain temperature and pressure, silicone rubber samples can heal mechanical damage and electrical breakdown damage with high healing efficiency. The sample can be reprocessed through the cutting-hot pressing process, and the reprocessed sample can still retain certain mechanical and electrical insulation properties.

silicone rubber  /  dynamic hindered urea bonds  /  healable
王大为, 尚英强, 刘青, 郑天宇, 徐毅明, 吕泽鹏, 张磊. 基于动态受阻脲键的可修复硅橡胶绝缘材料制备与性能研究. 绝缘材料, 2025 , 58 (5) : 22 -29 . DOI: 10.16790/j.cnki.1009-9239.im.2025.05.004
Dawei WANG, Yingqiang SHANG, Qing LIU, Tianyu ZHENG, Yiming XU, Zepeng LÜ, Lei ZHANG. Preparation and performance of healable silicone rubber insulating materials based on dynamic hindered urea bonds[J]. Insulating Materials, 2025 , 58 (5) : 22 -29 . DOI: 10.16790/j.cnki.1009-9239.im.2025.05.004
正文
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0 引言
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硅橡胶绝缘材料由于其独特的化学结构，相比传统的环氧树脂绝缘材料，具有良好的电气绝缘性、耐高温性、耐候性、耐污性及憎水性等优点，同时还具有高弹性、低硬度等特性，已被广泛应用于电气绝缘领域[1-2]。但硅橡胶绝缘材料在运输、安装以及长期服役的过程中容易产生机械损伤和电气损伤，这些损伤及二者的协同作用会影响硅橡胶使用寿命，甚至威胁电力系统的安全稳定运行。同时传统硅橡胶具有永久交联结构，属于热固性材料，在网运行期间无法自主修复内部损伤，造成安全隐患，且在报废后无法用处理热塑性材料的方式对其进行再加工，不符合可持续发展与“碳达峰”、“碳中和”的要求[3]。
向硅橡胶网络中引入动态化学键等使其具有可修复性是解决上述问题的理想方案。可修复性是指绝缘材料能识别损伤并对其进行修复，恢复损伤前性能的特性，在解决材料损伤、延长设备使用寿命、实现可持续发展等方面具有重要应用[4-5]。动态化学键可以赋予材料修复功能，具有分子结构设计灵活、修复效率高以及可多次修复等优点，是目前制备可修复电气材料普遍采用的一种策略[6]。将动态化学键引入硅橡胶交联网络后，可以在一定条件下，通过触发动态化学键的解离-重组过程实现传统硅橡胶绝缘材料不具备的再加工性与可修复性。目前常见的引入动态化学键的反应包括酯交换反应[7]、Diels-Alder反应[8]、二硫键交换反应[9]、亚胺键交换反应[10]和氢键交换反应[11]等。
受阻脲键是指脲键中氮原子被大基团取代导致共轭结构共平面特性受阻的化学结构。相比于其他动态化学键修复条件苛刻、修复过程复杂、修复时间较长、对环境变化敏感等缺点，受阻脲键具有反应条件温和、制备过程简便、化学性质较稳定的特征，可以引入至绝缘材料提升其修复能力，并且不影响绝缘材料在正常工况下的绝缘性能[12-14]。孙文杰等[15]在环氧树脂体系中的试验说明了当脲键中的氮原子引入庞大的取代基团时会干扰脲键的轨道共平面，使得脲键在较为温和的条件下可以解离为胺基和异氰酸酯基，进而实现链段的动态变化。在此基础上，该研究团队利用N,N-双（叔丁基）乙烯二胺和多元异氰酸酯制备了含受阻脲键的可修复聚氨酯。WANG Shujuan等[16]通过叔丁基受阻胺与聚醇的反应成功合成了具有修复性的聚合物网络。SUN W J等[17]通过哌嗪与氨丙基封端聚二甲基硅氧烷的反应合成了具有修复性的硅橡胶网络，证明了动态受阻脲键可以应用于硅橡胶基体。
上述已开发的硅橡胶虽然具有较好的修复性，但是在交联密度控制方式与反应物成本方面仍需改进。本研究通过向羟基封端聚二甲基硅氧烷线性大分子内引入氨丙基侧基，合成梳状硅氧烷前体，再与异氰酸酯、受阻仲胺反应直接生成具有高交联密度的三维网络结构，旨在提升硅橡胶电气强度与体积电阻率的同时降低反应成本。为了实现硅橡胶网络的修复性与再加工性，本研究将动态共价脲键引入硅橡胶网络体系内，利用动态受阻脲键反应条件温和、修复效率高等特点，实现硅橡胶网络在温和的条件下的良好修复性和再加工性，赋予材料不同于传统热固性材料与传统热塑性材料的新特性，降低硅橡胶绝缘材料在网运行时出现故障的概率，延长其使用寿命。
1 试验
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1.1 原材料
双羟基封端聚二甲基硅氧烷（PDMS），分子量Mn=2 000 g/mol，纯度为97%，天津佰码科技有限公司；γ-氨丙基甲基二乙氧基硅烷（APPD），纯度为97%，N,N-双（叔丁基）乙烯二胺（TBEA），纯度为98%，N,N-二甲基乙二胺（TEEA），纯度为98%，阿拉丁生化科技股份有限公司；六亚甲基二异氰酸酯（HDI），纯度为99%，麦克林生化科技股份有限公司；二氯甲烷，纯度为99%，天津市富宇精细化工有限公司；二月桂酸二丁基锡（DBTDL），纯度为95%，安耐吉（上海）医药化学有限公司。
1.2 合成工艺
本研究中硅橡胶的合成反应主要分为两个步骤进行。
第一步，取2 g PDMS与0.19 g APPD置于反应容器内，加入二氯甲烷使其充分溶解后，向所得溶液滴加2～3滴DBTDL，在100℃条件下搅拌反应 1 h，得到含氨丙基侧基的线性梳状硅氧烷前体（CSP），如图1(a)所示。
第二步，将第一步反应所得的CSP溶液与 0.17 g TBEA在烧杯内充分混合，再将所得溶液升温至80℃，并向其中加入0.25 g HDI。在此反应中，HDI不仅充当了构成受阻脲键的原料，也充当了合成聚合物网络的交联剂。当溶液在80℃下反应30 min后，将其转移入模具内，在真空烘箱中以80℃的条件固化12 h，从而得到具有动态受阻脲键的硅橡胶样品，如图1(b)所示，合成样品记作PJTH-1。将0.17 g TBEA反应物更换为0.09 g TEEA，其余条件不变，合成样品记作PJTH-0。
1.3 测试方法
使用Nicolet IN10+IZ10型傅里叶显微红外光谱仪对样品进行结构表征，测量范围为4 000～500 cm-1；使用Mettler DSC822e型差示扫描量热仪表征材料的热性能，升温速率为10℃/min，氮气气氛，测试温度范围为-150～100℃；使用CMT4503-5kN型万能试验机测试样品的力学性能，将样品加工成总长为35 mm、宽度为2 mm、标距为20 mm的哑铃型试样，以2 mm/min的速率在室温下进行拉伸，得到应力-应变曲线；使用6517B型高阻计测试样品的直流体积电阻率；使用球-球电极系统，将样品与电极浸没在硅油内，在2 kV/s的升压速率下持续升压直到样品击穿，记录此时的击穿电压，并使用Weibull模型对样品的电气强度进行分析；使用洁净美工刀将哑铃型试样中间切开以模拟机械损伤，再将切口拼接后在100℃、一定压力的条件下修复12 h，测试试样的修复能力；将样品剪碎成小块放置在模具中，在150℃下热压60 min，得到回收后的样品，测试试样的可再加工性。
2 硅橡胶绝缘材料各基础性能
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使用傅里叶红外光谱仪对两步反应的反应物和生成物进行分析，结果如图2所示。
图2(a)为合成线性大分子的反应物与生成物红外光谱（FTIR）。从图中可以看出，3 275 cm-1处的羟基伸缩振动特征峰与1 100 cm-1处的C-O键伸缩振动特征峰在线性大分子谱图上消失，证明了羟基与乙氧基已成功反应，而3 325 cm-1处氨基特征峰的存在证明该反应合成的线性大分子结构符合预期。图2(b)为合成动态硅橡胶的反应物与生成物红外光谱，由PJTH-1的红外光谱可见，2 250 cm-1处无特征峰出现，说明制备过程中添加的HDI已经完全参与反应；3 325 cm-1处的宽峰是N-H的伸缩振动特征峰，1 600 cm-1处是C=O伸缩振动特征峰，两者的存在说明受阻脲键结构已经被引入至动态网络中。溶胀实验可以直接反映样品内部高分子网络的交联情况，从图2(c)中可以观察到，在二氯甲烷中浸泡24 h，PJTH-1仅出现了体积的膨胀，并没有出现溶解的现象，说明交联结构成功产生。
图3(a)为PJTH-1样品的差示扫描量热（DSC）曲线。样品玻璃化转变温度定义为热流变化的中点，从热流曲线可见PJTH-1存在两个玻璃化转变温度，其中-123℃的转变温度与硅橡胶的结构有关，是橡胶的固有属性；39℃的玻璃化转变温度则与网络中引入的受阻脲键结构有关，可引起样品热流的变化。图3(b)为PJTH-1样品的热重分析（TGA）曲线。Td5%定义为样品损失5%原始质量时对应的温度，从测试结果可得PJTH-1的Td5%为234℃，说明其具有良好的热稳定性。
电气绝缘材料的介电性能对于其在实际工况下的应用具有重要意义。图4为PJTH-1样品的相对介电常数与介质损耗因数随频率变化的曲线。聚合物的相对介电常数由单位体积内偶极子的数量以及偶极子在变化电场中的运动能力决定；介质损耗主要包括电导损耗与松弛损耗两部分，宏观上表现为电介质单位时间内所消耗的能量，由介质损耗因数来定量表征。在所测量的频率范围内，样品的相对介电常数与介质损耗因数都呈现随着频率的升高而逐渐减小的趋势，这是由于低频下所有偶极子都可以跟上电场的变化，极化充分，然而随着频率的升高，偶极子的转向极化滞后于电场变化，极化不充分，因此相对介电常数与介质损耗因数降低。与文献[18-19]中报道的硅橡胶介电性能进行对比，可以发现PJTH-1的相对介电常数在10～104 Hz频段内均高于文献[18]中硅橡胶的相对介电常数（2.7），这是由于PJTH-1内部含有极性基团N-H与C=O，在硅橡胶网络中引入极性基团后，增大了材料的偶极矩，因此增大了材料的介电常数；PJTH-1的介质损耗因数大于文献[19]中报道的介质损耗因数（0.08），这同样与PJTH-1中引入了极性基团有关。
直流电气强度和直流体积电阻率作为电气绝缘材料的重要性能参数，是决定材料能否得到实际应用的重要性质。本研究在向硅橡胶网络中引入动态键赋予其可修复性的同时，还保持了硅橡胶良好的绝缘性能。样品特征电气强度的表述如式（1）所示。
PE=1-exp -EE0β
式（1）中：P为失效概率；E为测得的电气强度；E0为特征电气强度；β为形状参数。
PJTH-1样品直流电气强度的Weibull分布如图5所示。经测试，PJTH-1样品的直流体积电阻率为（5.63±0.35）×1014 Ω·m，根据式（1）计算得到特征电气强度为60.97 kV/mm，分别高于文献[20]报道的普通硅橡胶材料的体积电阻率（约1.7×1014 Ω·m）与特征电气强度（约37 kV/mm），因此本研究合成的动态硅橡胶具有一定的应用潜力。
3 可修复性
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在硅橡胶绝缘材料的运输、安装以及服役期间，容易由于外部的应力导致硅橡胶网络中出现机械损伤，这些机械损伤容易造成局部应力集中从而影响材料的使用寿命。因此研究动态硅橡胶绝缘材料对机械损伤的修复具有重要意义。机械损伤的修复实验可以用来判断样品内部动态键的引入是否赋予样品修复表面损伤的能力。使用洁净美工刀分别将PJTH-1、PJTH-0样品切断，在100℃、5 MPa的条件下对断口修复12 h。使用偏光显微镜（POM，BX51-P型）对样品修复前后的形貌进行观察。图6(a)～(b)展示了断口修复前后的POM图，可以发现由于内部动态受阻脲键的作用，图6(a)中PJTH-1样品表面的断口在修复后只见很浅的痕迹，说明含动态受阻脲键的硅橡胶样品具有一定的机械损伤修复能力。图6(b)为对比组，可以看出不含动态受阻脲键的PJTH-0在同样修复条件下，划痕并未出现愈合现象，说明样品的可修复性是由动态受阻脲键给予的。图6(c)为PJTH-1表面划痕修复前后的SEM图，可以看出PJTH-1表面修复后已无明显划痕，进一步证明了含动态受阻脲键的硅橡胶样品具有机械损伤修复能力。
通过测量样品修复前后的力学性能可以判断材料修复性的优劣，力学性能通过万能试验机进行测试。样品的修复效率（η）通过公式（2）进行计算。
η=PhPo×100%
式（2）中：Ph为修复后试样的拉伸强度或断裂伸长率；Po为修复前试样的拉伸强度或断裂伸长率。
图7展示了PJTH-1样品在经历机械损伤的修复过程后，外观上呈现较好的一体性，且可以承受100 g砝码的重力，说明样品具有一定可修复性；PJTH-0样品结构则由于不具有动态性，没有修复现象的发生。图8是PJTH-1样品切断修复前后的应力-应变曲线。从图8可以看出，PJTH-1样品修复后力学性能恢复较好，应用公式（2）可以计算出PJTH-1样品的拉伸强度修复效率为78.3%，断裂伸长率修复效率为69.6%。
电击穿损伤的修复性关乎电力设备的安全稳定运行，是样品修复性研究的重要部分。本文对PJTH-1样品的电击穿损伤修复能力进行了定性研究。图9为在100℃、5 MPa条件下PJTH-1样品电击穿损伤修复12 h前后的POM和SEM图，从图中可以发现，样品的电击穿孔洞在经历修复后已经基本愈合，说明动态受阻脲键的引入使得硅橡胶网络具有修复电击穿损伤的能力。
含动态受阻脲键的硅橡胶网络具有动态性的原因主要是酰胺键中氮原子连接大取代基后，其位阻效应扰乱了酰胺键电子轨道的共面性，因此受阻脲键的强度比普通脲键弱。在一定温度和压力的作用下，受阻脲键可以动态解离为异氰酸酯与受阻胺；在受阻脲键动态解离的过程中，聚合物的链段也发生流动，促进异氰酸酯与受阻胺的动态结合，此过程即为动态网络的解离-重组过程。在一定温度和压力的作用下，高交联度样品内部链段移动受限制，因此产生的异氰酸酯与受阻胺无法充分重新结合，宏观上表现为修复效率与再加工效率较低。而动态键含量越高，网络内部在一定温度和压力作用下产生的异氰酸酯与受阻胺浓度越大，越容易发生动态结合过程，宏观上表现为修复效率与再加工效率的升高。
4 可再加工性
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再加工性是动态硅橡胶材料区别于传统硅橡胶材料的重要性质，可以反映交联网络的动态性，同时动态硅橡胶材料可以回收再利用也符合绿色发展战略的要求。样品的再加工效率（μ）通过公式（3）进行计算。
μ=PrPo
式（3）中：Pr为样品再加工后的拉伸强度、断裂伸长率、直流体积电阻率或电气强度；Po为样品再加工前的拉伸强度、断裂伸长率、直流体积电阻率或电气强度。
图10所示的再加工试验说明PJTH-1样品可以在切块后通过热压成形，再加工成整块均一光滑的硅橡胶，证明了所合成的硅橡胶网络具有动态性，可以通过一定温度和压力下动态键的解离-重组过程使得交联网络重排为新的动态交联网络。作为对比，PJTH-0样品则由于内部不存在动态化学键，链段无法在热效应下发生解离-重组过程，因此无法再形成完整均一的硅橡胶，不具有可再加工性。
测试PJTH-1再加工前后的力学性能，得到的应力-应变曲线如图11所示。从图11可以看出，样品再加工后可以恢复一定的力学性能。根据公式（3）计算得到样品的拉伸强度再加工效率与断裂伸长率再加工效率分别为81.4%、77.0%。
测试PJTH-1样品再加工前后的介电性能，结果如图12所示。从图12可以看出，再加工后样品的相对介电常数与介质损耗因数随频率的变化趋势与再加工前的基本相同，但同频率下的介电性能数据相比于再加工前有着明显的增加。这主要是由于在剪碎-热压的物理过程中，网络中被引入了较多的短支链、端基等基团，这些新引入的基团在电场中较易极化，因此造成介电性能数据的上升。
PJTH-1样品再加工后的直流电阻率为（3.93±0.20）×1014 Ω·m，根据公式（3）计算得到直流体积电阻率再加工效率为69.75%。PJTH-1样品再加工后的电气强度Weibull分布如图13所示，结合式（1）计算得到特征电气强度为47.69 kV/mm，根据公式（3）计算得到电气强度再加工效率为78.22%。由试验结果可见，含动态受阻脲键的样品在再加工后可以保留一定的绝缘性能。
5 结论
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通过硅烷偶联剂与羟基封端聚二甲基硅氧烷的反应，将反应活性基团氨基引入线性梳状硅氧烷前体内，再通过异氰酸酯、受阻仲胺的引入，成功制备了具有动态性的硅橡胶绝缘材料，且其绝缘性能达到了绝缘材料的标准。
在100℃、5 MPa作用下，含动态受阻脲键的样品可以修复断裂损伤与电击穿损伤，且断裂修复后的样品可以保留一定的力学性能。在150℃、20 MPa作用下，样品可以通过剪碎-热压的过程被重新加工成整块均一性好、表面光滑的硅橡胶，且再加工后的样品可以保留一定的力学性能与绝缘性能。
基金
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  • 国网北京市电力公司科技项目(ZYKCJS[2023]010)
文献
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2025年第58卷第5期
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doi: 10.16790/j.cnki.1009-9239.im.2025.05.004
  • 接收时间：2024-05-14
  • 首发时间：2025-12-04
  • 出版时间：2025-05-20
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  • 收稿日期：2024-05-14
  • 修回日期：2024-08-05
基金
国网北京市电力公司科技项目(ZYKCJS[2023]010)
作者信息
    1.国网北京市电力公司，北京 100022
    2.西安交通大学 电工材料电气绝缘全国重点实验室，陕西 西安 710049

通讯作者:

张磊（1988-），汉族，浙江宁波人，副教授，博士，主要从事聚合物电介质的研究。
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2种不同金属材料的力学参数
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Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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