Article(id=1304921608804651456, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921585991836085, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.08.001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1752595200000, receivedDateStr=2025-07-16, revisedDate=1756310400000, revisedDateStr=2025-08-28, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047155810, onlineDateStr=2026-09-10, pubDate=1787155200000, pubDateStr=2026-08-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047155810, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047155810, creator=13701087609, updateTime=1789047155810, updator=13701087609, issue=Issue{id=1304921585991836085, tenantId=1146029695717560320, journalId=1149653034449285133, year='2026', volume='59', issue='8', pageStart='1', pageEnd='160', issueExtLink='null', onlineDate='null', pubDate='1787155200000', pubDateStr='2026-08-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1789047150370, creator='13701087609', updateTime=1789117776362, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1305217812939698326, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921585991836085, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1305217812939698327, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921585991836085, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1, endPage=9, ext={EN=ArticleExt(id=1304921609068892609, articleId=1304921608804651456, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Enhancing corona resistance performance of polyimide film via catalyst induced molecular chain ordered alignment, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

Polyimide (PI) film has become a key material for turn-to-turn insulation in electric drive motors due to its excellent high-temperature stability, superior mechanical properties, and outstanding electrical insulation performance. In this paper, the aggregation structure of PI were regulated by change the types of catalysts during the chemical imidization process. The effects of different catalysts on the aggregation structure of PI were discussed, and the effects of catalyst types on electro-thermal-mechanical properties and corona resistance of PI were studied systematically. The results show that the aromatic catalyst isoquinoline can promote the orderly arrangement of molecular chains through π-π interactions, and significantly enhancing the dielectric and corona resistance properties of PI. The PI film prepared using isoquinoline catalyst exhibits excellent dielectric performances. At a frequency of 1 kHz, its dielectric constant can reach 3.47, while the dielectric loss factor reduces to 0.001 1, and the electric strength at room-temperature reaches 561.39 kV/mm. Furthermore, its corona resistance performance is greatly improved. Under 20 kHz, the corona resistance lifetime reaches 5.8 min, which is 1.68 times that of the thermally imidized film.

, authors=Changhai Zhang, Le Lu, Tiandong Zhang, Yongquan Zhang, Yue Zhang, Jiaqi Zhang*, Qingguo Chi, authorsList=Changhai Zhang, Le Lu, Tiandong Zhang, Yongquan Zhang, Yue Zhang, Jiaqi Zhang, Qingguo Chi, authorCompany=null, correspAuthors=Jiaqi Zhang, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1304921610796945881, articleId=1304921608804651456, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=通过催化剂诱导分子链有序排列实现聚酰亚胺薄膜耐电晕性能提升, columnId=1190369066813591720, journalTitle=绝缘材料, columnName=材料研究, runingTitle=null, highlight=null, articleAbstract=

聚酰亚胺(PI)薄膜凭借其优异的高温稳定性、良好的力学性能及绝缘性能,已成为当前驱动电机匝间绝缘的关键材料。本文通过改变化学亚胺化过程中的催化剂种类来调控PI的聚集态结构,探讨不同催化剂对PI聚集态结构的影响,并系统研究催化剂种类对PI电-热-力学性能及耐电晕性能的影响规律及机制。结果表明:芳香族催化剂异喹啉可通过π-π相互作用促进分子链有序排列,对PI的介电性能及耐电晕性能提升效果显著,采用异喹啉催化剂制备的PI薄膜具有优异的介电性能,在1 kHz频率下,介电常数可达到3.47,同时介质损耗因数降低至0.001 1,室温电气强度高达561.39 kV/mm。此外,其耐电晕性能得到大幅改善,在20 kHz测试条件下,耐电晕寿命达到了5.80 min,为热亚胺化薄膜的1.68倍。

, authors=张昌海, 鲁乐, 张天栋, 张永泉, 张月, 张佳琦*, 迟庆国, authorsList=张昌海, 鲁乐, 张天栋, 张永泉, 张月, 张佳琦, 迟庆国, authorCompany=null, correspAuthors=张佳琦, authorNote=

张昌海(1987-),男(汉族),山东菏泽人,教授,博士,主要从事先进电工绝缘材料与绝缘技术的研究

, correspAuthorsNote=
张佳琦(1999-),女(汉族),黑龙江佳木斯人,博士生,主要从事高温储能介质薄膜结构与性能的研究。
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张昌海(1987-),男(汉族),山东菏泽人,教授,博士,主要从事先进电工绝缘材料与绝缘技术的研究

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张昌海(1987-),男(汉族),山东菏泽人,教授,博士,主要从事先进电工绝缘材料与绝缘技术的研究

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remark=哈尔滨理工大学 电气与电子工程学院,黑龙江 哈尔滨 150080)])], figs=[ArticleFig(id=1304922208950834015, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921608804651456, language=EN, label=Fig.1, caption=Synthesis of PAA solution and preparation process of PI film, figureFileSmall=/Kr6EgXRT5E2FCGgwhZggA==, figureFileBig=BJQj2hxXo8tI2H+NHn2jIQ==, tableContent=null), ArticleFig(id=1304922209022137184, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921608804651456, language=CN, label=图1, caption=PAA溶液的合成以及PI薄膜的制备流程, figureFileSmall=/Kr6EgXRT5E2FCGgwhZggA==, figureFileBig=BJQj2hxXo8tI2H+NHn2jIQ==, tableContent=null), ArticleFig(id=1304922209168937825, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921608804651456, language=EN, label=Fig.2, caption=Structural formulas of four catalysts, figureFileSmall=gQAzdAqH/ZykCClNaE9gxA==, figureFileBig=oTBbbriinGuY7RUuIfHzvA==, tableContent=null), ArticleFig(id=1304922209236046690, 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journalId=1149653034449285133, articleId=1304921608804651456, language=CN, label=图10, caption=热亚胺化和化学亚胺化PI薄膜的耐电晕寿命, figureFileSmall=rUkqF8ucLCPbDnY3lPGTqw==, figureFileBig=JJffxn7tFIBOd6yeqGwCwQ==, tableContent=null), ArticleFig(id=1304922210569835380, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921608804651456, language=EN, label=Table 1, caption=

Pre-imidization degree of four chemically imidized PAA-PI films

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称PAA-PI-IQLPAA-PI-PyPAA-PI-TMGPAA-PI-TEA
ID/%62.352.541.437.8
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4种化学亚胺化PAA-PI薄膜的预亚胺化程度

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样品名称PAA-PI-IQLPAA-PI-PyPAA-PI-TMGPAA-PI-TEA
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Degree of order of four chemically imidized PI films

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样品名称PI-IQLPI-PyPI-TMGPI-TEA
有序度2.682.361.321.54
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4种化学亚胺化PI薄膜的有序度

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样品名称PI-IQLPI-PyPI-TMGPI-TEA
有序度2.682.361.321.54
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Average molecular chain spacing of thermally imidized and chemically imidized PI films

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样品名称PI-IQLPI-PyPI-TMGPI-TEAPI-0
平均分子链间距/nm0.4130.4290.4790.4640.450
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热亚胺化和化学亚胺化PI薄膜的平均分子链间距

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样品名称PI-IQLPI-PyPI-TMGPI-TEAPI-0
平均分子链间距/nm0.4130.4290.4790.4640.450
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Thermal performance data of thermally imidized and chemically imidized PI films

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样品名称Td5%/℃残碳率(800℃)/%
PI-0552.0255.56
PI-IQL587.5057.07
PI-Py572.3956.24
PI-TMG548.3455.48
PI-TEA542.3254.78
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热亚胺化和化学亚胺化PI薄膜的热性能数据

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通过催化剂诱导分子链有序排列实现聚酰亚胺薄膜耐电晕性能提升
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张昌海 , 鲁乐 , 张天栋 , 张永泉 , 张月 , 张佳琦 * , 迟庆国
绝缘材料 | 材料研究 2026,59(8): 1-9
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绝缘材料 |材料研究 2026 , 59 (8) : 1 -9
通过催化剂诱导分子链有序排列实现聚酰亚胺薄膜耐电晕性能提升
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张昌海, 鲁乐, 张天栋, 张永泉, 张月, 张佳琦*, 迟庆国
作者信息
  • 哈尔滨理工大学 电气与电子工程学院,黑龙江 哈尔滨 150080
通讯作者:
张佳琦(1999-),女(汉族),黑龙江佳木斯人,博士生,主要从事高温储能介质薄膜结构与性能的研究。
作者简介:

张昌海(1987-),男(汉族),山东菏泽人,教授,博士,主要从事先进电工绝缘材料与绝缘技术的研究

Enhancing corona resistance performance of polyimide film via catalyst induced molecular chain ordered alignment
Changhai Zhang, Le Lu, Tiandong Zhang, Yongquan Zhang, Yue Zhang, Jiaqi Zhang*, Qingguo Chi
Affiliations
  • School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150080, China
出版时间: 2026-08-20 doi: 10.16790/j.cnki.1009-9239.im.2026.08.001
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聚酰亚胺(PI)薄膜凭借其优异的高温稳定性、良好的力学性能及绝缘性能,已成为当前驱动电机匝间绝缘的关键材料。本文通过改变化学亚胺化过程中的催化剂种类来调控PI的聚集态结构,探讨不同催化剂对PI聚集态结构的影响,并系统研究催化剂种类对PI电-热-力学性能及耐电晕性能的影响规律及机制。结果表明:芳香族催化剂异喹啉可通过π-π相互作用促进分子链有序排列,对PI的介电性能及耐电晕性能提升效果显著,采用异喹啉催化剂制备的PI薄膜具有优异的介电性能,在1 kHz频率下,介电常数可达到3.47,同时介质损耗因数降低至0.001 1,室温电气强度高达561.39 kV/mm。此外,其耐电晕性能得到大幅改善,在20 kHz测试条件下,耐电晕寿命达到了5.80 min,为热亚胺化薄膜的1.68倍。

聚酰亚胺薄膜  /  催化剂  /  分子链有序度  /  耐电晕性能

Polyimide (PI) film has become a key material for turn-to-turn insulation in electric drive motors due to its excellent high-temperature stability, superior mechanical properties, and outstanding electrical insulation performance. In this paper, the aggregation structure of PI were regulated by change the types of catalysts during the chemical imidization process. The effects of different catalysts on the aggregation structure of PI were discussed, and the effects of catalyst types on electro-thermal-mechanical properties and corona resistance of PI were studied systematically. The results show that the aromatic catalyst isoquinoline can promote the orderly arrangement of molecular chains through π-π interactions, and significantly enhancing the dielectric and corona resistance properties of PI. The PI film prepared using isoquinoline catalyst exhibits excellent dielectric performances. At a frequency of 1 kHz, its dielectric constant can reach 3.47, while the dielectric loss factor reduces to 0.001 1, and the electric strength at room-temperature reaches 561.39 kV/mm. Furthermore, its corona resistance performance is greatly improved. Under 20 kHz, the corona resistance lifetime reaches 5.8 min, which is 1.68 times that of the thermally imidized film.

polyimide film  /  catalyst  /  molecular chain ordering  /  corona resistance performance
张昌海, 鲁乐, 张天栋, 张永泉, 张月, 张佳琦, 迟庆国. 通过催化剂诱导分子链有序排列实现聚酰亚胺薄膜耐电晕性能提升. 绝缘材料, 2026 , 59 (8) : 1 -9 . DOI: 10.16790/j.cnki.1009-9239.im.2026.08.001
Changhai Zhang, Le Lu, Tiandong Zhang, Yongquan Zhang, Yue Zhang, Jiaqi Zhang, Qingguo Chi. Enhancing corona resistance performance of polyimide film via catalyst induced molecular chain ordered alignment[J]. Insulating Materials, 2026 , 59 (8) : 1 -9 . DOI: 10.16790/j.cnki.1009-9239.im.2026.08.001
在全球能源绿色转型的大背景下,新能源汽车用驱动电机正朝着高功率密度、高频、高电压方向快速发展[1-5],这对匝间绝缘的介电性能、耐电晕性能及绝缘可靠性提出了更高的要求[6-8]。聚酰亚胺(PI)是指分子结构主链中含有酰亚胺环(-CO-NH-CO-)的高分子聚合物,凭借其优异的高温稳定性、良好的力学性能及绝缘性能,已成为当前驱动电机匝间绝缘的关键材料[9-12]。然而在高电场强度、高频脉冲及高温等极端工况作用下,传统PI薄膜极易发生局部放电,进而导致电晕击穿甚至引发绝缘失效[13-16]。因此,开发具有高耐电晕寿命和可靠性的PI薄膜,对于驱动电机的安全稳定运行至关重要。
当前,聚酰亚胺合成普遍采用“两步法”,即由二胺与二酐在非质子溶剂中聚合得到聚酰胺酸前驱体(PAA),再经过酰亚胺化反应将PPA转化为聚酰亚胺。传统的亚胺化工艺主要为热亚胺化法,是通过高温促进脱水环化反应,获得高性能的聚酰亚胺薄膜。然而,在高温处理过程中,亚胺化反应通常伴随溶剂蒸发、水分脱除以及聚合物链取向等过程[17-18],因此难以精准地调控PAA向PI转化时分子链的排列方式以及有序程度。化学亚胺化法在温和条件下借助催化剂和脱水剂实现环化。在工艺上,可以通过调整化学亚胺化试剂的种类、比例以及亚胺化时间实现对分子链聚集态结构更灵活的调控,得到更致密、性能更稳定的薄膜结构,为进一步提升其介电性能及绝缘性能提供了一种可行途径。
翟燕等[19]、王昕熠等[20]先通过化学亚胺化法对PAA溶液进行不同程度的预亚胺化,再进行热亚胺化,最终得到了聚集态结构有序程度不同的PI薄膜,研究发现随着PAA溶液预亚胺化程度的提高,PI薄膜聚集态结构的有序性也随之提高,力学性能也得到提升。冯婷婷等[21]通过控制化学亚胺化过程中的催化剂添加量来改变亚胺化反应的速率,研究发现相同时间内聚合物中的亚胺环数量越多,PI薄膜的聚集态结构有序性越高。Hao F Y等[22]通过化学亚胺化法制备了一系列不同亚胺化程度的PI薄膜,研究发现一定程度的化学亚胺化可以促进薄膜内部分子链的面内取向,提高薄膜的机械强度,降低热膨胀系数(CTE)和介电常数。Wang Z H等[23]系统研究比较了化学亚胺化法与热亚胺化法对PI薄膜性能和聚集态结构的影响,研究发现,与热亚胺化法相比,化学亚胺化法制备的PI薄膜分子链具有更高的面内取向度和更紧密堆积,有助于制备性能更加稳定的PI薄膜。
但是,当前关于催化剂种类对PI薄膜介电性能和耐电晕性能影响的研究存在较大空白。因此,本研究以均苯四甲酸酐(PMDA)和4,4′-二氨基二苯醚(ODA)为单体,乙酸酐为脱水剂,系统探究不同亚胺化方式及催化剂种类对PI薄膜介电性能及耐电晕寿命的影响规律。揭示亚胺化方式、催化剂种类与薄膜聚集态结构及性能间的构效关系,本研究为开发面向高可靠性应用的高性能聚酰亚胺材料提供了理论和实践基础。
4,4′-二氨基二苯醚(ODA,纯度为98%)、均苯四甲酸二酐(PMDA,纯度为99%),均购自阿拉丁试剂(上海)有限公司;乙酸酐(纯度≥99%)、异喹啉(IQ,纯度为97%)、三乙胺(TEA,纯度为99%)、吡啶(Py,纯度为99%)、四甲基胍(TMG,纯度为98%)、N,N-二甲基乙酰胺(DMAC,纯度≥99.8%),均购自上海麦克林生化科技有限公司。
PAA溶液的合成以及PI薄膜的制备流程如图1所示,按照PAA固含量为15%,PMDA与ODA的摩尔比为1∶1.02称取药品,将ODA加入DMAC中持续搅拌至ODA完全溶解,然后分3次加入PMDA,在真空搅拌箱内搅拌6 h得到透明澄清的PAA溶液。
预亚胺化PAA-PI薄膜的制备。向PAA溶液中加入催化剂(异喹啉、吡啶、四甲基胍、三乙胺,4种催化剂的结构式如图2所示)与脱水剂(乙酸酐)的混合溶液,为了尽量减少反应后的试剂残留,并且保证溶液不发生凝胶现象,选择脱水剂与催化剂摩尔比为1∶1,催化剂与溶液中二胺的摩尔比为0.8∶1,将混合溶液在真空搅拌箱中搅拌6 h,然后停止搅拌,使溶液在真空环境中静置消泡,得到4组含不同催化剂的PAA-PI溶液。使用自动涂膜器将PAA-PI溶液均匀涂覆在玻璃板上,将其在50℃烘箱中干燥48 h,得到预亚胺化薄膜。根据使用的催化剂名称将各样品分别命名为PAA-PI-IQL、PAA-PI-Py、PAA-PI-TMG、PAA-PI-TEA。
化学亚胺化薄膜的制备。使用自动涂膜器将PAA-PI溶液均匀涂覆在玻璃板上,将其置于鼓风烘箱中进行梯度升温烘干,梯度升温程序为100℃/2 h+150℃/1 h+200℃/1 h+250℃/1 h+300℃/2 h+350℃/2 h,烘干完成后得到4组化学亚胺化薄膜,分别命名为PI-IQL、PI-Py、PI-TMG、PI-TEA。
将PAA溶液放在真空环境中静置直至气泡消失,使用自动涂膜器将PAA溶液均匀涂覆在玻璃板上,将其置于鼓风烘箱中进行梯度升温烘干,梯度升温程序为100℃/2 h+150℃/1 h+200℃/1 h+250℃/1 h+300℃/2 h+350℃/2 h,烘干完成后得到热亚胺化薄膜,命名为PI-0。
采用德国Bruker公司生产的EQUINOX 55型傅里叶变换红外(FT-IR)光谱仪表征薄膜的特征基团,测试波数为400~4 000 cm-1。亚胺化程度(ID)计算公式如式(1)所示[19]
ID(%)=(S1375/S1516)T(S1375/S1516)T=350×100%
式(1)中:Sν为波数为ν处对应的吸收峰面积,将波数为1 375 cm-1处的C-N键吸收峰作为计算时的亚胺特征峰,将波数为1 516 cm-1处的苯环吸收峰作为内标峰;(S1375/S1516)T为温度T下C-N键吸收峰与苯环吸收峰面积的比值;(S1375/S1516)T=350为完全亚胺化时的吸收峰面积比值,默认经过350℃热亚胺化的PI薄膜亚胺化程度为100%。
使用荷兰PANARKO公司生产的Empyrean型锐影X射线衍射仪(XRD)对薄膜聚集态结构进行分析,测试电压为40 kV,测试电流为40 mA,辐射源为Cu Kα,波长λ=1.541 8 Å,2θ为10°~90°。有序度(X)计算公式如式(2)所示[20]
X(%)=U0I0×IsUs×100%
式(2)中:U0I0表示参考样品的背景和衍射峰积分强度,选择热亚胺化薄膜作为参考样品并将其有序度归一化为1;UsIs表示测试样品的背景和衍射峰积分强度。
计算平均分子链间距所用的布拉格方程如式(3)所示。
nλ=2dsinθ
式(3)中:n为衍射级次,通常取n=1;λ为入射X射线的波长,辐射源为Cu Kα时,λ=1.541 8 Å;d为晶面间距;θ为X射线入射角与晶面法线之间的夹角。
使用日本日立公司生产的SU8020型扫描电子显微镜(SEM)对薄膜的断面形态进行表征。为确保薄膜的断面平整,能够清晰地观察到薄膜断面的缺陷、孔隙分布情况,采用液氮脆断的处理方法,将薄膜放置在液氮中浸泡一段时间使薄膜更易断裂,将处理后的薄膜粘贴在有导电胶的方台上。为了增强薄膜样品的导电性,对薄膜的断面进行真空镀金(Au)处理。
使用德国耐驰公司生产的STA449型同步热分析仪(TG)测试薄膜的热性能,在氮气氛围下以20℃/min的升温速率进行测试。采用德国Novocontrol公司生产的Alpha-A型宽频介电谱分析仪对薄膜进行介电常数和介质损耗因数测试,测试前需在真空下镀金属铝电极,铝电极直径为9 mm,测试频率为100~106 Hz。耐电晕寿命测试采用桂林合程电子科技有限公司生产的HCGF3-5型高频脉冲测试电源,依据GB/T 22566—2017和JB/T 12421—2015相关要求,在室温、电压为2 kV、频率为15 kHz、上升沿为100 ns、电极直径为5 mm、薄膜测试厚度为25 μm的条件下进行测试。测试前保持薄膜表面干净整洁,并将薄膜放入烘箱中在80℃温度下干燥24 h以除去水分,每种样品测试5次,取其平均值并计算标准差。采用PolyK Technologies公司的介电铁电综合测试系统,对复合薄膜的电气强度进行测试,升压速率为200 V/s,测试前保持薄膜表面干净整洁,并将薄膜放入烘箱中在80℃温度下干燥24 h以除去水分,为增强测试的稳定性和可靠性,测试环境为硅油环境。在常温和150℃环境下进行测试,每组样品至少选取10个有效数据,然后采用双参数威布尔(Weibull)分布模型进行数据拟合,Weibull分布用于电气强度计算的拟合公式如式(4)所示。
P(Eb)=1-exp-Ebαβ
式(4)中:P为电气强度小于某一值时的累计概率;Eb为电气强度,单位为kV/mm;α为尺度参数,是P达到63.2%时的电气强度,单位为kV/mm;β为形状参数,反映电气强度数值的离散程度。
采用美特斯工业系统有限公司生产的SANS型电子式万能试验机测试薄膜的力学性能,选用哑铃状试样进行拉伸强度以及断裂伸长率测试。拉伸速率为50 mm/min。选取表面光滑完整无缺陷的样品,每种样品重复测试5次,为确保数据准确性,选取薄膜的断裂位置在中间的试样数据,对测试数据取平均值作为力学性能测试结果。
为了探究亚胺化方式及催化剂对PI微观结构的影响,采用FTIR和XRD对热亚胺化PI薄膜及4种化学亚胺化PI薄膜的微观结构进行表征。图3为热亚胺化PI薄膜和4种化学亚胺化PI薄膜的红外吸收图谱。
图3可以看出,热亚胺化PI薄膜和化学亚胺化PI薄膜均在波数为1 775、1 726、1 375、726 cm-1处出现强吸收峰,分别对应酰亚胺环中C=O的非对称伸缩振动峰和对称伸缩振动峰,C-N键的伸缩振动峰及酰亚胺环的弯曲振动峰。同时,热亚胺化和化学亚胺化PI薄膜并未在波数为1 632 cm-1和1 556 cm-1处出现聚酰胺酸的吸收峰,且未在波数为1 800 cm-1处观察到异酰亚胺的吸收峰,表明两种亚胺化方法得到的PI薄膜都实现了完全的亚胺化反应,并且没有出现明显的异构化副反应。
为了探究不同催化剂类型对PAA溶液亚胺化程度的影响,使用式(1)对不同催化剂制备的PAA-PI薄膜进行预亚胺化程度计算,结果如表1所示。从表1可以看出,4种PAA-PI薄膜均实现了一定程度的亚胺化,其中异喹啉作为催化剂时,PAA-PI-IQL薄膜的预亚胺化程度最高,说明在相同条件下,该催化剂能有效促进亚胺化的进行,并且生成更多的刚性亚胺环,也有助于后续分子链的有序性排列[24]
热亚胺化PI薄膜和4种化学亚胺化PI薄膜的XRD图谱如图4所示。从图4可以看出,在2θ为10°~30°的范围内,5种薄膜的衍射峰均呈现典型的无定形结构的弥散峰,均为非晶态结构。
但值得注意的是,化学亚胺化PI薄膜的衍射峰强度均高于热亚胺化PI薄膜,这是因为PAA中含有大量的柔性链段,化学亚胺化过程中,PAA在脱水剂和催化剂的共同作用下脱水成环,形成刚性酰亚胺环结构,使得PAA分子链段刚性增强,刚性的酰亚胺环结构会诱导分子链进行规整排列,并且在后续热处理过程中继续保持取向,使得分子链有序度较高[25-26]。其中,异喹啉催化的PI薄膜表现出最强的衍射峰强度和最大的峰位偏移量,这是因为异喹啉为芳杂环碱催化剂,刚性芳香环骨架不仅赋予了其适中的碱性和较强的亲核性,能够有效促进亚胺化反应,而且不会产生显著的空间位阻效应,有利于分子链段运动。此外,芳香环之间的π-π堆积相互作用增强了分子链间作用力,从而增大了分子堆积密度。相比之下,三乙胺和四甲基胍催化的PI薄膜虽然衍射峰强度也有所增强,但峰位向低角度方向偏移。这是由于这两种脂肪族催化剂分子结构的空间位阻较大,在催化过程中阻碍了分子链的紧密排列[27]。进一步对XRD图谱进行定量分析,根据式(2)和式(3)计算PI薄膜的有序度和平均分子链间距,结果分别如表2表3所示。
表2表3可以看出,PI-IQL薄膜表现出最高的有序度和最小的平均分子链间距。这一结果表明,异喹啉作为催化剂能够促进分子链在亚胺化过程中形成更为规整的堆积结构,使得分子链间更为紧密。
为了更直观地表征薄膜的微观结构和形貌,对热亚胺化PI薄膜以及4种化学亚胺化PI薄膜的断面进行扫描电子显微镜(SEM)测试,结果如图5所示。从图5可以看出,5种PI薄膜的断面整体较为平整、厚度均匀,未观察到明显的相分离现象和孔隙等结构缺陷,表明所制备的PI薄膜均具备较好的成膜性和结构完整性。其中,PI-IQL薄膜的断面形貌最为光滑致密,进一步佐证了异喹啉可促进聚酰亚胺聚集态结构的致密堆积与分子链有序排列。
为探究不同亚胺化方式及催化剂种类对PI薄膜热稳定性的影响,对热亚胺化PI薄膜及4种化学亚胺化PI薄膜进行热重测试,结果如图6所示。从图6可以看出,5种PI薄膜在450℃以下质量没有明显变化,说明在这个温度范围内,5种PI薄膜都具有较好的热稳定性,并且都实现了完全的亚胺化。但当温度升高到550℃左右时,5种PI薄膜质量开始下降,表明聚合物的分子链开始断裂,分解成小分子逸出,在温度升高到700℃之后,失重速率明显减缓,曲线趋于平坦,表明聚合物的主要分解过程已经结束。
进一步对热亚胺化PI薄膜和4种化学亚胺化PI薄膜的热失重温度和残碳率进行统计,结果如表4所示。从表4可以看出,PI-IQL薄膜的5%分解温度(Td5%)达到了587.50℃,最终残碳率为57.07%,具有较好的热稳定性,这是因为异喹啉催化的聚酰亚胺(PI-IQL)薄膜具有更规整的分子链堆积和更强的分子间相互作用,在高温环境下,分子链段发生热震荡和热分解所需克服的能量势垒提高。相比之下,脂肪族催化剂(如三乙胺和四甲基胍)虽然也能催化亚胺化反应,但其较大的空间位阻限制了分子链的紧密堆积,导致薄膜的热稳定性相对较低。因此,异喹啉催化的PI薄膜表现出更高的热分解温度和残碳率,在高温应用中更具优势。
为了分析不同亚胺化方式及催化剂种类对PI薄膜介电性能的影响,对热亚胺化PI薄膜及4种化学亚胺化PI薄膜的介电常数和介质损耗因数进行测试,结果如图7所示。
相较于热亚胺化(PI-0)薄膜,使用催化剂处理过的化学亚胺化PI薄膜具有更高的介电常数。但值得注意的是,使用异喹啉作为催化剂时,聚合物的分子链排列更加规整紧凑,分子链间距较小,分子链间作用力更强,抑制了偶极子的运动能力,有利于降低偶极弛豫损耗,因此PI-IQL薄膜具有相对低的介电常数和介质损耗因数,在1 kHz下,介电常数为3.47,介质损耗因数为0.001 1。
进一步,采用双参数威布尔分布函数对热亚胺化PI薄膜及4种化学亚胺化PI薄膜的电气强度(Eb)测试结果进行分析,结果如图8所示。
图8可以看出,化学亚胺化的4种PI薄膜电气强度均高于热亚胺化的PI薄膜,其中异喹啉催化的PI-IQL薄膜具有最高的电气强度,在室温下Eb可达到561.39 kV/mm,较PI-0薄膜提升了26%,在150℃下Eb可达到458.42 kV/mm,较PI-0薄膜提升了25%。这是因为PI-IQL薄膜的分子链排列更加规整、堆积更为紧密,分子链段运动受到限制,减小了分子链间的自由体积,限制了载流子在电场作用下的迁移,减少电子在电场下的平均自由程,使得电子积累足够能量引发碰撞电离的难度增加[28],进而增强PI薄膜的绝缘性能。
对热亚胺化PI薄膜和4种化学亚胺化PI薄膜的力学性能进行测试,结果如图9所示。
图9可以看出,异喹啉催化的PI-IQL薄膜具有较优的力学性能,断裂伸长率和拉伸强度分别为14.32%和129 MPa,这是由于致密的结构和紧密的分子链排列有利于增强分子链间的作用力,减少薄膜内部缺陷,使其具有良好的力学性能。相比之下,四甲基胍(TMG)催化的PI-TMG薄膜力学性能显著降低,断裂伸长率仅为5.81%,拉伸强度为104.68 MPa,这是因为四甲基胍具有较强的碱性,在催化过程中可能会导致局部分子链段断裂[29],不利于高分子量聚合物的形成,因此PI-TMG薄膜力学性能显著降低。
对热亚胺化PI薄膜及4种化学亚胺化PI薄膜进行耐电晕性能测试,结果如图10所示。从图10可以看出,热亚胺化PI-0薄膜的耐电晕寿命为3.46 min,而经化学亚胺化的PI薄膜表现出更优异的耐电晕性能。其中,以异喹啉为催化剂制备的PI-IQL薄膜耐电晕寿命达到了5.80 min,为热亚胺化PI薄膜的1.68倍。
已知研究结果表明,电晕放电会通过多个方面影响PI薄膜的性能。首先,经过电场加速的电子会与气体分子发生碰撞电离,产生具有高动能的活性粒子直接轰击聚酰亚胺表面,使聚酰亚胺的分子链发生断裂;其次电晕放电的过程中还伴随着大量热能的释放,产生局部高温,会加速材料热老化[30]。化学亚胺化PI薄膜的分子链段紧密堆积,排列有序,孔隙率较低,其致密的结构抵御高能粒子冲击的能力更强。尤其是以异喹啉为催化剂制备的PI-IQL薄膜,其优异的耐热性、介电性能及力学性能协同作用,不仅可以有效抑制高电场下的能量积聚,同时可以减缓热老化进程,从而使其耐电晕寿命得到显著提升。
本文设计制备了4种不同催化剂(异喹啉、吡啶、三乙胺和四甲基胍)催化的聚酰亚胺(PI)薄膜,系统研究了催化剂种类对PI薄膜微观结构与绝缘性能、介电性能和耐电晕性能的调控机制,并与传统热亚胺化工艺制备的PI薄膜进行了对比分析。主要研究结论如下:
(1)FTIR图谱表明各催化体系得到的PI薄膜均呈现完全的亚胺化,且未出现异构化或副反应。XRD结果显示,相比于热亚胺化方式,化学亚胺化可以有效促进PI分子链的有序排列和致密堆积。
(2)芳香族催化剂异喹啉具有良好的诱导效应,可以通过π-π相互作用增强分子链间作用力,提高链段规整性,显著改善PI薄膜的介电性能。PI-IQL薄膜在1  kHz频率下,介电常数可达到3.47,介质损耗因数低至0.001 1。且其具有较高的电气强度,在室温下电气强度高达561.39 kV/mm,较热亚胺化PI薄膜提升了26%;150 ℃下电气强度仍可达到458.42 kV/mm。
(3)PI-IQL薄膜的力学、耐热和耐电晕性能得到提升,在力学性能方面,断裂伸长率和拉伸强度分别达到14.32%和129 MPa,在耐热性能方面,5%分解温度达到587.5℃,高于热亚胺化PI薄膜的552.02℃。在20 kHz测试条件下,耐电晕寿命达到5.80 min,较热亚胺化PI薄膜提升了68%。
综上所述,在化学亚胺化过程中,芳香族催化剂异喹啉对PI分子链的结构诱导作用显著,有助于构建高规整度、高致密性的聚酰亚胺分子链排列结构,提升薄膜的介电性能和耐电晕性能。本研究为开发面向高可靠性应用的高性能聚酰亚胺材料提供了理论和实践基础。

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19
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30
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2026年第59卷第8期
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doi: 10.16790/j.cnki.1009-9239.im.2026.08.001
  • 接收时间:2025-07-16
  • 首发时间:2026-09-10
  • 出版时间:2026-08-20
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  • 收稿日期:2025-07-16
  • 修回日期:2025-08-28
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    哈尔滨理工大学 电气与电子工程学院,黑龙江 哈尔滨 150080

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张佳琦(1999-),女(汉族),黑龙江佳木斯人,博士生,主要从事高温储能介质薄膜结构与性能的研究。
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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