Article(id=1304921813402800919, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921686403474081, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.06.001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1760803200000, receivedDateStr=2025-10-19, revisedDate=1764950400000, revisedDateStr=2025-12-06, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047204590, onlineDateStr=2026-09-10, pubDate=1781884800000, pubDateStr=2026-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047204590, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047204590, creator=13701087609, updateTime=1789047204590, updator=13701087609, issue=Issue{id=1304921686403474081, tenantId=1146029695717560320, journalId=1149653034449285133, year='2026', volume='59', issue='6', pageStart='1', pageEnd='188', issueExtLink='null', onlineDate='null', pubDate='1781884800000', pubDateStr='2026-06-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1789047174311, creator='13701087609', updateTime=1789118019323, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1305218831971021057, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921686403474081, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1305218831971021058, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921686403474081, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1, endPage=9, ext={EN=ArticleExt(id=1304921813562184472, articleId=1304921813402800919, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Molecular structural design and research progress of low-dielectric, low-loss polyimide film materials, columnId=null, journalTitle=Insulating Materials, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Polyimide (PI), as a type of special polymer materials with excellent comprehensive properties, is widely used in various fields such as electronics and electrical engineering, electrical insulation, and aerospace. However, with the rapid advancement of 5G/6G high-frequency communication technologies, higher requirements have been put forward on the dielectric properties of dielectric layer materials in electronic devices. PI faces significant challenges, including its inherently high dielectric constant (Dk) and dielectric loss (Df), as well as relatively high-water absorption, which restrict its further development in related applications. In this paper, the intrinsic action mechanism of Dk and Df of polymers under electric field was introduced at first, and then the main research progress of low-Dk and low-Df polyimide films in recent years, as well as the modification strategies of polymer molecular structure and dielectric properties were reviewed respectively. Finally, the research direction of low-Dk and low-Df polyimide films was summarized and prospected.

, authors=Yonghao LIU1, Chenggang ZHANG2, Lan JIANG1, Peng XIAO1, 2, *, authorsList=Yonghao LIU, Chenggang ZHANG, Lan JIANG, Peng XIAO, authorCompany=null, correspAuthors=Peng XIAO, 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=1304921815919383345, articleId=1304921813402800919, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=低介电低损耗聚酰亚胺薄膜材料的分子结构设计及研究进展, columnId=null, journalTitle=绝缘材料, columnName=, runingTitle=null, highlight=null, articleAbstract=

聚酰亚胺(PI)作为一类具有优异综合性能的特种高分子材料,被广泛应用于电子电气、电工绝缘和航天航空等诸多领域。然而随着5G/6G高频通信技术的快速发展,对电子器件介电层材料的介电性能提出了更高要求,PI面临固有介电常数(Dk)和介电损耗(Df)过高、吸水率较大等难题,限制了其在相关领域的发展。本文首先介绍了聚合物在电场下DkDf的内在作用机制,然后分别综述了近些年关于低Dk和低Df聚酰亚胺薄膜的主要研究进展,以及聚合物分子结构与介电性能的改性策略,最后对低Dk和低Df聚酰亚胺薄膜的研究方向进行了总结和展望。

, authors=刘永浩1, 张铖钢2, 蒋岚1, 肖鹏1, 2, *, authorsList=刘永浩, 张铖钢, 蒋岚, 肖鹏, authorCompany=null, correspAuthors=肖鹏, authorNote=

刘永浩(2003-),男(汉族),安徽亳州人,硕士生,主要从事聚酰亚胺分子设计与合成

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肖鹏(1994-),男(汉族),江西赣州人,副教授,博士,主要从事高性能聚酰亚胺材料的研究。
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Comparison on properties of PI, LCP, PTFE, PPS, and PPE

, figureFileSmall=null, figureFileBig=null, tableContent=
性能PILCPPTFEPPSPPE
Dk/(10 GHz)3.52.9~3.12.23.42.7
Df/(10 GHz)0.020.002~0.0050.0020.003 80.001
吸水率/%1~30.20.010.020.01
长期服役温度/℃-200~350-50~240-200~200<200<120
热膨胀系数/(×10-6 K-1)5~40171162552
热分解温度/℃>500400~500400530350
抗拉强度/MPa150~400100~20025~406780
断裂伸长率/%20~805~10250~4008.030
成本较低很高
加工难度较低高(工艺难)高(粘附性低)
可设计性单一单一单一一般
), ArticleFig(id=1304921893052633594, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921813402800919, language=CN, label=表1, caption=

PI、LCP、PTFE、PPS和PPE 性能比较

, figureFileSmall=null, figureFileBig=null, tableContent=
性能PILCPPTFEPPSPPE
Dk/(10 GHz)3.52.9~3.12.23.42.7
Df/(10 GHz)0.020.002~0.0050.0020.003 80.001
吸水率/%1~30.20.010.020.01
长期服役温度/℃-200~350-50~240-200~200<200<120
热膨胀系数/(×10-6 K-1)5~40171162552
热分解温度/℃>500400~500400530350
抗拉强度/MPa150~400100~20025~406780
断裂伸长率/%20~805~10250~4008.030
成本较低很高
加工难度较低高(工艺难)高(粘附性低)
可设计性单一单一单一一般
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低介电低损耗聚酰亚胺薄膜材料的分子结构设计及研究进展
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刘永浩 1 , 张铖钢 2 , 蒋岚 1 , 肖鹏 1, 2, *
绝缘材料 | 2026,59(6): 1-9
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绝缘材料 | 2026 , 59 (6) : 1 -9
低介电低损耗聚酰亚胺薄膜材料的分子结构设计及研究进展
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刘永浩1, 张铖钢2, 蒋岚1, 肖鹏1, 2, *
作者信息
  • 1宁波工程学院 微纳材料与器件创新研究院,浙江 宁波 315211
  • 2同济大学 化学科学与工程学院,上海 200092
通讯作者:
肖鹏(1994-),男(汉族),江西赣州人,副教授,博士,主要从事高性能聚酰亚胺材料的研究。
作者简介:

刘永浩(2003-),男(汉族),安徽亳州人,硕士生,主要从事聚酰亚胺分子设计与合成

Molecular structural design and research progress of low-dielectric, low-loss polyimide film materials
Yonghao LIU1, Chenggang ZHANG2, Lan JIANG1, Peng XIAO1, 2, *
Affiliations
  • 1Institute of Micro/Nano Materials and Devices, Ningbo University of Technology, Ningbo 315211, China
  • 2School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China
出版时间: 2026-06-20 doi: 10.16790/j.cnki.1009-9239.im.2026.06.001
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聚酰亚胺(PI)作为一类具有优异综合性能的特种高分子材料,被广泛应用于电子电气、电工绝缘和航天航空等诸多领域。然而随着5G/6G高频通信技术的快速发展,对电子器件介电层材料的介电性能提出了更高要求,PI面临固有介电常数(Dk)和介电损耗(Df)过高、吸水率较大等难题,限制了其在相关领域的发展。本文首先介绍了聚合物在电场下DkDf的内在作用机制,然后分别综述了近些年关于低Dk和低Df聚酰亚胺薄膜的主要研究进展,以及聚合物分子结构与介电性能的改性策略,最后对低Dk和低Df聚酰亚胺薄膜的研究方向进行了总结和展望。

聚酰亚胺薄膜  /  介电常数  /  介电损耗  /  结构改性

Polyimide (PI), as a type of special polymer materials with excellent comprehensive properties, is widely used in various fields such as electronics and electrical engineering, electrical insulation, and aerospace. However, with the rapid advancement of 5G/6G high-frequency communication technologies, higher requirements have been put forward on the dielectric properties of dielectric layer materials in electronic devices. PI faces significant challenges, including its inherently high dielectric constant (Dk) and dielectric loss (Df), as well as relatively high-water absorption, which restrict its further development in related applications. In this paper, the intrinsic action mechanism of Dk and Df of polymers under electric field was introduced at first, and then the main research progress of low-Dk and low-Df polyimide films in recent years, as well as the modification strategies of polymer molecular structure and dielectric properties were reviewed respectively. Finally, the research direction of low-Dk and low-Df polyimide films was summarized and prospected.

polyimide films  /  dielectric constant  /  dielectric loss  /  structural modification
刘永浩, 张铖钢, 蒋岚, 肖鹏. 低介电低损耗聚酰亚胺薄膜材料的分子结构设计及研究进展. 绝缘材料, 2026 , 59 (6) : 1 -9 . DOI: 10.16790/j.cnki.1009-9239.im.2026.06.001
Yonghao LIU, Chenggang ZHANG, Lan JIANG, Peng XIAO. Molecular structural design and research progress of low-dielectric, low-loss polyimide film materials[J]. Insulating Materials, 2026 , 59 (6) : 1 -9 . DOI: 10.16790/j.cnki.1009-9239.im.2026.06.001
随着全球正在加速迈入以数字经济为核心的智能时代,大数据、人工智能、元宇宙等新兴产业对无线高频通信的传输速率、延迟、范围与容量均提出了严格的要求[1]。5G/6G通信技术是实现万物智联时代的关键技术,其通信频率由MHz向GHz/THz频段拓展,进而成为各国科技竞争的焦点[2-3]。然而,随着通信频率的提高,使得信号在传输过程中需要具备更快的传输速度(>10 Gb/s)、更低的延迟(<1 ms)和更高的连接密度[4-5]。因此,对通信电子器件的电介质层材料提出了严格的要求。信号传输速度(v)和信号传播损耗(L)是高速高频传输技术中的两个关键指标。v值和L值都与电介质层绝缘材料的介电常数(Dk)和介电损耗(Df)密切相关,关系如式(1)和(2)所示[6-8]
vK×cDk
LK×fc×Df×Dk
式(1)~(2)中:K是常数;c是真空中的光速;f是信号传输的频率。
由式(1)和式(2)可知,v值与介电材料的Dk值呈负相关,L值与DfDk值呈正相关,特别是在高频情况下,DfL的影响更大。综上所述,在高频传输技术领域中,介电层材料迫切需要更低的DfDk,以实现更低的信号损失和更快的传输速率。此外,介电层材料在实际应用中需要面临各种复杂的环境,不仅需要优异的介电特性,还需具备低的吸水率、良好的热学和力学性能等。
极化是介电材料在外加电场下重要的电学特性之一,其本质是聚合物内部的电荷迁移现象,如图1所示。根据聚合物极化的微观机理,极化主要有4种基本形式[9-11]:电子极化、离子极化、偶极矩极化以及界面极化。①电子极化是指在外加电场作用下,原子或分子内部的正、负电荷中心发生相对位移,形成偶极。由于电子质量极小,其响应速度极快(约 10-16~ 10-14 s),极化过程近似弹性形变,撤去电场后位移立即恢复,极化消失,几乎不产生能量损耗。②离子极化是指在外加电场作用下,聚合物中具有离子特性结构单元的正、负离子发生相对位移,由于离子质量大于电子,响应时间较长,通常与晶格振动周期相当,约为 10-13 ~ 10-12  s。③偶极矩极化也叫取向极化[12],是指聚合物内部极性分子或链段(偶极子)在外加电场作用下发生的转向与排列。在无外加电场时,这些偶极子呈无序状态;外加电场后,它们会克服链段运动的阻力,逐步沿电场方向取向。该过程与分子链运动密切相关,响应速度较慢,弛豫时间约为10-9~10-2 s,由于分子链发生该极化时会受其自身惯性和链间链内旋转阻力等的影响,因此偶极矩极化会产生能量损耗。④界面极化常出现在非均匀体系,如复合材料、多相聚合物或局部结晶区域,是指自由电荷载流子(电子、空穴或杂质)在电场中迁移,被相界面或缺陷捕获而形成电荷积聚,产生极化,其弛豫时间通常较长,大约为在10-4  s 以上。
介电常数(Dk)是表征介电材料在外加电场下极化能力的重要参数[13-15]。一般材料的Dk都很小(10-12),因此常用相对Dk来表征介电材料的极化能力,即材料Dk与真空介电常数(Dk0,8.85×10-12 F/m)的比值。根据Clausius-Mossotti公式(3)可知,聚合物的极化越大,极化种类越多,Dk就越大。4种极化和频率的关系如图2所示[3,16-17]。在弛豫态,聚合物的Dk主要由偶极矩极化和界面极化决定;在谐振态,界面极化和偶极矩极化逐渐消失,Dk主要由剩下的电子极化和离子极化决定。在5G/6G频率下,Dk大小基本由偶极矩极化决定。聚合物极化能力与聚合物官能团极性、分子链结构和聚集态密切相关,由Clausius-Mossotti简化公式(4)可知[18-19]Dk与聚合物官能团的摩尔极化率(P)和摩尔体积(V)密切相关。综上所述,对于聚合物的Dk主要可以通过结构改性(引入低极化率结构或大自由体积基团)以及复合改性(引入低介电组分)来调控。
Dk-1Dk+2=N3Dk0α
Dk=1+2PV1-PV
式(3)~(4)中:N为单位分子/原子数;Dk0为真空介质下的介电常数;α为极化率;P为摩尔极化率;V为摩尔体积。
介电损耗(Df)主要由分子极化过程中跟不上外加交变电场的变化速度产生的松弛损耗,以及极化过程中分子或原子内部的摩擦和碰撞等导致的能量转换和损耗组成[13,20-22],其计算公式如式(5)和式(6)所示。
ε*=ε'-iε
Df=tanδ=ε.ε'
式(5)~(6)中:ε*为复介电常数;ε'为复介电常数实部;ε为复介电常数虚部。
由式(5)和式(6)、图2和德拜弛豫理论可知,弛豫时间(τ)反映在外加电场下聚合物链段运动能力或偶极子翻转的快慢。当介电材料的τ足够小时,极化完全跟上频率变化(例如电子极化和离子极化),属于理想状态下的弹性变化,则Df接近零;而当介电材料的τ无限大,极化基本不随施加电场而变化时,Df也接近零[23]。在5G/6G频率下,界面极化跟不上电场频率的变化,可以直接忽略,此时材料的Df主要分为两部分:①由偶极极化滞后于电场频率变化引起的松弛损耗;②电介质内部分子链、偶极矩的翻转运动以及小分子(水分子)或电荷间的摩擦碰撞导致的能量损耗。因此,降低Df的方法可以归结于以下3个方面:①降低聚合物极性;②减少偶极矩和分子链随交变频率运动而产生的摩擦和碰撞次数;③减少电介质内部的极性小分子数量。
在众多的高分子材料中,通常被用于通信领域的聚合物主要有聚四氟乙烯(PTFE)、聚苯硫醚(PPS)、聚芳醚腈(PEN)、聚苯醚(PPE)、液晶聚合物(LCP)和聚酰亚胺(PI),相应的性能对比如表1所示。然而,面临5G/6G高频通信领域的严格介电要求,仍然存在许多严峻的挑战。例如PTFE和LCP等虽然具有低的DkDf值,但其具有可加工性差、结构单一、粘附性低、工艺复杂和力学性能不足等缺点,在面对复杂的应用场景和多样化的材料性能需求,难以满足其在工业上规模化应用。PI是指主链上含有酰亚胺环结构单元的一类聚合物(如图3所示),其又可以分为全芳香族、半芳香族和脂环族PI。由于PI特殊的刚性共轭芳杂环结构以及强大的分子间作用力,从而被赋予了极其优异的综合性能(耐高低温、高强高模、高绝缘、耐腐蚀、耐辐射、设计性强和加工性好等),被广泛应用于航天航空、高频通信、柔性显示及集成电路等众多领域,被材料界称为“解决问题的能手”[24-26]。PI薄膜自上世纪70年代开始因其优异的耐热性能和力学性能被用于金属间连接的绝缘介质层,一直以来在电子通信领域备受关注[27-29]。随着5G/6G时代的到来,通信波段正在从低频波段向毫米波(GHz)和太赫兹(THz)高频波段拓展。而传统PI薄膜的DkDf较大(分别约为3.5和0.02),限制了其在高频通信器件上的应用。因此,迫切需要对PI的分子结构进行设计和改性,降低其DkDf,以满足高频通信领域应用的严格要求。
降低聚合物介电常数的基本原理是降低极化率和增大自由体积,主要方法有聚合物分子结构改性和聚合物复合材料设计。其中分子结构设计主要有引入含氟基团、引入大体积基团以及引入脂环结构等。复合材料设计主要有:①引入空气孔洞结构(Dk=1),提高基体孔隙率,降低单位体积极化分子密度[30];②引入低Dk填料[31-32],例如POSS、介孔二氧化硅和玻璃微球等;③采用多层结构设计[33]。这些方法都能有效降低PI薄膜的Dk,有些方法甚至可以将Dk降至2.0以下,下面主要总结本征型低Dk的PI改性策略。
将含氟基团引入到PI分子链中,前期是为了提高其疏水性和透明性,后来研究人员发现含氟基团还可以有效降低聚合物的Dk。这是由于氟原子具有很强的吸电子能力(电负性最大,达到4.0),可以结合电子并表现出弱极化倾向,将氟引入到PI分子结构中可以有效减少分子极化。特别是三氟甲基的引入可以破坏PI分子链的规则性,增大PI的自由体积,从而有效减少摩尔体积的极化分子数量。此外,氟原子的引入还可以显著降低PI的吸水性,从而表现出稳定的低介电性。通常,氟主要以“F”和“CF3”两种形式将氟原子引入到PI分子结构中,得到含氟聚酰亚胺(FPI)。Y WATANABE等[34]报道了通过氟原子取代苯环氢原子的合成策略,制备得到一系列FPI(图4中1),这些FPI的Dk在10 GHz下可以低至2.73。PENG W等[35]报道了一种新型含全氟环丁基苯基醚基PI(图4中2和3),它们具有优异的抗湿性,即使在高湿度环境仍能长时间保持超低的Dk(<2.5)。相比之下,大部分FPI是通过三氟甲基的形式引入到PI结构中,例如2,2-双(4-氨基苯基)六氟丙烷(FA)、2,2′-双(三氟甲基)联苯胺(TFMB)和4,4′-(六氟异丙基)二苯二酸酐(6FDA)等。G HOUGHAM等[36-38]制备了一系列含氟单体及PI(图4中4~11),这些PI均具有超低的Dk(2.55~2.85),进一步研究发现含氟基团的数目、类型和位置对Dk均有影响,含氟基团越多且对称取代,可以更有效地降低Dk
根据Clausius-Mossotti公式(4)可知,聚合物的自由体积越大或极化越小,其Dk越低。目前构建大自由体积PI是降低Dk非常有效的方法,主要包括引入大侧基和大体积非共平面结构(扭结、螺环和Cardo型结构)。这类结构通过扭曲主链结构和大刚性分子侧基,增大分子链间距离,减少分子链堆积密度,从而减少单位体积极化分子的数量,降低PI的Dk
(1)引入大侧基结构
在PI主链上引入大侧基通常有两种,一种是引入柔性非极性脂肪族长侧链,一定程度上可以增大分子链之间的距离,使PI的Dk小幅下降,但其耐热性会明显下降;另外一种是引入刚性芳香族大侧基和氟化侧基,可以有效地限制分子链紧密堆积,使PI表现出超低的Dk。LIU Y等[39]将三苯甲烷大侧基引入到PI中得到6FDA-TriPMPDA(图5中1)。由于引入大侧基三苯甲烷及形成扭曲主链结构,PI薄膜在10 kHz下的Dk低至2.33。LIU C等[40]报道了一种含叔丁基和4-叔丁基苯基的PI(图5中2),由于这两种大侧基的引入,PI表现出低Dk(2.78,1 MHz)和优异的溶解性。LIU Y等[41]还设计了一种含刚性主链和大刚性非平面共轭侧链聚酰亚胺(图5中3和4),其具有超低Dk(1.52),但是引入大体积侧链导致PI吸水率过高、耐热性能下降等。
(2)引入大体积非共平面结构
引入非共平面刚性结构也是改善PI性能的常用方法之一。研究人员开发出众多非共平面PI结构,利用空间位阻效应增大整体分子链的扭曲,与传统芳香族直线型PI相比,构建大体积非共平面结构PI可以明显增大自由体积,有效降低Dk。LIU Y等[42-43]合成了一类非共平面结构的PI(图6中1)。由于含芴基结构和三氟甲基都可以降低分子极性,同时非共平面大体积含芴结构能够限制分子链的紧密堆积,增大自由体积,使PI的Dk低至1.83(10 kHz),并且在接近Tg(400℃)依然能保持稳定。JIAN L F等[44]在二胺中引入非共平面2,2′-螺二芴基团(图6中2),通过调节单体结构大扭转角来调控PI分子链刚性和分子间相互作用,得到的PI薄膜在高频60 GHz下表现出超低Dk(2.81)和Df(0.006 3)。XIAO P等[45]报道了一系列含螺双茚并双苯并恶唑PI(图6中3和4),由于螺双茚结构和CF3基的引入,大幅降低了PI的摩尔极化率和自由体积,使PI薄膜不仅表现出超高的透明性和耐热性,还表现出极低的Dk(2.32,10 GHz)。
早期引入脂环结构是为了降低芳香族PI分子链间和链内电荷转移络合物(CTC)的形成,从而得到无色透明PI薄膜[46],随后研究人员发现脂环结构的引入,可以有效增大自由体积,同时降低极化,从而显著降低Dk。最常见的脂环二酐有氢化均苯四甲酸二酐(H-PMDA)、氢化3,3′,4,4′-联苯四羧酸二酐(H-BPDA)、环丁烷四甲酸二酐(CBDA)、双螺[4,7]桥亚甲基异苯并呋喃-5(3H)-酮二胺(CpODA)等二酐单体(如图7所示)。对于脂环二胺,大部分都是半脂肪半芳香二胺单体为主,如图7中的DAPI和ADMDA[47]。对于全脂二胺,如图7中的DAHC和MMCA,由于单体氨基活性较低、耐热性和溶解性差等缺点,在实际应用中没有成为主流二胺。这些脂环单体制备得到的PI通常不仅具有低Dk(2.44~2.80),还具有高透明性。例如ZHI X X等[48]使用脂环二酐(HBPDA)代替联苯二酐制备得到半脂环PI,不仅有效降低了Dk(2.56,1 MHz),而且提高了PI薄膜的透明性,但耐热性能下降明显。
随着高频通信技术的全面发展,对介电绝缘材料的Df提出了更高的要求。根据式(5)和式(6),Df和信号损耗呈线性正相关,Df决定了信号的稳定和效率,且频率越高,影响越大。现阶段研究中常见降低Df的方法主要有减小极化、增大刚性结构和引入酯基。
极化不仅会影响Dk,还会影响Df,极化小的聚合物在高频电场下,偶极矩转动更小,因此产生的弛豫和能量损耗就更小。QIAN C等[49-50]基于β弛豫设计了一种长侧链结构来降低PI的DkDf,如图8所示。其中TmBPHF在10 kHz下表现出极好的介电性能,DkDf分别低至2.09和0.001 2。其机理为:在低于Tg时,整体链段被冻结,但是作为垂直基团的三苯基单元仍可以进行β弛豫,即在小范围内旋转运动,增大自由体积,同时偶极矩变化引起的Df随着分子链之间相互作用的减弱而减小。然而,随着频率的增大,偶极矩变化速度加快,Df随之增大。根据相同的理论,LI H等[51]制备了一批含有大量CF3的PI薄膜,这些PI薄膜的Df在1 MHz时低至0.001 3~0.002 8,这归因于其低极化率和大自由体积,但是随着频率升高,Df均呈上升趋势。因此,通过该方法降低高频Df仍有待进一步研究。
根据介电损耗的偶极弛豫理论,损耗主要来自偶极子为克服摩擦阻力而产生的能量损失。因此认为限制交变电场下偶极矩偏转幅度是降低介电损耗的有效策略之一,通常可通过减少分子链间距和增大分子链间相互作用力来实现。ZUO H等[52]利用氢键来增大分子链间的相互作用力,抑制分子链的运动,如图9(a)所示,得到的PI具有低Df(0.001 3),但仅限在10 kHz下,随着频率的升高,Df增大;而酰胺键极性较高且极易吸水,导致Dk偏高,PI介电稳定性较差。HE J J等[53]制备了一系列具有不同比例刚性和柔性骨架的PI(如图9(b)所示),PI薄膜的Df在10 GHz下达到0.004 5~0.005 9。通过增加线性联苯结构的比例,减弱偶极矩的偏转,也可以降低PI的Df
与PI相比,LCP同样是高频通信器件中非常理想的介电材料之一,其特点是在低频时Df高、高频时Df[54],主要原因为:LCP是半结晶聚合物,有序的晶区与无序的非晶区之间形成大量界面,低频时界面极化占主要贡献,导致Df较高;而在高频时,其分子结构中的酯基C=O对高频电场不敏感,且结晶和高取向限制了内部偶极矩和分子链随交变电场的运动,导致Df显著降低。由此研究人员尝试在PI中构建LCP结构,希望兼顾两者的优点。由于酯基的刚性和高取向结构可以限制分子链运动,最初被用来降低聚合物的CTE,随后发现其还可以降低聚合物的Df[55-56]。M HASEGAWA等[57]合成了一系列含酯基二酐和二胺单体,通过聚合制得具有低Df(0.001 9)、低CTE和低吸水率的PI薄膜。研究发现芳酯基片段在亚胺化诱导下呈现棒状面内取向,高度取向的芳酯基片段限制了偶极矩和分子链随高频电场的内部旋转,因而可以有效降低Df,而且酯基对高频电场信号响应较差,抑制了弛豫现象。为进一步研究酯基对PI性能的影响,他们研究了不同侧基-CH3、-OCH3、-Ph等对PI介电性能的影响(图10(a)[58-59],发现增大自由体积可以增大溶解性和降低Dk,但代价是取向破坏,Df随之上升。同时,他们还通过增加芳香族数量来进一步改善PI的性能(图10(b)[60],发现降低主链中酰亚胺键可以有效降低薄膜的吸水率和极性,但力学性能有所下降。ZHANG C等[61]设计合成了一系列含多酯基的二胺(AXEB,X=1、2或3),与6FDA或对亚苯基双(偏苯三酸酐)(TA2EB)进行聚合制备PI,由于酯基的调控作用,导致PI偶极弛豫时间延长和吸水率大幅降低,得到的两种PI薄膜表现出极低的Df(分别为0.003 0和0.001 3)。因此,通过引入酯基调控PI的介电性能是非常有效的策略,也是今后研究的一个方向
基于LCP、PTFE等聚合物具有一定的结晶性,限制了分子链运动,使其Df较低。根据该思路,研究人员尝试设计制备类液晶型PI,但常见的液晶型PI往往会引入极性片段,进而导致Dk升高。YIN Q等[62]采用酯基作为液晶基元,6FDA作为柔性基元,通过酯基二酐和含氟二胺进行聚合制备类液晶型PI(图11(a))。这类PI在低频和高频下(1 MHz~0.75 THz)均保持低Df(0.001 8~0.004 7),但结晶的形成导致力学性能降低,特别是断裂伸长率下降明显。另外,ZHANG C等[63]提出一种醚键柔性平衡策略,即在聚酯酰亚胺中引入醚键得到聚醚酯酰亚胺(图11(b)),通过调控酯基与醚键的比例和萘环的“侧步”效应改善其相关性能。结果表明这些PI具有超低Df(<2×10-3)、低吸湿率(<0.7%)、高耐热性能(Tg>420℃)和力学性能。
面向未来5G/6G高频通信、智能互联等领域的迫切需求,低介电低损耗PI薄膜的研究将向更深层次、更综合化的方向发展。在分子结构设计上,可继续开发新型特种单体(如含酯基、氟基团、大体积骨架单体),进一步突破PI介电性能的极限。另外,通过交联、超支化、构建本征微孔结构等方式对PI进行结构改性,同样是降低PI介电性能的重要途径。值得注意的是,研究方向从过去单一的介电性能转向“介电-热-机械”等综合性能平衡,确保PI在复杂的高频环境下保持长期的可靠性。最后,随着人工智能(AI)时代的到来,“AI+新材料”新模式通过数据驱动和相关算法高效揭示PI高分子材料的构效关系。例如机器学习和高分子合成相结合已受到广泛关注,未来可通过高通量计算指导实验设计,高效开展分子结构设计,大幅加速新型低介电PI材料的研发进程。

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2026年第59卷第6期
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doi: 10.16790/j.cnki.1009-9239.im.2026.06.001
  • 接收时间:2025-10-19
  • 首发时间:2026-09-10
  • 出版时间:2026-06-20
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  • 收稿日期:2025-10-19
  • 修回日期:2025-12-06
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    1宁波工程学院 微纳材料与器件创新研究院,浙江 宁波 315211
    2同济大学 化学科学与工程学院,上海 200092

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肖鹏(1994-),男(汉族),江西赣州人,副教授,博士,主要从事高性能聚酰亚胺材料的研究。
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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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