Article(id=1304921814854037580, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921686403474081, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.06.014, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1757692800000, receivedDateStr=2025-09-13, revisedDate=1760976000000, revisedDateStr=2025-10-21, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047204936, onlineDateStr=2026-09-10, pubDate=1781884800000, pubDateStr=2026-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047204936, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047204936, creator=13701087609, updateTime=1789047204936, 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=141, endPage=148, ext={EN=ArticleExt(id=1304921814988255309, articleId=1304921814854037580, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Co-curing of TAIC with TMBPA-MPPO: synchronous enhancement of bulk properties for high-speed and low-loss substrates, columnId=null, journalTitle=Insulating Materials, columnName=null, runingTitle=null, highlight=null, articleAbstract=

In this study, tetramethylbisphenol A (TMBPA) was used as the bisphenol source, and a dihydroxy-terminated oligomeric polyphenylene ether resin (TMBPA-MPPO) was synthesized via monomer copolymerization. Further, through a nucleophilic substitution reaction, TMBPA-MPPO was end-capped with chloromethylstyrene (VBC) to prepare a crosslinkable polyphenylene ether resin MPPO-VBC. The product structure was characterized by FT-IR, and the dielectric properties, thermal properties, and moisture absorption of the cured product were systematically evaluated. The results show that MPPO-VBC has good curing activity, and after curing it exhibits excellent dielectric properties (dielectric constant is 2.60, dielectric loss factor is 0.004 5 at 1 MHz) and heat resistance (Tg=200℃). On this basis, MPPO-VBC was blended with triallyl isocyanurate (TAIC), coated onto glass fiber cloth, and a composite was prepared. Its dielectric loss factor further decreased to 0.001 4, the glass transition temperature increased to 221.4℃, and the tensile strength and flexural strength reached 212 MPa and 267 MPa, respectively, demonstrating application potential in high-frequency copper-clad laminates.

, authors=Zhenzhen TAN1, Xu WANG2, Lingyu LI1, Jiachun ZHONG1, *, Mengjie YUE1, Kaijie YANG1, authorsList=Zhenzhen TAN, Xu WANG, Lingyu LI, Jiachun ZHONG, Mengjie YUE, Kaijie YANG, authorCompany=null, correspAuthors=Jiachun ZHONG, 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=1304921817173487720, articleId=1304921814854037580, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=TAIC协同TMBPA-MPPO共固化:高速低损耗基板本体性能的同步增强, columnId=null, journalTitle=绝缘材料, columnName=, runingTitle=null, highlight=null, articleAbstract=

本研究以四甲基双酚A(TMBPA)为二元酚源,通过单体共聚法合成了双端羟基低聚聚苯醚树脂(TMBPA-MPPO)。进一步通过亲核取代反应,使用氯甲基苯乙烯(VBC)对TMBPA-MPPO进行封端,制得可交联聚苯醚树脂MPPO-VBC。采用FT-IR对产物结构进行表征,并系统评价了其固化物的介电性能、热性能及吸湿性。结果表明:MPPO-VBC具有良好的固化活性,固化后表现出优异的介电性能(1 MHz下介电常数为2.60,介电损耗因子为0.004 5)和耐热性(Tg=200℃)。在此基础上,将MPPO-VBC与三烯丙基异氰脲酸酯(TAIC)共混涂敷于玻纤布上制备出复合材料,其介电损耗因子进一步降低至0.001 4,玻璃化转变温度提高至221.4℃,拉伸强度和弯曲强度分别达到212 MPa和267 MPa,显示出其在高频覆铜板领域的应用潜力。

, authors=谭珍珍1, 王旭2, 李玲玉1, 钟家春1, *, 岳梦洁1, 杨开杰1, authorsList=谭珍珍, 王旭, 李玲玉, 钟家春, 岳梦洁, 杨开杰, authorCompany=null, correspAuthors=钟家春, authorNote=

谭珍珍(2001-),女(汉族),四川绵阳人,硕士生,主要从事低聚聚苯醚及其复合材料的研究

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钟家春(1980-),男(汉族),四川自贡人,教授,博士,主要从事特种工程塑料、特种化学品、功能性聚酯和生物基高分子的产业化合成关键技术及其功能复合材料应用的研究。
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谭珍珍(2001-),女(汉族),四川绵阳人,硕士生,主要从事低聚聚苯醚及其复合材料的研究

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谭珍珍(2001-),女(汉族),四川绵阳人,硕士生,主要从事低聚聚苯醚及其复合材料的研究

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caption=

Dielectric constant and dielectric loss factor of MPPO-VBC/TAIC resin systems at 1 MHz

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名称介电常数介电损耗因子
MPPO-VBC2.600.004 50
TM-9/12.710.001 29
TM-8/22.720.001 97
TM-7/32.790.001 55
TM-6/42.940.001 40
), ArticleFig(id=1304921948417446870, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921814854037580, language=CN, label=表1, caption=

MPPO-VBC/TAIC树脂体系在1 MHz时的介电常数与介电损耗因子

, figureFileSmall=null, figureFileBig=null, tableContent=
名称介电常数介电损耗因子
MPPO-VBC2.600.004 50
TM-9/12.710.001 29
TM-8/22.720.001 97
TM-7/32.790.001 55
TM-6/42.940.001 40
), ArticleFig(id=1304921948484555735, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921814854037580, language=EN, label=Table 2, caption=

Initial energy storage modulus, glass transition temperature, and cross-linking density of the MPPO-VBC/TAIC resin systems

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名称初始储能模量/MPaTg/℃交联密度/(mol/m3)
MPPO-VBC1 894200.01 791.5
TM-9/12 249210.85 916.6
TM-8/22 351215.09 131.5
TM-7/32 432221.19 230.6
TM-6/42 744221.414 025.6
), ArticleFig(id=1304921948555858904, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921814854037580, language=CN, label=表2, caption=

MPPO-VBC/TAIC树脂体系的初始储能模量、玻璃化转变温度和交联密度

, figureFileSmall=null, figureFileBig=null, tableContent=
名称初始储能模量/MPaTg/℃交联密度/(mol/m3)
MPPO-VBC1 894200.01 791.5
TM-9/12 249210.85 916.6
TM-8/22 351215.09 131.5
TM-7/32 432221.19 230.6
TM-6/42 744221.414 025.6
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Thermal stability data of MPPO-VBC/TAICresin systems

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称Td5%/℃Td10%/℃Tdmax/℃
MPPO-VBC356387442
TM-9/1375410449
TM-8/2379411452
TM-7/3380414450
TM-6/4404427458
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MPPO-VBC/TAIC树脂体系的热稳定性数据

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称Td5%/℃Td10%/℃Tdmax/℃
MPPO-VBC356387442
TM-9/1375410449
TM-8/2379411452
TM-7/3380414450
TM-6/4404427458
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TAIC协同TMBPA-MPPO共固化:高速低损耗基板本体性能的同步增强
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谭珍珍 1 , 王旭 2 , 李玲玉 1 , 钟家春 1, * , 岳梦洁 1 , 杨开杰 1
绝缘材料 | 2026,59(6): 141-148
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绝缘材料 | 2026 , 59 (6) : 141 -148
TAIC协同TMBPA-MPPO共固化:高速低损耗基板本体性能的同步增强
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谭珍珍1, 王旭2, 李玲玉1, 钟家春1, *, 岳梦洁1, 杨开杰1
作者信息
  • 1四川轻化工大学 材料科学与工程学院,四川 自贡 643000
  • 2昊华宇航化工有限公司,河南 焦作 454002
通讯作者:
钟家春(1980-),男(汉族),四川自贡人,教授,博士,主要从事特种工程塑料、特种化学品、功能性聚酯和生物基高分子的产业化合成关键技术及其功能复合材料应用的研究。
作者简介:

谭珍珍(2001-),女(汉族),四川绵阳人,硕士生,主要从事低聚聚苯醚及其复合材料的研究

Co-curing of TAIC with TMBPA-MPPO: synchronous enhancement of bulk properties for high-speed and low-loss substrates
Zhenzhen TAN1, Xu WANG2, Lingyu LI1, Jiachun ZHONG1, *, Mengjie YUE1, Kaijie YANG1
Affiliations
  • 1College of Materials Science and Engineering, Sichuan University of Science & Engineering, Zigong 643000, China
  • 2Haohua Yuhang Chemical Company Limited, Jiaozuo 454002, China
出版时间: 2026-06-20 doi: 10.16790/j.cnki.1009-9239.im.2026.06.014
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本研究以四甲基双酚A(TMBPA)为二元酚源,通过单体共聚法合成了双端羟基低聚聚苯醚树脂(TMBPA-MPPO)。进一步通过亲核取代反应,使用氯甲基苯乙烯(VBC)对TMBPA-MPPO进行封端,制得可交联聚苯醚树脂MPPO-VBC。采用FT-IR对产物结构进行表征,并系统评价了其固化物的介电性能、热性能及吸湿性。结果表明:MPPO-VBC具有良好的固化活性,固化后表现出优异的介电性能(1 MHz下介电常数为2.60,介电损耗因子为0.004 5)和耐热性(Tg=200℃)。在此基础上,将MPPO-VBC与三烯丙基异氰脲酸酯(TAIC)共混涂敷于玻纤布上制备出复合材料,其介电损耗因子进一步降低至0.001 4,玻璃化转变温度提高至221.4℃,拉伸强度和弯曲强度分别达到212 MPa和267 MPa,显示出其在高频覆铜板领域的应用潜力。

聚苯醚  /  可交联树脂  /  氰酸酯  /  介电性能  /  复合材料

In this study, tetramethylbisphenol A (TMBPA) was used as the bisphenol source, and a dihydroxy-terminated oligomeric polyphenylene ether resin (TMBPA-MPPO) was synthesized via monomer copolymerization. Further, through a nucleophilic substitution reaction, TMBPA-MPPO was end-capped with chloromethylstyrene (VBC) to prepare a crosslinkable polyphenylene ether resin MPPO-VBC. The product structure was characterized by FT-IR, and the dielectric properties, thermal properties, and moisture absorption of the cured product were systematically evaluated. The results show that MPPO-VBC has good curing activity, and after curing it exhibits excellent dielectric properties (dielectric constant is 2.60, dielectric loss factor is 0.004 5 at 1 MHz) and heat resistance (Tg=200℃). On this basis, MPPO-VBC was blended with triallyl isocyanurate (TAIC), coated onto glass fiber cloth, and a composite was prepared. Its dielectric loss factor further decreased to 0.001 4, the glass transition temperature increased to 221.4℃, and the tensile strength and flexural strength reached 212 MPa and 267 MPa, respectively, demonstrating application potential in high-frequency copper-clad laminates.

polyphenylene ether  /  crosslinkable resin  /  cyanate ester  /  dielectric properties  /  composite materials
谭珍珍, 王旭, 李玲玉, 钟家春, 岳梦洁, 杨开杰. TAIC协同TMBPA-MPPO共固化:高速低损耗基板本体性能的同步增强. 绝缘材料, 2026 , 59 (6) : 141 -148 . DOI: 10.16790/j.cnki.1009-9239.im.2026.06.014
Zhenzhen TAN, Xu WANG, Lingyu LI, Jiachun ZHONG, Mengjie YUE, Kaijie YANG. Co-curing of TAIC with TMBPA-MPPO: synchronous enhancement of bulk properties for high-speed and low-loss substrates[J]. Insulating Materials, 2026 , 59 (6) : 141 -148 . DOI: 10.16790/j.cnki.1009-9239.im.2026.06.014
随着5G/6G通信技术的快速发展,高频高速电子设备对基板材料的介电性能提出了前所未有的高要求。传统环氧树脂基材料(介电常数Dk>3.5,介电损耗因子Df>0.02)难以满足毫米波频段的应用需求,开发新型低介电损耗高分子材料成为当前研究的热点[1]。聚苯醚(PPO)树脂因其独特的分子结构特征,表现出优异的介电特性(Dk≈2.5~2.7,Df≈0.001~0.002)[2-4]、低吸湿性(<0.1%)和良好的耐热性(Tg>200℃)[5],被认为是高频基板材料的理想选择[6]。然而,高分子量PPO存在加工温度高、熔融黏度大、溶解性差等缺点[7-10],严重限制了其在覆铜板领域的规模化应用。
为了克服上述问题,研究人员开发了多种改性策略。其中,通过端基功能化将热塑性PPO转化为热固性PPO树脂被认为是最有效的解决方案之一[11]。针对这一改性思路,现已发展出多种合成方法,其中“单体共聚法”因其能够精确控制分子量和端基数量而备受青睐。该方法以2,6-二甲基苯酚和二元酚为单体,在铜-胺络合物催化下通过氧化偶联聚合反应,一步合成双端羟基聚苯醚(MPPO)[12]。在各类二元酚中,四甲基双酚A(TMBPA)由于其分子结构中甲基的给电子效应,能够增强酚羟基的共轭作用,提高其反应活性,因此TMBPA型MPPO具有更高的分子量和更窄的分子量分布[13],TMBPA型MPPO的结构式如图1所示。
近年来,通过在MPPO末端引入可交联官能团来制备热固性PPO树脂成为研究重点。研究人员成功开发了多种功能化改性方法,包括酯化、醚化、亲核取代等反应,接枝乙烯基、环氧基、氰酸酯基等可交联基团[14]。其中,通过氯甲基苯乙烯(VBC)封端得到的MPPO-VBC树脂兼具PPO优异的介电性能和乙烯基的高反应活性,表现出良好的应用前景[15]图2为MPPO-VBC的结构式。
然而,研究发现单一MPPO-VBC树脂存在交联密度不足、固化温度高、材料脆性大等问题,影响其在实际应用中的性能表现[16]。为了克服这些局限性,研究人员提出了共交联策略,即将可交联PPO与其他高活性热固性树脂共混,通过协同固化形成互穿网络或共交联结构,以此改善树脂的综合性能。在众多热固性树脂中,氰酸酯树脂特别是三烯丙基异氰脲酸酯(TAIC)展现出独特优势[17]。如图3所示,TAIC分子中含有3个烯丙基,可与乙烯基发生高效的共聚反应,而其核心的异氰脲酸酯环则赋予材料更高的热稳定性和刚性[3]。这种复合固化体系不仅能显著降低固化温度,还能形成更致密的交联网络,从而全面提升材料的综合性能[18]
基于以上研究背景,本研究采用单体共聚法合成TMBPA-MPPO,并通过亲核取代反应制备了MPPO-VBC树脂。在此基础上,系统研究MPPO-VBC与TAIC的复合固化体系,详细探讨不同配比对复合体系固化行为、介电性能、热力学性能和吸湿性的影响规律。
2,6-二甲基苯酚(DMP,纯度为99%)、三烯丙基异氰脲酸酯(TAIC,纯度为98%)、甲醇(分析纯)上海阿拉丁生物科技股份有限公司;四甲基双酚A(TMBPA,纯度为99%),湖北齐飞医药化工有限公司;二正丁胺(纯度为99%)、氯化亚铜(CuCl,纯度为99%),成都市科隆化学品有限公司;甲苯(分析纯)、N,N-二甲基甲酰胺(DMF,分析纯),成都市科隆化学品有限公司;三乙基苄基氯化铵(纯度为98%)、双叔丁基过氧异丙基苯(交联引发剂,纯度为96%),上海麦克林生化科技有限公司;氯甲基苯乙烯(VBC,纯度为99%),中山远达新材料有限公司。所有试剂均直接使用,未经进一步纯化。
傅里叶变换红外光谱仪(FT-IR,Nicolet 6700型,赛默飞世尔公司)、热重分析仪(TGA,TGA/DSC3+型,梅特勒-托利多公司)、阻抗分析仪(4294A型,安捷伦公司)、动态热机械分析仪(DMA,Q800型,TA Instruments公司)、扫描电子显微镜(SEM,Sigma 300型,蔡司显微技术有限公司)以及微机控制电子万能试验机(CMT4104型,美特斯工业系统(中国)有限公司)。
采用单体共聚法合成TMBPA-MPPO。将二正丁胺(44.35 g)、氯化亚铜(1.13 g)加入到1 000 mL四口烧瓶中,超声分散至均相,加入300 mL甲醇,升温至30℃后向溶液中通入氧气反应15 min。再加入TMBPA(23.28 g)和甲醇(400 mL),搅拌至均相。将DMP(100.00 g)溶于甲醇(120 mL)中,滴入上述反应溶液,滴加时间控制在2.5~3 h。滴加完毕后,将混合溶液升温至40℃反应5.0 h。反应结束后,过滤得到粗产品,经溶解、洗涤、析出、干燥后得到TMBPA-MPPO树脂。
在氮气保护下,将TMBPA-MPPO(20 g)溶于甲苯(60 mL)和DMF(10 mL)混合溶剂中,加入三乙基苄基氯化铵(0.14 g)和NaOH水溶液(50%,5 g),升温至90℃后滴加VBC(4.77 g),滴加完毕后反应8 h。反应结束后,经酸洗、沉淀、过滤、干燥得到MPPO-VBC树脂。
MMPPO-VBC固化树脂的制备:将MPPO-VBC与TAIC按不同质量比(9∶1、8∶2、7∶3、6∶4)混合,溶于丁酮中,加入浓度为1.5%的交联引发剂,浇注到模具中,经50℃真空干燥24 h后,按150℃/2 h+170℃/2 h+190℃/4 h的程序进行固化。根据不同质量比分别命名为MPPO-VBC、TM-9/1、TM-8/2、TM-7/3、TM-6/4。
MPPO-VBC/TAIC/GF复合材料的制备:将MPPO-VBC与TAIC按不同质量比(9∶1、8∶2、7∶3、6∶4)混合,加入浓度为1.5%的交联引发剂,溶于丁酮后涂覆于玻纤布(GF)上,经干燥后热压固化制得MPPO-VBC/TAIC/GF复合材料。根据不同质量比分别命名为MPPO-VBC/GF、TM/GF-9/1、TM/GF-8/2、TM/GF-7/3、TM/GF-6/4。
图4主要展示了MPPO-VBC树脂的合成及固化工艺路线。首先,DMP与TMBPA经氧化偶联聚合制备羟基封端的MPPO,再以VBC进行端基改性得到乙烯基封端的MPPO-VBC。将MPPO-VBC与多官能团交联剂TAIC共混后涂敷于GF上,在一定条件下,MPPO-VBC末端的乙烯基与TAIC的烯丙基发生自由基共聚反应,形成三维交联网络,实现树脂的固化定型。
图5为MPPO、MPPO-VBC与MPPO-VBC/TAIC的红外光谱图。由图5可知,MPPO-VBC在波数为3 200~3 700 cm-1之间的羟基振动峰相较于MPPO明显减弱,说明MPPO-VBC的羟基明显减少。MPPO-VBC曲线在波数为910 cm-1处出现了1个微弱小峰,可以判断是乙烯基上C=C的伸缩振动峰,表明VBC成功与MPPO发生了亲核取代反应,乙烯基成功引入到MPPO的两侧。MPPO-VBC/TAIC 固化后在波数为1 737 cm-1处出现微弱的C=O吸收峰,归属TAIC中的C=O的振动峰;同时在波数为910 cm-1处的乙烯基特征峰消失,表明C=C双键已被自由基反应耗尽。芳醚骨架峰位保持不变,证实交联过程仅消耗侧链乙烯基,未破坏主链结构。
采用阻抗分析仪测试MPPO-VBC/TAIC树脂体系在室温下(30℃)的介电常数与介电损耗因子,测试频率为100 Hz~1 MHz,测试结果如图6图7所示,1 MHz下的介电常数与介电损耗因子如表1所示。
图6表1可知,随着测试频率升高,MPPO-VBC/TAIC树脂体系的介电常数呈下降趋势。当频率为1 MHz时,MPPO-VBC、TM-9/1、TM-8/2、TM-7/3、TM-6/4的介电常数依次为2.60、2.71、2.72、2.79、2.94,均低于3.0。值得注意的是,随着TAIC含量增加,介电常数逐渐增大。这是由于,一方面MPPO-VBC/TAIC树脂体系中的共聚结构增多,不对称单元比例上升,取向极化增强;另一方面TAIC本身含有极性较强的异氰酸酯基团,固化后仍有部分未参与交联反应的碳碳双键残留,进一步提高了分子极化程度,从而导致树脂体系的介电常数升高。
图7表1可知,随着测试频率升高,MPPO-VBC/TAIC树脂体系的介电损耗整体呈下降趋势。当频率为1 MHz时,MPPO-VBC、TM-9/1、TM-8/2、TM-7/3、TM-6/4的介电损耗因子分别为0.004 50、0.001 29、0.001 97、0.001 55、0.001 40,均低于0.005。介电损耗下降的原因是,在较高频率下分子链松弛远滞后于外加电场的变化,松弛损耗贡献减小;同时,随着TAIC含量增加,树脂体系交联密度提高,树脂分子极化程度减弱,因而介电损耗进一步降低。
采用动态热机械分析仪(DMA)对MPPO-VBC/TAIC树脂体系的热力学性能进行表征,测试结果如图8所示,其初始储能模量、力学损耗角正切值所代表的玻璃化转变温度(Tg)、交联密度如表2所示。
图8表2可以看出,随着TAIC含量增加,MPPO-VBC/TAIC树脂体系的初始储能模量逐渐升高,表明其刚性逐渐增强。这一现象主要源于两方面:其一,TAIC本身分子量较小,且含有高刚性的六元杂环结构;其二,TAIC分子的烯丙基双键可与MPPO-VBC的乙烯基双键发生反应,交联密度随之增大,从而进一步提升了刚性。
此外,MPPO-VBC/TAIC树脂体系的力学损耗角正切值曲线呈对称峰形,表明树脂体系形成了均相结构。值得注意的是,随着TAIC含量增加,Tg逐渐升高,而正切值峰值高度却逐渐降低,进一步证实了交联密度的增大[20]
共混体系的交联密度计算公式如式(1)所示。
ρ=E'/3RT
式(1)中,ρ为材料的交联密度,单位为mol/m3E′为Tg+40 K时的储能模量,单位为MPa;R为理想气体常数,其值为8.314 J/(K·mol);TTg+40 K时的绝对温度,单位为K。
根据式(1)计算得到,MPPO-VBC、TM-9/1、TM-8/2、TM-7/3、TM-6/4的交联密度分别为1 791.5、5 916.6、9 131.5、9 230.6、14 025.6 mol/m3,表明TAIC作为交联剂能够有效增大树脂体系的交联密度。
采用TGA对MPPO-VBC/TAIC树脂体系的热稳定性进行表征,结果如图9所示,其5%质量损失的温度(Td5%)、10%质量损失的温度(Td10%)、最大失重温度(Tdmax)如表3所示。
表3可以看出,所有树脂体系的Td5%均大于350℃,表明树脂体系具有良好的热稳定性。随着TAIC含量的增加,树脂体系的Td5%逐渐增加,结合树脂体系的DMA数据,随着TAIC含量的增加,树脂体系的交联密度增大,树脂形成更为致密的交联网络,因此树脂的热稳定性上升。
MPPO-VBC、TM-9/1、TM-8/2、TM-7/3、TM-6/4树脂体系的Tdmax也展现出类似的规律,即随着TAIC含量的增加,树脂体系的Tdmax逐渐增加(具体数据见表3)。综上,随着TAIC含量增加,树脂体系热稳定性有一定提升,整体表现出优异的热稳定性。
进一步对共混体系的吸水性能进行表征,将样品置于去离子水中浸渍24 h,测量浸渍前后的质量变化,连续测量一周,通过式(2)计算吸水率(W)。
W=mi-m0m0×100%
式(2)中:m0为样品置于100℃烘箱中干燥2 h时测得的质量;mi为将样品置于去离子水中24 h取样测得的质量。
根据式(2)计算得到的吸水率作图并拟合,结果如图10所示。由图10可知,MPPO-VBC、TM-9/1、TM-8/2、TM-7/3、TM-6/4在置于水中一周后的吸水率分别为1.4%、0.57%、0.50%、0.57%、0.58%,随着TAIC的加入,树脂体系的吸水率呈现不同程度的下降。
这是由于随着树脂体系中TAIC的引入,固化物的交联密度增加,固化物内部的自由体积减小,水分的“储存空间”减小,吸水率下降。此外,TAIC自身具有类似三嗪环刚性结构,使得水分子更加难以进入固化物内部,导致树脂体系的吸水率下降。综上,改性后的树脂体系吸水率小于1%,表明树脂体系是一种吸湿性较低的基体树脂。
前述通过研究MPPO-VBC/TAIC树脂体系的固化行为、介电性能、热性能等,证明了MPPO-VBC/TAIC树脂体系是一种综合性能优异的基体树脂。为探究玻纤增强的改性效果,测试并分析了MPPO-VBC/TAIC/GF复合材料的力学性能。图11为MPPO-VBC/TAIC/GF复合材料的拉伸强度。由图11可知,MPPO-VBC/GF复合材料的拉伸强度为68 MPa。随着TAIC含量的增加,MPPO-VBC/TAIC/GF复合材料的拉伸强度逐渐增大。当MPPO-VBC与TAIC的质量比为6∶4时,MPPO-VBC/TAIC/GF复合材料的拉伸强度为212 MPa。
图12为MPPO-VBC/TAIC/GF复合材料的弯曲强度和弯曲模量。由图12可知,MPPO-VBC/GF复合材料的弯曲强度和弯曲模量分别为58.4 MPa和11.5 GPa。随着TAIC的加入,MPPO-VBC/TAIC/GF复合材料的弯曲强度和弯曲模量均有不同程度的提高。当MPPO-VBC与TAIC的质量比为6∶4时,MPPO-VBC/TAIC/GF复合材料的弯曲强度和弯曲模量达到最大值,分别为267 MPa和19.7 GPa。
MPPO-VBC/TAIC/GF复合材料的力学性能提高,一方面可能是由于TAIC中具有极性的异氰酸酯能够增加基体树脂在玻纤中的粘附效果和浸渍效果,另一方面根据MPPO-VBC/TAIC树脂的DMA和TGA数据可知,在相同固化条件下,加入TAIC改性后基体树脂具有更高的交联密度和更稳定的交联网络。因此,TAIC的加入能够有效提高MPPO-VBC/TAIC/GF复合材料的力学性能。MPPO-VBC/TAIC/GF复合材料的弯曲强度未达到IPC-4101中标准的≥310 MPa的通用要求,未能满足“刚性PCB基板”通用标准,其原因是高交联密度与刚性芳环骨架,导致复合材料脆性增加。
为了进一步研究MPPO-VBC/TAIC树脂基体对纤维浸渍及复合界面粘接情况,采用扫描电镜(SEM)对MPPO-VBC/TAIC/GF复合材料的断面进行分析,结果如图13所示。从图13可以看出,MPPO-VBC/TAIC基体树脂与纤维的浸润性较好,断面基体树脂均匀的分布在纤维四周,断面处出现了粘接紧密的纤维簇团。
与MPPO-VBC/GF复合材料的SEM图相比,MPPO-VBC/TAIC/GF复合材料中树脂的分布更加均匀,堆积密度相对较高,纤维与纤维之间的基体树脂没有出现贫胶现象和富胶现象,没有明显的气泡和裂缝,在断面处能够观察到纤维的断裂,说明MPPO-VBC/TAIC/GF复合材料中基体树脂与玻纤之间具有较强的相界面作用力,因此其综合强度相对较高。
本研究成功制备了TMBPA-MPPO及其衍生物MPPO-VBC可交联聚苯醚树脂,并进一步制备了MPPO-VBC/TAIC树脂。当MPPO-VBC与TAIC的质量比为6∶4时,树脂体系在1 MHz下的介电常数由2.6提高至2.94,介电损耗因子由0.004 50降低至0.001 40,玻璃化转变温度从200℃升高至221.4℃。随着TAIC含量增加,树脂体系的交联密度和储能模量增大,刚性增强,热稳定性得到改善,同时吸水率由1.4%降至0.58%。与MPPO-VBC/GF材料相比,MPPO-VBC/TAIC/GF复合材料表现出更优异的弯曲与拉伸性能,归因于TAIC引入致密化交联结构及增强的树脂-纤维界面结合作用。本研究制备的复合材料综合性能突出,可适用于超高频通信领域。

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2026年第59卷第6期
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doi: 10.16790/j.cnki.1009-9239.im.2026.06.014
  • 接收时间:2025-09-13
  • 首发时间:2026-09-10
  • 出版时间:2026-06-20
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  • 收稿日期:2025-09-13
  • 修回日期:2025-10-21
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    1四川轻化工大学 材料科学与工程学院,四川 自贡 643000
    2昊华宇航化工有限公司,河南 焦作 454002

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钟家春(1980-),男(汉族),四川自贡人,教授,博士,主要从事特种工程塑料、特种化学品、功能性聚酯和生物基高分子的产业化合成关键技术及其功能复合材料应用的研究。
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2种不同金属材料的力学参数

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Genus
种数
Number of
species
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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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