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Article(id=1210601628638515287, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210601623135581115, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.10.010, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1722182400000, receivedDateStr=2024-07-29, revisedDate=1725292800000, revisedDateStr=2024-09-03, acceptedDate=null, acceptedDateStr=null, onlineDate=1766559520158, onlineDateStr=2025-12-24, pubDate=1729353600000, pubDateStr=2024-10-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766559520158, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766559520158, creator=13701087609, updateTime=1766559520158, updator=13701087609, issue=Issue{id=1210601623135581115, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='10', pageStart='1', pageEnd='141', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766559518846, creator=13701087609, updateTime=1766564021205, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620507448275814, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210601623135581115, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620507448275815, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210601623135581115, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=78, endPage=83, ext={EN=ArticleExt(id=1210601628923727972, articleId=1210601628638515287, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation and performance of fluorinated polythioetherimide with low dielectric constant, columnId=1203281640207393262, journalTitle=Insulating Materials, columnName=Special Issue on High Performance Polyimide Materials, runingTitle=null, highlight=null, articleAbstract=

A series of fluorinated polythioetherimide films were synthesized by copolymerization using 4,4′-diaminodiphenyl sulfide (SDA) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP) as diamine monomers, and 4,4′-biphenylene ether dianhydride (ODPA) as dianhydride monomer. The thermal, electrical, optical properties, and water absorption of the PI films were tested. The results show that the PI films have good thermal, dielectric properties and optical transparency. The glass transition temperature of the film is in the range of 240.7-251.6℃, the 5% and 10% heat loss temperature is above 480℃ and 514℃, respectively, and the residual carbon rate reaches 50% at 800℃. Under the frequency of 1 MHz, the dielectric constant of the PI films are 2.27-2.99, the dielectric loss factors are 0.004 7-0.005 6. The highest transmittance of the films reaches 88.75% in the range of visible light, and the water absorption rate is 0.95%-2.26%.

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采用4,4′-二氨基二苯硫醚（SDA）、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷（HFBAPP）为二胺单体，4,4′-联苯醚二酐（ODPA）为二酐单体进行共聚，制备了一系列含氟聚硫醚酰亚胺薄膜，并对其热学性能、电学性能、光学性能及吸水性进行测试。结果表明：该系列聚酰亚胺薄膜具有良好的耐热性能、介电性能及光学透明性；薄膜的玻璃化转变温度为240.7～251.6℃，5%和10%热失重温度分别高于480℃和514℃，800℃下残碳率达50%；1 MHz下的介电常数为2.27～2.99，介质损耗因数低至0.004 7～0.005 6；可见光范围内，薄膜的最高透过率可达88.75%；薄膜的吸水率为0.95%～2.26%。

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王经逸（1988-），男（汉族），福建泉州人，教授，主要从事功能复合材料的研究。
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陈晓玲（1988-），女（汉族），福建泉州人，讲师，主要从事电子化学品的研究。

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陈晓玲（1988-），女（汉族），福建泉州人，讲师，主要从事电子化学品的研究。

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陈晓玲（1988-），女（汉族），福建泉州人，讲师，主要从事电子化学品的研究。

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language=CN, orderNo=3, keyword=三氟甲基), Keyword(id=1218266781001630432, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601628638515287, language=CN, orderNo=4, keyword=介电常数)], refs=[Reference(id=1218266783425938264, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601628638515287, doi=null, pmid=null, pmcid=null, year=2023, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[1], rfOrder=0, authorNames=韩磊, journalName=null, refType=null, unstructuredReference=韩磊.低介电常数聚酰亚胺薄膜的制备及其性能研究[D].沈阳:沈阳工业大学,2023., articleTitle=低介电常数聚酰亚胺薄膜的制备及其性能研究, refAbstract=null), Reference(id=1218266783497241436, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601628638515287, doi=null, pmid=null, pmcid=null, year=2023, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[1], rfOrder=1, authorNames=HANL, journalName=null, refType=null, 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Physical Review B, 1993,47(20):13395-13400., articleTitle=Frequency dependence of dielectric loss in thin aromatic polyimide films, refAbstract=null), Reference(id=1218266787804791740, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601628638515287, doi=null, pmid=null, pmcid=null, year=2020, volume=53, issue=9, pageStart=1, pageEnd=6, url=null, language=null, rfNumber=[19], rfOrder=35, authorNames=钟绍信, 蒋智杰, 朱亚明, journalName=绝缘材料, refType=null, unstructuredReference=钟绍信,蒋智杰,朱亚明,等.聚苯硫醚低介电改性的研究进展[J].绝缘材料,2020,53(9):1-6., articleTitle=聚苯硫醚低介电改性的研究进展, refAbstract=null), Reference(id=1218266787901260736, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601628638515287, doi=null, pmid=null, pmcid=null, year=2020, volume=53, issue=9, pageStart=1, pageEnd=6, url=null, language=null, rfNumber=[19], rfOrder=36, authorNames=ZHONGS X, JIANGZ J, ZHUY M, journalName=Insulating Materials, refType=null, unstructuredReference=ZHONGS X, JIANGZ J, ZHUY M, et al. 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低介电含氟聚硫醚酰亚胺的制备与性能研究
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陈晓玲 1 , 王经逸 1 , 王志文 1 , 王华欣 1 , 刘凯 2 , 卢鑫 3
绝缘材料 | 高性能聚酰亚胺材料专题 2024,57(10): 78-83
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绝缘材料 | 高性能聚酰亚胺材料专题 2024, 57(10): 78-83
低介电含氟聚硫醚酰亚胺的制备与性能研究
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陈晓玲1, 王经逸1, 王志文1, 王华欣1, 刘凯2, 卢鑫3
作者信息
  • 1黎明职业大学 新材料与鞋服工程学院，福建 泉州 362000
  • 2福建旭丰新材料科技有限公司， 福建 泉州 362000
  • 3福建省橡塑新材料重点实验室，福建 泉州 362000

    • 陈晓玲（1988-），女（汉族），福建泉州人，讲师，主要从事电子化学品的研究。

通讯作者:

王经逸（1988-），男（汉族），福建泉州人，教授，主要从事功能复合材料的研究。
Preparation and performance of fluorinated polythioetherimide with low dielectric constant
Xiaoling CHEN1, Jingyi WANG1, Zhiwen WANG1, Huaxin WANG1, Kai LIU2, Xin LU3
Affiliations
  • 1College of New Materials and Shoes & Clothing Engineering, Liming Vocational University, Quanzhou 362000, China
  • 2Fujian Xufeng New Material Technology Co., Ltd., Quanzhou 362000, China
  • 3Fujian Key Laboratory of Rubber and Plastic New Materials, Quanzhou 362000, China
出版时间: 2024-10-20 doi: 10.16790/j.cnki.1009-9239.im.2024.10.010
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摘要
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采用4,4′-二氨基二苯硫醚（SDA）、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷（HFBAPP）为二胺单体，4,4′-联苯醚二酐（ODPA）为二酐单体进行共聚，制备了一系列含氟聚硫醚酰亚胺薄膜，并对其热学性能、电学性能、光学性能及吸水性进行测试。结果表明：该系列聚酰亚胺薄膜具有良好的耐热性能、介电性能及光学透明性；薄膜的玻璃化转变温度为240.7～251.6℃，5%和10%热失重温度分别高于480℃和514℃，800℃下残碳率达50%；1 MHz下的介电常数为2.27～2.99，介质损耗因数低至0.004 7～0.005 6；可见光范围内，薄膜的最高透过率可达88.75%；薄膜的吸水率为0.95%～2.26%。

聚酰亚胺  /  硫醚基团  /  三氟甲基  /  介电常数

A series of fluorinated polythioetherimide films were synthesized by copolymerization using 4,4′-diaminodiphenyl sulfide (SDA) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP) as diamine monomers, and 4,4′-biphenylene ether dianhydride (ODPA) as dianhydride monomer. The thermal, electrical, optical properties, and water absorption of the PI films were tested. The results show that the PI films have good thermal, dielectric properties and optical transparency. The glass transition temperature of the film is in the range of 240.7-251.6℃, the 5% and 10% heat loss temperature is above 480℃ and 514℃, respectively, and the residual carbon rate reaches 50% at 800℃. Under the frequency of 1 MHz, the dielectric constant of the PI films are 2.27-2.99, the dielectric loss factors are 0.004 7-0.005 6. The highest transmittance of the films reaches 88.75% in the range of visible light, and the water absorption rate is 0.95%-2.26%.

polyimide  /  sulfur ether group  /  trifluoromethyl  /  dielectric constant
陈晓玲, 王经逸, 王志文, 王华欣, 刘凯, 卢鑫. 低介电含氟聚硫醚酰亚胺的制备与性能研究. 绝缘材料, 2024 , 57 (10) : 78 -83 . DOI: 10.16790/j.cnki.1009-9239.im.2024.10.010
Xiaoling CHEN, Jingyi WANG, Zhiwen WANG, Huaxin WANG, Kai LIU, Xin LU. Preparation and performance of fluorinated polythioetherimide with low dielectric constant[J]. Insulating Materials, 2024 , 57 (10) : 78 -83 . DOI: 10.16790/j.cnki.1009-9239.im.2024.10.010
正文
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0 引言
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低介电常数材料通常是指介电常数低于3.9的一类绝缘材料，主要用作集成电路、印刷电路板等的层间介质材料，具有减少信号传输的能量损耗、降低信号延迟、减小串扰干扰等作用[1-2]。聚酰亚胺（PI）因其优异的介电性能在微电子领域备受关注，随着现代微电子工业的发展，集成电路元器件集成度不断提高，加工尺寸不断缩小，易造成电路信号传输的损耗与延迟，降低芯片中层间及金属间PI材料的介电常数可有效解决这一问题。目前，用于降低PI介电常数的方法主要包括在PI分子结构中引入含氟基团、脂环族结构、非平面大共轭结构和在材料中引入多孔结构[3-8]。虽然这些结构的引入能在一定程度上降低PI的介电常数，但通常以牺牲PI其他性能为代价。如PI中多孔结构的增加会造成力学性能下降，而含大体积、非平面结构的单体合成工艺复杂，不利于PI的工业化生产。可见，单独某种结构的引入难以制得具有优良综合性能的低介电PI。
共聚为聚合物的结构改性提供了无限可能，是调控聚合物综合性能的有效途径。含氟单体作为制备低介电聚酰亚胺的重要原料，将其与其他单体共聚，有望获得综合性能优良的低介电PI。黄孝华等[9]合成了一种含三氟甲基及硫醚基团的二胺单体，并将其与6种芳香二酐进行聚合，制备了一系列含氟及硫醚基团的聚酰亚胺，该系列薄膜表现出良好的光学性能，在1 310 nm和1 550 nm光通讯波段的折射率分别为1.540 1～1.614 2和1.538 9～1.612 4，是一种良好的光波导材料。鲁云华等[10]合成了一种新型二胺单体4,4′-双(4-氨基-2-三氟甲基苯氧基)二苯硫醚，将其与均苯四甲酸二酐聚合，所得PI表现出良好的热学稳定性，5%热失重温度超过527℃。可见，通过含氟基团和硫醚的共聚可以获得具有良好光学性能和热学性能的聚酰亚胺，但目前关于含氟聚硫醚聚酰亚胺电学性能的相关研究报道较少。
本文以4,4′-二氨基二苯硫醚（SDA）、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷（HFBAPP）为二胺单体，与4,4′-联苯醚二酐（ODPA）进行共聚，制备一系列含氟聚硫醚酰亚胺薄膜，并对其结构、热学性能、光学性能、电学性能和吸水性进行表征，探讨两种基团对其各项性能的影响，期望通过调控两种二胺单体的比例获得一种综合性能优良的低介电PI。
1 实验
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1.1 原料与试剂
4,4′-二氨基二苯硫醚（SDA，纯度≥99%）、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷（HFBAPP，纯度≥97%）、4,4′-联苯醚二酐（ODPA，纯度≥97%），上海麦克林生化科技有限公司；N,N-二甲基乙酰胺（DMAC，化学纯），西陇科学股份有限公司。
1.2 试样制备
含氟聚硫醚酰亚胺酸的配方如表1所示，制备过程如下：称取配方量的ODPA于100 mL三口烧瓶中，加入溶剂DMAC搅拌至完全溶解。然后缓慢加入配方量的HFBAPP与之反应，反应完全后加入配方量的SDA继续反应，反应结束后所得浅黄色透明黏稠液体即为含氟聚硫醚酰亚胺酸溶液。该反应始终在冰水浴条件下进行，体系固含量控制在25%。
含氟聚硫醚酰亚胺薄膜的制备：将得到的含氟聚硫醚酰亚胺酸溶液用刮刀均匀地刮涂在干净的玻璃板上，放入马弗炉中，依次在50、80、120、150℃下各加热30 min除去溶剂，随后按照梯度升温的方式将其在200℃和250℃下各加热1 h，自然冷却降至室温后取出，并浸泡于100℃的热水中脱膜，将得到的薄膜于100℃下烘干，得到浅色透明含氟聚硫醚酰亚胺薄膜，合成反应方程式如图1所示。
1.3 测试与表征
采用傅里叶变换红外光谱仪（FTIR，Nicolet iS10型，美国赛默飞世尔科技公司）表征PI的结构，扫描范围为400～4 000 cm-1，扫描次数为32次，分辨率为4 cm-1；采用差示扫描量热仪（DSC，Q2000型，美国TA INSTRUMENTS公司）测定PI的玻璃化转变温度，测试温度为室温至350℃，样品质量为 5～10 mg，氮气气氛，氮气流量为50 mL/min，升温速率为5℃/min；采用热失重分析测试仪（TGA，Q5000型，美国TA INSTRUMENTS公司）测试PI的热稳定性，测试温度为室温至800℃，升温速率为20℃/min，氮气气氛，流量为20 mL/min；采用紫外可见光谱（UV-Vis，UV-4802H，尤尼柯（上海）仪器有限公司）测试PI的光学性能，测试波长为190～1 100 nm；采用自动元件分析仪（TH2828s型，常州市同惠电子有限公司）测试PI的介电性能，测试频率为20 Hz～1 MHz，最小分辨率为1 MHz，介电常数的计算公式为式（1）。
ε=kCd/(ε0S)
式（1）中：ε为样品的介电常数；k为修正系数，已知所用仪器k=3.5；C为试样的电容；d为薄膜厚度；ε0为真空介电常数，ε0=8.85×10-12 F/m；S为电极面积，S=2.25 cm2。
根据GB/T 1034—2008测试PI薄膜的吸水率，将薄膜裁剪成60 mm×60 mm的尺寸，用分析天平称量初始质量（m0）并记录，于室温下浸泡24 h，取出后擦除薄膜表面水分，再用分析天平称量薄膜吸水后的质量（m1），通过式（2）计算薄膜的吸水率W，每个薄膜测量3次后取平均值。
W=m1-m0m0×100%
2 结果与讨论
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2.1 FTIR分析
5种PI薄膜的FTIR光谱如图2所示。图2中均显现出聚酰亚胺的特征吸收峰，包括1 777 cm-1和1 713 cm-1处酰亚胺环上羰基（C=O）的对称和不对称伸缩振动吸收峰，1 366 cm-1处酰亚胺环上C-N键的伸缩振动吸收峰以及738 cm-1处酰亚胺环的弯曲振动吸收峰，同时在668 cm-1处可观察到-S-的伸缩振动吸收峰[11]，且随着SDA含量的增加，其强度逐渐增加；在1 100～1 250 cm-1处观察到C-F的伸缩振动吸收峰，且随着配方中HFBAPP含量的降低，其强度逐渐减弱，以上基团特征吸收峰的存在证明了含氟聚硫醚酰亚胺的成功亚胺化。
2.2 热学性能分析
图3为5种PI薄膜的DSC曲线。从图3可以看出，5种PI的玻璃化转变温度为240.7～251.6℃，虽然柔性基团的引入会降低聚酰亚胺的耐热性，但随着SDA含量的增加，PI的玻璃化转变温度却表现出先增后降的趋势，当nSDA∶nHFBAPP=3∶2时，薄膜的Tg最高，可达251.6℃。对比SDA和HFBAPP两种单体结构可知，SDA结构中含有一个硫醚键，而HFBAPP中含有两个氧醚键和两个大体积侧基三氟甲基，随着分子结构中的氧醚键逐渐被硫醚键代替，PI中柔性基团数量下降，刚性增加，耐热性提高，但大体积侧基三氟甲基含量的减少，降低了PI分子链的位阻效应，使得PI分子链运动更为容易，反而降低了PI的耐热性，因此，在两种基团数量变化的综合作用下，PI的耐热性出现先上升后下降的趋势。
图4为5种PI薄膜的热重分析曲线，相关数据列于表2中。因为SDA中的硫醚键和HFBAPP中的氧醚键均为不耐热的弱键，受热时易断裂，加上含氟基团的引入，减弱了PI分子间的电荷转移络合（CTC）作用，不利于PI热稳定性能的提高，所以从图4和表2可以看出5种PI薄膜在较低温度下便开始分解，5%热失重温度（T5%）为482.93～493.08℃，10%热失重温度（T10%）为514.91～522.32℃，当nSDA∶nHFBAPP=1∶1时，薄膜（PI-S5）的T5%和T10%最高，分别为493.08℃和522.32℃。虽然SDA含量的增大在一定程度上提高了分子的刚性，同时侧基三氟甲基的减少使得分子堆砌更加紧密，有利于热稳定性的提高，但硫醚键的键能较氧醚键小，更易氧化，其含量较高时会加速PI的分解，这也是5种PI热分解温度随硫醚基团含量提高先升高后降低的缘故。同时，随着结构中O、F等杂原子含量的减少，800℃时的残留率递增，且均大于50%。
2.3 电学性能分析
图5(a)和(b)分别为5种PI薄膜介电常数和介质损耗因数随频率变化的关系图。从图5可以看出，随着频率的升高，各PI薄膜的介电常数和介质损耗因数基本保持不变，表现出良好的电学稳定性。 1.0 MHz频率下，5种PI薄膜的介电常数为2.27～2.99，介质损耗因数为0.004 7～0.005 6。
聚酰亚胺的介电常数主要与分子极化率和分子自由度有关[12-13]，材料中可以降低分子极化率的强电负性原子含量越高，或者分子自由体积越大，材料的介电常数越小。在本研究制备的PI中影响介电常数的主要结构有硫醚基团、氧醚基团和三氟甲基，随着SDA含量的增加，PI分子中的氧醚基团和三氟甲基含量减少，而硫醚基团含量增多，硫元素比氧元素更易失去电子，使得PI的分子极性增强，分子极化率增大[14-15]；同时具有高电负性的氟原子含量降低，也使得PI的极化率增大；此外，三氟甲基含量的减少，降低了PI分子的摩尔自由体积，进一步提高了极化分子密度[16-17]，以上因素均会导致PI介电常数的增大，因此，随着SDA含量的增加，PI的介电常数逐渐增大。
介质损耗因数是评价PI介电性能的另一重要指标。从图5可以看出，PI-S2～PI-S6的介质损耗因数随SDA含量的增加而增大，这是由于当SDA的含量较低时，三氟甲基对介质损耗因数的影响占主导地位，随着体系中三氟甲基含量的降低，PI分子的CTC作用增强，分子混合层间堆砌更为紧密，产生的偶极矩不能及时响应，导致介质损耗因数增大[18]；当nSDA∶nHFBAPP=4∶1时，薄膜（PI-S8）的介质损耗因数减小，这可能是由于高含量的SDA提高了PI分子结构的对称性，有利于极性偶极矩的相互抵消，且极化率较高的S原子位于主链上，取向困难，有利于介质损耗因数的减小[19]。
2.4 光学性能分析
5种PI薄膜的紫外可见光谱如图6所示，相关光学性能数据如表3所示。从图6和表3可以看出，5种PI薄膜均表现出良好的光学透明性，可见光范围内的最大透过率（Tmax）均在85%以上，这归因于柔性硫醚基团和大体积侧基三氟甲基的引入，破坏了大分子链的紧密堆积，提高了薄膜的透光性；同时，具有强电负性的氟原子可以破坏PI分子链中具有发色功能的共轭结构，减少分子内或分子间电荷转移络合物的形成，从而降低PI的光学损耗，提高透明性。由于三氟甲基的电负性更强，随着PI分子中硫醚基团含量的增加，PI的光学性能呈下降趋势。
2.5 吸水性分析
5种PI薄膜的吸水率如表4所示。从表4可以看出，5种薄膜的吸水率随SDA含量的增加呈先上升后下降的趋势。PI的吸水性主要受到亲水基团数量和分子链堆砌密度的影响。当亲水基团含量增多，或分子链的堆砌密度变小时，PI的吸水性提高。硫醚基团的亲水能力比三氟甲基强，其含量的提高会造成PI吸水率的增大，但是三氟甲基具有较大的体积，含量少时分子堆砌紧密，会降低吸水性，因此在两种因素的综合作用下，PI的吸水率呈先上升后下降的趋势。
3 结论
收起
（1）随着SDA含量的增加，PI薄膜的玻璃化转变温度及热失重温度呈先上升后下降的趋势，当nSDA∶nHFBAPP=3∶2时，薄膜（PI-S6）的Tg最高，可达251.6℃；当nSDA∶nHFBAPP=1∶1时，薄膜（PI-S5）的5%和10%热失重温度最高，分别为493.08℃和522.32℃，说明硫醚基团的引入对提高含氟聚酰亚胺的热性能具有一定作用。
（2）5种薄膜的介电常数均小于3，具有良好的介电性能，当nSDA∶nHFBAPP=1∶4时，薄膜（PI-S2）在1.0 MHz下的介电常数为2.27，介质损耗因数为0.004 7，介电性能总体表现最佳。
（3）5种含氟聚硫醚酰亚胺薄膜的光学透过率均高于85%。随着PI结构中硫醚基团含量的增加，薄膜的紫外透过率略有下降，说明相比于硫醚基团，三氟甲基的引入更有利于提高PI的光学性能。
（4）SDA中的硫醚基团和HFBAPP中的醚键都具有较强的吸水能力，不利于PI吸水性的降低，随着SDA含量的提高，薄膜的吸水率先上升后下降，均在0.95%～2.26%。
基金
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  • 黎明职业大学科研基金资助项目(LMPT21001)
  • 福建省中青年教师教育科研项目(JAT191449)
文献
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2024年第57卷第10期
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doi: 10.16790/j.cnki.1009-9239.im.2024.10.010
  • 接收时间：2024-07-29
  • 首发时间：2025-12-24
  • 出版时间：2024-10-20
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  • 收稿日期：2024-07-29
  • 修回日期：2024-09-03
基金
黎明职业大学科研基金资助项目(LMPT21001)
福建省中青年教师教育科研项目(JAT191449)
作者信息
    1黎明职业大学 新材料与鞋服工程学院，福建 泉州 362000
    2福建旭丰新材料科技有限公司， 福建 泉州 362000
    3福建省橡塑新材料重点实验室，福建 泉州 362000

通讯作者:

王经逸（1988-），男（汉族），福建泉州人，教授，主要从事功能复合材料的研究。
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
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光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
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