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Article(id=1242756976950755641, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1242756974576775191, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2021.11.009, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1612454400000, receivedDateStr=2021-02-05, revisedDate=1615478400000, revisedDateStr=2021-03-12, acceptedDate=null, acceptedDateStr=null, onlineDate=1774225952613, onlineDateStr=2026-03-23, pubDate=1637510400000, pubDateStr=2021-11-22, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1774225952613, onlineIssueDateStr=2026-03-23, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1774225952612, creator=13701087609, updateTime=1774225952612, updator=13701087609, issue=Issue{id=1242756974576775191, tenantId=1146029695717560320, journalId=1149653034449285133, year='2021', volume='54', issue='11', pageStart='1', pageEnd='139', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1774225952044, creator=13701087609, updateTime=1774226047274, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1242757374059066044, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1242756974576775191, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1242757374059066045, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1242756974576775191, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=69, endPage=74, ext={EN=ArticleExt(id=1242756977655398733, articleId=1242756976950755641, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation and Properties of Quinoline-imidized Transparent Polyimide at Low Temperature, columnId=1198664996516360309, journalTitle=Insulating Materials, columnName=Polyimide Film Special Issue, runingTitle=null, highlight=null, articleAbstract=

A polyamide acid was prepared using 4,4′-diamino-2,2′-bistrifluoromethyl benzene (TFMB) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) as raw materials. The azocyclic quinoline (QL) was used to promote its imidization at lower temperature, and the amount of QL, maximum imidization temperature, and curing time were optimized. The imidization degree of polyimide (PI) film was determined by infrared spectroscopy. The results show that when the molar addition of QL is twice that of BPDA, the polyamide acid is only cured for 4 h at 200℃, the imidization degree is more than 99%. After treated at 250℃ for 0.5 h to remove the residual solvent and QL, the thermal stability of the PI is improved greatly, while its light transmittance is basically unchanged. Compared with the PI film imidized at 300℃, the 5% weight loss temperature (T5%), glass transition temperature (Tg), and tensile strength of the PI film whose imidization promoted by QL decrease slightly, but the elongation at break increases, and the light transmittance at 400 nm increases from 4.5% to 34.4%.

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以4，4′-二氨基-2，2′-双三氟甲基苯（TFMB）和3，3′，4，4′-联苯四羧酸二酐（BPDA）为原料制备聚酰胺酸，采用氮杂环类喹啉（QL）促进其在较低温度下亚胺化，并对QL用量、最高亚胺化温度及固化时间进行了优化。利用红外光谱法测定所得聚酰亚胺（PI）薄膜的亚胺化程度。结果表明：当QL添加量为BPDA物质的量的两倍时，聚酰胺酸在200℃下固化4 h，亚胺化程度即可超过99%；在250℃下处理0.5 h除去残留溶剂和QL后，PI的热稳定性大幅提高，而透光率基本不变。与300℃高温下亚胺化制备的PI薄膜相比，采用QL促进亚胺化的PI薄膜5%热失重温度（T5%）、玻璃化转变温度（Tg）和拉伸强度仅略有下降，而断裂伸长率提高，400 nm处的透光率从4.5%提高到34.4%。

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刘述梅（1968-），女（汉族），湖南岳阳人，教授，主要从事高分子合成、改性与成型加工的研究。
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马诚（1996-），男（汉族），湖北武汉人，硕士生，主要从事高分子合成改性的研究。

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马诚（1996-），男（汉族），湖北武汉人，硕士生，主要从事高分子合成改性的研究。

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马诚（1996-），男（汉族），湖北武汉人，硕士生，主要从事高分子合成改性的研究。

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journalId=1149653034449285133, articleId=1242756976950755641, language=EN, label=Tab.1, caption=TGA and Tg parameters of Q-PI, Q-PI-250, and PI-0, figureFileSmall=null, figureFileBig=null, tableContent=
样品T5%/℃T10%/℃残留率/%Tg/℃
PI-0580.3608.160.5389.8
Q-PI556.9599.358.2386.2
Q-PI-250578.6606.560.0387.5
), ArticleFig(id=1245100058211893796, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756976950755641, language=CN, label=表1, caption=

Q-PI、Q-PI-250和PI-0热失重及Tg参数

, figureFileSmall=null, figureFileBig=null, tableContent=
样品T5%/℃T10%/℃残留率/%Tg/℃
PI-0580.3608.160.5389.8
Q-PI556.9599.358.2386.2
Q-PI-250578.6606.560.0387.5
), ArticleFig(id=1245100058279002663, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756976950755641, language=EN, label=Tab.2, caption=Tensile properties of Q-PI, Q-PI-250, and PI-0 films, figureFileSmall=null, figureFileBig=null, tableContent=
样品拉伸强度/MPa拉伸模量/GPa断裂伸长率/%
PI-0183.5±1.657.9±0.136.0±0.22
Q-PI174.6±1.447.3±0.178.4±0.24
Q-PI-250175.8±1.467.5±0.167.1±0.27
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Q-PI、Q-PI-250和PI-0薄膜的拉伸性能

, figureFileSmall=null, figureFileBig=null, tableContent=
样品拉伸强度/MPa拉伸模量/GPa断裂伸长率/%
PI-0183.5±1.657.9±0.136.0±0.22
Q-PI174.6±1.447.3±0.178.4±0.24
Q-PI-250175.8±1.467.5±0.167.1±0.27
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样品λ0/nmT400/%T450/%
PI-0342.34.578.7
Q-PI344.634.584.3
Q-PI-250344.634.484.2
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Q-PI、Q-PI-250和PI-0薄膜的透光性能

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样品λ0/nmT400/%T450/%
PI-0342.34.578.7
Q-PI344.634.584.3
Q-PI-250344.634.484.2
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喹啉低温亚胺化透明聚酰亚胺的制备与性能
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马诚 , 刘述梅 , 赵建青 , 陈植耿 , 黄皓浩
绝缘材料 | 聚酰亚胺薄膜专题 2021,54(11): 69-74
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绝缘材料 | 聚酰亚胺薄膜专题 2021, 54(11): 69-74
喹啉低温亚胺化透明聚酰亚胺的制备与性能
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马诚, 刘述梅, 赵建青, 陈植耿, 黄皓浩
作者信息
  • 华南理工大学 材料科学与工程学院，广东 广州 510640

    • 马诚（1996-），男（汉族），湖北武汉人，硕士生，主要从事高分子合成改性的研究。

通讯作者:

刘述梅（1968-），女（汉族），湖南岳阳人，教授，主要从事高分子合成、改性与成型加工的研究。
Preparation and Properties of Quinoline-imidized Transparent Polyimide at Low Temperature
Cheng MA, Shumei LIU, Jianqing ZHAO, Zhigeng CHEN, Haohao HUANG
Affiliations
  • College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China
出版时间: 2021-11-22 doi: 10.16790/j.cnki.1009-9239.im.2021.11.009
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摘要
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以4，4′-二氨基-2，2′-双三氟甲基苯（TFMB）和3，3′，4，4′-联苯四羧酸二酐（BPDA）为原料制备聚酰胺酸，采用氮杂环类喹啉（QL）促进其在较低温度下亚胺化，并对QL用量、最高亚胺化温度及固化时间进行了优化。利用红外光谱法测定所得聚酰亚胺（PI）薄膜的亚胺化程度。结果表明：当QL添加量为BPDA物质的量的两倍时，聚酰胺酸在200℃下固化4 h，亚胺化程度即可超过99%；在250℃下处理0.5 h除去残留溶剂和QL后，PI的热稳定性大幅提高，而透光率基本不变。与300℃高温下亚胺化制备的PI薄膜相比，采用QL促进亚胺化的PI薄膜5%热失重温度（T5%）、玻璃化转变温度（Tg）和拉伸强度仅略有下降，而断裂伸长率提高，400 nm处的透光率从4.5%提高到34.4%。

聚酰亚胺  /  喹啉  /  低温亚胺化  /  断裂伸长率  /  透光性

A polyamide acid was prepared using 4,4′-diamino-2,2′-bistrifluoromethyl benzene (TFMB) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) as raw materials. The azocyclic quinoline (QL) was used to promote its imidization at lower temperature, and the amount of QL, maximum imidization temperature, and curing time were optimized. The imidization degree of polyimide (PI) film was determined by infrared spectroscopy. The results show that when the molar addition of QL is twice that of BPDA, the polyamide acid is only cured for 4 h at 200℃, the imidization degree is more than 99%. After treated at 250℃ for 0.5 h to remove the residual solvent and QL, the thermal stability of the PI is improved greatly, while its light transmittance is basically unchanged. Compared with the PI film imidized at 300℃, the 5% weight loss temperature (T5%), glass transition temperature (Tg), and tensile strength of the PI film whose imidization promoted by QL decrease slightly, but the elongation at break increases, and the light transmittance at 400 nm increases from 4.5% to 34.4%.

polyimide  /  quinoline  /  low-temperature imidization  /  elongation at break  /  light transmittance
马诚, 刘述梅, 赵建青, 陈植耿, 黄皓浩. 喹啉低温亚胺化透明聚酰亚胺的制备与性能. 绝缘材料, 2021 , 54 (11) : 69 -74 . DOI: 10.16790/j.cnki.1009-9239.im.2021.11.009
Cheng MA, Shumei LIU, Jianqing ZHAO, Zhigeng CHEN, Haohao HUANG. Preparation and Properties of Quinoline-imidized Transparent Polyimide at Low Temperature[J]. Insulating Materials, 2021 , 54 (11) : 69 -74 . DOI: 10.16790/j.cnki.1009-9239.im.2021.11.009
正文
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0 引言
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聚酰亚胺（PI）凭着优异的力学性能、耐化学性能和介电性能等，在微电子器件、液晶显示等领域获得广泛的应用[1-2]。聚酰亚胺的制备工艺中，传统的两步法需要对前驱体聚酰胺酸（PAA）进行高温亚胺化处理（一般超过300℃），这种高温处理的方法不仅能耗大，而且易造成聚酰亚胺分子链的断裂和降解[3]、氧化黄变[4]，引起薄膜透光性降低。此外，在封装过程中，高温容易破坏电子元器件的表面，如在彩色液晶显示器中作取向膜时，PAA亚胺化温度超过200℃则会使滤色镜脱色[4]。因此，探究PI亚胺化温度不高于200℃的方法具有极其重要的意义，尤其是对于具备无色透明要求的应用领域。
羟基羧酸、叔胺[5]、氮杂环类等化合物可以促进PAA在较低温度下实现亚胺化。A NELSON等[6]探索了氮杂环类苯并咪唑对不同PAA体系亚胺化的作用，发现添加苯并咪唑后，PAA在80℃下亚胺化程度达到了65%。喹啉（QL）是一种具有弱碱性和吸水性的氮杂环类化合物，在一步法制备PI薄膜中有应用[7-8]，但在两步法中却鲜有报道。本研究选用QL作为亚胺化助剂，研究其对4,4′-二氨基-2,2′-双三氟甲基苯（TFMB）-3,3′,4,4′-联苯四羧酸二酐（BPDA）型PAA亚胺化过程的影响，并将所得PI薄膜与常规高温热亚胺化薄膜的性能进行对比分析，为无色透明PI薄膜的制备提供有效的方法。
1 实验
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1.1 主要原材料
4,4′-二氨基-2,2′-双三氟甲基苯（TFMB），北京伊诺凯科技有限公司，80℃真空干燥12 h；3,3′,4,4′-联苯四羧酸二酐（BPDA），梯希爱（上海）化成工业发展有限公司，140℃真空干燥12 h；N,N-二甲基乙酰胺（DMAc），分析纯，广州化学试剂厂，氢化钙干燥24 h，减压蒸馏；喹啉（QL），梯希爱（上海）化成工业发展有限公司。
1.2 PI薄膜的制备
在室温、氮气氛围下，将2.00 g（6.24 mmol）TFMB溶于28.16 g DMAc中，然后一次性加入1.84 g（6.26 mmol）BPDA，搅拌12 h制得PAA溶液。取部分该溶液加入QL后于氮气保护下搅拌4 h，制得含有QL的PAA（Q-PAA）溶液。
采用溶液流延法，将上述Q-PAA溶液均匀地涂覆于干燥洁净的玻璃板上，在真空烘箱中静置至无气泡且溶液充分流平，随后升温至70℃真空干燥4 h，再在氮气氛围中采用梯度升温法进行热亚胺化处理，得到Q-PI薄膜，其合成反应式如图1所示。
1.3 测试与表征
傅里叶红外光谱分析：德国Bruker公司Vertor-22型傅里叶变换红外光谱仪（FT-IR），采用全反射模式，扫描范围为500～3 700 cm-1，薄膜厚度为30 μm。通过文献[9-11]方法计算PI薄膜的亚胺化程度（degree of imidization，ID）：选用1 357 cm-1处C-N的伸缩振动吸收峰为目标峰，以1 489 cm-1处对应的苯环骨架上C-C的伸缩振动吸收峰为内标峰，定义亚胺化程度为式（1）。
ID=S1357/S1489CS1357/S1489C0×100%
式（1）中：S1357和S1489分别表示波数1375 cm-1和1489 cm-1处吸收峰的面积；C为不同亚胺化条件下制得的PI薄膜；C0为300℃下亚胺化完全的标准PI薄膜。
热重分析仪（TGA）：NETZSCH公司TG-209F1型热重分析仪，氮气氛围，升温速率为20℃/min。
动态热机械分析（DMA）：TA公司DMA-Q800型热机械分析仪，升温速率为5℃/min，氮气气氛，温度范围为30～400℃。
拉伸性能测试：Instron公司5967型万能材料试验机，拉伸速率为8 mm/min。
紫外-可见光吸收光谱测试：日本Hitachi公司UV-3010型紫外-可见分光光度计，扫描波长为300～800 nm。
2 结果与讨论
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2.1 低温亚胺化条件的探索
PAA环化脱水是一个复杂的过程，氮杂环类QL的促进作用主要基于以下两点：①QL有一定的亲核性，易与酰胺基上的氢原子结合后离去，致使酰胺基上氮原子的亲核性增加，进攻羧基上的碳原子，使羟基离去，实现脱水闭环，这一过程如图2所示；②QL具有吸水性，在亚胺化反应中可吸收环化反应生成的小分子水，促进反应正向进行。
QL促进PAA亚胺化主要的影响因素有QL用量、最高亚胺化温度及固化时间，下面重点探索这3个因素与PAA亚胺化程度的关系，以综合时间成本，在尽可能低的温度下制备出亚胺化完全的PI薄膜。
2.1.1 最高亚胺化温度（Tmax）的影响
固定QL、二酐摩尔比为2∶1，对Q-PAA按100℃/1 h+150℃/1 h+Tmax/1 h的升温程序进行亚胺化，控制Tmax分别为180、200、220、240℃，得到4种Q-PI薄膜，它们的反射红外光谱如图3所示。同时对未加QL的PAA控制Tmax为180、200、220、240、300℃分别进行亚胺化，所得PI薄膜的反射红外光谱如图4所示。
从图4可以看出，PI谱图上1 540 cm-1（C-NH）和1 680 cm-1（C=O（CONH））处代表酰胺酸的特征吸收峰强度随Tmax的增大逐渐减弱，而代表酰亚胺环的特征吸收峰（1 778 cm-1、1 357 cm-1）强度则随着Tmax的增大逐渐增强。然而，即使Tmax为240℃时，酰胺酸特征吸收峰仍然存在，直到Tmax提高至300℃才基本消失。而图3的Q-PI谱图中，各Tmax下1 680 cm-1处的吸收峰均不明显，1 540 cm-1处代表酰胺酸的特征吸收峰随着Tmax的增大不断减弱，当Tmax为240℃时，酰胺酸特征吸收峰几乎完全消失，说明此温度下Q-PAA亚胺化完全。
利用式（1）计算得到两个系列PI薄膜的ID，并对Tmax作图，结果如图5所示。从图5可以清楚地看到，随着Tmax的增大，Q-PI的ID不断提高，当Tmax为180℃时，ID达到了81%，而Tmax升到240℃时，ID超过99%。相比之下，PI在Tmax为180℃时ID还不到45%，Tmax升至240℃时ID也仅为72%。由此可得出，QL对PAA的亚胺化有明显的促进作用，按设定的升温程序在240℃下便可实现完全亚胺化。
2.1.2 QL用量的影响
QL通过促进酰胺酸的环化脱水和吸收生成的水分促进亚胺化反应进行，其添加量直接影响PAA的亚胺化效果。控制QL、二酐摩尔比为1.0、1.5、1.8、2.0和2.2，制得5种Q-PAA，按100℃/1 h+150℃/1 h+200℃/1 h的升温程序进行亚胺化，所得Q-PI薄膜的ID与QL/二酐摩尔比的关系如图6所示。从图6可以看出，两者摩尔比小于2.0时，Q-PI的ID随比值的增加而提高。这是因为QL的物质的量尚未达到可被亲核攻击的酸酐的量，在这一阶段，QL用量越大，亲核攻击造成的酰胺酸环化脱水越多，且吸水作用越强，促进亚胺化效果越好。而当两者摩尔比为2.2时，ID不再增加，对提升Q-PAA的固化作用不明显。由此可知，在相同的亚胺化条件下，QL的最佳添加量为二酐物质的量的两倍。
2.1.3 Tmax下固化时间的影响
对于QL物质的量为二酐两倍的Q-PAA溶液，先按100℃/1 h+150℃/1 h升温，然后在180℃和200℃下增加固化时间，探讨两种Tmax下完全亚胺化所需时间，所得Q-PI的ID随固化时间的变化如图7所示。从图7可以看出，在180℃和200℃下延长固化时间，所得Q-PI的ID均不断增加。但是180℃下，固化时间为4 h时Q-PI的ID不到90%，延长至10 h时ID也仅达到96.6%；而200℃下固化4 h，Q-PI的ID已超过99%，继续延长固化时间，ID无明显变化，可认为已实现完全亚胺化。由此可知，在Tmax为200℃下固化4 h可使Q-PAA亚胺化完全。
2.2 低温亚胺化PI的性能
根据上述结果，按两倍二酐物质的量添加QL制得Q-PAA，按100℃/1 h+150℃/1 h+200℃/4 h程序升温亚胺化得到Q-PI。另对未添加QL的PAA按100℃/1 h+150℃/1 h+200℃/1 h+250℃/1 h+300℃/1 h程序升温制得PI薄膜（PI-0）进行对比。下面对Q-PI与PI-0的热性能、力学性能与透光性能进行比较，以评价低温亚胺化PI的性能。
2.2.1 热性能
Q-PI与PI-0的TGA曲线如图8所示。从图8可以看到，Q-PI在220℃时开始有轻微的质量损失，损失2.3%后，在250℃热失重逐渐趋于平缓。鉴于DMAc溶剂能够与PAA形成稳定的络合物[12]以及QL的沸点接近240℃，而Q-PI最高固化温度只有200℃，故该失重应该是由残留的溶剂和QL引起。为消除两者的影响，将Q-PI于250℃真空烘箱中再处理0.5 h，所得Q-PI-250的TGA曲线与PI-0比较如图9所示，并由DMA测得Tg，Q-PI、Q-PI-250及PI-0的热失重参数和Tg数据列于表1。
从图9和表1可知，经过250℃处理0.5 h后，Q-PI的热稳定性得到提高，500℃的失重曲线与PI-0的基本重合，表明残留的溶剂和QL基本除尽。5%失重温度（T5%）从556.9℃提高到578.6℃，10%失重温度（T10%）从599.3℃提高到606.5℃，Tg也提高了1.3℃。相比于PI-0，Q-PI-250在T5%及T10%上仅略有下降。随着亚胺化温度的提高，PI分子链的有序化和堆砌密度增加，进而导致Tg增大[13]，Q-PI-250的Tg较经300℃处理过的PI-0仅低2.3℃。
2.2.2 力学性能
Q-PI、Q-PI-250薄膜的应力-应变曲线与PI-0比较如图10所示，拉伸性能数据见表2。由图10及表2可知，Q-PI的断裂伸长率明显高于PI-0和Q-PI-250，这可能是残留溶剂的增塑作用所致[14]。Q-PI-250的断裂伸长率较Q-PI略有下降，但仍高于PI-0；拉伸强度、拉伸模量增加，十分接近于PI-0的结果，力学性能良好。
2.2.3 透光性能
可见光波长范围内具有高透过率是PI在柔性电子器件中应用的关键，厚度为30 μm 的Q-PI、Q-PI-250和PI-0薄膜的紫外-可见光谱如图11所示，将截止波长（λ0）、400 nm和450 nm处的透光率结果列于表3。从图11及表3可知，低温亚胺化对PI薄膜的透光性能有明显的提高，在400 nm处，PI-0的透光率只有4.5%，而Q-PI的透光率则达到了34.5%；在450 nm处，Q-PI的透光率从PI-0的78.7%增加到84.3%。这主要是较低温度下亚胺化，PI分子链间电子转移络合效应有所减弱。通过对比Q-PI和Q-PI-250的透光率可知，将薄膜在250℃下处理0.5 h不会降低透光性能。图11还展示了厚度30 μm的Q-PI、Q-PI-250及PI-0薄膜的实物照片，可以较为明显地看到Q-PI-250与Q-PI的透明性基本相同，且较PI-0颜色浅。
3 结论
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（1）TFMB-BPDA型PAA中按两倍二酐摩尔量添加氮杂环类喹啉，在200℃下固化4 h，可制得亚胺化程度超过99%的Q-PI薄膜，进一步将其在250℃下处理0.5 h，可除去残留溶剂和喹啉，所得Q-PI-250在T5%和Tg上均得到提高，与PI-0相比，T5%和Tg仅分别下降1.7℃和2.3℃，热稳定性良好。
（2）Q-PI的断裂伸长率为8.4%，明显高于PI-0；Q-PI-250的断裂伸长率下降至7.1%，但拉伸强度、拉伸模量增加，与PI-0的结果趋近，力学性能良好。
（3）Q-PI-250与Q-PI透明性基本相同，相比于PI-0，两者透光性能显著提高，400 nm处Q-PI-250的透光率从PI-0的4.5%提高到34.4%，450 nm处的透光率从78.7%提高到84.2%。
基金
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  • 广东省重点领域研发计划项目(2019B010940001)
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2021年第54卷第11期
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doi: 10.16790/j.cnki.1009-9239.im.2021.11.009
  • 接收时间：2021-02-05
  • 首发时间：2026-03-23
  • 出版时间：2021-11-22
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  • 收稿日期：2021-02-05
  • 修回日期：2021-03-12
基金
广东省重点领域研发计划项目(2019B010940001)
作者信息
    华南理工大学 材料科学与工程学院，广东 广州 510640

通讯作者:

刘述梅（1968-），女（汉族），湖南岳阳人，教授，主要从事高分子合成、改性与成型加工的研究。
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2种不同金属材料的力学参数
科
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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