Article(id=1210601630274293907, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210601623135581115, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.10.002, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1709654400000, receivedDateStr=2024-03-06, revisedDate=1715184000000, revisedDateStr=2024-05-09, acceptedDate=null, acceptedDateStr=null, onlineDate=1766559520548, onlineDateStr=2025-12-24, pubDate=1729353600000, pubDateStr=2024-10-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766559520548, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766559520548, creator=13701087609, updateTime=1766559520548, 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=9, endPage=15, ext={EN=ArticleExt(id=1210601630584672417, articleId=1210601630274293907, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation and properties of copolyimide films containing pyridine ring structures, columnId=1203281640207393262, journalTitle=Insulating Materials, columnName=Special Issue on High Performance Polyimide Materials, runingTitle=null, highlight=null, articleAbstract=

Firstly, a Y-shape diamine monomer 4-(4′-tertbutyl)phenyl-2,6-di(4′-aminophenyl)pyridine (TPAPP) containing pyridine ring structure and tertbutyl group was synthesized. Then, it was polymerized with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 4,4′-(4,4′-isopropyldiphenyloxy)bis(phthalic anhydride) (BPADA), and a series of copolyimide (PI) films were prepared by thermal imidization. The structure and optical, mechanical, and thermal properties as well as solubility of the PI films were investigated by infrared spectroscopy, X-ray diffraction, UV visible spectra, tensile tests, dynamic thermo-mechanical analysis, thermogravimetric analysis, and solubility tests. The results show that as the molar ratio of TPAPP increases, the optical transparency and glass transition temperature of the copolyimide films exhibit an increasing trend. When the molar ratio of diamine and dianhydride is 5:5, the copolyimide film shows the best mechanical properties, with the tensile strength of 144.9 MPa, the Young's modulus of 3.4 GPa, and the elongation at break of 9.3%. In addition, these copolyimides demonstrate good solubility in aprotic polar solvents.

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首先,合成了一种同时含有吡啶环结构和叔丁基的“Y型”二胺单体4-(4′-叔丁基)苯基-2,6-二(4′-氨基苯基)吡啶(TPAPP),然后与2,2-双(3-氨基-4-羟基苯基)六氟丙烷(6FAP)和4,4′-(4,4′-异丙基二苯氧基)双(邻苯二甲酸酐)(BPADA)聚合,经热酰亚胺化制备出一系列共聚聚酰亚胺(PI)薄膜。通过红外光谱、X-射线衍射、紫外-可见光谱、拉伸测试、动态热机械分析、热重分析和溶解性测试,对PI薄膜的结构和光学性能、力学性能、热性能及溶解性进行研究。结果表明:随着TPAPP摩尔分数的增加,共聚聚酰亚胺薄膜的光学透明性和玻璃化转变温度均表现出增加趋势。当二胺与二酐的物质的量之比为5∶5时,共聚聚酰亚胺薄膜的力学性能最好,拉伸强度达到144.9 MPa,杨氏模量为3.4 GPa,断裂伸长率可达9.3%。此外,这些共聚聚酰亚胺在非质子极性溶剂中均表现出较好的溶解性。

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李品儒(2000-),女(汉族),辽宁庄河人,硕士生,研究方向为功能性聚酰亚胺材料的制备;

肖国勇(1973-),男(汉族),辽宁台安人,副教授,研究方向为功能性高分子材料的开发。

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李品儒(2000-),女(汉族),辽宁庄河人,硕士生,研究方向为功能性聚酰亚胺材料的制备;

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李品儒(2000-),女(汉族),辽宁庄河人,硕士生,研究方向为功能性聚酰亚胺材料的制备;

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肖国勇(1973-),男(汉族),辽宁台安人,副教授,研究方向为功能性高分子材料的开发。

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肖国勇(1973-),男(汉族),辽宁台安人,副教授,研究方向为功能性高分子材料的开发。

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Preparation and properties of copolyimide film materials containing pyridine rings[D]. Anshan: University of Science and Technology Liaoning,2022., articleTitle=Preparation and properties of copolyimide film materials containing pyridine rings, refAbstract=null), Reference(id=1218266790094881749, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601630274293907, doi=null, pmid=null, pmcid=null, year=2023, volume=683, issue=null, pageStart=121764, pageEnd=null, url=null, language=null, rfNumber=[24], rfOrder=32, authorNames=YERZHANKYZYA, WANGY G, XUF, journalName=Journal of Membrane Science, refType=null, unstructuredReference=YERZHANKYZYA, WANGY G, XUF, et al. Structural evolution and gas separation properties of thermally rearranged polybenzoxazole (TR-PBO), polymer-carbon transition (PCT) and early-stage carbon (ESC) membranes derived from a 6FDA-hydroxyl-functionalized Tröger's base polyimide[J]. Journal of Membrane Science,2023,683:121764., articleTitle=Structural evolution and gas separation properties of thermally rearranged polybenzoxazole (TR-PBO), polymer-carbon transition (PCT) and early-stage carbon (ESC) membranes derived from a 6FDA-hydroxyl-functionalized Tröger's base polyimide, refAbstract=null)], funds=[Fund(id=1218266785426621306, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601630274293907, awardId=22278051, language=CN, fundingSource=国家自然科学基金面上项目(22278051), fundOrder=null, country=null), Fund(id=1218266785514701693, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601630274293907, awardId=LJKMZ20220659, language=CN, fundingSource=辽宁省教育厅项目(LJKMZ20220659), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1218266777688130140, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601630274293907, xref=null, ext=[AuthorCompanyExt(id=1218266777692324445, 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样品数均分子量(Mn)重均分子量(Mw)分子量分布
PAA(6-T-B)-10∶0128 947178 2341.348 2
PAA(6-T-B)-7∶3114 382148 8281.339 5
PAA(6-T-B)-5∶594 621115 9831.330 8
PAA(6-T-B)-3∶782 17495 8791.328 4
PAA(6-T-B)-0∶1066 20687 3141.318 8
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PAA的分子量

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样品数均分子量(Mn)重均分子量(Mw)分子量分布
PAA(6-T-B)-10∶0128 947178 2341.348 2
PAA(6-T-B)-7∶3114 382148 8281.339 5
PAA(6-T-B)-5∶594 621115 9831.330 8
PAA(6-T-B)-3∶782 17495 8791.328 4
PAA(6-T-B)-0∶1066 20687 3141.318 8
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样品λc/nmT450/%Tg/℃拉伸强度/MPa杨氏模量/GPa断裂伸长率/%
PI(6-T-B)-10∶037880.7253101.7±2.02.8±0.27.2±0.2
PI(6-T-B)-7∶337681.7271122.5±1.02.8±0.18.6±0.1
PI(6-T-B)-5∶538482.8275144.9±1.03.4±0.29.3±0.1
PI(6-T-B )-3∶738384.1276143.7±2.03.1±0.18.9±0.2
PI(6-T-B)-0∶1038685.3288104.7±2.02.7±0.28.3±0.1
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PI(6-T-B)共聚物薄膜的光学、力学和热性能

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样品λc/nmT450/%Tg/℃拉伸强度/MPa杨氏模量/GPa断裂伸长率/%
PI(6-T-B)-10∶037880.7253101.7±2.02.8±0.27.2±0.2
PI(6-T-B)-7∶337681.7271122.5±1.02.8±0.18.6±0.1
PI(6-T-B)-5∶538482.8275144.9±1.03.4±0.29.3±0.1
PI(6-T-B )-3∶738384.1276143.7±2.03.1±0.18.9±0.2
PI(6-T-B)-0∶1038685.3288104.7±2.02.7±0.28.3±0.1
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样品DMFDMACDMSONMP乙酸乙酯THF乙醇
PI(6-T-B)-10∶0+++++++++-+---
PI(6-T-B)-7∶3+++++++++-+--
PI(6-T-B)-5∶5+++++++++-+---
PI(6-T-B)-3∶7+++++++++-+---
PI(6-T-B)-0∶10+++++++++-+---
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PI(6-T-B)共聚物薄膜的溶解性测试结果

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样品DMFDMACDMSONMP乙酸乙酯THF乙醇
PI(6-T-B)-10∶0+++++++++-+---
PI(6-T-B)-7∶3+++++++++-+--
PI(6-T-B)-5∶5+++++++++-+---
PI(6-T-B)-3∶7+++++++++-+---
PI(6-T-B)-0∶10+++++++++-+---
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含吡啶环结构的共聚聚酰亚胺薄膜的制备及性能研究
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李品儒 , 鲁云华 , 雷敏 , 肖国勇 , 赵洪斌 , 胡知之
绝缘材料 | 高性能聚酰亚胺材料专题 2024,57(10): 9-15
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绝缘材料 | 高性能聚酰亚胺材料专题 2024, 57(10): 9-15
含吡啶环结构的共聚聚酰亚胺薄膜的制备及性能研究
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李品儒, 鲁云华, 雷敏, 肖国勇, 赵洪斌, 胡知之
作者信息
  • 辽宁科技大学 化学工程学院,辽宁 鞍山 114051
  • 李品儒(2000-),女(汉族),辽宁庄河人,硕士生,研究方向为功能性聚酰亚胺材料的制备;

    肖国勇(1973-),男(汉族),辽宁台安人,副教授,研究方向为功能性高分子材料的开发。

Preparation and properties of copolyimide films containing pyridine ring structures
Pinru LI, Yunhua LU, Min LEI, Guoyong XIAO, Hongbin ZHAO, Zhizhi HU
Affiliations
  • School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China
出版时间: 2024-10-20 doi: 10.16790/j.cnki.1009-9239.im.2024.10.002
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首先,合成了一种同时含有吡啶环结构和叔丁基的“Y型”二胺单体4-(4′-叔丁基)苯基-2,6-二(4′-氨基苯基)吡啶(TPAPP),然后与2,2-双(3-氨基-4-羟基苯基)六氟丙烷(6FAP)和4,4′-(4,4′-异丙基二苯氧基)双(邻苯二甲酸酐)(BPADA)聚合,经热酰亚胺化制备出一系列共聚聚酰亚胺(PI)薄膜。通过红外光谱、X-射线衍射、紫外-可见光谱、拉伸测试、动态热机械分析、热重分析和溶解性测试,对PI薄膜的结构和光学性能、力学性能、热性能及溶解性进行研究。结果表明:随着TPAPP摩尔分数的增加,共聚聚酰亚胺薄膜的光学透明性和玻璃化转变温度均表现出增加趋势。当二胺与二酐的物质的量之比为5∶5时,共聚聚酰亚胺薄膜的力学性能最好,拉伸强度达到144.9 MPa,杨氏模量为3.4 GPa,断裂伸长率可达9.3%。此外,这些共聚聚酰亚胺在非质子极性溶剂中均表现出较好的溶解性。

吡啶环  /  共聚聚酰亚胺  /  光学性能  /  力学性能  /  热性能

Firstly, a Y-shape diamine monomer 4-(4′-tertbutyl)phenyl-2,6-di(4′-aminophenyl)pyridine (TPAPP) containing pyridine ring structure and tertbutyl group was synthesized. Then, it was polymerized with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 4,4′-(4,4′-isopropyldiphenyloxy)bis(phthalic anhydride) (BPADA), and a series of copolyimide (PI) films were prepared by thermal imidization. The structure and optical, mechanical, and thermal properties as well as solubility of the PI films were investigated by infrared spectroscopy, X-ray diffraction, UV visible spectra, tensile tests, dynamic thermo-mechanical analysis, thermogravimetric analysis, and solubility tests. The results show that as the molar ratio of TPAPP increases, the optical transparency and glass transition temperature of the copolyimide films exhibit an increasing trend. When the molar ratio of diamine and dianhydride is 5:5, the copolyimide film shows the best mechanical properties, with the tensile strength of 144.9 MPa, the Young's modulus of 3.4 GPa, and the elongation at break of 9.3%. In addition, these copolyimides demonstrate good solubility in aprotic polar solvents.

pyridine ring  /  copolyimide  /  optical properties  /  mechanical properties  /  thermal properties
李品儒, 鲁云华, 雷敏, 肖国勇, 赵洪斌, 胡知之. 含吡啶环结构的共聚聚酰亚胺薄膜的制备及性能研究. 绝缘材料, 2024 , 57 (10) : 9 -15 . DOI: 10.16790/j.cnki.1009-9239.im.2024.10.002
Pinru LI, Yunhua LU, Min LEI, Guoyong XIAO, Hongbin ZHAO, Zhizhi HU. Preparation and properties of copolyimide films containing pyridine ring structures[J]. Insulating Materials, 2024 , 57 (10) : 9 -15 . DOI: 10.16790/j.cnki.1009-9239.im.2024.10.002
聚酰亚胺(PI)作为一种综合性能优异的工程材料,常被应用于航空航天、微电子、气体分离和能源储存等领域[1-4]。传统的PI由于具有高度芳香共轭性,且分子内或分子间的相互作用力较强,易在电子给体(二胺单体)和电子受体(二酐单体)之间形成电荷转移络合物(CTC),对可见光表现出强烈的吸收,使得膜材料呈现出较深的颜色,极大限制了其在光电子、柔性显示器件和光波导等领域的应用[5-9]。为了抑制CTC的形成,得到高透明性的PI膜材料,研究者常通过分子结构设计来增加大分子链间的距离,减少共轭结构,如引入Cardo、Spiro结构、三氟甲基、大体积侧基、不对称或非共平面结构和脂环结构等[10-15]。例如,CHANG J H[16]以4,4′-(4,4′-异丙基二苯氧基)双(邻苯二甲酸酐)(BPADA)为二酐单体,分别与3种不同结构的二胺单体反应制备无色透明PI薄膜,所得3种PI薄膜的颜色均较浅,并表现出优异的光学透明性。WEN P等[17]将具有螺二芴结构的两种二胺单体分别与3种二酐单体均苯四甲酸二酐(PMDA)、1,2,3,4-环丁烷四酸二酐(CBDA)和4,4′-(六氟异丙烯)二酞酸酐(6FDA)进行聚合,制备了6种PI薄膜,发现采用6FDA合成的PI薄膜透光率超过了90%,说明六氟异丙基的存在有利于提高PI薄膜的透明性。杨海霞等[18]合成了一种含有吡啶环结构的二酐单体,并将其与1,4-双(2-三氟甲基-4-氨基苯氧基)苯聚合,得到一系列PI薄膜。与未引入吡啶环的PI薄膜相比,该PI薄膜具有更好的光学性能。
传统PI的溶解性差,造成加工困难,也限制了其进一步应用。研究表明,在PI分子链中引入柔性链段、大体积取代基、非对称结构、含氟基团等能有效改善其溶解性[19-21]。例如,赵丽萍等[21]合成了一种二胺单体4-苯基-2,6-双[4-(4-氨基苯氧基)苯]吡啶,并与BPADA反应合成了PI。该PI在N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)和三氯甲烷(CHCl3)等溶剂中均具有良好的可溶性。
吡啶环具有类似苯环的刚性结构和可质子化的氮原子,向其引入氟原子、羟基和醚键可抑制CTC的形成,从而有效提升PI的溶解性和透明性,同时使PI保持良好的热性能。因此,本研究通过分子结构设计合成一种同时含有吡啶环和叔丁基(大体积侧基)的“Y型”二胺单体,然后与2,2-双(3-氨基-4-羟基苯基)六氟丙烷(6FAP)和BPADA共聚,经热酰亚胺化制备出一系列共聚PI薄膜,探究不同二胺摩尔分数对共聚PI薄膜结构和性能的影响。
对硝基苯乙酮(纯度>98%),上海鸿鹄生物医药科技有限公司;对叔丁基苯甲醛(纯度>98%),萨恩化学技术(上海)有限公司;醋酸铵(纯度>98%)、冰醋酸(分析纯)、钯/碳(10%Pd)、水合肼(体积分数为80%)、二甲基亚砜(DMSO,分析纯)、乙酸乙酯(分析纯)、四氢呋喃(THF,分析纯)、N,N-二甲基甲酰胺(DMF,分析纯)、N,N-二甲基乙酰胺(DMAC,分析纯),国药集团化学试剂有限公司;N-甲基吡咯烷酮(NMP,分析纯),天津市科密欧化学试剂有限公司;2,2-双(3-氨基-4-羟基苯基)六氟丙烷(6FAP,纯度>98%)、4,4′-(4,4′-异丙基二苯氧基)双(邻苯二甲酸酐)(BPADA,纯度>98%),天津众泰化工科技有限公司。
首先,将4.867 g(0.03 mol)对叔丁基苯甲醛、9.909 g(0.06 mol)对硝基苯乙酮、30.000 g醋酸铵和75.0 mL冰醋酸加入到250 mL三口圆底烧瓶中。然后,在氮气气氛下,升温至120℃回流12 h进行反应。待反应液冷却至室温后,抽滤得到红棕色固体。先用50%的冰醋酸洗涤,然后用乙醇反复洗涤,抽滤并进行干燥得到初产物。最后,用DMF进行重结晶,并在120℃下真空干燥24 h,得到淡黄色的二硝基化合物4-(4′-叔丁基)苯基-2,6-二(4′-硝基苯基)吡啶(TPNPP),收率为50.4%。液相相对纯度为98.6%,熔点为269.9℃。
将5.000 g(0.011 4 mol)TPNPP、0.400 g的Pd/C和200.0 mL无水乙醇加入到带有氮气保护装置的三口烧瓶中,加热到80℃回流。然后,将10.0 mL水合肼和20.0 mL无水乙醇通过恒压滴液漏斗缓慢滴入反应液中。持续反应12 h后,将混合液趁热抽滤除去Pd/C,所得滤液注入大量去离子水中,静置后析出白色二氨基化合物4-(4′-叔丁基)苯基-2,6-二(4′-氨基苯基)吡啶(TPAPP)。收率为78.4%,液相相对纯度为99.1%,熔点为227.4℃。具体合成路线如图1所示[21-23]
基于6FAP、TPAPP和BPADA的共聚聚酰亚胺PI(6-T-B)薄膜的制备路线如图2所示,以6FAP与TPAPP物质的量之比为5∶5的样品为例,具体制备过程如下:首先,将0.005 mol(1.831 g)6FAP和0.005 mol(1.986 g)TPAPP和51.1 mL DMAC加入到装有机械搅拌装置的250 mL两口圆底烧瓶中。搅拌至二胺单体完全溶解后,加入0.010 mol(5.205 g)二酐BPADA,并在冰水浴中连续反应12 h得到聚酰胺酸(PAA)溶液(固含量为15%)。然后,将PAA溶液刮涂到洁净的玻璃板上,在40℃的热台上干燥 4 h,再放置于远红外烘箱中按照80℃/1 h+150℃/ 1 h+200℃/1 h+250℃/1 h的程序进行阶段性升温处理。脱膜后将薄膜转移至氮气保护的管式炉中,在300℃下保持1 h,得到PI(6-T-B)-5∶5薄膜样品。其他二酐与二胺配比的共聚物薄膜的制备按照相似的过程进行,并分别命名为PI(6-T-B)-10∶0、PI(6-T-B)-7∶3、PI(6-T-B)-3∶7和PI(6-T-B)-0∶10。
采用核磁共振波谱仪(NMR,Agilent-500型)对TPNPP和TPAPP进行化学结构分析,溶剂为氘代二甲基亚砜(DMSO),内参比为四甲基硅烷。采用凝胶渗透色谱仪(Waters E2695型)测定PAA的分子量。采用红外光谱仪(FTIR,Nicolet Is10型)在500~4 000 cm-1的范围内对薄膜的化学结构进行表征。采用差热分析仪(DSC 4000型,美国PerkinElmer公司)测试化合物的熔点,测试温度范围为50~400℃,升温速率为10℃/min。采用热失重分析仪(TGA,STA 449F3型,德国耐驰公司)在室温至800℃对薄膜的热性能进行分析,N2气氛,升温速率为10℃/min。采用动态热机械分析仪(DMA 8000,美国PerkinElmer公司)在50~400℃对薄膜进行性能表征,高纯N2气氛,升温速率为10℃/min,拉伸频率为1 Hz。采用万能材料拉伸试验机(HY-0580型,上海恒翼精密仪器有限公司)对薄膜进行力学性能测试,样品尺寸为7 cm×1 cm,拉伸速率为10 mm/min。采用X-射线衍射仪(XRD,BLKⅡ-5FF-S型,荷兰帕纳科有限公司)对薄膜进行微观结构分析,扫描范围为2θ=5°~70°,并根据布拉格方程=2dsinθn=1),计算样品的平均晶面间距(d),波长λ=1.54 Å。采用紫外/可见/近红外分光光度计(UV-VIS-NIR,Lambda-750S型,美国PerkinElmer公司),在200~800 nm波长范围内对薄膜的光学性能进行表征。常温下,称取10 mg薄膜样品置于1 mL的溶剂中,24 h后观察样品的溶解程度,对于不溶的样品加热后再进行观察。
图3为所合成的二硝基化合物TPNPP和二胺单体TPAPP的核磁共振氢谱图[23]。从图3(b)可以看出,在δ=5.49处出现了氨基氢的特征峰,说明经过还原后,TPNPP上吸电子的硝基变成供电子的氨基,已成功地合成了目标化合物。
图4为PI(6-T-B)共聚物薄膜的红外光谱图。从图4可以看出,在1 778 cm-1和1 715 cm-1处出现了酰亚胺环中C=O的不对称和对称伸缩振动峰,同时1 372 cm-1处出现了C-N的伸缩振动峰,表明酰亚胺环结构已经存在[20-22]。此外,羟基的伸缩振动峰出现在3 300 cm-1左右,在2 960 cm-1处出现了叔丁基甲基的C-H伸缩振动峰,1 540 cm-1和1 426 cm-1处出现了吡啶环的伸缩振动峰[23]
表1为所合成的PAA的分子量测试结果。从表1可以看出,随着6FAP摩尔分数的增加,PAA的分子量逐渐升高,说明6FAP可能比TPAPP具有更高的反应活性。
图5为PI(6-T-B)共聚物薄膜的X-射线衍射图。从图5可以看出,所有薄膜均呈现出一个较宽的“馒头峰”,为典型的无定形结构[21]。随着二胺TPAPP摩尔分数的增加,共聚物薄膜的晶面间距(d)随之增大,由0.48 nm增大到0.52 nm。这主要是因为TPAPP中的“Y型”吡啶环结构及其叔丁基取代基改变了大分子链的对称线型结构,使分子链更加扭曲,并增加了大分子链间的距离,减少了链与链间的相互作用,阻碍了分子链的紧密排列。此外,共聚也破坏了大分子链的结构规整性,使共聚物薄膜表现出较大的d值。
PI(6-T-B)共聚物薄膜的紫外-可见光谱如图6所示,表2给出了光学相关数据,其中λc表示紫外截止波长,T450表示450 nm处的透光率。从图6表2可以看出,共聚物薄膜的紫外截止波长集中在376~386 nm,且450 nm处的透光率均超过了80%,说明这些薄膜材料具有良好的光学透明特性。PI(6-T-B)-10∶0薄膜在450 nm处的透光率为80.7%,随着TPAPP摩尔分数的增加,PI(6-T-B)共聚物薄膜的透光率呈线性增长趋势,PI(6-T-B)-0∶10的透光率达到85.3%。这主要是因为吡啶环结构及其叔丁基取代基有效地增大了分子链间距离,减少了链间相互作用,抑制了CTC的形成,从而降低了对可见光的吸收[8]
PI(6-T-B)共聚物薄膜的DMA测试结果如图7所示。从图7可以看出,这些薄膜均表现出一个显著的tanδ峰,对应玻璃态和橡胶态之间的α转变。根据该峰的位置可以确定聚合物的玻璃化转变温度(Tg),数据见表2。从表2可以看出,随着TPAPP摩尔分数的增加,共聚物薄膜的Tg由253℃上升至288℃。这主要归因于二胺TPAPP中含有的“Y型”吡啶环结构增加了PI大分子链的刚性,同时叔丁基的存在进一步阻碍了聚合物分子链段的自由旋转,从而提高了聚合物的Tg[26]。但是,由于二酐BPADA中存在较多的醚键链接,增加了聚合物链的柔顺性,从而使PI的Tg整体偏低。
PI(6-T-B)共聚物薄膜的TGA和DTG曲线如图8所示。从图8可以看出,这些样品主要出现两个失重过程:第一个失重峰出现在450℃附近,主要是由于含羟基的酰亚胺环发生了重排反应形成苯并噁唑结构,并释放出小分子CO2气体[24]。显然,随6FAP摩尔分数的增加,该失重峰显著增强;第二个明显的失重过程发生在550℃左右,归因于聚酰亚胺主链的断裂以及侧基的分解。
图9为PI(6-T-B)共聚物薄膜的应力-应变曲线,其相应的力学性能数据见表2。从图9表2可以看出,PI(6-T-B)共聚物薄膜由于含有柔性的BPADA二酐,成膜性较好,且均表现出优异的力学性能。 PI(6-T-B)共聚物薄膜的拉伸强度为101.7~144.9 MPa,杨氏模量为2.7~3.4 GPa,断裂伸长率为7.2%~9.3%。其中,PI(6-T-B)-5∶5薄膜的力学性能最优,这说明适当添加二胺共聚能够有效地提高PI薄膜的力学性能。
表3为PI(6-T-B)共聚物薄膜的溶解性测试结果。从表3可以看出,所有薄膜试样在常温下都易溶于NMP、DMF、DMAC和DMSO等极性溶剂,且在加热后可微溶于乙酸乙酯和THF中。这主要是由于PI大分子链中存在的大体积吡啶环结构、叔丁基、六氟异丙基和羟基等基团,有效阻碍了分子链的规整堆砌,获得了较大的分子链间距离,有利于溶剂分子的渗入[19-21]。而且,吡啶环中氮原子的极化作用也有利于提高薄膜在极性有机溶剂中的溶解性[23]。因此,这些PI薄膜表现出良好的可溶性,有利于改善其加工性。
(1)合成了一种含有吡啶环结构的“Y型”二胺单体4-(4′-叔丁基)苯基-2,6-二(4′-氨基苯基)吡啶(TPAPP),并与二胺6FAP和二酐BPADA共聚,经热酰亚胺化后得到共聚聚酰亚胺薄膜材料。测试结果表明,PI(6-T-B)共聚物薄膜均为无定形结构,且由于TPAPP的引入,表现出较大的d值。
(2)随TPAPP摩尔分数的增加,PI(6-T-B)共聚物薄膜在450 nm处的透光率由80.7%增加到85.3%,玻璃化转变温度Tg由253℃提高到288℃。
(3)共聚后,薄膜材料的力学性能也有不同程度的提升,其中PI(6-T-B)-5∶5的力学性能最好,拉伸强度为144.9 MPa,杨氏模量达到3.4 GPa,断裂伸长率可达9.3%。
(4)所有PI(6-T-B)共聚物薄膜在非质子极性溶剂中均表现出较好的溶解性,有利于改善其加工性能。
  • 国家自然科学基金面上项目(22278051)
  • 辽宁省教育厅项目(LJKMZ20220659)
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2024年第57卷第10期
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doi: 10.16790/j.cnki.1009-9239.im.2024.10.002
  • 接收时间:2024-03-06
  • 首发时间:2025-12-24
  • 出版时间:2024-10-20
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  • 收稿日期:2024-03-06
  • 修回日期:2024-05-09
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国家自然科学基金面上项目(22278051)
辽宁省教育厅项目(LJKMZ20220659)
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    辽宁科技大学 化学工程学院,辽宁 鞍山 114051
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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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