Article(id=1242756977143689270, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1242756974576775191, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2021.11.007, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1619280000000, receivedDateStr=2021-04-25, revisedDate=1621958400000, revisedDateStr=2021-05-26, acceptedDate=null, acceptedDateStr=null, onlineDate=1774225952658, onlineDateStr=2026-03-23, pubDate=1637510400000, pubDateStr=2021-11-22, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1774225952658, onlineIssueDateStr=2026-03-23, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1774225952658, creator=13701087609, updateTime=1774225952658, 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=55, endPage=61, ext={EN=ArticleExt(id=1242756977567313986, articleId=1242756977143689270, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=N-substituted Poly(benzimidazole-imide) Films: Improved Solubility and Transmittance, columnId=1198664996516360309, journalTitle=Insulating Materials, columnName=Polyimide Film Special Issue, runingTitle=null, highlight=null, articleAbstract=

Two novel diamines contained N-phenyl substituted benzimidazole were synthesized, and their difference was that the ortho-position of N-phenyl was substituted by methyl and fluorine atom, respectively. The novel diamines and commercially available dianhydrides 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4′-oxydiphthalic anhydride (ODPA) were used to prepare poly(benzimidazole-imide) (PBII) films by two-step thermal imidization. The properties of new diamine monomer and PBII films were tested and characterized. The results show that the PBII films exhibit good thermal properties (glass transition temperature Tg=341-381℃) and mechanical properties (σ=95-135 MPa). The N-phenyl groups with different ortho units destroy the effective molecular packing, which improves the solubility and optical transmittance of the PBII films.

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试验合成了两种新型的N-苯基取代苯并咪唑二胺,区别在于N-苯基的邻位分别由甲基和氟原子取代。将新型二胺分别与二酐4,4′-(六氟异丙烯)二酞酸酐(6FDA)和4,4′-氧双邻苯二甲酸酐(ODPA)通过两步热亚胺法制备聚苯并咪唑酰亚胺(PBII)薄膜,并对新型二胺单体及PBII薄膜进行了性能测试与表征。结果表明:新型PBII薄膜表现出良好的耐热性(玻璃化转变温度Tg=341~381℃)和拉伸强度(σ=95~135 MPa)。不同邻位取代的N-苯基破坏了分子的有效堆积,使得PBII薄膜的溶解性和光学透明性得到改善。

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钱广涛(1989-),男(汉族),安徽马鞍山人,博士后,主要从事改性聚酰亚胺等的研究。
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柯钊(1994-),男(汉族),湖北大冶人,硕士生,主要从事低介电聚酰亚胺的研究。

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柯钊(1994-),男(汉族),湖北大冶人,硕士生,主要从事低介电聚酰亚胺的研究。

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柯钊(1994-),男(汉族),湖北大冶人,硕士生,主要从事低介电聚酰亚胺的研究。

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PBIIηinh/(dL/g)吸水率/%λcut-off/nmT500/%
6a-ODPA1.382.441150
6b-ODPA0.882.239960
6a-6FDA1.182.337777
6b-6FDA0.872.236280
PABZ-BPDA[7]5.9
), ArticleFig(id=1245100057297535492, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756977143689270, language=CN, label=表1, caption=

PBII前躯体聚酰胺酸的特性黏度,PBII薄膜的吸水率与光学性能

, figureFileSmall=null, figureFileBig=null, tableContent=
PBIIηinh/(dL/g)吸水率/%λcut-off/nmT500/%
6a-ODPA1.382.441150
6b-ODPA0.882.239960
6a-6FDA1.182.337777
6b-6FDA0.872.236280
PABZ-BPDA[7]5.9
), ArticleFig(id=1245100057402393096, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756977143689270, language=EN, label=Tab.2, caption=Solubility of PBIIs, figureFileSmall=null, figureFileBig=null, tableContent=
溶剂PBII
6a-ODPA6b-ODPA6a-6FDA6b-6FDA
间甲酚(m-cresol)-±-±
N-甲基吡咯烷酮(NMP)±±++
二甲基亚砜(DMSO)---±
N,N′-二甲基乙酰胺(DMAc)±±++
N,N′-二甲基甲酰胺(DMF)--±+
四氢呋喃(THF)---±
), ArticleFig(id=1245100057498862093, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756977143689270, language=CN, label=表2, caption=

PBII的溶解性

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溶剂PBII
6a-ODPA6b-ODPA6a-6FDA6b-6FDA
间甲酚(m-cresol)-±-±
N-甲基吡咯烷酮(NMP)±±++
二甲基亚砜(DMSO)---±
N,N′-二甲基乙酰胺(DMAc)±±++
N,N′-二甲基甲酰胺(DMF)--±+
四氢呋喃(THF)---±
), ArticleFig(id=1245100057595331088, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756977143689270, language=EN, label=Tab.3, caption=Physical properties of PBII films, figureFileSmall=null, figureFileBig=null, tableContent=
PBIITg/℃(DSC)Tg/℃ (DMA)Td5%/℃σ/MPaE/GPaε/%
6a-ODPA3463464961354.05.9
6b-ODPA3453415491263.65.1
6a-6FDA373381498954.92.5
6b-6FDA364375537954.13.5
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PBII薄膜的物理性能

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PBIITg/℃(DSC)Tg/℃ (DMA)Td5%/℃σ/MPaE/GPaε/%
6a-ODPA3463464961354.05.9
6b-ODPA3453415491263.65.1
6a-6FDA373381498954.92.5
6b-6FDA364375537954.13.5
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N位取代聚苯并咪唑酰亚胺薄膜:改善的溶解性与透过率
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柯钊 , 陈海权 , 张轶材 , 闫晓莹 , 李慧 , 钱广涛 , 于有海
绝缘材料 | 聚酰亚胺薄膜专题 2021,54(11): 55-61
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绝缘材料 | 聚酰亚胺薄膜专题 2021, 54(11): 55-61
N位取代聚苯并咪唑酰亚胺薄膜:改善的溶解性与透过率
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柯钊, 陈海权, 张轶材, 闫晓莹, 李慧, 钱广涛, 于有海
作者信息
  • 东华大学 材料科学与工程学院 纤维材料改性国家重点实验室 先进低维材料中心,上海 201620
  • 柯钊(1994-),男(汉族),湖北大冶人,硕士生,主要从事低介电聚酰亚胺的研究。

通讯作者:

钱广涛(1989-),男(汉族),安徽马鞍山人,博士后,主要从事改性聚酰亚胺等的研究。
N-substituted Poly(benzimidazole-imide) Films: Improved Solubility and Transmittance
Zhao KE, Haiquan CHEN, Yicai ZHANG, Xiaoying YAN, Hui LI, Guangtao QIAN, Youhai YU
Affiliations
  • Center for Advanced Low-Dimension Materials, State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, China
出版时间: 2021-11-22 doi: 10.16790/j.cnki.1009-9239.im.2021.11.007
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试验合成了两种新型的N-苯基取代苯并咪唑二胺,区别在于N-苯基的邻位分别由甲基和氟原子取代。将新型二胺分别与二酐4,4′-(六氟异丙烯)二酞酸酐(6FDA)和4,4′-氧双邻苯二甲酸酐(ODPA)通过两步热亚胺法制备聚苯并咪唑酰亚胺(PBII)薄膜,并对新型二胺单体及PBII薄膜进行了性能测试与表征。结果表明:新型PBII薄膜表现出良好的耐热性(玻璃化转变温度Tg=341~381℃)和拉伸强度(σ=95~135 MPa)。不同邻位取代的N-苯基破坏了分子的有效堆积,使得PBII薄膜的溶解性和光学透明性得到改善。

聚苯并咪唑酰亚胺  /  耐热稳定性  /  光学透过率

Two novel diamines contained N-phenyl substituted benzimidazole were synthesized, and their difference was that the ortho-position of N-phenyl was substituted by methyl and fluorine atom, respectively. The novel diamines and commercially available dianhydrides 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4′-oxydiphthalic anhydride (ODPA) were used to prepare poly(benzimidazole-imide) (PBII) films by two-step thermal imidization. The properties of new diamine monomer and PBII films were tested and characterized. The results show that the PBII films exhibit good thermal properties (glass transition temperature Tg=341-381℃) and mechanical properties (σ=95-135 MPa). The N-phenyl groups with different ortho units destroy the effective molecular packing, which improves the solubility and optical transmittance of the PBII films.

poly(benzimidazole-imide)  /  heat resistance  /  optical transmittance
柯钊, 陈海权, 张轶材, 闫晓莹, 李慧, 钱广涛, 于有海. N位取代聚苯并咪唑酰亚胺薄膜:改善的溶解性与透过率. 绝缘材料, 2021 , 54 (11) : 55 -61 . DOI: 10.16790/j.cnki.1009-9239.im.2021.11.007
Zhao KE, Haiquan CHEN, Yicai ZHANG, Xiaoying YAN, Hui LI, Guangtao QIAN, Youhai YU. N-substituted Poly(benzimidazole-imide) Films: Improved Solubility and Transmittance[J]. Insulating Materials, 2021 , 54 (11) : 55 -61 . DOI: 10.16790/j.cnki.1009-9239.im.2021.11.007
聚苯并咪唑酰亚胺(PBII)是一类主链含有苯并咪唑(BI)单元的改性聚酰亚胺,在材料工程和科学领域有着广阔的应用前景[1-3]。PBII有着优异的热学性能,例如超过400℃的玻璃化转变温度、优异的热稳定性和低热膨胀系数。研究表明,PBII优异的性能得益于BI单元上丰富的质子供体(N-H)和酰亚胺环上质子受体(-N=或者C=O)易形成分子间氢键[4]。此外,基于BI的二胺单体表现出强的给电子性,加速了分子间电荷转移络合物(CTC)的形成。BI单元的引入可以有效地提高PBII的热性能,然而BI单元同样会导致衍生聚酰亚胺高的亲水性,吸水率高达15%~18%,这会破坏聚酰亚胺优异的绝缘性能和介电性能,同时水分会加速亚胺环的降解,使金属粘合失效,从而缩短亚胺制品的工作寿命[5]。同时,由于分子间氢键和强CTC作用,PBII表现出差的溶解性、低的光学透过率和不理想的加工性,限制了其在微电子领域的应用[6]
本课题组之前的研究表明,在BI环中引入适当的N-甲基取代基可以解决PBII高吸水率的问题[7]。但是由于分子间形成氢键的阻碍,这一系列N-甲基取代的PBII玻璃化转变温度相对较低。研究证明,大刚性侧基的引入可以通过其空间位阻增强聚合物的热性能[8-9]。同时大刚性侧基,尤其是非共平面,可以破坏分子链的有效堆积,改善衍生聚合物的溶解性和光学透过率。
本研究设计并合成了具有N-苯基取代的苯并咪唑二胺,N-苯基的邻位分别被甲基和氟原子取代。这类N-苯基取代的PBII有望在牺牲可接受的热学性能的同时改善聚合物的溶解性和光学透过率。通过比较不同取代N-苯基的空间位阻作用对分子链堆积及对聚合物性能的影响,探讨聚合物分子结构与性能的关系。
2,4-二硝基氟苯、苯胺和4-硝基苯甲酰氯分别购自上海皓鸿生物医药技术有限公司和阿拉丁化学有限公司,其他化学药品均购自国药化学试剂有限公司。二酐4,4′-(六氟异丙烯)二酞酸酐(6FDA)和4,4′-氧双邻苯二甲酸酐(ODPA)使用前在80℃的真空干燥箱干燥12 h,N,N′-二甲基乙酰胺(DMAc)使用前通过真空蒸馏进行纯化。其他市售试剂均在没有进一步纯化的情况下使用。
核磁共振氢谱图(1H NMR)和二维核磁共振氢谱图(1H-1H COSY)采用Bruker公司 600AVANCE Ⅲ型光谱仪进行测试,使用氘代二甲基亚砜(DMSO-d6)作为溶剂。单体的元素分析采用Elmentar公司Vario EL-III型元素分析仪进行测定。聚酰胺酸(PAA)的特性黏度(ηinh)通过配制0.1 mol/L的DMAc聚合物稀释液在25℃下的乌氏黏度计(NASREN公司的SBQ81834型乌氏黏度计)中测得。衰减全反射傅里叶变换红外光谱(ATR-FTIR)使用Thermo Scientific公司Nicolet 6700型光谱仪在4 000~400 cm-1的波数范围内获得。紫外可见光谱(UV)采用Shimadzu公司UV-3600型分光光度计在300~700 cm-1波长范围内,通过透射模式记录。广角X射线衍射光谱(WAXD)通过Rigaku公司Denki D/MAX-2500型转靶X射线衍射仪在室温下收集。聚合物的热重分析(TGA)采用TA公司Discovery TGA 550型热重分析仪进行,氮气氛围,升温速率为10℃/min。聚合物的动态热力学分析(DMA)通过TA公司DMA Q800型动态热机械分析仪采用拉伸模式进行测试,其中频率为1 Hz,升温速率为5℃/min。聚合物的玻璃化转变温度同时通过差示扫描量热法(DSC)采用TA公司Discovery 250型示差扫描量热仪进行测试记录。采用Shimadzu公司AG-I型万能试验机以5.0 mm/min的速度测试聚合物的拉伸性能,其中拉伸强度(σ)、拉伸模量(E)和断裂伸长率(ε)取5个平行样品的平均值。二胺单体中氮原子的净电荷分布和能量最小化结构通过B3LYP(Becke,three-parameter,Lee-Yang-Parr)Gaussian 09W中6-311G(d,p)基集基的交换-相关函数获得。
将2,4-二硝基氟苯(10.00 g,53.7 mmol)、邻甲基苯胺(5.75 g, 53.7 mmol)和50 mL甲醇的混合物在室温下搅拌18 h(TLC检测),然后过滤,再在80℃下真空干燥24 h,得到产物2,4-二硝基-N-(邻甲苯基)苯胺(12.25 g,产率为83.5%),无需纯化,直接用于下一步反应。将2,4-二硝基-N-(邻甲苯基)苯胺(12.00 g,43.9 mmol)、碳酸氢钠(5.54 g,65.9 mmol)、硫化钠(5.14 g,65.9 mmol)、80 mL乙醇溶液和40 mL水的混合物在80℃搅拌过夜,TLC检测后放入冰水浴中降温,再倒入水中,最后使用减压抽滤收集沉淀物,水洗2~3次后干燥,得红色粉末产物4-硝基-N1-(邻甲苯基)苯-1,2-二胺(9.11 g,产率为85.3%)。将4-硝基-N1-(邻甲苯基)苯-1,2-二胺(9.0 g,37.0 mmol)、三乙胺(5.62 g,55.5 mmol)和50 mL四氢呋喃混合并置于冰水浴中,在0.5 h内等份加入4-硝基苯甲酰氯(8.15 g,44.4 mmol),在室温下搅拌反应16 h。倒入水中沉淀,过滤干燥。将上述产物溶解在乙酸(200 mL)中120℃回流反应过夜。TLC检测后倒入水中沉淀,反复洗涤2~3次,过滤干燥,通过从二甲基亚砜中重结晶得到黄色粉末化合物5-硝基-2-(4-硝基苯)-1-(邻甲基苯基)-苯并咪唑(6.6 g,产率为47.5%)。1H NMR (600 MHz, DMSO-d6):δ=8.79(d,J=2.1 Hz,1H),8.28~8.25(m,1H),8.24(dd,J=8.9,2.2 Hz,3H),7.88~7.76(m,2H),7.59(t,J=7.3 Hz,2H),7.56(d,J=7.3 Hz,1H),7.51~7.46(m,1H),7.26(d,J=8.9 Hz,1H),1.87(s,3H)。C20H14N4O4理论元素含量:C,64.17%;H,3.77%;N,14.97%。实测元素含量:C,64.3%;H,3.81%;N,15.20%。
将二硝基化合物5a(5.0 g,15.9 mmol)、钯催化剂(10%钯/碳,0.5 g)和50 mL乙醇的混合物加热到80 ℃,然后滴加7.0 mL水合肼。回流反应4~5 h,然后冷却至室温。趁热过滤去除钯催化剂,减压旋蒸除去大部分乙醇溶液,然后将浓缩液倒入100 mL水中,收集沉淀,干燥得到白色目标二胺(3.7 g,产率为88.1%)。1H NMR(600 MHz,DMSO-d6)δ=7.49~7.36 (m,3H),7.31(dd,J=7.5,1.3 Hz,1H),7.17~7.11 (m,2H),6.82(dd,J=2.0,0.6 Hz, 1H),6.53(dd,J=8.4,0.6Hz,2H),6.49(dd,J=8.4,2.0 Hz,2H),6.44-6.38(m,2H),5.43(s,2H),4.79(s,3H)。C20H18N4理论元素含量:C,76.41%;H,5.77%;N,17.82%。实测元素含量:C,77.35%; H,5.23%;N, 17.42%。
合成方法与5a相似,除了使用2-氟苯胺。1H NMR(600 MHz,DMSO-d6)δ=8.80(d,J=2.0 Hz,1H),8.32~8.25(m,3H),7.88~7.82(m,3H),7.72(dd,J=7.0,4.9 Hz,1H),7.61~7.54(m,1H),7.52(td,J=7.7,1.2 Hz,1H),7.47(d,J=9.0 Hz,1H)。C19H11FN4O4理论元素含量:C,60.32%;H,2.93%;N,14.81%。实测元素含量:C,61.04%;H,2.55%;N,15.11%。
合成方法与6a相似。1H NMR (600 MHz,DMSO-d6)δ=7.58(m,1H),7.53(m,1H),7.46(m,1H),7.40(m,1H),7.15(d,J=12.0 Hz,2H),6.83(d,J=2.4 Hz,1H),6.70(d,J=3.6 Hz,1H),6.53(dd,J=2.4,1.8 Hz,1H),6.45(d,J=8.4 Hz,2H),5.47(s,2H),4.83(s,2H)。C19H15FN4理论元素含量:C,71.68%;H,4.75%;N,17.60%。实测元素含量:C,72.33%;H,4.45%;N,18.10%。
采取传统的两步热酰亚胺化反应制备聚酰亚胺薄膜。以6a-ODPA为例,具体的实验步骤为:将二胺单体6a(2.000 0 g,6.36 mmol)和超干DMAc(14.09 g)装入带有氮气氛围的三口瓶中,搅拌至二胺单体完全溶解,再将二酐单体ODPA(1.973 0 g,6.36 mmol)等量分批加入,继续搅拌反应24 h。将得到的透明澄清聚酰胺酸溶液减压除去气泡,然后刮涂在洁净平整的玻璃板上。在80℃烘箱中过夜缓慢烘干大部分溶剂。之后,聚酰胺酸(PAA)薄膜在200、300、400℃下各加热1 h,以完成亚胺化过程。最后将玻璃板冷却至室温,并浸泡在去离子水中,得到PBII膜。
将不同的N-苯基取代单元引入到苯并咪唑中的反应式如图1所示。通过一维核磁氢谱对新二胺单体进行了表征,结果如图2所示。从图2可以看出,在核磁氢谱中,没有观察到BI单元中-N-H质子的信号,并且4组峰(7.58~7.36)归因于芳族质子,证明在BI上的不同取代苯基。胺基质子氢的出现(5.40~6.60)表明二硝基中间体已被完全还原为目标二胺。为了进一步确定二胺单体上芳香质子的归属,通过二维核磁氢谱进行分析,结果如图3示。从图3不难看出,与BI相连的胺基质子氢的化学位移要小于苯环上胺基的质子氢,这表明前者具有更高的亲核性[10]
通过传统两步热亚胺法制备了PBII薄膜,合成路线如图4所示,所有薄膜显示出理想的柔性与韧性。通过红外光谱表征了聚合物的分子结构,结果如图5所示。从图5可以看出,典型的聚酰亚胺特征峰分别出现在1 783、1 719、1 367 cm-1处,分别对应于酰亚胺中羰基不对称拉伸、对称拉伸和环状C-N拉伸,在1 660 cm-1(灰色带域)处几乎没有观察到特征吸收峰,说明酰亚胺化过程已完全完成。BI环在1 303 cm-1处的特征吸收(咪唑环呼吸峰)证实了BI单元的成功引入[11-13]。另外,PBII中C=O的特征吸收峰与游离羰基的值非常吻合,即在制备的PBII中没有氢键形成,表明N-苯基在咪唑上限制了分子间氢键的形成。
基于密度泛函数理论(DFT)对PBII的重复单元空间构象进行了最优模拟,并且总结了不同刚性平面之间的扭结角,包括亚胺环与BI单元上的苯环(α)、BI单元上咪唑环与邻位苯胺的苯环(β)、邻位苯胺的苯环与酰亚胺环(γ)、N-取代苯环与BI单元上的咪唑环(δ),结果如图6所示。从图6不难看出,BI单元上N-苯环引入破坏了分子主链的线性和共面性[14],同时BI上N位取代的不同间位取代(甲基与氟原子)的苯环由于不同的空间位阻效应显示出差异性的扭结角。比如,PI-6b具有比PI-6a更大的β扭结角,这使得前者衍生聚合物的分子堆积更为松散。此外,较大的δ扭结角(58°,62°)表明N-苯基与分子主链的非共面性,这也有利于大的自由体积分数(FFV)的形成。进一步通过广角X射线衍射仪表征聚合物的微观形貌和分子堆积,结果如图7所示。从图7可以看出,所得衍射光谱表现出一个以2θ=22°为中心的宽衍射峰,表明所得聚合物为典型的非晶材料。松散的分子堆积是由于主链中存在大量的N-苯基导致链间距离增加。相比之下,已报道的苯并咪唑基聚酰亚胺由于强的分子间相互作用通常表现出高度有序的分子排列和紧密的链堆积[15-16]。可见,通过N-苯基这样的大侧基且非共面单元来破坏分子紧密堆积是可行的。
表1为PBII前躯体聚酰胺酸的特性黏度以及PBII的吸水率与光学性能,可以看出,PBII前驱体聚酰胺酸溶液表现出理想的特性黏度。表2为PBII的溶解性。传统的PBII由于强的分子间相互作用而表现出差的有机溶解性和加工型,本研究所得PBII薄膜由于大侧基的存在,分子链间距被打开,分子松散堆积,表现出改善的有机溶剂溶解性,如表2所示,特别是6b-6FDA在室温下NMP、DMA和THF中表现出良好的溶解性。含BI单元的聚合物通常对水具有高亲和力,主要原因是亲水的咪唑N-H基团可以与水形成氢键。因此,通过对咪唑上N-H的质子氢进行取代可能会阻碍与氢键结合的水分子的形成,从而改善了此类聚合物高吸水率的问题。N-苯基取代PBII的吸水率在2.2%~2.4%,与报道的PABZ-BPDA相比吸水率显著下降(见表1)。可见,在咪唑N位取代是解决PBII系列高吸水率问题可行的技术之一。
聚酰亚胺薄膜的颜色通常与CTC的形成理论有关,CTC的形成很容易受到二酐的吸电子性、二胺的给电子性和链段的堆积状态的影响,而具有大的吸电子单元、柔性基团或非共面结构的聚酰亚胺往往具有较浅的颜色[17-18]。通过紫外可见光谱对PBII薄膜进行了研究,结果如图8所示,薄膜的截止波长(λcut-off)和在500 nm处的透射率(T500)列于表1。从图8可以看出,N-苯基大侧基单元的引入削弱了分子间的CTC作用,使得PBII薄膜的光学透过性得到改善。值的注意的是,基于6FDA的PBII薄膜比基于ODPA的PBII薄膜表现出更高的光学透过率,这是由于三氟甲基单元更大的空间位阻作用以及氟原子更强的电负性弱化了分子间的CTC作用。此外,与分子的空间最优构象模拟相吻合,在N-苯基邻位取代的官能团中,由于更大的空间扭结角,氟原子取代表现出比甲基单元更好的改性潜力,包括更好的有机溶解性和光学透过率。
PBII薄膜的热学性能通过TGA、DSC和DMA进行评估,结果如图910表3所示。PBII薄膜表现出理想的耐热性,初始分解温度大于400℃,5%热失重温度在496~549℃(见图9表3)。一般而言,具有强共轭分子骨架的分子往往具有高耐热性的潜力,这是由于共轭π体系有利于热的传导[4,19]。此外,基于6FDA的PBII薄膜显示出比基于ODPA更高的耐热稳定性,这归因于氟原子固有的耐热性。在以前的研究中,PBII薄膜突出的高Tg(>400℃)可以从两个方面来解释。一方面,源自BI单元的分子间氢键限制了链段运动;另一方面,含BI二胺的较高亲核性导致当这些PBII经历高温时,CTC和链间增强的物理相互作用增加了分子链运动的难度[20-22]。本研究中,即使PBII的二酐段分别由柔性桥联醚键和大侧基三氟甲基组成并且不存在分子间氢键相互作用,所得PBII薄膜仍具有理想的Tg(如图10表3所示,345~373℃/341~381℃)。除了N-苯基BI二胺段仍保留的强CTC作用外,更重要的是,刚性的N-苯基限制了PI骨架周围的旋转自由度。
图11为PBII薄膜的应力-应变曲线,力学性能数据列于表3。从图11表3可以看出,PBII薄膜的拉伸强度(σ)为95~135 MPa,模量(E)为3.6~4.9 GPa,断裂伸长率(ε)为2.5%~5.9%,证实了其良好的柔韧性。研究表明,具有较高结晶度和分子间相互作用的PI具有较高的力学性能[23-25]。在表3中观察到基于6FDA的PBII力学性能下降,这是由于三氟甲基单元更大的空间位阻破坏了分子链的有效堆积,降低了物理相互作用。然而,其拉伸强度接近100 MPa,初始模量超过2 GPa,能够满足商业用途的要求[4]
本研究成功制备了一系列含有N-苯基取代的新型PBII薄膜。N-苯基阻碍了分子间氢键的形成,从而使衍生聚合物显示出较低的吸水率。N-苯基大侧基还破坏了分子的有效堆积,削弱了分子间的CTC效应,最终PBII薄膜的有机溶解性和光学透过性得到改善。此外,N-苯基大侧基扭曲了分子链骨架,削弱了分子链段的流动性,从而使PBII薄膜具有良好的热学性能和力学性能。
  • 广东省重点领域研究开发计划项目(2020B010182002)
  • 东华大学研究启动基金项目(285-07-005702)
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2021年第54卷第11期
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doi: 10.16790/j.cnki.1009-9239.im.2021.11.007
  • 接收时间:2021-04-25
  • 首发时间:2026-03-23
  • 出版时间:2021-11-22
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  • 收稿日期:2021-04-25
  • 修回日期:2021-05-26
基金
广东省重点领域研究开发计划项目(2020B010182002)
东华大学研究启动基金项目(285-07-005702)
作者信息
    东华大学 材料科学与工程学院 纤维材料改性国家重点实验室 先进低维材料中心,上海 201620

通讯作者:

钱广涛(1989-),男(汉族),安徽马鞍山人,博士后,主要从事改性聚酰亚胺等的研究。
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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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