摘要
以2,2′-联苯二甲酸为原料,制备了3,3′,5,5′-四硝基-2,2′-联苯二羧酸(Ⅰ),二硝基化合物Ⅰ再经铁粉还原得到含杂芘结构的二胺单体2,7-二氨基-5,10-二酮-4,9-二氮杂芘(Ⅱ)。二胺单体Ⅱ分别与4,4′-氧双邻苯二甲酸酐、3,3′,4,4′-二苯甲酮四甲酸二酐、3,3′,4,4′-联苯四羧酸二酐、2,3,3′,4′-联苯四甲酸二酐缩聚反应,合成了4种聚酰胺酸(PAA)胶液,经刮膜制备了4种PI薄膜(PI-1~PI-4)。采用^(1)HNMR和^(13)CNMR对二硝基化合物Ⅰ和二胺单体Ⅱ进行了鉴定,采用FTIR、GPC对4种PI薄膜和PAA胶液进行了表征,通过色彩雾度仪、TGA、TMA、DMA、电子万能试验机测试了PI薄膜的光学特性、热性能和力学性能。结果表明,PAA数均相对分子质量(Mn)为9.90×10~4~1.29×10~5,满足成膜要求;PI薄膜在400~750 nm的平均透过率为1.10%~3.27%,薄膜亮度(L*)值为9.79~21.08,属于黑色薄膜;PI薄膜的玻璃化转变温度(T_(g))≥413℃,其中,PI-3的T_(g)高达482℃;PI薄膜的5%热失重温度均≥557℃,50~350℃之间的热膨胀系数为4.70×10^(–7)~9.92×10^(–6) K^(–1);PI薄膜的拉伸强度为132.1~156.5 MPa,拉伸模量为4.4~5.3 GPa,断裂伸长率为3.33%~5.14%。
Four types of polyamide acid(PAA)glue were synthesized from polycondensation of 2,7-diamino-5,10-diketo-4,9-diazapyrene(Ⅱ),a diamine monomer containing a pyrene structure obtained from iron powder reduction of 3,3′,5,5′-tetranitro-2,2′-biphenyldicarboxylic acid(Ⅰ)which was prepared from 2,2′-diphenyl dicarboxylic acid,with 4,4′-oxyphthalic anhydride,3,3′,4,4′-benzophenone tetracarboxylic anhydride,3,3′,4,4′-biphenyl tetracarboxylic anhydride,and 2,3,3′,4′-biphenyl tetracarboxylic anhydride,respectively,and the corresponding four polyimide(PI)films(PI-1~PI-4)were then constructed by film casting.Dinitro compoundⅠand diamine monomerⅡwere identified by 1HNMR and 13CNMR,while the four PI films and PAA glues were characterized by FTIR and GPC.The thermal properties and mechanical properties of PI films were evaluated by color haze meter,TGA,TMA,DMA,and universal electro-mechanical tester.The results indicated that the number-average relative molecular mass(Mn)of PAA ranged from 9.90×10^(4) to 1.29×10^(5),while the average transmittance of these PI films ranged from 1.10%to 3.27%between 400 nm and 750 nm,with light(L*)values between 9.79 and 21.08,classifying the films as black.The glass transition temperature(T_(g))of PI films were equal or greater than 413℃,with that of PI-3 reaching 482℃.The 5%decomposition temperature of PI films were equal or great than 557℃,and their coefficients of thermal expansion ranged from 4.70×10^(–7) to 9.92×10^(–6) K^(–1) in the temperature range of 50℃to 350℃.The PI films exhibited tensile strengths of 132.1~156.5 MPa,tensile modulus of 4.4~5.3 GPa and elongations at break of 3.33%~5.14%.
作者
廉萌
郑凤
刘玉花
刘军
LIAN Meng;ZHENG Feng;LIU Yuhua;LIU Jun(Shandong Engineering Laboratory for Clean Utilization of Chemical Resources,Weifang University of Science and Technology,Weifang 262700,Shandong,China;School of Chemical Science and Engineering,Tongji University Shanghai 200092,China)
出处
《精细化工》
北大核心
2026年第2期271-277,共7页
Fine Chemicals
基金
山东省自然科学基金青年项目(ZR2021QB194)。
关键词
杂芘结构
二胺制备
黑色聚酰亚胺
薄膜
高耐热
功能材料
heteropyrene structure
diamine synthesis
black polyimides
films
high thermal resistance
functional materials
