基于酚酞结构高可溶性聚酰亚胺的合成与性能  

Synthesis and properties of highly soluble polyimides containing phenolphthalein structure

作　　者：蔡华娟 耿凯 汪称意 李坚 任强 CAI Huajuan;GENG Kai;WANG Chenyi;LI Jian;REN Qiang(School of Materials Science and Engineering,Changzhou University,Changzhou 213164,Jiangsu,China)

机构地区：[1]常州大学材料科学与工程学院,江苏常州213164

出　　处：《精细化工》2023年第6期1287-1293,共7页Fine Chemicals

基　　金：江苏省重点研发计划(BE2022102);江苏省高校基础科学研究重大项目(22KJA430002)。

摘　　要：以百里香酚酞、对氟硝基苯为起始原料,通过芳香亲核取代和氧化还原反应得到新型芳香二胺单体5,5'-二异丙基-4,4'-二氨基苯氧基-2,2'-二甲基酚酞。该二胺单体分别与3,3',4,4'-二苯醚四甲酸二酐、3,3',4,4'-二苯酮四羧酸二酐和3,3',4,4'-联苯四甲酸二酐以一步法高温缩聚制得了一系列同时含酚酞Cardo结构及异丙基和甲基侧基的高可溶性聚酰亚胺(PI-1、PI-2和PI-3)。该系列聚酰亚胺具有优异的溶解性,室温下不仅可溶于高沸点溶剂N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜,而且能溶于低沸点溶剂氯仿,二氯甲烷和四氢呋喃,可通过其溶液浇铸制得一系列高性能聚酰亚胺薄膜。所制聚酰亚胺薄膜具有较高的光学透明性,截断波长在324~365 nm之间,450 nm的透过率在56%~78%之间。该系列薄膜玻璃化转变温度在266~289℃之间,在N2和O2下10%热失重温度均≥432℃。其拉伸强度在77~95 MPa之间,断裂伸长率在9.1%~13.0%之间,1 MHz下介电常数为2.79~3.01 F/m,表现出良好的力学性能和介电性能。A series of high soluble polyimides containing both phenolphthalein Cardo structure and isopropyl and methyl side groups(PI-1,PI-2 and PI-3)were prepared by one step high temperature condensation polymerization of diamine monomer 5,5'-diisopropyl-4,4'-diaminophenoxy-2,2'-dimethylphenolphthalein,newly synthesized from thymolphthalein and 4-fluoronitrobenzene through aromatic nucleophilic substitution and oxidation-reduction reaction,and three commoditized aromatic dianhydrides(4,4'-oxydiphthalic anhydride,4,4'-arbonyldiphthalic anhydride and 4,4'-biphthalic anhydride).The polyimides obtained exhibited excellent solubility were in both high boiling point solvents,such as N-methylpyrrolidone,N,N-dimethylacetamide,N,N-dimethylformamide,dimethyl sulfoxide,and low boiling solvents chloroform,dichloromethane and tetrahydrofuran.A series of high-performance polyimide membranes,prepared from the polyimides via solution casting method,displayed better optical transparency with cutoff wavelengths in the range of 324~365 nm and transmittance of 56%~78%at the wavelength of 450 nm.Furthermore,The glass transition temperature of the polyimide membranes was 266~289℃,and the temperatures of 10%mass loss were≥432℃in both N2 and O2.Meanwhile,these polyimides exhibited good mechanical and dielectric properties,with the tensile strength and elongation at break ranging 77~95 MPa and 9.1%~13.0%respectively,and the dielectric constants of 2.79~3.01 F/m at 1 MHz.

关 键 词：聚酰亚胺 酚酞 烷基 溶解性 介电性能 功能材料 

分 类 号：TQ323.7[化学工程—合成树脂塑料工业]