Page 137 - 《精细化工》2023年第6期
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第 40 卷第 6 期                             精   细   化   工                                  Vol.40, No.6
             20 23 年 6 月                             FINE CHEMICALS                                 June  2023


              功能材料
                    基于酚酞结构高可溶性聚酰亚胺的合成与性能



                                                                *
                                  蔡华娟,耿   凯,汪称意 ,李   坚,任   强
                                     (常州大学  材料科学与工程学院,江苏  常州  213164)


                 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 N 2 和 O 2 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。
                 关键词:聚酰亚胺;酚酞;烷基;溶解性;介电性能;功能材料
                 中图分类号:TQ323.7                         文献标识码:A
                 文章编号:1003-5214 (2023) 06-1287-07      开放科学 (资源服务)  标识码 (OSID):



                             Synthesis and properties of highly soluble polyimides
                                      containing phenolphthalein structure


                                                                     *
                                CAI Huajuan, GENG Kai, WANG Chenyi , LI Jian, REN Qiang
                     (School of Materials Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu, China)

                 Abstract:  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 N 2 and O 2. 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.
                 Key words: polyimides; phenolphthalein; alkyl; solubility; dielectric properties; functional materials

                 收稿日期:2022-09-17;  定用日期:2022-12-01; DOI: 10.13550/j.jxhg.20220856
                 基金项目: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)
                 作者简介:蔡华娟(1994—),女,硕士生,E-mail:1174491583@qq.com。联系人:汪称意(1981—),男,教授,E-mail:
                 wangcy@cczu.edu。
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