基于氧杂蒽含氟二酐单体的聚酰亚胺薄膜的制备与性能研究  

Study on preparation and properties of polyimide films based on xanthene-based and fluoro-containing dianhydride monomer

作　　者：王振中 何志斌 任茜 杨昶旭 韩淑军 齐悦新 于海峰[2] 刘金刚[1] WANG Zhenzhong;HE Zhibin;REN Xi;YANG Changxu;HAN Shujun;QI Yuexin;YU Haifeng;LIU Jingang(Engineering Research Center of Ministry of Education for Geological Carbon Storage and Low Carbon Utilization of Resources,School of Materials Science and Technology,China University of Geosciences,Beijing 100083,China;Key Laboratory of Polymer Chemistry and Physics of Ministry of Education,School of Material Science and Engineering,Peking University,Beijing 100871,China)

机构地区：[1]中国地质大学(北京)材料科学与工程学院地质碳储与资源低碳利用教育部工程研究中心,北京100083 [2]北京大学材料科学与工程学院教育部高分子化学与物理重点实验室,北京100871

出　　处：《绝缘材料》2024年第10期42-52,共11页Insulating Materials

基　　金：深圳市科技计划项目(JSGG20210629144539012)。

摘　　要：采用含氟二酐单体9,9-双(三氟甲基)氧杂蒽-2,3,6,7-四酸二酐(6FCDA,Ⅱ)分别与3种芳香族二胺单体,包括2,2'-双(三氟甲基)-4,4'-二氨基二苯醚(6FODA,a)、1,4-双[(4-氨基-2-三氟甲基)苯氧基]苯(6FAPB,b)以及2,2-双[(4-氨基苯氧基)苯基]丙烷(BAPP,c),通过两步化学亚胺化工艺制备了3种含氟聚酰亚胺树脂PI-Ⅱa、PI-Ⅱb、PI-Ⅱc。采用同样的工艺,将6FCDA替换为4,4'-(六氟异亚丙基)双邻苯二甲酸酐(6FDA,Ⅰ)制备了3种参比树脂PI-Ⅰa、PI-Ⅰb、PI-Ⅰc。然后采用高温固化工艺制备了6种PI薄膜,并研究其性能。结果表明:PI-Ⅱa、PI-Ⅱb、PI-Ⅱc树脂在有机溶剂中的溶解性比PI-Ⅰa、PI-Ⅰb、PI-Ⅰc树脂更低。PI-Ⅱa、PI-Ⅱb、PI-Ⅱc薄膜较PI-Ⅰa、PI-Ⅰb、PI-Ⅰc薄膜表现出更高的玻璃化转变温度(Tg)、更低的线性热膨胀系数(CTE)以及略有下降的光学透明性和相对较高的介电常数(Dk)。其中PI-Ⅱa(6FCDA-6FODA)薄膜显示出最优的综合性能,Tg与CTE分别为362.5℃和39.6×10-6K-1,在450 nm波长处的透光率(T450)和10 GHz时的Dk值分别为83.9%和3.00。Three fluoro-containing polyimide(PI)resins(PI-IIa,PI-II_(b),and PI-II_(c))were prepared by two-step chemical imidization procedure using a fluoro-containing dianhydride 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride(6FCDA,II)and three kinds of aromatic diamines,including 2,2ʹ-bis(trifluoromethyl)-4,4ʹ-diaminodiphenylether(6FODA,a),1,4-bis[(4-amino-2-trifluoromethyl)phenoxy]benzene(6FAPB,b)and 2,2-bis[(4-aminophenoxy)benzene]propane(BAPP,c),respectively.For comparison,the referenced PI resins(PI-Ia,PI-I_(b),and PI-I_(c))were prepared with the same procedure except that 6FCDA was replaced by 4,4ʹ-(hexafluoroisopropylidene)diphthalic anhydride(6FDA).And then six kinds of PI films were prepared by high temperature curing process,and their properties were studied.The results show that the solubility of PI-IIa,PI-II_(b),and PI-II_(c)resins in organic solvents is lower than that of PI-Ia,PI-I_(b),and PI-I_(c)resins.Compared with PI-Ia,PI-I_(b),and PI-I_(c)films,PI-IIa,PI-II_(b),and PI-II_(c)films show higher glass transition temperature(T_(g)),lower linear coefficient of thermal expansion(CTE),little lower optical transparency,and relatively higher dielectric constant(Dk).The PI-IIa film has the optimal comprehensive properties,its Tg and CTE is 362.5℃and 39.6×10^(-6)K^(-1),respectively,its optical transmittances at the wavelength of 450 nm(T450)is 83.9%,and the Dk at the frequency of 10 GHz is 3.00.

关 键 词：聚酰亚胺 三氟甲基 氧杂蒽 光学性能 热性能 

分 类 号：TM215[一般工业技术—材料科学与工程] TQ323.7[电气工程—电工理论与新技术]