共缩聚法制备含芴大侧基无色透明聚酰亚胺薄膜及其性能  

Colorless and Transparent Polyimide Film with Fluorene-Containing Large Side Groups Prepared by Copolycondensation Method

作　　者：韩龙 李静静 窦垚 奚桢浩[1] 郭旭虹[1] 王杰[1] HAN Long;LI Jingjing;DOU Yao;XI Zhenhao;GUO Xuhong;WANG Jie(State Key Laboratory of Chemical Engineering,School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;Maoming Branch R&D Institute,SINOPEC,Maoming 525000,Guangdong,China)

机构地区：[1]华东理工大学化工学院,化学工程联合国家重点实验室,上海200237 [2]中国石油化工股份有限公司茂名分公司研究院,广东茂名525000

出　　处：《功能高分子学报》2022年第4期365-371,I0004,共8页Journal of Functional Polymers

基　　金：国家自然科学基金(51403062)。

摘　　要：以4,4′-二氨基二苯醚(ODA)和含芴大侧基的9,9-双(3-氟-4-氨基苯基)芴(FFDA)为二胺单体,4,4′-联苯醚二酐(ODPA)为二酐单体,经常温下溶液共缩聚反应得到含FFDA的聚酰胺酸(PAA)溶液,再经化学亚胺化得到无色透明聚酰亚胺(PI)薄膜。使用傅里叶红外光谱(FT-IR)、差示扫描量热(DSC)、热重分析(TGA)、X射线衍射(XRD)分析、紫外-可见分光光度计(UV-Vis)、万能材料试验机等对PI进行了结构及性能表征。结果表明:随着n(FFDA)∶n(ODPA)的投料比增加,PI的热性能和力学性能均相应提高,当该比例达到50%时,PI的可见光透过率达到85%,且室温下在常见极性溶剂中的溶解性较好。A colorless and transparent polyimide(PI)film with excellent comprehensive properties was synthesized via chemical imidization process by using 4,4'-diaminodiphenyl ether(ODA)and 9,9-bis(3-fluoro-4-aminophenyl)fluorene(FFDA)as diamine monomers,4,4'-oxydiphthalic anhydride(ODPA)as a dianhydride monomer in dimethylformamide(DMF).The relationship between the content of FFDA and the performance of PI was studied.The optical properties,heat resistance,mechanical properties and solubilities of PI were characterized by ultraviolet-visible spectrophotometer(UV-Vis),differential scanning calorimeter(DSC),thermogravimetric analyzer(TGA),universal material testing machine,etc.The addition of diamine monomer with asymmetric large side group can increase the degree of distortion of the molecular chain to a certain extent,increase the free volume between molecules,reduce the stacking of molecular chains,and reduce the interaction among molecular chains,which weakening the charge transfer complexing effect and improving the optical transparency of the PI film.The addition of ether bonds can increase the flexibility of PI molecular chains and improve the solubility.The fluorine-containing group of the diamine part has a strong electron withdrawing effect,which significantly reduces the electron donating effect of the diamine monomer,thereby inhibiting the charge transfer complexing(CTC)effect and improving the optical performance of PI film.The results show that the PI sample with n(FFDA):n(ODPA)of 50%exhibits excellent solubility and the film presents good optical property.At ambient temperature,PI is soluble in many strong polar solvents such as N-methyl pyrrolidone(NMP),dimethyl formamide(DMF),dimethyl acetamide(DMAc)and dimethyl sulfoxide(DMSO),which also has good solubility in weak polar solvents such as tetrahydrofuran(THF).The transmittance of PI film at 500 nm attains 85%,and its UV cutoff wavelength is as low as 365 nm.Meanwhile,the PI film has excellent thermal stability and mechanical properties.

关 键 词：聚酰亚胺 共缩聚 化学亚胺化 无色透明薄膜 

分 类 号：TQ323.7[化学工程—合成树脂塑料工业]