共聚法制备低热膨胀透明聚酰亚胺薄膜
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摘要
针对含氟聚酰亚胺薄膜透明度高但热膨胀系数大的问题,以4,4'-(六氟异丙烯)二酞酸酐(6FDA)为含氟二酐,4,4'-二氨基-2,2'-双三氟甲基联苯(TFMB)为原料,采用引入分子结构相对对称的刚性单体1,2,4,5-均苯四甲酸二酐(PMDA)进行共聚的方法合成了三种含氟比例不同的透明聚酰亚胺薄膜,编号为PI-1、PI-2、PI-3,作为对照,以PMDA和ODA(4,4-二氨基二苯醚)合成了PI-4,并对其性能进行了表征。热重分析表明,引入刚性单体共聚提高了含氟薄膜的热稳定性;介电测试显示,含氟薄膜的介电常数小于传统聚酰亚胺薄膜,PI-1的介电常数小于共聚薄膜PI-2和PI-3.;紫外-可见光谱图表明含氟聚酰亚胺薄膜的透光率明显大于传统薄膜,PI-1、PI-2、PI-3的截断波长分别为355 nm、360 nm和372 nm,黄色指数分别为6. 4、6. 9和8. 94,三种薄膜在波长500 nm处的透过率均超过90%;拉伸试验显示含氟聚酰亚胺薄膜的拉伸强度远低于传统聚酰亚胺,在添加部分刚性单体后,其力学强度有所增大;四种薄膜的热膨胀系数分别为14. 8×10~(-5)/℃、9. 9×10~(-5)/℃、5. 4×10~(-5)/℃和4. 0×10~(-5)/℃,随着PMDA含量的增加,薄膜的热膨胀系数明显降低。
To overcom the shortcoming of fluorinated polyimide films such as low reaction activity and high coefficien of thermal expansiont,rigid monomer pyromellitic dianhydride( PMDA) were used to copolymerize with two Fluorinated monomers 4,4-( hexafluoroisopropylidene) diphthalic anhydride( 6 FDA) and 2,2-bis( trifluoromethyl) benzidine( TFMB) to form a serials of PAA solution,as control,PI-4 were synthesized by PMDA and ODA( 4,4-two amino two phenyl ether). After that,the obtained PAA solution was heated at the following order to produce transparent polyimide films,80℃/1 h,110℃/2 h,150℃/2 h,200℃/1 h,250℃/30 min,300℃/30 min,the obtained PI films which had pyromellitic dianhydride content of 0%,20% and 40% were numbered as PI-1,PI-2,PI-3, relatively, and its phsical and chemical properties were characterized. The thermogravimetric analysis showed that thermal stability of fluorinated films is slightly lower than that of traditional film; the dielectric tests showed that the fluoride film's dielectric constants were smaller than traditional polyimide film,the dielectric constant of PI-1 is less than PI-2 and PI-3 copolymer films; the UV-Vis spectra showed that the transmittance of fluorinated polyimide film was significantly higher than that of conventional film,cutoff wavelength and yellow index of PI-1,PI-2,PI-3 was 355 nm,360 nm,372 nm,and 6. 4,6. 9,8. 94,relatively. All three films' transmittance at the wavelength of 500 nm were more than 90%; the tensile test showed that the tensile strength of fluorinated polyimide films was much lower than that of the conventional polyimide,but it increased after the addition of rigid monomers; the thermal expansion coefficients of four kinds of films were 14. 8 × 10~(-5)/℃,9. 9× 10~(-5)/℃,5. 4 × 10~(-5)/℃ and 4. 0 × 10~(-5)/℃,respectively,which were decreased with the increase of the content of of PMDA content.
To overcom the shortcoming of fluorinated polyimide films such as low reaction activity and high coefficien of thermal expansiont,rigid monomer pyromellitic dianhydride( PMDA) were used to copolymerize with two Fluorinated monomers 4,4-( hexafluoroisopropylidene) diphthalic anhydride( 6 FDA) and 2,2-bis( trifluoromethyl) benzidine( TFMB) to form a serials of PAA solution,as control,PI-4 were synthesized by PMDA and ODA( 4,4-two amino two phenyl ether). After that,the obtained PAA solution was heated at the following order to produce transparent polyimide films,80℃/1 h,110℃/2 h,150℃/2 h,200℃/1 h,250℃/30 min,300℃/30 min,the obtained PI films which had pyromellitic dianhydride content of 0%,20% and 40% were numbered as PI-1,PI-2,PI-3, relatively, and its phsical and chemical properties were characterized. The thermogravimetric analysis showed that thermal stability of fluorinated films is slightly lower than that of traditional film; the dielectric tests showed that the fluoride film's dielectric constants were smaller than traditional polyimide film,the dielectric constant of PI-1 is less than PI-2 and PI-3 copolymer films; the UV-Vis spectra showed that the transmittance of fluorinated polyimide film was significantly higher than that of conventional film,cutoff wavelength and yellow index of PI-1,PI-2,PI-3 was 355 nm,360 nm,372 nm,and 6. 4,6. 9,8. 94,relatively. All three films' transmittance at the wavelength of 500 nm were more than 90%; the tensile test showed that the tensile strength of fluorinated polyimide films was much lower than that of the conventional polyimide,but it increased after the addition of rigid monomers; the thermal expansion coefficients of four kinds of films were 14. 8 × 10~(-5)/℃,9. 9× 10~(-5)/℃,5. 4 × 10~(-5)/℃ and 4. 0 × 10~(-5)/℃,respectively,which were decreased with the increase of the content of of PMDA content.
引文
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[20]俞娟,蒋远媛,阔正波,等.高模量、低热膨胀系数聚酞亚胺杂化薄膜的制备[J].材料导报,2009,23(14):58.
[2]孙涛,张颜,郭建,等.石墨烯/氧化锡复合透明导电薄膜的制备及性能[J].哈尔滨理工大学学报,2017,22(1):114.
[3] HSU S C,WHANGg W T,HUNG C H,et al. Effect of the Polyimide Structure and ZnO Concentration on the Morphology and Characteristics of Polyimide/ZnO Nanohybrid Films[J]. Macromolecular Chemistry and Physics,2005,206(2):291.
[4] MEADOR A B,MALOW E J,SILVER,et al. Mechanically Strong,Flexible Polyimide Aerogels Cross-linked with Aromatic Triamine[J]. ACS Applied Materials&Interfaces,2012,4(2):536.
[5] QIU X M,WANG H Q,ZHOU C Y,et al. Polyimide/Kaolinite Composite Films:Synthesis and Characterization of Mechanical,Thermal and Waterproof Properties[J]. Journal of the Taiwan Institute of Chemical Engineers,2014,45:2021.
[6] GHOSH D S,CHEN T L,MKHITARYAN V,et al. Ultrathin Transparent Conductive Polyimide Foil Embedding Silver Nanowires[J]. ACS Applied Materials&Interfaces,2014; 6(23):20943.
[7] DAMACEANU M D,SAVAI,CONSTANTIN C P. The Chromic and Electrochemical Response of CoCl2-Filled Polyimide Materials for Sensing Applications[J]. Sensors&Actuators:B. Chemical,2016,234:549.
[8] WANG Y,WU X J,FENG C G,et al. Improved Dielectric Properties of Surface Modified BaTiO3/polyimide Composite Films[J].Microelectronic Engineering,2016,154:17.
[9] SONG K,NOH J,JUN T,et al. Fully Flexible Solution-Deposited ZnO Thin-Film Transistors[J]. Advanced Materials,2010,22(10):4308.
[10]张明艳,程同磊,高升,等.碳纳米管的表面处理对MWNTs/PI杂化薄膜拉伸性能的影响[J].哈尔滨理工大学学报,2017,22(4):87.
[11] TIAN G F,ZHANG H,LIU J,et al. Enhanced Conductivity and Mechanical Properties of Polyimide Based Nanocomposite Materials with Carbon Nanofibers via Carbonization of Electrospun Polyimide Fibers[J]. Polymer Science Series A,2014,56(4):505.
[12] HYOUNG W,JAESUNG P,SUNG H S,et al. Transparent Flexible Organic Transistors Based on Monolayer Grapheme Electrodes on Plastic[J]. Advanced Materials,2011,23(5):1752.
[13] BESSONOV M I,ZUBKOV V A. Polyamic Acids and Polyimides:Synthesis,Transformations,and Structure[P]. CRC Press:Boca Raton,FL. 1993. 3.
[14] CHOIA H,SOHN B,CHANG J H. Synthesis and Characterization of Transparent Copolyimide Films Containing CF3Groups:Comparison with Copolyimide Nanocomposites[J]. Aplied Clay Science,2010,48(1/2):117.
[15]徐庆玉,范和平,王洛礼.低热膨胀聚酰亚胺研究进展[J].高分子材料科学与工程,2002,18(6):29.
[16]吕静,党智敏.低热膨胀系数纳米碳化硅/聚酰亚胺复合薄膜的制备与性能[J].复合材料学报,2011,28(5):41.
[17] SULLIVAN L M,LUKEHART C M. Zirconium Tungstate(Zr W2O8)/Polyimide Nanocomposites Exhibiting Reduced Codfficient of Thermal Exoansion[J]. Chemistry of Materials,2005,17:2136.
[18] NUMATA M,SHUNICHIS O. Imaizumi Junich,et al. Thermal expansion behavior of various aromatic polyimide[J]. Polymer Journal,1985,17(8):981.
[19]黄孝华.新型功能性聚酰亚胺的合成与性能研究[D].上海:上海交通大学,2011.
[20]俞娟,蒋远媛,阔正波,等.高模量、低热膨胀系数聚酞亚胺杂化薄膜的制备[J].材料导报,2009,23(14):58.