基于苯醚型含氟二胺的聚酰亚胺膜材料的合成与表征

SYNTHESIS AND CHARACTERIZATION OF POLYIMIDES BASED ON PHENYL ETHER TYPE TRIFLUROMETHYL-CONTAINING DIAMINES

4,4′-二羟基二苯醚和2-氯-5-硝基三氟甲苯经Williamson反应得到4,4′-双(4-硝基-2-三氟甲基苯氧基)二苯醚;在Pd/C-水合肼还原作用下得到4,4′-双(4-氨基-2-三氟甲基苯氧基)二苯醚(p-6FAPE).采用3种苯醚型含氟二胺1,4-双(3-氨基-5-三氟甲基苯氧基)苯、1,4-双(4-氨基-2-三氟甲基苯氧基)苯和p-6FAPE分别与3,3′,4,4′-二苯醚四酸二酐(ODPA)和均苯四甲酸二酐通过两步法制备出6种含氟聚酰亚胺(PI),对其溶解性、热性能和光学性能进行研究.这些PI具有较好的溶解性,且具有良好的热稳定性;ODPA基PI在可见光波长范围具有优良的透明性,450 nm处的透光率超过80%.

4,4′-Bis（4-nitro-2-trifluoromethylphenoxy）diphenylether（p-6FNPE） was synthesized by the Williamson reaction between 4,4′-dihydroxydiphenyl ether and 2-chlorine-5-nitro-trifluoromethyl benzene.Then,the reduction systems of Pd/C-hydrazine hydrate were adopted to obtain the corresponding products 4,4′bis（4-amino-2-trifluoromethylphenoxy）diphenylether（p-6FAPE）.Using three kinds of phenyl ether type trifluoromethyl-containing diamine,i.e.,1,4-bis（3-amino-5-trifluoromethylphenoxy）benzene（m-6FAPB）,1,4-bis（4-amino-2-trifluoromethyl phenoxy）benzene（p-6FAPB） and p-6FAPE,and two kinds of dianhydride,i.e.,3,3′,4,4′-oxydiphthalic anhydride（ODPA） and pyromellitic dianhydride（PMDA）,six kinds of fluorine-containing polyimide（PI） films were prepared by the two-step method.The chemical structure and properties of the PI were characterized by FTIR,UV-Vis and TGA.The six kinds of fluorine-containing PI showed good solubility in aprotic polar organic solvents such as NMP,DMF and DMAc.PI obtained from m-position diamine showed better solubility.All the fluorine-containing PI films had good thermal stability,with a 5% weight loss temperature at 540℃ or higher.In the case of a same dianhydride,PI based on 6FAPE possessed higher thermal resistance than 6FAPB.Compared with PI based on PMDA,fluorine-containing PI films based on ODPA exhibited more excellent transparency in the visible wavelength range（400～700 nm）,and their transmittance at 450 nm was over 80%.PI based on p-6FAPB exhibited better transparency than p-6FAPE.PI films obtained from m-6FAPB tended to be colorless and transparent.The PI synthesized in this work could be expected to be used in the applications such as solar cell substrate and waveguide board materials.