Preparation and Characterization of Atomic Oxygen-Resistant, Optically Transparent and Dimensionally Stable Copolyimide Films from Fluorinated Monomers and POSS-Substituted Diamine

Optically transparent polyimide (PI) films with good atomic oxygen (AO) resistance have been paid extensive attention as thermal controls, optical substrates for solar cells or other components for low Earth orbit (LEO) space applications. However, for common PI films, it is usually quite difficult to achieve both high optical transparency and AO resistance and maintain the intrinsic thermal stability of the PI films at the same time. In the current work, we aimed to achieve the target by using the copolymerization methodology using the fluorinated dianhydride 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), the fluorinated diamine 2,2-bis [4-(4-aminophenoxy)phenyl]hexafluoropropane (BDAF) and the polyhedral oligomeric silsesquioxane (POSS)-containing diamine N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS) as the starting materials. The fluoro-containing monomers were used to endow the PI films with good optical and thermal properties, while the silicon-containing monomer was used to improve the AO resistance of the afforded PI films. Thus, the 6FCDA-based PI copolymers, including 6FCPI-1, 6FCPI-2 and 6FCPI-3, were prepared using a two-step chemical imidization procedure, respectively. For comparison, the analogous PIs, including 6FPI-1, 6FPI-2 and 6FPI-3, were correspondingly developed according to the same procedure except that 6FCDA was replaced by 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Two referenced PI homopolymers were prepared from BDAF and 6FDA (PI-ref1) and 6FCDA (PI-ref2), respectively. The experimental results indicated that a good balance among thermal stability, optical transparency, and AO resistance was achieved by the 6FCDA-PI films. For example, the 6FCDA-PI films exhibited good thermal stability with glass transition temperatures (Tg) up to 297.3 °C, good optical transparency with an optical transmittance at a wavelength of 450 nm (T450) higher than 62% and good AO resistance with the erosion yield (Ey) as low as 1.7 × 10−25 cm3/atom at an AO irradiation fluence of 5.0 × 1020 atoms/cm2. The developed 6FCDA-PI films might find various applications in aerospace as solar sails, thermal control blankets, optical components and other functional materials.