Preparation and Properties of Atomic-Oxygen Resistant Polyimide Films Based on Multi-Ring Fluoro-Containing Dianhydride and Phosphorus-Containing Diamine

Colorless and transparent polyimide (CPI) films with good atomic oxygen (AO) resistance and high thermal endurance are highly required in low earth orbit (LEO) space exploration. Conventional CPI films based on fluoro-containing 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) have been widely used in space applications. However, the AO erosion yields and glass transition temperatures (Tg) of the 6FDA-based CPI films have to be modified in order to meet the severe serving environments. In the current work, novel CPI films based on a multi-ring fluoro-containing 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylicdianhydride (6FCDA) monomer were developed. In order to enhance the AO resistance of the derived CPI film, a phosphorus-containing aromatic diamine, 2,5-bis[(4-aminophenoxy)phenyl]diphenylphosphine oxide (BADPO) was used to polymerize with the dianhydride to create the organo-soluble resin. Then, two phosphorus-containing CPI films (PPI), including PPI-1 (6FDA-BADPO) and PPI-2 (6FCDA-BADPO) were prepared by thermally curing of the PPI solutions at elevated temperatures. The PPI films maintained good optical transparency with transmittance values over 80% at a wavelength of 450 nm. PPI-2 exhibited a Tg value of 311.0 °C by differential scanning calorimetry (DSC) measurement, which was 46.7 °C higher than that of the PPI-1 counterpart (Tg = 264.3 °C). In addition, the PPI-2 film showed a coefficient of linear thermal expansion (CTE) value of 41.7 × 10−6/K in the range of 50~250 °C, which was apparently lower than that of the PPI-1 sample (CTE = 49.2 × 10−6/K). Lastly, both of the two PPI films exhibited good AO resistance with the erosion yields (Ey) of 6.99 × 10−25 cm3/atom for PPI-1 and 7.23 × 10−25 cm3/atom for PPI-2 at an exposure flux of 5.0 × 1020 atoms/cm2. The Ey values of the current PPI films were obviously lower than that of the standard polyimide (PI) film based on pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) (Ey = 3.0 × 10−24 cm3/atom).