Preparation and characterisation of heat‐resistant fluorinated co‐polyimides and their gas transport characteristics

A series of fluorinated co-polyimide films based on the 6FDA-FTPPA/BAFL backbone were prepared from 4-(3-fluoro-4-(trifluoromethyl)phenyl)-2,6-bis(4-aminophenyl)pyridine (FTPPA),commercial 9,9-bis(4-aminophenyl)fluorene (BAFL), and 4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), with varying ratios of FTPPA:BAFL units (3:1, 2:1, 1:1, 1:2, and 1:3). Co-polyimides not only exhibit high thermal stability ( T g > 357°C), good optical properties (λ cutoff > 327 nm) and hydrophobicity (contact angle >91.4°), but also favorable solubility properties in both high and low boiling organic solvents. The fractional free volume of the polymers was simulated using molecular mechanics and molecular dynamics and correlated with experimental gas separation data. The presence of bulky groups led to high FFVs (>17.8%) and the formation of large microcavities with diameters ranging from 5.48 to 5.72 Å, which efficiently increased gas permeability. In pure gas permeation experiments, the permeability coefficients of CO 2 and He for the 6FDA-FTPPA/BAFL (3:1) film were 41.48 and 79.38 bar, respectively, which were superior to those of commercial Matrimid and Kapton in terms of gas permeability. In especial, the 6FDA-FTPPA/BAFL (1:2) and 6FDA-FTPPA/BAFL (1:3) in co-polyimide membranes exhibited the most attractive separation performance for O 2 /N 2 gas pairs, approaching the 1991 Roberson upper limit.