Aromatic Polyimide Membranes with tert -Butyl and Carboxylic Side Groups for Gas Separation Applications-Covalent Crosslinking Study.

A set of aromatic copolyimides was obtained by reaction of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), and mixtures of the diamines 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,5-di- tert -butylbenzene (CF 3 TBAPB) and 3,5-diamino benzoic acid (DABA). These polymers were characterized and compared with the homopolymer derived from 6FDA and CF 3 TBAPB. All copolyimides showed high molecular weight values and good mechanical properties. The presence of carboxylic groups in these copolymers allowed their chemical crosslinking by reaction with 1,4-butanediol. Glass transition temperatures (Tg) were higher than 260 °C, showing the non-crosslinked copolyimides had the highest Tg values. Degradation temperature of crosslinked copolyimides was lower than their corresponding non-crosslinked ones. Mechanical properties of all polymers were good, and thus, copolyimide (precursor, and crosslinked ones) films could be tested as gas separation membranes. It was observed that CO 2 permeability values were around 100 barrer. Finally, the plasticization resistance of the crosslinked material having a large number of carboxylic groups was excellent.