Synthesis, cross-linking and carbonization of co-polyimides containing internal acetylene units for gas separation

Cross-linkable polyimides containing internal acetylene units have been synthesized by random copolymerization of 6FDA dianhydride, 2,3,5,6-tetramethyl-1,4-phenylenediamine (Durene) and 4,4′-diaminodiphenylacetylene (p-intA) diamine as materials for gas separation. Compared with 6FDA-Durene polyimide, 6FDA-Durene/p-intA co-polyimide shows denser polymer chain packing, which is confirmed by wide-angle X-ray diffraction (WAXD). The thermally treated co-polyimides are insoluble in various solvents and show an increase in T_g, indicating the formation of network structures among the polymer chains. Differential scanning calorimetry (DSC) and FT-Raman suggest that cross-linking arises from Diels-Alder cycloaddition between the internally arranged acetylene units along the polymer main chain, resulting in extended conjugated aromatic structures. The thermally cross-linked membranes show enhanced resistance to CO₂ plasticization up to around 5 × 10⁶ Pa (700 psi). The rigidified membrane structure provides increased gas selectivity without severely compromising gas permeability. The gas separation performance of carbonized membranes is remarkably superior to those of neat and cross-linked copolyimides because of a large increase in rigidification in the polymer matrix. A Diels-Alder cycloaddition reaction produces a much more rigid and planar conjugated aromatic structure in the polymer chains and results in a higher degree of graphitization during carbonization, which is confirmed by XPS and WAXD. Carbon membranes derived from co-polyimides with more internal acetylene units show much better gas separation performance than those derived from polyimides without internal acetylene units.