Mainchain and sidechain-involving H-bonded asymmetric polyimides containing rigid amide and flexible ether linkages

Hydrogen bonds (H-bonds), usually mainchain amide H-bonds, have been well recognized to play important roles in modulating the properties of polyimides (PIs) by strengthening macromolecular interaction. While the structure-properties relationships of symmetric mainchain amide H-bonded PIs have been extensively researched, the asymmetric H-bonded PIs, particularly those containing rigid-flexible backbone structure, and sidechain-involving H-bonds, have been rarely explored. Herein, starting from designed synthesis of diamine monomers, we present two series of asymmetric PIs containing rigid amide and flexible ether linkages that form mainchain amide-amide and amide-imide H-bonds, lacking or bearing pendent trifluoromethyls (-CF₃) that form sidechain-involving amide-CF₃ H-bonds. The presence of these three types of H-bonds were revealed by RDF simulation and confirmed by FTIR. Mainchain H-bonded PIs (PI-A_x) show higher T_g than sidechain-involving H-bonded PIs (PI-T_x), while PI-T_x series exhibit higher optical transparency and hydrophobicity, lower dielectric constant (ε′) and better mechanical properties than PI-A_x. The general researches on the PIs’ solubility, WAXD spectra, thermal properties, fluorescence emission and optical transparency, the dihedral angles (φ), fractional free volume (FFV), theoretical gas transport properties, chain geometry optimization and HOMO-LUMO energy gap (ΔE) values have been comprehensively carried out from the aspects of both experiments and theoretical calculation.