Construction of novel Cu-α-diimide interactions for enhancing thermal resistance and dimensional stability of polyimide films

Abstract

The new-generation polyimide films with simultaneously outstanding thermal stability and low coefficient of linear thermal expansion (CTE) are urgently needed. Herein, coordination bonds were employed to improve polyimide films' heat resistance and dimensional stability. Polyimide-Cu complex films were fabricated by incorporating α-diimide units (bidentate ligands) into the BPDA-ODA (the structure of commercially available Upilex-R® polyimide films) backbones. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Energy dispersive X-ray mapping results showed that the coordination interactions occur between α-diimide and copper ions. Wide-angle X-ray diffraction (WAXD) and two-dimensional small-angle X-ray scattering (SAXS) spectra demonstrated that Cu-α-diimide coordination structures introduced in intermolecular chains leading polyimide films transformed from a semi-crystalline state to amorphous state, and inhibited the long-period formation structures. The plateau modulus and longer characteristic relaxation time (τ∗ = 1996.5 s) revealed by dynamic thermomechanical analysis indicated that crosslink networks were successfully formed by constructing coordination bonds. As a result, polyimide films' thermal resistance and dimensional stability were simultaneously enhanced. The typical PI-Cu50 films exhibited elevated glass transition temperatures of 353 °C (pristine PI-Cu0 ∼ 302 °C) and a lower CTE of 47.4 ppm/K (pristine PI-Cu0 films ∼ 64.4 ppm/K) in ranges of 300–400 °C, showing a promising application in the field of high-temperature environments.

Keywords

• Polyimide
• Coordination interaction
• Thermal resistance
• Dimensional stability