Aromatic polyimides have excellent thermal stability, mechanical strength and toughness, high electric insulating properties, low dielectric constants and dissipation factors, and high radiation and wear resistance, among other properties, and can be processed into a variety of materials, including films, fibers, carbon fiber composites, engineering plastics, foams, porous membranes, coatings, etc. Aromatic polyimide materials have found widespread use in a variety of high-tech domains, including electric insulating, microelectronics and optoelectronics, aerospace and aviation industries, and so on, due to their superior combination characteristics and variable processability. In recent years, there have been many publications on aromatic polyimide materials, including several books available to readers. In this review, the representative progress in aromatic polyimide films for electronic applications, especially in our laboratory, will be described.

Fluorinated aromatic polyimide (FAPI) films with rigid polymer backbones have been prepared by chemical imidization approach. The polyimide films exhibited excellent mechanical properties including elastic modulus of up to 8.4 GPa and tensile strength of up to 326.7 MPa, and outstanding thermal stability including glass transition temperature (T_g) of 346.3–351.6 °C and thermal decomposition temperature in air (T_d5) of 544.1–612.3 °C, as well as high colorless transmittance of >81.2% at 500 nm. Moreover, the polyimide films showed stable dielectric constant and low dielectric loss at 10–60 GHz, attributed to the close packing of rigid polymer backbones that limited the deflection of the dipole in the electric field. Molecular dynamics simulation was also established to describe the relationship of molecular structure and dielectric loss.

The thermal and mechanical properties of the chemically imidized polyimide (CIPI) films and thermally imidized polyimide (TIPI) films were investigated systematically. Experimental results indicated that the CIPI films show dramatically enhanced tensile strength and modulus with obviously reduced coefficient of thermal expansion (CTE) in comparison with TIPI films. These enhancements results from the high in-plane orientation and close packing of the CIPI backbones. Compared with thermal imidization which starts at about 140 °C, the chemical imidization activated by acetic anhydride and isoquinoline initiates the cyclization even at room temperature. The resulting imide rings restrict the mobility of polymer chains and lead to the in-plane orientation with solvent evaporation. Additionally, fewer small molecules remain in the films after treated at 120 °C by chemical imidization than by thermal imidization. The polymer chain plasticization caused by the evaporation of small molecules at high temperature is obviously restricted. Moreover, the partially imidized polymer inhibits the decomposition of mainchains that occurs at subsequent high temperature process, being beneficial to the formation of high molecular weight PI films. Hence, chemical imidization pathway shows apparent advantage to produce PI films with great combined properties, including high modulus, strength and toughness, as well as high thermal dimension stability etc.