A novel approach for environmentally benign synthesis and solid-state polymerization of fluorinated polyimides in aqueous co-solvent

Abstract

This study presents a novel approach that enables an environmentally benign water-based co-solvent synthesis of fluorinated polyimides (FPIs) using conventional fluorine-based monomers such as 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 2,2′-bis(trifluoromethyl)benzidine (TFMB). The high surface tension inherent in fluorine-based materials, which inhibits water solubility, can be overcome by mixing water with an alcohol-based solvent. The surface tension of the co-solvent decreases proportionally with the alcohol content, facilitating synthesis from fluorine-based monomers that were previously inaccessible in water. Oligomeric fluorinated poly(amic acid) salt (FPAAS) can be rapidly synthesized in aqueous solutions containing alcohol, particularly 1-propanol (PrOH). Subsequent coating and thermal treatment processes allow high molecular weight FPI films to be produced by solid-state polymerization. A comprehensive analysis of the resulting FPI films shows excellent physical properties comparable to conventionally synthesized FPI films. The 6FDA-TFMB-based FPI exhibits remarkable thermal stability up to 570 °C (Td,5%), low yellow index of 1.37, high transparency of 92.9 % and tensile strength of 116.5 MPa. The presented synthetic strategy allows the adoption of monomers with different fluorine-based substituents, thus providing insights for future aqueous synthesis. The thermal, mechanical, and optical qualities of FPIs can be utilized to create optically clear heating devices. The transparent heater, fabricated on the FPI film utilizing a laser patterning technique to create electrodes from silver nanowires, was capable of increasing the temperature up to 100 °C under a 9 V voltage application.