Preparation and Characterization of Fluorine-containing Aromatic Condensation Polymers VIII. Aromatic Polyether and Copolyethers from 2,2-Bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-Bis(4-hydroxyphenyl)propane, or both and Bis(4-fluorophenyl)phenylphosphine Oxide

Abstract

A series of hexafluoroisopropylidene group-containing aromatic polyether and copolyethers with a wide range of unit ratios were synthesized by high-temperature solution polycondensation of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (1a), 2,2-bis(4-hydroxyphenyl)propane (1b), or both with bis(4-fluorophenyl)phenylphosphine oxide, and the effect of fluorine substitution on the properties of these polymers is discussed in relation to the fluorine contents. High- to moderate-molecular-weight polyethers with reduced viscosities of 0.39–0.55 dL g−1 were obtained in high yields by using anhydrous potassium carbonate as a base and N,N-dimethylacetamide as a medium at 160 °C for 48 h. Regardless of the fluorine contents, these polymers all were soluble in various organic solvents, including benzene, chloroform, and tetrahydrofuran, and afforded colorless, transparent, and tough films by solution casting. The contact angles of the films to water increased significantly with increasing fluorine content. The glass transition temperatures also increased monotonously with the increase of fluorine content, whereas the temperatures of 5% weight loss and 10% weight loss under nitrogen were scarcely affected by fluorine substitution. These films with and without fluorine exhibited a very sharp cutoff at a wavelength shorter than 290 nm and are colorless. Optically estimated dielectric constant of 1a-based homopolyether was 2.79, which was remarkably lower than the value of 1b-based homopolyether, 2.97.