Preparation and characterization of fluorine-containing aromatic condensation polymers. I. Preparation and characterization of fluorine-containing polycarbonate and copolycarbonates by two-phase phase-transfer-catalyzed polycondensation of 2,2-bis (4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and/or 2,2-bis (4-hydroxyphenyl)propane with trichloromethyl chloroformate

A series of fluorine-containing homopolycarbonate and copolycarbonates with a wide range of unit ratio were synthesized by the two-phase phase-transfer-catalyzed plycondensation of 2,2-bis (4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (Bisphenol AF) and/or 2,2-bis (4-hydroxy-phenyl) propane (Bisphenol A) with trichloromethyl chloroformate, and the effect of the fluorine substitution on the synthesis and properties of these polymers was investigated by comparing with those of Bishphenol A-based homopolycarbonate without fluorine. Film-forming moderate-to high-molecular-weight fluorine-containing polycarbonates with reduced viscosities up to 0.54 dL/g were obtained in high yields by using tetra-n-butylammonium bromide as a catalyst, sodium hydroxide as a base, and 1,2-dichloroethane as a medium. The reduced viscosity, however, decreased markedly with increasing feed ratio of Bisphenol AF. Their solubility in common organic solvents was clearly improved by the introduction of fluorine atom. The pliability of the films also increased remarkably with increasing fluorine content. The contact angles formed by water were larger than 90°, regardless of their fluorine contents, at 25°C in air. The critical surface tension and refractive index of Bisphenol AF-based homopolycarbonate were ca. 20 dyn/cm and 1.426, respectively. The glass transition temperatures and thermal stability increased monotonously with increasing fluorine content.