Abstract

A series of semi-fluorinated polymers were obtained by Friedel-Crafts polymerization of hexafluoroacetone trihydrate (HFAH) with a variety of activated and non-activated aromatic monomers. Interfacial (water/dichloroethane) electrophilic aromatic substitution (EAS) polymerizations were carried out with trifluoromethanesulfonic anhydride (Tf2O) and Aliquat® 336 as phase transfer catalyst. This versatile and straightforward method achieved the synthesis of moderate to high molecular weight (12.0–29.6 kDa) polyaryl ethers and polyphenylenes with 1,1,1,3,3,3-hexafluoroisopropylene (6F) main chain linkages. Predominantly amorphous film-forming materials were obtained with low branching, high solubilities in common organic solvents, thermo-oxidative stabilities up to 500 °C, and glass transitions (Tg) ranging from 157 to 250 °C. The optical and dielectric properties of these materials were also studied from which high visible region transmittance and low dielectric constant values comparable with commercial materials were found.

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