Abstract: | The challenges and opportunities in the preparation of new fluoro- polymers are illustrated by the synthesis of fluorinated poly(ether sulfones), polyimides, and polyethers. Synthetic methods used for the preparation of new fluorinated monomers and polymers include anion-radical substitutions of perfluoroalkyl diiodides, nucleophilic additions to fluorinated olefins, perfluoroalkylsulfonyl-mediated nucleophilic sub-stitutions, and direct fluorinations with elemental fluorine. Properly placed fluorinated substituents can have significant effects on the dielectric properties, thermal stability, moisture absorption, permeability, phase transitions, and reactivity of the resulting polymers. In addition, fluorinated groups can enhance nonlinear optical effects and provide a method for chromophore alignment. The special behavior of partially fluorinated substituent groups offers unique tools for tailoring macro-molecular properties. |