Fluorinated styrene-based monomers for cyclopolymerizations

The synthesis of versatile fluorine compounds and monomers for conducting polymer research and cyclopolymerizations is presented. Semiprotected 2,3,5,6-tetrafluoroterephthaldehyde 1 could be elaborated through Wittig olefination chemistry, deprotection and reduction to the previously unknown 4-vinyl-2,3,5,6-tetrafluorobenzylalcohol 8 in good yields. Compound 8 can be reacted to form the malonate ester, and then alkylation on the malonate moiety in mild conditions affords difunctional monomer 3. Through sequential esterifications on the malonate moiety, and subsequent alkylation, compound 4, a difunctional monomer for cyclopolymerization bearing one styrene and one perfluoroaryl styrene moiety, has been obtained. Preliminary experiments show that it is possible to cyclopolymerize 4 under free radical conditions.