Several new benzoate ester derivatives of ethyl a-hydroxymethylacrylate were synthesized using phase transfer catalysis and found to display unexpectedly rapid photopolymerization; i.e., from 2 to 8 times faster than MMA. New derivatives described here include the 4fluoro-, 4-trifluoromethyl-, 4-methyl-, 2-hydroxy-, 4-nitro-, 4-methoxy-, 4-cyano-, and 3,4,5trimethoxybenzoate esters along with the parent benzoate ester. Relative reactivities of these monomers in photopolymerizations were compared with those of the nonaromatic formate, acetate, hexanoate, and stearate derivatives. Reactivities of the nonaromatic ester derivatives increased with the length of the side chain while for the more reactive aromatic esters, rates increased in the order 4-methyl-, 4-flUOrO-and benzoate < 4-trifluoromethyland 2-hydroxy-< 4-cyano-< 4-methoxy-< 3,4,5-trimethoxybenzoate. Tgs of the benzoate polymers ranged from 125°C for the 4-fluoro to 163OC for the 4-cyanobenzoate while those of the alkyl ester derivatives ranged from 15 to 78°C. Number average molecular weights of photoinitiated polymers (ca 10,000-20,000) were lower than those found for bulk and solution polymers (20,000-708,000) consistent with higher radical concentrations from photoinitiation. These materials greatly expand the number of candidates available for rapid photocure in thin film and coating applications, especially because their physical properties are those of linear rather than highly crosslinked structures formed from multifunctional systems. 0