Visible light photopolymerization: Synthesis of new fluorone dyes and photopolymerization of acrylic monomers using them

Several 3-alkoxy-5, 7-diiodo-6-fluorones (λ_max ≈ 470 nm) have been synthesized and evaluated as initiators for photopolymerization triggered with the 515.5 nm line of an Ar⁺ laser. 2-Acyl- and 2-alkyl-4,5,7-triiodo-3-hydroxy-6-fluorones were also tested at 515.5 nm. 9-Cyano-2-Acyl- and 9-cyano-2-alkyl-4,5,7-triiodo-3-hydroxy-6-fluorones were studied and could be excited with the 632 nm line of a He–Ne laser. Dyes with long linear carbon chain alkoxy groups at C-6 showed larger molar extinction coefficients and formed polymers with better mechanical properties than did compounds with shorter carbon chains, or did the corresponding C-6 phenols. The optimum side chain length of the C-6 ether alkyl group is between 4–7 carbon atoms. With longer carbon chain alkoxy groups at C-8, e.g., octyl, the mechanical properties of the formed polymers are inferior to systems formed with the butyl isomer as photoinitiator. In the case of alkoxy groups with branched alkyl groups (e.g., 2-ethylbutyl), the relationship between dye structure and the properties of the polymers formed is less straightforward. Though the dyes react from their triplet state, the fluorescence quantum yields of the dyes and the performance of the dyes as photoinitiators appear directly related. © 1995 John Wiley & Sons, Inc.