화학공학소재연구정보센터
Polymer, Vol.36, No.24, 4665-4674, 1995
Photochemistry and Photoinitiator Properties of 2-Substituted Anthraquinones .2. Photopolymerization and Flash-Photolysis
The photoinduced polymerization activities of fifteen 2-substituted anthraquinones have been determined in different monomers and prepolymers using real-time Fourier-transform infra-red spectroscopy and photocalorimetry. The relative order in photoinitiator efficiency is found to be highly dependent upon the method used, the nature of the light source, amine co-synergist and monomer being crucial factors. Oxygen quenching in all cases indicates that the triplet state is the active precursor. Without an amine co-synergist, absolute quantum-yield measurements show that anthraquinones with electron-withdrawing groups are more active than those which are electron-donating. However, in the presence of a tertiary amine and under polychromatic illumination, the effects are different. In the latter case amido derivatives with long-wavelength charge-transfer bands and mixed n pi*pi pi* triplet states tend to be more reactive. Fluorescence and phosphorescence analyses indicate a high rate of intersystem crossing to the triplet state. The relative positions of the lowest excited singlet pi pi* and second excited n pi* triplet states play an important role in determining their photoactivities, as shown in paper 1. Seraiquinone radical and radical-anion intermediates are observed using microsecond flash phorolysis and the data interrelated to their spectroscopic and photopolymerization activities. The haloanthraquinones are shown to undergo an additional mechanism involving dehalogenation.