Investigations on polymeric and monomeric intramolecularly hydrogen-bridged UV absorbers of the benzotriazole and triazine class

Various copolymers of MA-TPN 1,2-[2-hydroxy-3-tert-butyl-5-(O-[2-hydroxy-3-(2-methylpropenoyloxy)-propyl]-2-carbonyloxyethyl)phenyl]benzotriazole, and MA-TZ 1,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(2-hydroxy-3-[2-methylpropenoyloxy])propoxyphenyl]-1,3,5-triazine, with styrene, methyl methacrylate, and methacrylic acid have been synthesized by radical polymerization. Their absorption spectra in the long-wavelength UV region appear unchanged compared to those of the monomeric UV absorbers, indicating the stabilizer chromophore to remain unimpaired in the course of the polymerization. Both the monomeric and the polymeric stabilizers exhibit a strongly Stokes-shifted, temperature-dependent, low-quantum-yield fluorescence which arises from an intermediate species formed by intramolecular proton transfer. The intramolecular hydrogen bond which is essential for the photostability of this type of UV absorbers thus is still intact in the copolymers. Activation energies for the radiationless deactivation process can be evaluated from the temperature dependence of the proton-transferred fluorescence. These energies lie between 4 and 5 kJ/mol for most of the benzotriazole and triazine stabilizers investigated and show hardly any matrix dependence. Fluorescence-decay measurements with crystalline MA-TIN 1 at different temperatures reveal a close correspondence of the temperature dependence between decay times and relative quantum yields. The radiationless process thence is concluded to originate from the proton-transferred level S-1'. The decay time at room temperature is estimated at 70 ps, close to the value for crystalline TIN P. The proton-transfer-red fluorescence of MA-TIN 1, in contrast, exhibits a biexponential decay profile.