Photopolymerization of pigmented thiol–ene systems

Photopolymerization kinetics and optical properties of pigmented thiol–ene coatings were investigated using photo-DSC, real-time FTIR, colorimetry, and AFM. Pigment has no deleterious effect on the unique ability of thiol–ene systems to photopolymerize in air. When trimethylolpropane tris-(3-mercaptopropionate) is incrementally added to tripropylene glycol diacrylate with and without calcium lithol rubine, a red organic pigment, the photopolymerization rate in nitrogen steadily decreases due to a shift in the polymerization mechanism from an acrylate homopolymerization to a thiol–ene copolymerization. However, the photopolymerization rate of pigmented and non-pigmented systems in air significantly increases with increasing thiol concentration, ultimately reaching a maximum at approximately 35 mole percent trifunctional thiol. The increase in rate is due to chain transfer from the non-reactive peroxy radical to the thiol. Thiol groups reduce oxygen inhibition to a greater degree than standard additives such as N-methyldiethanolamine, N-vinyl pyrrolidinone, and thioether containing trifunctional vinyl esters. For a typical acrylate based pigmented photocurable system, greater than 10 wt% photoinitiator is required to achieve a photopolymerization rate equivalent to a comparable thiol–ene system with 1 wt% photoinitiator in air. AFM and colorimetric data indicate that addition of trifunctional thiol has no deleterious effect on pigment dispersion and may in fact increase dispersion quality.