Network formation and compositional drift during photo-initiated copolymerization of dimethacrylate monomers

The copolymerization of viscous monomers with a nonviscous diluent comonomer was investigated. Overall, photopolymerization kinetics was compared for equimolar mixtures of triethylene glycol dimethacrylate (TEGDMA), a low viscosity monomer, with either a rigid aromatic dimethacrylate (Bis-GMA) or a flexible aliphatic urethane dimethacrylate (UDMA), as examples of viscous comonomers. Sol fraction analysis from partial cure polymerizations provided individual monomer reactivities as a function of conversion. The resin containing UDMA reached greater maximum polymerization rate and final conversion compared with the resin based on Bis-GMA. The viscous monomers (Bis-GMA or UDMA) were found to be less reactive than the diluent comonomer (TEGDMA) at nearly all stages of the photopolymerization process. The reactivity differential was especially dramatic at the latter stages of the polymerization.