Photoinitiated polymerization in ionic liquids: Kinetics and viscosity effects

The photo-induced polymerization of poly(ethylene glycol) dimethacrylate and poly(ethylene glycol) monomethacrylate (crosslinking and linear, resp.) in four imidazolium-based ionic liquids (ILs) containing the same cation or the same anion in pairs is reported. The kinetic studies were accompanied by detailed viscosity measurements, which showed the occurrence of an interesting phenomenon - a viscosity synergism in monomer/IL mixtures (i.e. the viscosity of the mixture is higher than the simple additive combination of viscosities of the two components). Viscosity synergism, very important for kinetic considerations, is especially strong for ILs of low viscosity and its magnitude depends on the monomer structure. The polymerization conducted in ILs was considerably faster than in a reference solvent. The propagation rate coefficients were influenced mainly by the anion structure whereas the termination rate coefficients by viscosity of the initial monomer/IL mixture (taking into account the synergistic effect). FTIR studies showed the existence of specific interactions between the carbonyl group in the monomer and C2-H of the imidazolium ring; the polymerization rates were directly related to the magnitude of the monomer/IL interaction.