Reaction behaviour and kinetic constants for photopolymerizations of multi(meth)acrylate monomers

Abstract

The polymerization behaviour of a series of multifunctional methacrylate and acrylate monomers was studied using differential scanning calorimetry to characterize the reaction rate profiles. The polymerization rates, double-bond conversion and kinetic constants were determined for each of the monomers, as well as the effects of monomer type, functionality and rates of polymerization on the reaction behaviour. In particular, by quantifying the kinetic constants for termination and propagation, the controlling mechanism for each of these processes was determined as a function of conversion. In contrast to linear polymerizations, the termination mechanism for these reactions proceeded primarily through reaction diffusion. This behaviour was seen as the termination kinetic constant became proportional to the propagation kinetic constant at very low double-bond conversions. In comparing the acrylates to the methacrylates, the increased reactivity of the acrylates was apparent in the greater values (by three orders of magnitude) of both the termination and propagation kinetic constants. Also, as the number of acrylate or methacrylate groups in the monomer was increased, the kinetic constants correspondingly decreased. This decrease resulted mainly from the greater viscosity of the higher-functionality monomers, attributed to their large molecular weights. Finally, with the exception of the trimethacrylate and triacrylate, the average number of double bonds reacted per monomer at the maximum conversion was near unity, independent of the monomer type or functionality.