The curing behaviour of a long-chain dimethacrylate with a series of peroxide initiators was examined by temperature-tamping DSC. The effect of oxygen inhibition on the onset and peak temperatures cure was confirmed and the peak exotherm temperature was correlated with the decomposition rate of the initiator. The gel point temperature, obtained from temperature-tamping rheology studies, was directly related to the onset of cure from temperature-tamping DSC measurements. A combination of two peroxides with significantly different initiation rates was found to reduce the maximum heat flow and spread the polymerization process over a broader range of temperatures, thus effectively counteracting the auto-acceleration effect without significantly affecting the degree of cure. This behaviour was also predicted by with a free radical polymerization kinetic model. In order to further improve the cure behaviour, Nofmer was used as a chain transfer agent to control the propagation reaction in the polymerization. The use of a dual initiator system in the presence of Nofmer yielded a smooth polymerization process occurring over a wide range of temperatures and with low heat flow. Isothermal theological studies confirmed the delay in the gel point by Nofmer.