The thermal radical curing of four diallylic monomers were studied and was found to be very similar. Dynamic DSC of diallyl orthophthalate (DAOP) showed a strong correlation between the cure rate and the half life temperature of the initiator employed. The extent of allylic cure was found by DSC to be very dependent on the reactivity of the initiator due to a dead-end effect, and to rise towards a plateau value with increasing initiator levels. DAOP was blended with poly(vinyl chloride) (PVC) in various weight ratios by both solution and melt compounding. The compatibility between DAOP and PVC was analysed by measuring the glass transition temperatures of mixtures with dynamic mechanical thermal analysis which showed that DAOP monomer and PVC were fully miscible regardless of the composition. The cure rate of the DAOP/PVC blends was found by dynamic DSC and isothermal NIR to increase with higher levels of PVC due to a gel effect accentuated by grafting to the PVC, while the final extent of cure decreased because of topological constraints. (c) 2007 Elsevier Ltd. All rights reserved.