Cross-linking and ring opening during polymerization of heterocyclic methacrylates and acrylates

Heterocyclic methacrylates have been shown to have low polymerization shrinkage. In this paper, the extent of ring opening has been assessed by the degree of consequent cross-linking. In polymers of tetrahydrofurfuryl methacrylate and acrylate, tetrahydropyranyl and tetrahydropyran-2-ylmethyl methacrylate, fewer than 1% monomer units were involved in cross-linking and hence ring-opening reactions. 2-epoxypropyl methacrylate, when polymerized, was very extensively cross-linked indicating prolific ring opening. However, the polymerization shrinkage of this material was the highest of the heterocyclic methacrylates studied and was that predicted from the known molar volume change of methacrylate esters. Ring opening does not, therefore, appear to be a significant factor in the polymerization shrinkage of heterocyclic methacrylates.