Cure kinetics and thermomechanical properties of thermally stable photopolymerized dimethacrylates

A range of dimethacrylates with varying backbone flexibility were partially photocured to various conversions using p-xylylene bis-(NN-diethyldithiocarbamate) as a photoiniferter and their glass transition region investigated by dynamic mechanical thermal analysis. For isothermally cured samples, the final degree of conversion was found to increase as the length of the spacer group in the monomer was increased or as the crosslink density in the resin was lowered due to the reduced glass transition temperature which allowed greater mobility and, hence, higher cure. Increasing the curing temperature also resulted in a higher degree of conversion as the network was able to polymerize further before vitrification occurred. For the partially photocured samples, the glass transition temperature was raised as the degree of conversion was increased. Most of the measures of the breadth of the glass transition were found to increase with increased conversion for dimethacrylates with short or stiff backbones (TETDMA and bisGMA) while the transition breadth was independent of conversion for either a more flexible dimethacrylate (NEGDMA) or a dimethacrylate network with a lower crosslink density (50 wt % bisGMA/50 wt % PGEMA). This conclusion was generally confirmed by analysis of the viscoelastic parameters in the frequency domain. It is not clear whether these behaviors resulted from differences in the range of molecular motions available in tight networks or if they were due to spatially heterogeneous regions in the network. (C) 2003 Wiley Periodicals, Inc.