Experimental dental resins composed of triethyleneglycol dimethacrylate, urethane dimethacrylate, ethoxylated bisphenol-A-dimethacrylate and bisphenol A glycidyl methacrylate containing an organoclay as filler were prepared by photopolymerization. The addition of organoclay fillers results in slower polymerization rates (0.59 and 0.24 mol L-1 min-1, for the formulations without and with 15% of organoclay, respectively) and lower degrees of conversion (0.50 and 0.35 for the formulations without and with 15% of organoclay), as determined by photocalorimetry. The influence of the organoclay on the thermal and mechanical properties of the resins was evaluated using thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) techniques. The (tan δ) and E´ curves indicate the formation of more rigid materials and the damping curve data indicates more homogeneous materials. An increase of storage modulus, E’, was observed for composites with the higher organoclay filler contents. These effects are due to the higher viscosity of the systems with organoclay, resulting in a lower mobility of the radicals during the propagation step of polymerization, as well as to the scattering of the incident photopolymerizing radiation, which lowers the amount of initiation centres.

The organoclay/poly(methyl methacrylate) (PMMA) nanocomposites were prepared by in situ photopolymerization method using two solvents, ethanol and acetonitrile. The influences of organoclay loading, solvent nature and length of attached surfactant (C8 or C16) on thermal and mechanical properties were studied by thermogravimetric analysis and dynamic mechanical analysis. Alkylammonium surfactants with C8 and C16 chain lengths were evaluated as clay modifiers. All the nanocomposites prepared in acetonitrile exhibited improvement in their thermal stability, mainly due to the interaction between the clay and the polymer which is maximized by the exfoliated clay structure. In the case of PMMA and nanocomposites synthesized in ethanol, the thermal stability of polymer and nanocomposites remained practically the same once the clay structure is predominantly of the intercalated type. In comparison with pure PMMA, glass transition temperature and storage modulus of polymer are notably increased by the presence of clay. It was found that the chain length of surfactant attached to the SWy-1 clay affects the Tg values. Glass transition temperatures of nanocomposites SWy-1-C16/PMMA were significantly higher than the values obtained for nanocomposites SWy-1-C8/PMMA. This can be attributed to the modifying agent C16, which has a greater hydrophobic chain length. The organic tail can provide a better dispersion of the MMA monomer in the organoclay, resulting in a nanocomposite with predominant exfoliated structure. Another significant factor to be considered was the effect of solvent used in the nanocomposite preparation. Considering nanocomposites with the same chain length (C8 or C16), Tg values obtained for nanocomposites prepared with ethanol is higher than those observed for those prepared in acetonitrile. This was attributed to the influence of the average molecular weight; once the nanocomposites prepared in ethanol exhibited higher polymeric chains.