Development of dental restorative materials based on visible light-cured multi-methacrylates

The studies described in this dissertation focus on new visible light-curing (VLC) oligomers exhibiting low shrinkage, low water sorption, and improved mechanical properties. A family of multi-methacrylates, based on poly(isopropylidenediphenol) resin (BPA), was synthesized, characterized, and evaluated. The commercial BPA resin is prepared from enzymatic polymerization (oligomerization) of bisphenol A. The BPA resin, having an average of eight phenolic hydroxyl groups per molecule, was treated with propylene carbonate, and the resultant product, i.e., propoxylated BPA (PEBPA) oligomer, was confirmed by Fourier transform infrared spectroscopy (FT-IR) and {dollar}sp{lcub}13{rcub}{dollar}C nuclear magnetic resonance (NMR). The propoxylated BPA was subsequently treated with methacryloyl chloride to produce the multi-methacrylates, identified by FT-IR and NMR. The PEBPA oligomer multimethacrylate: triethylene glycol dimethacrylate (TEGDMA) (50:50/wt:wt) blends were combined with 0.5 wt. % camphoroquinone (CQ) and 1.0 wt. % N,N-dimethylaminoethyl methacrylate (DMAEMA). The control polymers were 2,2-bis(4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl) propane (BisGMA): TEGDMA(50:50/wt:wt) blends having the same levels of CQ/DMAEMA. Differential photocalorimetry (DPC) and differential scanning calorimetry (DSC) showed these multimethacrylate/TEGDMA (neat resin) blends have polymerization characteristics comparable to the BisGMA/TEGDMA controls. These new multifunctional oligomers have lower polymerization shrinkage and lower uptake of water and other liquids, compared to BisGMA based materials. In addition, two experimental oligomers, PEBPA #2 and #3, have higher compressive strength than the BisGMA control. A biocompatibility test of the polymerized multi-methacrylate resins was performed and compared with the conventional BisGMA/TEGDMA resin and blank controls, using cell culture techniques. Human gingival fibroblasts were used for biocompatibility evaluation of these resins. The results revealed that the BPA oligomer (multi-methacrylate) based resin significantly favored the cell growth of the human gingival fibroblasts, compared to the control. An experimental composite was made from EPBPA oligomers (multi-methacrylates). The compressive strength of the experimental EPBPA containing composite was not significantly different than the commercial composite Herculite HXR. SEM photomicrographs revealed more voids in the experimental composites than the commercial composite on both the external surfaces of the prepared specimens and the subsequent fractured surfaces. This is due to the molding technique for specimen preparation and lack of good mechanical mixing for filler incorporation prior to placement of the resin in the mold for subsequent photopolymerization. However, the water sorption for the experimental EPBPA-based composite was significantly lower than the commercial Herculite (HXR) composite. This is most likely related to the hydrophobic nature of the experimental resin. These results suggest that the new type of polyfunctional methacrylate oligomers (PEBPA) have potential application in formulating dental composites as direct esthetic restorative materials with improved properties.