Novel dental restorative materials having low polymerization shrinkage stress via stress relaxation by addition-fragmentation chain transfer

ObjectivesTo produce a reduced stress dental restorative material while simultaneously maintaining excellent mechanical properties, we have incorporated an allyl sulfide functional group into norbornene–methacrylate comonomer resins. We hypothesize that the addition-fragmentation chain transfer (AFCT) enabled by the presence of the allyl sulfide relieves stress in these methacrylate-based systems while retaining excellent mechanical properties owing to the high glass transition temperature of norbornene-containing resins.MethodsAn allyl sulfide-containing dinorbornene was stoichiometrically formulated with a ring-containing allyl sulfide-possessing methacrylate. To evaluate the stress relaxation effect as a function of the allyl sulfide concentration, a propyl sulfide-based dinorbornene, not capable of addition-fragmentation, was also formulated with the methacrylate monomer. Shrinkage stress, the glass transition temperature and the elastic modulus were all measured. The composite flexural strength and modulus were also measured. ANOVA (CI 95%) was conducted to determine differences between the means.ResultsIncreasing the allyl sulfide content in the resin dramatically reduces the final stress in the norbornene–methacrylate systems. Both norbornene–methacrylate resins demonstrated almost zero stress (more than 96% stress reduction) compared with the conventional BisGMA/TEGDMA 70/30 wt% control. Mechanical properties of the allyl sulfide-based dental composites were improved to the point of being statistically indistinguishable from the control BisGMA–TEGDMA by changing the molar ratio between the methacrylate and norbornene functionalities.SignificanceThe allyl sulfide-containing norbornene–methacrylate networks possessed super-ambient Tg, and demonstrated significantly lower shrinkage stress when compared with the control (BisGMA/TEGDMA 70–30 wt%). Although additional development remains, these low stress materials exhibit excellent mechanical properties which are appropriate for use as dental restorative materials.