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Objectives: To detail the development of ester-free thiol-ene dental resins with enhanced mechanical performance, limited potential for water uptake/leachables/degradation and low polymerization shrinkage stress., Methods: Thiol-terminated oligomers were prepared via a thiol-Michael reaction and a bulky tetra-allyl monomer containing urethane linkages was synthesized. The experimental oligomers and/or monomers were photopolymerized using visible light activation. Several thiol-ene formulations were investigated and their performance ranked by comparisons of the thermo-mechanical properties, polymerization shrinkage stress, water sorption/solubility, and reactivity with respect to a control comprising a conventional BisGMA/TEGDMA dental resin., Results: The ester-free thiol-ene formulations had significantly lower viscosities, water sorption and solubility than the BisGMA/TEGDMA control. Depending on the resin, the limiting functional conversions were equivalent to or greater than that of BisGMA/TEGDMA. At comparable conversions, lower shrinkage stress values were achieved by the thiol-ene systems. The polymerization shrinkage stress was dramatically reduced when the tetra-allyl monomer was used as the ene in ester-free thiol-ene mixtures. Although exhibiting lower Young's modulus, flexural strength, and glass transition temperatures, the toughness values associated with thiol-ene resins were greater than that of the BisGMA/TEGDMA control. In addition, the thiol-ene polymerization resulted in highly uniform polymer networks as indicated by the narrow tan delta peak widths., Significance: Employing the developed thiol-ene resins in dental composites will reduce shrinkage stress and moisture absorption and form tougher materials. Furthermore, their low viscosities are expected to enable higher loadings of functionalized micro/nano-scale filler particles relevant for practical dental systems., (Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Objectives: To assess the performance of thiol-ene dental composites based on selected ester-free thiol-ene formulations. Further, to point out the benefits/drawback of having a hydrolytically stable thiol-ene matrix within a glass filled composite., Methods: Composite samples containing 50-65wt% of functionalized glass microparticles were prepared and photopolymerized in the presence of a suitable visible light photoinitiator. Shrinkage stress measurements were conducted as a function of the irradiation time. Degrees of conversion were measured by FT-IR analysis by comparing the double bond signals before and after photopolymerization. Mechanical tests were carried out on specimens after curing as well as after extended aging in water. Dynamic mechanical analysis was employed to track the changes in storage modulus near body temperature. The properties of the thiol-ene composites were compared with those of the BisGMA/TEGDMA control., Results: Depending on the resin type, similar or higher conversions were achieved in thiol-ene composites when compared to the dimethacrylate controls. At comparable conversions, lower shrinkage stress values were achieved. Although exhibiting lower initial elastic moduli, the thiol-ene composites' flexural strengths were found to be comparable with the controls. Contrary to the control, the mechanical properties of the ester-free thiol-ene composites were shown to be unaffected by extensive aging in water and at least equaled that of the control after aging in water for just five weeks., Significance: Employing non-degradable step-growth networks as organic matrices in dental composites will provide structurally uniform, tough materials with extended service time., (Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)