Photopolymerization shrinkage-stress reduction in polymer-based dental restoratives by surface modification of fillers

[Display omitted] •Polymer brush surface modification of filler particles reduces shrinkage stress compared to conventional silane treatment.•Level of shrinkage stress reduction is proportional to oligomer length and inversely proportional to reactive groups number.•Reduced shrinkage stress is due to delayed development of stress with respect to double bond conversion development. This research explores the use of polymer brushes for surface treatment of fillers used in polymer-based dental restoratives with focus on shrinkage stress reduction. The influence of interfacial reactive groups on shrinkage stress is explored. Oligomers of varying lengths and with varying number of reactive groups along the length were synthesized by modifying commercial oligomers. Surface of silica fillers (OX50) was treated with methylaminopropyltrimethoxysilane and this was further reacted with the synthesized oligomers to obtain a series of polymer brushes on the surface. Fillers modified with γ-methacryloxypropyltrimethoxysilane were used as a control. Filler surface treatment was confirmed using diffuse reflectance spectroscopy and thermogravimetric analysis. Fillers were added at 30 wt % to a resin made of BisGMA/TEGDMA and polymerization kinetics, shrinkage stress, volumetric shrinkage, flexural strength and modulus, viscosity were measured. Composites with polymer brush functionalized fillers showed up to a 30 % reduction in shrinkage stress as compared to the control, with no reduction in flexural strength and modulus. Shrinkage stress reduced with increasing length of the polymer brush and increased with increase in number of reactive groups along the length of the polymer brush. The interface between inorganic fillers and an organic polymer matrix has been utilized to reduce shrinkage stress in a composite with no compromise in mechanical properties. This study gives insights into the stress development mechanism at the interface.