A study of shrinkage stress reduction and mechanical properties of nanogel-modified resin systems

A series of nanogel compositions were prepared from urethane dimethacrylate (UDMA) and isobornyl methacrylate (IBMA) in the presence of a thiol chain transfer agent. The linear oligomer of IBMA was synthesized by a similar solution polymerization technique. The nanogels were prepared with different crosslinker concentrations to achieve varied branching densities and molecular weights. The prepolymers were dispersed in triethylene glycol dimethacrylate at loading levels ranging from 10 wt.% to 50 wt.%. Photopolymerization reaction kinetics of all prepolymer modified systems were enhanced relative to the nanogel-free control during early stage polymerization while limiting conversion was similar for most samples. Volumetric polymerization shrinkage was reduced proportionally with the prepolymer content while the corresponding decrease in polymerization stress was potentially greater than an additive linear behavior. Flexural strength for inert linear polymer-modified systems decreased significantly with the increase in the prepolymer content; however, with an increase in the crosslinker concentration within the nanogel additives, and an increase in the concentration of residual pendant reactive sites, flexural strength was maintained or improved regardless of the nanogel loading level. This demonstrates that covalent attachment rather than just physical entanglement with the polymer matrix is important for effective polymer mechanical reinforcement by nanogel additives. Reactive nanogel additives can be considered as a practical, generic means to achieve substantial reductions in polymerization shrinkage and shrinkage stress in common polymers.

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► Several nanogels were synthesized with different crosslinking densities and residual double bond concentration.
► With nanogel presents in a resin system, reaction rate can be reinforced and a similar final conversion.
► Mechanical properties can be maintained at a high level with control for the nanogel with highest crosslinking density.
► Nanogels can reduce shrinkage and stress during network formation in a proportional manner.
► Nanogel swelling behavior can be evaluated from tan δ profiles.