Long-term toughness of photopolymerizable (meth)acrylate networks in aqueous environments

Photopolymerizable (meth)acrylate networks are potentially advantageous biomaterials due to their ability to be formed in situ, their fast synthesis rates and their tailorable material properties. The objective of this study was to evaluate how immersion time in phosphate-buffered saline (PBS) affects the toughness of photopolymerizable methyl acrylate (MA)-co-methyl methacrylate-co-poly(ethylene glycol) dimethacrylate networks containing various concentrations of MA. Stress-strain behavior was determined by performing tensile strain to failure testing after soaking in PBS for different periods (1 day up to 9 months). In tandem, differential scanning calorimetry and PBS content measurements were undertaken at each time point in order to determine whether time-dependent changes in toughness were related to changes in T(g) or PBS absorption. The effect of immersion time on network toughness was shown to be dependent upon composition in a manner related to the viscoelastic state of the polymer upon initial immersion in PBS. The results demonstrate that tough acrylate-based materials may not maintain their toughness after several months in PBS. In addition, decreasing the PBS content by changing the network hydrophobicity resulted in better toughness maintenance after 9 months. The results provide a possible means to toughen various amorphous acrylate-based implant materials that are being explored for load-bearing biomedical applications, beyond the systems considered in this work.