Probing stress relaxation behavior in glassy methacrylate networks containing thio-carbamate additives

The incorporation of thiourethane prepolymer (TU) into either the organic phase or as a surface treatment for filler particles in composites reduces polymerization stress and improves fracture toughness. The aim of this study was to gain insight into the influence of the inclusion of thiourethanes on the resulting network of methacrylate-based materials polymerizedviafree-radical mechanisms. Dynamic mechanical analysis was used to elucidate network parameters and potential stress relaxation behavior of these networks. TU oligomers were synthesized using a combination of trimethylol-tris-3-mercaptopropionate and dicyclohexylmethane 4,4′-diisocyanate and added into composite formulations at 20 wt% replacing part of the organic matrix and/or as TU-silanes used to functionalize filler particles (TU-matrix, TU-Sil or TU-matrix/sil). Materials not containing any form of TU were used as the control (in those cases, 3-(trimethoxysilyl)propyl methacrylate was used as the silane agent). Filler was added at 50 wt%. Degree of conversion was evaluated by near-IR spectroscopy, mechanical properties by 3-point bending and rotational rheometry. Dynamic mechanical analysis was used to obtain network parameters (glass transition temperature (T_g), storage modulus, cross-link density, and breadth of tan delta a proxy for network homogeneity - temperature sweep experiments) and to evaluate the potential for network relaxation (stress relaxation). TU-containing formulations showed 10% higher DC than the control. The time to reach storage/loss modulus crossover in the rheometer experiments was significantly longer for TU-matrix and TU-matrix/sil in comparison with the control (21.6, 27.9, and 5.1 s, respectively). TU-matrix and TU-matrix/sil presented significant lowerT_gthan the control (151.5, 153.8, and 161.3 °C, respectively). There were no statistical differences among the groups in terms of shear modulus, cross-link density, breadth of tan delta, flexural strength/modulus, and toughness. For at least one group (TU-matrix/sil), the relaxation time was four times faster than for the control at 105 °C. The addition of TU additives into dental polymers resulted in a stark reduction in the stress relaxation time. This behavior, in tandem with the network characterization and mechanical properties seems to indicate the TU networks undergo a variety of reversible associative and dissociative chemical reactions which facilitate enhanced stress relief.