The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers.

The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities-that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0-10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150°C for up to five hours or to 125°C for up to 24 hours if stabilized with 10,000 ppm BQ and could also be heated to 125°C for up to 5 hours if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal stabilization of radiation sensitizers, thereby facilitating further development of radiation crosslinkable thermoplastic SMPs.

Photo-cross-linked poly(thioether-co-carbonate) networks derived from the natural product quinic acid.

Polycarbonate networks derived from the natural product quinic acid that can potentially return to their natural building blocks upon hydrolytic degradation are described herein. Solvent-free thiol-ene chemistry was utilized in the copolymerization of tris(alloc)quinic acid and a variety of multifunctional thiol monomers to obtain poly(thioether-co-carbonate) networks with a wide range of achievable thermomechanical properties including glass transition temperatures from -18 to +65 °C and rubbery moduli from 3.8 to 20 MPa. The network containing 1,2-ethanedithiol expressed an average toughness at 25 and 63 °C of 1.08 and 2.35 MJ/m(3), respectively, and an order-of-magnitude increase in the average toughness at 37 °C of 15.56 MJ/m(3).