Catalytic Hydrogenation of Polyurethanes to Base Chemicals: From Model Systems to Commercial and End-of-Life Polyurethane Materials.

Polyurethane (PU) is a highly valued polymer prepared from diisocyanates and polyols, and it is used in everyday products, such as shoe soles, mattresses, and insulation materials, but also for the construction of sophisticated parts of medical devices, wind turbine blades, aircrafts, and spacecrafts, to name a few. As PU is most commonly used as a thermoset polymer composed of cross-linked structures, its recycling is complicated and inefficient, leading to increasing PU waste accumulating every year. Catalytic hydrogenation represents an atom-efficient means for the deconstruction of polyurethanes, but so far the identification of an efficient catalyst for the disassembly of real-life and end-of-life PU samples has not been demonstrated. In this work, we reveal that a commercially available catalyst, Ir- iPrMACHO, under 30 bar H2 and 150-180 °C, is a general catalyst for the effective hydrogenation of the four cornerstones of PU: flexible solid, flexible foamed, rigid solid, and rigid foamed, leading to the isolation of aromatic amines and a polyol fraction. For the first time, a variety of commercial PU materials, including examples of foams, inline skating wheels, shoe soles, and insulation materials, has been deconstructed into the two fractions. Most desirable, our reaction conditions include the use of isopropyl alcohol as a representative of a green solvent. It is speculated that a partial glycolysis at the surface of the PU particles is taking place in this solvent and reaction temperatures in the presence of catalytic amounts of base. As such a more efficient hydrogenation of the solubilized PU fragments in isopropyl alcohol becomes possible. As the isolated anilines are precursors to the original isocyanate building blocks, and methods for their conversion are well-known, the work reported in this paper provides a realistic indication of a potential circular plastic economy solution for PU. Preliminary experiments were also undertaken applying Mn- iPrMACHO for the deconstruction of a commercial flexible PU foam. Although successful, more forcing conditions were required than those when applying Ir- iPrMACHO.