LAUSR

The synthesis of isocyanurate-free, linear poly(oxazolidin-2-one)s starting from diepoxides and aromatic as well as aliphatic diisocyanates is reported. N-Heterocyclic carbenes (NHCs), liberated in situ from thermally labile CO2 adducts, in combination with Lewis acids of the simplest kind (metal halides such as LiCl and MgCl2) were employed in a cooperative manner to prepare linear polymers with molecular weights (Mn) ranging from 6 to 50 kg/mol. Crucially, it is demonstrated that action of either NHC (Lewis base) or metal halide (Lewis acid) alone entails the formation of significant amounts of trimerized isocyanates (isocyanurate) and concomitant gelling of the thus cross-linked material, highlighting the advantages of a cooperative, dual catalytic approach. Reactions were conducted at 200 °C with low NHC loadings (0.5 mol %) to deliver isolated yields of 60–90% within 3–8 h polymerization time. Investigations regarding regioselectivity revealed that exclusively 5-substituted oxazolidin-2-one was forme...