Polyurethanes from Direct Organocatalytic Copolymerization of p‐Tosyl Isocyanate with Epoxides

The direct copolymerization of p -tosyl isocyanate (TSI) with epoxides, initiated by onium salts in the presence of trialkylborane, to produce polyurethanes is reported. The rate of copolymerization and the (regio)selectivity were investigated in relation to the trialkylborane and initiator used. Under optimized conditions such copolymerizations have been successfully performed for a wide range of epoxides, including ethylene oxide, propylene oxide, 1-octene oxide, cyclohexene oxide, and allyl glycidyl ether. These copolymerizations afford a new category of polyurethanes, clear of side products such as cyclic oxazolidinone, isocyanurate, and poly(isocyanate) linkages. The experimental conditions used in this work are compatible with those for the organocatalytic (co)polymerization of other oxygenated monomers and CO 2 , holding the potential for their terpolymerization with p -tosyl isocyanate and the development of new materials with unprecedented properties.