Polyurethanes are an important class of polymers that are used for a multitude of industrial applications. However, the toxicity and non-renewability of the monomer diols, catalysts, and in particular, the diisocyanate reagents have led to the investigation of more environmentally-friendly alternatives. Polymerizations involving the reaction of diamines with cyclic carbonates and the use of diols with methyl or phenyl dicarbamates have been studied extensively. Nonetheless, there has been limited research using the more labile di(p-nitrophenyl)carbamates with diols to form polyurethanes. Inspired by the potential for di(p-nitrophenyl)carbamates to exhibit increased reactivity over methyl or phenyl dicarbamates, the work that will be presented has involved screening of conditions for polyurethane synthesis using di(p-nitrophenyl)carbamates, organocatalyst bases, and bio-sourced diols such as methyl 4,6-O-benzylidene-α-(D)-glucopyranoside. Unlike the linear dimethyl and diphenyl carbamates researched thus far, this system does not require excessive temperatures or reduced pressures to achieve reasonable polymer chain growth. Thus, a rigorous optimization of the molecular weight by varying reaction parameters was undertaken and will be discussed. Additionally, these polymers are soluble in non-polar organic solvents, unlike some of the polyhydroxyurethanes produced by condensation of diamines with cyclic carbonates. The other bio-sourced diols screened will probe the compatibility of these di(p-nitrophenyl)carbamates with primary, secondary, and even tertiary alcohols. Thus, this work will also add to the existing library of bio-sourced and renewable monomers to replace petrochemical feedstocks in polyurethane synthesis. The properties of the resulting polyurethanes will also be discussed. The fundamental study of this new class of diisocyanate analogue is expected to have far-reaching implications for improving the sustainability of polyurethane synthesis, with the alternative synthetic route being of broad interest.

Diisocyanate-free polyurethane synthesis with bio-sourced polyhydroxyls

254th National Meeting (2017)

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