Lignin-Inspired Polymers with High Glass Transition Temperature and Solvent Resistance from 4-Hydroxybenzonitrile, Vanillonitrile, and Syringonitrile Methacrylates

We here report on the synthesis and polymerization of nitrile-containing methacrylate monomers, prepared via straightforward nitrilation of the corresponding lignin-inspired aldehyde. The polymethacrylates reached exceptionally high glass transition temperatures (T-g values), i.e., 150, 164, and 238 degrees C for the 4-hydroxybenzonitrile, vanillonitrile, and syringonitrile derivatives, respectively, and were thermally stable up to above 300 degrees C. Copolymerizations of the nitrile monomers with styrene and methyl methacrylate, respectively, gave potentially melt processable materials with tunable T-g values and enhanced solvent resistance. The use of lignin-derived nitrile-containing monomers represents an efficient strategy toward well-defined biobased high T-g polymer materials.