Semicrystalline Polymers from Lignin-Derivable Monomers

Semicrystalline chain-growth polymers from lignin-derivable compounds are desirable for their potential to combine material sourcing from renewable feedstocks with performance-advantaged material properties (<i>e.g.</i>, higher tensile strengths and improved barrier properties in comparison to their amorphous polymer counterparts). Despite significant effort in the synthesis of vinyl monomers from lignin-derivable molecules, the resulting chain-growth polymers to date have been dominantly amorphous. Here, we describe the chemical transformation of lignin-derivable molecules into monomers that enable the generation of semicrystalline macromolecules. We harness living polymerization strategies to synthesize these polymers with stereoregularity under mild conditions, and we further probe the impacts of synthesis conditions on molecular weights, crystallinities, and thermal properties. This work introduces a strategy for utilizing lignin-derivable molecules to generate semicrystalline polymers with tunable properties, providing a pathway to valorize lignin for a new range of polymer applications.