title: Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-TgPolymeric Materials.
abstract: As viable precursors to a diverse array of macromolecules, biomass-derived compounds must impart wide-ranging and precisely controllable properties to polymers. Herein, we report the synthesis and subsequent reversible addition-fragmentation chain-transfer polymerization of a new monomer, syringyl methacrylate (SM, 2,6-dimethoxyphenyl methacrylate), that can facilitate widespread property manipulations in macromolecules. Homopolymers and heteropolymers synthesized from SM and related monomers have broadly tunable and highly controllable glass transition temperatures ranging from 114 to 205 °C and zero-shear viscosities ranging from ∼0.2 kPa·s to ∼17,000 kPa·s at 220 °C, with consistent thermal stabilities. The tailorability of these properties is facilitated by the controlled polymerization kinetics of SM and the fact that one vs twoo-methoxy groups negligibly affect monomer reactivity. Moreover, syringol, the precursor to SM, is an abundant component of depolymerized hardwood (e.g., oak) and graminaceous (e.g., switchgrass) lignins, making SM a potentially sustainable and low-cost candidate for tailoring macromolecular properties.
authors.affiliation: Department of Chemical and Biomolecular Engineering, Center for Composite Materials, and Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Angela L
authors.initials: AL
authors.lastname: Holmberg
authors.affiliation: Department of Chemical and Biomolecular Engineering, Center for Composite Materials, and Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Kaleigh H
authors.initials: KH
authors.lastname: Reno
authors.affiliation: Department of Chemical and Biomolecular Engineering, Center for Composite Materials, and Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Ngoc A
authors.initials: NA
authors.lastname: Nguyen
authors.affiliation: Department of Chemical and Biomolecular Engineering, Center for Composite Materials, and Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Richard P
authors.initials: RP
authors.lastname: Wool
authors.affiliation: Department of Chemical and Biomolecular Engineering, Center for Composite Materials, and Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Thomas H
authors.initials: TH
authors.lastname: Epps