A one-pot biomimetic synthesis of selectively functionalized lignins from monomers: a green functionalization platform

Abstract

Lignin is the most abundant renewable source of phenolic compounds with great application potential in renewable materials, biofuels and platform chemicals. The current technology for producing cellulose-rich fibers co-produces heterogeneous lignin, which includes an untapped source of monomeric phenolics. One such monomer also happens to be the main monomer in soft wood lignin biosynthesis, namely coniferyl alcohol. Herein, we investigate the potential of coniferyl alcohol as a platform monomer for the biomimetic production of tailored functionalized oligolignols with desirable properties for material synthesis. Accordingly, a bifunctional molecule with at least one carboxyl-ended functionality is included with coniferyl alcohol in biomimetic lignin synthesis to, in one pot, produce a functionalized lignin. The functionalization mechanism is a nucleophilic addition reaction to the quinone methide intermediate of lignin polymerization. The solvent system applied was pure water or 50% aqueous acetone. Several bi-functional molecules differing in the second functionality were successfully inserted in the lignin demonstrating the platform component of this work. Detailed characterization was performed by a combination of NMR techniques which include ¹H NMR, COSY-90, ³¹P NMR, ¹³C NMR, ¹³C APT, HSQC, HMBC and HSQC TOCSY. Excellent selectivity towards benzylic carbon and a high functionalization degree were noted. The structure of lignin was tailored through the solvent system choice, with 50% aqueous acetone producing a skeletal structure favorable for a high degree of functionalization. Finally, material concepts are demonstrated using classical thiol–ene- and Diels–Alder-chemistries to show the potential for the thermoset and thermoplastic concepts, respectively. The functionalization concept presents unprecedented opportunities for the green production of lignin-based recyclable biomaterials.