Formaldehyde-free self-polymerization of lignin-derived monomers for synthesis of renewable phenolic resin

Abstract

Most phenolic resins are synthesized with non-renewable petroleum-based phenol and formaldehyde, which have adverse effects on the environment and human health. To achieve green and sustainable production of phenolic resins, it is important to replace non-renewable toxic phenol and formaldehyde. Herein, a new strategy was proposed to completely replace phenol and formaldehyde, using lignin-derived monomers to synthesize renewable phenolic resins. Lithium aluminum hydride was utilized to reduce lignin-derived monomers, including vanillin, methyl vanillate, and syringaldehyde, to generate the corresponding vanillyl and syringic alcohol. With oxalic acid as the catalyst, vanillyl and syringic alcohol could be polymerized to phenolic resins without using formaldehyde. The structure of the phenolic resins based on lignin-derived monomers was analyzed by Fourier transform infrared spectroscopy and 13C and 31P nuclear magnetic resonance spectroscopy. Differential scanning calorimetry and thermogravimetric analysis were performed to characterize the thermal properties of the phenolic resins. The phenolic resins based on lignin-derived monomers exhibited excellent adhesion strength (6.14 MPa), glass transition temperature (Tg) (107–115 °C), and thermal stability, and its performance was similar to that of the commercial Novolak phenolic resin. This study presents a promising green and sustainable approach to synthesize renewable phenolic resins based on lignin-derived monomers without using formaldehyde.