Dual-functional,aromatic, epoxy-methacrylate monomers from bio-based feedstocks and their respective epoxy-functional thermoplastics

Dual-functional monomers consist of two distinctly different functional groups that enable chemical versatility. The most readily available epoxy-methacrylate dual-functional monomer is glycidyl methacrylate (GMA). In an effort to produce bio-based, aromatic complements to GMA, asymmetric phenolic diols (vanillyl alcohol, syringyl alcohol, gastrodigenin, and tyrosol) were identified and selectively epoxidized at the aromatic hydroxyl followed by subsequent esterification at the aliphatic hydroxyl to prepare dual functional monomers, vanillyl alcohol epoxy-methacrylate (VAEM), syringyl alcohol epoxy-methacrylate (SAEM), gastrodigenin epoxy-methacrylate (GDEM), and tyrosol epoxy-methacrylate (TEM). These monomers are viable platforms for a multitude of applications due to their unique chemical functionalities. VAEM, SAEM, GDEM, and TEM were homopolymerized individually to produce aromatic, bio-based epoxy-functional thermoplastics analogous to poly(GMA). The molecular weight distributions and thermal properties of each polymer were evaluated, as were the surface characteristics of flow-coated thin films from these polymers. Most of the newly prepared epoxy-functional thermoplastics exhibited increased thermal stability (initial decomposition temperatures >260 °C in air) relative to poly(GMA), while retaining similar glass transition temperatures (~ 65 °C) and surface energies (~ 53 mJ m^?2); thus, these materials could be substituted for poly(GMA) and enable use in higher-temperature applications. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 673–682