Stereolithography (SLA) is a well-established additive manufacturing (AM) technique that allows a resin to be photopolymerized into high resolution parts with rapid production times. Vanillin, a naturally occurring molecule as well as a derivative easily obtained from biomass, including lignin, can be used as a building block for vinyl ester resins (VERs) and AM-ready materials. A vanillin-based VER, prepared via a 100% atom efficient and solventless technique, was investigated for AM applications due to its low viscosity and demonstrated ability to photopolymerize. The resin was additively manufactured via SLA and the effect of postprocessing after printing was investigated. The extent of cure between the printed and postprocessed samples was found to have the highest effect on polymer properties, increasing extent of cure by approximately 23%. With postprocessing, the printed material was shown to have a glass transition temperature (T g ) of 153 °C and Young’s modulus of 4900 MPa, comparable to the same resin cured via traditional thermal techniques. This resin system has the potential to be used as a standalone high strength and high T g material for SLA. Furthermore, the resin system also has potential as a formulation base for tunable SLA cure characteristics and final desired printed polymer properties while retaining significant biobased content.

No abstract

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

No abstract