Furanic (Meth)acrylate Monomers as Sustainable Reactive Diluents for Stereolithography

We have successfully demonstrated the capability of six bioderived furanic (meth)-acrylates to perform as reactive diluents in stereolithography resin compositions. Produced from 5-hydroxymethylfurfural, a biobased platform chemical, via a series of simple transformations, the furanic diluents can reduce the viscosity of commercial stereolithography resins, participate in photocuring with high conversion of polymerizable groups, and satisfy performance requirements. Compared to 1,6-hexanediol diacrylate, a widely used petroleum-based difunctional diluent, several furanic acrylate and methacrylate monomers offer significantly improved thermal and mechanical properties (glass transition temperature, Young's modulus, tensile strength, tensile, and fracture toughness). Incorporating a long n-butyl substituent as a side chain into the diluent structure increases the fracture strain of the 3D printed samples compared to the unsubstituted counterpart but causes a reduction in strength, glass transition temperature, and thermal stability. Using an allyl group as a side chain improves the cross-link density of the system but increases brittleness. Of the six furanic diluents, 2,5-bis-(hydroxymethyl)-tetrahydrofuran diacrylate and 2,5-bis-(hydroxymethyl)-furan dimethacrylate demonstrated the best combination of properties. After the necessary optimization, the production of furanic (meth)-acrylates has the potential to become more sustainable than the manufacturing of 1,6-hexanediol diacrylate. The potential for sustainability and the high performance of the biobased furanic monomers make them promising alternatives to petroleum-derived components in sustainable stereolithography resin compositions.