Superior Properties through Feedstock Development for Vat Photopolymerization Additive Manufacturing of High-Performance Biobased Feedstocks

Vat photopolymerization additive manufacturing (Vat AM) technologies have found niche industrial use being able to produce personalized parts in moderate quantity. However, Vat AM lacks in its ability to produce parts of satisfactory thermal and mechanical properties for structural applications. The purpose of this investigation was to develop high-performance resins with glass transition temperatures (Tg) above 200 °C for Vat AM, evaluate the properties of the produced thermosets and establish a structure–property relationship of the thermosets produced. Herein, we have developed SLA-type resins that feature bio-derived monomer hesperetin trimethacrylate (HTM) synthesized from the flavonone hesperetin. Diluents 4-acryloyl morpholine, styrene, 4-methyl styrene and 4-tert butylstyrene (tbutylsty) were photocured with HTM as the monomer and all produced thermosets with Tg values above 200 °C. Investigations of suitable crosslinkers urethane dimethacrylate, the vinyl ester CN 151 and Ebecryl 4859 (Eb4859) showed that each crosslinker displayed different benefits when formulated with HTM as the monomer and tbutylSty as the diluent (HTM:crosslinker:tbutylSty with mass ratio 2:1:2). The crosslinker CN 151 produced the thermoset of greatest onset of thermal decomposition temperature (T(0)) of 352 °C. Eb4859 produced the thermoset of highest tensile strength, 19 ± 7 MPa, amongst the set of varied crosslinkers. The formulation featuring UDM (HTM:UDM:tbutysty) offered ease of processing and was seemingly the easiest to print. Investigations of reactive diluent showed that styrene produced the thermoset of the highest extent of cure and the overall highest tensile strength, 25 ± 5 MPa, while tbutylSty produced the thermoset with the greatest Tan-δ Tg, 231 °C. HTM was synthesized, formulated with diluents, crosslinkers and initiators. The HTM resins were then 3D printed to produce thermosets of Tg values greater than 200 °C. The polymer properties were evaluated and a structure–reactivity relationship was discussed.