Chemical Circularity in 3D Printing with Biobased Δ-Valerolactone

Digital Light Processing (DLP) is a vat photopolymerization-based 3D printing technology that fabricates parts typically made of chemically crosslinked polymers. The rapidly growing DLP market has an increasing demand for polymer raw materials, along with growing environmental concerns. Therefore, circular DLP printing with a closed-loop recyclable ink is of great importance for sustainability. The low-ceiling temperature alkyl-substituted δ-valerolactone (VL) is an industrially accessible biorenewable feedstock for developing recyclable polymers. In this work, acrylate-functionalized poly(δ-valerolactone) (PVLA), synthesized through the ring-opening transesterification polymerization of VL, is used as a platform photoprecursor to improve the chemical circularity in DLP printing. A small portion of photocurable reactive diluent (RD) turns the unprintable PVLA into DLP printable ink. Various photocurable monomers can serve as RDs to modulate the properties of printed structures for applications like sacrificial molds, soft actuators, sensors, etc. The intrinsic depolymerizability of PVLA is well preserved, regardless of whether the printed polymer is a thermoplastic or thermoset. The recovery yield of virgin quality VL monomer is 93% through direct bulk thermolysis of the printed structures. This work proposes the utilization of depolymerizable photoprecursors and highlights the feasibility of biorenewable VL as a versatile material platform toward circular DLP printing.