Biobased Itaconate Polyester Thermoset with Tunable Mechanical Properties

Biobased synthetic products derived from renewable feedstock offer a more sustainable alternative to traditional nonrenewable counterparts. To ensure the sustainability of thermosets, a fully biobased thermoset poly(1,3-propanediol-co-1,12-dodecanedioate-co-itaconate) (PPDDI) via catalyst-free polyesterification was designed using commercially available 1,3-propanediol (PD), 1,12-dodecanedioic acid (DDA), and itaconic acid (IA). Synthesized oligomers with different molar ratios showed low dispersity (Đ) values (≈2), ensuring consistent properties. We explored free-radical cross-linking at various dicumyl peroxide (DCP) contents and curing durations to achieve materials with diverse mechanical properties, ranging from flexible (UTS = 3.2 MPa, Young's modulus = 10.6 MPa, and elongation at break = 200%) to rigid (UTS = 31.0 MPa, Young's modulus = 196.4 MPa, and elongation at break = 64%). All samples exhibited hydrolytic degradability to different extents, offering a more sustainable end-of-life solution. This study highlights the potential of PPDDI as a biobased material with tunable mechanical properties and favorable environmental characteristics.