Towards Greener Polymers: Poly(octamethylene itaconate-co-succinate) Synthesis Parameters

A group of renewable, unsaturated resins from itaconic acid, 1,8-octanediol, and succinic anhydride were synthesized in a non-solvent and non-catalyst melt polycondensation reaction. The study addresses the need for sustainable polymeric materials suitable for additive manufacturing by investigating the influence of synthesis parameters-namely itaconic acid content, reaction time, and temperature-on the properties of poly(octamethylene itaconate-<i>co</i>-succinate) (POItcSc). The Box-Behnken mathematical planning method was applied to optimize the reaction conditions. The optimal synthesis conditions of POItcSc were achieved with an itaconic acid molar fraction = 0.50:0.50, reaction time t = 7 h, and reaction temperature T = 150 °C. The conversion of the carboxyl group (by titration) was 83.3%, and the maintenance of C=C bonds (by NMR) was 88.7%. Structural characterization confirmed the formation of the desired polymer through FTIR and ¹H NMR analyses. Molecular weight (<i>M</i>_n = 1001 g/mol for an optimal product), thermal behavior (DSC, TG, DTG), and rheological properties (<i>η</i> = 14.4 and 3.6 Pa∙s for an optimal product at 25 and 36.6 °C) were systematically evaluated. The synthesized POItcSc resins were transparent and exhibited physicochemical properties favorable for extrusion-based 3D printing techniques such as Direct Ink Writing, offering a promising alternative to conventional petrochemical-based inks.