Unsaturated polyesters from maleic acid Towards novel bio-based photocurable resins for additive manufacturing

• Autores: Claire Morand
• Directores de la Tesis: Haritz Sardón Muguruza (dir. tes.)
• Lectura: En la Universidad del País Vasco - Euskal Herriko Unibertsitatea ( España ) en 2025
• Idioma: inglés
• Programa de doctorado: Programa de Doctorado en Química Aplicada y Materiales Poliméricos por la Universidad del País Vasco/Euskal Herriko Unibertsitatea
• Menciones:
  • Internacional
• Calificación: Sobresaliente Cum Laude
• Materias:
  • Química
• Enlaces
  • Tesis en acceso abierto en: ADDI
• Resumen

  • Plastic is deeply embedded in modern society, found in countless everyday products. Polymers versatility and functionality make them indispensable for many applications. However, increasing concerns over environmental pollution, climate change and the depletion of fossil resources have driven researchers and industries to seek more sustainable alternatives within the plastic economy. A key strategy is replacing petroleum-based feedstocks with renewable, bio-based sources. Among emerging bio-based polymers, aliphatic polyesters derived from diacids and diols have gained attention for their renewable origin and tunable properties. These materials show potential in applications such as biomedical devices, packaging, and particularly 3D printing, where material versatility and sustainability are crucial. This thesis focuses on polyesters derived from maleic acid and various diols, to develop photocurable biobased resins for additive manufacturing. The polyesters were synthetized via polycondensation, catalyzed by bio-sourced molecules, targeting low molecular weight polymers, which are better suited for additive manufacturing due to their improved flow and processability. First, biobased catalysts of increased nucleophilicity were investigated in the polycondensation of maleic acid and 1,3-propanediol to control the isomerization in the synthesized polyesters. The results indicate that higher catalyst nucleophilicity leads to greater isomerization, producing polyesters with varying cis/trans content. Next, diols of different chain lengths and structures were examined to create a library of polyesters with diverse isomerization degree, flexibility, thermal behavior, and mechanical properties. Finally, reactive diluents were incorporated into the synthesized polyesters, to overcome high viscosity and low reactivity, improving processability. The resulting resins were successfully printed using both DLP and volumetric printing techniques. The quality of the printed objects demonstrates the potential of these materials as sustainable options for additive manufacturing.