High Tg Bio-Based Aliphatic Polyesters from Bicyclic d‑Mannitol

• Published in: Biomacromolecules 2013-03, Vol.14 (3), p.781-793
• Main Authors: Lavilla, Cristina, Alla, Abdelilah, Martínez de Ilarduya, Antxon, Muñoz-Guerra, Sebastián
• Format: Article
• Language: English
• Subjects: Applied sciences; Enginyeria química; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polièsters; Polycondensation; Polyesters; Preparation, kinetics, thermodynamics, mechanism and catalysts; Àrees temàtiques de la UPC
• ISSN: 1525-7797; 1526-4602
• DOI: 10.1021/bm301854c

The carbohydrate-based diol 2,4:3,5-di-O-methylene-d-mannitol (Manx) has been used to obtain aliphatic polyesters. Manx is a symmetric bicyclic compound consisting of two fused 1,3-dioxane rings and bearing two primary hydroxyl groups. In terms of stiffness, it is comparable to the widely known isosorbide, but it affords the additional advantages of being much more reactive in polycondensation and capable of producing stereoregular polymers with fairly high molecular weights. A fully bio-based homopolyester (PManxS) has been synthesized by polycondensation in the melt from dimethyl succinate and Manx. The high thermal stability of PManxS, its relatively high glass transition temperature (T g = 68 °C) and elastic modulus, and its enhanced sensitivity to the action of lipases point to PManxS as a polyester of exceptional interest for those applications where biodegradability and molecular stiffness are priority requirements. In addition, random copolyesters (PB x Manx y S) covering a broad range of compositions have been obtained using mixtures of Manx and 1,4-butanediol in the reaction with dimethyl succinate. All PB x Manx y S were semicrystalline and displayed T g values from −29 to +51 °C steadily increasing with the content in Manx units. The stress–strain behavior of these copolyesters largely depended on their content in Manx and they were enzymatically degraded faster than PBS.