High Tg Bio-Based Aliphatic Polyesters from Bicyclicd-Mannitol

Abstract

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 (Tg = 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 (PBxManxyS) covering a broad range of compositions have been obtained using mixtures of Manx and 1,4-butanediol in the reaction with dimethyl succinate. All PBxManxyS were semicrystalline and displayed Tg 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.

High Thermal Stability of Bio-Based Polycarbonates Containing Cyclic Ketal Moieties

“…Since the two cyclic ketal rings are linked to rigid norbornane moiety, a fairly high degree of rigidity should be expected for CaG. The rigidity of the monomer induces the stiffness leading to high glass transition temperature rather than independently linked by single C−C bond, 23 which is critical for the preparation of polymers. 24 Moreover, recent bio-based monomers for improvement of the mechanical and/or the thermal properties of polycarbonates have several steps for preparation, but CaG, as it is synthesized in one step, needs no protection and deprotection steps, and the organic acid catalyst was simply removed by work-up process.…”

Synthetic Polymers from Sugar-Based Monomers

“…These were hydrolytically degradable under physiological conditions. 41 During the last 5 years, Munõz-Guerra, Galbis, and coworkers have been reporting on a new series of biodegradable linear polyesters and copolyesters from bicyclic acetalized monosaccharide monomers derived from galactaric acid (58) (Scheme 8), 42,43 D-mannitol (27), 44 D-glucitol (24), and Dglucaric acid (59) (Scheme 9). 45 Homopolyesters and random copolyesters covering a broad range of compositions were obtained.…”

Synthesis, Properties and Applications of Biodegradable Polymers Derived from Diols and Dicarboxylic Acids: From Polyesters to Poly(ester amide)s

“…In addition, random copolymers have been obtained using mixtures of the carbohydrate diol and 1,4-butanediol in the reaction with dimethyl succinate. All copolymers were semicrystalline, degraded enzymatically faster than PBS and displayed tunable thermal and mechanical properties according to the content in Manx units [136]. …”