Search

This work explores for the first time the enzymatic synthesis of poly(butylene-co-e-caprolactone) (PBSCL) copolyesters in bulk using commercially available monomers (dimethyl succinate (DMS), 1,4-butanediol (BD), and e-caprolactone (CL)). A preliminary kinetic study was carried out which demonstrated the higher reactivity of DMS over CL in the condensation/ring opening polymerization reaction, catalyzed by Candida antarctica lipase B. PBSCL copolyesters were obtained with high molecular weights and a random microstructure, as determined by 13C NMR. They were thermally stable up to 300 °C, with thermal stability increasing with the content of CL in the copolyester. All of them were semicrystalline, with melting temperatures and enthalpies decreasing up to the eutectic point observed at intermediate compositions, and glass transition temperatures decreasing with the content of CL in the copolyester. The use of CALB provided copolyesters free from toxic metallic catalyst, which is very useful if the polymer is intended to be used for biomedical applications., Peer Reviewed, Objectius de Desenvolupament Sostenible::11 - Ciutats i Comunitats Sostenibles, Postprint (published version)

The synthesis, characterization, and thermal properties of partially renewable poly(butylene terephthalate) copolyesters containing alditol units are described. These copolyesters were obtained by polycondensation in solution from mixtures of 1,4-butanediol and 2,3-di-O-benzyl-L-threitol with terephthaloyl chloride. Copolyesters with weight-average molecular weights oscillating between 4 000 and 12 000 g·mol-1 and dispersities around 1.5 were obtained. All them had a random microstructure and were thermally stable well above 300°C. Copolyesters containing up to 30% of dibenzyl threitol units were found to be crystalline and to adopt the same crystal structure as the parent homopolyester poly(butylene terephthalate). The melting temperature and crystallinity were observed to decrease, and the glass transition temperature to increase, with increasing amounts of alditol units incorporated in the copolyester. Furthermore, the crystallizability was depressed by copolymerization., Peer Reviewed, Postprint (author's final draft)

Poly(gamma-glutamic acid) (gamma-PGA) is one of the few bacterial polymers in nature; as such, it possesses the added value of a “green birth” (fermentation) and “green death” (biodegradability), which is ideal for sustainable macromolecular platforms. Efficient functionalization strategies are required in order to transform the native bacterial biopolymer into a material with tailored properties for bulk scale or biomedical applications. We report on a novel approach to the facile functionalization of bacterial gamma-PGA, realized with several levels of control: (a) the modulation of the molecular weight through sonication, and the solubilization in organic solvents through counterion exchange with suitable quaternary ammonium salts, (b) the introduction of reactive functionalities through reactions in homogeneous conditions in organic solvents, to afford homo- or copolymers; (c) a second tier functionalization using copper(I)-catalyzed alkyne–azide cycloaddition (CuAAC) click chemistry., Peer Reviewed, Postprint (published version)

The enzymatic ring-opening copolymerization (eROP) of globalide (Gl) and pentadecalactone (PDL) was performed in solution from mixtures of the two macrolactones at ratios covering the whole range of comonomeric compositions. The resulting P(Glx-r-PDLy) random copolyesters were aminofunctionalized by thiol-ene reaction with aminoethanethiol. ROP of ¿-benzyl-l-glutamate N-carboxyanhydride initiated by P(Glx-r-PDLy)-NH2 provided neutral poly(¿-benzyl-L-glutamate)-grafted copolyesters, which were converted by hydrolysis into negatively charged hybrid copolymers. Both water-soluble and nonsoluble copolymers were produced depending on copolymer charge and their grafting degree, and their capacity for self-assembling in nano-objects were comparatively examined. The emulsion solvent-evaporation technique applied to the chloroform-soluble copolymers grafted with benzyl glutamate rendered well-delineated spherical nanoparticles with an average diameter of 200–300 nm. Conversely, micellar solutions in water were produced from copolyesters bearing grafted chains composed of at least 10 units of glutamic acid in the free form. The copolymer micelles were shown to be able to load doxorubicin (DOX) efficiently through electrostatic interactions and also to release the drug at a rate that was markedly pH dependent., Peer Reviewed, Postprint (published version)

In this work, we study for the first time, the isothermal crystallization behavior of isodimorphic random poly(butylene succinate)-ran-poly(e-caprolactone) copolyesters, PBS-ran-PCL, previously synthesized by us. We perform nucleation and spherulitic growth kinetics by polarized light optical microscopy (PLOM) and overall isothermal crystallization kinetics by differential scanning calorimetry (DSC). Selected samples were also studied by real-time wide angle X-ray diffraction (WAXS). Under isothermal conditions, only the PBS-rich phase or the PCL-rich phase could crystallize as long as the composition was away from the pseudo-eutectic point. In comparison with the parent homopolymers, as comonomer content increased, both PBS-rich and PCL-rich phases nucleated much faster, but their spherulitic growth rates were much slower. Therefore, the overall crystallization kinetics was a strong function of composition and supercooling. The only copolymer with the eutectic composition exhibited a remarkable behavior. By tuning the crystallization temperature, this copolyester could form either a single crystalline phase or both phases, with remarkably different thermal properties, Peer Reviewed, Postprint (published version)

Two series of partially biobased ABA triblock copolyesters were successfully prepared by ring-opening polymerization (ROP) of L-lactide initiated by two telechelic polyester polyols using an organic catalyst. B blocks were made of telechelic poly(hexamethylene terephthalate) (PHT) and poly(hexamethylene 2,5-furandicarboxylate) (PHF), respectively, with average molar masses of around 3500¿g¿mol-1 and A blocks were made of poly(lactic acid)s (PLA) of different block lengths. For each series, four copolymers with different PHT/PLA and PHF/PLA compositions were prepared by varying the feed molar ratios. The triblock structure of the obtained copolymers was ascertained by 13C NMR, which confirms that the organic catalyst employed does not promote transesterification reactions at the low temperatures used for the reaction. All copolyesters were thermally stable under inert atmosphere up to around 300¿°C. For all synthesized copolyesters, the PLA blocks were unable to crystallize, mainly due to racemization reactions taking place during L-lactide ROP. Both, PHT and PHF blocks were able to crystallize and their thermal and structural properties (Tm, Tc, Xc and lamellar thickness) were independent on PLA content until its concentration was very high and topological restrictions difficulted crystallization. According to SAXS, most copolymers were found to be miscible in the melt. Both PLA-b-PHT-b-PLA or PLA-b-PHF-b-PLA triblock copolymers showed a single Tg indicating that the components are miscible in the amorphous state, Peer Reviewed, Postprint (author's final draft)

Macrocyclic oligoesters (MCOs) derived from biomass such as those prepared from alkylene alkanedioates and 2,5-furandicarboxylates are suitable compounds for ring opening polymerization (ROP) to produce high molecular weight bio-based polyesters. The synthetic procedures that have been recently developed to obtain these MCOs in good yields, their ROP either alone or together with other cyclic compounds, and their recovery by cyclodepolymerization of the final polyesters are the main topics covered in this review. Both organometallic compounds and enzymes such as Candida antarctica lipase B are the catalytic systems used for all reactions. This synthetic approach based on ROP of MCOs derived from renewable sources opens a green pathway for a circular economy in plastics., Postprint (author's final draft)