Remarkable elasticity and enzymatic degradation of bio-based poly(butylene adipate-co-furanoate): replacing terephthalate (original) (raw)
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Polymer, 2014
To synthesize high quality (co)polyesters derived from 2,5-furandicarboxylic acid (FA), an acetic acid refluxing/pH-swing method was proposed to purify FA. 2-Carboxyl furfural and other impurities were removed completely from FA with this method. Using highly purified FA, biobased polyester poly(butylene furnadicarboxylate) (PBF) and aliphatic-aromatic copolyesters poly(butylene adipate-cobutylene 2,5-furandicarboxy-late)s (PBAFs) were synthesized via melt (co)polycondensation. The (co) polyesters were characterized with GPC, FTIR, 1 H NMR, DSC and TGA, and their tensile mechanical properties were also assessed. The copolyesters possess random chain structure, monomer feed ratiocontrolled copolymer composition and excellent thermal stability (T d,5% > 340 C) in full composition range. Both BA-rich and BF-rich PBAFs are crystalline polymers. The crystallizability decreases with composition, up to nearly amorphous at moderate f BF (40e60%). PBAFs with f BF no more than 50% exhibit obvious high-elastic deformation and rebound resilience, and possess tensile properties (E 18 e160 MPa, s b 9e17 MPa, ε b 370e910%) comparable to poly(butylene adipate). PBAFs with higher f BF behave like nonrigid plastics with low tensile moduli (42e110 MPa), moderate strength (30e42 MPa) and high elongation at break (310e470%). In comparison, PBF is a strong and tough thermoplastic having balanced mechanical properties, namely, much higher tensile modulus (1.9 GPa) and strength (56 MPa) and high elongation at break (260%). It seems necessary and effective to use highly purified FA for synthesizing high performance FA-derived (co)polyesters.
Polymer, 2018
A class of eco-friendly copolyesters based on poly(butylene 2,5-thiophenedicarboxylate) (PBTF) is presented. The main goal of the study was to enhance the biodegradation rate of PBTF homopolymer. To this purpose, aliphatic sequences based on adipic acid have been introduced in the macromolecular backbone. The synthesized polymers have been characterized from thermal and structural point of view and their properties have been compared to those of the two homopolymers, i.e. PBTF and poly(butylene adipate). The peculiar microstructure of PBTF, due to the presence of an uninduced 2D-ordered phase, i.e. meso-phase, impacted also the copolymers' behavior, e.g. causing an increase of the materials' stiffness. Biodegradation rate in compost increased with the increase of mobile aliphatic sequences that allowed for an easier access to the ester bonds by the enzymes responsible for chain depolymerization. Lastly, gas permeability resulted strictly dependent on copolymer composition. Copolymers rich in thiophenedicarboxylate co-units displayed a gas barrier behavior comparable to poly(ethylene furanoate), while with the increase of adipate content the permeability increased, remaining however competitive with respect to that of polyolefines and polylactic acid.
Materials, 2017
In the present study, three new biobased furanoate polyesters with potential use in food packaging applications, named poly(isosorbide furanoate) (PIsF), poly(methyl-propylene furanoate) (PMePF) and poly(1,4-cyclohexane-dimethylene 2,5-furanoate) (PCHDMF) were synthesized. As monomers for the preparation of the polyesters, 2,5-furandicarboxylic acid (FDCA) and diols with irregular or complicated structure were used, including isosorbide (IS), 2-methyl-1,3-propanediol (MPD) and 1,4-cyclohexane-dimethanol (CHDM). The polymerization process was carried out via melt polycondensation method. The structural characteristics and thermal behavior of the polymers were studied. The kinetic fragility of the amorphous phase of the polymers was evaluated. The thermal degradation was studied by means of thermogravimetry and a pyrolysis Py-GC/MS (Pyrolysis-Gas Chromatography/Mass Spectroscopy) system to estimate the degradation mechanism.
Materials, 2020
In the era of polymers from renewable resources, polyesters derived from 2,5 furan dicarboxylic acid (FDCA) have received increasing attention due to their outstanding features. To commercialize them, it is necessary to synthesize high molecular weight polymers through efficient and simple methods. In this study, two furan-based polyesters, namely poly (propylene furanoate) (PPF) and poly(butylene furanoate) (PBF), were synthesized with the conventional two-step melt polycondensation, followed by solid-state polycondensation (SSP) conducted at different temperatures and reaction times. Molecular weight, structure and thermal properties were measured for all resultant polyesters. As expected, increasing SSP time and temperature results in polymers with increased intrinsic viscosity (IV), increased molecular weight and reduced carboxyl end-group content. Finally, those results were used to generate a simple mathematical model that prognosticates the time evolution of the materials’ IV...
Macromolecular Chemistry and Physics, 2014
5-Furandicarboxylic acid is a promising renewable-based monomer essentially used in polymer synthesis to prepare renewable-based counterparts to petrochemical polyesters. In general, they are entirely based on renewable resources and have a myriad of very interesting thermal and mechanical properties; however, this study is the fi rst to tackle their (bio)degradability, a worldwide-demanded property. To address this demand, an entirely new generation of furandicarboxylate-derived copolyesters, based on both poly(ethylene 2,5-furandicarboxylate) (PEF) and poly(lactic acid) (PLA), is developed for the fi rst time. These copolyesters are characterized by several techniques, including attenuated total refl ectance-Fourier transform IR (ATR-FTIR), 1 H, and 13 C NMR spectroscopy, thermogravimetric analysis (TGA), DSC, and X-ray diffraction (XRD), and their degradability behavior is evaluated by water-absorption studies and hydrolytic degradation. They are essentially stiff amorphous polymers possessing high T g s, e.g., ca. 69 °C for 29% of lactyl units. Importantly, the data show also that they have improved degradability when compared with the PEF homopolyester counterpart.
Fusible, Elastic, and Biodegradable Polyesters of 2-Pyrone-4,6-Dicarboxylic Acid (PDC)
Polymer Journal, 2009
2-Pyrone-4,6-dicarboxylic acid (PDC), a chemically stable metabolic intermediate of lignin, 1,4-butanediol, and succinic anhydride were polymerized in the presence of an appropriate catalyst, such as Sb 2 O 3 , TiO(acac) 2 , and CH 3 SO 3 H, to afford the corresponding polyesters. The molecular weight (M n) of the polyesters exceeded 10,000, but they were soluble in the common organic solvents when the PDC feed ratio was <10 mol %. Furthermore, the polyesters showed well-defined melting points ranging from 82 to 107 C and, consequently, the fusibility was realized for the first time for the PDC polymers. Films of these PDC polyesters lacked sufficient mechanical strength, but blended films with poly(L-lactic acid) were found to improve the elastic features. The degradation behaviors of the PDC polyesters were investigated by the biodegradability test or the accelerated hydrolysis tests. Comparison between the obtained PDC polyester and poly(butylene succinate) revealed a remarkable increase in the biodegradability by copolymerization with PDC.
Polymers, 2021
Different copolymers incorporating terpene oxide units (e.g., limonene oxide) have been evaluated considering thermal properties, degradability, and biocompatibility. Thus, polycarbonates and polyesters derived from aromatic, monocyclic and bicyclic anhydrides have been considered. Furthermore, ring substitution with myrcene terpene has been evaluated. All polymers were amorphous when evaluated directly from synthesis. However, spherulites could be observed after the slow evaporation of diluted chloroform solutions of polylimonene carbonate, with all isopropene units possessing an R configuration. This feature was surprising considering the reported information that suggested only the racemic polymer was able to crystallize. All polymers were thermally stable and showed a dependence of the maximum degradation rate temperature (from 242 °C to 342 °C) with the type of terpene oxide. The graduation of glass transition temperatures (from 44 °C to 172 °C) was also observed, being higher ...