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The continuous search for novel biobased polymers with high-performance properties has highlighted the role of monofuranic-based polyesters as some of the most promising for future plastic industry but has neglected the huge potential for the polymers' innovation, relatively low cost, and synthesis easiness of 5,5'-isopropylidene bis-(ethyl 2-furoate) (DEbF), obtained from the platform chemical, worldwide-produced furfural. In this vein, poly(1,12-dodecylene 5,5'-isopropylidene -bis(ethyl 2-furoate)) (PDDbF) was introduced, for the first time, as a biobased bisfuranic long-chain aliphatic polyester with an extreme flexibility function, competing with fossil-based polyethylene. This new polyester in-depth characterization confirmed its expected structure (FTIR, 1H, and 13C NMR) and relevant thermal features (DSC, TGA, and DMTA), notably, an essentially amorphous character with a glass transition temperature of -6 °C and main maximum decomposition temperature of 340 °C. Furthermore, PDDbF displayed an elongation at break as high as 732%, around five times higher than that of the 2,5-furandicarboxylic acid counterpart, stressing the unique features of the bisfuranic class of polymers compared to monofuranic ones. The enhanced ductility combined with the relevant thermal properties makes PDDbF a highly promising material for flexible packaging.

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Poly (hexamethylene succinate) (PHS) is a biobased and biodegradable polyester. In this research, two fully biobased high-molecular-weight poly (hexamethylene succinate-co-2,5-furandicarboxylate) (PHSF) copolyesters with low hexamethylene furandicarboxylate (HF) unit contents (about 5 and 10 mol%) were successfully synthesized through a two-step transesterification/esterification and polycondensation method. The basic thermal behavior, crystal structure, isothermal crystallization kinetics, melting behavior, thermal stability, and tensile mechanical property of PHSF copolyesters were studied in detail and compared with those of PHS. PHSF showed a decrease in the melt crystallization temperature, melting temperature, and equilibrium melting temperature while showing a slight increase in the glass transition temperature and thermal decomposition temperature. PHSF copolyesters displayed the same crystal structure as PHS. Compared with PHS, PHSF copolyesters showed the improved mechanical property. The presence of about 10 mol% of HF unit increased the tensile strength from 12.9 ± 0.9 MPa for PHS to 39.2 ± 0.8 MPa; meanwhile, the elongation at break also increased from 498.5 ± 4.78% to 1757.6 ± 6.1%.

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Of the 25 million tons of plastic waste produced every year in Europe, 40% of these are not reused or recycled, thus contributing to environmental pollution, one of the major challenges of the 21st century. Most of these plastics are made of petrochemical-derived polymers which are very difficult to degrade and as a result, a lot of research efforts have been made on more environmentally friendly alternatives. Bio-based monomers, derived from renewable raw materials, constitute a possible solution for the replacement of oil-derived monomers, with furan derivatives that emerged as platform molecules having a great potential for the synthesis of biobased polyesters, polyamides and their copolymers. This review article summarizes the latest developments in biotechnological production of furan compounds that can be used in polymer chemistry as well as in their conversion into polymers. Moreover, the biodegradability of the resulting materials is discussed.

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Environmental regulation and depletion of fossil resources are boosting the search for new polymeric materials produced from biomass. Here, the synthesis of a new diester bearing a pendant lactam unit from methyl levulinate and aspartic acid is reported. The palladium-catalyzed reductive amination/cyclization sequence was carefully optimized to afford the diacid with high yield (>95 %). In a second step, the compound was esterified to give the corresponding diester. The latter monomer was copolymerized with α-ω linear diols, yielding polyesters with molecular weights up to 20.5 kg mol-1 .

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In situ forming implants (ISFI) are proved to be effective drug delivery systems in various local therapies. This research focuses on preliminary characteristics of a new biodegradable ISFI formulation based on poly(isosorbide succinate) (PISU) for modulated, over 3-week, release of doxycycline hyclate (DOXY). The Alamar Blue cytotoxicity assay was carried out for PISU using FK-1 and AoSMC cell lines. PISU resin was found to be non-toxic in wide range of concentrations. The formulation viscosity, dependent on shear rate, facilitates its easy injection into required site where solid depot is formed immediately after injection. DOXY, incorporated into this formulation, was released in vitro within 21 days, during which collected solutions exhibited antibacterial activity against gram-positive and gram-negative bacteria Staphylococcus aureus and Escherichia coli, respectively. The morphology of the precipitated depots was characterized by scanning electron microscopy (SEM). The obtained results suggest potential applicability of this new PISU-based formulation as injectable drug delivery system forming implant at an injection site by phase separation and precipitation of the polymer.

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Poly(propylene 2,5-furan dicarboxylate) (PPF), or poly(trimethylene 2,5-furan dicarboxylate) (PTF), is a biobased alipharomatic polyester that is expected to replace its fossil-based terephthalate (PPT) and naphthate (PPN) homologues. PPF possesses exceptional gas barrier properties, but its slow crystallization rate might affect its success in specific applications in the future. Therefore, a series of PPF based nanocomposites with the nanoclays Cloisite®-Na (MMT), Cloisite®-20A (MMT 20A), and halloysite nanotubes (HNT) were synthesized via the in situ transterification and polycondensation method. The effect of the nanoclays on the structure, thermal, and crystallization properties of PPF was studied with several methods including infrared spectroscopy (IR), Nuclear Resonance Spectroscopy (¹H-NMR), Wide Angle X-ray Diffraction (WAXD), Thermogravimetric Analysis (TGA), and Differential Scanning Calorimetry (DSC). The insertion of the nanofillers in the polymer matrix altered the crystallization rates, and TGA results showed good thermal stability, since no significant mass loss occurred up to 300 °C. Finally, the degradation mechanism was studied in depth with Pyrolysis-Gas Chromatography/Mass Spectroscopy, and it was found that ß-scission is the dominant degradation mechanism.

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Three series of polyalkanoates (adipates, suberates and sebacates) were synthesized using as monomers three sugar-based bicyclic diols derived from D-glucose (Glux-diol and isosorbide) and D-mannose (Manx-diol). Polycondensations were conducted in the melt applying similar reaction conditions for all cases. The aim was to compare the three bicyclic diols regarding their suitability to render aliphatic polyesters with enhanced thermal and mechanical properties. The ensuing polyesters had molecular weights (Mw) in the 25,000-50,000 g mol-1 range with highest values being attained for Glux-diol. All the polyesters started to decompose above 300 °C and most of them did not display perceivable crystallinity. On the contrary, they had glass transition temperatures much higher than usually found in homologous polyesters made of alkanediols, and showed a stress-strain behavior consistent with their Tg values. Glux-diol was particularly effective in increasing the Tg and to render therefore polyesters with high elastic modulus and considerable mechanical strength.

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Nowadays, "green" is a hot topic almost everywhere, from retailers to universities to industries; and achieving a green status has become a universal aim. However, polymers are commonly considered not to be "green", being associated with massive energy consumption and severe pollution problems (for example, the "Plastic Soup") as a public stereotype. To achieve green polymers, three elements should be entailed: (1) green raw materials, catalysts and solvents; (2) eco-friendly synthesis processes; and (3) sustainable polymers with a low carbon footprint, for example, (bio)degradable polymers or polymers which can be recycled or disposed with a gentle environmental impact. By utilizing biobased monomers in enzymatic polymerizations, many advantageous green aspects can be fulfilled. For example, biobased monomers and enzyme catalysts are renewable materials that are derived from biomass feedstocks; enzymatic polymerizations are clean and energy saving processes; and no toxic residuals contaminate the final products. Therefore, synthesis of renewable polymers via enzymatic polymerizations of biobased monomers provides an opportunity for achieving green polymers and a future sustainable polymer industry, which will eventually play an essential role for realizing and maintaining a biobased and sustainable society.