In this work, new bio-based copoly(ester amide)s were synthesized by a two-step melt polycondensation process, using 2,5-furanedicarboxylic acid dimethyl ester (DMFDC), 1,3-propanediol (PDO), and 1,3-diaminopropane (DAP), with different DAP content. The chemical structure of the obtained poly(trimethylene 2,5-furandicarboxylate)-co-poly(propylene furanamide) (PTF-co-PPAF) copolymers was confirmed by nuclear magnetic resonance (1H NMR) and Fourier-transform infrared (FTIR) spectroscopy. Gas chromatography/mass spectrometry was used to provide more details of the polycondensation process. Thermal properties of the obtained materials were characterized by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic–mechanical thermal analysis (DMTA). The copolymers were amorphous and their glass transition temperature increased with the increase in the poly(propylene furanamide) (PPAF) content. The synthesized PTF-co-PPAF copolymers exhibited improved thermal and thermo-oxidative stability up to 300 °C. In addition, from the performed mechanical tests, it was found that along with the increase in PPAF content, Young's modulus increased, while at the same time, the value of elongation at break decreased. Graphical Abstract

The growing ecological awareness of society created the tendency to replace petrochemically based materials with alternative energy carriers and renewable raw materials. One of the most requested groups of polymer materials with significant technological importance is thermoplastic elastomers (TPE). They combine the properties of elastomers such as flexibility with the typical properties of thermoplastics, like easy processing. Herein, one compares the influence of rigid segments on the properties of copoly(ester-ether). Thermoplastic polyesters based on bio-1,6-hexanediol and terephthalic (T), furanic (F), and napthalate (N) diesters, i.e., PHT, PHF, and PHN, were obtained employing melt polycondensation. Additionally, to grant elastic properties of polyesters, systems containing 50 wt.% of bio-based polyTHF®1000 (pTHF) with a molecular mass of 1000 g/mol, have been prepared. The composition and chemical structure have been determined by 1H nuclear magnetic resonance (NMR) and Fourier transformed infrared spectroscopy (FTIR) analyses. The temperatures corresponding to phase transition changes were characterized by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) analyses. The crystalline structure was examined by X-ray diffraction (XRD) analysis. Additionally, the influence of pTHF–rich segment on the tensile properties, water absorption, as well as thermal and thermo-oxidative stability, has been analyzed. It was found that incorporation of soft phase allows creation of thermoplastic elastomers with tensile characteristics comparable to the commercially available ones, by means of elongation at break higher than 500%, low values of tensile modulus, without exhibiting yield point.

A fully plant-based sustainable copolyester series, poly(butylene 2,5-furandicarboxylate)-block-poly(caprolactone)s, were successfully synthesized by melt polycondensation combining butylene 2,5-furandicarboxylate with polycaprolactone diol at different weight ratios.

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A series of poly(ester amide)s based on dimethyl furan 2,5-dicarboxylate (DMFDC), 1,3-propanediol (PDO), 1,6-hexylene glycol (HDO), and 1,3-diaminopropane (DAP) were synthesized via two-step melt polycondensation. The phase transition temperatures and structure of the polymers were studied by differential scanning calorimetry (DSC). The positron annihilation lifetime spectroscopy (PALS) measurement was carried out to investigate the free volume. In addition, the mechanical properties of two series of poly(ester amide)s were analyzed. The increase in the number of methylene groups in the polymer backbone resulted in a decrease in the values of the transition temperatures. Depending on the number of methylene groups and the content of the poly(propylene furanamide) (PPAF), both semi-crystalline and amorphous copolymers were obtained. The free volume value increased with a greater number of methylene groups in the polymer backbone. Moreover, with a lower number of methylene groups, the value of the Young modulus and stress at break increased.

For several decades, polymer nanocomposites (PNCs) have received the interest of the scientific community and industry. [1,2] PNCs can be described as a system consisting of two or more phases, with one or more dispersed phases in the nanoscale within the polymer matrix phase. [3,4] It is possible to improve the thermal, mechanical, barrier, electrical, and biological properties of a polymer matrix with a small addition of a nanofiller. Several factors affect the improvement in properties: the particle size, the degree of surface development, and the distribution of nanoparticles in the polymer matrix. [5] Carbon-based Nanomaterials can be classified according to the number of dimensions they display on the nanoscale: 1D fibers such as carbon nanofibers (CNFs); 2D platelets, for example, graphene and layered silicate; and 3D particles like spherical silica, semiconductor nanoclusters, and quantum dots. [6][7][8] CNFs have excellent mechanical, thermal, and electrical properties. The tensile strength and Young's modulus of CNF are in the range of 1.5-7 and 228-724 GPa, respectively. [9] The range of these values varies depending on processing methods and fiber diameter. The graphene nanoplatelets (GNPs) are 2D carbon-based nanoparticles with a plate-like shape. Adding GNPs to a polymer matrix generally increases the value of barrier properties, thermal conductivity, and mechanical properties. The value of Young's modulus was reported to be 1.1 TPa, and the tensile strength was 125 GPa for GNPs. [10] Moreover, hybrid polymer composites are growing in popularity in the scientific community. These composites are obtained by adding at least two nanofillers to the polymeric matrix, which can achieve a synergistic effect that improves thermal, mechanical, barrier, and electrical properties.However, it is not only the type of nanoparticles that determines the properties of PNCs, but also the polymer matrix. Thermoplastic elastomers (TPEs) are a class of materials that combine the mechanical properties of elastomers and the processing properties of thermoplastics. [11] This is because of their morphology, which can be divided into rigid and flexible segments. Compared to traditional elastomers, the rigid TPE segment forms physical crosslinking instead of chemical

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In recent years, there has been a trend toward replacing petrochemical raw materials with so-called “bio” plastics, i.e. plastics from renewable sources. Herein, the susceptibility of degradation in the compost heap of three types of packaging polyesters, by means of PET and biobased PEF and PLA, with other thermoplastic polyesters with more methylene groups (three and six) bio—(PTF and PHF, respectively) and petrochemically-based (PTT and PHT, respectively) has been studied. Two series of polymer materials based on ethylene, propylene, and hexamethylene glycols and two diesters (dimethyl terephthalate and dimethyl 2,5-furandicarboxylate) were thus obtained and compared with “double green” PLA. Moreover, the assessment of the influence of the subsequent processing cycle (injection moulding) on the utilitarian properties of these materials, constitutes the analogy to the subsequent recycling cycle. The susceptibility to degradation was assessed in the context of changes in the structure (analyzed by FTIR and DSC), intrinsic viscosity, and mechanical performance. In addition, chromatographic analysis of the solutions of the analyzed samples in methanol was carried out in order to determine whether and what low-molecular compounds were released from the analyzed polyesters. It has been shown that furan-based polyesters have great potential to replace materials based on dimethyl terephthalate-based polyesters.