By means ofin situmelt polycondensation of polyethylenterephathalate accompanied with simultaneous reduction of introduced graphene oxide, the composite of polyethylenterephathalate filled with reduced graphene oxide was prepared. Melting and crystallization of the reduced graphene oxide – polyethyleneterephthalate composite was studied by the differential scanning calorimetry method, and the rheological test was carried out by rotational rheometry and compared to the pristine polyethylenterephathalate. The morphology of the reduced graphene oxide – polyethyleneterephthalate composite was studied using optical microscopy. The reduced graphene oxide was isolated from the reduced graphene oxide – polyethyleneterephthalate composite and characterized by thermogravimetry, X-ray photoelectron spectroscopy and X-Ray diffraction methods. Since a part of polymer could not be removed from reduced graphene oxide particles by trifluoroacetic acid, the hypothesis about probable grafting of polyethyleneterephthalate on reduced graphene oxide sheets was suggested. Rheological behaviour of the reduced graphene oxide – polyethyleneterephthalate composite melt confirms this suggestion. According to the calculations based on thermogravimetry, the reduced graphene oxide, isolated from the reduced graphene oxide – polyethyleneterephthalate composite, consists of about 80% polyethyleneterephthalate.
A series of novel copolyesters based on polyethylene terephthalate (PET) and 4′-hydroxy-biphenyl-4-carboxylic acid (HBCA) was obtained by melt polycondensation of bis(2-hydroxyethyl) terephthalate and 4′-acetoxybiphenyl-4-carboxylic acid (ABCA) as co-monomers with Sb2O3 as a catalyst. Using this synthetic procedure, a set of copolymers containing 20–80 mol% of HBCA units was prepared. According to NMR spectroscopy, the copolymers were of random composition. Copolyesters comprising 60–80 mol% of HBCA possessed increased heat resistance and formed nematic melts at 270 °C and higher. The liquid crystal (LC) phase formation was accompanied by transition to non-Newtonian characteristics of the melt flow, as well as an equalization of storage and loss moduli values. According to XRD and polarizing microscopy, the LC glassy phase of the copolyesters coexists with crystalline regions of poly-(4′-hydroxy-4-biphenylcarboxylate), non-melting up to 400 °C and above. The mechanical characteristics of these LC copolyesters showed similar or better values than those of well-known LC polymers. These novel copolyesters can be useful in obtaining heat-resistant materials with an ordered structure and, as a consequence, improved performance.
Several series of new polymers were synthesized in this study: binary copolyesters of vanillic (VA) and 4′-hydroxybiphenyl-4-carboxylic (HBCA) acids, as well as ternary copolyesters additionally containing 4-hydroxybenzoic acid (HBA) and obtained via three different ways (in solution, in melt, and in solid state). The high values of logarithmic intrinsic viscosities and the insolubility of several samples proved their high molecular weights. It was found that the use of vanillic acid leads to the production of copolyesters with a relatively high glass transition temperature (~130 °C). Thermogravimetric analysis revealed that the onset of weight loss temperatures of ternary copolyesters occurred at 330–350 °C, and the temperature of 5% mass loss was in the range of 390–410 °C. Two-stage thermal destruction was observed for all aromatic copolyesters of vanillic acid: decomposition began with VA units at 420–480 °C, and then the decomposition of more heat-resistant units took place above 520 °C. The copolyesters were thermotropic and exhibited a typical nematic type of liquid crystalline order. The mechanical characteristics of the copolyesters were similar to those of semi-aromatic copolyesters, but they were much lower than the typical values for fully aromatic thermotropic polymers. Thus, vanillic acid is a mesogenic monomer suitable for the synthesis of thermotropic fully aromatic and semi-aromatic copolyesters, but the processing temperature must not exceed 280 °C.
Binary thermotropic fully aromatic copolyesters based on 4-hydroxybenzoic and 4'-hydroxybiphenyl-4-carboxylic acids and ternary copolyesters of 4-hydroxybenzoic, 4'-hydroxybiphenyl-4-carboxylic, and 3‑hydroxybenzoic acids containing 60–80% of 4-hydroxybenzoic acid units are synthesized by the melt polycondensation of corresponding acetyl derivatives. The melting temperature of the copolyesters is below 400°С, and the most promising among them melt at temperatures below 340°С which allows their melt processing by extrusion, molding, and injection molding. The tensile properties of some copolyesters are comparable with the corresponding mechanical properties of such commercially available analogs as Vectra A‑950 and Zenite HX-8000. All the synthesized copolyesters are stable in an inert atmosphere at least up to 450°С. The thermal stability of the copolyesters slightly decreases with an increase in the content of 3‑hydroxybenzoic acid units.
A series of new copolyesters of poly(ethylene terephthalate) and 4'-hydroxybiphenyl-4-carboxylic acid copolyesters were synthesized by transesterification in the melt of polyethylene terephthalate with 4'‑acetoxybiphenyl-4-carboxylic acid. The chemical composition and compositional homogeneity of the copolyesters were determined by FTIR and 1H NMR spectroscopy: the data obtained suggest the absence of block sequences in macromolecules. The effect of the composition on the melting and glass transition temperatures of the copolyesters and their thermal stability was analyzed by DSC and TGA. The intrinsic viscosity and Huggins constants were determined by viscosimetry of diluted solutions of the copolyesters in dichloroacetic acid.
A series of new wholly aromatic (co)polyesters based on m-substituted bifunctional comonomers—4′-hydroxybiphenyl-3-carboxylic (3HBCA) and 3-hydroxybenzoic (3HBA) acids with molar ratios of 3HBCA:3HBA from 0:100 to 60:40, respectively—was synthesized. NMR and FTIR spectroscopy methods proved the full compliance of the copolymer composition with the target ratio of comonomers, as well as high compositional homogeneity (absence of block sequences). The resulting copolyesters have a sufficiently high molecular weight and their intrinsic viscosity values are in the range of 0.6–0.8 dL/g. Thermal analysis showed that all 3HBCA-3HBA copolyesters are amorphous, and with an increase in the content of biphenyl units (3HBCA), the glass transition temperature increases significantly (up to 190 °C). The onset of the intense thermal decomposition of the synthesized polyesters occurs above 450 °C. Thus, this indicates a sufficiently high thermal stability of these polyesters. Rheological measurements have shown that melts of copolyesters with a high content of 3HBCA units exhibit anisotropic properties. At the same time, the method of polarization optical microscopy did not confirm the transition to the liquid crystal state for these polyesters. These results confirm that it is possible to obtain high-performance polyesters based on 3HBCA, but not a mesogenic comonomer. Thus, 3HBCA is a promising comonomer for the synthesis of new thermotropic copolyesters with controlled anisotropic properties.