Interchain exchange, proceeded by the transesterification mechanism, allows one to obtain polyethylene terephthalate-based polyester products, bypassing the stage of molecular weight reduction and polycondensation used in classical methods of chemical recycling. A kinetic model is presented, which describes the change in the concentrations of bound and terminal units of ethylene glycol from PET and glycol from another polyester, as well as free molecules of ethylene glycol and another glycol, during transesterification reactions for the first time. Experimental data on the dependence of the degree of randomness and conversion on timeduring the interaction of polyethylene terephthalate and oligodiethylene terephthalate with terminal hydroxyl groups with a number-average molecular weight of 860 g/mol in different ratios were obtained. Molecular weight characteristics of the products of PET and oligoesters with hydroxyl end group interchain exchange, with number-average molecular weights from 610 to 860 g/mol, were also investigated. The simulation results were also compared with published data on the dependence of the degree of randomness and conversion on time during ether exchange in PET/PEN blends. The developed kinetic model was found to be in agreement with the experimental data.

The compositions and structures of methyl MQ resins with different M/Q ratios were studied using NMR and IR spectroscopy, as well as gel permeation chromatography (GPC). It was found that the M/Q ratio affects the molecular weight of the siloxanes under consideration and the activity of hetero- and homopolycondensation. Depending on the M/Q ratio, MQ resins can act as plasticizers or reagents.

Lactide is one of the most popular and promising monomers for the synthesis of biocompatible and biodegradable polylactide and its copolymers. The goal of this work was to carry out a full cycle of polylactide production from lactic acid. Process conditions and ratios of reagents were optimized, and the key properties of the synthesized polymers were investigated. The influence of synthesis conditions and the molecular weight of lactic acid oligomers on the yield of lactide was studied. Lactide polymerization was first carried out in a 500 mL flask and then scaled up and carried out in a 2000 mL laboratory reactor setup with a combined extruder. Initially, the lactic acid solution was concentrated to remove free water; then, the oligomerization and synthesis of lactide were carried out in one flask in the presence of various concentrations of tin octoate catalyst at temperatures from 150 to 210 °C. The yield of lactide was 67–69%. The resulting raw lactide was purified by recrystallization in solvents. The yield of lactide after recrystallization in butyl acetate (selected as the optimal solvent for laboratory purification) was 41.4%. Further, the polymerization of lactide was carried out in a reactor unit at a tin octoate catalyst concentration of 500 ppm. Conversion was 95%; Mw = 228 kDa; and PDI = 1.94. The resulting products were studied by differential scanning calorimetry, NMR spectroscopy and gel permeation chromatography. The resulting polylactide in the form of pellets was obtained using an extruder and a pelletizer.

The simple approach of increasing the elastic properties of atactic poly(propylene carbonate) (PPC) with Mn = 71.4 kDa, ĐM = Mw/Mn = 1.86, and predominantly carbonate units (>99%) is suggested by selecting the appropriate hot pressing temperature for PPC between 110 and 140 °C. Atactic PPC is synthesized through ring-opening copolymerization of (rac)-propylene oxide and CO2 mediated by racemic salen complex of Co(III). Hot pressing PPC results in the release of a small amount of propylene carbonate (PC), sufficient to lower the glass transition temperature from 39.4 to 26.1 °C. Consequently, increasing the pressing temperature from 110 to 140 °C generates materials with a reduced modulus of elasticity (from 1.94 to 0.09 GPa), yield strength (from 38 to 2 MPa) and increased tensile elongation (from 140 to 940%). Thermomechanical analysis has shown a significant expansion in sample volume by hundreds of percent within the 80–130 °C range. PPC also displays large, reversible deformations, which can be utilized by creating shape memory materials.

There are various approaches to managing polyethylene terephthalate waste, including methods for recycling PET. However, at present, only the cleanest wastes that can already be efficiently recycled using known methods are considered in the scientific literature. The study aims to look at other forms of polyethylene terephthalate waste that pose a challenge: low quality PET flakes, polyester tire cord, PET dust and prepolymer waste. The waste was characterized by FTIR spectroscopy, viscosimetry, differential scanning calorimetry, laser diffraction and sieve analysis. The findings describe the composition and properties of various forms of polyethylene terephthalate waste. Low quality PET flake waste and polyethylene terephthalate dust have been shown to be suitable for all chemical recycling methods. When recycling waste polyester tire cord, it is difficult to completely separate the rubber, so its presence in the final product must be taken into account. The most promising way to process a prepolymer is its depolymerization by hydrolysis, alcoholysis or glycolysis to produce monomers for the synthesis of PET, similar in properties to the primary one.

The racemic salen complex of cobalt(iii) with pentafluorobenzoate axial ligand provides the synthesis of high molecular weight amorphous polypropylene carbonate and its full conversion into propylene carbonate.

Binary and ternary copolymers of acrylonitrile (AN), tert-butyl acrylate (TBA), and n-butyl acrylate (BA) are synthesized through conventional radical polymerization in DMSO in the presence of 2-mercaptoethanol. The thermal behavior of binary and ternary copolymers is studied under argon atmosphere and in air. It is demonstrated that the copolymers of AN contain 1–10 mol.% of TBA split isobutylene upon heating above 160 °C, resulting in the formation of the units of acrylic acid in the chain. The carboxylic groups formed in situ are responsible for the ionic mechanism of cyclization, which starts at lower temperatures compared with pure polyacrylonitrile (PAN) or AN copolymer with BA. The activation energy of cyclization through ionic and radical mechanisms depends on copolymer composition. For the ionic mechanism, the activation energy lies in the range ca. 100–130 kJ/mole, while for the radical mechanism, it lies in the range ca. 150–190 kJ/mole. The increase in the TBA molar part in the copolymer is followed by faster consumption of nitrile groups and the evolution of a ladder structure in both binary and ternary copolymers. Thus, the incorporation of a certain amount of TBA in PAN or its copolymer with BA allows tuning the temperature range of cyclization. This feature seems attractive for applications in the production of melt-spun PAN by choosing the appropriate copolymer composition and heating mode.

RAFT polymerization was applied for the synthesis of hydrophilic poly(N,N-dimethylaminoethyl methacrylate) and random copolymers of N,N-dimethylaminoethyl methacrylate, containing 5 or 10 mol

The influence of alkyl acrylate comonomers in the rank of methyl- (MA), butyl- (BA), ethylhexyl- (EGA), and lauryl- (LA) in ternary copolymers based on acrylonitrile, alkyl acrylate and acrylamide (PAN-alkyl acrylate) on their solutions rheological behavior in dimethyl sulfoxide (DMSO), and mechanical properties of the spun fibers have been investigated. To reveal the role of molecular weight, two series of copolymers with molecular weights of ~50 and 150 kg/mol have been studied. It was shown that the nature of the alkyl acrylate does not significantly affect the rheological behavior of their solutions regardless of the length of the alkyl substituent and the content of the alkyl acrylate in copolymers. An exception is the high-molecular PAN-LA, which is characterized by a non-Newtonian behavior at lower concentrations. Two series of fibers were spun from the characterized ranks of low and high-molecular-weight copolymer solutions. For all copolymers, a 2.5–5-fold increase in the strength and elastic modulus of the fiber was found with an increase in Mw. It has been shown that PAN-MA and PAN-LA fibers have a tensile strength of 800 MPa that is 1.5–3 times higher than that of other copolymers spun in the same conditions.

In this research, we have developed the approach to controlled synthesis of acrylonitrile-acrylamide copolymers with narrow molecular weight distribution and various monomer sequence distributions. By using dibenzyl trithiocarbonate and batch/semibatch polymerization, we have first synthesized random, gradient, and block-gradient copolymers containing 3.4–10.2 mol. % of acrylamide and revealed the influence of the monomer sequence on the cyclization behavior of poly(acrylonitrile-co-acrylamide) by combination of differential scanning calorimetry and Fourier transform infrared spectroscopy. This allowed us to find differences in cyclization behavior of the copolymers in argon and air atmosphere. Intramolecular cyclization was the main process proceeding in argon atmosphere. The radical mechanism of cyclization was suppressed already at the molar part of acrylamide units in copolymer exceeding ~3 mol. % for random copolymer and ~6 mol. % for block-gradient copolymer. The activation energy of ionic cyclization was equal to 89 ± 3 kJ·mol−1 and was not influenced by both copolymer composition and chain microstructure in contrast to the rate of cyclization. The latter was increased with the rise of acrylamide content, the content of hetero-triads and in the range block-gradient < gradient < random structure. In air atmosphere, the oxidation reactions dominated over cyclization. The oxidation reactions were found to be less sensitive to copolymer composition and chain microstructure.

Terpolymers of acrylonitrile with acrylic acid and alkyl acrylates, including methyl-, butyl-, 2-ethylhexyl-, and lauryl acrylates, were synthesized using the reversible addition–fragmentation chain transfer method. In this study, the focus was on the investigation of the impact of different monomer addition methods (continuous and batch) on both the rheological behavior of the spinning solutions and the mechanical properties of the resulting fibers. Our findings revealed that the method of monomer addition, leading either to non-uniform copolymers or to a uniform distribution, significantly influences the rheological properties of the concentrated solutions, surpassing the influence of the alkyl-acrylate nature alone. To determine the optimal spinning regime, we examined the morphology and mechanical properties at different stages of fiber spinning, considering spin-bond and orientation drawings. The fiber properties were found to be influenced by both the nature and introducing method of the alkyl-acrylate comonomer. Remarkably, the copolymer with methyl acrylate demonstrates the maximum drawing ratios and fiber tensile strength, reaching 1 GPa. Moreover, we discovered that continuous monomer addition allows for reaching the higher drawing ratios and superior fiber strength compared to the batch method.

The copolymers of acrylonitrile and 1-vinylimidazole with a narrow molecular weight distribution (MWD) were synthesized for the first time by the reversible addition–fragmentation chain transfer (RAFT) polymerization in a DMSO solution in the presence of acetic acid. Their thermal behavior difference upon heating in argon and in air along with ability to melt make them promising precursors for carbon fiber production.

Polymer composites with various recycled poly(ethylene terephthalate)-based (PET-based) polyester matrices (poly(ethylene terephthalate), copolyesters, and unsaturated polyester resins), similar in properties to the primary ones, can be obtained based on PET glycolysis products after purification. PET glycolysis allows one to obtain bis(2-hydroxyethyl) terephthalate and oligo(ethylene terephthalates) with various molecular weights. A kinetic model of poly(ethylene terephthalate) homogeneous glycolysis under the combined or separate action of oligo(ethylene terephthalates), bis(2-hydroxyethyl) terephthalate, and ethylene glycol is proposed. The model takes into account the interaction of bound, terminal, and free ethylene glycol molecules in the PET feedstock and the glycolysis agent. Experimental data were obtained on the molecular weight distribution of poly(ethylene terephthalate) glycolysis products and the content of bis(2-hydroxyethyl) terephthalate monomer in them to verify the model. Homogeneous glycolysis of PET was carried out at atmospheric pressure in dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) solvents with catalyst based on antimony trioxide (Sb2O3) under the action of different agents: ethylene glycol at temperatures of 165 and 180 °C; bis(2-hydroxyethyl) terephthalate at 250 °C; and oligoethylene terephthalate with polycondensation degree 3 at 250 °C. Homogeneous step-by-step glycolysis under the successive action of the oligo(ethylene terephthalate) trimer, bis(2-hydroxyethyl) terephthalate, and ethylene glycol at temperatures of 250, 220, and 190 °C, respectively, was also studied. The composition of products was confirmed using FTIR spectroscopy. Molecular weight characteristics were determined using gel permeation chromatography (GPC), the content of bis(2-hydroxyethyl) terephthalate was determined via extraction with water at 60 °C. The developed kinetic model was found to be in agreement with the experimental data and it could be used further to predict the optimal conditions for homogeneous PET glycolysis and to obtain polymer-based composite materials with desired properties.

The review summarizes recent advances in the production of carbon fiber precursors based on melt-spun acrylonitrile copolymers. Approaches to decrease the melting point of polyacrylonitrile and acrylonitrile copolymers are analyzed, including copolymerization with inert comonomers, plasticization by various solvents and additives, among them the eco-friendly ways to use the carbon dioxide and ionic liquids. The methods for preliminary modification of precursors that provides the thermal oxidative stabilization of the fibers without their melting and the reduction in the stabilization duration without the loss of the mechanical characteristics of the fibers are discussed. Special attention is paid to different ways of crosslinking by irradiation with different sources. Examples of the carbon fibers preparation from melt-processable acrylonitrile copolymers are considered in detail. A patent search was carried out and the information on the methods for producing carbon fibers from precursors based on melt-spun acrylonitrile copolymers are summarized.

Qualitative and quantitative composition of unsaturated polyester resin derived from known monomers mixture was investigated by means of NMR spectroscopy. To obtain the most comprehensive data of polyester microstructure 1H, 13C и {1H;1H} COSY NMR spectra were registered. NMR spectroscopy has been proven to be accurate and highly reliable method for composition analysis of unsaturated polyester resins.

A new method for the recycling of a polyester tire cord under the action of oligoethylene terephthalates, bis(2-hydroxyethyl) terephthalate and ethylene glycol has been proposed. The method involves simultaneous homogeneous glycolysis of polyethylene terephthalate and devulcanization of crumb rubber. Polyester cord and glycolysates were characterized by FTIR spectroscopy and gel permeation chromatography (GPC). The devulcanization process was investigated by swelling-based methods. The rate of the proposed method of homogeneous glycolysis in a melt phase was proved to be higher than one of the heterogeneous glycolysis. The assumption of a more efficient devulcanization in the presence of a softener was also confirmed. The degree of devulcanization 46.07%, the apparent degree of swelling 167.4%, and the apparent swelling rate constant 0.0902 min−1 were achieved. The results indicate that the proposed method made it possible to carry out the glycolysis of the polyester cord of the tire more deeply than the known heterogeneous glycolysis with various agents, but further research is needed for industrial implementation.

Controlled synthesis of terpolymers of acrylonitrile with acrylamide and alkyl acrylate of similar composition but differing in the alkyl substituent (methyl, butyl, 2-ethylhexyl, and lauryl) has been performed for the first time via the reversible addition-fragmentation chain transfer polymerization under the action of dibenzyl trithiocarbonate. Investigation of thermal behavior of the terpolymers under inert atmosphere has allowed determination of the activation energy of the ionic cyclization as of ~80 kJ/mol irrespectively of the alkyl acrylate nature. Mechanism of chemical transformations of the terpolymers under isothermal treatment at 250°C has not differed from this known for the binary acrylonitrile–acrylamide and acrylonitrile–alkyl acrylate copolymers. At the same time, the rate of the polyconjugated structure formation has been higher in comparison with the analogous terpolymers with acrylic acid. The rate of the stabilization has changed along the following series of alkyl acrylates: methyl acrylate < butyl acrylate ≈ 2-ethylhexyl acrylate < lauryl acrylate. Concentration ranges of the dilute, semidilute, and concentrated solutions have been determined for the synthesized terpolymers.

Copolymers of acrylonitrile (AN) and 1-vinyl imidazole (VIM) are synthesized through free radical and reversible addition–fragmentation chain transfer (RAFT) polymerization in DMSO. It is demonstrated that reactivity of VIM in copolymerization is lower than that of AN ( r VIM = 0.22 ± 0.02 and r AN = 0.88 ± 0.02). The copolymer composition is held constant throughout copolymerization in the range of monomer feed up to 30 mol % of VIM providing the formation of copolymers with high compositional homogeneity. RAFT mechanism provides additionally the low dispersity of the copolymers. The study of thermal stabilization processes of the synthesized copolymers reveals that molecular weight distribution plays minor role in the thermal behavior of acrylonitrile copolymers with 1-vinyl imidazole in contrast to copolymer composition. The activation energy of cyclization reaction increases linearly with the increase of VIM content in copolymer. The increase of VIM molar part in the copolymer is followed by slower evolution of the ladder structure. Generally, VIM may be considered as an inert monomer. At a constant temperature, the rate of the formation of ladder structure under inert atmosphere and in air differs drastically. The conversion of nitrile groups in –C=N– groups equal to 10% is achieved after 2.5 h of thermal treatment in argon or in 15 min in air. The essential difference in the rates of cyclization reactions in argon and air allow to develop new strategy for production of melt-processable precursors of carbon fiber.

A method for producing nanocomposites of unsaturated polyester resins (UPR) based on recycled polyethylene terephthalate (PET) as a matrix has been proposed. The upcycling method involves three successive stages: (1) oligoesters synthesis, (2) simultaneous glycolysis and interchain exchange of oligoesters with PET, (3) interaction of the obtained resins with glycol and maleic anhydride. UPRs were characterized by FTIR spectroscopy and gel permeation chromatography. The mechanical properties of nanocomposites obtained on the basis of these resins and titanium dioxide have been investigated. It has been shown that 1,2-propylene glycol units, despite their lower reactivity, significantly improve the properties of UPR. The most promising nanocomposite sample exhibited tensile strength 112.62 MPa, elongation at break 157.94%, and Young's modulus 29.95 MPa. These results indicate that the proposed method made it possible to obtain nanocomposites with high mechanical properties based on recycled PET thus allowing one to create a valuable product from waste.

Radical polymerization of acrylonitrile in the presence of N-methylmorpholine N-oxide has been performed for the first time. It has been shown that the presence of N-methylmorpholine N-oxide leads to the decrease in the molecular mass of the polymer and induces its partial cyclization. These features have been preserved when N-methylmorpholine N-oxide has been introduced in the polymerization simultaneously with the monomer and the initiator as well as when it has been added at high conversion of the monomer. The introduction of N-methylmorpholine N-oxide into polyacrylonitrile has led to the cyclization of the nitrile units in two stages, the low-temperature one being initiated by N-methylmorpholine N-oxide and the high-temperature one, typical of pure polyacrylonitrile. The ratio between the intensity of these processes has been governed by the content of N-methylmorpholine N-oxide.