


Vol 65, No 4 (2023)
КАТАЛИЗ
High-Performance Catalysts Based on Hybrid Salicylaldarylimine Complexes of Titanium(IV) Dichloride for the Synthesis of Ultrahigh Molecular Weight Polyethylene with Unentangled Macromolecules
Abstract
The features of ethylene polymerization in the presence of dichloridobis(salicylaldaryliminato)titanium(IV) complexes containing a 4-allyloxy-2,3,5,6-tetrafluorophenylimino group, namely, {2‑[(4-CH2=CH-CH2O)C6F4N=CH]-6-R1-4-R2-C6H2O}2TiCl2 (R1 = t-Bu, CMe2(Ph); R2 = H, Me, OMe, t-Bu, CMe2(Ph), Cl, Br) in the presence of methylalumoxane, have been studied. All the complexes exhibit high catalytic activity (27.8×106 гПЭ∙мольTi‐ 1∙МПаC2H4-1∙ч‐ 1)) in the temperature range of 10‒60°C and form powdered ultrahigh molecular weight polyethylene (UHMWPE) (M = (4.4–16.0) × 106 g/mol) with a low number of intermolecular entanglements. It has been shown that during polymerization, the complexes are immobilized on UHMWPE macromolecules.



Neutral Red and Safranin Т in the Photopolymerization of Methyl Methacrylate and Other (Meth)Acrylate Monomers
Abstract
Features of the polymerization of methyl methacrylate and a number of other (meth)acrylate monomers in the presence of catalytic systems based on phenazine dyes (Neutral Red and Safranin Т) under visible light irradiation are investigated. It is shown that amines of various structure as well as air oxygen affect the kinetic features of polymerization and the molecular weight characteristics of polymers. It is found that polymerization may proceed in the controlled mode up to high conversions at room temperature and a low photocatalyst concentration, among them without preliminary degassing of the reaction medium.



ПОЛИМЕРИЗАЦИЯ
Синтез биоразлагаемых полимеров на основе L-лактида в присутствии безметаллового органического катализатора
Abstract
Исследован процесс полимеризации L-лактида под действием органического катализатора 1,8-диазабицикло[5.4.0]ундец-7-ена. Определены частные порядки реакции по мономеру и катализатору, рассчитана константа скорости полимеризации. Синтезированы перспективные для применения в медицине линейные поли-L-лактиды со среднемассовой молекулярной массой от 29 × 103 до 125 × 103 и индексом полидисперсности не выше 1.25. Показана возможность использования комбинации органокатализатора и гидроксилсодержащих инициаторов для синтеза звездообразного полилактида и амфифильного сополимера полилактид–блок–полиэтиленоксид.



СИНТЕЗ
Synthesis of Composite Polymer Particles by Seeded Emulsion Polymerization and Formation of Photonic Crystals Based on Them
Abstract
Submicron composite particles with the core/shell structure are synthesized by the seeded emulsion polymerization of a mixture of various acrylates in the presence of a redox initiation system. The diameter, morphology, and surface structure of particles as well as their ability to self-assemble into 3D ordered thin-film structures are studied by scanning electron microscopy, FTIR spectroscopy, thermogravimetry, and dynamic light scattering. It is shown that under the used experimental conditions particles with a shell thickness of 10‒35 nm are synthesized. The effect of shell composition (in particular, the alkyl chain length of acrylate comonomers) on the morphology and structure of the surface layer of the obtained composite particles is traced.



ХИМИЧЕСКИЕ ПРЕВРАЩЕНИЯ
Reactivity of New Monomers of the Polyurethanes Green Chemistry, the Reaction Mechanism, and the Medium Effect
Abstract
The influence of the substituents inductive effect and the proton-donor OH group in the substituted cyclocarbonates differing in the alkyl chain length on the activation barrier of their aminolysis reaction, which underlies the process of urethane formation without the participation of isocyanates, has been studied. Account for the solvent molecules has allowed quantitative interpretation of the process regularities. Kinetics of the model aminolysis reaction of a series of monomers in DMSO has been investigated.



ФУНКЦИОНАЛЬНЫЕ ПОЛИМЕРЫ
Special Features of Multiple Luminescence of the Dyad Containing Imidazole and Coumarin Fragments in Photocured Network Acrylate Polymers
Abstract
The conditions to prepare luminescent acrylate polymers containing the organic dyad, molecule of which combines two different emitting fragments, hydroxyl-substituted 2,4,5–triarylimidazole and 8-azomethine-7-hydroxycoumarine moieties, via photocuring have been optimized. The effect of the nature of the photocured network acrylate polymers on luminescent properties of the dyad has been investigated. The prepared aliphatic network polymers have exhibited independent fluorescence of both molecule fragments, dependent on the excitation wavelength. At the same time, the aromatic network polymers and the aliphatic network polymers containing ether links have revealed only the imidazole fragment fluorescence. The fluorescence nature has been stronger dependent on the polymer repeat unit structure and the content of the aromatic fragments in the polymer matrix than on the presence of the hydroxyl groups in the polymer. It has been shown that the emission of the imidazole fragment of the dyad in the aliphatic network polymers depends on the internode distance and conditional polarity of the medium.



Synthesis of Aromatic Polyamidines by the [2+2]-Cycloaddition Reaction
Abstract
Aromatic polyamidines based on 4,4′-diphenylmethane diisocyanate and bisamides have been synthesized and studied. The one-step reaction of bisamides with diazocyanate according to the [2+2]-cycloaddition mechanism includes a concerted process of the formation of two new σ-bonds in the transition state. The formation of polyamidine occurs as a result of decarboxylation, which completes this reaction. Due to the availability of starting compounds, ease of synthesis, good solubility, and high heat resistance and thermal stability of the resulting polymers, there are wide opportunities for producing new materials by conventional industrial processes. Polyamidines have a sufficiently large set of important technological properties, which suggest their greater potential in relation to applied problems. The resulting film materials and glass-reinforced plastics based on polyamidines show high mechanical properties that are not inferior to those of materials made from commercial polyamides and polybenzimidazoles.



Graft Polymerization of 5-Vinyltetrazole onto Chitosan
Abstract
Polymerization of 5-vinyltetrazole under conditions of radical initiation in aqueous media in the presence of chitosan gave network graft copolymers, the structure of which is built from chitosan macromolecules crosslinked by chain fragments of poly(5-vinyltetrazole). It was determined that the polymerization is preceded by the formation of a saltlike product between chitosan macromolecules and vinyl monomer, which affects its polymerization activity. The obtained graft copolymers are prone to limited swelling in water to form pH-sensitive ampholytic hydrogels.


