Poly(siloxane-urethane)s are an unique class of organosilicon copolymers that combine valuable properties of both silicones and polyurethanes. In this study a series of polymer films based on poly(siloxane-urethane) was prepared and fully characterized. A modern synthetic route developed by our group earlier based on utilization of organoeuropiumsiloxanes as luminescent agents for the preparation of luminescent polymers was used. The effect of the nature of phenyleuropiumsiloxanes of different structures on mechanical, thermal as well as optical properties of composites was studied. It was shown that oligomeric phenyleuropiumsiloxane in combination with β-diketone ligand provides the most prospect composite materials with intense luminescence.

Siloxane–ethylene oxide–urethane block copolymers were synthesized by the interaction of oligosiloxane organodiols of the general formula HO(CH2)2OCH2Me2SiO–[SiR2O]n–SiMe2CH2O(CH2)2OH (R = Me, Et) and oligo(ethylene oxide) (OEO) (–CH2CH2O–)m with 4,4'-diphenylmethane diisocyanate. The copolymers obtained were studied by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The effect of the bulk composition on the composition and structure of the surface was established.

New polysiloxane–butylene oxide–urethane–ureas based on α,ω-bis[(3-aminopropyl)diethoxy]oligodimethylsiloxane, oligobutylene oxide, and fractions of dicyclohexylmethane 4,4'-diisocyanate (H12-MDI) with different contents of a trans-trans isomer have been synthesized. The mechanical properties of the films have been tested. It is established that the strength and relative elongation at break increase with the increasing content of the trans-trans isomer.

The development of photocurable compositions is in high demand for the manufacture of functional materials for electronics, optics, medicine, energy, etc. The properties of the final photo-cured material are primarily determined by the initial mixture, which needs to be tuned for each application. In this study we propose to use simple systems based on di(meth)acrylate, polyimide and photoinitiator for the preparation of new photo-curable compositions. It was established that a fluorinated cardo copolyimide (FCPI) based on 2,2-bis-(3,4-dicarboxydiphenyl)hexafluoropropane dianhydride, 9,9-bis-(4-aminophenyl)fluorene and 2,2-bis-(4-aminophenyl)hexafluoropropane (1.00:0.75:0.25 mol) has excellent solubility in di(met)acrylates. This made it possible to prepare solutions of FCPI in such monomers, to study the effect of FCPI on the kinetics of their photopolymerization in situ and the properties of the resulting polymers. According to the obtained data, the solutions of FCPI (23 wt.%) in 1,4-butanediol diacrylate (BDDA) and FCPI (15 wt.%) in tetraethylene glycol diacrylate were tested for the formation of the primary protective coatings of the silica optical fibers. It was found that the new coating of poly(BDDA–FCPI23%) can withstand prolonged annealing at 200 °C (72 h), which is comparable or superior to the known most thermally stable photo-curable coatings. The proposed approach can be applied to obtain other functional materials.

Nowadays organosilicon luminescent materials are of increasing interest due to the variety of their synthetic or modification techniques and application fields. Ladder polyphenylsilsesquioxanes (L-PPSQ) are a unique class of organosilicon polymers, which can be ideal matrices for the luminescent composites due to their high thermal stability, optical transparency and mechanical strength. In this work, new mechanically strong, heat-resistant, transparent and sensitive to ammonia vapor luminescent composite films based on L-PPSQ have been obtained. As the source of Europium ions oligophenyleuropiumsiloxane was used, demonstrating perfect compatibility to the matrix due to the similar nature. To improve luminescent properties of the films, new organosilicon ligands were introduced into the composites and their influence on the properties of the materials was studied. Valuable properties of described composites may allow their further application as multifunctional coatings.

Cross-linked polyurethanes (PUs) were obtained by curing with MQ resins bearing oxymethyldimethylsiloxane or oxyethoxymethyldimethylsiloxane groups, their mixtures with 1,4-butanediol, and neat 1,4-butanediol and studied for their physico-mechanical properties. The MQ resins with functional hydroxy groups were found to act as polyols during curing of a urethane prepolymer. The network PU, obtained by curing with the MQ resins, represents a hybrid organic–inorganic polymer with bulk cross-links of inorganic nature, the surface groups of which are chemically bound to the polymer matrix. At a concentration of the MQ resins of 0.5 ppm, the properties of hybrid polyurethanes are comparable to those of the polyurethane obtained using 0.63 ppm of 1,4-butanediol.

The condensation of cis-hexaphenylcyclohexasiloxanehexaol and phenylsilanetriol in an ammonia medium was studied. The soluble high-molecular ladder polyphenylsilsesquioxanes (L-PPSSs) were obtained, which are capable of forming transparent and strong films. The structure and properties of the resulting L-PPSSs were investigated using different physicochemical methods, including 1H NMR spectroscopy, UV-vis and IR spectroscopy, viscometry in solution, GPC, TGA, mechanical analysis.

Polynaphthoylenebenzimidazoles containing functional sulfo groups were synthesized by a one-step method in a sulfuric acid medium with oleum. A polymer-analogous transformation of these polymers with aqueous solutions of metal salts (K, Ca, and Cr) was carried out. Their chemical structure was characterized by FTIR, NMR, and elemental analysis. Polymer salt coatings were deposited on QCM sensor surfaces by electron beam-induced vacuum deposition. The morphology of the coatings was characterized by AFM. It was shown that the coatings formed from a series of polymer salts have different adsorption activity in acetaminophen–water solution compared to distilled water. The QCM results indicate that sensor signal correlates with polymer coating thickness, morphology, and its chemical composition.

Five low-dispersity star-shaped polydimethylsiloxanes were synthesized. The macromolecules of the poly-mers contain the same branching-out center, a cis-tetraphenylcyclotetrasilsesquioxane moiety, and the same number of arms, but with different lengths (n = 15, 21, 48, 75, and 123 Si(Me)2O units). Their properties were studied by a set of physicochemical analytical methods. Viscometric studies showed that the macromolecules of the Ph4-15, Ph4-21, Ph4-48, and Ph4-75 polymers are small-sized dense balls both in solution and in melt. DSC studies identified an unusual effect of the cyclic core on the thermal behav-ior of the Ph4-15, Ph4-21, and Ph4-48 polymers. Its incorporation suppresses the crystallization of PDMS-arms (up to n = 48 Si(Me)2O units) at concentrations four times lower than those of known modifiers and does not affect the glass transition temperature (ca.-124 degrees C).(c) 2023 Elsevier B.V. All rights reserved.

Crosslinked polysiloxanes with boron bis(dibenzoylmethanate) complexes used as crosslink junctions of polymer networks are first synthesized, and their physicochemical, mechanical, thermal, and fluorescent properties are studied. It is shown that the polymers under study feature the elastic behavior, possess high thermal and thermo-oxidative stability, and exhibit intense fluorescence in a wide wavelength range (400‒700 nm).

New network poly(siloxane–propylene oxide–urethane–ureas) based on α,ω-bis[(3-aminopropyl)diethoxy]oligodimethylsiloxanes, oligo(propylene oxide), and cycloaliphatic diisocyanates are synthesized. The resulting polymers are studied by differential scanning calorimetry and thermogravimetric analysis; their stress–strain characteristics are elucidated. These polymers are found to feature microphase separation and, consequently, two glass transition temperatures, defined by the chemical structures of the microphases. It is shown that an increase in the molecular weight and mass content of siloxane blocks leads to a decrease in the elastic modulus and tensile strength.

In this work, polycarboranosiloxanes with well-defined structures and a varying content of the carborane moiety (2–15 wt%) were obtained. Data of rheological studies indicate that phase separation occurs in such hybrid carboranosiloxane systems.

A series of Ti(IV) dichloride and dialkoxide complexes with phenoxyimine ligands containing fluorinated and nonfluorinated aliphatic imine fragments have been synthesized. The molecular structures of complexes 1 and 4 were established by single-crystal X-ray diffraction studies. The complexes adopt a distorted octahedral coordination structure around the titanium atom and two oxygen atoms are situated in trans position while two nitrogen atoms and two outgoing ligands (Cl or i PrO) are situated in cis position. Effect of activators (MMAO-12 and combinations Et n AlCl 3− n + Bu 2 Mg) and outgoing ligand (Cl or i PrO) nature on the catalytic activity and properties of the resulting polymers was studied. The Ti complexes, despite the nature of the outgoing ligands (Cl or i PrO) in the presence of Al/Mg activators, was found to display a high ethylene polymerization activity in the range 1600–3830 kg polymer ·mol Ti −1 ·h −1 ·atm −1 with a viscosity average molecular weight ( M v ) value in the range 1.1×10 6 −7.1×10 6 Dalton (Da). The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films. The rheological characteristics of a polymer melt have been studied. The absence of a cross-over point did not allow to compare the values of the molecular weight distribution of polymers obtained on fluorinated and non-fluorinated pre-catalysts, however, the estimation of the entanglement density is in good agreement with the mechanical characteristics of oriented films. Upon activation with methylalumoxane, the activity of the complexes decreased very significantly; however, a polymer with a molecular weight of about 12 million Da was obtained. In the process of ethylene/octene-1 copolymerization, fluorine-containing precatalysts showed a clear advantage over non-fluorinated analogues both in activity and in comonomer content.

In the present work, a method for the preparation of the new luminescent polymer compositions was described. A series of polymer films based on organosilicon dimethylsiloxane-phenylsilsesquioxane block-copolymer con-taining flexible linear dimethylsiloxane and rigid polycyclic phenylsilsesquioxane blocks in the structure of the macromolecule and polyfunctional phenyleuropiumethoxysiloxane [C6H5Si(OC2H5)2O]3Eu, as a molecular luminescent filler, was prepared and fully characterized. Physicochemical, mechanical, optical, and thermal properties all the polymer films were investigated. The polymer films form stable 3D networks and demonstrate a high thermal and thermo-oxidative stability. The study of mechanical properties showed that the tensile strength is in the range of 14-19 MPa, elongation at break is in the range of 5-8% and the Young's modulus is in the range of 380-560 MPa for the investigated polymers. The optical properties of the polymers were studied in the solid state at room temperature. It was shown, that upon excitation with 310 nm UV light the emission spectra of all samples show the five emission peaks that are characteristic for the Eu3+ ion arising from the 5D0 -> 7FJ (J = 0-4) transitions.

The catalytic activity of the systems based on titanium(iv) alkoxides (Ti(OPri)4, Ti(OPri)2(OCH(CF3)2)2, and Ti(OCH(CF3)2)4) and mixtures of alkylaluminum chlorides (Et2AlCl or Et3Al2Cl3) with dibutylmagnesium in ethylene polymerization and ethylene copolymerization with propylene and 5-ethylidene-2-norbornene was studied. Ultrahigh-molecular-weight polyethylene with the molecular weight reaching 4.9 · 106 Da was found to be formed in the homopolymerization reaction, whereas copolymerization gives ter-copolymers containing propylene (up to 35 mol.%) and 5-ethylidene-2-norbornene (4.3 mol.%) units.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A series of bis(phenoxy-imine) (FI) titanium(IV) and zirconium(IV) complexes have been synthesized. The effect of the nature of the activator (MAO, combinations EtnAlCl3-n + Bu2Mg and iBu3Al + [Ph3C]+[B(C6F5)4]−) on the catalytic activity and properties of the resulting polymers was studied. It was found that Ti-Fi complexes, despite the nature of the outgoing ligands (Cl or iPrO) in the presence of Al/Mg activators, effectively catalyze the polymerization of ethylene (with the formation of UHMWPE); copolymerization of ethylene with 1-octene (with the formation of ultra-high molecular weight copolymers); and the ternary copolymerization of ethylene, propylene and 5-vinyl-2-norbornene (with the formation of polyolefin elastomers). It has been shown that Zr-FI complexes are not activated by these Al/Mg compositions. The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films; however, their mechanical characteristics do not exceed those obtained using MAO.

A series of new cross-linked polysiloxane polymers based on functionalized cyclo- and oligosiloxane precursors was prepared by UV-induced hydrothiolation "click"-reaction using DMPA as the initiator and their physico-mechanical properties were studied. The study of a morphology of prepared polymers by scanning electron microscopy (SEM) shows that the microstructure of all samples is homogenous. The mechanical properties of all the samples were studied by the tension and compression tests. It was shown that mechanical properties of studied materials, which significantly depends on precursors nature, can be fine-tuned by changing the structure of the initial vinyl precursor. The Young's modulus varies in the range of 4.5-117 MPa in the tension test and in the rage of 6.3-209 MPa in the compression test. The tensile strength varies in the range of 0.3-3.9 MPa in the tension test and in the rage of 2.3-28 MPa in the compression test. The thermal stability of the samples was evaluated by thermal gravimetric analysis (TGA). The weight loss was observed in the range of 275-333 degrees C in air and 322-370 degrees C in argon for prepared samples. All samples were characterized by DSC method. It was shown that only DSC curves for polymers 1 and 3 contain transitions related to glass formation (-78 and -35 degrees C, respectively). All polymer samples have a similar water contact angle in the range of 90-102 degrees.

In order to increase the thermal stability of olefin polymerization precatalysts, new titanium(IV) complexes with diolate ligands differing in the degree of steric hindrances were synthesized from readily available precursor (±)camphor. The structures of the complexes 1–2 were established by X-ray diffraction. Complexes 1–4 in the presence of an activator {EtnAlCl3-n + Bu2Mg} catalyzed the synthesis of UHMWPE with an Mv up to 10 million and a productivity of up to 3300 kg/molTi·atm·h. The obtained polymers are obviously characterized by a low density of macromolecular entanglement, which makes it possible to use the solid-phase method for their processing. The mechanical characteristics of the oriented UHMWPE films had a breaking strength up to 2.7 GPa and an elastic modulus of up to 151 GPa. The precatalysts 1–4 were also active in ethylene/1-octene copolymerization. The comonomer content was in the range of 1.4–4.6 mol%. The use of a rigid linker and an increase in the steric load of the diolate complexes ensured the thermal stability of the catalytic system in the range of 50–70 °C.

Complex cations with a vacant coordination site are considered as the most plausible catalytically active centers of metallocene and post-metallocene polymerization catalysts. For the first time we demonstrated that cationic titanium (III) complexes stabilized with crown ether can be used as pre-catalysts for ethylene polymerization. In the presence of alkyl aluminum chlorides and MgBu2 as cocatalysts, these complexes catalyze ethylene polymerization to produce Ultra High Molecular Weight Polyethylene (UHMWPE) with productivity up to 4650 kgPE/mol Ti h.atm and molecular weight up to 1.8.106 Da. UHMWPE powders were processed by the solid-phase method with subsequent orientation drawing into high-strength (1.4-2.1 GPa) and high-modulus (91-118 GPa) films.