A novel grafting-onto approach was applied to the synthesis of star-shaped poly(2-alkyl-2-oxazoline)s with macrocyclic calix[4]arene core. Cationic polymerizations of 2-ethyl-2-oxazoline and 2-isopropyl-2-oxazoline were terminated using calix[4]arene tetrahydrazide as a multifunctional termination agent. Molecular-weight and structural characteristics of obtained four-arm star poly(2-alkyl-2-oxazoline)s were determined by size exclusion chromatography and light scattering. The thermosensitivity of aqueous solutions of obtained star polymers was studied. Cloud points, determined for 1% wt. aqueous solutions were equal to tcp50% = 27.5 degrees C for CA4-PiPrOx and tcp50% = 73.1 degrees C for CA4-PEtOx. Critical micelle concentrations of aqueous solutions of star polymers were determined using UV-Vis absorption spectroscopy, they were equal to 2.20 x 10-4 g/mL for CA4-PEtOx and 1.68 x 10-4 g/mL for CA4-PiPrOx. It was shown that studied poly(2-alkyl-2-oxazoline)s form water-soluble complexes with hydrophobic curcumin. The composition of curcumin-polymer complexes and their stability in aqueous solutions were studied using UV-Vis absorption spectroscopy. Obtained Job's plots indicated the formation of bimolecular curcumin-polymer complexes. Binding constants of curcumin by studied calixarene-centered star polymers were equal to (5-7)x 104 L/mol.

A novel grafting-onto approach was applied to the synthesis of star-shaped poly(2-alkyl-2-oxazoline)s with macrocyclic calix[4]arene core. Cationic polymerization of 2-alkyl-2-oxazoline was terminated using calix[4]arene tetrahydrazide as a multifunctional termination agent. Molecular-weight and structural characteristics of obtained four-arm star poly(2-alkyl-2-oxazoline)s were determined by size exclusion chromatography and light scattering. The thermosensitivity of aqueous solutions of obtained star polymers was studied. Critical micelle concentrations of aqueous solutions of star polymers were determined using UV-Vis absorption spectroscopy. It was shown that star-shaped poly(2-alkyl-2-oxazoline)s with calix[4]arene branching center form water-soluble complexes with hydrophobic curcumin. The composition of obtained polymer complexes and their stability in aqueous solutions were studied.

A new approach to the synthesis of sulfonyl chloride initiators with the calixarene core for the cationic polymerization of 2-oxazolines is developed. The kinetics of 2-ethyl-2-oxazoline polymerization with the synthesized octafunctional initiator at 100°С in sulfolane is studied. It is shown that the decelerated initiation of polymerization is observed in the system and the rate constant of chain propagation is kp = 1.20 × 10–3 L/(mol s). Using the cationic ring-opening polymerization of 2-alkyl-2-oxazolines initiated by calix[8]arene functionalized by sulfonyl chloride groups in the lower rim, star-shaped thermosensitive polymers are synthesized, and the molecular weight characteristics of the polymers are investigated. The critical micelle concentration of star-shaped poly(2-isopropyl-2-oxazoline) is determined (СCMC = 6.25 × 10–5 g/mL), and the solubilizability of the synthesized polymers is investigated using hydrophobic dye curcumin as an example.

Both hydrophilic N-methylpyridinium p-toluenesulfonate and hydrophobic 5,10,15,20-tetraphenylporphyrin additives decrease the phase transition temperature of thermoresponsive poly-2-isopropyl-2-oxazoline star-shaped polymer in aqueous solutions.

On the basis of macroinitiators of polyester type, hybrid comb-shaped polymers with poly-2-isopropyl- 2-oxazoline side fragments are prepared via ring-opening cationic polymerization. A method for estimating the length of polyoxazoline side chains and their grafting density is proposed. It is shown that, at the given ratio of the length of backbone and side chains, which depends on the chemical structure of the initiator, the graft copolymers are capable of formation of micellar aqueous solutions with a lower critical solution temperature.

Multicenter polyester initiators intended for the cationic polymerization of oxazolines were synthesized via high-temperature polycondensation of 2-(4-(2-bromoethyl)phenyl sulfonyl hydroquinone with a number of aromatic and alkylene-aromatic dichloroanhydrides. The Kuhn segment values, liquid-crystalline properties, and molecular-mass characteristics of the macroinitiators are determined. The synthesized macroinitiators were used in cationic ring-opening polymerization to obtain hybrid comb polymers containing poly(2-oxazoline) side chains. It was suggested the method for estimating the length of poly(oxazoline) side fragments and graft density. It was demonstrated that at a certain ratio between backbone length and side chain length (which depends on chemical structure of the initiator), comb copolymers The graft copolymers form aqueous micellar solutions with a narrow particle-size distribution. They possess a lower critical solution temperature.

The heats of wetting have been measured experimentally for some of the solvents used for the preparation of electrolytes of supercapacitors. For the first time, the heat of wetting has been measured for a new promising solvent—tributyl phosphate. Using acetonitrile as an example, the possible orientation of the molecule at the adsorbing surface has been investigated by the technique of surface-enhanced Raman scattering (SERS) (effect of giant enhancement of the scattering by a conducting surface). The calculated estimates have been obtained for the quantities found in the experiment.

Multicenter alkylene-aromatic polyester initiators for the cationic polymerization of oxazolines are synthesized via the high-temperature polycondensation of 2-[4-(2-Br-ethyl)]phenylsulfonyl hydroquinone with 4,4'- (alkanoyldioxydibenzoyl)dichlorides. The Kuhn segment values, liquid-crystalline properties, and molecularmass characteristics of the macroinitiators are determined. It is shown that the obtained polyesters may be used as initiators for the cationic polymerization of 2-ethyl-2-oxazoline. The graft copolymers form aqueous micellar solutions with a narrow particle-size distribution and possess a lower critical solution temperature.

Экспериментально измерены теплоты смачивания для некоторых растворителей, используемых для приготовления электролитов суперконденсаторов. Впервые измерена теплота смачивания для нового перспективного растворителя --- трибутилфосфата. На примере ацетонитрила методом SERS (SERS --- эффект гигантского усиления рассеяния проводящей поверхностью) исследована возможная ориентация молекулы у адсорбирующей поверхности. Получены расчетные оценки для величин, найденных в эксперименте.

This work describes the synthesis of thermosensitive eight-point star-shaped polymers with a central core comprised of residual octa-ester-tert-butylcalix[8]arene with oligo-2-ethyl-2-oxazoline-block-2-isopropyl-2-oxazoline rays. It is found that, despite the presence of two blocks with substantially different temperatures of the coil – globule transition, block copolymers exhibit only one lower critical solution temperature (LCST), and the phase transition is observed at a temperature close to the transition temperature of the homopolymer with a lower LCST. For the first time it is found that, upon incubating for some time in an aqueous solution above the LCST, star polymers with temperature-sensitive polyoxazoline rays self-assemble to form nanofibers and structures with more complex morphology.

Aggregation of 4-[5-(4-hydroxyphenyl)-3-oxopenta-1,4-dienyl]benzoic acid (chromophore) and its potassium salt in optically neutral polymeric matrices was studied. The dependence of the third-order nonlinear optical properties of the chromophore-polymer composites on the aggregate size was determined.

The structure and supramolecular ordering of polymer complexes formed as the result of a combination of ionic and hydrophobic-hydrophilic interactions are determined. The efficiency of the combined use of the X-ray diffraction analysis, the second-harmonic generation technique, and luminescence spectroscopy in solids for determining the structure and supramolecular ordering is demonstrated using ionic polypseudorotaxane, which is based on poly(2-acrylamido-2-methyl-propanesulfonic acid), N,N-dimethyl-N′-(4-nitrophenyl)-decane-1,10-diamine, and α-cyclodextrin and contains photophysically active groups in side chains.

The time dependence of the nonlinear optical properties of the films prepared from silicon-containing poly(o-hydroxyamide) with a covalently bound 4-nitroazobenzene-based chromophore in a side chain is investigated in isothermal and thermally stimulated modes. It is revealed that, when the onium salt, i.e., triphenylsulfonium hexafluorophosphate, is added to a polymer solution, the second harmonic generation signal is characterized by an unusual time dependence. The assumption is made that the introduction of the onium salt favors the formation of the benzoxazole structure during the process of polarization (poling). This structure facilitates the orientation of nonlinear optical fragments and, hence, leads to an improvement of the nonlinear optical properties of the polymer film.

For a set of comblike polymers manufactured by polymer-analogue conversions, nonlinear optical and photosensitive properties are investigated. On the basis of the chemical modification, the interaction between polyamidoimides with side carboxyl groups with glycidyl ethers of commercially manufactured azo dyes (DR-1, DO-13, DY-7) is used. It is shown that transparent films of these polymers have a reasonably high electrophotographic photosensitivity (at a level of 10 4 cm 2 /J), and the coefficient d 33 of second-harmonic generation describing nonlinear optical properties is within 4.5–6 pm/V.

A new heat-resistant copolymer (II) with a nonlinear optical chromophore in a side chain was synthesized by the etherification of side hydroxyl groups in chains of silicon-containing poly(o-hydroxyamide) (I) with 4′-{(6-chlorohexyl)methylamino}-4-nitroazobenzene (chromophore) under conditions of phase-transfer catalysis. The structure and phase (aggregate) states of copolymer II were investigated using x-ray diffraction and differential scanning calorimetry. It was shown that the substitution of chromophore molecules for up to 15% of hydrogen atoms in hydroxyl groups of amorphous copolymer I most likely leads to an independent arrangement of the chromophoric groups and the formation of crystal domains. It was established that this ordering substantially affects the stability and efficiency of the nonlinear optical properties of films prepared from copolymer II and is probably responsible for the slow decay of the second-harmonic generation signal in the sample.

A combined wide angle X-ray diffraction (WAXD)/small-angle X-ray scattering (SAXS)/scanning electron microscopy (SEM)/density study of structure and morphology was carried out for a large series of pyromellitic dianhydride-oxydianiline (PMDA-ODA) polyimide (M) samples processed using different powder metallurgy techniques. Using a combined DSC/creep rate spectroscopy (CRS)/long-term creep resistance (LTCR) approach, their molecular dynamics, thermal and elastic properties, and creep resistance in the temperature range from 20 to 470 degrees C were also studied. Both a choice of the method of formation of fine PI particles and the order of applying high pressure relative to high temperature to form the monolithic samples led to the observation of significant property differences. Relationships between the processing conditions, structure, and properties were determined. As a result, the conditions for optimizing certain PMDA-ODA polyimide properties, especially creep resistance and elastic properties at extreme temperatures, were determined.