The aggregation in aqueous systems of hydrophobically modified poly(ethylene imines) and their mixtures with cationic surfactants, as well as the catalytic activity of these compositions in the hydrolysis of O -4-nitrophenyl- O -ethylchloromethylphosphonate, are studied by conductometry, tensiometry, light-scattering, and viscometry methods. Critical association concentration, hydrodynamic radii of polymer and polymer-colloid aggregates formed in such systems, as well as kinetic parameters of hydrolysis are determined.

Методами кондуктометрии, тензиометрии, светорассеяния и вискозиметрии исследованы агрегация в системах полиэтиленимин (полиэтиленгликоль)–каликс[4]резорцинарен–вода–диметилформамид (30 об. %) и каталитическая активность этих композиций в реакции гидролиза 4-нитрофенилбис(хлорметил)фосфината. Определены критические концентрации ассоциации, гидродинамические радиусы полимер-коллоидных агрегатов и кинетические параметры реакции гидролиза.

The influence of the fluoride ion on the aggregation behavior and catalytic properties of neutral and alkaline aqueous solutions of cetyltrimethylammonium bromide in nucleophilic substitution reactions of phosphorus acid esters was studied by tensiometry, small-angle neutron scattering, and UV spectrophotometry. The critical micelle concentrations and the radii, aggregation numbers, and shape of micelles forming in these systems, as well as the kinetic parameters of the nucleophilic substitution reactions of phosphorus acid esters, were determined.

Self-assembling in systems poly(ethylene) imine-aminomethylated calix[4]resorcinarene-water-DMF (30 vol%) and catalytic properties of these compositions in hydrolysis of 4-nitrophenylbis (chloromethyl)phosphinate are studied. Critical concentrations of association, aggregates radii, and kinetic parameters of the reaction are established.

The aggregation in poly(ethylene imine) (poly(ethylene glycol))-calix[4]resorcinarene-water-dimethylformamide (30 vol %) systems and the catalytic activity of these compositions in hydrolysis of 4-nitrophenylbis(chloromethyl)phosphinate are studied by conductometry, tensiometry, lightscattering, and viscometry. Critical association concentrations, hydrodynamic radii of polymer-colloid aggregates, and kinetic parameters of hydrolysis are determined.

Методами кондуктометрии, тензиометрии, светорассеяния и вискозиметрии исследована агрегация в водных системах гидрофобно-модифицированных полиэтилениминов и их смесей с катионными поверхностно-активными веществами, а также каталитическая активность этих композиций в реакции гидролиза О-4-нитрофенил-О-этилхлорметилфосфоната. Определены критические концентрации ассоциации, гидродинамические радиусы полимерных и полимер-коллоидных агрегатов, формирующихся в этих системах, кинетические параметры реакции гидролиза.

Aggregation in poly(ethylenimine)-calix[4]resorcinarene-water-DMF systems was studied by the methods of conductometry and dynamic light scattering. The sizes (radii) of the aggregates formed and the critical micelle concentrations were determined. The catalytic activity for these systems in the hydrolisys of phosphorus acid esters was shown.

The aggregation of binary mixtures of branched polyethylenimine with a molecular mass of 30 000 and cationic surfactants, such as cetyltrimethylammonium bromide, cetyldimethylethylammonium bromide, or cetyldimethyl(2-hydroxyethyl)ammonium bromide, in aqueous solutions is studied. The critical micellization concentrations, as well as the sizes and shapes of aggregates, are determined by conductometry, small-angle neutron scattering, and dynamic light scattering methods. Catalytic activity of cationic surfactant-polyethylenimine compositions in the hydrolysis of tetracoordinated phosphorus acid 4-nitrophenyl esters is studied via spectrophotometry. The influence of spatial characteristics of aggregates on the catalytic activity and selectivity of nanostructured polymeric systems is revealed.

The kinetics of decomposition of 4-nitrophenyl ethyl ethylphosphonate in the system 4-octylphenol-NaOH-water was studied spectrophotometrically. Electrophoretic, tensimetric, and kinetic studies proved formation of cationic associates in which phenolysis or base hydrolysis occurs, depending on the concentration ratio of 4-octylphenol and NaOH.

The influence of micellar (Mi) and hexagonal (E) mesophases of the cetyldimethylethylammonium bromide—NaOH—water system (I) on the rates on alkaline hydrolysis ofO-p-nitrophenyl-O,O-diethyl phosphate (2),O-p-nitrophenyl-O-ethylethyl phosphonate (3), andO,O-di(p-nitrophenyl)methyl phosphonate (4) was studied by UV spectrophotometry. The binding constants of the substrates, critical micelle concentrations, and rate constants of reactions in the micellar phase were determined. In micellar solutions of systemI, a tenfold increase in the rates of alkaline hydrolysis of2–4 was observed. An increase in the degree of medium ordering during the formation of the E-phase results in a twofold acceleration of alkaline hydrolysis of2 and3 and in the inhibition of this process in the case of4.

While investigating the reaction mechanism in the triple system N+H4X−+CH2O+H3PP3, much attention was paid to determining the stages of the interaction which can be presented as follows: The mechanism of the stage (2) and the possible alternative processes have not been sufficiently developed. If phosphite-anion is present in the system, one might assume that hydrogen attached to phosphorus can be involved in the hydride transfer reactions: Indeed, the reactions of ammonium salts of phosphorous acid with aldehydes in aqueous media result in ammonium salts of phosphoric acid, i.e. the reduction of the intermediately formed a-oxymethylamine to tertamine occurs and the oxidation of phosphite-anion to phosphate-anion takes place.

Mit wachsender Polarität der C‐Cl‐Bindung der im Titel‐ genannten Verbindungen (I) steigt bei der Umsetzung mit Säureamiden des dreiwertigen Phosphors (II) die Tendenz für die Reaktion am Phosphor.