The paper shows the similarity of kinetic regularities of vinyl monomers polymerization in the presence of Laprol 6003, regardless of the degree of solubility of the monomers in water. It is assumed that this feature of polymerization is due to the same mechanism of formation of polymer-monomer particles (PMP) – from monomer microdroplets. The interfacial adsorption layer of PMPs, the main site of polymerization, is formed from a surfactant adsorbed from the bulk of the monomer phase and a polymer formed in the adsorption layer upon initiation of polymerization. The formation of complex structures in the interfacial adsorption layer of particles, the incompatibility of the surfactant and the resulting polymer, and high viscosity cause the formation of a strong interfacial layer that ensures the stability of polymer suspensions from the early stages of polymerization.

Изучено влияние условий синтеза – соотношения фаз и концентраций компонентов – на закономерности полимеризации стирола в присутствии не растворимого в воде кремнийорганического ПАВ – α,ω-бис-(10-карбоксидецил)полидиметилсилоксана и его смеси с неионным ПАВ – плюроником F-68.

The review presents schemes for obtaining homologous series of the linear α,ω-carbofunctional oligodimethylsiloxanes with the silicone chain length from 6 to 60 siloxane units containing carboxydecyl, aminopropyl and glycidoxypropyl groups at the chain ends allowing to obtain organosilicon surfactants with reproducible structure and properties. Data on the surfactant colloidchemical properties and kinetic regularities of styrene polymerization in their presence are provided. Systematic research of heterophase styrene polymerization kinetic regularities in the presence of water-insoluble α,ω-carbofunctional oligodimethylsiloxane allowed to formulate the fundamental differences of polymerization kinetic regularities from those observed in the presence of water-soluble surfactants. The mechanism of interfacial adsorption layers formation with water-insoluble α,ω-carbofunctional oligodimethylsiloxanes on the surface of monomer drops and polymer-monomeric particles was considered. This mechanism consists in the forced surfactant replacement by the formed polymer (because of their incompatibility) to the interfacial adsorption layer and in the formation of the surfactant supermolecular structures. The latter in total with the polymer provide its high durability.

The effect of synthesis conditions, such as the phase and concentration ratios of components, on the mechanism of styrene polymerization in the presence of the water-insoluble organosilicon surfactant α,ω-bis(10-carboxydecyl)polydimethylsiloxane and its mixture with the nonionic surfactant Pluronic F-68 is studied.

Polystyrene suspensions with an average particle diameter of 0.1–0.25 μm and a narrow particle size distribution were synthesised in the presence of a mixture of surfactants – sodium alkyl sulphonate (E-30), oxyethylated sulphated alkylphenol (AP-9), and organosilicon surfactant α,ω-bis[10-carboxydecyl] polydimethylsiloxane (CS). It was shown that the absence of a highly disperse particle fraction in the suspension is observed only when the polymerisation of styrene is carried out with an ionogenic surfactant content close to the critical micelle concentration (CMC).

The review presents schemes for obtaining homologous series of the linear α,ω-carbofunctional oligodimethylsiloxanes with the silicone chain length from 6 to 60 siloxane units containing carboxydecyl, aminopropyl and glycidoxypropyl groups at the chain ends allowing to obtain organosilicon surfactants with reproducible structure and properties. Data on the surfactant colloidchemical properties and kinetic regularities of styrene polymerization in their presence are provided. Systematic research of heterophase styrene polymerization kinetic regularities in the presence of water-insoluble α,ω-carbofunctional oligodimethylsiloxane allowed to formulate the fundamental differences of polymerization kinetic regularities from those observed in the presence of water-soluble surfactants. The mechanism of interfacial adsorption layers formation with water-insoluble α,ω-carbofunctional oligodimethylsiloxanes on the surface of monomer drops and polymer-monomeric particles was considered. This mechanism consists in the forced surfactant replacement by the formed polymer (because of their incompatibility) to the interfacial adsorption layer and in the formation of the surfactant supermolecular structures. The latter in total with the polymer provide its high durability.

The kinetics of methyl methacrylate polymerization in the presence of α,ω-functional polydimethylsiloxanes is investigated. The formation of polymer suspensions with a narrow particle-size distribution is explained by the ability of the surfactants to form strong adsorption layers in the interfacial layers of polymer–monomer particles. This assumption is confirmed by data obtained via the Langmuir method with the use of model systems: thin films of the mentioned organosilicon compounds.

The article presents the results of a study on the behavior of water-insoluble ethoxylated surfactants of different nature on the phase boundary by the method of oscillating drops and by the method of Langmuir-Blodgett films. It was shown that the water-insoluble ethoxylated surfactants form supramolecular structures and stable layers at the water/air interface.

Polysterene suspensions with particle diameters of 0.05-0.2 microns and narrow distribution by sizes can be synthesized at polymerization of styrene in high-disperse emulsions at high temperature and low concentration of monomer in the presence of ionic surfactant. Monodisperse polymeric suspensions with a diameter of particles 0.2 microns were prepared only in the presence of water-soluble inhibitor.

Linear and branched copolylactides of various structures are synthesized and characterized. Polystyrene suspensions with various particle diameters are obtained via heterophase polymerization with the use of copolylactides as biodegradable surfactants. The influence of the surfactant structure on the polymer microsphere size and the type of size distribution is studied.

A number of linear and comb-shaped organosilicon surfactants containing poly(ethylene oxide) blocks were synthesized and studied. The structures of the copolymers were varied systematically, and the obtained copolymers were characterized via elemental analysis, GPC, and 1 H NMR. A comparative study of the surface activities of amphiphilic organosilicon block copolymers was performed. Their structures were shown to considerably affect the surface activities as well as the styrene polymerization rates and the sizes of microparticles obtained with the use of the studied copolymers as surfactants.

Синтезирован и исследован ряд линейных и гребнеобразных кремнийорганических ПАВ, содержащих полиэтиленоксидные блоки. Строение сополимеров систематически варьировали; полученные сополимеры были охарактеризованы с помощью элементного анализа, ГПХ и ЯМР 1H. Проведено сравнительное исследование поверхностно-активных свойств амфифильных кремнийорганических блок-сополимеров. Показано, что их строение оказывает существенное влияние на поверхностно-активные свойства, а также на скорость полимеризации стирола и размер микрочастиц, полученных с использованием исследованных сополимеров в качестве ПАВ.