I. R. Mullagaliev

Ionic and coordination diene polymerization and organic derivatives of main group metals

The effects of the nature of an organic derivative of a main group metal (cocatalyst), its composition, the cocatalyst : transition metal compound ratio, and the way of introducing the cocatalyst on the formation and operation of the active sites in the Ziegler—Natta catalytic systems in the polymerization of conjugated dienes are discussed. A correlation between the cocatalyst nature and the number and kinetic heterogeneity of the active sites is shown.

Luminescence Monitoring of Lanthanide Catalysts for Diene Polymerization

Changes in the luminescence characteristics of Tb3+ and Ce3+ lanthanide ions in the interaction of LnCl3 · 3(BuO)3PO complexes with iso-Bu3Al in the absence and presence of piperylene were studied. As a result, a new luminescence approach was proposed to study reaction mechanisms in the synthesis of lanthanide catalysts for diene polymerization.

On the Kinetic Parameters of Butadiene Polymerization on Titanium - Magnesium Catalytic Systems

Abstract During the polymerization of butadiene on catalytic systems, containing TiI2Cl2 or Ti(O-nC4H9)4 in combination with n-butyl-(2 ethyl)hexytmagnesium, the constants of chain propagation reaction were determined by the method of dose adding of inhibitor and by kinetic method. It was shown, that the addition of organomagnesium compound instead of organoaluminium cocatalyst changes the activity and stereospecificity of system. It shows the great influence of organic compound of nontransition metal not only on the formation, but also on the functioning of active centers of metallocomplex catalysts.

Polymerization of isoprene with vanadium-containing catalysts: Kinetic nonuniformity of active centers

For the polymerization of isoprene catalyzed by vanadium-based ion-coordination systems, the kinetic nonuniformity of active centers was studied and active centers of three to four types were revealed. By the solution of inverse kinetic problems, kinetic parameters were first estimated for individual active centers. It was demonstrated that the nature of an organoaluminum compound affects the kinetic nonuniformity of a catalyst, kinetic parameters of individual active centers, and molecular characteristics of polyisoprene.

Interaction of LnCl3 · 6H2O crystal hydrates with the alkoxy derivatives of aluminum in organic solvents

The interaction of LnCl3 · 6H2O (Ln = Pr, Nd, and Tb) with the alkoxy derivatives of aluminum (RO)nAlCl3−n (where R = Et or iso-Bu; n = 1–3) in organic solvents was studied. It was found that the reaction of the crystal water of LnCl3 · 6H2O with (RO)nAlCl3−n resulted in the partial dehydration of the crystal hydrates with the formation of an alcohol (ROH) and the LnCl3 · 3H2O · 3(RO)mAl(OH)Cl2−m complex (m = 1, 2). The solid colloidal particles of this complex and a solvent form a lanthanide-containing gel. The physicochemical (including luminescence) and catalytic properties of the complex in butadiene polymerization and 1,1-gem-dibromo-2-phenylcyclopropane dehalogenation were studied.

The influence of vanadium catalyst preparation method on butadiene polymerization

The butadiene polymerization in toluene at 25°C using a VOCl3–Al(iso-C4H9)3 catalytic system was studied. The maximum of activity corresponded to the ratio . The polymer contained 90% 1,4-trans- and 10% 1,2-units. The kinetic parameters of polymerization and molecular characteristics of polybutadiene were determined, and they testify to the influence of catalytic complex preparation and polymerization conditions on them. It was suggested that there are several types of active centers that differ in activity, stereospecificity of action, and stability.

Oxidative Destruction of Chitosan During Ozonization

Abstract Ozonization of water suspension of chitosan leads to oxidation of amino groups which accompanied by deamination and crosslinkihg of macromolecules. The clearing of 1,4-β-v-glucoside bonds in macromolecule is a basic process in the protection of amino groups by protonation with acid. The polymerization degree of ozonolysis products in acidic medium can be varied in wide ranges depending on reaction conditions. The rate of the interaction of ozone with chitosan depends on the conformation of polysaccharide macromolecules.

Distributions of active sites of titanium-containing catalytic system in terms of stereoregulating power and kinetic nonuniformity in butadiene polymerization

The nonuniformity of active sites of a titanium-containing catalytic system in terms of their stereoregulating ability and kinetic activity during butadiene polymerization was studied. It was shown that active sites of three types differing in stereoregulating power and kinetic activity can be formed under polymerization conditions corresponding to the maximum catalyst activity. By solving inverse kinetic problems, the rate parameters for active sites of different types were obtained.

Molecular Characteristics of 1,4-trans-Polybutadiene and Nature of Organoaluminum Compound in Vanadium-Containing Catalytic Systems

The influence of the nature of an organoaluminum compound on the molecular characteristics of 1,4-trans-polybutadiene prepared with vanadium-containing catalytic systems was studied.

Oligomerization of trimethylsilylacetylene in the presence of catalytic systems based on group III–VI transition metal halides

The features of the reaction of oligomerization of trimethylsilylacetylene in the presence of group III–VI transition metal compounds combined with triisobutylaluminum were investigated. The effect of the nature of the transition metal, cocatalyst, and conditions of conducting the oligomerization reaction on the yield and composition of the products of the reaction were studied. It was shown that it is possible to obtain either linear products of oligomerization or the cyclic trimer, or a mixture of both by varying the nature of the catalyst.