A. I. Kirillov

New fluorine-containing polyorganosilsesquioxanes: Preparation and properties

It has been found that hydrolysis of three-functional alkoxysilanes, such as RFOCH2Si(ORF)3, RF = CH2CF3, CH2CF2CF3, CH2CF2CF2CF3, and CH2CF2CF2CF2CF3, under mild conditions upon exposure to air moisture in the presence of λ-aminopropyltriethoxysilane results in the formation of hydrophobic coatings from fluorine-containing polyorganosilsesquioxanes directly on the substrate. Polymers have a layered ladder structure. The hydrophobicity and low values of refractive indices, surface energy, and its polar component, as well as the simplicity of the preparation, determine the possibility of using polyorganosilsesquioxane films as antireflection protective coatings for laser optics.

The structure of fullerene films and their metallocene doping

Hexagonal close-packed (HCP) C60 and C70 films have been prepared by the Langmuir method and examined by electron microscopy and electron-diffraction analysis. It has been shown that the vacuum deposition of a C60+C70 mixture results in the formation of a film with small sized grains and a distorted C60-HCP structure. The simultaneous deposition of C60 and ferrocene results in the formation of a film with a changed morphology and an electron-diffraction pattern that contains a variable amount of ferrocene depending on the experimental conditions. The electron-diffraction pattern corresponds to the presence of the known molecular complex C60[(C5H5)2Fe]2. The analogous simultaneous deposition of fullerene C60 and cobaltocene results in the formation of a C60 film stable in air and water, which contains carbon and cobalt (from the data of X-ray fluorescence, electron microscopy and microdiffraction). It has a different morphology and different diffraction patterns than pure C60 films and, depending on the cobaltocene content (relative to that of fullerene), appears to be a fullerite film doped with various amounts of cobaltocenium fullende, which is an ionic compound.

New polyfunctional silicon-containing amines C6[CH2CH2SiMe(OCH2CH2NR2)2]6 (R = H, Me) and their reactions with cobalt(ii) chloride and dicobalt octacarbonyl

Hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene and hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene C6[(NR2CH2CH2O)2SiMeCH2CH2]6 (4, R = H; 5, R = Me) were prepared from hexakis(methyldichlorosilylethyl)benzene C6(Cl2MeSiCH2CH2)6 and 2-aminoethanol or N,N-dimethyl-2-aminoethanol, respectively. Compounds 4 and 5 react with anhydrous cobalt (ii) chloride to give poorly soluble dodecachloro{hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene}hexacobalt and dodecachloro{hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene}hexacobalt {Co6[(NR2CH2CH2O)2SiMeCH2CH2]6C6}Cl12 (R = H or Me), respectively. Polyfunctional amine 4 reacts with dicobalt octacarbonyl to produce hexakis[bis(2-aminoethoxy)methylsilylethyl]benzenedicobalt(ii) tetrakis(tetracarbonylcobaltate) {Co2[(NH2CH2CH2O)2SiMeCH2CH2]6C6}[Co(CO)4]4. N,N-Dimethyl-substituted polyfunctional amine 5 is lowly reactive in the reaction with Co2(CO)8, whereas the simplest model of this compound, viz., bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane (NMe2CH2CH2O)2SiMe2, slowly reacts with Co2(CO)8 to give tris[bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane]cobalt(ii) bis(tetracarbonylcobaltate) {Co[(NMe2CH2CH2O)2SiMe2]3}[Co(CO)4]2. Thermal decomposition and transformations of the resulting complexes under the action of oxygen and water were studied.

Reaction of Perylene-3,4,9,10-tetracarboxylic Acid Dianhydride with 3-Aminopropyltriethoxysilane and Hexamethyldisilazane

The reaction of perylene-3,4,9,10-tetracarboxylic acid dianhydride with 3-aminopropyltriethoxysilane and hexamethyldisilazane was investigated. A possibility of obtaining a new dye resistant to UV light and heating (up to 300°C), consisting of structural fragments of perylene-3,4,9,10-tetracarboxydiimede, diethoxysiloxane, and 3-aminopropylethoxysiloxane was demonstrated. A compound obtained in 43% yield by heating (7 h, 180–200°C) perylene-3,4,9,10-tetracarboxylic acid dianhydride with excess 3-aminopropyltriethoxysilane in the presence of catalytic amounts of zinc acetate is an oligomer appropriate for the solgel process, displays strong luminescence in the red spectral region (540–620 nm), and has good film-forming properties. The participation of hexamethyldisilazane consists in binding water molecules formed in the reaction of perylene-3,4,9,10-tetracarboxylic acid dianhydride with 3-aminopropyltriethoxysilane and in the formation of trimethylsilanol which replaces a part of the EtO groups at the silicon atoms by a more bulky Me3SiO groups, causing significant increase in the solubility of the dye in organic solvents and silicon sol-gel monomers. The hydrolysis of silicon-containing dye and subsequent dehydration of the resulting gel lead to the formation of insoluble xerogel.

Алгоритм решения WSD-задачи на основе нового способа вычисления близости контекстов с учётом эпсилон-фильтрации слов

The problem of word sense disambiguation (WSD) is considered in the article. Set of synonyms (synsets) and sentences with these synonyms are taken. It is necessary to automatically select the meaning of the word in the sentence. 1285 sentences were tagged by experts, namely, one of the dictionary meanings was selected by experts for target words. To solve the WSD problem, an algorithm based on a new method of vector-word contexts proximity calculation is proposed. A preliminary epsilon-filtering of words is performed, both in the sentence and in the set of synonyms, in order to achieve higher accuracy. An extensive program of experiments was carried out. Four algorithms are implemented, including the new algorithm. Experiments have shown that in some cases the new algorithm produces better results. The developed software and the tagged corpus have an open license and are available online. Wiktionary and Wikisource are used. A brief description of this work can be viewed as slides (https://goo.gl/9ak6Gt). A video lecture in Russian about this research is available online (https://youtu.be/-DLmRkepf58).The problem of word sense disambiguation (WSD) is considered in the article. Given a set of synonyms (synsets) and sentences with these synonyms. It is necessary to select the meaning of the word in the sentence automatically. 1285 sentences were tagged by experts, namely, one of the dictionary meanings was selected by experts for target words. To solve the WSD-problem, an algorithm based on a new method of vector-word contexts proximity calculation is proposed. In order to achieve higher accuracy, a preliminary epsilon-filtering of words is performed, both in the sentence and in the set of synonyms. An extensive program of experiments was carried out. Four algorithms are implemented, including a new algorithm. Experiments have shown that in a number of cases the new algorithm shows better results. The developed software and the tagged corpus have an open license and are available online. Wiktionary and Wikisource are used. A brief description of this work can be viewed in slides (this https URL). Video lecture in Russian on this research is available online (this https URL).

Модель геометрической структуры синсета

The goal of formalization, proposed in this paper, is to bring together, as near as possible, the theoretic linguistic problem of synonym conception and the computer linguistic methods based generally on empirical intuitive unjustified factors. Using the word vector representation we have proposed the geometric approach to mathematical modeling of synset. The word embedding is based on the neural networks (Skip-gram, CBOW), developed and realized as word2vec program by T. Mikolov. The standard cosine similarity is used as the distance between word-vectors. Several geometric characteristics of the synset words are introduced: the interior of synset, the synset word rank and centrality. These notions are intended to select the most significant synset words, i.e. the words which senses are the nearest to the sense of a synset. Some experiments with proposed notions, based on RusVectores resources, are represented.

Physicomechanical properties of polyurethane foam filled with pyrolytic chromium coated aluminosilicate ash microspheres

The possibility of depositing pyrolytic chromium on the surface of aluminosilicate ash microspheres and preparing rigid polyurethane foam filled with aluminosilicate ash microspheres was examined. The physicomechanical properties of the materials obtained were studied.

Heterophase synthesis of polymeric organosilanes

A new procedure was suggested for preparing polymeric organosilanes and silanosiloxanes without using a dispersion of an alkali metal in an organic solvent. The procedure allows preparation of linear organopolysilanes —(R2Si)n—, whereas reactions of methyl-, phenyl-, and n-hexyltrichlorosilanes with Na/NaCl yield silanosiloxane derivatives [(RSi)x(RSiOy].