Method for preparing metallopolycarbosilanes

FIELD: chemical technology.

SUBSTANCE: invention describes a method for preparing metallopolycarbosilanes. Method involves interaction of polycarbosilanes with molecular mass above 200 Da and with the main chain consisting of links of the formula: [-(R)2Si-CH2-] wherein R means hydrogen atom (H), (C1-C4)-alkyl or phenyl groups with metalloorganic compounds of the formula MXz wherein M means transient metal of III-VIII group of Periodic system; z = 2-4; X means NR12 wherein R1 means (C1-C4)-alkyl group in organic solvent medium at temperatures from 20°C to 400°C under pressure from 5.05 MPa to 0.2 kPA. Method provides preparing fusible soluble polymers with homogeneous distribution of chemically bound metal atoms that elicit high capacity for fiber- and film-formation from solutions or melts that are hardened in thermochemical treatment and provides high yield of ceramic residue in pyrolysis (up to 85 wt.-%).

EFFECT: improved preparing method.

1 tbl, 9 ex

 

The invention relates to methods for producing metallopolimerov (MPX) General formula:

[-Si(R)2-CH2-]m[-M(N)k-]n (I)

where: m≥6, n=1, k=0-2,

R is H, alkyl (C1-C4or phenyl group,

M is a transition metal III - VIII groups of the Periodic system.

MPCS are predeterminada polymers. Thermochemical processing of them receive components of high-strength heat-resistant oxygen-free composite ceramics with stable structure. These components include: reinforcing fiber, matrix, protective covering and alloyed fine ceramic powders. An important application of metal polymers is their use as impregnating compositions for sealing and hardening of ceramics and graphite. In all these cases the presence of homogeneous distributed at the molecular level chemically bound metal in monophasic structure of the polymer matrix of metropolitanamilan contributes to the stabilization obtained on the basis of homogeneous ultramelodiousness ceramics having high thermo-mechanical properties.

Previously [U.S. Pat. RF 2125579 1 08 G 77/60, 1999] were obtained containing metal clusters polycarbosilane. Their formation occurred due to the interaction of coordination compounds of transition metals of III-VIII the Rupp Periodic system with silanes or carbosilane at inlet 150 up to 450° C. For the introduction of titanium and zirconium used mainly dicyclopentadienyltitanium titanium and zirconium. When this took place very high activity of the reactants at the temperature, which corresponded to thermal decomposition of metal-containing compounds. When the metal content is higher than 3.0 wt.% lost control of rapid rearrangements in the polymer thus formed high molecular weight fraction and disappeared fibre-forming ability MPX. In addition, when using dicyclopentadienyltitanium titanium and zirconium in polymers remained from 33 to 85 wt.% the initial concentration of chlorine, which is an undesirable impurity in the further processing predtermined MPX in ceramics. Structural studies have shown that the data contained in the received predtermined nano-metropolitanamilan nano-particles had a composition and structure, resembling the composition and structure of the cluster subgalactic zirconium. [Gubin S.P., zirlin A. M., Popova N.A., Florina E.K., frost EM // Neorg. mater. Russian Academy of Sciences, 2001, V.37, №11, S].

The closest in technical essence of the present invention and adopted for the prototype is the way to get metallopolimerov with a molecular weight of from 700 to 100000 interaction polycarbosilane with a molecular mass of from 200 to 10000, the main chain of which is worth of units of the formula [-(R) 2Si-CH2-], where R is H, alkyl (C1-C4or phenyl group, with ORGANOMETALLIC compounds of the formula MX, where M is Ti, Zr, and X - alkoxygroup (C1-C20), fenoxaprop or acetylacetone group, in an organic solvent. The ratio in the polymer chains (-Si-CH2-) and (-M-O-) is from 2:1 to 200:1. At least one silicon atom is linked to the metal atom through an oxygen bridge. The resulting metallpoliererei melt in the range of 50-400°S, soluble in organic solvents. These polymers are subjected to heat treatment at 1700°for the manufacture of SiC ceramics [U.S. Pat. EPO 0 030105 1 08 G 77/60, 1985].

The drawback of such metallopolimerov is the presence in the main and side chains of the macromolecules of oxygen atoms that are moving in ceramics, forming oxides of silicon and type of metals. This adversely affects oxidative and thermal stability of articles made of silicon carbide (SiC). For such materials, as they contain up to 10 wt.% oxygen, temperature limit for continuous operation in an oxidizing atmosphere does not exceed 1000-1100°C. In the presence of these materials free of carbon, usually in the same rate between oxygen and carbon at a temperature of 1100-1200°strong reaction with gaseous components. C is the at the same temperature begins growth of SiC crystallites, it leads to degradation of the ceramic structure.

The objective of this invention to provide MPX free from undesirable impurities oxygen and chlorine and intended for the manufacture of components of a modern ceramic composite materials such as SiC/SiC with a matrix of silicon carbide and silicon carbide fibers with high heat resistance and durability.

To solve this problem, a method for obtaining EX interaction in the environment of organic solvent polycarbosilane with a molecular weight above 200, the main chain of which is composed of units of the formula [-(R)2Si-CH2-], where R is H, alkyl (C1-C4or phenyl groups, ORGANOMETALLIC compounds, in which, according to the invention, as ORGANOMETALLIC compounds using the compounds of formula MXzwhere M is a transition metal III-VIII groups of the Periodic system, z=2-4, X-NR12where R1- alkyl (C1-C4) group, or-Si(CH3)3. That is, the use of ORGANOMETALLIC compounds that are not composed of oxygen and chlorine, and contained nitrogen is a useful item, as in the manufacture of ceramics on the basis of the obtained MPX, residual nitrogen forms a homogeneous distributed in ceramics high-temperature nitride. About the ECC obtain MPX variables is carried out at a temperature of from 20 to 400° C and a pressure of from of 5.05 MPa to 0.2 kPa.

Synthesis MPX carried out as follows: first, to a solution of polycarbosilane in an organic solvent, add a solution of M[NR12]4in an organic solvent, is maintained with stirring for 1 hour at 20-25°and 1 hour at the boiling temperature of the solvent. Then the solvent is distilled off. Next, perform a polycondensation reaction, first at atmospheric or pressure, and then at a residual pressure of 0.2-0.4 kPa, the reaction mass is heated from 20 to 285-400°With (optimally 310-390° (C) for 1-2 hours, then maintained at a given temperature 4-10 hours with distillation of light fractions. Get anoxic MPX with homogeneous distribution of chemically related metal atoms in the polymer, and the atoms of M are either directly related to the Si atoms, or a chemical bond via atom N. Obtained MPX soluble in organic solvents and have the General formula (I). Metal content in MPCS is from 0.1 to 20 wt.%. The average molecular weight obtained MPX according to gel chromatography (GPC) above 600. Dropping temperature (melting point) of 50 to 400°C.

The control synthesis MPX carry out the method of sampling, which are analyzed by NMR1H,13C,29Si, IR spectroscopy, GPC. Determine what the temperature of the softening - T1, fiberizing - T2and dropping - T3. In addition, for the end of the polymer is conducted thermogravimetric (TGA) and elemental analyses.

The NMR spectra of1H synthesized MPX contain the signals of the protons of methyl groups at the silicon atom (0,37 ppm) and the proton signals associated with the silicon atom (4.47 ppm). The NMR spectrum13C - observed characteristic of carbosilane polymer broad multiplet at 1,73 of 2.92 ppm, and the NMR spectrum29Si registered signals of silicon atoms associated with carbon atom (0.64 ppm) and hydrogen atom (-15.83 ppm).

In the IR spectra MPX observed absorption bands in the regions 800-900, 1250, 1405 cm-1(Si-CH3), 950, 1150 cm1(≡Si-N-Si≡), 1025 and 1355 cm-1(Si-CH2-Si), 2100 cm-1(Si-H), 2900, 2950 cm-1(C-H), 3380 cm-1(≡Si-NH-), and in some cases 1480 cm-1(≡Si6H5).

Analyzing the data of NMR, IR spectra and elemental analysis, it can be seen that the metal, completely losing their organic frame remains in the final polymer, and the amount of nitrogen depends on the duration (τtotal) and maximum temperature (τmaxthe second stage of the process - polycondensation under vacuum. The longer the process and above Tmaxthe less nitrogen remains in the synthesized polymer.

The essence of the image is etenia is illustrated by the following examples.

Example 1.

Apparatus equipped with a stirrer, a thermocouple, a metering funnel, reflux condenser, inert fill gas and a load of 200 g of the solution of the PCB with a molecular mass Mn=400 in hexane (50 wt.%). Of the dosing funnel for 30 minutes at 20°add 40 g of a solution in hexane Zr[N(C2H5)2]4(35 wt%), stand under stirring for 1 hour at 20-25°and 1 hour at 69° (TKip.hexane). Then the reaction mass is then cooled to room temperature in a current of inert gas to replace the reflux condenser to direct the fridge for removal of solvent and low molecular weight products of the synthesis. Distilled hexane and side product of the reaction, diethylamin HN(C2H5)2. Next, at atmospheric pressure, conducting the polycondensation reaction, for which the reaction mass is heated from 29 to 300°C for 1-2 hours and is maintained at the set temperature for 10 hours with light distillate fractions. Then at a residual pressure of 0.2-0.4 kPa, the reaction mass is heated to 325°and incubated for 4 hours at this temperature for full light distillate fractions. Get 60 g (yield 57%by weight.) zirconiabased (CPX) with the following characteristics: composition by elemental analysis With 38,35, N Of 7.95, N 2,81, Si 43,05, Zr 6,30 wt.%; Mn(Civil) - 610; softening temperature T1=220°C, bolognabreath the Oia - T2=240°and dropping - T3=300°C. On the basis of data on the composition and size of Mn CPX corresponds to the empirical formula C20H46N1,3Si10Zr0,45or in relative form SiC2N0,13Zr0,045. Output inorganic product after thermal treatment of the polymer in an inert atmosphere up to 1000°With (according to TGA) is 84 wt.%, the content of Zr - 7,47 wt.%.

Other examples are performed analogously to example 1, the data in the table.

Advantages of the invention can be seen from comparison of the composition of the ceramics obtained on the basis of CPX synthesized by the proposed method and CPCS obtained by a known method [U.S. Pat. EPO 0 030105 1 08 G 77/60, 1985].

The surface topography of the samples of ceramics obtained by heat treatment CPCS in an inert atmosphere up to 1600° (heated for 20 hours to 1000°and then for 8 hours to 1600° (C) were examined by the method of transmission electron microscopy (TEM) high-resolution installation JEM-1008 JEOL. PE-pictures of the surface of ceramics, with magnification of 200,000 times, show the formation of a homogeneous ceramic evenly distributed zirconium. The diffraction of electrons on the surface of ceramics speaks about the formation of crystalline structure.

The study of these same samples by the method of x-ray phase analysis showing the characteristic, that are present in the diffraction pattern line angles 2θ=45,0°; 78,0°; 95,0°; 100,5°typical for silicon carbide β-SiC, and lines angles 2θ=45,5°; 72,3°; 87,8°; 93,0°; 113,5°; 131, 5mm°characteristic carbonitride, zirconium Zr2NC. Additionally, there are lines that correspond to SiC polytypes and zirconium silicides SiZr3.

Heat treatment CPCS obtained on the basis of the PCB and tetratetracontane zirconium [U.S. Pat. EPO 0 030105 1 08 G 77/60, 1985], in an inert atmosphere up to 1600° (heated for 20 hours to 1000°and then for 8 hours to 1600° (C) according to x-ray phase analysis leads mainly to the formation of SiO2(in the form of cristobalite - line angles 2θ=27,4°; 35,8°; 45,4°; 78,0°; 92,5° and alpha-quartz - lines at the corners 2θ=34,0°; 64,5°; 78,0°) and zirconium dioxide ZrO2(line angles 2θ=38,0°; 44,0°; 44,5°), with admixture of zirconium silicides ZrSi2and oxanilide zircon ZrSiO4.

Thus, the proposed method of synthesis MPX allows to obtain a fusible soluble polymers with homogeneous distribution of chemically related metal atoms. These polymers have a high affinity for the fibre and plenkoobrazovatel from solutions or melts, otverzhdajutsja thermochemical processing, give a high yield of ke is omicheskogo residue in the pyrolysis (up to 85 wt.%). In addition, such polymers contain nitrogen, positively influencing properties of ceramics (as it forms a homogeneous distributed high-temperature nitride), instead of undesirable impurities of oxygen and chlorine. This gives the opportunity to use NX to manufacture components for a modern ceramic composite material with high heat resistance and strength-type SiC/SiC with a matrix of silicon carbide and silicon carbide fibers.

The method of producing metallopolimerov interaction in the environment of organic solvent polycarbosilane with a molecular weight above 200, the main chain of which is composed of units of the formula [-(R)2Si-CH2-], where R is H, alkyl (C1-C4or phenyl group, with ORGANOMETALLIC compounds, characterized in that as ORGANOMETALLIC compounds using the compounds of formula MXzwhere M is a transition metal III-VIII groups of the Periodic system, z=2-4, X is-NR12where R1- alkyl (C1-C4) group, or-Si(CH3)3when this process is carried out at variable temperatures from 20 to 400°and the pressure of 5.05 MPa to 0.2 kPa.



 

Same patents:

The invention relates to methods of modifying polydimethylsiloxane rubber, not having in its composition of active groups, UV light and can be used to obtain a new silicon-containing polymers with a wide range of applications, including

The invention relates to a method for SiOH-functional dendrimeric of carbosilane

The invention relates to a method of obtaining new undescribed in the literature polylithium derivatives karbosilanovykh compounds (PLCS), which can find application in the chemical industry as intermediates for various materials organiseorganised

The invention relates to methods of producing organosilicon polymer of polymer of the formula:

< / BR>
(patent N 4220600, CL

FIELD: chemical technology.

SUBSTANCE: invention describes a method for preparing metallopolycarbosilanes. Method involves interaction of polycarbosilanes with molecular mass above 200 Da and with the main chain consisting of links of the formula: [-(R)2Si-CH2-] wherein R means hydrogen atom (H), (C1-C4)-alkyl or phenyl groups with metalloorganic compounds of the formula MXz wherein M means transient metal of III-VIII group of Periodic system; z = 2-4; X means NR12 wherein R1 means (C1-C4)-alkyl group in organic solvent medium at temperatures from 20°C to 400°C under pressure from 5.05 MPa to 0.2 kPA. Method provides preparing fusible soluble polymers with homogeneous distribution of chemically bound metal atoms that elicit high capacity for fiber- and film-formation from solutions or melts that are hardened in thermochemical treatment and provides high yield of ceramic residue in pyrolysis (up to 85 wt.-%).

EFFECT: improved preparing method.

1 tbl, 9 ex

FIELD: organosilicon polymers.

SUBSTANCE: polydimethylsilane is obtained by reaction of dimethyldichlorosilane with sodium at 150-170°C followed by decomposition of unreacted sodium with methyl alcohol, isolation of desired polymer, washing on filter with distilled water, drying on air and the in vacuum. Process is characterized by that sodium reagent is added as deposited on water-soluble solid, incombustible, inorganic substrate.

EFFECT: reduced fire risk of synthesis process and labor intensity of polymer isolation stage.

2 dwg, 1 tbl, 5 ex

FIELD: organosilicon polymers.

SUBSTANCE: novel polycyclic poly- and copolyorganocyclocarbosiloxanes with variable cycle size including structural motif of general formula: , wherein (1) x=3 or 4 and y=1, (2) x=2 and y=2, (3) x=3, and suitable as preceramic templates for manufacturing oxygen-free silicon carbide ceramics are prepared by Würtz reaction in toluene via interaction of chloro-derivatives of organocarbosilanes with metallic sodium in the form of suspension.

EFFECT: enlarged assortment of preceramic templates.

2 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of chemical technology of silicon-organic compounds. Technical task lies in synthesis of novel polyarylsilane links including dendrimers of large generations suitable for application as luminescent materials for organic electronics and photonics. Claimed are dendrimers of general formula (I) where R1 stands for substituent from group: linear or branched C1-C20alkyl groups; linear or branched C1-C20alkyl groups separated by at least one oxygen atom; linear or branched C1-C20 alkyl groups separated by at least one sulphur atom; branched C3-C20 alkyl groups separated by at least one silicon atom; C2-C20alkenyl groups; Ar represents, independently for each n and m, similar or different arylene radicals, selected from group: substituted or non-substituted thienyl-2,5-diyl of general formula (II-a) substituted or non-substituted phenyl-1,4-diyl of general formula (II-b) substituted or non-substituted 1,3-oxazol-2,5-diyl of general formula (II-c) substituted fluorene-4,4'-diyl of general formula (II-d) where R2, R3, R4, R5, R6 represent independently on each other H or said above for R1; R7 stands for said above for R1; K is equal 2 or 3 or 4; L is equal 1 or 3 or 7 or 15; m and n represent whole numbers from series from 2 to 6. Method of obtaining dendrimers lies in the following: monodendron of general formula (III) where X represents H or Br or I, first reacts with lithiumising agent of general formula R8Li, where R8 represents linear or branched C1-C10alkyl group, dialkylamide or phenyl group; then obtained compound reacts with functional compound selected from group of compounds of formula (CH3)4-KSiYK, where Y represents Cl, or Br, or -OCH3, or -OC2H5, or -OC3H7, or -OC4H9. Claimed method is technological, use of expensive catalysts is not required.

EFFECT: elaboration of technological method of synthesising novel polyarylsilane dendrimers which does not require use of expensive catalysts.

24 cl, 12 dwg, 1 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel branched oligoarylsilanes and their synthesis method. The engineering problem is obtaining branched oligoarylsilanes which contain not less than 5 functional arylsilane links and have a set of properties which enable their use as luminescent materials. The disclosed branched oligoarylsilanes have general formula where R denotes a substitute from: straight or branched C1-C20 alkyl groups; straight or branched C1-C20 alkyl groups separated by at least one oxygen atom; straight or branched C1-C20 alkyl groups separated by at least one sulphur atom; branched C3-C20 alkyl groups separated by at least one silicon atom; C2-C20 alkenyl groups; Ar denotes identical or different arylene or heteroarylene radicals selected from: substituted or unsubstituted thienyl-2,5-diyl, substituted or unsubstituted phenyl-1,4-diyl, substituted or unsubstituted 1,3-oxazole-2,5-diyl, substituted fluorene-4,4'-diyl, substituted cyclopentadithiophene-2,7-diyl; Q is a radical selected from the same group as Ar; X is at least one radical selected from the same group as Ar and/or a radical selected from: 2,1,3-benzothiodiazole-4,7-diyl, anthracene-9,10-diyl, 1,3,4-oxadiazole-2,5-diyl, 1-phenyl-2-pyrazoline-3,5-diyl, perylene-3,10-diyl; L equals 1 or 3 or 7 and preferably 1 or 3; n is an integer from 2 to 4; m is an integer from 1 to 3; k is an integer from 1 to 3. The method of obtaining branched oligoarylsilanes involves reaction of a compound of formula where Y is a boric acid residue or its ester or Br or I, under Suzuki reaction conditions with a reagent of formula (IV) A - Xm - A (IV), where A denotes: Br or I, provided that Y denotes a boric acid residue or its ester; or a boric acid residue or its ester, provided that Y denotes Br or I.

EFFECT: obtaining novel compounds distinguished by high luminescence efficiency, efficient intramolecular transfer of energy between molecule fragments and high thermal stability.

24 cl, 12 dwg, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to macromolecular compounds with a nucleus-shell structure. The invention discloses macromolecular compounds with a nucleus-shell structure, whereby the nucleus has a macromolecular dendritic and hyperbranched structure based on carbon or based on silicon and carbon is bonded to at least three, in particular at least six external atoms through a carbon-based coupling chain (V) which is selected from a group consisting of straight and branched alkylene chains with 2-20 carbon atoms, straight or branched polyoxyalkylene chains, straight or branched siloxane chains or straight or branched carbosilane chains, with straight chains based on carbon oligomeric chains (L) with conjugated double bonds on the entire length. Conjugated chains (L) in each separate case are bonded at the end opposite the coupling chain (V) to one more, specifically, aliphatic, arylaliphatic or oxyaliphatic chain (R) without conjugated double bonds. The chains (V), (L) and (R) form the shell. The invention also discloses a method for synthesis of the said compounds.

EFFECT: novel organic compounds which can be synthesised using conventional solvents and have good semiconductor properties.

16 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing polycarbosilanes. Disclosed is a method of producing polycarbosilane via thermal decomposition of polydimethylsilane in the presence of zirconium tetrachloride in an inert atmosphere at excess pressure of 0.4-0.5 MPa in three steps: holding at 350-380°C for 2-10 hours, releasing low-boiling point components and then holding at 350-420°C for 20-30 hours.

EFFECT: method of producing polycarbosilane which enables to cut time and lower temperature of the process.

1 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemical engineering of organosilicon compounds. Disclosed are novel dendronised polyarylsilanes of general formula

, where R denotes a substitute from: linear C1-C12 or branched C3-C20 alkyl groups; linear C1-C12 or branched C3-C20 alkyl groups, separated by at least one oxygen atom; linear C1-C12 or branched C3-C20 alkyl groups, separated by at least one sulphur atom; branched C3-C20 alkyl groups, separated by at least one silicon atom; C2-C20 alkenyl groups; Ar denotes identical or different arylene or heteroarylene radicals selected from: substituted or unsubstituted thienyl-2,5-diiyl; substitured or unsubstituted phenyl-1,4-diiyl, substituted fluorene-4,4'-diiyl. X denotes identical or different arylene or heteroarylene radicals selected from said group for Ar and/or a radical from 2,1,3-benzothiodiazole-4,7-diiyl, anthracene-9,10-diiyl; L equals 0 or a an integer from 1, 3, 7, 15; k is an integer from 1 to 6; m is an integer from 1 to 6; t is an integer from 2 to 10; n is an integer from 5 to 10000. A method of producing said compounds is also disclosed.

EFFECT: synthesis of novel chemical compounds, characterised by high efficiency of luminescence, high molar absorption coefficient and high thermal stability.

FIELD: physics.

SUBSTANCE: invention relates to organic light-emitting diode (OLED) solid-state light sources used to make colour information screens and colour display devices with high consumer properties, as well as cheap and efficient light sources. Disclosed is an OLED, having a base in form of a transparent substrate having a transparent anode layer and a metal cathode layer with a light-emitting layer in between, which is based on a dendronised polyaryl silane of general formula (I) or (II) , where n is an integer from 5 to 1000.

EFFECT: wide range of OLEDs with high operational characteristics, particularly in the radiation range of 400-700 nm, which enables use thereof as light sources.

7 cl, 3 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: disclosed are novel branched oligoarylsilanes of general formula (I) , where R denotes a substitute selected from: linear or branched C1-C20 alkyl groups; including separated by at least one oxygen or sulphur atom; branched C3-C20 alkyl groups, separated by at least one silicon atom; C2-C20 alkenyl groups; Ar denotes identical or different arylene or heteroarylene radicals selected from: substituted or unsubstituted thienyl-2,5-diiyl, substituted or unsubstituted phenyl-1,4-diiyl, substituted or unsubstituted 1,3-oxazole-2,5-diiyl, substituted fluorene-4,4'-diiyl, substituted cyclopentadithiophene-2,7-diiyl; Q denotes a radical selected from the series for Ar; X denotes at least one radical selected from the series for Ar and/or a radical selected from: 2,1,3-benzothiiodiazole-4,7-diiyl, anthracene-9,10-diiyl, 1,3,4-oxadiazole-2,5-diiyl, 1-phenyl-2-pyrazoline-3,5-diiyl, perylene-3,10-diiyl; n is an integer from 2 to 4; m is an integer from 1 to 3; k is an integer from 1 to 3. Also disclosed is a method of producing said compounds.

EFFECT: obtaining novel compounds characterised by high luminescence efficiency, efficient intramolecular energy transfer from some molecule fragments to others and high thermal stability.

20 cl, 5 dwg, 1 tbl, 15 ex

Up!