Polycarbosilane containing metal clusters, and the method of production thereof

 

(57) Abstract:

Polycarbosilane (Clpx) containing metal clusters, the General formula

< / BR>
where n is 6; m = 0,001 - 1; R1, R2, R3= -CH3, - C2H5, - CH = CH2, -CH2CH = CH2; CL - clusters of transition metals III-VIII groups, can be used to obtain high-strength heat-resistant composite ceramics. Coordination compounds of transition metals of III-VIII groups put together in 150 - 450oC with silanes of the General formula (2) or (3) or carbosilane General formula (4) or mixtures thereof, optionally maintaining the reaction mixture after addition of the metal compounds at 150 - 450oC 0.5 to 5 hours

R1R2SiR3R4,

< / BR>
or cyclo

< / BR>
or cyclo-

< / BR>
where and 2; b 4; k = 0 to 10; r = 1 to 10; R, R1, R2, R3, R4- H, -CH3, - C2H5- C6H5, -CH=CH2, -CH2-CH=CH2. 2 S. p. f-crystals, 2 tab.

The invention relates to the field of reception of polycarbosilane (PKS), specifically, to the field of obtaining polycarbosilanes containing metal clusters, the General formula

< / BR>
where n is 6, m = 0,001 - 1;

R1, R2, R3= -CH3-The C-VIII groups.

The organosilicon polymers of the class of polycarbosilanes are mainly used as raw material for high-strength heat-resistant composite ceramics. To preserve the strength of ceramics at high temperatures, the metal should be distributed in the ceramic phase evenly, almost at the molecular level, and, in addition, the composition of the ceramic phase should be excluded oxygen.

The presence of uniformly distributed chemically bound metal in the matrix PKC contributes to the stabilization of homogeneous ultramelodiousness microstructure of SiC ceramics with high thermo-mechanical properties. Filled with metal such PLCs can also significantly extend the scope of SiC ceramics, as can be used to produce films, coatings, binders, impregnating compositions, and also for processing in SiC powders, fibers, matrix and other components of the heat-resistant composite ceramic materials. Substances of this type can also be used as polymeric and ceramic compositions having specific electrical and magnetic properties.

The present invention allows the metal nanoparticles in a cluster form.

Cluster polycarbosilane (Clpx) is a transparent viscous or solid products from light yellow to dark brown in color, soluble in aromatic hydrocarbons: carbon tetrachloride, chloroform, tetrahydrofuran, dioxane, hexane, and other saturated hydrocarbons.

Clpx mentioned General formula, its structure, physico-chemical properties and the way to obtain not described in literature.

A method of obtaining the PCB with the use of anhydrous halides of metals II-VIII groups (MHaIn), mainly Al, Ti, V, Cr, Mn, Co or mixtures thereof, taken in an amount of 1-5 wt.% by thermal decomposition of polydimethylsilane at a temperature of 350-470oC and atmospheric pressure (U.S. Pat. The UK 210665528, 1983).

This method does not allow to get polycarbosilane containing metals as the metal halide, playing the role of catalysts for polycondensation, are not bound chemically to the polymer, and comes in the form of insoluble reaction products. In addition, the process is different duration, multi-stage, as well as the necessity of using high temperatures.

The closest in technical essence to predlagaemuyu containing metallocene units (U.S. Pat. 30105 EPO, 1980).

< / BR>
or

< / BR>
where M = Ti, Zr.

The polymers get a long-term heat treatment of polydimethylsilane in an inert atmosphere in the presence of tetraethoxysilane, tetramethoxysilane or politicalparticipation.

The disadvantage of this method is the presence of oxygen atoms in the main and side chains of the macromolecules, which affects oxidative and thermal stability of articles made of silicon carbide.

The objective of the invention is to obtain polycarbosilane containing metal clusters of General formula (I).

The technical result is achieved by the fact that the obtained polycarbosilane containing metal clusters, the General formula (I). These substances are obtained as follows: the initial mass containing silanes and/or carbosilane, is subjected to the interaction with the metal-containing compounds or mixtures thereof with inlet 150 up to 450oC and use the silanes of General formula (2) or (3) and/or carbosilane General formula (4)

R1R2SiR3R4(2)

< / BR>
< / BR>
where a 2, b 4, r = 1-10, R, R1, R2, R3, R4-H, -CH3, -C2H5, -C6H5, -CH=CH2, -CH2-CH=CH2.

In about heated at a temperature of 150 450oC for 0.5 - 5 hours. When applied at temperatures below 150oC or less than 0.5 hours, the reaction is at a temperature above 450oC or with increasing time of heating more than 5 hours formed consobrina insoluble products.

The invention consists in the following: coordination compounds of metals injected preferably in an amount of 0.1-10% by weight of the initial mixture at a temperature exceeding 50oC, but not higher than 450oC. adding compounds in quantities less than 0.1 wt.% the effect of the introduction of metal insignificant, adding more than 10 wt.% in the process of synthesis is the formation of insoluble by-products.

In the process of testing were used coordination compounds of transition metals of III - VIII groups, such as Ti, Zr, Hf, V, Fe, Ni, Co, Cr, W, Mo, Mn, Re, Pt, Pd, Rh, B with organic carbonyl, carbolineum, dialkyl(aryl)amide, trialkyl(aryl)silyl, bis[hexaacyl(aryl)disill] amide and other ligands. In addition to this list can be used mixed, bi - and multi-core systems, and any coordination compounds of metals, excluding those in which there is a direct connection, the metal-oxygen.

Examples use the B>)2ZrCl2, (CH3C5H4)2HfBr2, Fe(CO)5, Fe3(CO)12, Fe2(CO)9, -C3H5Fe(CO)3Cl, [(C5H5)Fe(CO)2]2, -C3H5Co(CO)3, Co(C5H5)2,

C5H5Co(CO)2, Co(CO)8, Ni(CO)4, [C5H5Ni(CO)]2, (C3H5)2Ni, (C5H5)2Ni, (CH3C6H4)2Cr, CH3C5H4Cr(CO)3, Cr(CO)6W(CO)6, (CH3C6H4)2W, C3H5MoC5H5(CO)2C3H5Mn(CO)4, (C3H5)2Pd, C3H5PdC5H5C3H5RhC5H5C5H5Rh(CO)2, (CH3)4Pt, C3H5PtC5H5Ti(CH2C6H5)4, Zr(CH3)4,

Ti[N(CH3)2]4Zn{N[Si(CH3)]2}2and other

Introduction complexes or mixtures thereof in the reaction mass consisting of mono-(2) or polysilane (3) and/or carbosilane (4) allowed in all cases to obtain positive results. This confirms the validity of the volume of claims.

According to IR-spectroscopy the basic skeleton Clpx status) and methyl Si-CH3(1250 and 1400 cm-1), and in some cases phenyl Si - Ph (1480 cm-1and vinyl Si-CH=CH2(1600 cm-1) group. The resulting polymers according to NMR data29(Si) spectroscopy has a ratio HSiC3and SiC4groups ( -16 memorial plaques memorial plaques and 0, respectively) is close to unity, which indicates the regularity of the structure Clpx. The metal present in the polymer in the form of cluster particles (5 to 80) defined by x-ray small-angle scattering, in amounts of 0.1 - 10 wt.% The average molecular weight Clpx according to gel chromatography (1200 - 2500. During synthesis Clpx does not form a side of insoluble products, which allows not to use operation, dissolution, filtration, distillation of the solvent. Clpx shows a well-pronounced ability to fiberizing, easy cures thermochemical processing, gives a high yield of SiC ceramic residue.

Introduction coordination compounds in a pre-heated reaction mixture allows not only to improve the quality ceramicbased polymer, but also to accelerate the process of regrouping and polycondensation of the raw materials.

The invention is illustrated with what ronkay, reflux condenser, a nozzle with a straight fridge for removal of solvent and low molecular weight products of the synthesis, filled with inert gas and load it with 100 g of a mixture of oligomeric products (OP) obtained by thermal decomposition of polydimethylsilane, representing a mixture containing silanes of formula 3 (a = 2 - 7, b = 5, 6, R1-R4=H, -CH3R=H) and carbosilane formula 4 (k = 2, 3, r = 2 - 4) with Mp= 300 - 500. The reaction mixture is heated to 250oC for 0.5 hour add 1 g of Fe(CO)5in the form of a 3% solution in hexane. Then the reaction mass is then cooled in a stream of inert gas and unload 70 g of polymer with Mp= 1800 and softening temperatures (ToEXT.) 150 - 160oC and fiberizing (ToV/o) 200 - 220oC. the iron Content in the polymer of 0.5 wt.%, the cluster size is 50 , the ratio of the HSiC3and SiC4groups is 0.95. Output inorganic product after thermal treatment of the polymer in an inert atmosphere to 1100oC is 65 wt.%, the iron content of SiC ceramics 1 wt%, oxygen not more than 0.1 wt.%.

Other examples are given in table 1.

Advantages of the invention are seen from a comparison of the properties Clpx and policetinkerbell obtained by Aidstest fusible soluble polymers regular patterns, easily processed into products of various shapes and forming a ceramic phase with a large output. Clpx contain uniformly distributed nanoparticles of metals (size 5-80 ), forming strong links with the polymer matrix and contain almost no oxygen, which gives the opportunity to use them to obtain a heat-resistant oxidation of ceramics on the basis of stable crystalline silicon carbide. The synthesized polymers and inorganic materials based on them may also find application in electronic and chemical industries due to the specific electro-magnetic and catalytic properties.

1. Polycarbosilane containing metal clusters with the General formula

< / BR>
where n is 6;

m = 0,001 - 1;

R1, R2, R3= -CH3, -C2H5, -C6H5, -CH= CH2, -CH2CH=CH2,

CL-clusters of transition metals III - VIII group average mol. m 1200 - 2500.

2. The method of producing polycarbosilanes formula (1), characterized in that a starting material containing silanes of General formula (2) or (3) and/or carbosilane General formula (4)

< / BR>
or cyclo-

< / BR>
< / BR>
or cyclo-

< / BR>
where a 2;

b 4;

k=0 - 2, -CH2CH=CH2,

subjected to interaction with the coordination compounds of metals or mixtures thereof at 150 - 450oC.

 

Same patents:

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

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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.

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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 350-380C for 2-10 hours, releasing low-boiling point components and then holding at 350-420C 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.

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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

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