The catalyst accelerated vulcanization


(57) Abstract:

Use: in the manufacture of catalysts for the synthesis of organosilicon compounds and synthetic rubber. The inventive catalyst accelerated vulcanization is a reaction product sulfoxide of platinum complexes with unilateraily the siloxanes. As the use of platinum complexes of the compounds of General f - crystals: {Pt(L2X2} and {Pt(L1L2Cl2} , L L1, L2(CH3)2SO ; (C2H5)2SO ; (C3H7)2SO ; (i-C3H7)2SO ; (C6H5CH2)2SO ; (p-C4H9)2SO ; (p-CH3C6H4)(CH3)SO ; X Is Cl, Br. The concentration of platinum complexes in minilateral the siloxane is 510-8-110-5Mr. al/ml. table 1.

The invention relates to chemical technology, namely catalytic processes cured polysiloxane compositions by polyaddition reaction. This invention can be used in manufacturing silicon - organic compounds and synthetic rubber, and the products produced by the curing reaction, can find application in newly developing areas is Noah technique.

Known use as a catalyst vulcanization [U.S. Pat. USA. N 3775452] product processing mixture haloesters complex of platinum (H2tCl6TO2tCl4, L2tCl2with vinylsilanes solutions foundations with the subsequent separation of the phases and vacuum.

The catalyst is a mixture of an uncertain, unstable composition with a lower content of halogen and its preparation involves considerable difficulties and inevitable losses of platinum.

This patent has the following disadvantages.

Catalysis in some cases takes place in heterogeneous conditions because of the formation of insoluble products of interaction of the catalyst components of the mixture.

Obtained catalysts, the composition and activity of which is difficult to standardize, resulting in poor reproducibility and controllability of the process, especially high-speed thermal reactions of the type.

There is a lack of viability of the compositions at room temperature.

To stabilize compositions using various additives to hexachloroplatinic acid, which inhibi-

The closest analogue is the prototype of the claimed invention is the use as catalyst of platinum-containing compounds, mainly of N2tCl6with additions of organic sulfoxidov in the number of 200-2000 mol per mol of the platinum complex (3). These supplements sulfoxidov allow to inhibit the curing process system based on vinyl - and heritagebased kremniyorganika - ical oligomers up to the required temperature. However, the uncertainty of the complex formed in situ, it is difficult for the regulation of the catalytic properties of systems, and large excess sulfoxide in the polymer composition is undesired hair - tion of low-molecular-weight impurity, impairing its properties. At the same time when the ratio of the additive to the complex, close to equimolecular not achieve the desired inhibition of the rate of curing. In addition, extremely high hygroscopicity of hexachloroplatinic acid (initially applied in the form of uranyl), as well as most of the sulfoxidov complicates prevent secondary process dehydrocondensation N groups of the oligomer with water molecules, which is accompanied by emission (H2and, as a consequence, the violation of ognore the years the proposed curing catalyst.

The technical effect is to increase the rate of vulcanization, and reducing consumption of platinum.

The technical effect is achieved by the fact that as a catalyst for accelerated vulcanization use the products of interaction sulfoxide of platinum complexes with unilateraily the siloxanes, and as complexes according to the invention it contains platinum compounds of General formula

[Pt(L)2X2] and [PtL1L2Cl2] , where L, L1, L2- (CH3)2S = 0,

(C2H5)2S = 0, (C3H7)2S = 0, (i-C3H7)2S = 0, (C6H5CH2)2S = 0,

(n-C4H9)2S = 0, (p-CH3C6H4)(CH3S = 0; X-Cl, Br and the concentration of platinum complexes in minilateral the siloxane is 5 x 10-8-1 x 10-5g-at/ml.

The invention consists in the application of individual sulfoxide complexes of platinum (II), General formula

[Pt(L)2X2] , [PtL1L2X2] , where L, L1, L2< / BR>
- (CH3)2S = 0, (C2H5)2S = 0, (C3H7)2S = 0,

(i-C3H7)2S = 0, (n-C4H9)2S = 0, (Care stable, hygroscopic substance in the crystalline state, are well soluble components of the reaction mixture. As a result of interaction sulfoxide complexes with vinylsilanes formed stable homogeneous catalytic solution with precisely controlled content of platinum. As vinylsilane used hexaphenyldisilane (GUDS), tetramethyldisiloxane (TMDS) or oligomerisation mol. wt. 5-6 thousand received by polyarizatsiei cyclic trimer [CH3(CH2= = CH)SiO]3. If the consumption of platinum is greater than 10-5the curing process does not significantly improved, but increased consumption of platinum, if the consumption of platinum in less than 10-8then there is no consistency in reproducing the results of experiments on solidification. Depending on the structure sulfoxide ligand and selected vinylsilane can be regulated temperature range curing from 100 to 400aboutAnd the cure time from 6 min to 2-3 (see table).

A comparison of the proposed technical solutions with the prototype showed that the claimed solution is characterized by the fact that as complexes of platinum is used as a compound of General formula [Pt(L)2X2] , [Pt(LS = 0, (C3H7)2S = 0,

(i-C3H2)S = 0, (C6H5CH2)2S = 0, where X Is Cl, Br, and the concentration of platinum in minilateral the siloxane is 5 x 10-8-1x x 10-5g-al Pt/ml and, therefore, meets the criteria of the invention of "novelty."

The study of other known technical solutions in this field of technology has shown that the present invention stems from them in subtle ways and, therefore, meets the criterion of "inventive step".

Description of the process.

A portion of the complex weight of 0.03 g was dissolved in 5 ml of vinylcyclohexane at 20-50aboutWith received homogeneous catalytic solution with a certain amount of platinum. The catalytic activity of the solution remains 6-12 months. under conditions of storage at 20aboutC.

Thus obtained catalysts used in the preparation of siloxane compositions used for the primary coating of an optical fiber. The process of making siloxane polymer compositions is as follows:

to a mixture of liquid silicon rubber with vinyl groups CH2= CH--O O O i CH= CH2where R = CH2
n = 10m when R = C6H5n = 3-3,5 m n = 1000-1500 added texturing agent with gramnegative groups H O O O H where R = CP3CH2CH2; n = 7m; l = 3-5 = 5000-7000 when R = C6H5; n = 2-3m ; l = 3-5 then the solution sulfoxidation catalyst.

The composition is thoroughly mixed and brought the viscosity to the desired operating level. Resilience in the composition at 8-10aboutWith about 30 days.

The invention allows to standardize the catalyst, as all the components are stable at normal temperatures and does not lose its properties during storage. Sulfoxide complex catalysts represent individual compounds that are resistant under normal conditions, non-hygroscopic crystalline substances, soluble components of the reaction mixture. Unlike the used catalysts on the basis of H2PtCl6these complexes do not contain active functional groups and do not cause side processes associated with the presence of acid or other functions.

In addition, the catalyst allows you to keep the stability at room temperature for 6-12 months without loss of activity and to ensure the viability of Konoe few seconds. (56) U.S. Patent N 3775452, CL 08 G 31/26, publ. 1970.

U.S. patent N 3453234, CL 08 G 31/26, publ. 1968.

The CATALYST ACCELERATED VULCANIZATION based on the product of the interaction sulfoxide complexes of platinum (II) with unilateraily the siloxanes, characterized in that as complexes of platinum catalyst provides compounds of General formula

[Pt (L)2X2] and [Pt L1L2X2] ,

where L1and L2for example, (CH3)2S = 0, (C2H9)2S = 0, (C3H7)2S = 0, (i - C3H7)2S = 0, (C6H5CH2)2S = 0, (n = C4H9)2S = 0, (p = CH3C6H4) (CH3S = 0; where X Is Cl, Br,

the concentration of platinum in minilateral the siloxane is 5 10-8- 1 10-5mol Pt/ml


Same patents:

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for preparing acetic acid by gas-phase oxidation of ethane and/or ethylene with oxygen using catalyst comprising molybdenum and palladium. For realization of method gaseous feeding comprising ethane, ethylene or their mixture and oxygen also are contacted at enhanced temperature with catalyst that comprises elements Mo, Pd, X and Y in combination with oxygen of the formula (I): MoaPdbXcYd wherein X and Y have the following values: X means V and one or some elements optionally taken among the following group: Ta, Te and W; Y means Nb, Ca and Sb and one or some elements optionally taken among the following group: Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr and Hf; indices a, b, c and d mean gram-atom ratios of corresponding elements wherein a = 1; b = 0.0001-0.01; c = 0.4-1, and d = 0.005-1. Niobium is added to the catalyst structure using niobium ammonium salt. Preferably, niobium ammonium salt is used as the niobium source. The continuance of contact time and composite values of the parent gaseous mixture are so that taken to provide output value by acetic acid to be above 470 kg/(m3 x h). The selectivity of oxidation reaction of ethane and/or ethylene to acetic acid is above 70 mole %. Invention provides enhancing stability and output of catalyst.

EFFECT: improved preparing method.

14 cl, 1 tbl, 6 ex

FIELD: petrochemical synthesis catalysts.

SUBSTANCE: invention discloses a method for preparation of palladium catalyst comprising impregnation of alumina carrier with palladium chloride solution in presence of aqueous hydrochloric acid, treatment with reducing agent (hydrogen), washing with water, and drying, said carrier being preliminarily decoked exhausted catalyst containing alumina and group I and/or II, and/or VI, and/or VIII metals and subjected to washing with aqueous hydrochloric or nitric acid and then with water. Exhausted ethylene oxide production catalyst or methylphenylcarbinol dehydration catalysts can also be suitably used.

EFFECT: increased selectivity and activity of catalyst.

2 cl, 2 tbl, 21 ex

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises applying palladium compound onto silica cloth and heat treatment. Palladium compound is applied by circulation of toluene or aqueous palladium acetate solution through fixed carrier bed until palladium content achieved 0.01 to 0.5%. Palladium is introduced into cloth in dozed mode at velocity preferably between 0.1 and 5.9 mg Pd/h per 1 g catalyst. Heat treatment includes drying at temperature not higher than 150oC under nitrogen or in air and calcination in air or nitrogen-hydrogen mixture flow at temperature not higher than 450oC. Original silica cloth can be modified with 0.6 to 6.5% alumina. Palladium is uniformly distributed in silica cloth and has particle size preferably no larger than 15 Å. Invention can be used in treatment of industrial gas emissions and automobile exhaust to remove hydrocarbons.

EFFECT: deepened oxidation of hydrocarbons.

5 cl, 1 tbl, 4 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.

EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.

1 dwg, 1 tbl, 12 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: preparation of catalyst comprises depositing active components on γ-alumina carrier at stirring, carrier being preliminarily treated with concentrated NaOH solution. Active components are deposited consecutively in three steps. In the first step, preliminarily prepared chitosan in acetic acid solution with KCl solution is deposited for 60-65 min; in the second step, sodium tetrachloropaladate(II) trihydrate Na2PdCl4·3H2O solution is deposited for 60-65 min; and, in the third step, hydrazine hydrate solution as reducing agent is added for 180-240 min. After each step, resulting suspension is filtered off, washed, and dried at 293-303K for 1-2 h in vacuum. Catalyst can be used in chemical industry and in processing of industrial and household wastes.

EFFECT: enhanced nitrate hydrogenation efficiency.

6 cl, 1 dwg, 6 ex

FIELD: textile, paper and chemical industries; protection of environment in production of bleachers, biocides and components of oxidizing processes.

SUBSTANCE: proposed catalyst contains one or more metals of platinum group used as active component, one or more polyolefines and activated carbon carrier. It is preferably, that polyolefines have molecular mass above 400 and are selected from ethylene homopolymers and ethylene copolymers with alpha-olefines, propylene homopolymers and propylene copolymers with alpha olefines, butadiene homopolymers and copolymers with styrene and other olefines, isoprene homopolymers and copolymers with other olefines, ethylene-propylene copolymers, ethylene-propylene diolefine three-component copolymers, thermoplastic elastomers obtained from butadiene and/or isoprene and styrene block-copolymers, both hydrogenized and non-hydrogenized. Hydrogen peroxide is produced in presence of said catalyst from hydrogen and oxygen in reaction solvent containing halogenated and/or acid promoter. Proposed catalyst makes it possible to increase degree of conversion and selectivity of process, to obtain aqueous H2O2 solutions at content of acids and/or salts at level of trace amount.

EFFECT: enhanced efficiency.

48 cl, 1 tbl,18 ex

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention relates to a methyl ethyl ketone production process via catalytic oxidation of n-butenes with oxygen and/or oxygen-containing gas. Catalyst is based on (i) palladium stabilized with complexing ligand and (ii) heteropolyacid and/or its acid salts, in particular molybdo-vanado-phosphoric heteropolyacid having following composition: H11P4Mo18V7O87 and/or acid salt Na1.2H9.3Mo18V7O87, said complexing ligand being notably phthalocyanine ligand. Catalyst is regenerated by making it interact with oxygen and/or oxygen-containing gas at 140-190°C and oxygen pressure 1 to 10 excessive atmospheres. Oxidation of n-butenes is conducted continuously in two-stage mode at 15 to 90°C in presence of above-defined catalyst.

EFFECT: enhanced process efficiency due to increased stability of catalyst resulting in considerably increased productivity and selectivity.

7 cl, 1 dwg, 3 tbl, 8 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst for modifying colophony contains, as carrier, high-porosity cellular α-alumina-based block material and, as active catalyst fraction, sulfated group IV metal oxide and metallic palladium.

EFFECT: increased modification rate due to developed catalyst surface and eliminated disintegration and carry-over of catalyst.

5 ex

FIELD: reduction-oxidation catalysts.

SUBSTANCE: invention relates to catalytic chemistry and, in particular, to preparation of deep-oxidation supported palladium catalysts, suitable, for example, in afterburning of motor car exhaust. Preparation involves depositing palladium from aqueous solution of palladium precursors followed by drying and calcination. Precursors are selected from nitrite anionic or cationic palladium complexes [Pd(NO2-)(H2O)3]Anx or [Pd(NO2-)n(H2O)m](Kat)y, wherein An are anions of acids containing no chloride ions, Kat is proton or alkali metal cation, n=3-4, m=0-1, x=1-2, and y=1-2. Nitrite ions are introduced into impregnating solution in the form of nitrous acid salts or are created in situ by reducing nitrate ions or passing air containing nitrogen oxides through impregnating solution. Ratio [Pd]/[NO2-] in impregnating solution is selected within a range 1:1 to 1:4.

EFFECT: eliminated chlorine-containing emissions, increased stability of chlorine-free impregnating solutions, reduced their acidity and corrosiveness, and increased catalytic activity in deep oxidation reactions.

2 cl, 1 tbl, 16 ex

FIELD: polymers.

SUBSTANCE: described is method for production of siloxane oligomers of general formula I or II , wherein oligomer has at least one functionalized alkyl group in molecule. Claimed method includes oligomerization of haloalkyltrihalosilanes in presence of alcohol and water and optionally cooligomerization with C1-C18-alkyl-, phenyl, aryl- or alkyltrihalosilanes and/or silicium tetrachloride; and in the further step haloalkyl functionality is optionally modified.

EFFECT: improved method for production of siloxane oligomers.

7 cl, 10 ex

FIELD: organosilicon compounds.

SUBSTANCE: invention relates to dicarboxy group-containing polyorganosiloxanes, which can used as anticorrosion additives in treatment of metallic surfaces, and provides polyorganosiloxanes depicted by general formula X(R4R5SiO)p(R6ASiO)qY (I), where X represents terminal triorganosilyl group SiR3R2R1 or OH; Y terminal triorganosilyl group SiR3R2R1 or H; R1-R6 alkyl or phenyl; A is radical with two carboxyl group of formula -(CH2)3-CH(COOH)-CH2COOH (1') or one of the salts thereof; p ranges from more than 0 to 1000; q ranges from 1 to 100; ratio of the number of terminal OH and H groups to number of terminal X and Y groups ranges between 0/100 to 75/100. Invention also discloses method of preparing above-defined compounds, anticorrosive treatment method, and aqueous lubricating solution.

EFFECT: expanded synthetic possibilities and increased assortment of organosilicon special-destination materials.

10 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry of organosilicon compounds with a branched structure. Disclosed are novel carbosilane-siloxane dendrimers from zero G-O(Cycle) to sixth generation G-6(Cycle), containing in the outer layer the corresponding number of eight-member dimethylsiloxane cycles connected with a silicon atom of the outer layer of the dendrimer by a propyl group of general formula , where a, b, c, d, e, f and g denote the number of groups bonded with the branching centre and for the zero generation dendrimer, a equals 4, b, c, d, e, f and g equal 0; for the first generation dendrimer a equals 2, b equals 4, c, d, e, f and g equal 0; for the second generation dendrimer, a and b equal 2, c, d, e, f equal 0, g equals 4; for the third generation dendrimer, a, b and c equal 2, d, e, f equal 0, g equals 4; for the fourth generation dendrimer, a, b, c and d equal 2, e, f equal 0, g equals 4; for the fifth generation dendrimer a, b, c, d and e equal 2, f equals 0, g equals 4; for the sixth generation dendrimer, a, b, c, d, e and f equal 2, g equals 4.

EFFECT: obtaining novel chemical compounds.

FIELD: chemistry.

SUBSTANCE: disclosed is a method of producing methylphenylsiloxane resins through acidolysis of corresponding alkoxysilanes with acetic acid in the presence of an acid catalyst at high temperature using an activation step and batchwise neutralisation of the obtained polyorganosiloxanes. Disclosed also is a method of producing methylphenylsiloxane resins modified with organic resins selected from polyethers and epoxy resins, involving modification at the solvent distillation step.

EFFECT: disclosed method enables to obtain a wide range of polyorganosiloxanes with different radicals along with silicon, fewer process steps, shorter duration of the process, lower amount of washing water, and the obtained polyorganosiloxanes are characterised by improved heat resistance, melting point and rheological properties.

3 cl, 6 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a method which involves heterofunctional polycondensation of polyphenylsilsesquioxane and polydiorganosiloxane of formula (I), where n=100-640, in an organic solvent medium in the presence of diethylhydroxyl amine at temperature 110-120C and weight ratio of polyphenylsilsesquioxane to polydiorganosiloxane ranging from 10:90 to 50:50.

EFFECT: method enables to obtain block copolymers, cold curing vulcanisates of which, along with good physical and mechanical properties, have good oil-and-petrol resistance.

1 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: antifouling coating composition contains a curable polymer which is an organosiloxane-containing polymer and an organosilicon polymer which is liquid, having general formula: , where R1 can be identical or different and are selected from alkyl, aryl and alkenyl groups, optionally substituted with an amino group, an oxygen-containing group of formula OR5, where R5 is hydrogen or C1-6 alkyl, and a functional group of formula (I): -R6-N(R7)-C(O)-R8-C(O)-XR9 (i) where R6 is selected from alkyl, hydroxyalkyl, carboxyalkyl containing 1-12 carbon atoms, and polyoxyalkylene containing up to 10 carbon atoms; R7 is selected from hydrogen, alkyl, hydroxyalkyl, carboxyalkyl containing 1-6 carbon atoms, and polyoxyalkylene containing 1-10 carbon atoms; R7 can be bonded with R8 to form a ring; R8 is an alkyl group containing 1-20 carbon atoms; R9 is hydrogen an alkyl group containing 1-10 carbon atoms, optionally substituted with oxygen- or nitrogen-containing groups; X is selected from O, S and NH; under the condition that, at least one R1 group in the organosilicon polymer is a functional group of formula (I) given above or a salt derivative thereof; R2 can be identical or different and are selected from alkyl, aryl and alkenyl; R3 and R4, which can be identical or different, are selected from alkyl, aryl, blocked or non-blocked polyoxyalkylene, alkaryl, aralkylene and alkenyl; a is a whole number from 0 to 50000; and b is a whole number from 0 to 100, where a+b is equal to at least 25.

EFFECT: obtaining a composition with low surface tension, suitable elastomeric properties, which reduces attack by fouling organisms and their adhesion strength and can be used as a transparent coating which does not have turbidity or a milk-white colour.

8 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention discloses novel comb-like polymethylsiloxanes of general formula (I), where X denotes the same radical from: -Si(CH3)2CH=CH2, -Si(CH3)3, -Si(CH3)2H; Y denotes the same radical from: -CH3, -CH=CH2; n is a whole number from 12 to 600; m equals 0 or a whole number from 1 to 11. The invention also discloses a method of obtaining said polymethylsiloxanes through a reaction in an organic solvent medium between poly(sodium oxy)methylsiloxane and a siloxane oligomer selected from oligomers of general formula X-[OSi(CH3)2]m-Z, where X and m assume values given above; Z denotes - Cl or -OC(O)CH3.

EFFECT: novel comb-like polymethylsiloxanes have polydispersity on the number of beams and have sufficiently high molecular weight, and the method enables to obtain high output of the product.

FIELD: chemistry.

SUBSTANCE: disclosed cosmetic compositions contain silicone copolymers, terpolymers and higher-order polymers, which contain polyether-substituted structural units and epoxy- and oxirane structural units which react with acrylate compounds in the presence of a free-radical initiator.

EFFECT: disclosed compositions are self-emulsifying and can swell either in water or in oil, thus providing emulsification, thickening, adhesion, lustre and longevity of hydrophilic active substances.

54 cl, 33 tbl, 42 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compositions used in cosmetic compounds containing cross-linked silicone copolymers, where the cross links are acrylate oligomers or polymers. The disclosed compositions, which are used cosmetic compounds, contain silicone copolymers, terpolymers and higher-order polymers, which contain polyether-substituted repeating units and epoxy- and oxirane repeating units which react with acrylate compounds in the presence of a free-radical initiator.

EFFECT: disclosed compositions are hydrophilic, are compatible with a wide range of polar and non-polar media and can swell either in water or oil, thereby enabling emulsification, thickening, adhesion, lustre, longevity and removal of hydrophilic agents.

54 cl, 33 tbl, 42 ex

FIELD: chemistry.

SUBSTANCE: disclosed are oligoethoxy siloxanes with hydrophilic N,N-bis(1,2-dihydroxypropyl)-aminoalkyl groups of general formula


where x=1, 3, 4; m=5, 10, 15; Et=C2H5. Disclosed also is a synthesis method thereof via condensation of corresponding oligoethoxy(aminoalkyl)siloxanes with glycidyl at room temperature.

EFFECT: obtaining compounds with high hydrophilisation capacity and which are suitable for endowing fibre materials with hydrophilic properties.

2 cl, 2 dwg, 2 tbl, 1 ex