JPH0692248B2 - Method of disproportionation of silanes - Google Patents

Description

TECHNICAL FIELD The present invention disproportionates halogenated silanes, alkylsilanes, alkylhalogenated silanes and the like represented by the general formula RnSiX _(4- n ₎ to obtain raw materials such as monosilane and dichlorosilane. The present invention relates to a method for producing a silane compound different from silanes, and more specifically, a monosilane which causes a disproportionation reaction by using as a catalyst a carrier of an amine salt obtained by a reaction of amines and sulfonic acids in advance. , A method for producing silanes such as dichlorosilane different from the starting silanes at low cost, easily and extremely efficiently.

[Background technology]

With the development of the electronics industry in recent years, monosilane and chlorosilane have become particularly important as raw materials for producing polycrystalline silicon, single crystal silicon, amorphous silicon and the like. That is, monosilane (Si
H ₄ ) has been prized as a raw material for the above-mentioned high-purity silicon, a semiconductor raw material for solar cells, a raw material for a silicon epitaxial film, etc., and it is expected that the demand will greatly increase in the future. Therefore, an inexpensive and easy method for producing monosilane is desired. On the other hand, chlorosilane such as dichlorosilane is also in great demand as a raw material for manufacturing silicon for semiconductors. Further, a large demand for alkylsilanes, alkylhalogenated silanes and the like as raw materials for silicones, polycarbosilanes and the like is expected in the future.

The following methods are generally known as conventional methods for producing monosilane (SiH ₄ ).

(1) Method of using hydrochloric acid in magnesium silicide (Mg ₂ Si); (2) Method of reacting magnesium silicide with ammonium chloride or ammonium bromide in liquid ammonia; (3) Silicon tetrachloride and hydrogen in ether solvent A method of reacting lithium aluminum; (4) A method of redistributing or disproportionating trichlorosilane using an anion exchange resin containing a tertiary amino group or a quaternary ammonium group as a catalyst; (5) Lithium chloride and potassium chloride A method of reacting lithium hydride with silicon tetrachloride in the molten salt of (6); (6) a method of reacting hydrogen gas with metallic silicon under high temperature and high pressure conditions in the presence of a Ni catalyst.

However, in the method (1), a higher silicon compound (SinH ₂ n ₊₂ ) in addition to monosilane, where n is an integer of 2 or more. ) Is produced as a by-product, and the yield of monosilane is low. Furthermore, Mg is expensive and not economical. In the method (2), the yield of monosilane is high, but the reaction step such as separation of ammonia is complicated, and in addition, Mg is expensive and economically poor. According to the method (3), high-purity monosilane can be obtained in high yield, but lithium aluminum hydride used as a reducing agent is expensive, and there is a problem in continuous process.
It is difficult to industrialize. In the method (5), by-produced lithium chloride is electrolyzed, and metal lithium is hydrogenated and returned to lithium hydride, which can be used as a recycle system. However, there are problems such as corrosion of the device, and it has not yet been put to practical use. Since the method (6) is a high-temperature, high-pressure reaction, the cost of equipment and the like is high, and in addition, since the temperature is high, the product is decomposed and is not practical.

However, the method (4) is a catalytic reaction, and in addition, it is possible to hydrogenate the by-produced silicon tetrachloride and reuse it as trichlorosilane, which does not require extremely high temperature and high pressure. Is also advantageous, the apparatus is simple, and the method is economical. In this silane production method, a chlorosilane disproportionation catalyst is required, and liquid phase homogeneous and gas-solid and liquid-solid phase heterogeneous catalysts are known. Although tertiary amines, α-oxoamines, etc. are known as liquid phase catalysts, they are not suitable for mass production by continuous flow reaction. Further, in a gas-solid or liquid-solid heterogeneous reaction with a solid catalyst, a tertiary amine or 4
A quaternary ammonium salt type ion exchange resin catalyst is known and is suitable for producing a large amount of monosilane by a continuous flow reaction. However, these catalysts have low thermal stability, and deterioration of the catalyst can be easily recognized by long-term reaction, and it is difficult to regenerate the catalyst, and in addition, the ion exchange resin is expensive and has a great influence on the economical efficiency. It has drawbacks such as

On the other hand, the above method (4) is known as a method for producing dichlorosilane, and the problems related to this production include the same as the above-mentioned production of monosilane. In addition, there is a method of obtaining dichlorosilane as a by-product when producing trichlorosilane from metallic silicon, but the yield is low and it is not practical.

Further, in the disproportionation reaction of alkylsilane and the like, the method according to the above (4) is known, but it also has the above-mentioned drawbacks. Although other methods using aluminum halide as a catalyst are known, the reaction is extremely slow when aluminum halide is used as a catalyst, and the conversion rate is usually low even at 500 to 600 ° C.

[Object of the Invention]

Therefore, the object of the present invention is to use monosilanes as a raw material from halogenated silanes or hydrocarbon-containing silanes, as in the method (4) above using trichlorosilane, which is the most abundant supply source of silicon, as a raw material. Another object of the present invention is to provide a disproportionation method for producing silanes different from raw silanes.

Another object of the present invention is extremely high thermal stability as compared with the conventionally known heterogeneous solid catalysts such as tertiary amine type or quaternary ammonium salt type anion exchange resins, and therefore, for example It is possible to carry out a reaction at a high temperature that is advantageous for products (monosilane, monochlorosilane, dichlorosilane, and tetrachlorosilane) on the reaction equilibrium such as a disproportionation reaction of chlorosilane, and has a long life and is inexpensive at the same time. An object of the present invention is to provide a disproportionation method of contacting with a catalyst that can be prepared very easily.

[Disclosure of Invention]

According to the present invention, it is represented by the general formula RnSiX _(4- n ₎ (wherein n is an integer of 1 or more and 4 or less, R is a hydrogen or a hydrocarbon group, and X is a halogen atom or an alkoxy group). Provided is a disproportionation method of silanes, which comprises contacting silanes with a reaction product of amines and sulfonic acids supported on a carbonaceous material.

Hereinafter, the present invention will be described in detail.

The silanes used as a raw material in the present invention are represented by the general formula RnSiX _(4- n ₎ (where n is an integer of 1 or more and 4 or less, R is hydrogen or an alkyl group having 1 to 10 carbon atoms, and 1 carbon atom). A hydrocarbon group such as an aryl group having 10 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms,
X is a halogen atom such as fluorine, chlorine, bromine or iodine or an alkoxy group such as methoxy or ethoxy, and is represented by, for example, halogenated silane, alkylsilane, alkylhalogenated silane, alkoxysilane or alkoxyhalogen. Silane, alkylhalogenated alkoxysilane, alkylalkoxysilane, alkenylsilane, alkenylhalogenated silane,
Examples include arylsilane, arylhalogenated silane, arylalkoxysilane, arylalkylsilane, alkylarylhalogenated silane, and arylhalogenated alkoxysilane. Specifically, trichlorosilane,
Dichlorosilane, monochlorosilane, tribromosilane, dibromosilane, monobromosilane, triiodosilane, diiodosilane, monoiodosilane, trifluorosilane, difluorosilane, monofluorosilane, monomethylsilane, diethylsilane, monoethylsilane,
Methylchlorosilane, dimethylchlorosilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, monoethylsilane, diethylsilane, triethylsilane, ethylchlorosilane, ethyldichlorosilane, ethyltrichlorosilane, diethylchlorosilane, diethyldichlorosilane, triethylchlorosilane, methylbromo Silane, methyldibromosilane, methyltribromosilane, dimethylbromosilane, dimethyldibromosilane, trimethylbromosilane, ethylbromosilane, ethyldibromosilane, ethyltribromosilane, diethylbromosilane, diethyldibromosilane, triethylbromosilane, methylfluoro Silane,
Methyldifluorosilane, methyltrifluorosilane,
Dimethylfluorosilane, trimethylfluorosilane,
Ethylfluorosilane, ethyldifluorosilane, ethyltrifluorosilane, diethylfluorosilane, diethyldifluorosilane, triethylfluorosilane, methyliodosilane, methyldiiodosilane, methyltriiodosilane, trimethyliodosilane, ethyliodosilane, ethyltriiodo Silane, phenylsilane, diphenylsilane, triphenylsilane, phenylchlorosilane, diphenylchlorosilane, triphenylchlorosilane, diphenylchlorosilane, triphenylchlorosilane, phenylbromosilane, diphenylbromosilane, triphenylbromosilane, diphenyldibromosilane, triphenylbromosilane , Phenylfluorosilane, diphenylfluorosilane, triphenylfluorosilane, diphe Rudifluorosilane, triphenylfluorosilane, vinylsilane, divinylsilane, vinylchlorosilane, vinyltrichlorosilane, methoxysilane, dimethoxysilane, trimethoxysilane, ethoxysilane, diethoxysilane, triethoxysilane, chloromethoxysilane, dichloromethoxysilane, Trichloromethoxysilane, methylmethoxysilane, methyldimethoxysilane, methyltriethoxysilane, chloroethoxysilane, dichloroethoxysilane, trichloroethoxysilane, chlorodiethoxysilane, vinylmethoxysilane, divinylmethoxysilane, trivinylmethoxysilane, vinylchloromethoxy Silane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriethoxysilane, trivinylethoxysilane Emissions, methyl ethyl silane, a halogen-containing and / or carbon-hydrogen groups and / or containing alkoxysilanes such as methyl phenyl silane, ethyl phenyl silane, ethyl phenyl chlorosilane is these one or a mixture of two or more.

In the present invention, the above-mentioned silanes are used as a raw material and brought into contact with a reaction product of an amine and a sulfonic acid supported on a carbonaceous substance to carry out a disproportionation reaction.

The reaction product of amines and sulfonic acids in the present invention is produced by the following reaction.

(However, R'is a hydrocarbon group, and R "is H and a hydrocarbon group, which may be different groups or the same groups.) In the present invention, amines which are reacted with sulfonic acids to form sulfonates of amines And (a) a nitrogen hydride compound such as ammonia or hydrazine; (b) an aliphatic, aromatic or alicyclic primary, secondary or tertiary monoamine or a polyamine such as a diamine or triamine; (C) a monoamine or polyamine which is a cyclic amine containing a condensed ring and contains at least one nitrogen atom in the ring skeleton; (d) amino acids, amides, alcohol amines, ether amines, imides or lactams Oxygen-containing amine; (e) Hetero-element-containing amine having a hetero atom such as O, S, Se; and the like, and in the case of secondary or tertiary amine, N Each substituent is identical or different from each other or to, or 1 or more may have a different one of any of the substituents.

Specifically, as ammonia, hydrazine, and primary amines; monomethylamine, monoethylamine, monopropylamines, monobutylamines, monopentylamines, monohexylamines, monoheptylamines, vinylamine, allylamine, Butenylamines,
Pentenylamines, hexenylamines, pentadienylamines, hexadienylamines, cyclopentylamine, cyclohexylamine, cyclooctylamine, p-menthylamine, cyclopentenylamines,
Cyclohexenylamines, cyclohexadienylamines, aniline, benzylamine, naphthylamine, naphthylmethylamine, toluidine, tolylenediamines, anisole, ethylenediamine, ethylenetriamine, monoethanolamine, aminothiophene, glycine, alanine, phenylalanine, amino Acetone etc. are mentioned.

The secondary amine includes dimethylamine, diethylamine, dipropylamines, dibutylamines, dipentylamines, dihexylamines, methylethylamine, methylpropylamines, methylbutylamines, methylpentylamines, methylhexyl. Amines, ethylpropylamines, ethylbutylamines,
Ethyl pentyl amines, propyl butyl amines, propyl pentyl amines, propyl hexyl amines,
Butylpentylamines, pentylhexylamines,
Divinylamine, diallylamine, dibutenylamines, dipentenylamines, dihexenylamines, methylvinylamine, methylallylamine, methylbutenylamines, methylpentenylamines, methylhexenylamines, ethylvinylamine, ethylallylamine, ethylbutane Tenyl amine, ethyl pentenyl amines, ethyl hexenyl amines, propyl vinyl amines, propyl allyl amines, propyl butenyl amines, propyl pentenyl amines, propyl hexenyl amines, butyl vinyl amines, butyl allyl amines, butyl butenyl Amines, butylpentenylamines, butylhexenylamines, vinylallylamine,
Vinyl butenyl amines, vinyl pentenyl amines,
Vinylhexenylamines, allylbutenylamines,
Allyl pentenyl amines, allyl hexenyl amines, butenyl pentenyl amines, butenyl hexenyl amines, dicyclopentyl amine, dicyclohexyl, methyl cyclopentyl amine, methyl cyclohexyl amine, methyl cyclooctyl amine, ethyl cyclopentyl amine, ethyl cyclohexyl amine, ethyl Cyclooctylamine, propylcyclopentylamines, propylcyclohexylamines, butylcyclopentylamines, butylcyclohexylamines, hexylcyclopentylamines, hexylcyclohexylamines, hexylcyclooctylamines, vinylcyclopentylamine, vinylcyclohexylamine, vinylcyclo Octylamine, allylcyclopentylamine, allylcyclohexyl Ruamine, allylcyclooctylamine, butenylcyclopentylamines, butenylcyclohexylamines, butenylcyclooctylamines, dicyclopentenylamines, dicyclohexenylamines, dicyclooctenylamines, methylcyclopentenylamines , Methylcyclohexenylamines, methylcyclooctenylamines, ethylcyclopentenylamines, ethylcyclohexenylamines,
Ethylcyclooctenylamines, propylcyclopentenylamines, propylcyclohexenylamines,
Butylcyclopentenylamines, butylcyclohexenylamines, vinylcyclopentenylamines, vinylcyclohexenylamines, vinylcyclooctenylamines, allylcyclopentenylamines, allylcyclohexenylamines, butenylcyclopentenylamines, Butenylcyclohexenylamines, dicyclopentadienylamine, dicyclohexadienylamines, dicyclooctadienylamines, methylcyclopentadienylamine, methylcyclohexadienylamines, ethylcyclopentadienylamine, Ethylcyclohexadienylamines, propylcyclopentadienylamines, propylcyclohexadienylamines, dicyclooctatrienylamines, methylcyclooctatrienylamines , Ethylcyclooctatrienylamines, vinylcyclopentadienylamine, vinylcyclohexadienylamines, allylcyclopentadienylamine, allylcyclohexadienylamines, diphenylamine, ditolylamines, dibenzylamine, dinaphthylamine , N-methylaniline, N
-Ethylaniline, N-propylanilines, N-butylanilines, N-methyltoluidine, N-ethyltoluidine, N-propyltoluidines, N-butyltoluidines, N-methylbenzylamine, N-ethylbenzylamines , N-propylbenzylamines, N-butylbenzylamines, N-methylnaphthylamines, N
-Ethylnaphthylamines, N-propylnaphthylamines, N-vinylaniline, N-allylaniline, N-
Vinylbenzylamine, N-allylbenzylamine, N
-Vinyltoluidine, N-allyltoluidine, phenylcyclopentylamine, phenylcyclohexylamine, phenylcyclooctylamine, phenylcyclopentenylamine, phenylcyclohexenylamine, phenylcyclopentadienylamine, N-methylanisole, N-ethylanisole, N-vinyl anisole,
N-allylanisole, N-methylethylenediamine,
N, N 'dimethylethylenediamine, N-ethylethylenediamine, N, N'-diethylethylenediamine, N, N'-
Dimethyltolylenediamines, N, N'-diethyltolylenediamines, N-methylethylenetriamine, N, N '
-Dimethylethylenetriamine, pyrrole, pyrrolidine, imidazole, piperidine, piperazine, methylpyrroles, methylpyrrolidines, methylimidazoles, methylpiperidines, methylpiperazines, ethylpyrroles, ethylpyrrolidines, ethylimidazoles, ethyl Piperidines, ethylpiperazines, phthalimide, maleimide, caprolactam, pyrrolidone, morpholine, N-methylglycine, N-ethylglycine, N-methylalanine, N-ethylalanine, N-
Methyl-aminothiophene, N-ethylaminothiophene, 2,5-piperazinedione, N-methylethanolamine, N-ethylethanolamine, purine and the like can be mentioned.

Further, as the tertiary amine: trimethylamine, triethylamine, tripropylamines, tributylamines, tripentylamines, trihexylamines,
Dimethylethylamine, dimethylpropylamines, dimethylbutylamines, dimethylpentylamines, dimethylhexylamines, diethylpropylamines,
Diethylbutylamines, diethylpentylamines,
Diethylhexylamines, dipropylbutylamines, dipropylpentylamines, dipropylhexylamines, dibutylpentylamines, dibutylhexylamines, dipentylhexylamines, methyldiethylamine, methyldipropylamines, methyldibutylamines , Methyldipentylamines, methyldihexylamines, ethyldipropylamines, ethyldibutylamines, ethyldipentylamines, ethyldihexylamines, propyldibutylamines, propyldipentylamines, propyldihexylamines, butyldipentylamine , Butyldihexylamines,
Pentyldihexylamines, methylethylpropylamines, methylethylbutylamines, methylethylhexylamines, methylpropylbutylamines, methylpropylhexylamines, ethylpropylbutylamine, ethylbutylpentylamines, ethylbutylhexylamines, propylbutyl Pentylamines, propylbutylhexylamines, butylpentylhexylamines, trivinylamine, triallylamine, tributenylamines, tripentenylamines, trihexenylamines, dimethylvinylamine, dimethylallylamine, dimethylbutenylamines , Dimethyl pentenyl amines, diethyl vinyl amine, diethyl allyl amine, diethyl butenyl amines, diethyl pentenyl amines, di Tylhexenylamines, dipropylvinylamines, dipropylallylamines, dipropylbutenylamines, methyldivinylamine, methyldiallylamine, methyldibutenylamines, ethyldivinylamine, ethyldiallylamine, tricyclopentylamine, tricyclohexylamine , Tricyclooctylamine, tricyclopentenylamine, tricyclohexenylamine, tricyclopentadienylamine, tricyclohexadienylamines, dimethylcyclopentylamine, diethylcyclopentylamine, dipropylcyclopentylamines, dibutylcyclopentylamines, dimethyl Cyclohexylamine, diethylcyclohexylamine, dipropylcyclohexylamines, dimethylcyclopentenylamine Amines, diethylcyclopentenylamines, dipropylcyclopentenylamines, dimethylcyclohexenylamines, diethylcyclohexenylamines, dipropylcyclohexenylamines, methyldicyclopentylamine, ethyldicyclopentylamine, propylcyclopentylamines, Methyldicyclohexylamine, ethyldicyclohexylamine, propylcyclohexylamines,
Methyldicyclopentenylamines, ethyldicyclopentenylamines, propyldicyclopentenylamines, N, N-dimethylaniline, N, N-dimethylbenzylamine, N, N-dimethyltoluidines, N, N-dimethylnaphthylamine , N, N-diethylaniline, N, N-diethylbenzylamine, N, N-diethyltoluidine, N, N-diethylnaphthylamine, N, N-dipropylaniline, N, N-dipropylbenzylamine , N, N-dipropyltoluidines, N, N-dipropylnaphthylamines,
N, N-divinylaniline, N, N-diallylaniline, N, N
-Divinyltoluidines, N, N-diallylaniline, diphenylmethylamine, diphenylethylamine, diphenylpropylamines, dibenzylmethylamine, dibenzylethylamine, dibenzylcyclohexylamine, dibenzylvinylamine, dibenzylallylamine, ditolylmethyl Amines, ditolylethylamines, ditolylcyclohexylamines, ditolylvinylamines, triphenylamine, tribenzylamine,
Tri (tolyl) amines, trinaphthylamines, N, N,
N ', N'-tetramethylethylenediamine, N, N, N', N '
-Tetraethylethylenediamine, N, N, N ', N'-tetramethyltolylenediamines, N, N, N', N'-tetraethyltolylenediamines, N-methylpyrrole, N-methylpyrrolidine, N-methyl Imidazole, N, N'-dimethylpiperazine, N-methylpiperidine, N-ethylpyrrole, N-methylpyrrolidine, N-ethylimidazole, N, N'-diethylpiperazine, N-ethylpiperidine, pyridine, pyridazine, pyrazine, quinoline , Quinazoline, quinuclidine, N-methylpyrrolidone, N-methylmorpholine, N-ethylpyrrolidone, N-ethylmorpholine, N, N-dimethylanisole, N, N-diethylanisole, N, N-dimethylglycine, N, N- Diethylglycine, N, N-dimethylalanine, N, N-diethylalanine, N, N-dimethylethanolamine, N, N -Dimethylaminothiophene and the like. Therefore, the amines are aliphatic or alicyclic, saturated or unsaturated hydrocarbon groups; aromatic hydrocarbon groups; oxygen-containing and / or sulfur-containing and / or selenium-containing hydrocarbon groups and the like having one or more nitrogen atoms. Is a compound bound to.

In the present invention, the sulfonic acids forming a reaction product with amines are aliphatic and aromatic sulfonic acids, specifically; methanesulfonic acid, ethanesulfonic acid, n-
Aliphatic saturated mono- and polysulfonic acids such as propanesulfonic acid, i-propanesulfonic acid, n-butanesulfonic acid, n-hexanesulfonic acid, methanedisulfonic acid, 1,2-ethanedisulfonic acid and 1,3-propanedisulfonic acid Aliphatic unsaturated sulfonic acids such as ethylenesulfonic acid, 1-propene-1-sulfonic acid, 1-propyne-3-sulfonic acid, and 1,2-ethylenedisulfonic acid; iodomethanesulfonic acid, β-bromoethanesulfonic acid , Halogen-containing aliphatic sulfonic acids such as perchlorooctanesulfonic acid, octanesulfonic acid chloride, trifluoromethanesulfonic acid; β-aminoethanesulfonic acid, N-methyltaurine, 2-acryloylamino-2-methyl-1-propane Sulfonic acid, hydroxymethanesulfonic acid, N-β-
Hydroxyhexytaurine, sulfoacetic acid, 3-propargyloxypropylsulfonic acid, 3- (ω-diethylenedioxy) -1-propanesulfonic acid, methacryloyloxypropylsulfonic acid, acetonedisulfonic acid,
1,2-dihydroxyethanesulfonic acid, sulfooctanoic acid, sulfosuccinic acid, lauryl sulfoacetate, α
-Sulfopalmitic acid, sorbitol ester, N-octadecylsulfosuccinamide and other nitrogen-containing and / or oxygen-containing aliphatic hydrocarbon sulfonic acids; benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, benzenepyrosulfonic acid, naphthalene Aromatic sulfonic acids such as sulfonic acid, ethylbenzenesulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, methylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, styrenesulfonic acid; fluorobenzenesulfonic acid, difluorobenzenesulfonic acid , Chlorobenzene sulfonic acid, dichlorobenzene sulfonic acid, bromobenzene sulfonic acid, dibromobenzene sulfonic acid, iodobenzene sulfonic acid Halogenated aromatic sulfonic acids such as chloro naphthalenesulfonic acids; Aniline sulphonic acids, amino-toluene sulfonic acid, diaminobenzene sulfonic acid, diaminotoluene sulphonic acids, aniline disulfonic acid, aniline tri sulfonic acids, naphthylamine sulfonic acid, naphthylamine disulphonic acids,
Naphthylamine trisulfonic acids, chloroaniline sulfonic acids, aminochlorotoluene sulfonic acids, nitrobenzene sulfonic acids, nitrotoluene sulfonic acids,
Dinitrobenzenesulfonic acids, nitrochlorobenzenesulfonic acids, nitroanilinesulfonic acids, aminoazobenzenesulfonic acids, phenylhydrazinesulfonic acids, phenolsulfonic acids, cresolsulfonic acids, dihydroxybenzenesulfonic acids, aminophenolsulfonic acids, methoxybenzenesulfonic acids, aminomethoxy Benzenesulfonic acid, methoxynitrobenzenesulfonic acid, sulfobenzenedicarboxylic acid,
N, N-dimethylanilinesulfonic acid, sulfobenzenecarboxylic acid, disulfobenzoic acid, naphthylaminesulfonic acid, naphthylaminedisulfonic acid, naphthylaminetrisulfonic acid, nitronaphthalenesulfonic acid, nitronaphthalenetrisulfonic acid, naphtholsulfonic acid, naphtholdisulfonic acid, Examples thereof include oxygen-containing and / or nitrogen-containing aromatic sulfonic acids such as naphthol trisulfonic acid, aminonaphthol sulfonic acid, benzoylaminonaphthalene sulfonic acid, acetylnaphthalene sulfonic acid, nitronaphthol sulfonic acid and azonaphthalene sulfonic acid.

The carbonaceous material used as a carrier in the present invention is an allotrope of carbon and does not show a clear crystalline state,
Or it has a crystal lattice similar to graphite, but is a collection of small crystals with random arrangement of this lattice,
Or crystalline carbon such as graphite,
Specifically, wood, charcoal, fruit shells, peat, grass peat, lignite,
Examples include activated carbon obtained from various raw materials such as brown coal, coal, pitch and tar, acetylene black, carbon black, bone charcoal, graphite and charcoal.

In addition, the form of the carrier and the supported catalyst may be any form such as powder and granules, and in the case of granules, rod-shaped, cylindrical, fibrous, mesh-shaped or crushed ones may be used. It is possible.

The amount of the amine sulfate supported in the present invention is between 0.02% by weight and 100% by weight, preferably 0.1% by weight, based on the weight of the carrier.
Wt% to 70 wt%, more preferably 0.5 wt% to 50
Between% by weight. When these sulfonates are loaded on the carbonaceous material, one or more sulfonates may be loaded.

In order to support the sulfonate of an amine used as a catalyst in the present invention on a carrier, the following preparation method can be adopted, for example. The present invention is of course not limited to these preparation methods.

(1) A commercially available or preliminarily prepared amine sulfonate is dissolved in a solvent in a container, a certain amount of carbonaceous substance is added thereto and sufficiently impregnated, and then the solvent is heated under normal pressure or reduced pressure if necessary. (2) A certain amount of carbonaceous substance is put in a reaction tube in advance, and a sulfonate solution of amines is allowed to flow into the reaction tube to be adsorbed on the carbonaceous substance, and then a solvent is added. (3) A sulfonate of amines and a carbonaceous substance are put in a container, a solvent for the sulfonate is added, and the mixture is stirred.
After dissolving the sulfonate, the solvent is removed, dried and supported; (4) The sulfonate of amines is dissolved in the solvent in a container, a certain amount of carbonaceous substance is added to the solvent, and the mixture is stirred. Then, the excess substance is dried and supported; (5) A carbonaceous substance is put in a container in advance to reduce the pressure in the atmosphere, and then a sulfonic acid solution of amine is injected, and then excess or solvent is removed, Further drying and supporting method: (6) Other known supporting methods such as a spray method and a kneading method.

These supported catalysts can be used as they are or after being subjected to treatments such as crushing and molding.

In the present invention, the disproportionation reaction is carried out using the reaction product of the amines and sulfonic acids supported on the carbonaceous material, which is prepared as described above, as a catalyst.

The disproportionation reaction in the present invention is a raw material silane RnSiX _(4- n ₎
Therefore, it means an equilibrium reaction in which silanes richer in X and silanes richer in R are produced. For example, in the case where the starting silanes are trichlorosilane (R = H, X = 1), the following reactions are meant, and they are a combination thereof.

2SiHCl ₃ SiH ₂ Cl ₂ + SiCl ₄ 2SiH ₂ Cl ₂ SiH ₃ Cl + SiHCl ₃ 2SiH ₃ ClSiH ₄ + SiH ₂ Cl ₂ That is, an equilibrium reaction in which more chlorine-rich silanes and more hydrogen-rich silanes are produced from the raw chlorosilanes. .

When the supported catalyst of the present invention is used, the disproportionation reaction rate itself is extremely fast and the equilibrium is reached in a short time. From the equilibrium composition, it is desirable that the temperature is as high as possible in the range where the stability of the catalyst can be maintained. From this viewpoint, the reaction temperature for disproportionation (or redistribution) in the present invention is 0 to 300 ° C, preferably 50 to 200 ° C.

Next, a specific mode of carrying out the disproportionation reaction by bringing silanes into contact with a catalyst will be described. Basically, it can be carried out by any method of atmospheric pressure, pressurization or reduced pressure reaction in gas phase-solid phase or liquid phase-solid phase. For example, the following reaction method can be adopted as a method that is easy to carry out.

(1) A method in which the supported catalyst and the raw material silanes are placed in a container and a stirring and heating reaction is carried out under reflux at normal pressure; (2) The supported catalyst and the raw material silanes are placed in a pressure resistant vessel and the stirring and heating reaction is performed under a pressure. Method: (3) A catalyst is packed in a single tube and the raw material silanes are continuously flowed into the catalyst layer as a liquid or gas under pressure, atmospheric pressure or reduced pressure to carry out the reaction; To treat a large amount of silanes The method (3) is desirable, but the present invention is not limited to these above methods.

Raw material silanes used for this reaction and silanes such as products such as monosilane and halogenated silanes are active and easily decomposed by water, alcohol, aqueous alkali solution or the like. Further, some of them react violently with oxygen to cause pyrolysis and decomposition. Therefore, the reaction needs to be carried out in an atmosphere inert to the raw material silanes and the product silane.
For example, it is preferable that the reaction system is preliminarily reacted in an atmosphere of an inert gas such as helium or argon, which has been sufficiently dehydrated and dried and deoxidized, or hydrogen or nitrogen, and then the reaction is performed.

[Operation according to the invention]

According to the present invention, the catalyst itself, which has been a great drawback in the catalytic reaction method for disproportionating halogenated silane, which is a conventional method for producing monosilane, is expensive, and deterioration due to thermal instability of the catalyst, Therefore, it is advantageous for the product in the disproportionation reaction (that is, it brings about a high conversion rate of the raw material (a drawback such as inability to carry out a high-temperature reaction, etc.) is caused by the amines and sulfonic acids supported on the carbonaceous material in the present invention. By using the reaction product as a disproportionation catalyst such as a novel halogenated silane, it is possible to prevent deterioration due to its thermal stability as a characteristic of sulfonate, and also to obtain a high reaction conversion rate in a high temperature range. In addition to the conventional anion exchange resin-type disproportionation catalyst, the catalyst of the present invention is extremely cheaper than the conventional anion exchange resin type disproportionation catalyst. Be such, therefore has excellent advantages in disproportionation process for the preparation of the monosilane or the like, economic effects which the process results are enormous.

〔Example〕

 The present invention will be specifically described below with reference to examples.

In the following Examples and Comparative Examples, when gas phase silanes were used, the analysis was carried out by heating the reactor outlet to 70 ° C. and letting the generated gas flow into a constant temperature gas sampler for gas chromatography maintained at 70 ° C. The composition was analyzed in a gaseous state by Totograph. The analytical value was an analytical value after the reaction became stationary, and it was confirmed that the time required for the reaction to reach stationary was within 1 hour.

Example 1 The amine sulfonate shown in Table 1 below was added to activated carbon (white heron Lc 8/32 coconut husk charcoal manufactured by Takeda Pharmaceutical Co., Ltd.) in an amount of 5 against the activated carbon.
A Pyrex glass tube having an inner diameter of 11 mmφ was filled with the catalyst having a length of 50 mm by carrying the catalyst in which water was used as a solvent by the method of the above (1) so that the weight ratio became 1%. (Filling volume 4.75 ml) After that, the reaction tube was heated to 100 ° C. in an oil bath and trichlorosilane having a purity of 99.9% was supplied at an inflow rate of 25 g / hr to carry out a disproportionation reaction. As shown in Table 1, the composition of the produced gas was equilibrium at 100 ° C. for each amine sulfate, and it was an extremely highly active catalyst that reached disproportionation equilibrium within a contact time of several seconds.

Example 2 Triethylammonium p-toluenesulfonate supported on activated carbon (white heron Lc 8/32) in an amount of 5% by weight was charged into the same apparatus as in Example 1 in the same amount, and the starting material trichlorosilane inflow rate and reaction temperature were adjusted. Instead, a disproportionation reaction was performed.

The results are as shown in Table 2. Some results of Example 1 are also shown.

As mentioned above, the reaction equilibrium is reached at an inflow rate of trichlorosilane of 25 g / hr over a wide range of temperatures, and it is a catalyst that exhibits extremely high reaction activity even at an inflow rate of more than this, and in addition, a catalyst that can withstand high temperature use. I understood.

Example 3 p-toluenesulfonic acid-triethylammonium was loaded on activated carbon (white heron Lc 8/32) at 50, 10, 5, and 0.5 weight percent, respectively, as a catalyst, and the same reactor and the same catalyst as in Example 1 were used. The disproportionation reaction was carried out at a filling amount of 100 ° C. and an inflow rate of trichlorosilane of 25 g / hr. The results were as shown in Table 3 below. The results of Example 1 are also partially shown.

Example 4 Triethylammonium p-toluenesulfonate was used as activated carbon SGL 8/30 (product of Toyo Calgon Co., Ltd., coal coal), carbon black: Continex T (product of Mitsui Toatsu Chemicals, Inc.), carbon black: Ketjen Black EC (Lion -Axo Co., Ltd.) and graphite (genuine chemical products) loaded with 5% by weight of each carrier as a catalyst with the same reactor and catalyst loading as in Example 1 with an inflow rate of trichlorosilane of 25 g / hr and The disproportionation reaction was carried out at 100 ° C.

As shown in Table 4, the catalyst supported on each carbonaceous carrier showed excellent reaction activity.

As described above, each of the materials supported on the carbonaceous material exhibited extremely high activity within a contact time of several seconds. In activated carbon, a significant difference due to the difference in the raw materials was not observed, and the reaction equilibrium was sufficiently reached.

Comparative Example 1 Triethylammonium p-toluenesulfonate and activated carbon (white heron Lc 8/32) were separately charged in the same apparatus as in Example 1 in the same amount as the catalyst loading amount of Example 1 in a solid state. The disproportionation reaction of trichlorosilane was carried out under the same reaction conditions as in No. 4. As a result, almost no disproportionation activity was observed when only p-toluenesulfonate triethylammonium was filled, and the raw material trichlorosilane was recovered. When only activated carbon was charged, the conversion rate of initial trichlorosilane was 6%, but after 30 minutes, the conversion rate became 0, and the raw material trichlorosilane was only recovered. From the above results, it was found that the catalytic activity is first expressed by using the carbonaceous substance and the sulfonate of amine in the disproportionation reaction in the form of supporting the sulfonate on the carbonaceous substance. did.

Example 5 Using the same catalyst as in Example 2, the disproportionation reaction was carried out at the respective reaction temperatures at the inflow rate of 20 g / hr of dichlorosilane with the same reactor and the same catalyst loading as in Example 1. As shown in Table 5, the disproportionation reaction proceeded at a very high conversion rate in a short time to obtain monosilane.

Example 6 Using the same catalyst as in Example 2, the disproportionation reaction was carried out at the same reactor and the same catalyst loading as in Example 1 at an inflow rate of trichlorosilane of 25 g / hr and at 150 ° C. The reaction products were analyzed 1 hour and 40 hours after the start of the reaction. As a result, as shown in Table 6, no decrease in catalyst activity was observed.

Comparative Example 2 Using the same reaction apparatus as in Example 1, using the same amine as the tertiary amine type anion exchange resin, Amberlyst A-21 (manufactured by Rohm and Haas Co.) as a catalyst, the same amount of catalyst loading as in Example 1. The disproportionation reaction was carried out at an inflow rate of trichlorosilane of 25 g / hr and 120 ° C. for 1 hour, and the composition of the produced gas at the time of 40 hours was analyzed. As a result, as shown in Table 7, a remarkable decrease in catalytic activity was recognized. As a result, it became clear that the catalyst had deteriorated.

Comparative Example 3 Using the same reaction apparatus as in Example 1, tri-n-butylamine was carried on 5 weight percent activated carbon (white heron Lc 8/32) by an impregnation method using ethanol as a solvent, and this was carried out as a tentacle. With the same catalyst loading as in Example 1, the inflow rate of trichlorosilane was 25 g / m as in Example 6 and Comparative Example 1.
The disproportionation reaction was carried out at a reaction temperature of 120 ° C. for 1 hour, and the composition of the produced gas was analyzed after 1 hour and 40 hours. As shown in Table 8, the results are (i) lower than the initial activity at 100 ° C. (Example 1, Table 1), and (ii) in addition to the catalyst of the present invention, the remarkable catalyst Degradation of activity over time was observed.

Example 7 Into a 100 ml autoclave, 5.0 g of the same catalyst as in Example 2 and 40 g of methyldichlorosilane (CH ₃ SiHCl ₂ ) were charged and reacted at 150 ° C. for 2 hours while stirring, and then the reaction solution was formed by gas chromatography. Was analyzed. The results showed high disproportionation activity as follows.

Example 8 A 100 ml autoclave was charged with 5.0 g of the same catalyst as in Example 2, 20.1 g of methyldichlorosilane (CH ₃ SiHCl ₂ ) and 13.7 g of trichlorosilane (SiHCl ₃ ) (charge composition methyldichlorosilane 63.4%, trichlorosilane). 36.6
%), And after reacting for 2 hours with stirring at 150 ° C., the composition of the reaction solution was analyzed by gas chromatography. The results showed extremely high activity as follows.

Claims (10)

[Claims] 1. A compound represented by the general formula RnSiX _(4- n _), wherein n is an integer of 1 or more and 4 or less, R is a hydrogen or a hydrocarbon group, and X is a halogen atom or an alkoxy group. A method for disproportionating silanes, which comprises contacting silanes with a reaction product of amines and sulfonic acids supported on a carbonaceous material. 2. The method according to claim 1, wherein the amines are hydrogenated nitrogen compounds. 3. The method according to claim 2, wherein the hydrogenated nitrogen compound is ammonia or hydrazine. 4. The process according to claim 1, wherein the amines are aliphatic, aromatic or cycloaliphatic primary, secondary or tertiary monoamines or polyamines. 5. The method according to claim 1, wherein the amines are cyclic amines containing a condensed ring, and the amines are monoamines or polyamines having at least one nitrogen atom contained in the ring skeleton. 6. The method according to claim 1, wherein the amines are oxygen-containing amines such as amino acids, amides, alcohol amines, ether amines, imides or lactams. 7. The method according to claim 1, wherein the amine is a hetero-element-containing amine compound having a hetero atom such as O, S or Se. 8. A sulfonic acid is represented by the general formula R'-SO ₃ H (wherein R'is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and oxygen-containing, nitrogen-containing, and nitrogen-containing compounds). The method according to claim 1, which is a hydrocarbon group containing a hetero atom such as sulfur. 9. The method according to claim 1, wherein the disproportionation temperature is 0 ° C. or higher and 300 ° C. or lower. 10. The method according to claim 1, wherein the disproportionation temperature is 50 ° C. or higher and 200 ° C. or lower.