JPH0339964B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD OF THE INVENTION The present invention relates to the disproportionation and/or
Or it relates to a method for producing silanes, particularly monosilane and/or chlorosilane, by a redistribution reaction. BACKGROUND OF THE INVENTION Silane, particularly monosilane, is a raw material useful for semiconductors, amorphous solar cells, IC devices, photoreceptors, and the like. It is known that chlorosilane or monosilane can be obtained by a disproportionation or redistribution reaction using chlorosilane as a raw material, as shown in the following formula. Catalysts useful for these reactions are being developed. 2SiHCl ₃ SiH ₂ Cl ₂ +SiCl ₄ 2SiH ₂ Cl ₂ SiHCl ₃ +SiH ₃ Cl 2SiH ₃ ClSiH ₄ +SiH ₂ Cl _2The above catalyst is an insoluble solid anion exchange resin containing amino groups etc. ), trimethylamine or dimethylethylamine (JP-A-59-121110), palladium (JP-A-54-59230), inorganic solid bases (JP-A-59-Sho 59)
-174515) Compounds containing an α-oxoamine group (Japanese Unexamined Patent Application Publication No. 59-54617), tetraalkylureas (Japanese Patent Publication No. 14046-1983) with a hydrocarbon group
Substituted α-pyrrolidone (Japanese Patent Publication No. 55-14045), cation exchanger having a sulfonic acid group (Japanese Patent Publication No. 59-164614), reaction product of amino alcohol and silica (Japanese Patent Publication No. 59-156907) Publication No.),
and so on. In particular, heterogeneous catalysts that allow easy separation of reaction products and catalysts are attracting attention. Problems to be Solved by the Invention Several catalysts useful for the disproportionation and/or redistribution reaction of chlorohydrogenated silanes have been proposed, but in particular, conventional solid anion exchange resin-based catalysts have poor heat resistance, It was inferior in mechanical strength, had problems such as swelling peculiar to ion exchange resins, and had an unsatisfactory catalyst life. On the other hand, homogeneous catalysts such as Lewis acids and amines require a large amount of energy to separate the product from the catalyst. Means for Solving the Problem Summary of the Invention The technique of chemically modifying a solid surface is already known as a treatment method using a silane coupling agent. That is, it is already known in the art that by chemically modifying the inorganic surface with a silane coupling agent, it is possible to improve the adhesion between organic and inorganic materials of various composite materials, and to significantly improve the strength and electrical properties. However, while researching and developing useful catalysts for the disproportionation or redistribution reaction of chlorosilane, the present inventors found that a porous inorganic solid chemically modified with an amine-based organosilicon compound was particularly useful for the above reaction. The present invention was completed based on the discovery that this catalyst has high activity and good heat resistance. That is, the present invention provides SiHnCl _4-o (where 1≦n
A silane characterized by disproportionation and/or redistribution of a chlorosilane represented by ≦3),
In particular, it relates to a method for producing monosilane and/or chlorosilane. Surface Modification with a Surface Modification Reagent The organosilicon reagent that can be used to modify the surface of a porous inorganic solid with an organosilicon group containing a nitrogen atom bonded to carbon is represented by the following general formula. (Y-R-) _l SiZ _4-l (l = 2 or 3) or AmN (-R-SiZ ₃ ) _3-n (m = 0 or 1) or AnN (-R-SiZ ₃ ) _4-o X (n=0, 1 or 2) Y is an amino group represented by _-NH2 , ^-NHR1 , ^{-NR1R2 ,} or _-NH3.X , -N
H ₂ R ¹・X, −NHR ¹ R ²・X, −N
Ammonium group represented by R ¹ R ² R ³・X, or

【formula】

【formula】

It may be a nitrogen atom-containing group such as an α-oxoamino group represented by the formula, or a functional group that can be converted into a nitrogen atom-containing group by a substitution reaction or an addition reaction. The functional groups include chlorine, bromine,
Halogen atoms such as iodine, or acetic acid groups

There are carboxylic acid groups and hydrocarbon groups having unsaturated bonds useful in addition reactions, such as the formula: In this case, Y-R- may be a vinyl group as in divinyldiethoxysilane. R ¹ , R ² , R ³ are hydrogen atoms or have 1 to 20 carbon atoms
It is a hydrocarbon group that may contain atoms other than carbon or hydrogen such as oxygen atoms or halogen atoms, and may be saturated or unsaturated, linear or have a side chain, and may contain a ring or a halogen atom. It can be a formula or an acyclic formula.
In addition, when Y is an amino group, R ¹ and R ² may be connected to each other, and when Y is an ammonium group, R 1 and R 2 may be connected to each other.
Two or all of R ¹ , R ² and R ³ may be connected to each other, and when Y is an α-oxoamino group, two or all of R ¹ , R ² and R ³ may be connected to each other. It may be connected or may be a part of R. R is a hydrocarbon group having 1 to 20 carbon atoms, which may contain atoms other than carbon and hydrogen such as oxygen atoms or halogen atoms, and may be saturated or unsaturated, and may be linear or have a side chain. It may be cyclic or acyclic. Z is a group in which at least one of the groups bonded to one silicon atom is a hydrolyzable group, which has the function of reacting with the surface of a porous inorganic solid, desorbing it, and bonding with the surface. Hydrolyzable groups include halogen, alkoxy groups, amino groups, and acetoxy groups. The bonding mechanism with solids is described, for example, in "Kogyo Zaizai", Vol. 27, No. 9, pp. 34-38.
Also, Z other than the hydrolyzable group has 1 to 20 carbon atoms.
is a hydrocarbon group which may contain an oxygen atom or a halogen atom, and may be the same or different from each other. A is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may contain atoms other than carbon and hydrogen, such as a halogen atom and an oxygen atom. X is fluorine, chlorine, bromine, iodine, _BF4 ,
Anions such as ClO ₄ , CN, and carboxylic acid groups. The above general formula is shown in more detail as follows. In the formula, Y′, Y″, Y are the above Y, R′, R″,
R and R''''' are the above-mentioned R, A' is the above-mentioned A, and Z ¹ to Z ¹²
is expressed by the same definition as Z above. If Y does not have a nitrogen atom bonded to carbon, the reagent may be modified to contain a nitrogen atom by an addition or substitution reaction using a nitrogen compound such as an amine, amide, or urea before or after modifying the surface of the porous inorganic solid. The catalyst according to the present invention may have a group. As the surface modifier, bis[3-(N,N
-dimethylamino)propyl]dimethoxysilane, tris[3-(N,N-diethylamino)propyl]methoxysilane, bis[3-(triethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]methyl Amine, bis[p-(trimethoxysilyl)phenylmethyl]
Ethylamine, Tris[3-(triethoxysilyl)propyl]amine, Tris[p-(trimethoxysilyl)phenylmethyl]amine, Bis[3
-(triethoxysilyl)propyl]dimethylammonium chloride, bis[p-(trimethoxysilyl)phenylmethyl]dimethylammonium bromide, tris[3-(triethoxysilyl)
Propyl]benzylammonium chloride, Tris[p-(trimethoxysilyl)phenylmethyl]
Methyl ammonium chloride, tetrakis [3-
(triethoxysilyl)propyl]ammonium chloride, methyltris(γ-trimethoxysilylpropyl)ammonium chloride, tris[3
In addition to nitrogen atom-containing modification reagents such as -(trimethoxysilyl)propyl]ammonium chloride,
As the nitrogen atom-free modification reagent, bis(3-chloropropyl)dichlorosilane, tris(3-chloropropyl)chlorosilane, divinyldiethoxysilane, trivinylmonoethoxysilane, etc. can be used. The chemical modification method (silylation) on the surface of porous inorganic solids involves heating both at room temperature or above room temperature.
Preferably, only contacting at 30-300°C is required;
Water may be present in order to promote hydrolysis of the hydrolyzable group, or a water-alcohol solvent or the like may be used if the solvent has poor solubility in water. Porous inorganic solid Porous inorganic solids that can be used in the present invention include silica such as quartz, novaquilite, wet process silica, colloidal silica, silica aerogel, silica sand, silica stone, diatomaceous earth, tridymite, cristobalite, kaolin, talc, and wolast. Night, asbestos, calcium silicate, aluminum silicate, zeolite, bentonite, activated clay, porous glass,
Silicates such as magnesium silicate and zirconium silicate, carbonates such as calcium carbonate and magnesium carbonate, magnesium hydroxide, aluminum hydroxide,
Hydroxides such as calcium hydroxide and titanium hydroxide; metal oxides such as zinc oxide, iron oxide, magnesium oxide, titania, silica/alumina, zirconia, chromium oxide, calcium oxide, vanadium oxide, tin oxide, and bismuth oxide; silicon carbide, titanium carbide, zirconium carbide, boron carbide,
carbides such as silicon nitride, boron nitride, titanium nitride, zirconium nitride and other nitrides, aluminum, copper, iron, nickel, titanium, zirconium,
Metals such as tungsten can be used, with silica, titania or porous glass being particularly preferred. In addition, its surface area is 1 m ² /g or more, usually 2 ~
1000m ² /g is used. Disproportionation and/or redistribution reaction The disproportionation and/or redistribution reaction of chlorosilane may be carried out in liquid phase or gas phase, and may be carried out in a flow type or batch type, but gas phase can be carried out at lower pressure, and catalyst A gas phase is preferable because it allows easy separation of the product and
A flow type is preferred. The reaction temperature is 0 to 300°C, preferably 20 to 200°C, and the pressure is normal pressure to 50Kg/cm ²
(gauge pressure) and contact time in the range of 0.1 to 20 seconds. The raw material chlorosilane is a chlorohydrogenated silane represented by SiHnCl _4-o (where 1≦n≦3). That is, one or two of monochlorosilane, dichlorosilane or trichlorosilane
A mixture of any composition of more than one type can be used, and may be diluted with an inert fluid such as nitrogen gas. Effects of the Invention When carrying out the disproportionation and/or redistribution reaction of chlorosilane in the presence of a catalyst in which the surface of a porous inorganic solid is chemically modified with an organic silicon salt having a nitrogen atom bonded to carbon, conventional anion exchange resins can be used. It can be carried out at a higher temperature than the catalyst in the system, and monosilane and/or chlorosilane different from the raw material can be obtained in good yield. Examples Hereinafter, it will be explained in more detail with reference to examples.
This is not intended to limit the invention. In addition, all the analyzes of reaction products in the examples were
2m OV-1 packed column, column temperature 160℃
The analysis was performed using a gas chromatograph using TCD (carrier gas is helium). Example 1 11.06 g of γ-aminopropyltriethoxysilane, 19.86 g of γ-chloropropyltrimethoxysilane, and 25 ml of N,N-dimethylformamide as a solvent were placed in a 100 ml flask that was sufficiently purged with nitrogen and placed in an oil bath at 165°C. Heated at reflux for 24 hours. Then, the solvent was distilled off under reduced pressure (3 mmHg),
25.2 g of tris[3-(trialkoxysilyl)propyl]ammonium chloride in the form of an oil;
HN [CH ₂ CH ₂ CH ₂ Si(OR) ₃ ] ₃ Cl (where R=
_{CH3 or C2H5} ) was obtained. This ammonium salt 3.0
g and silica (Fuji Tabison ID gel, 30-60
7.0 g of mesh (dried in air at 120°C for 10 hours) and 50 ml of chlorobenzene were heated in a 100 ml flask at 130°C for 3 hours under a nitrogen atmosphere, and then 100 ml of
After washing with methanol 3 times and air drying,
℃ for 5 hours, tris[3-(trialkoxysilyl)propyl]amine N[CH ₂ CH ₂ CH ₂ Si
8.8 g of silica surface-modified with (OR) ₃ ] ₃ (where R=CH ₃ or C ₂ H ₅ ) was obtained. 2.0 cc (0.72 g) of the modified silica was filled in a glass gas phase flow reactor (inner diameter 10 mm) and heated at 110°C for 1 hour in a nitrogen stream.The raw material gas was then heated under normal pressure while keeping the reaction layer at a predetermined temperature. (SiHCl ₃ /N ₂ mixed gas, molar ratio 30/70) was fed to carry out the reaction. Analyze the product 1 hour after setting the conditions,
The results are shown in Table-1.

[Table] Example 2 4.1 g of N[CH ₂ CH ₂ CH ₂ Si (OR) ₃ ] ₃ modified silica obtained in Example 1 was placed in a flask with 10 ml of methanol, 1.0 ml of methyl iodide was added, and nitrogen The mixture was heated at 60° C. for 1 hour in an atmosphere. Next, this was filtered to recover the modified silica, which was washed twice with 50 ml of methanol, and then washed with an aqueous sodium hydrogen carbonate solution (2 g/
100 ml) twice and then with water. 6N to this silica
100 ml of diluted hydrochloric acid was added to replace hydrogen carbonate ions with chlorine ions. Next, wash with water twice, wash with 50ml methanol three times, air dry, and store in air at 100℃.
Drying was performed for 12 hours to obtain 4.1 g of silica modified with methyltris(γ _- trialkoxysilylpropyl)ammonium chloride, CH3 _- N [ _{CH2CH2CH2CH2 -} Si(OR) ₃ ] _3Cl ,. Using 2.0cc (0.74g) of this modified silica as a catalyst,
The disproportionation reaction of trichlorosilane was carried out in the same manner as in Example 1. The results are shown in Table-2.

[Table] Example 3 4.9 g of bis(3-chloropropyl)dimethoxysilane (this was synthesized from bis(3-chloropropyl)dichlorosilane manufactured by Chitsuso Co., Ltd. and excess methanol) was placed in a 100 ml flask purged with nitrogen. , dimethyl-n-dodecylamine (manufactured by Tokyo Kasei Co., Ltd.) 10
g and 40 ml of N,N-dimethylformamide were added thereto, and the mixture was heated under reflux for 12 hours under normal pressure. The solvent and unreacted amine were removed at 120°C under reduced pressure (1 mmHg), and the remaining fraction was washed with toluene (150 ml) at 100°C, filtered, and 13.1 g of ammonium salt [Cl.
(n _{- C12H25} )( _CH3 ) _{2NC3H6 ] 2Si} ( _{OCH3 ) 2} was obtained. 2.0 g of the ammonium salt and silica (manufactured by Fuji Davison, ID gel, 30 to 60 mesh) were added in air at 120 g.
℃ 10 hours drying) 5.0 g and 60 ml of N,N-dimethylformamide were heated in a 100 ml flask at 140° C. in a nitrogen atmosphere for 8 hours, the silica was filtered off, and the silica was washed 5 times with 100 ml of methanol. After air-drying, dry in air at 100°C for 12 hours to coat the surface with [Cl・(n-C ₁₂ H ₂₅ ) (CH ₃ ) ₂ NC ₃ H ₆ ] ₂ Si
Silica modified with an ammonium salt (OCH ₃ ) ₂ was obtained. A disproportionation reaction of trichlorosilane was carried out in the same manner as in Example 1 using 2.0 cc (0.73 g) of the modified silica. The results are shown in Table-3.

【table】

Claims (1)

[Claims] 1. SiHnCl _4-o (however,
1≦n≦3) A method for producing silane, characterized by disproportionation and/or redistribution of chlorosilane (Y-R-) _l SiZ _4-l (l = 2 or 3) or AmN (-R-SiZ ₃ ) _3-n (m = 0 or 1) or AnN (-R-SiZ ₃ ) _4-o X (n = 0, 1 or 2) (Y is primary to tertiary amino R is a nitrogen atom-containing group selected from a primary to quaternary ammonium group or an α-oxoamino group, and R is a C ₁ to C ₂₀ hydrocarbon that may contain a halogen atom, an oxygen atom, etc. group, Z is bonded to a silicon atom, at least one of which is a hydrolyzable group, the others are _C1 to _C20 hydrocarbon groups that may contain halogen atoms, oxygen atoms, etc., A is a hydrogen atom; or a C ₁ to C ₂₀ hydrocarbon group which may contain a halogen atom or an oxygen atom, X is a halogen, BF ₄ , OH, ClO ₄ ,
Anions such as CN and carboxylic acid groups. )