JPS6246916A - Production of silane - Google Patents

Abstract

PURPOSE:To carry out the disproportionation or redistribution of chlorosilanes at a high rate of conversion by using a catalyst obtd. by bonding one or more kinds of groups such as amino and ammonium to a polysiloxane matrix. CONSTITUTION:One or more kinds of groups selected among amino, ammonium, phosphino and phosphonium are bonded to a polysiloxane matrix to obtain a catalyst. A gaseous mixture of chlorosilanes represented by a formula SiHnCl4-n (where n=1-3) with N2 or the like is fed to the catalyst to carry out the disproportionation or redistribution of the chlorosilanes. The catalyst causes no swelling and has superior heat and chemical resistances. Functional groups can be introduced by a large amount to attain high activity.

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing silanes, in particular monosilanes and/or chlorocrunes, by disproportionation and/or redistribution reactions of chlorohydrogenated silanes.

BACKGROUND OF THE INVENTION Silane, particularly monosilane, is a raw material useful in semiconductors, amorphous solar cells, IO 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.

2SiH(!/, ko 1llliB, C/, +81
c/.

2 days 1m, at, 3 5iT1cz, 4-stH,a
t281 horse at: SIH, -4-stm, at.

Examples of the above-mentioned catalysts include insoluble solid anion exchange resins containing amine groups (Japanese Patent Application Laid-open No. 119798/1983), trimethylamine or dimethylethylamine (Japanese Patent Application Laid-Open No. 59-1989),
-121110), palladium (JP-A-54-5
No. 9250), inorganic solid base (Japanese Patent Application Laid-Open No. 174-1983)
No. 515) Compounds containing an α-oxoamine group (Japanese Patent Publication No. 59-54617), tetraalkylureas (Japanese Patent Publication No. 55-14046) α-pyrrolidone substituted with a hydrocarbon group (Japanese Patent Publication No. 55-14046) Publication No. 14045),
Cation exchanger having sulfonic acid group (JP-A-59-1
61614), a reaction product of amino alcohol and silica (Japanese Unexamined Patent Publication No. 156907/1983), and the like. 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 silica have been proposed, but in particular, the heat resistance of conventional solid anion exchange resin-based catalysts, 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 Problems Summary of the Invention The present inventors have developed a novel catalyst system for solving the above problems by chemically converting the surface of a porous inorganic solid into an organosilicon group containing a nitrogen atom bonded to carbon. Modified (patent application 1986)
-11019 and Japanese Patent Application No. 60-69966), a phosphino group or a phosphonium group bonded to carbon on the surface of a porous inorganic solid? A product chemically modified with a silicon group contained therein (Japanese Patent Application No. 20802/1982) was proposed.

As a result of continued research, the present inventors discovered a catalyst system with even higher activity than the above catalyst. That is, in the present invention, 5iHnC/4-! The present invention relates to a method for producing 7-run, characterized by disproportionation and/or redistribution of chlorosilane represented by l (where 1≦n≦3).

Polysiloxane has siloxane bonds! 1i-0-Uranus 1-
It is a polymer having I in the main chain and organic groups in all or part of the side chains, and is well known in the art. The catalyst used in the present invention, in which at least one of an amino group, an ammonium group, a phosphino group, and a phosphonium group is bonded to a polysiloxane matrix, can be prepared by a known method, such as a sol-gel method.

That is, a functional group-containing polysiloxane can be obtained by hydrolyzing, dehydrating and condensing an organosilicon reagent (such as a silane coupling agent) having a functional group and a hydrolyzable group with a silicic acid compound, and then drying this. At that time, if the functional group in the organosilicon reagent having the above-mentioned functional group and hydrolyzable group is an amine group, ammonium group, phosphino group, or phosphonium group bonded to carbon, the polysiloxane produced is directly treated with Amagi. Can be used as an invention catalyst. If the functional group is a substitutable group or a group capable of addition reaction, after the porous polysiloxane is formed, it becomes an amino group, an ammonium group, a phosphine group, or a phosphonium group! ':x f
The catalyst of the present invention can be obtained by bonding by Tl conversion or addition reaction. The amine group or phosphino group is particularly preferably 5th class, and the ammonium group or haphosphonium group is particularly preferably quaternary.

Organosilicon reagent having a functional group and a hydrolyzable group As an organosilicon reagent having a functional group and a hydrolyzable group, Japanese Patent Application No. 1986-
．． No. 11019, No. 60-20802, and No. 60-
69966, Y is a primary to tertiary amino group -nR1p/'', a primary to quaternary ammonium group -NR "R'R" There are leaving groups such as carbo/acid groups that can be converted into functional groups, and hydrocarbon groups with unsaturated bonds useful for addition reactions, such as vinyltriethoxy7rane. Y-R- may be a vinyl group. In the above general formula, R is an organic group having a negative to C2 degree, may contain an oxygen atom or a halogen atom, and may be saturated or unsaturated. , may be linear or have a side chain, and may be cyclic or acyclic.When Y is a nitrogen atom-containing group, R1 to R1.
is a hydrogen atom or a C1 to C1° hydrocarbon group, and may contain atoms other than carbon and hydrogen, such as halogen and oxygen atoms. In addition, in the case of an amino group, 1 and 1 are the same, and in the case of an ammonium group, 2 or all of R'', R', and R' are
And in the case of α-oxoamino group -! , or N,! ? , and trowel. Two or all of them may be connected to each other, or itchi~R16 may be a part of R. X- of the ammonium group includes anions such as fluorine, chlorine, bromine, iodine, BF, ON, OH, and carboxylic acid groups.At least one of y, y, and 7 is a hydrolyzable group, Typical examples include chloride, bromide, iodide, alkoxide, amine 7 group, acetoxy group, etc. d, z4.r other than hydrolyzable groups contain an oxygen atom or halogen atom between 1 and 3 degrees like R. Another good hydrocarbon □ group R1R1~RIO
It may be the same or different.

If Y already has a nitrogen atom bonded to carbon, for example if Y has an amine group, an ammonium group, an α-oxoamino group, etc., the polysiloxane formed can be directly disproportionated and/or redistributed into chlorosilane. Can be used as a reaction catalyst. In addition, when Y does not contain a nitrogen atom bonded to carbon, that is, when Y is a halogen atom, carboxylic acid group, vinyl group, etc., after producing polysiloxane, a nitrogen compound such as amine, amide, urea, etc. A catalyst suitable for the present invention having an organic silicon group containing a nitrogen atom bonded to carbon can be obtained by carrying out an addition or substitution reaction.

The above organosilicon reagents include γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltris(
β-methoxyethoxy)silane, acetoxyethyltrichloro7rane, r-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, bis(2-hydroxyethyl)aminopropyltriethoxysilane , γ-nyreidopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, 4-chlorophenyltrichlorosilane, chloromethyltrimethoxysilane,
2-chloroetheltrichlorosilane, chloromethyltrichlorosilane, chloromethylmethoxydimethylsilane,
8-bromooctyltrichlorosilane, P (chloromethyl)phenyltrichlorosilane, trimethyl (γ-
trimethoxysilylpropyl) ammonium chloride,
Trimethyl(p-4rimethoxysilylbenzyl)ammonium chloride, octadecyldimethyl(3-()rimethoxysilyl)propyl]ammonium chloride 17),
7-4 cutinyltrichlorosilane, dodecyldimethyl γ
-(trimethoxysilyl)propylammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, methyl(γ-methyldimethoxysilylpropyl)morpholinium chloride)”,
2-(2-() IJdichlorolyl)ethylcopyridine, 1-trimethoxysilyl-2-(p,m-chloromethyl)phenylethane, N-()rimethoxysilylbrobyl)imidazole, N-)rimethoxy A silicon compound such as silylpropyl-N,N,N-)dimethylammonium chloride can be used.

In other examples, the organosilicon reagent can be an organic group that already contains a phosphorus atom, or a functional group that can be converted into a phosphorus atom-containing group by a substitution or addition reaction. Typical functional groups that can be converted into phosphorus atom-containing groups through substitution or addition reactions include:
Hydrocarbon groups with halogen atoms such as chlorine dibromine and iodine, or leaving groups such as carboxylates represented by acetate (-o-a-aH,), and unsaturated bonds useful for addition reactions. There is.

In this case, like vinyltriethoxysilane, Y7R
- may be a vinyl group.

In the above general formula, R is an organic group of ~C2°, and may contain an oxygen atom or a halogen atom,
It may be saturated or unsaturated, may be linear or have a side chain, and may be cyclic or acyclic. When Y is a phosphorus atom-containing group, R1 and R'' are hydrocarbon groups of ~C!・, and even if they contain atoms such as halogen or oxygen atoms, even if the trowel and ax are connected. Good. 1 to R1 are hydrocarbon groups or hydrogen atoms similar to R' and R'' (however, R4, R1
only one of them may be a hydrogen atom), and they may be connected to each other. X- of the phosphonium group is fluorine, chlorine, bromine, iodine, BF, , 1010. .

ON, 01 (, is an anion of carboxylate 4).

At least one of zt, 7, and zS is a hydrolyzable group, typically chloride, bromide, iodide, alkoxide, amine group, acetoxy group, or the like.

Other than the hydrolyzable group, y and 7.7 are C1 to C2 as in R.
R is a hydrocarbon group which may contain an oxygen atom or a halogen atom, and may be the same as or different from R and RE to l. If Y already has a phosphorus atom bonded to carbon, that is, if Y is a phosphite group or a phosphonium group, the generated polysiloxane can be used as a catalyst for the disproportionation and/or redistribution reaction of chlorosilane. Can be used. In addition, when Y is a phosphorus atom bonded to carbon, that is, a functional group that can be converted into a phosphorus atom-containing group such as a halogen atom without a phosph-ino group or a phosphonium group, a carboxylate, or a hydrocarbon group having an unsaturated bond. By adding or substituting a phosphorus compound after producing polysiloxane, it is possible to produce the desired polysiloxane containing a phosphino group or phosphonium group bonded to carbon.

The above-mentioned phosphino group may be primary to tertiary, but tertiary is preferable. In addition, the phosphonium group is the first
It may be of grade to grade 4, but tertiary or quaternary is preferable.

Examples of the phosphorus compounds include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, trichlorohexylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

Dimethylphenylphosphine/, triphenylphosphine, tris(2,6-cymethoxyphenyl)phosphine,
Diphenylphosphine, dimethylphosphine, diethylphosphine, dicyclohexylphosphine, bis(2,
Examples include 6-cymethoxyphenyl)phosphine.

The reagents include triphenyl(γ-trimethoxysilylpropyl)phosphonium chloride, trimethyl(trimethoxysilylmethyl)phosphonium chloride, and triphenyl(trimethoxysilylmethyl)phosphonium chloride.

In addition to those that already have a phosphino group or phosphonium group such as diethyl (trimethoxysilylmethyl) phosphine and triphenyl (p-1rimethoxyphenyl) phosphonium chloride, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, and vinyltriethoxy Silane.

Vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, vinylmethyldichlorosilane, vinyldimethylchlorosilane.

Acetoxyethyltrichlorosilane, 4-chloroo7
z = trichloro7rane, chloromethyltrimethoxysilane, 2-chloroetheltrichlorosilane, chloromethyltrichlorosilane, chloromethylmethquine dimethylsilane, 8-bromooctyltrichlorosilane, p-(
Chloromethyl) phenyltrichlorosilane, 7-octynyltrichlorosilane, 1-trimethoxysilyl-2-
An organosilicon compound having a functional group convertible to a phosphorus atom-containing group such as (p, m -10 methyl) phenylethane can be used.

In yet another example, the organosilicon reagent is represented by the general formula:

(Y-R-) zsiZ4-z (1=
2 or 5) or AmN(-R-EliZ,), rrl(
m as O or 1) or AnNe(-R-8iZ3
) a-HXe (n -0, 1 or 2) Yi, -NH,,
-NHRI, -NRlm te surface 7 mino group,
Al-Iha, -HeH,,ze, -N”E[,RE-
Xe.

-N'f3HRIRLxe, -N$RIR"um-x
It may be a nitrogen atom-containing group such as '9 Teab Salel 77 Mo' or a functional group that can be converted into a nitrogen atom-containing group by a substitution reaction or an addition reaction.

The functional group is a halogen atom such as chlorine, bromine, 'iodine, or an acetate group (CH, -(!-0-)
There are carboxylic acid groups such as , and hydrocarbon groups having unsaturated bonds useful in addition reactions. In this case, Y-R- may be a vinyl group as in divinyljethoxysilane.

R1, H snow, % is hydrogen atom or carbon number 1-20
It is a hydrocarbon group that may contain atoms other than carbon and hydrogen such as oxygen atoms or nitrogen atoms, and may be saturated or unsaturated, and may be linear or have side chains. , may be cyclic or acyclic. Further, when Y is an amino group, R1 and R'' may be connected to each other, and when Y is an ammonium group, two or all of RE, R1, and R1 may be connected to each other, and Y is α- In the case of an oxo-amino group, R1, R1, two or all of R1 may be connected to each other, or may be just a part of them.

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.

Among those bonded to one silicon atom, at least one of 2 is a hydrolyzable group, and representative hydrolyzable groups include halogen, alkoxy7 group, amine group, and acetoxy group. Also, among 2, those other than the hydrolyzable group have 1 to 2 carbon atoms.
0 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 2 a carbon atoms, and may contain atoms other than carbon and hydrogen, such as a halogen atom and an oxygen atom.

Xe is fluorine, chlorine, bromine, iodine + B'4 ect
o, , ON, an anion such as a carboxylic acid group.

The above general formula is shown in more detail as follows.

, m-R,n/'St In the formula, Y', Y'l, Ylll are the above Y,
R', R''.

yellow, RIll are the above R, A', A''
is represented by the above A, and zl to z12 are represented by the same definition as in 2 above.

The above organosilicon reagent includes bis(S-(N).

N-dimethylamino)propyl]dimethoxy7rane, tris(5-(N,N-diethylamino)propyl]methoxy7rane, bis(3-()ethoxysilyl)propyl)amine, bis[5-(triethoxysilyl) ) propylcomethylamine, bis(p-()rimethoxysilyl)phenylmethyl]ethylamine, trisC3-Ctriethoxysilyl)propyl]amine, tris(p-(
triethoxy7lyl)phenylmethyl]amine, bis(
3-()ethoxysilyl)propyl fudimethylammonium chloride, bis(p-()!Jmethoxysilyl)
phenylmethyl]dimethylammonium bromide, tris[3-(triethoxy7lyl)propyl]benzylammonium chloride, tris(p-()rimethoxysilyl)phenylmethylcomethylammonium chloride,
Tetrakis(3-()ethoxysilyl)propyl]ammonium chloride, Methyltris(γ-trimethoxysilylpropyl)ammonium chloride, Tris(!S
In addition to nitrogen-containing reagents such as -(tritoxysilyl)propyl]ammonium chloride, nitrogen-free reagents include bis(3-chloropropyl)dichlorosilane, tris(3-chloropropyl)chlorosilane, and divinyljethoxysilane. , trivinylmonoethoxysilane,
etc. can be used.

silicic acid compound As a silicic acid compound, 81(OR)4 (R is methyl.

These are alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 80C-butyl, and tertiary-butyl, and they may all be the same or different from each other. In addition to silicic acid esters represented by ] and water-soluble silicates such as sodium silicate and potassium silicate, silicic acid compounds oligomerized by siloxane bonds, that is, (RO),
5i-o-at (oR), Schiffoxane.

Trisiloxanes such as OR (RO), 5l-o-sl-o-sl (oR) [ROR is defined as above], or colloidal silica in which an inorganic silicate forms a colloid can be used.

Examples of silicic acid compounds include the following.

Esters: ethyl silicate, methyl silicate, silicon ff1
-n-propyl, isopropyl silicate, n-butyl silicate, 080-butyl silicate, ibutyl silicate, kirgt (2-ethylhexyl).

Silicic acid (2-methoxyethyl), Phenyl ioate, hexaethoxydisi Roxane.

Silicates: Sodium orthosilicate, water glass, sodium metasilicate, colloidal silica.

A known method can be used to produce polysiloxane from the above raw materials. For example, metal alkoxides?
Hydrolysis, dehydration condensation, gelation, and drying to form a porous gel? This is well known in the art as the so-called sol-gel process. In this case, it is also known to use an acid and/or alkali as a catalyst and an alcohol as a solvent. As the acid, a dilute aqueous acid solution such as dilute hydrochloric acid or dilute sulfuric acid is preferably used, and as the alkali, a weakly basic one such as aqueous ammonia is preferably used. In particular, the presence of an alkaline catalyst tends to produce a porous gel. In addition to alcohol, polar solvents such as N,N-dimethylformamide are preferably used as the heart medium.

In addition, the gelation temperature is usually selected within the range of 0°C to 100'C, but in order to obtain a porous gel, the raw material.

The catalyst is chosen in conjunction with other factors such as catalyst concentration (pH), gelling time, etc. That is, care should be taken to obtain a porous gel with a large average pore diameter, which is particularly preferable as a catalyst for disproportionation of chlorosilane.

These are commonly found in, for example, Chapter 18 of the 1984 edition of "New Glasses and Their Physical Properties" (published by Hong Ying System Research Institute) or Journal of Chromatography (1976), Vol. 125, pp. 115-117. An explanation or specific method is described.

Next, some embodiments of the method for preparing polysiloxane will be illustrated, but these do not necessarily limit the present invention.

(1) Add an acid catalyst and an alcohol solvent to a silicate ester and an organosilicon reagent containing a functional group and a hydrolyzable group, perform hydrolysis and dehydration condensation to produce a functional group-bonded polyalkoxysiloxane, and further add aqueous ammonia and alcohol. gelatinized,
After drying, a functionalized polysiloxane is obtained.

(2) Adding acid catalyst and alcohol to silicate ester,
□ A polyalkoxysiloxane is obtained, an organosilicon reagent containing a functional group and a hydrolyzable group, water and alcohol are added thereto, and an alkali catalyst is further added to gel it to obtain a functional group-bonded polysiloxane.

(3) Adding an acid catalyst, water and alcohol to colloidal silica and an organosilicon reagent containing a functional group and a hydrolyzable group,
Dry to obtain functional group-bonded silica.

(4) An acid catalyst and water are added to an aqueous solution of sodium silicate and a water-soluble silane coupling agent to obtain a polysiloxane to which functional groups are bonded.

Disproportionation and/or Redistribution Reaction Or:I The disproportionation and/or redistribution reaction of silane may be carried out in a liquid phase or a gas phase, and may be a flow type or a batch type, but the gas phase can be performed at a lower pressure, In addition, a gas phase is preferable because it allows easy separation of the catalyst and products, and a flow type is preferable. The reaction temperature is 0 to 500°C, preferably 20 to 200°C, and the pressure is normal pressure to 50 kl/crx" (gauge pressure).
The contact time can be in the range of 11 to 20 seconds.

Further, the raw material chlorosilane is a chlorohydrogenated silane represented by BLHrxOlin (where 1≦n≦3). That is, one type of monochlorosilane, dichlorosilane, or trichlorosilane, or a mixture of two or more types of arbitrary composition can be used, and it may be diluted with an inert fluid such as nitrogen gas.

Effects of the Invention The catalyst of the present invention, in which at least one type of 7mino group, ammonium group, phosphino group, or phosphonium group is bonded to the polysiloxa/matrix, does not have the problem of swelling unlike previous ion exchange resin-based catalysts. It has excellent heat resistance and chemical resistance, and is highly active because it has a larger amount of functional groups that can be introduced than those obtained by chemically modifying the surface of a porous inorganic solid with a silane coupling agent or the like.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited thereto.

In addition, in the examples, all analyzes of reaction products were performed using a ChromoSorp 102 full-term column with a column temperature of 130°C.
The analysis was performed using a gas chromatograph using OD (carrier gas is helium).

Example-1 1) Preparation of 3-chloropropyl group-containing polysiloxane Ethyl silicate 51.2- and 3-chloropropyltrimethoxysilane 119F are mixed with 25-ethanol, and 101N hydrochloric acid 5-5- After reacting at room temperature for 1 hour, ethanol was distilled off under reduced pressure to obtain 24 tons of non-volatile liquid. To this nonvolatile liquid were added 12-cyclohexane, 20-ethanol, and 60 WLt of water, and 10-rich concentrated aqueous ammonia was added dropwise while stirring. The generated white precipitate was collected by filtration, washed with water, dried at 100℃, and heated to 16F.
A 3-chloropropyl group-containing polysiloxane was obtained.

2.02F of the 3-chloropropyl group-containing polysiloxane prepared in 1) above, 2.0-dimethyl-n-dodecylamine and 20-N,N-dimethylformamide as a solvent were heated in a nitrogen atmosphere with a cooling tube. 1 out of 50 go flasks
It was heated at 50°C for 20 hours. The boria 0 xane solid was collected by filtration, washed with methanol and chloroform, air-dried, and then dried in the air at 100°C for 12 hours to obtain a porous polysiloxane solid 2.2Sf with quaternary ammonium groups bonded. .

The porous polysiloxane solid prepared in 2) above was placed as a catalyst in a glass gas-phase atmospheric pressure flow reactor (inner diameter 5 mm), heated at 110°C for 1 hour in a nitrogen stream, and then the reaction layer was maintained at a predetermined temperature. The disproportionation reaction was carried out using 51 acl/horse (5/7) mixed gas (1 atm) as feed. The results are shown in Table-1.

Table-1 Example-2 3-chloropropyl group-containing polysiloxane prepared in Example-1 1.60r, 1. Oml of di-n-octylamine and 20-ml of N,N-dimethylformamide were placed in a 50wt flask equipped with a condenser and heated to 150ml under a nitrogen atmosphere.
℃ for 12 hours. Subsequently, the product was treated in the same manner as in Example 2 to obtain 1.8 St of porous polysiloxane solid to which a tertiary amine was bonded.

Using the porous polysiloxane solid prepared in Example 21) as a catalyst, a disproportionation reaction of trichlorosilane was carried out in the same manner as in Example 15). The results are shown in Table-2.

Table-2 Example-3 3-chloropropyl group-containing polysiloxane t35f prepared in Example-11), tri-n-butylphosphine 0
．． 511+7! and 10-N.

150% N-dimethylformamide in the same manner as in Example-2.
℃ for 20 hours, followed by washing with methanol and chloroform, air drying, and then drying in the air at 100℃ for 10 hours to obtain a porous polysiloxane solid 1.46 F to which a quaternary phosphonium group was bonded.

2) Disproportionation reaction of trichlorosilane A disproportionation reaction of trichlorosilane was carried out by the method of Example 13) using the porous polysiloxane solid prepared in Example 51) above as a catalyst. The results are shown in Table-5.

Table 5 Example 4 The 3-chloropropyl group-containing polysiloxane t89f prepared in 1) of Example 1 was placed in a three-hole flask equipped with a condenser, and the inside was sufficiently replaced with nitrogen. 1.41-moE/1 of 4-(lithiated methyl)pyridine in tetrahydrofuran solution (tetrahydro-7
During the run, gold (prepared from 11J thium, bromobenzene, and r-picoline) was added and heated under reflux for 1 hour. After cooling, 10-methanol was added to decompose the remaining lithium reagent.
Collect the filtered solid portion and dilute with methanol solvent.
Soxhlet extraction was performed for 2 hours. 10 in fresh air after air drying
It was dried at 0° C. for 10 hours to obtain a porous polysiloxane solid to which r-alkylpyridine was bonded.

A disproportionation reaction of trichlorosilane was carried out by the method of Example 13) using the porous polysiloxa/solid 451n9 prepared in Example 41) as a catalyst. The results are shown in Table 4.

Table-4

Claims (1)

[Claims] In the presence of a catalyst in which at least one type of amino group, ammonium group, phosphino group, or phosphonium group is bonded to a polysiloxane matrix, chlorosilane represented by SiHnCl_4_-_n (however, 1≦n≦3) is disproportionated and/or A method for producing silane characterized by redistribution