JPS61183111A - Preparation of silane - Google Patents

Abstract

PURPOSE:To prepare silane compds. in high yield at high temp. by disproportionating chlorosilane in the presence of a catalyst comprising a porous inorg. solid having the surface modified chemically with organosilicon groups contg. phosphino group bonded to the carbon atom. CONSTITUTION:Clorosilane expressed by SiHnCl4-n(1<=n<=3) is disproportionated and/or redistributed in the presence of a catalyst comprising a porous inorg. solid having the surface modified (silylated) chemically with organosilicon group contg. phosphino or phosphonium group bonded to C atom. An organosilicon compd. such as triphenyl(gamma-trimethoxysilyl propyl)phosphonium chloride, etc. is used for the surface modifier, and silica, quartz, etc. is used for the porous inorg. solid. The disproportionation and/or redistribution is carried out at 0-300 deg.C reaction temp. under normal pressure - 50kg/cm<2>, for 0.1-20sec contact time. By this method, monosilane and other chlorosilanes different from the starting material are prepd. efficiently.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing silanes, particularly monosilanes and chlorosilanes, by disproportionation and/or redistribution of chlorohydrogenated silanes.

Silane, especially 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 disproportionation or redistribution reaction using chlorosilane as a raw material as shown in the following formula. Catalysts useful for these reactions are being developed.

28 l HOIs d 8 LH*04 + 81
CLa281shiO1,,=Th El 1TIO13+
Si H30t2 BiHlOl g ssH
, + S ta, Ctt As the above catalyst, an insoluble solid anion exchange resin containing an amino group etc. (%
-119798), trimethylamine or dimethylethylamine (JP-A-59-121110)
, palladium (JP-A-54-59230), inorganic solid bases (JP-A-59-174515), compounds containing α-oquinamine groups (JP-A-59-54617), tetraalkylureas (JP-A-59-54617), Kosho 55-14045
Publication No. 2), N-substituted with a hydrocarbon group and nine α-pyrrolidone (
% Publication No. 55-14045), a cation exchanger having a sulfonic acid group (Japanese Unexamined Patent Publication No. 59-164614)
, reaction product of amino alcohol and silica (Unexamined Japanese Patent Publication No. 1983
156907), etc., heterogeneous catalysts are attracting attention.

The aforementioned catalysts that have been proposed as useful catalysts for disproportionation and/or redistribution reactions of chlorohydrogenated silanes, especially those based on solid anion exchange resins, have poor heat resistance, poor mechanical strength, and ion exchange There were problems such as swelling peculiar to the resin, and the catalyst life was also unsatisfactory. 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.

SUMMARY OF THE INVENTION In researching and developing useful catalysts for disproportionation or redistribution reactions of chlorosilanes, the present inventors have particularly focused on organic silicon containing phosphino or phosphonium groups that bond the surface of porous inorganic solids to carbon. The present invention was completed based on the discovery that a catalyst chemically modified with a group has high activity and good heat resistance.

That is, the present invention provides a catalyst in which the surface of a porous inorganic solid is chemically modified with an organosilicon group containing a primary to tertiary phosphino group or a primary to quaternary phosphonium group bonded to carbon. , s 1ancz4-n (where 1≦n≦'5), silanes characterized by disproportionation and /l or redistribution of chlorosilane,
In particular, it relates to a method for producing monosilane and/or chlorosilane.

Techniques for chemically modifying solid surfaces are already well known, such as the treatment of silane with a pulling agent. In other words, silane improves the adhesion between organic and inorganic materials in various composite materials by treating the inorganic surface with a pulling agent.
Although it is already known in the art that strength and electrical properties can be improved, it is surprising that materials chemically modified by the method of the present invention exhibit excellent catalytic activity.

Surface Modification with a Surface Modification Reagent It can be used to modify the surface of a porous inorganic solid with an organosilicon group containing a phosphino group or a phosphonium group bonded to carbon, and Y is a primary to tertiary group. phosphino group, -P/R1 or primary to quaternary
\R1 may be an organic group containing a phosphorus atom, or may be a functional group that can be converted into a syringe atom-containing group by a substitution reaction or an addition reaction. Typical functional groups that can be converted into phosphorus atom-containing groups through substitution or addition reactions are halogen atoms such as chlorine, bromine, and iodine, or acetate (-o-g-aH*) There are leaving groups such as carboxylate represented by , and hydrocarbon groups having unsaturated bonds useful for addition reactions. In this case, Y-R- may be a vinyl group as in vinyltriethoxysilane.

In the above general formula, R is an organic group of 01 to C8°, and may contain an oxygen atom or a 10-gen atom, and may be saturated or unsaturated, and may be linear or have a side chain. may be cyclic or acyclic. When Y is a phosphorus atom-containing group, R1 and R1 are C1 to C1° hydrocarbon groups, and may contain atoms such as halogen and oxygen atoms, and R1 and R1 may be connected. R3-R5 is R
1. Hydrocarbon group or hydrogen atom similar to R1 (however, H
Only one of M, R4, and R1 may be a hydrogen atom), even if they are connected to each other. X- of the phosphonium group is fluorine, chlorine, or bromine.

Iodine + B1'4, Cl0a + ON, OH
, carboxylate, etc. z', z”
, z'' has at least one hydrolyzable group, where the hydrolyzable group reacts with the surface of the porous inorganic solid, leaves it,
Create a bond with the surface or bond the silicon reagents to each other.
-t)-st6 means a group having the function of connecting through a bond. A typical example is chloride.

Bromides, iodides, alkoxides.

These include amine groups and acetoxy groups. Zl, Zl, Zl other than the hydrolyzable group are c, ~Cto +7 as in R
) A hydrocarbon group which may contain an oxygen atom or a halogen atom, which may be the same as or different from H and R1 to R'. When Y already has a phosphorus atom bonded to carbon, that is, when Y is a phosphino group or a phosphonium group, the surface-treated porous inorganic solid can be directly used to disproportionate chlorosilane and /-! or as a catalyst for redistribution reactions. In addition, Y is a phosphorus atom bonded to carbon,
That is, in the case of a functional group that can be converted into a phosphorus atom-containing group such as a halogen atom, a carboxylate, or a hydrocarbon group having an unsaturated bond that does not have a phosphino group or a phosphonium group, the organosilicon modification reagent is (by adding or substituting a phosphorus compound before or after chemical bonding (silylation) to the surface of a solid),
It is possible to prepare a porous inorganic solid catalyst modified with an organosilicon group containing a phosphino group or a phosphonium group bonded to the desired carbon.

The above-mentioned phosphino group may be primary to tertiary, but tertiary is preferable. In addition, the phosphonium group is the first
The phosphorus compounds may be quaternary, but tertiary or quaternary are preferable. Examples of the above phosphorus compounds include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, and tricyclohexylphosphine. , methyldiphenylphosphine, dimethylphenylphosphine, dimethylphenylphosphine, triphenylphosphine, tris(2,6-cymethoxyphenyl)phosphine, diphenylphosphine, dimethylphosphine, diethylphosphine, dicyclohexylphosphine, bis(2,6- ') methoxyphenyl) phosphyl, etc.

The above surface modification reagents include triphenyl(r-trimethoxysilylmethyl)phosphonium chloride, trimethyl(trimethoxysilylmethyl)phosphonium chloride, triphenyl(trimethoxysilylmethyl)phosphonium chloride, and diethyl(trimethoxysilylmethyl)phosphonium chloride.
In addition to those that already have a phosphino group or a phosphonium group such as phosphine, triphenyl(p-)rimethoxyphenyl)phosphonium chloride, r-chloropropyltrimethoxysilane, vinyltrichlorosilane, hinyltriethoxysilane, vinyltrimethoxysilane, Vinyltris(β-MeFoxyethoxy)silane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, acetoxyethyltrichlorosilane, 4-chlorophenyltrichlorosilane, chloromethyltrimethoxysilane, 2
-Chloroethyltrichlorosilane, chloromethyltrichlorosilane, chloromethylmethoxydimethylsilane.

8-bromooctyltrichlorosila/, p-(chloromethyl)phenyltrichlorosilane 7-octynyltrichloro7rane, 1-trimethoxysilyl-2-(p y
An organosilicon compound having a functional group convertible into a phosphorus atom-containing group such as m-chloromethyl)phenylethane can be used. In addition, the method of chemically modifying the surface of a porous inorganic solid (silylation) requires only contacting the two at room temperature or a temperature higher than room temperature, preferably 30 to 300°C, which promotes hydrolysis of the hydrolyzable group. Therefore, water may be present together, or a water-alcohol solvent may be used to improve solubility in water.

Porous inorganic solid Porous inorganic solids that can be used in the present invention include silica, quartz, tubaculite, wet process silica, colloidal silica, and silica aerogel.

Silicon oxide-containing substances such as silica sand, silica stone, diatomaceous earth, tridymite, cristobalite, and kaolin.

Mica, talc, wollastonite, 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, calcium hydroxide, water Hydroxides such as titanium oxide, zinc oxide, and liquefied iron.

Alumina, magnesium oxide, titania, silica/alumina, zirconia, chromium oxide.

Calcium oxide, vanadium oxide, tin oxide.

Metal oxides such as bismuth oxide, carbides such as silicon carbide, titanium carbide, zirconium carbide, and boron carbide, and nitrides such as silicon nitride, boron nitride, titanium nitride, and zirconium nitride.

Aluminum, copper, iron, nickel, titanium.

Metals such as zirconium and tungsten can be used, and the surface area is 1rr? /1 or more 2 usually 2-100oy/
I is used.

The disproportionation and/or redistribution reaction of chlorosilane may be carried out in the liquid phase or gas phase, and may also be carried out in a flow or batch manner, but the gas phase allows for lower pressure and easier separation of the catalyst and products. A gas phase is preferable, and a flow type is preferable. The summer temperature is 0 to 300°C, preferably 20 to 200°C, the pressure is normal pressure to so kg/cd (gauge pressure), and the contact time is 0.1 to 20 seconds.

The raw material chlorosilane is a chlorohydrogenated silane represented by 81HnCtn-n (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.

In the presence of a catalyst in which the surface of a porous inorganic solid is chemically modified with an organosilicon group having a phosphino group or a phosphonium group bonded to carbon, conventional anions are It can be carried out at higher temperatures than exchange resin catalysts, and monosilane and/or chlorosilane different from the raw material can be obtained in good yield.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited thereto. In the Examples, all reaction products were analyzed using a gas chromatograph using helium as a carrier gas (QV-1 column with a column temperature of 160°C).
CD).

Example-1 5.
711 γ-chloropropyltrimethoxysilane (Nippon Unicar-Shiba trade name A-143).

7.5 g of triphenylphosphine (manufactured by Kokan Kagaku).

[L2p of nickel chloride (Ntct, .6H,O) and 40% liter of dimethylformamide (hereinafter abbreviated as DM'F) were added and heated under reflux for 4 hours under normal pressure. then 1 m
The pressure was reduced to HE and volatile components were removed by heating to 150° C. to obtain 1 sg of viscous triphenyl.r-()rimethoxysilylpropyl)phosphonium chloride. This phosphonium salt 50N and 5.57N silica (ID type silica gel manufactured by Fujida Hisson Co., Ltd., 30-60 mesh, pore volume 1,04 cclI #surface area 550 n17
g, dried in air at 120°C for 24 hours) was placed in a 15 ONl flask with a condenser purged with nitrogen,
8G of monochlorobenzene was added, and the mixture was heated under reflux for 3 hours under normal pressure. The insoluble solid components are then collected by filtration,
This was washed three times with 100% methanol and twice with 100% chloroform, air-dried, and then heated to 120°C in the air.
was dried for 12 hours to obtain a quaternary phosphonium group-containing organosilicon-modified silica of &86.9. This solid component α721
(1,92 cc) was filled into a glass vapor phase normal pressure flow reactor (inner diameter 10 M) and heated at 110°C in a nitrogen stream for 1 hour.Then, while keeping the reaction layer at a predetermined temperature, An equalization reaction was performed.

Trichlorosilane is a mixed gas with nitrogen (81[Ot.

/Nz: molar ratio 3/7) and pure dichlorosilane gas were continuously supplied to the reactor. After each reaction condition was specified, the products were analyzed by gas chromatography. The results are shown in Table-1.

Table-1 B1mt3/N, 120 47 - Q, 9
1[L7 74.4 14.0# 62 15
- α6 &7 737 12.0#
24 15 - Q, 4 7.6 82.1
9.9BiEI, OL, 103 28 155
12.0 3&8 3&7 (L9# 65
40 14.5 11.0 3&0 37.9 12
#25. 36 7.0 1&7 46.8
29.4 α1 Example-2 Under nitrogen atmosphere, in a 100-flask with a condenser, 2
Ii r-chloropropyltrimethoxysilane at 251
Dissolve 1 in toluene and add 7.0 I of silica (Fuji Davison Macrobead Silica Gel 5D, 30-6
0 mesh, pore volume t2 S cc/, 9, surface area 260 rr? / I #In air 120℃.

(dried for 12 hours) was added and heated at 110°C for 4 hours. After cooling in the air, filter, and remove the solid components with 50 C of toluene.
After washing twice and air drying, dry in air at 100°C for 8 hours.7.
41! γ-chloropropyltrimethoxysilane modified silica was obtained. 5.0 g of this modified silica! : (L
5-methyldiphenylphosphine, 25-DMF
, and 11 g of nickel chloride (NICt, .6H,O
) was placed in a 50° flask and heated at 150°C under a nitrogen atmosphere.
heated for an hour.

After cooling in the air, it was filtered, the solid component was washed three times with 504 methanol, and after air drying, it was dried in the air at 100°C for 10 hours.
．． 6Il of methyldiphenyl(r-trimethoxysilylpropyl)phosphonium, chloride-modified silica was obtained.

Using this modified silica 175J (1.9 cc), trichlorosilane (BIHc1m
/Nte molar ratio 3/7).

The results are shown in Table-2.

Table-2 1 TIC43/'Hz 12 Q 40 per day
αB 11.0 74°6 1
56# 6255 (1444
859 ρ3# 25 12
(L2 !L5 87.7
46 Example-3 Z to triphenyl γ-(trimethoxysilyl)propylphosphonium chloride asII synthesized in Example-1
sII Titania (manufactured by Diamond Catalyst ■, product name D)
C-312420~60 mesh in air at 100℃24
) and 20-7-chlorobenzene were added, and the mixture was heated under reflux under normal pressure in a nitrogen-purged condenser flask. Next, insoluble solids were separated by filtration, washed twice with 100 sj of chloroform, and after air drying,
It was dried in air at 100° C. for 12 hours to obtain titania 2.8I with quaternary phosphonium chloride chemically bonded to the surface. Using this modified titania t3J (2,0 cc) as a catalyst, trichlorosilane (' 8 i HOL@/N
*; molar ratio 3/7) disproportionation reaction was carried out in the same manner as in Example-1.

The results are shown in Table-3.

Table-3 ('C) (m1n-1) stu, cz stH,
cz, 81304 BICL4S1wts/H*9
9! 18 α1 016 711L9 1
α3# 61 4ONO34,57,
5# 215 4G
4.7 9G, 9 4.4 Example-
4 Under a nitrogen atmosphere, in a flask with a condenser, γ-chloropropyltriethoxysilane h q I
and heated under reflux for 12 hours. Next, by vacuum distillation,
Removal of volatile components yielded 7.711 viscous tri-n-butyl γ-(triethoxysilylprobyl)phosphonium chloride.

This phosphonium salt α45,9 and 58 g of silica (same as that used in Example 1) were placed in a flask equipped with a condenser, 20 g of monochlorobenzene was added, and the mixture was heated under reflux under a nitrogen atmosphere.

After cooling in air, insoluble solid components were separated by filtration, washed three times with 100 methanol, air-dried, and heated to 100°C in air.
The mixture was dried for 12 hours to obtain 4.211 tetraalkylphosphonium-type organosilicon-modified silica. Using the modified silica as a catalyst, trichlorosilane (
A disproportionation reaction was carried out at a molar ratio of 81HO4/N3 (3/7).

The results are shown in Table 4.

Table-4! 31H(:!4/)I, 99 40 CL
5 9.5 8[L7 9.6# 61 5
7 α2 44 8z3&1s 23
57 2.7 9482.5 Example-5 In a 100-flask with a condenser under a nitrogen atmosphere,
679 γ-chloropropyltrimethoxysilane to 50
- dissolved in toluene and added 16.5M+ silica (
The same material used in Example 1) was added thereto, and the mixture was heated under reflux for 5 hours under normal pressure.

After cooling in air, the solid component obtained by filtration was washed three times with 50-g of toluene, air-dried, and then dried in air at 120°C for 12 hours. T-chloropropyltrimethoxysilane modified silica was obtained.

This modified silica15. O, i9 into a 250-flask, 50. - Add the tetrahydrofuran solution of R1 and stir under nitrogen atmosphere, and add 100 d of the tetrahydrofuran solution of bis(O-methoxyphenyl)phosphinolithium ()lis(0-methoxyphenyl)phosphine 52I and 3 g of metal lithium LL in tetrahydrofuran at 0°C. It is obtained by reacting inside. 2-311 bis(0-methoxyphenyl)phosphinolithium present in 1004) was gradually added over 30 minutes and reacted at this temperature for 1 hour. Next, an aqueous solution 20- containing ammonium chloride of No. 11 was added to decompose the excess bis(〇-methoxyphenyl)phosphinolithium, and then the insoluble solid was separated and treated twice with 100 No. of tetrahydrofuran under a nitrogen atmosphere. 100m
The resulting product was washed twice with methanol, air-dried, and then dried under reduced pressure at 100° C. for 2 hours to obtain organosilicon compound-modified silica 1&8I to which diallylphosphino groups were bonded. This modified silica 2
．． Using OCQ (Q, 79 g), a disproportionation reaction of trichlorosilane (5 tucLs/L, molar ratio 5/7) was carried out in the same manner as in Example-1.

The results are shown in Table-5.

Table-5 B'H"As/'Hz 110 42 a4
a8 8a6 1a262 38 0.1 4.
4 9α64.9# 35 41 0
2.2 95.4 2.4 Procedural Amendment Written March y, 1985

Claims (1)

[Claims] In the presence of a catalyst in which the surface of a porous inorganic solid is chemically modified with an organic silicon group containing a phosphino group or a phosphonium group bonded to carbon,
≦3) A method for producing silane, which comprises disproportionation and/or redistribution of chlorosilane.