JPS61232214A - Production of silane - Google Patents

Abstract

PURPOSE:To carry out the disproportionation and/or redistribution reaction of a chlorosilane, in high efficiency, by using a highly active heat-resistant catalyst obtained by modifying a porous inorganic solid with an amine-type organic silicon compound. CONSTITUTION:Silane is produced by the disproportionation and/or redistribution reaction of a chlorosilane of formula SiHnCl4-n (1<=n<=3) in the presence of a catalyst obtained by the chemical modification of the surface of a porous inorganic solid with an organic silicon reagent of formula I (l is 2 or 3), formula II (m is 0 or 1) or formula III (n is 0, 1 or 2). In the formulas I-III, Y is a nitrogen-containing group selected from primary - tertiary amino group, pri mary - quaternary ammonium group and alpha-oxoamino group; R is 1-20C hydro carbon group which may contain halogen atom, oxygen atom, etc.; Z groups are bonded to Si atom; at least one of Z is hydrolyzable group and the others are 1-20C hydrocarbon group which may contain halogen atom, oxygen atom, etc.; A is H or 1-20C hydrocarbon group which may contain halogen atom, oxygen atom; X is anion such as halogen, BF4, OH, ClO4, CN, carboxylic acid group, etc.

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing silanes, particularly monosilanes and/or chlorosilanes, by disproportionation/or redistribution reactions of chlorohydrogenated silanes.

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

281HC4: 81404 + 8101m2Si
H204ヰ 81HOts +81H3Ct2B1HI
Ct: 81H4+5iHIC4 The above catalysts include insoluble solid anion conversion resins containing amino groups etc. (Japanese Unexamined Patent Publication No. 50-119798), trimethylamine or dimethylethylamine (Japanese Unexamined Patent Publication No. 59-121110), palladium (Unexamined Japanese Patent Publication No. 59-121110), (Bulletin No. 54-59250)
, inorganic solid base (% Kaimei No. 59-174515) α
-Compounds containing oxoamine groups (JP-A-59-5161
7), tetraalkylurea (Special Publication No. 140, 1983)
No. 46) N-substituted α-pyrrolidone with a hydrocarbon group (% Komei No. 55-14045), a cation exchanger having a sulfonic acid group (Japanese Unexamined Patent Publication No. 59-164614), amino alcohol and silica Reaction product (Unexamined Japanese Patent Publication No. 5
9-156907), etc. 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 or redistribution reaction of chlorohydrogenated silanes have been proposed, but in particular, conventional solid anion exchange resin-based catalysts have poor heat resistance. However, the mechanical strength was poor, there were problems such as swelling peculiar to ion exchange resins, 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.

Means for Solving the Problems 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, by chemically modifying the inorganic optical surface with a silane coupling agent,
Although it is already known in the art that the organic-inorganic adhesion, strength, and electrical properties of various composite materials can be significantly improved, the present inventors have discovered that chlorosilane can be disproportionated or recycled. While researching and developing useful catalysts for partition reactions, it has been found that porous inorganic solids are chemically modified with amine-based organosilicon compounds for the above reactions.
Discovered that it is a catalyst with high activity and good heat resistance.
This is a perfect companion to the present invention.

That is, the present invention provides a method for treating a chlorosilane represented by 81Hn04-n (where 1≦n≦3) in the presence of a catalyst in which a different surface of a porous inorganic solid is chemically modified with an organosilicon group containing a nitrogen atom bonded to carbon. It relates to a process for the development of silanes, in particular monosilanes and/or chlorosilanes, characterized by disproportionation and/or redistribution.

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 general formula as follows. .

(Y -R-)t S i Z4-Z (Z
=2 or 3) or mN(-R-8iZs)s-m
(m''' or 1) or mNe (-R-sizs)
4-nxe (n=o* 1 or 2) Y is -NH,,
-N plate 1, -NRIR” armie/i
,sruih,-y'Bm, ,xC',-Ne)H
! R1-xe.

-NeHx! xz-xe, -x%*RzRs-x'
The element υ may be a nitrogen atom-containing group, or it may be a functional group that can be converted into a nitrogen atom-containing group through a substitution reaction or an addition reaction.

The functional groups include chlorine and bromine.

There are hydrocarbon groups with useful unsaturated bonds, such as halogen atoms such as iodine, or acetic acid groups. In this case, KY-R- may be a vinyl group as in divinyljethoxysilane.

R1, R”, R1 is a hydrogen atom or has 1 to 2 carbon atoms
The hydrocarbon group of ゜a) may contain atoms other than carbon or hydrogen, such as oxygen atoms or halogen atoms, and may be saturated or unsaturated, and may be linear or have a side chain. , may be cyclic or acyclic. Furthermore, when Y is an amino group, R1 and R1 may be connected to each other, and when Y is an ammonium group, two or all of R1, R2, and Rm may be connected to each other (, Y is α- In the case of an oxo-amino group, two or all of R1, 1%N, and R3 may be connected to each other, or may be only a part of them.

R is a hydrocarbon group having 1 to 20 carbon atoms, which may contain atoms other than carbon or 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.

In 2, 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 bare surface. Examples of 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. 34-58. Also, of 2, those other than the hydrolyzable group have 1 carbon number.
~20 hydrocarbon groups, which may contain an oxygen atom or a halogen atom, and may be the same or different from each other.

The group 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.

xe is fluorine, chlorine, bromine, iodine #BP4e
These are anions such as OtO, ON, and carbon radicals.

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

In the formula, Y, Y, and Y are the above Y and R, R, and R.

R-'F1 Said FL t, A', A't! Said A, Z1
~zll has the same definition as 2 above.

When Y does not have a nitrogen atom bonded to carbon, the reagent may be subjected to 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 nitrogen atom-containing group.

The above-mentioned different surface modification reagent includes bis(3-(N).

N-dimethylamino)propyl fudimethoxysilane, tris(5-(N,N-diethylamino)propyl]methoxysilane, bis(3-()IJethoxysilyl)propyl)amine, bis[3-(triethoxysilyl)propyl comethylamine y, and
Vmethoxysilyl)phenylmethyl]amine, bisC3
-Ctriethoxysilyl)propyl fudimethylammonium chloride, bis(p-()rimethoxysilyl)phenylmethyl]dimethylammonium bromide, tris[3-(triethoxysilyl)propyl]benzylammonium chloride, tris(p-() methyltris(r-trimethoxysilyl)phenylmethyl]methylammonium chloride, tetrakis(5-()ethoxysilyl)propyl)ammonium chloride, methyltris(r-trimethoxysilylglobil)anthoniumchloride)'%)'JS[5 −
In addition to nitrogen-containing modification reagents such as (()rimethoxysilyl)propyl]ammonicum chloride, nitrogen-free modification reagents include bis(3-chloropropyl)dichlorosilane, tris(5mchloropropyl)chlorosilane,
Divinyljethoxysilane/trivinylmonoethoxysilane, etc. can be used.

In the method of chemically modifying the optical surface of a porous inorganic solid (silylation), both of them are heated at room temperature or above room temperature, preferably at
It is sufficient to contact the material at 0 to 300°C, and water may be allowed to coexist to promote hydrolysis of the hydrolyzable group. For substances with poor solubility in water, a solvent such as water-alcohol type may be used. You can also do it.

Porous inorganic solids Porous inorganic solids that can be used in the present invention include quartz, Novaki≧lite, wet process silica, colloidal silica, silica aerogel, silica sand, and silica stone.

Silica such as diatomaceous earth, tridymite, cristobalite, kaolin, talc, wollastonite, asbestos, calcium silicate,! acid aluminum.

Zeolite, bentonite, activated clay, porous glass,
Silicic salts such as magnesium silicate and zirconium silicate, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as liquefied magnesium, aluminum hydroxide, calcium hydroxide, and titanium hydroxide, zinc oxide, iron oxide, and magnesium oxide. , metal intensifiers such as titania, silica/alumina, zirconia, & chloride, calcium oxide, vanadium oxide, tin oxide, bismuth oxide, carbides such as silicon carbide, titanium carbide, zirconium carbide, boron 1 carbide, silicon nitride.

Nitrides such as boron nitride, titanium nitride, and zirconium nitride, and metals such as aluminum, copper, iron, nickel, titanium, zirconium, and tungsten can be used, and particularly preferred are silica, titania, and porous glass. Its surface area is 1-/f or more, usually 2~IQO
Om''/f is used.

Disproportionation and/or Exploration Distribution Reaction The disproportionation and/or redistribution reaction of chlorosilanes may be carried out in liquid phase or gas phase, and may be carried out in flow or batchwise manner, but gas phase allows for lower pressure, and is easier to carry out with a catalyst. A gas phase is preferable because it allows separation of substances easily, and a flow type is preferable. The reaction temperature is 0 to 300°C, preferably 20 to 200°C, and the pressure is normal pressure to 50 Yu/c! n'' (gauge pressure) and contact time α in the range of 1 to 20 seconds.

In addition, the raw material chlorosilane is 81Hn (t4-n (
However, it is a chlorohydrogenated silane in which 1≦n≦3). That is, a mixture of monochlorosilane, dichlorosilane, or trichlorosilane having a Sakura composition of Class 111i or Class 281 or higher may be used, and may be diluted with an inert fluid such as nitrogen gas.

Effects of the Invention When a porous inorganic solid optical surface is chemically modified with an organosilicon salt having nine nitrogen atoms bonded to carbon and a chlorosilane disproportionation and/or redistribution reaction is carried out in the presence of a nine-nitrogen catalyst, conventional negative The ion-exchange resin-based catalyst F can be carried out at high temperatures, 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 by way of examples, but the present invention is not limited thereto.

In addition, in the examples, all analyzes of reaction products were carried out using a 2 m
The analysis was performed using a TOD gas chromatograph using a v-1 packed column and a column temperature of 160°C (carrier gas is helium).

Example-1 γ-Aminopropyltriethoxysilane j1.06f was placed in a 100-ml flask that was sufficiently purged with nitrogen.

r-chlorozlobiltrimethoxysilane19. ．． 861
, and 25-N,N-dimethylformamide as a solvent, and heated under reflux for 24 hours in an oil bath at 165°C. Then, the solvent was distilled off under reduced pressure (5 mHf), and 2
5.2f oily tris(5-()alkoxysilyl)propyl]ammo=f)mu1 mouth')Y, m(a4
ca, aH, 51(OR)s)! eC1e (however, R=
= OH3 or O, 'Fis) was obtained. This ammonium salt & Of silica (7 gel from Ditabiline, 50
~60 mesh, dried in air at 120°C for 10 hours) 7.
Of, and 50-chlorobenzene were heated in a 100-flask at 150°C for 5 hours under a nitrogen atmosphere, and then 1
After washing with 00m methanol 3 times and air drying,
After drying at 0°C for 5 hours, the surface was Modified silica a8ft- was obtained.

2.0 cc (α72f) of the modified silica was filled in a glass gas phase flow reactor (inner diameter 10 mm), heated at 110°C for 1 hour in a nitrogen stream, and then heated under normal pressure while keeping the reaction layer at a predetermined temperature. The reaction was carried out using raw material gas (5iHOts/N, mixed gas, molar ratio 50/70). Analyze the product 1 hour after setting the conditions and report the results.
Shown in 1.

Takashi-1 Example-2 N(CHiOHi(Hi5i(OR)) obtained in Example-1
sEs-modified silica 1L1f was placed in a flask with 10-methanol, 1.0-methyl iodide was added, and the mixture was heated at 60C for 1 hour under a nitrogen atmosphere. This was then filtered to recover the modified silica and diluted with 5C1d methanol.
After washing twice, sodium hydrogen carbonate aqueous solution (2f/100m
) and then washed with water.

6N dihydrochloric acid (100) was added to the silica to replace hydrogen carbonate ions with chlorine ions. Next, wash twice with water,
After washing 3 times with 50-methanol and air drying, 100
C. Dry for 12 hours to obtain methyltris(r-)alkoxysilylglobyl)ammonium chloride.

(H3-a6B(aH!aa, cc2-sl(oR)s
)sc! tes'' was modified to obtain L Tasilica 4.1f.

Using 2.0 cc (IIL74 t )l of this modified silica as a catalyst, a disproportionation reaction of trichlorosilane was carried out in the same manner as in Example-1. The results are shown in Table-2.

Table 2 □ Example 3 4.9 f of bis(5-chloropropyl)dimethoxysilane (this was manufactured by Chisso Co., Ltd.) and excess methanol was added to a 100ad7 flask purged with nitrogen. ) and dimethyl-n
-Dodecylamine (manufactured by Tokyo Kasei Co., Ltd.) 10 and 40
- Add N,N-dimethylformamide and 1
Reflux heating was performed for 2 hours. Under reduced pressure (1wmHf) 1
The solvent and unreacted amine were removed at 20 t: and the remaining fraction was washed with toluene (150 m) at 100°C, filtered, and treated with ammonium salt of IAlF (Ct”(n-CuHu)(CHs) x NeCsHs).
zSl(OCHs)zt was obtained.

The ammonium salt2. Of and silica (Fuji Davison Co., Ltd., gel, 50~6o mesh in air at 120℃ 10
drying time) 5at and 60d, N,N-dimethylformamide 1100 - in a flask under nitrogen atmosphere 140
C. After heating for 8 hours, the silica was filtered out and this silica was
After washing 5 times with 0-methanol and air-drying, 100-
'C.

After drying for 12 hours, the surface was
Hs) z81 (OCHs) Obtained ammonium-modified silica.

Using 2.0 cc of the modified silica (I1752), a disproportionation reaction of trichlorosilane was carried out in the same manner as in Example-1. The results are shown in Table-3.

懺　　-3

Claims (1)

[Claims] SiHnCl_4_-_n (where 1≦n
≦3) A method for producing silane, characterized by disproportionation and/or redistribution of chlorosilane represented by (Y-R-)_lSiZ_4_-_l (l = 2 or 3)
or AmN(-R-SiZ_3)_3_-_m(n=0 or 1) or AnN^■(-R-SiZ_3)_4_-_nX^■(
n=0, 1 or 2) (Y is a nitrogen atom-containing group selected from a primary to tertiary amino group, a primary to quaternary ammonium group, or an α-oxo amino group, R is a halogen atom , a C_1 to C_2_0 hydrocarbon group which may contain an oxygen atom, etc., Z
is bonded to a silicon atom, at least one of which is a hydrolyzable group, the others are C_1 to C_2_0 hydrocarbon groups that may contain halogen atoms, oxygen atoms, etc., A is a hydrogen atom, or A halogen atom, a C_1 to C_2_0 hydrocarbon group that may contain an oxygen atom, X is a halogen,
These are anions such as BF_4, OH, ClO_4, CN, and carboxylic acid groups. )