JPS616116A - Manufacture of silane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel method for producing silane, particularly to a method for producing silane by disproportionation reaction of chlorosilane such as trichlorosilane and dichlorosilane.

(Prior art) Chlorone, which forms a silicon-hydrogen bond (Si-H), can cause addition reactions to organic compounds with unsaturated bonds, so it is used to synthesize various organic chloros/ranes. It is a very useful silicon compound with
Y, Lukevits & M, G, Voro
nkov.

“Organic Insanyong reaction of Group 1V elements
icInsertion Reactions o
f Group IV Elements)''
.

Con5ulants Bureau, New York
K, 1966). In the process of manufacturing semiconductor silicon from industrial metal silicon, trichloro7rane is widely known as an intermediate substance, but in order to manufacture semiconductor silicon of high purity, industrial metal silicon with many impurities is mixed with hydrogen chloride. It is reacted and converted to trichloro/ran, which is purified and then aged and reduced to obtain highly pure semiconductor silicon (tail (F,
A. Padovani, U.S. Pat. No. 4,092,466
issue).

As the semiconductor industry developed, the demand for semiconductor silicon increased, and there was a strong interest in improving its manufacturing process.Thus, trichloro-7rane was converted to dichloro-7rane and 7rane, which were easy to reduce and produce, and semiconductor silicon The method of obtaining θ has been improved (L, H, Coleman.

(U.S. Pat. No. 4,340,574). Therefore, the industrially important IW of chloro/ran is 1 day? If you have 1 high on the left, you will get 8.

Chloro-7rane, which forms the bond between silicon and hydrogen, is obtained by reacting bonded silicon and hydrogen chloride using copper as a catalyst, but since this reaction is exothermic, a fluidized reactor is used industrially. This removes the heat of reaction. This is because if reaction temperature #1 cannot be controlled, the amount of by-products will increase, making it uneconomical. However, even if the reaction conditions are well adjusted to section A, only a very small amount of the expected -nochlorosilane yf'r- is obtained, and the main product is trichloro 7 run, about 80 t is obtained, and then About 15% of tetrachloro7rane is obtained. Therefore, dichloro7rane and 7rane can be converted from trichloropuran to cyclolonrane and tetrachlorosilane by a disproportionation reaction, and then silane can be converted from this 2chlorosilane by the same method (
Litteral, C.J., U.S. Patent No. 411384
No. 5).

The disproportionation reaction is a reaction in which hydrogen bonded to silicon gathers only with hydrogen, and chlorine gathers only with chlorine, and they separate into compounds in which one contains more hydrogen and the other contains more chlorine.
This reaction always requires a catalyst, and various types of catalysts have been used in the past, but there are not many that are commercially viable.

(Problems to be Solved by the Invention) Conventionally, Lewis acids such as aluminum chloride and boron hexachloride have been used as catalysts (C, E, Erckson).

U.S. Pat.
, L, Baley, U.S. Pat. No. 2,732,282), carbon powder, alkali metal salts, etc. were used (M,
Kinger, US%ffff No. 36275 F1,
Catalysts such as aluminum chloride and boron hexachloride have a rating of 4 points, which allows them to be easily separated from the product. (The boiling point of trichloro/ran is 62°C, the boiling point of dichloro1] is 8°C, and the single point i of silane is -112°C. Therefore, if reaction 7A is to be carried out properly, the pressure in the reaction tank must be kept low.Therefore, there are many continuous points in the operation of the process. Since the temperature must be raised to 650℃, the practicality is extremely limited, and if nitrile or aminated additives are used as a catalyst, the reaction temperature is 100 to 150℃. However, the reaction time is long and the catalyst is exposed to the product after the reaction, making it difficult to fractionate the catalyst from the product. It must go through a distillation process.

In this way, you can separate the products from each other! ! ]-type catalysts must be able to act as a reaction source, and organic catalysts with low reaction temperatures have a light weight of Nf because the catalyst enters the product after the reaction. Therefore, a method that has the advantages of these two types of catalysts and uses an organic ion exchange resin substituted with a quaternary alkyl ammonium salt as a catalyst that complements the pano catalyst and converts it to trichloro7ran is recommended. (J, Bakay, US Pat. No. 3,928,542). Since the ion exchange resin is not soluble in chlorosilane, it is easily separated, and the reaction occurs at a temperature of 100° C. or less, and the reaction time is within 60 minutes, which is the shortest.

Ion exchange 3Q IJ fats that can be used for this purpose include:
Amberyst A-2 from Rohm and Hass in the United States
1 and 8-26, Amberite IRA-400, etc. are used, and Kochi['s Lord 1! It is known as the easiest catalyst to use in a medium. However, since such a catalyst has a low specific gravity of the ion-blended resin, it is troublesome that it must be packed together with a support to prevent rolling weight in continuous processes. The disadvantage is that it cannot be used for a long time because the bond between the quaternary alkyl ammonium salt and the quaternary alkyl ammonium salt is destroyed. It is considered to be something that comes. Therefore, in order to use these various ion-exchanged 194 fats as catalysts, there are two problems that must be solved: the problem stemming from the low specific gravity of the fat, and the problem of increasing the stability of the catalyst. .

(Another way to solve the problem) 4Q inorganic material Vi has a slightly reactive hydroxyl group bond, so a reactive organosilicon compound is bonded to this hydroxyl group 9 ( can be done (F,
R. Hartley & P. N. Vezey, “Advances in Organic Metal Chemistry” (Avd, in Organome
tal chem, )', volume 715, 18? Page, (1
978)). Combining a 4f silicon compound with such a functional group on the surface of a free surface is often used when formulating the surface of an inorganic filler used in plastisol.

In order to solve the above-mentioned problem, the present inventors proposed the following method.
As a result of repeated Klt, the special catalyst obtained by using the above technology for catalyst production is effective as a catalyst for the disproportionation reaction of chloro7-syn, and it is possible to efficiently produce s:j). The present invention has been achieved with the following steps:

That is, the present invention combines a silicon compound represented by the following general formula il+ with a silicon-containing inorganic substance and /' or the following general formula f
This is a method for producing silane, which involves bonding to a compound represented by i+1 and carrying out a disproportionation reaction of chlorosilane in the presence of 6Fl.

General formula (I) (RO)3Syu (CHz) n-, 'J''
-H3X - [In the formula, n is an integer of 1 to 4, R is an alkyl group of 1 to 4 carbon atoms, and R1 and R2i are the same as -
-1 is 7 different alkyl groups with 1 to 8 carbon atoms (・1
5f in Arcel Tachibana which is an aryl group and R3+d has an alkyl group having 1 to 20 carbon atoms or a dimethylamino group
), X, chlorine, bromine, and iodine are halogen atoms. ]
General formula (I)) % formula % [In the formula, ni is an integer from 1 to 4,)l 41-j Charcoal number 1 to 6 alkyl genius 7bi is aryl calendar, n take-H
4-8H, -CN, -NR2 (R5 is an alkyl OCR having 1 to 4 carbon atoms.

), -〇-C-c=cn, and X'
is chlorine\-5+wood,
-・Pot-II (1 to 4 argyl groups). ] In the present invention, the quaternary ammonium group in the general formula (if) is substituted. Desert, compounds such as silica and zeolite) J's inorganic substances 'v' and the next peach contains inorganic water I! A compound in which i co゛/^ and organic ii' compound are narrowed down and quaternary ammonium is combined in a graphical manner is I.
In this way, the unrestricted activation reaction of the product d chloro/zine 1/C, 1: How many N+ is used as an insect medium for 1 and 1 in the method of preparing the whole product? I said something.

The method of the present invention thus implemented (the catalyst is based on a known organic resin) compared to the catalyst bonded with a four-prone ammonium substrate.
81! It is easy to fill because the F roll does not weigh as much, and since the active quaternary ammonium salt is bonded to the surface of the inorganic material, it is easy to contact with reactants and has high spreadability. Furthermore, ifC is bonded to an inorganic substance and has a good characteristic of stability.

The compound of the above general formula (I) and the above general formula (If)
A suitable amount (preferably) of a compound capable of forming a silicone resin of general formula (Ill) to 1 mole of a compound of general formula (I
When the compound of 1 to 5 mol) is mixed, hydrolyzed, and subjected to 2-condensation polymerization, a solid silicon resin catalyst with a quaternary ammonium salt bonded to it is obtained by the following reaction,
This catalyst produces a similar effect to the effect of bonding a compound of general formula CI+ to the silica surface, and can be effectively used in the disproportionation reaction of chlorosilane in the present invention.

(Margin below)! R4(CH2)n5iX,g+(RO)3Si(C
H2), -N"-R3X -(CH2), R4 ■Furthermore, the mixture of the compound of the general formula (Il) and a silicon-containing inorganic substance such as silica or zeolite has the general formula f
The catalyst for disproportionation of chlororane, which can be effectively used in the present invention, can also be obtained by adding the compound (n) and performing hydrolysis.

Next, a method for manufacturing the catalyst used in the present invention will be specifically explained.

First, when combining the compound of general formula (I) with silica, the compound of general formula (I) is preferably dissolved in methanol at a concentration of 40 to 70%, and the silica to be reacted is added to this solution. Gradually add dilute hydrochloric acid solution for hydrolysis to obtain the catalyst.

In this case, a certain amount (preferably 0.01 to 10 moles per 1 mole of the compound of general formula Il) of a compound of general formula (n) having a 6th-class amino group is further mixed and hydrolyzed. A catalyst can also be obtained by filtration of an aqueous solution to remove water. Since quaternary ammonium salts decompose at high temperatures, they are distilled using solvents such as alcohols and benzene that boil together with water.
Evaporate the solvent under reduced pressure while maintaining the temperature below 150°C.

The step of bonding the compound of the general formula CI) to the zeolite involves first treating, for example, zeolite BX with an ammonium chloride solution to convert the sodium ions in the zeolite into ammonium ions, and converting the zeolite with the ammonium ions exchanged into 600 to 400 Evaporate the ammonia by heating at a temperature of °C (D, W.

The zeolite thus treated is treated with a solution of the compound of general formula (I) in methanol, preferably 55 to 85%, and the solvent methanol is removed by distillation. The zeolite bound with the compound of general formula (1) is treated again with a solution of dibutyltin dilaurate dissolved in toluene at a concentration of 5 ml and subjected to toluene/]l-distillation. The remaining solid is heated to about 100° C. while volatile components are removed in vacuum to complete the reaction.

In this case, the compound of general formula (I)) may be mixed as in the case of Noriyoku.

To produce a solid silicone resin bound with a quaternary ammonium salt, a compound of the general formula fi+ is dissolved in methanol and the amount of organic trialkoxine la/(general formula (
It is made by mixing with I)) and then adding weakly acidic water to hydrolyze it. When the hydrolysis is completed, a gel-like solid is obtained, which is separated from the aqueous solution by carbonization, washed several times with absolute alcohol, and dried in a vacuum dryer to obtain a hardened solid. In this step, when an appropriate amount of 2methylaminopropyltriethoxysilane is mixed and hydrolyzed, a product containing both a quaternary ammonium salt and a 6th class amine is obtained.

The catalyst used in the present invention produced as described above is suitable for both batch and continuous processes, but because the specific gravity of the catalyst is high, it is easy to fill into a reaction tank, and it does not get rolled up when passing chloro7 run. This is particularly advantageous for continuous systems.

In this method for producing silane using the catalyst produced by the above method, the reaction for producing dichlorosilane from trichlorosilane by disproportionation reaction is performed from 0°C to 20°C.
Although it is carried out at a temperature of 0°C, temperatures from room temperature to 100°C are suitable. The reaction pressure can be both normal pressure and high pressure, but at normal pressure, the boiling point of the reactants and products is low, so it becomes a gas phase reaction, so the reaction rate is uneven, whereas at high pressure, the reaction rate is uneven, because it becomes a liquid phase reaction. It's advantageous.

However, in this method, in addition to the reaction temperature and reaction pressure, another point to be noted is that sufficient contact time between the catalyst and the reactants must be provided. In batch reactions, this problem can be solved by increasing the number of catalysts and increasing the reaction time, while in continuous processes, it is possible to increase the length of the reactor filled with catalyst and slow down the flow rate of the reactants. Furthermore, in the present invention, silane is obtained by using dichlorosilane instead of trichlorosilane as the starting material and reacting with the same catalyst.

The invention will be explained in more detail by the following examples,
The present invention is not limited to this.

Example 1 200 g of finely divided silica gel was placed in a 1P volume three-necked round-bottomed flask equipped with a stirrer, a dropping funnel, and a condenser, and 3-()rimethoxysilyl)propyl dissolved in methanol at a concentration of 40% was added. Octadecyl nomethyla/
200 g (0.16 mol) of monium chloride solution was added. Water with a local acid solution added to the side to make it weakly acidic6
00d was placed in a dropping funnel, water was slowly added with the stirrer running vigorously, and the mixture was stirred for 1 hour to complete the reaction, after which a solid precipitate was obtained upon stopping. The solid is carbonized, washed twice with 200*z absolute ethanol, and distilled with 200 d of benzene to remove water, ethanol, and benzene contained in the solid. The trace amount of remaining solvent was removed by heating in a 90° C. trench under reduced pressure, and the solid was dried. The amount of catalyst produced in step 7 was 256 g.Next, 100 g of the obtained catalyst was placed in a 500 yt capacity glass tube reactor with a Teflon knob that can withstand slight pressure attached to the mouth. After adding 15ON/5iHCjl, tightening the Teflon valve and heating at 6100℃ for 1 hour, analysis by gas chromatography revealed that Si
HCfi3 is 809%, 5iCffi4 is 9.52chi, SiH, CP is 8.81min, Si H2ON is 0
Section 24 was obtained.

Example 2 A catalyst was prepared in the same manner as in Example 1 using 100 g (0.16 mol) of 6-(trimethoxynoryl)propyltrimethylammonium chloride in 40% methanol, and then the catalyst was 5i) When 12C12 is reacted in the same manner as in Example 1 using
6%, 3322% of 5iHC, 01% of 5iCA4 was produced, the remainder being starting material [91].

Example 6 600g of the catalyst obtained in Example 1 was transferred to stainless steel 61
The mixture was placed in a 6-type Buζ reaction tank, and a hot wire was wrapped around the outside of the reaction tank to maintain the temperature at 80°C using an automatic temperature controller.

A pump that can inject 5iHCfi is connected to the bottom of the reaction tank, and a valve that can adjust the pressure is connected to the top of the reaction tank.
The injection rate of 5iH (13) was adjusted so that the residence time in the reaction tank for 5iH (13) was 20 to 60 minutes. When reacted, 4 to 8% of 5iH2 (4
Cj! 5iH3C1 of 0.02 to 0.006 was obtained.

Reference Example 1 A catalyst was produced under the same conditions as in Example 1 by removing 0.01 mol of dimethylaminopropyltrimethquine.

Reference Example 2 94 g (Q, 5
3-()rimethoxinelyl)propyloctadecyldimethylammonium dissolved in methanol as a 40% solution with 3-mol) of cyanopropyltrimethoxysilane.
Chloride solution 66g (0.05 mol) f 5CJC
After adding heno water K fg Ka L 7't, put it in a dropping funnel and gradually open the cock of the funnel while setting up a stirrer and add 1NHC [
An additional 100+qz of the solution was added and stirred for 60 minutes. When the produced solid was carbonized, a hard lump-like solid was obtained. This solid was washed twice with absolute alcohol and dried in a vacuum dryer for 2 hours to produce a catalyst.

Reference Example 6 A catalyst was produced in the same manner as in Reference Example 2 using 5-(trimethoxysilyl)propylbenzyl dimethylammonium chloride instead of the 6-(trimethoxy7lyl)propyloctadecyldimethylammonium chloride solution. .

Reference Example 4 A catalyst was produced under the same conditions as in Reference Example 1 by adding 001 molar dimethylaminopropyltrimethoxysilane.

Reference Example 5 Put 100 g of zeolite (BX) into a solution of 29 g of ammonium chloride dissolved in 120-g of water, let it stand for 2 hours while heating it to 80°C, filter it, and repeat the same process twice to remove ammonium. ff for salt! After filtering and drying the zeolite, it was heated at 600 to 400℃ for 2 hours.
heated for an hour. When the zeolite treated in this way is distilled with 6-(trimethocyf/lyl)promethanol and the zeolite is dried, 2g of dibutyltin dilaurate = 540.
The zeolite was treated by dissolving it in g of toluene. A catalyst was produced by distilling toluene and evaporating volatile components in a vacuum while heating to 100°C to complete the reaction.

The catalyst obtained as described above could be effectively used in the chlorosilane disproportionation reaction in the present invention.

〔Effect of the invention〕

According to the present invention, a chlorosilane disproportionation reaction is carried out stably at a relatively low temperature using a catalyst that is easy to produce and easily filled into a reaction vessel, and heptans can be obtained in high yield.

1 convex 0

Claims (1)

[Claims] 1) The heterogeneous production of chlorosilane in the presence of a catalyst in which a silicon compound represented by the following general formula (I) is bonded to a silicon-containing inorganic compound and/or a compound represented by the following general formula (II). A method for producing silane, characterized by carrying out a chemical reaction. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are the same or different alkyl groups or aryl groups having 1 to 8 carbon atoms, and R
^3 is an alkyl group having 1 to 20 carbon atoms or an alkyl group having a dimethylamino group, and X is a halogen atom such as chlorine, bromine, or iodine. ] General formula (II) R^4(CH_2)_nSiX'_3 [In the formula, n is an integer of 1 to 4, and R^4 has a carbon number of 1 to
6 alkyl group or aryl group, or -H, -SH
, -CN, -NR^5_2 (R^5 is an alkyl group with 1 to 4 carbon atoms), ▲There are mathematical formulas, chemical formulas, tables, etc.▼
and X' is chlorine, bromine, iodine, or OR^6 group (R^6 is a carbon number of 1
~4 alkyl group). 2) The method for producing silane according to claim 1, wherein the chlorosilane is trichlorosilane, dichlorosilane, or a mixture thereof. 3) The method for producing silane according to claim 1, wherein the unequalization reaction is carried out after preheating the chlorosilane to 35 to 150°C. 4) The method for producing silane according to claim 1, wherein the silicon-containing inorganic compound is silica or zeolite.