JP2000169131A - Production of disproportionation reaction product from silane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the reaction activity for disproportionation of a hydrogenated halogenated silane by using a catalyst prepared by making a quaternary phosphonium compd. supported on silica. SOLUTION: As for the hydrogenated halogenated silane, trichlorosilane or the like expressed by the formula is preferable. In the formula, X is a halogen atom, and m and n are 1 to 3 satisfying m+n<=4. As for the catalyst, a tetraalkylphosphonium compd. having 4 to 12 carbon atoms in the alkyl group and having a sulfate ion as a counter anion is preferably used. As for the silica as the carrier, an amorphous silica such as silica gel preferably having 0.3 to 1.5 ml/g pore volume, 2 to 100 nm average pore diameter, 100 to 800 m2/g specific surface area, 50 μm to 1 mm particle size and >=95 wt.% SiO2 content based on the dry weight is used. The quaternary phosphonium compd. is supported by 0.1 to 20 wt.% of the total weight of the catalyst. The disproportionation reaction is carried out by a flow method using the catalyst as a fixed bed under conditions of normal pressure to 60 atoms, 40 to 300 deg.C and 0.01 to 300 sec contact time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a disproportionation reaction product of various silane compounds. More specifically, the present invention relates to a method for producing a disproportionation reaction product of a silane compound such as monosilane by disproportionating a hydrogenated silane such as dichlorosilane in the presence of a specific catalyst.

[0002]

2. Description of the Related Art Silane compounds such as monosilane and dichlorosilane are important materials in the semiconductor industry such as a raw material for silicon single crystal and epitaxial growth of silicon.
In recent years, demand has rapidly increased.

Various methods are known for producing these compounds. However, many disproportionation reaction products containing a target silane compound are obtained by disproportionating a hydrogenated silane. It is considered that the most economical method is to obtain the target compound by fractionating the compound by distillation or the like.

[0004] The disproportionation reaction of a hydrogenated silane refers to a method in which hydrogen and halogen are exchanged between molecules of the hydrogenated silane to form silane compounds different from the raw material halogenated silane. It is a reaction to be generated. Since the newly generated compound repeats the same exchange reaction, the reaction system has a mixed composition composed of several kinds of silane compounds.

The disproportionation of trichlorosilane will be described as an example. In the presence of a suitable catalyst, trichlorosilanes first exchange hydrogen and chlorine to form dichlorosilane and silicon tetrachloride, as shown below. Dichlorosilane also produces monochlorosilane and trichlorosilane. Monochlorosilane similarly produces monosilane and dichlorosilane. These reactions are repeated, and the system becomes a mixed composition comprising five components of monosilane, monochlorosilane, dichlorosilane, trichlorosilane, and silicon tetrachloride.

[0006]

Embedded image

For example, when the target substance is monosilane, it may be separated from the mixture by a method such as distillation. This disproportionation reaction is an equilibrium reaction, and the reaction system reaches an equilibrium composition when a sufficient reaction time (contact time) is taken. However, it is not always necessary for the system to reach equilibrium when separating and obtaining the target substance.

As for the catalyst used for the disproportionation reaction of the hydrogenated silane, many techniques are disclosed in patents and the like. For example, JP-A-60-96518 discloses that
A method is disclosed in which a quaternary phosphonium compound is directly added to a reaction system to act as a liquid phase homogeneous catalyst. JP-A-60-60915 also discloses that the above quaternary phosphonium compound is used as a catalyst, and this may be used by being supported on a carrier such as activated carbon, alumina and silica-alumina. It is disclosed.

[0009]

However, when a quaternary phosphonium compound is used, the disproportionation reaction can be carried out with considerably good catalytic activity, but the quaternary phosphonium compound can be used as it is in the reaction system. The method of adding and acting has a problem that a large amount of energy is required for separating a reaction product and a catalyst. This is described in Japanese Patent Application Laid-Open No. 60-60 / 1985.
As described in JP-A-915, if the quaternary phosphonium salt is supported on a carrier and used, the problem of the separation can be solved. In that case, activated carbon, alumina, silica-alumina as exemplified above. Use of such a carrier has a problem that the activity of the obtained catalyst is low.

[0010] Therefore, in the disproportionation reaction of the above-mentioned hydrogenated silane, it has been a problem to develop a supported catalyst having high catalytic activity and to carry out the reaction efficiently.

[0011]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that by using a catalyst in which a quaternary phosphonium compound is supported on silica, the disproportionation of the hydrogenated silane is reduced. The inventors have found that the reaction can be carried out with high reaction activity, and have completed the present invention.

That is, the present invention provides a process for disproportionating a silane compound, which comprises disproportionating a hydrogenated silane using a catalyst in which a quaternary phosphonium compound is supported on silica. It is a manufacturing method.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrogenated silane used in the present invention is a silane compound having at least one hydrogen atom and at least one halogen atom bonded to silicon. Such hydrogenated halogenated silanes include:
Generally, a compound represented by the following general formula (1) is used.

Y _(4-mn) SiH _n X _m (1) where Y represents an alkyl group or an aryl group;
Represents a halogen atom. M and n are 1 or more and 3
The following integer and m + n is 4 or less. As the alkyl group, one having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and as the aryl group, a phenyl group and the like are preferable. As a specific example,
Trichlorosilane, dichlorosilane, monochlorosilane, methyldichlorosilane, methylmonochlorosilane,
Examples thereof include dimethylmonochlorosilane, ethyldichlorosilane, ethylmonochlorosilane, diethylmonochlorosilane, phenyldichlorosilane, phenylmonochlorosilane, diphenylmonochlorosilane, and any mixture thereof.

Of these, a chlorosilane compound selected from trichlorosilane, dichlorosilane and monochlorosilane represented by the following general formula (2) SiH _n X _m (2), or a mixture thereof is particularly preferred.

Incidentally, hydrogenated silanes having no halogen atoms bonded to silicon atoms, such as monosilane and methylsilane, and halogenated silanes having no hydrogen atoms bonded to silicon atoms, such as silicon tetrachloride and methyltrichlorosilane. Silane alone does not cause a disproportionation reaction.
However, when co-existing with the above-mentioned hydrohalogenated silane, it participates in the disproportionation reaction and gives a corresponding mixture. Therefore, in the present invention, a hydrogenated silane may be used as a raw material, or these may be mixed with the above-mentioned halogenated silane having no hydrogen atom or hydrogenated silane.

In the present invention, as the quaternary phosphonium compound as a catalyst component, known compounds can be used without any limitation.
Examples of the hydrocarbon group bonded to the central phosphorus atom of the phosphonium ion include an alkyl group, an alkenyl group, an aryl group,
Aralkyl groups and the like are preferable, and these may be the same or different. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the alkenyl group include a vinyl group, an allyl group, and a hexenyl group. Examples of the aryl group include a phenyl group, a tolyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group. Further, these groups may have a substituent such as an alkoxyl group or an alkoxycarbonyl group. In the quaternary phosphonium compound, a polyvalent hydrocarbon group such as an alkylene group is bonded to a phosphorus atom together with the above-described monovalent hydrocarbon group, and a plurality of quaternary phosphonium compounds are bonded via the polyvalent hydrocarbon group. It may be a polyvalent quaternary phosphonium compound having a quaternary phosphonium group in the molecule.

The anion constituting the quaternary phosphonium compound is not particularly limited, but inorganic acid group ions such as fluoride ion, chloride ion, bromide ion, sulfate ion, hydrogen sulfate ion, nitrate ion, etc. Or,
Organic acid ions such as acetate ion, p-toluenesulfonate ion, croconate ion, rhodizonate ion, and,
Hydroxide ion and the like. In particular, inorganic acid ions or hydroxide ions are suitable.

Specific examples of these quaternary phosphonium compounds include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium fluoride, tetrabutylphosphonium sulfate, tetrabutylphosphonium hydrogen sulfate, tetrabutylphosphonium hydroxide,
Tetraoctylphosphonium chloride, tetraoctylphosphonium bromide, tetraoctylphosphonium fluoride, tetraoctylphosphonium sulfate, tetraoctylphosphonium hydrogen sulfate, tetraoctylphosphonium hydroxide,
Tetrapentyl phosphonium bromide, allyl triphenyl phosphonium bromide, vinyl triphenyl phosphonium bromide, (ethoxycarbonylmethyl) triphenyl phosphonium bromide, benzyl triphenyl phosphonium bromide, cyclopropyl triphenyl phosphonium bromide, methyl tri bromide Phenylphosphonium, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, pentyltriphenylphosphonium bromide, hexyltriphenylphosphonium bromide, heptyltriphenylphosphonium bromide, and octyl bromide Examples include, but are not limited to, triphenylphosphonium.

Among the above quaternary phosphonium compounds, those particularly preferably used in the present invention are those in which the hydrocarbon groups bonded to the phosphorus atom at the center of the phosphonium ion are the same or different alkyl groups, respectively. The counter anion is a tetraalkylphosphonium compound whose inorganic acid ion or hydroxide ion is used. Further, in this tetraalkylphosphonium compound, the alkyl group preferably has 4 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. The counter anion is preferably a sulfate ion.

In the present invention, the above quaternary phosphonium compound is used by using silica as a carrier and supporting it. By using silica as a carrier as described above, the catalytic activity of the disproportionation reaction of the hydrogenated silane is significantly improved. As described above, when activated carbon, alumina, silica-alumina or the like is used as a carrier, the activity of the quaternary phosphonium compound with respect to the disproportionation reaction is greatly reduced. It is a surprising finding that if is selected as a carrier, the activity of the disproportionation reaction is greatly improved.

In the present invention, the silica may be crystalline silica such as quartz, tridymite, cristobalite or the like, but usually, amorphous silica such as silica gel is preferably used. In particular, the pore volume is 0.1 to 10 ml / g,
It is preferably 0.3 to 1.5 ml / g, and the average pore diameter is 0.5 to 200 nm, preferably 2 to 100 nm,
Specific surface area is 10 to 1000 m ² / g, preferably 100 to 1000 m ² / g
It is preferable to use one having 800 m ² / g. Further, the particle diameter is preferably 30 μm to 3 mm, particularly preferably 50 μm to 1 mm. In the present invention, silica has a content of SiO ₂ of 80% by weight or more, preferably 95% by weight or more on a dry basis, and a content of Al ₂ O _{3 as} an impurity of 2% by weight or less. It is preferred that

In the present invention, a method for preparing a catalyst, that is,
The method for supporting the quaternary phosphonium compound on silica is not particularly limited. Specifically, in addition to the impregnation method of dissolving the quaternary phosphonium compound in a solvent and impregnating and drying the silica, a method of simply mechanically mixing the quaternary phosphonium compound and silica may be used. Preferably, the impregnation method is preferred because higher catalytic activity can be obtained.

The catalyst used in the present invention has higher activity as the amount of the quaternary phosphonium compound supported thereon increases. The suitable amount of loading varies depending on the type of the quaternary phosphonium compound, but it is usually desirably 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the total amount of the catalyst.

In the present invention, the disproportionation reaction is carried out by contacting the starting hydrogenated silane with the above catalyst. The method of contact is not particularly limited. It may be a batch type or a flow type. Further, it may be a gas phase or a liquid phase.

In order to carry out the present invention most effectively, a flow-type reaction using a fixed bed as a catalyst is desirable. This reaction is
The reaction can be performed under a wide range of reaction conditions from reduced pressure to increased pressure, but in consideration of reaction efficiency and safety, 0.5 to 100
It is desirable to perform the process at atmospheric pressure, and more preferably at normal pressure to 60
It is desirable to perform at atmospheric pressure. In addition, the reaction temperature can be varied over a wide range, but is preferably 0 ° C. or higher in order to promptly advance the reaction.
Considering the safety of the catalyst, the temperature is preferably 400 ° C. or lower.
More preferably, it is desirable to carry out the reaction in the range of 40 to 300 ° C.

The contact time (the time required for the raw material to pass through the catalyst layer) is desirably set so that the reaction system almost reaches the equilibrium composition. If the contact time is too short, the disproportionation reaction does not proceed sufficiently, so that the yield of the target product decreases. If the contact time is longer than necessary, the equilibrium composition has been sufficiently reached, and the yield of the target substance with respect to the raw material does not change.However, the ratio of the target substance cannot exceed the equilibrium composition, and as a result, the The yield of the desired product is reduced. The appropriate contact time depends on the reaction temperature, pressure, raw materials,
Depending on the catalyst and other factors, it is generally selected from 0.01 to 300 seconds.

According to the production method of the present invention, the hydrogenated silane as the raw material gives many disproportionation reaction products by the disproportionation reaction. Therefore, from the mixture,
The necessary components are separated using common methods such as distillation,
Just get it. In particular, as the hydrogenated silane, at least one selected from trichlorosilane, dichlorosilane, and monochlorosilane is used, if necessary, mixed with silicon tetrachloride, and as the disproportionation reaction product, the hydrogenated silane is used. It is preferred to obtain a higher order hydrogenated silane compound.

In particular, it is preferable that trichlorosilane is used as the hydrogenated silane and monosilane is obtained by performing a two-stage disproportionation reaction shown in FIG. 1 described below.

The raw material trichlorosilane is supplied from the drum 6 to the disproportionation reactor 1, for example, a fluidized bed type or fixed bed type reactor, and brought into contact with a quaternary phosphonium compound-supported catalyst. Thereby, a mixed system of various chlorosilane compounds, mainly dichlorosilane, trichlorosilane and silicon tetrachloride is generated. At this point, the proportion of the target monosilane is low. The mixture generated in the disproportionation reactor 1 is sent to a distillation column 3 which is a separation device in the next step. From the distillation column 3, low-boiling components centering on dichlorosilane and trichlorosilane are sent from the pipeline 8 to the distillation column 4, and silicon tetrachloride is discharged from the lower part of the distillation column 3. In the distillation column 4, low-boiling components centering on dichlorosilane are supplied from the pipeline 9 to the disproportionation reactor 2. Trichlorosilane is supplied from the lower part of the distillation column 4 to the drum 6.
And subjected to a disproportionation reaction. Disproportionation reactor 2
Then, similarly, a chlorosilane compound, mainly a mixed system of monosilane, monochlorosilane, dichlorosilane and trichlorosilane is formed by contacting with a catalyst. At this point, it is preferable that the target monosilane is contained in a ratio that can be sufficiently separated. This mixture is sent to the distillation column 5 and monosilane is obtained from the pipeline 10. Monochlorosilane, dichlorosilane and trichlorosilane are mainly recovered from the lower part of the distillation column 5 to the drum 7, and the low-boiling components mainly composed of monochlorosilane and dichlorosilane and trichlorosilane are mainly collected in the distillation column 4. High boiling components. The low-boiling component and the high-boiling component are supplied to the disproportionation reactor 2 and the disproportionation reactor 1 respectively.
And again subjected to the disproportionation reaction. Thus, monosilane can be obtained using trichlorosilane as a raw material.

Of course, when a silane compound other than monosilane, for example, dichlorosilane is used as the target substance, for example, when distillation is adopted as a separation step, the distillation conditions are changed to obtain only the target dichlorosilane. And the higher or lower boiling chlorosilane compound is recycled to the disproportionation reactor. In this way, any one of the disproportionation reaction products or two or more chlorosilane compounds can be obtained as the target product.

[0032]

According to the production method of the present invention, a silane compound can be produced in a shorter contact time than in the conventional method. That is, when the catalyst of the present invention is used, the reaction speed is high, so that the time required for sufficiently proceeding the disproportionation reaction can be set shorter than that of the conventional one.
Therefore, with the same amount of catalyst, the yield per unit time can be increased as compared with the conventional method. Conversely, to obtain the same yield, less catalyst is required.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to specific examples.

In the following Examples and Comparative Examples, the catalyst was prepared by the following method.

(Preparation of catalyst) Impregnation method Various quaternary phosphonium compounds were dissolved in methanol or water, silica was added thereto, and the mixture was dried at 250 ° C.

Mixing method Various quaternary phosphonium compounds and silica were prepared by mechanically mixing with a mortar.

Example 1 As silica, ID gel manufactured by Nishio Kogyo Co., Ltd. (particle size: 250
５００500 μm, specific surface area 310 m ² / g, pore volume 1.
(2 ml / g, average pore diameter 15 nm), and the catalysts shown in Table 1 were prepared.

Next, 0.5 ml of the catalyst 1 shown in Table 1 was filled in a glass reaction tube having an inner diameter of 4 mm, and 2.0 ml was filled in a reaction tube made of glass having an inner diameter of 8 mm, and each was heated to 80 ° C. Here, a 1: 1 mixed gas of trichlorosilane and helium was allowed to flow through a 4 mm reaction tube at 60, 30 ml / min, while flowing through an 8 mm reaction tube at 60, 24 ml / min. The contact time at this time is 0.5,
1.0, 2.0, and 5.0 seconds. The reaction was performed at normal pressure.

The gas passed through the catalyst layer was analyzed by gas chromatography to determine the conversion of trichlorosilane at each contact time, and the value was divided by the equilibrium conversion of trichlorosilane at 80 ° C. of 22.7%. . This value was defined as the equilibrium attainment rate. The results are shown in Table 2. At a contact time of 1.0 second, the equilibrium conversion reached a high rate of 93.3%.
The gas composition at a contact time of 5.0 seconds was: monosilane; 0.1 mol% monochlorosilane; 0.5 mol% dichlorosilane; 10.8 mol% trichlorosilane; 77.3 mol% silicon tetrachloride; 11.3 mol%. Was. This composition was consistent with the equilibrium composition of the disproportionation reaction of trichlorosilane at 80 ° C.

Examples 2 to 6 Five kinds of catalysts were selected from the catalysts shown in Table 1 and reacted according to Example 1. The results are shown in Table 2.

[0041]

[Table 1]

[0042]

[Table 2]

Example 7 According to Example 1, a reaction was carried out using dichlorosilane instead of trichlorosilane. Here, the equilibrium attainment rate was determined by dividing the conversion rate of dichlorosilane at each contact time by the equilibrium conversion rate of dichlorosilane at 80 ° C. of 65.0%. The results are shown in Table 3.
At a contact time of 1.0 second, the equilibrium conversion reached a high of 93.9%.

The gas composition at a contact time of 5.0 seconds was as follows: monosilane; 13.7 mol% monochlorosilane; 10.6 mol% dichlorosilane; 35.0 mol% trichlorosilane; 39.7 mol% silicon tetrachloride; 0.9 mol % Met. This composition was consistent with the equilibrium composition of the disproportionation reaction of dichlorosilane at 80 ° C.

Examples 8 to 12 Five kinds of catalysts were selected from the catalysts shown in Table 1, and the reaction was carried out according to Example 7. The results are shown in Table 3.

[0046]

[Table 3]

Example 13 0.1 g of the catalyst 1 shown in Table 1 was placed in a glass reaction tube having an inner diameter of 4 mm.
ml and 0.5 ml and heated to 200 ° C. Here, 120, 60, 30 m was charged into a reaction tube filled with 0.1 ml of a 1: 1 mixed gas of trichlorosilane and helium.
Each flow was carried out at 1 / min, while each flow was carried out at 60, 30 ml / min in a reaction tube filled with 0.5 ml. The contact time at this time was 0.05, 0.10, 0.20, 0.
50 and 1.0 seconds. The reaction was performed at normal pressure.

The gas passed through the catalyst layer was analyzed by gas chromatography to determine the conversion of trichlorosilane at each contact time, and the value was divided by the equilibrium conversion of trichlorosilane at 200 ° C. of 29.9%. . This value was defined as the equilibrium attainment rate. The results are shown in Table 4. At a contact time of 0.20 seconds, the equilibrium attainment rate reached a high rate of 87.1%.

The gas composition at a contact time of 1.0 second was as follows: monosilane; 0.1 mol% monochlorosilane; 0.9 mol% dichlorosilane; 13.0 mol% trichlorosilane; 70.1 mol% silicon tetrachloride; % Met. This composition was consistent with the equilibrium composition of the disproportionation reaction of trichlorosilane at 200 ° C.

Examples 14 to 22 Nine types were selected from the catalysts shown in Table 1, and
The reaction was carried out according to The results are shown in Table 4.

[0051]

[Table 4]

Example 23 According to Example 13, a reaction was carried out using dichlorosilane instead of trichlorosilane. Here, the equilibrium attainment rate is obtained by calculating the conversion rate of dichlorosilane at each contact time by 2
It was obtained by dividing by the equilibrium conversion of dichlorosilane at 00 ° C. of 62.0%. The results are shown in Table 5. At a contact time of 0.20 seconds, the equilibrium attainment rate reached a high rate of 88.1%.

The gas composition at a contact time of 1.0 second was as follows: monosilane; 10.7 mol% monochlorosilane; 13.7 mol% dichlorosilane; 38.0 mol% trichlorosilane; 36.2 mol% silicon tetrachloride; % Met. This composition was consistent with the equilibrium composition of the disproportionation reaction of dichlorosilane at 200 ° C.

Examples 24 to 32 Nine types were selected from the catalysts shown in Table 1, and
The reaction was carried out according to Table 5 shows the results.

[0055]

[Table 5]

Examples 33 to 36 Using silica (ID gel) manufactured by Nishio Industry Co., Ltd. as the silica,
A catalyst in which tetrabutylphosphonium bromide was supported in an amount shown in Table 6 by an impregnation method was prepared. A reaction was carried out according to Example 23 using these catalysts. The results are shown in Table 7. As for the catalytic activity per unit volume, the higher the supported amount of the quaternary phosphonium compound, the shorter the time required to reach equilibrium and the higher the activity.

[0057]

[Table 6]

[0058]

[Table 7]

Examples 37 to 43 Catalysts in which tetrabutylphosphonium bromide was supported on various silicas shown in Table 8 were prepared. The loading amount was 5% by weight in all cases, and was carried by the impregnation method.

Using these silicas, a reaction was carried out according to Example 23. The results are shown in Table 9.

[0061]

[Table 8]

[0062]

[Table 9]

Example 44 According to Example 7, a reaction was carried out using a 1: 2 mixture of dichlorosilane and trichlorosilane instead of dichlorosilane. At a contact time of 5.0 seconds, the gas composition after passing through the catalyst layer was: monosilane; 2.5 mol% monochlorosilane; 4.0 mol% dichlorosilane; 26.8 mol% trichlorosilane; 63.7 mol% silicon tetrachloride; It was 1 mol%. This composition was in agreement with the equilibrium composition of the disproportionation reaction when a 1: 2 mixture of dichlorosilane and trichlorosilane was used at 80 ° C.

Example 45 According to Example 7, a reaction was carried out using a 1: 2 mixture of dichlorosilane and silicon tetrachloride instead of dichlorosilane. At a contact time of 5.0 seconds, the gas composition after passing through the catalyst layer was: monosilane; 0 mol% monochlorosilane; 0 mol% dichlorosilane; 1.9 mol% trichlorosilane; 62.9 mol% silicon tetrachloride; 35.2 mol%. Was. This composition was in agreement with the equilibrium composition of the disproportionation reaction when a 1: 2 mixture of dichlorosilane and silicon tetrachloride was used at 80 ° C.

Comparative Example 1 As a catalyst, a weakly basic anion exchange resin Amberlyst A-21 manufactured by Rohm & Haas Co. (ion exchange capacity;
6 meq / g), and the reaction was carried out according to Example 7. The results are shown in Table 10. At a contact time of 2.0 seconds, the equilibrium attainment rate had reached only 63.2%.

Comparative Example 2 The reaction was carried out in the same manner as in Example 7 except that tetrabutylphosphonium bromide was not used as a catalyst.
The results are shown in Table 10. When used alone without supporting the quaternary phosphonium compound, the equilibrium attainment rate did not reach 20% even at a contact time of 5.0 seconds.

Comparative Examples 3 to 5 Silica (ID gel) manufactured by Nishio Kogyo was added to octylamine (O
A catalyst supporting cNH ₂ ), dioctylamine (Oc ₂ NH), and trioctylamine (Oc ₃ N) was prepared. The loading amount was 5% by weight in all cases, and was carried by the impregnation method.

Using these catalysts, a reaction was carried out according to Example 7. The results are shown in Table 10. With these catalysts, the equilibrium attainment rate was 80% even at a contact time of 5.0 seconds.
Had not been reached.

Comparative Examples 6 to 10 Catalysts in which tetrabutylphosphonium bromide was supported on a catalyst carrier (activated carbon, alumina, silica-alumina) other than silica shown in Table 11 were prepared. The loading amount was 5% by weight in all cases, and was carried by the impregnation method.

Using these catalysts, a reaction was carried out according to Example 7. The results are shown in Table 12. With these catalysts, the equilibrium attainment rate was 50% even at a contact time of 5.0 seconds.
Had not been reached.

[0071]

[Table 10]

[0072]

[Table 11]

[0073]

[Table 12]

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a typical embodiment of a manufacturing process for carrying out the present invention.

[Explanation of symbols] 1,2; disproportionation reactor 3,4,5; distillation tower 6,7; drum 8,9,10; pipeline

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[Procedure amendment]

[Submission date] January 5, 1999 (1999.1.5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

The gas passed through the catalyst layer was analyzed by gas chromatography to determine the conversion of trichlorosilane at each contact time, and the value was divided by the equilibrium conversion of trichlorosilane at 80 ° C. of 22.7%. . This value was defined as the equilibrium attainment rate. The results are shown in Table 2. At a contact time of 1.0 second, the equilibrium attainment rate reached a high rate of 93.3%.
The gas composition at a contact time of 5.0 seconds was: monosilane; 0.1 mol% monochlorosilane; 0.5 mol% dichlorosilane; 10.8 mol% trichlorosilane; 77.3 mol% silicon tetrachloride; 11.3 mol%. Was. This composition was consistent with the equilibrium composition of the disproportionation reaction of trichlorosilane at 80 ° C.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

Comparative Example 2 The reaction was carried out in the same manner as in Example 7 except that the compounds shown in Table 10 were used as catalysts without being carried on a carrier. Table 10 shows the results.
It was shown to. When used alone without supporting the quaternary phosphonium compound, the equilibrium attainment rate did not reach 20% even at a contact time of 5.0 seconds.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G069 AA01 AA03 BA03A BA03B BA21A BA21B BB13A BB13B BD07A BD07B BD11A BD13B CB41 DA06 EA01Y EB18Y EC03Y EC08Y EC13Y 4G072 AA05 AA06 AA11 GG03 HKK09 KK03 UKK03

Claims (3)

[Claims] 1. A process for producing a disproportionation reaction product of a silane compound, comprising disproportionating a hydrogenated silane using a catalyst in which a quaternary phosphonium compound is supported on silica. 2. The quaternary phosphonium compound, wherein the hydrocarbon group bonded to the central phosphorus atom is the same or different alkyl group, alkenyl group, aryl group, and aralkyl group, respectively, and the counter anion is an inorganic group. The method for producing a disproportionation reaction product of a silane compound according to claim 1, wherein the product is an acid ion. 3. A catalyst for the disproportionation reaction of a hydrogenated silane comprising a quaternary phosphonium compound supported on silica.