JP2002226586A - Active metal magnesium and method for producing polysilane by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an economically advantageous method for producing a polysilane, having excellent safety and productivity. SOLUTION: The polysilane is produced by reacting a halosilane compound in the presence of at least an active metal magnesium in the coexistence of an alkali metal compound and a metal halide in an aprotic solvent. The active metal magnesium is obtained by subjecting the halosilane compound and the metal magnesium to a stirring treatment in the presence of the alkali metal compound and the metal halide in the aprotic solvent. By the method, the induction time for the reaction can be shortened even if the amount of the used metal magnesium is small.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing polysilane at low cost with high productivity and safety.

[0002]

2. Description of the Related Art Polysilanes are ceramic precursors,
Attention has been paid to optoelectronic materials (eg, photoelectrophotographic materials such as photoresists and organic photoreceptors, optical transmission materials such as optical waveguides, optical recording materials such as optical memories, and materials for electroluminescent elements). Conventionally, as a method for producing polysilane, dialkyldihalosilane or dihalotetraalkyldisilane in a toluene solvent is prepared by using an alkali metal such as metallic sodium as a reducing agent.
A method of strongly stirring at a temperature of 00 ° C. or more and reductively coupling is known [J. Am. Chem. Soc., 103 (198)
1) 7352]. However, in such a method, it is necessary to heat, vigorously agitate and disperse the alkali metal ignited in the air, so that there is a large problem in safety in the production on an industrial scale, and also, the molecular weight distribution. There are also problems with quality, such as the multimodality.

[0003] In order to solve these problems, a method of reacting magnesium or a magnesium-based alloy with halosilane in the presence of a specific metal salt (WO 98/29).
476) has been proposed. In this method, it is possible to carry out the reaction at room temperature without using complicated operations, and to use a chemically stable metal magnesium as a reducing agent, and to produce a desired polysilane in high yield. can do. However, this method requires an induction time of several hours before the start of the reaction even if an excess amount of magnesium is twice or more than the theoretical amount, and furthermore, it is troublesome to separate and treat a large amount of excess magnesium remaining after the reaction. Costly. The reason for requiring excessive magnesium and requiring several hours of induction time is that the activity of magnesium is low,
This is probably because the reaction rate at the beginning of the reaction was low.
Therefore, it is conceivable to adopt a generally known method for activating magnesium, such as washing with hydrochloric acid, or a method of adding an activating agent such as iodine or 1,2-dibromoethane to the reaction system. Can be However, even when these activation methods are adopted, the activity cannot be increased in the reaction of the silane compound.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an active metal magnesium which is useful for producing high-quality polysilane with high productivity.

Another object of the present invention is to provide a method which is excellent in safety and economically and advantageously produces polysilane with high efficiency and productivity even when the amount of magnesium used is reduced.

Still another object of the present invention is to provide a method for easily and efficiently producing polysilane.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, produced metal polysilanes by reacting metal magnesium on a halosilane compound in the presence of an alkali metal compound and a metal halide. In the reaction system, the metal magnesium remaining after the reaction is very highly active, and when the raw material is newly added and reacted using the active metal magnesium, the amount of the metal magnesium used can be greatly reduced. The present inventors have found that the induction time until the start of the reaction can be significantly reduced, and completed the present invention.

That is, the active metal magnesium of the present invention can be obtained by treating a halosilane compound and a metal magnesium in an aprotic solvent in the presence of an alkali metal compound and a metal halide.

[0009] In the method of the present invention, the halosilane compound may be used in at least the presence of the active metal magnesium.
The reaction is carried out in an aprotic solvent in the presence of an alkali metal compound and a metal halide to produce a polysilane.
In the production of polysilane, a first step of producing active metal magnesium by reacting metal magnesium with a halosilane compound in an aprotic solvent in the presence of an alkali metal compound and a metal halide; A halosilane compound, an alkali metal compound, a metal halide and an aprotic solvent are added to a reaction system containing
And the above steps. Liquid components may be removed from the reaction mixture obtained in the first step. Also, the second
In the step, metal magnesium may be supplied.
Further, a small amount of active metal magnesium is generated in advance with respect to the volume of the reactor, and a halosilane compound, an alkali metal compound, a metal halide and an aprotic solvent are added to the reaction system containing the generated active metal magnesium. You may make it react. As the halosilane compound,
A compound represented by the following formula (1) can be used.

[0010]

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(Wherein R ¹ and R ² are the same or different and represent a hydrogen atom, a halogen atom, an organic group or a silyl group, and X ¹ and X ² are the same or different and represent a halogen atom) The alkali metal compound may be a lithium compound (such as lithium halide). The metal halide is a polyvalent metal halide (such as chloride or bromide such as samarium, titanium, vanadium, iron, cobalt, palladium, copper, zinc, aluminum, and tin).
It may be.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the following components are used as raw materials in the production of active metal magnesium and / or polysilane.

(Halosilane compound) Examples of the halosilane compound include halosilane compounds represented by the above formula (1), specifically, di to tetrahalosilanes represented by the following formulas (2) to (4). These halosilane compounds can be used alone or in combination of two or more.

[0014]

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(Wherein R ^{3 to} R ⁵ are the same or different,
Represents a hydrogen atom, an organic group or a silyl group, and X ^{1 to} X ⁴ are the same or different and represent a halogen atom.) When a plurality of halosilane compounds are used in combination, usually at least one selected from di to tetrahalosilane Two types are used, and a mixture in any ratio can be used. If necessary, a monohalosilane (X ¹ SiR ³ R ⁴ R ⁵ ) may be used in combination. In addition, as a silane compound, usually, at least dihalosilane is used.

The organic groups represented by R ^{1 to} R ⁵ include alkyl groups [C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl groups (preferably C _1-6 alkyl groups)]. Groups, especially C _1-4 alkyl groups)],
Cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group, particularly C _5-6 cycloalkyl group), aryl group (C _6-10 aryl group such as phenyl or naphthyl group), aralkyl group [benzyl, phenethyl A C _6-10 aryl-C _1-6 alkyl group (C _6-10 aryl-
C _1-4 alkyl group)], alkoxy group [methoxy,
C _1-10 alkoxy groups such as ethoxy, propoxy, isopropoxy, butoxy and t-butoxy groups (preferably C _1-6 alkoxy groups, especially C _1-4 alkoxy groups) and the like],
And an amino group, an N-substituted amino group (such as an N-mono- or di-substituted amino group substituted with the above-mentioned alkyl group, cycloalkyl group, aryl group, aralkyl group, acyl group, and the like). The alkyl group, a cycloalkyl group, an aryl group or an aryl group constituting an aralkyl group,
It may have one or more substituents. Examples of such a substituent include the aforementioned alkyl groups (particularly, C _1-6 alkyl groups and the like), the aforementioned alkoxy groups, and the like. Examples of the organic group having such a substituent include C _1-6 alkyl-C _6-10 aryl groups such as tolyl, xylenyl, ethylphenyl, and methylnaphthyl groups (preferably mono to tri-C _1-4 alkyl- groups). A C _6-10 aryl group, especially a mono- or di-C _1-4 alkylphenyl group);
And C _1-10 alkoxy C _6-10 aryl groups such as methoxyphenyl, ethoxyphenyl and _{methoxynaphthyl} groups (preferably C _1-6 alkoxy C _6-10 aryl groups, especially C _1-4 alkoxyphenyl groups). Can be

The silyl group may be a substituted silyl group substituted with the above-mentioned alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group and the like.

The halogen atoms represented by R ¹ and R ² and X ^{1 to} X ⁴ include F, Cl, Br and I, and Cl and Br (particularly Cl) are preferred.

The halosilane compound is preferably as pure as possible. For example, a liquid halosilane compound is preferably dried using a desiccant such as calcium hydride and then distilled and used, and a solid halosilane compound is purified and used by a recrystallization method or the like. Is preferred.

Such halosilane compounds can be used alone or in combination of two or more.

(Solvent) As the solvent used in the reaction, aprotic solvents can be widely used, and examples thereof include ethers (1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, diethyl ether, diisopropyl ether, , 2-dimethoxyethane, bis (2-methoxyethyl) cyclic or chain C _4-6 ethers such as ether), such as carbonates (propylene carbonate), nitriles (acetonitrile, benzonitrile), amides (dimethylformamide , Dimethylacetamide, etc.), sulfoxides (such as dimethylsulfoxide), halogen-containing compounds (such as halogenated hydrocarbons such as methylene chloride, chloroform, bromoform, chlorobenzene and bromobenzene), aromatic hydrocarbons (such as And aliphatic hydrocarbons (chain or cyclic hydrocarbons such as hexane, cyclohexane, octane and cyclooctane) and the like, and may be used as a mixed solvent. As the solvent, a polar solvent (for example, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane) alone, a mixture of two or more kinds of the polar solvents, and the like are preferable. In particular, it preferably contains at least tetrahydrofuran.

If the solvent contains a large amount of water, the halosilane compound reacts with the water to introduce siloxane bonds (Si-O bonds) into the main chain of the obtained polysilane, thereby deteriorating the quality of the polysilane. I do. Therefore, it is desirable that the solvent used is as dry as possible,
In particular, it is preferable to dry with a desiccant and further distill to use for the reaction.

(Alkali metal compound) As the alkali metal compound used in the present invention, lithium, sodium,
Compounds containing potassium or the like (halides, inorganic acid salts, etc.) can be used, but lithium compounds are preferred.

Examples of such lithium compounds include lithium halides (lithium chloride, lithium bromide, lithium iodide, etc.), inorganic acid salts (lithium nitrate, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium perchlorate, Lithium phosphate and the like can be used. These lithium compounds can be used alone or in combination of two or more. Preferred lithium compounds are lithium halides (particularly lithium chloride).

(Metal halide) Examples of the metal halide include polyvalent metal halides. Examples thereof include transition metals (for example, Group 3A elements of the periodic table such as samarium,
Group 4A element such as titanium, group 5A element such as vanadium, group 8 element such as iron, cobalt, palladium, group 2B element such as zinc), group 3B metal such as aluminum ), And chlorides, bromides or iodides of metals such as Group 4B metals (such as tin) of the periodic table. The valence of the metal constituting the metal halide is not particularly limited, but is preferably 2 to 4
Valence, especially divalent or trivalent. These metal halides can be used alone or in combination of two or more.

Examples of such metal halides include chlorides (iron chlorides such as FeCl ₂ and FeCl ₃ ;
lCl ₃ , ZnCl ₂ , SnCl ₂ , CoCl ₂ , VC
Examples thereof include l ₂ , TiCl ₄ , PdCl ₂ , SmCl ₂ , and CuCl ₂ ), bromide (eg, iron bromide such as FeBr ₂ , FeBr ₃ ), and iodide (eg, SmI ₂ ). Among these metal halides, iron chloride (FeCl ₂ ,
FeCl ₃ ), zinc chloride (ZnCl ₂ ) and copper chloride (Cu
Cl ₂ ) is particularly preferred.

[Magnesium magnesium component] The magnesium metal component only needs to contain at least magnesium, and may be a magnesium metal alone or a magnesium-based alloy, or a mixture containing the magnesium metal or alloy. The type of the magnesium alloy is not particularly limited, and examples thereof include a conventional magnesium alloy, for example, a magnesium alloy containing components such as aluminum, zinc, and rare earth elements (such as scandium and yttrium).
These metal magnesium components can be used alone or in combination of two or more.

The shape of the metal magnesium component is not particularly limited as long as the reactivity of the polymerization reaction of the halosilane compound is not impaired. A rod-shaped body, a flat plate, and the like are exemplified, and a shape having a particularly large surface area (powder, granular body, ribbon-shaped body, cut piece-shaped body, and the like) is preferable. When the metallic magnesium component is in the form of powder, the average particle size is 1 to 1000.
The thickness is about 0 μm, preferably about 10 to 5000 μm, and more preferably about 20 to 1000 μm.

It should be noted that a film (such as an oxide film) may be formed on the metal surface depending on the storage condition of the metallic magnesium component and the like. This film may adversely affect the reaction, and may be removed by cutting or the like as necessary.

[Production Method of Activated Metal Magnesium and Polysilane] In the present invention, a halosilane compound is prepared in a solvent (an aprotic solvent) in the presence of an alkali metal compound and a metal halide in the presence of at least active metal magnesium. The reaction is performed to produce polysilane. The active metal magnesium can be obtained by treating a halosilane compound and a metal magnesium in a solvent (an aprotic solvent) in the presence of an alkali metal compound and a metal halide. That is, the method for producing polysilane includes a first step of producing active metal magnesium (a step of producing active metal magnesium) and a second step of producing polysilane using the obtained active metal magnesium.
(Manufacturing process of polysilane using active metal magnesium).

(Production Process of Active Metal Magnesium / First)
Step) In the first step, a halosilane compound and a metal magnesium are treated in an aprotic solvent in the presence of an alkali metal compound and a metal halide,
Active metal magnesium is formed. When a di- or tetra-halosilane compound is used as the halosilane compound, polysilane is generated.

The treatment (activation treatment) may be carried out by dipping, stirring (preferably stirring) or the like as long as at least the alkali metal compound, metal halide and halosilane compound can be brought into contact with the metal magnesium. If necessary, a solvent (aprotic solvent) may be used.

The proportion of the alkali metal compound is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably about 10 to 40 parts by weight, based on 100 parts by weight of metallic magnesium.

The ratio of the metal halide is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably about 10 to 30 parts by weight, based on 100 parts by weight of the metal magnesium.

The ratio of magnesium metal to the halosilane compound is at least 0.5 times mol of magnesium relative to the halogen atom in the halosilane compound (for example,
0.5 to 10 mol), but preferably 1.
5 moles or more (for example, about 1.5 to 10 moles), more preferably 2.5 times mole or more (for example, 2.5 to 10 moles)
Mol). When only dihalosilane is used as the halosilane compound, the reactivity is low, so that it is preferable to use at least 1.5 times the mole of the halogen atom or more.

The proportion of the solvent (aprotic solvent) is not particularly limited as long as the alkali metal compound, metal halide and halosilane compound can be homogenized and acts on the metal magnesium. On the other hand, for example, 1 to 10000 parts by weight, preferably 1
0 to 5000 parts by weight, more preferably 100 to 400 parts by weight
It is about 0 parts by weight.

The temperature for the activation treatment is, for example, in the temperature range from -20 ° C to the boiling point of the component (solvent, etc.) used, for example, 0 to 100 ° C, preferably 10 to 70 ° C, more preferably 20 to 50 ° C. It is about ° C. The activation treatment may be performed under reduced pressure or increased pressure, but is usually performed at normal pressure.

The activation treatment may be performed under the same conditions as in the second step. For example, the concentration of the halosilane compound in the mixture or the reaction solution (solvent) is usually 0.05 to 20 mo.
l / l, preferably 0.2 to 15 mol / l, in particular 0.
It is about 3 to 13 mol / l. If the concentration is too low, the treatment (reaction) may not be performed efficiently. If the concentration is too high, the alkali metal compound and the metal halide may not be dissolved.

The concentration of the alkali metal compound in the mixture or the reaction solution (solvent) is usually 0.05 to 5 mol / mol.
l, preferably 0.1 to 4 mol / l, especially 0.15 to
It is about 3.0 mol / l. If the concentration is too low,
The reaction may not proceed, and if it is too high, the polarity of the reaction solution may increase, and the activity of the active metal magnesium and the molecular weight of the polysilane may decrease. The ratio of the alkali metal compound is based on 100 parts by weight of the halosilane compound.
It is about 0.1 to 30 parts by weight, preferably about 1 to 20 parts by weight, and more preferably about 5 to 20 parts by weight.

The concentration of the metal halide in the mixed solution or the reaction solution (solvent) is usually 0.01 to 6 mol / l, preferably 0.02 to 4 mol / l, particularly preferably 0.03 to 3 mol / l.
It is about 1 / l. If the concentration is too low, the reaction may not proceed sufficiently, and if it is too high, it may not be involved in the reaction. The ratio of the metal halide is 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the halosilane compound.
It is about 20 parts by weight.

There are no particular restrictions on the shape and structure of the reactor (reaction vessel) used as long as it can be sealed. The inside of the reaction vessel may be a dry atmosphere, but a dry inert gas (eg, nitrogen gas, helium gas, argon gas) atmosphere, particularly a deoxygenated and dried inert gas atmosphere is preferable.

The treatment or reaction temperature is usually in the temperature range from -20 ° C to the boiling point of the solvent used, preferably from 0 to 7 ° C.
0 ° C, more preferably about 10 to 50 ° C.

In the activation reaction in the first step, for example, a halosilane compound, an alkali metal compound, a metal halide and a metal magnesium component are accommodated together with a solvent if necessary in a sealable reaction vessel, and are preferably mechanically or magnetically. It can be carried out by agitation. The order of adding each component is not particularly limited.

The activation reaction varies depending on the type and concentration of the raw materials, the reaction temperature and the like, but is usually started after about 1 to 7 hours have elapsed from the start of stirring. When the reaction starts, the reaction solution turns black while generating heat. After the end of the exotherm, by stirring for about 2 to 24 hours,
A highly activated metallic magnesium (active metallic magnesium) can be obtained together with the high molecular weight polysilane.

When the subsequent production of polysilane (second step) is performed using the thus obtained active metal magnesium, regardless of the type of the raw material halosilane compound, the reaction occurs almost simultaneously when the halosilane compound is introduced. Start,
Since the induction period of the reaction can be greatly shortened as compared with the case where metallic magnesium is used, the reaction time can be greatly shortened, so that the productivity can be improved. (Production of Polysilane Using Active Metal Magnesium / Second Step) In the second step, the active metal magnesium obtained in the first step may be used, and a pre-treatment or an activation treatment is performed in the second step. To produce a polysilane. The pretreatment or the activation treatment may be performed under the same reaction conditions as in the production of polysilane.
Further, the second step may be repeatedly performed.

In the reaction mixture obtained in the first and second steps, part of the metal magnesium used reacts with the halosilane compound to form a magnesium halide,
Present in the reaction solution. Raw material components other than metallic magnesium and polysilane exist in the reaction solution (liquid component). On the other hand, the active metal magnesium remains in a solid state in the reaction system. Therefore, for example, (1) the active metal magnesium may be separated from the reaction mixture of the first step, and if necessary, purified and subjected to the second step. (2) The second metal may be directly separated from the reaction mixture without separation. May be used. Further, (3) the liquid component may be removed from the reaction mixture by decantation or filtration, and the remaining solid component may be used as it is in the second step. When a small amount of activated metal magnesium is produced in the first step with respect to the volume of the reactor, it is often used as it is without separation.

When the second step is performed a plurality of times, for example, n
Following the second step (n is an integer of 1 or more), (n +
1) The second step can be performed in the same manner as the transition from the first step to the second step. When the second step is performed a plurality of times, the above methods (1) to (3) may be used in combination.

When the active metal magnesium is taken out of the reactor, it is preferable to store the active metal magnesium in a container purged with nitrogen in order to prevent deactivation and minimize contact with moisture in the air.

In the second step, various forms (or modes)
The raw materials (halosilane compound, alkali metal compound, metal halide and aprotic solvent) used in the production of polysilane are added and reacted in the presence of the active metal magnesium obtained in the first step of Can be generated. In the second step, for example, the raw materials can be accommodated in a sealable reaction vessel containing at least active magnesium metal, and preferably reacted mechanically or magnetically by stirring. The order of addition of each component of the raw material is not particularly limited.

In this step, the reaction starts with the generation of heat immediately after the input of the raw materials, and after completion of the generation of heat, stirring is carried out for about 30 minutes to 12 hours to obtain a high molecular weight polysilane.

The activation reaction (first step) and the production of polysilane (second step) can be performed under the same conditions. That is, metal magnesium may be activated under the same or similar conditions as in the production of polysilane. For example, the first
The liquid component may be removed from the reaction mixture obtained in the step, and the reaction may be carried out by adding a halosilane compound, an alkali metal compound, a metal halide and an aprotic solvent to the reaction system in which the active metal magnesium remains.

The first step and the second step may have the same volume (reaction scale) or may have different volumes. The first step may be performed in a small amount in advance. For example, a small amount (1/100 of the reactor volume)
(1/3, preferably about 1/10 to 1/4) of an active metal magnesium, and a halosilane compound, an alkali metal compound, a metal halide and an aprotic compound are added to a reaction system containing the generated active metal magnesium. The reaction may be performed by adding a solvent. In the present invention, since the induction time until the start of the reaction and the reaction time can be greatly reduced by using the active metal magnesium, if a method of generating a small amount of the active metal magnesium in advance is used, a large amount of the raw material can be obtained in the second step. Is added, polysilane can be produced efficiently.

In the second step, metal magnesium may be replenished to supplement the consumed metal magnesium component. Further, a mixture of active metal magnesium and metal magnesium may be used in the second step. In particular, by adding or replenishing metallic magnesium in the second step while removing the liquid component in the reaction mixture in the first step, the reaction can proceed efficiently without being diluted more than necessary. By adding each component newly,
The second step can be repeated a plurality of times without washing the reaction vessel.

In the second step, polysilane can be produced with high efficiency, so that the amount of magnesium metal used can be greatly reduced. The ratio of the active metal magnesium in the second step is 0.5 to 1 mol as magnesium with respect to 1 mol of a halogen atom of the halosilane compound.
Preferably it is about 0.6 to 0.8 mol.

As described above, in the second step, the amount of active metal magnesium used can be reduced.
The use amount of the metal magnesium component throughout the step can also be reduced. The amount of the metal magnesium component used in the first and second steps is 1 to 4 moles, preferably 1 to 3 moles, particularly 1 to 2 moles as magnesium, based on 1 mole of the total amount of the halosilane compound used in all the steps. It can be reduced to about a mole. The amount used is 0.5 to 2 mol, preferably 0.5 to 1.5 mol, in terms of magnesium, relative to 1 mol of a halogen atom of the halosilane compound.
More preferably, it is about 0.5 to 1 mol.

In the present invention, since the reaction is carried out by converting into active metal magnesium having a high reaction activity, the amount of metal magnesium used can be largely reduced as a whole, and economic efficiency can be improved, and the amount of waste can be reduced. In addition, in a general-purpose reactor, polysilane can be easily and safely produced,
The quality (molecular weight, etc.) of polysilane can be controlled stably.

In the second step, the concentration of the halosilane compound in the reaction solution (solvent) is usually 0.05 to 20 mol.
l / l, preferably 0.2 to 15 mol / l, in particular 0.
It is about 3 to 13 mol / l. If the concentration is too low, the reaction may not be performed efficiently. If the concentration is too high, the alkali metal compound and the metal halide used in the reaction may not be dissolved.

The concentration of the alkali metal compound in the solvent (reaction liquid) is generally 0.05 to 5 mol / l, preferably 0.1 to 4 mol / l, particularly 0.15 to 3.0 mol / l.
It is about l. If the concentration is too low, the reaction may not proceed, while if it is too high, the polarity of the reaction solution may increase, and the activity of active metal magnesium and the molecular weight of polysilane may decrease. The proportion of the alkali metal compound is 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the halosilane compound.
About 20 parts by weight.

The concentration of the metal halide in the solvent (reaction liquid) is usually 0.01 to 6 mol / l, preferably 0.1 to 6 mol / l.
It is about 02 to 4 mol / l, especially about 0.03 to 3 mol / l. If the concentration is too low, the reaction may not proceed sufficiently, and if it is too high, it may not be involved in the reaction. The proportion of the metal halide is about 0.1 to 30 parts by weight, preferably about 1 to 20 parts by weight, and more preferably about 3 to 20 parts by weight, based on 100 parts by weight of the halosilane compound.

The shape and structure of the reactor (reaction vessel) used are not particularly limited as long as it can be sealed. The inside of the reaction vessel may be a dry atmosphere, but a dry inert gas (eg, nitrogen gas, helium gas, argon gas) atmosphere, particularly a deoxygenated and dried inert gas atmosphere is preferable.

In the second step, the polymerization reaction of the halosilane compound (reaction for forming polysilane) is usually carried out at -20 ° C.
To the boiling point of the solvent used, preferably 0
It is carried out at a temperature of about 70 to 70 ° C, more preferably about 10 to 50 ° C. The reaction may be carried out under reduced pressure or increased pressure, but is usually carried out at normal pressure.

(Polysilane) The polysilane obtained in the second step includes, for example, units represented by the following formulas (5) to (8).

[0063]

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(Wherein, R ^{3 to} R ⁵ are the same as above. M, n and p are each an integer of 2 to 1000) m, n and p are each preferably 10 to 500,
More preferably, it is about 10 to 100. The first
In the case where polysilane is obtained in the step (b), these units are usually included.

The polysilane obtained in the second step is
Even if the step is repeated a plurality of times, the variation in molecular weight and yield is small, and the quality is stable. The weight average molecular weight Mw of the obtained polysilane is, for example, 100 to 100,000, preferably 1000 to 50,000, and more preferably 20 to 100,000.
It is about 00 to 30,000. When polysilane is obtained in the first step, the weight average molecular weight of the polysilane is about the same as the polysilane obtained in the second step, and can be selected from the above range.

The obtained polysilane is subjected to conventional separation and purification means, for example, filtration, concentration, distillation, extraction, crystallization, recrystallization,
Separation and purification may be performed by means of separation and purification such as adsorption and column chromatography, or a means combining these.

[0067]

According to the present invention, since polysilane is produced by using active metal magnesium, the induction time until the start of the reaction can be greatly reduced, and the reaction time can also be shortened. Can be manufactured. In addition, since it is excellent in safety and the amount of magnesium used can be reduced, the amount of waste can be reduced, the waste treatment can be simplified, and it is economically advantageous. Further, in the present invention, polysilane can be easily and efficiently produced.

[0068]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (1) First Step: Production Step of Active Metal Magnesium (and Polysilane) Granular (particle diameter: 20 to 1000 μm) magnesium was placed in a 1000 ml round flask equipped with a three-way cock. 9 g (2.71 mol) of anhydrous lithium chloride (L
17.5 g of iCl), anhydrous zinc chloride (ZnCl ₂ ) 1
1.3 g was charged, and 1 mmHg (= 133 kP) at 50 ° C.
After heating and reducing the pressure in a) to dry the mixture, dry argon gas was introduced into the reactor, and 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was used.
Was added and stirred at room temperature for about 30 minutes. To this mixture, methylphenyldichlorosilane 1 previously purified by distillation was added.
15 g (600 mmol) was added via syringe. In this case, the amount of magnesium used is 4.5 times the theoretical amount. Approximately 3 hours after the start of stirring, heat generation due to polymerization started and continued for approximately 3 hours. After the generation of heat was completed, the mixture was further stirred at room temperature for about 16 hours. After completion of the reaction, the reaction mixture is decanted, and a solid component (active metal magnesium component) and a liquid component (including methylphenyl polysilane)
And separated into

(2) Second step (first time): Production of polysilane using active metal magnesium 17.5 g of anhydrous lithium chloride (LiCl) was added to the solid component (active metal magnesium component), and anhydrous zinc chloride (ZnCl
₂ ) 11.3 g and 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl were added, and the mixture was stirred at room temperature for about 30 minutes. 115 g of methylphenyldichlorosilane (6
00 mmol) was added via syringe and stirred. The exotherm started immediately after the introduction of methylphenyldichlorosilane, and the exotherm continued for 3 hours.
After the time, it was confirmed that the polysilane polymerization reaction was completed. After completion of the reaction, the reaction mixture was decanted to separate into a solid component (active metal magnesium component) and a liquid component (including methylphenyl polysilane).

(3) Second step (second time): Production of polysilane using active metal magnesium Anhydrous lithium chloride (LiCl) 17 was added to the solid component (active metal magnesium) obtained in step (2). .5
g, 11.3 g of anhydrous zinc chloride (ZnCl ₂ ) and 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl were added, and the mixture was stirred at room temperature for about 30 minutes.
To this mixture, 115 g (600 mmol) of methylphenyldichlorosilane, which was previously purified by distillation, was added with a syringe, followed by stirring. Exotherm started immediately after the introduction of methylphenyldichlorosilane, and the exotherm continued for 3 hours. After stirring at room temperature, it was confirmed that the polysilane polymerization reaction was completed after 8 hours.

In this example, the polymerization reaction could be carried out once in the first step and twice in the second step (three times in total) without replenishing new metallic magnesium. Therefore, the total ratio of metallic magnesium is 1.
It was 5 times mol.

(4) Post-treatment and purification Each of the liquid component obtained in the steps (1) and (2) and the reaction mixture obtained in the step (3) are
200 ml of 1N (= 1 mol / l) hydrochloric acid and 350 ml of toluene were added for extraction. Pure water 1
After washing four times with 50 ml, toluene was distilled off to obtain methylphenylpolysilane containing a low molecular weight substance. Methylphenylpolysilane is a good solvent toluene 10
Reprecipitation was performed using 0 ml and 500 ml of the poor solvent 2-propanol. The results of the weight average molecular weight Mw and the yield of polysilane in each step are as follows, and it was confirmed that polysilane of the same quality was obtained.

First Step Mw 16900 Yield 60% Second Step (First) Mw 17300 Yield 60% Second Step (Second) Mw 17000 Yield 60% Example 2 A 3000 ml internal volume equipped with a three-way cock In a round flask, 65.9 g of granular (particle diameter: 20 to 1000 μm) magnesium, 17.5 g of anhydrous lithium chloride (LiCl) were added.
g, anhydrous zinc chloride (ZnCl ₂ ) 11.3 g,
After heating and reducing the pressure to 1 mmHg (= 133 kPa) at 50 ° C. and drying the mixture, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at room temperature for about 30 minutes. did. 115 g of methylphenyldichlorosilane (600 m
mol) was added via syringe and stirred at room temperature for about 22 hours to produce polysilane and active metal magnesium in the reactor.

Next, anhydrous lithium chloride (LiC) was placed in the reactor.
l) 35.0 g, anhydrous zinc chloride (ZnCl ₂ ) 22.6
g, 1,000 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl, and added at room temperature for about 30 minutes.
For a minute. When 230 g (1.2 mol) of methylphenyldichlorosilane, which had been purified by distillation, was added to the mixture by means of a syringe, heat generation accompanying polymerization started immediately, and the mixture was stirred at room temperature for about 12 hours. After completion of the reaction, 500 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction solution, and the mixture was extracted with 1000 ml of toluene. The toluene layer was washed four times with 500 ml of pure water, and toluene was distilled off to obtain methylphenyl polysilane containing a low molecular weight substance. Use methylphenylpolysilane as a good solvent toluene 30
0 ml and poor solvent 2-propanol 1500 ml to obtain a weight average molecular weight of 17400
Was obtained with a yield of 63%.

Example 3 After completion of the reaction of the step (3) in Example 1, the solid portion obtained by removing the liquid portion by decantation is newly granulated (particle size: 20 to 1000 μm).
6 g (600 mmol), anhydrous lithium chloride (LiC
1) 17.5 g, anhydrous zinc chloride (ZnCl ₂ ) 11.3
g, 500 ml of tetrahydrofuran and 115 g (600 mmol) of methylphenyldichlorosilane were added to carry out the reaction in the second step (third time). The reaction started immediately after the introduction of methylphenyldichlorosilane, and after the heat generation continued for 3 hours, the mixture was further stirred at room temperature. As a result, the polysilane polymerization reaction was completed after 8 hours, and the weight average molecular weight was 16%.
700 methylphenyl polysilanes were obtained in 61% yield.

Example 4 After the first reaction was carried out in the same manner as in the first step of Example 1, the reaction solution was filtered, and a solid component (active metal magnesium) was removed from the reactor. The solid component (active metal magnesium) was placed in a vessel purged with argon, stored for 3 days, and then used in the following polysilane synthesis reaction.

In a 1000 ml round flask, 29.2 g (1.2 mol) of active metal magnesium, 17.5 g of anhydrous lithium chloride (LiCl), 16.2 g of anhydrous ferrous chloride (FeCl ₃ ), and tetrahydrofuran 500
ml and 115 g of methylphenyldichlorosilane (6
00 mmol) to synthesize methylphenylpolysilane. As a result, methylphenylpolysilane having a weight average molecular weight of 19,100 was obtained at a yield of 54%.

Example 5 In each step, 57.5 g (300 mmol) of methylphenyldichlorosilane was used instead of 115 g (600 mmol) of methylphenyldichlorosilane as the halosilane compound.
mmol) and 75.9 g of diphenyldichlorosilane
(300 mmol) was used in the same manner as in Example 1. As a result, a methylphenylpolysilane-diphenylpolysilane copolymer having a weight average molecular weight of 11,800 was obtained with a yield of 76%.

Example 6 The procedure of Example 1 was repeated except that methylphenyldichlorosilane (57.5 g, 300 mmol) and phenyltrichlorosilane 43.3 g (200 mmol) were used instead of 115 g (600 mmol) of methylphenyldichlorosilane as the halosilane compound. The same was done. as a result,
A methylphenylpolysilane-phenylpolysilane copolymer having a weight average molecular weight of 11,800 was obtained at a yield of 66%.

Example 7 The procedure of Example 1 was repeated except that 95.6 g (500 mmol) of methylphenyldichlorosilane and 4.3 g (25 mmol) of tetrachlorosilane were used instead of 115 g (600 mmol) of methylphenyldichlorosilane as the halosilane compound. I went. As a result, the corresponding copolymerized polysilane having a weight average molecular weight of 9300 was converted to a yield of 47%.
I got it.

Example 8 A reaction was carried out in the same manner as in Example 1 except that 11.1 g of CuCl ₂ was used as a metal halide to obtain methylphenylpolysilane having a weight average molecular weight of 12,000 and a yield of 59.
%.

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroki Sakamoto 4-1-2 Hirano-cho, Chuo-ku, Osaka-shi F-term in Osaka Gas Co., Ltd. (reference) 4J035 JA01 JB02 JB03 LB12 LB16 LB20

Claims (14)

[Claims] An active metal magnesium obtained by treating a halosilane compound and a metal magnesium in an aprotic solvent in the presence of an alkali metal compound and a metal halide. 2. A method for producing a polysilane by reacting a halosilane compound in the presence of an alkali metal compound and a metal halide in an aprotic solvent in the presence of at least the active metal magnesium according to claim 1. 3. A first step in which metal halide is allowed to act on a halosilane compound in an aprotic solvent in the presence of an alkali metal compound and a metal halide to form active metal magnesium; 3. The method according to claim 2, further comprising the step of: adding a halosilane compound, an alkali metal compound, a metal halide, and an aprotic solvent to the reaction system, and reacting the reaction system to form polysilane. 4. 4. A liquid component is removed from the reaction mixture obtained in the first step, and a halosilane compound, an alkali metal compound, a metal halide and an aprotic solvent are added to the reaction system in which the active metal magnesium remains. The production method according to claim 3, wherein the reaction is carried out. 5. The method according to claim 3, wherein in the second step, magnesium metal is supplied. 6. A small amount of active metal magnesium is previously generated with respect to the volume of a reactor, and a halosilane compound, an alkali metal compound, a metal halide and an aprotic solvent are added to a reaction system containing the generated active metal magnesium. The production method according to claim 3, wherein the reaction is carried out by adding. 7. The method according to claim 2, wherein a compound represented by the following formula (1) is used as the halosilane compound. Embedded image (Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom,
X ¹ and X ² represent a halogen atom, an organic group or a silyl group;
Represents the same or different and represents a halogen atom) 8. A halosilane compound represented by the following formula (2):
The method according to claim 2, wherein the compound represented by (4) is used. Embedded image (Wherein, R ^{3 to} R ⁵ are the same or different and represent a hydrogen atom, an organic group or a silyl group, and X ^{1 to} X ⁴ are the same or different and represent a halogen atom) 9. The method according to claim 2, wherein the polysilane contains units represented by the following formulas (5) to (8). Embedded image (Wherein, R ^{3 to} R ⁵ are the same or different and each represent a hydrogen atom, an organic group or a silyl group, and m, n, and p each represent 2
Is an integer of ~ 1000) 10. The method according to claim 2, wherein the alkali metal compound is a lithium compound. 11. The method according to claim 2, wherein the alkali metal compound is lithium halide. 12. The method according to claim 2, wherein the metal halide is a polyvalent metal halide. 13. The method according to claim 2, wherein the metal halide is at least one metal chloride or bromide selected from samarium, titanium, vanadium, iron, cobalt, palladium, copper, zinc, aluminum and tin. Method. 14. The method according to claim 2, wherein the metal halide is at least one selected from iron chloride, copper chloride and zinc chloride.