JP2009269820A - Method for producing basket-formed siloxane compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a basket-formed siloxane compound without containing a halogen component economically. <P>SOLUTION: This method for producing the basket-formed siloxane compound is characterized by comprising a reaction process of reacting the A moles of a basket-formed silicate compound with the B moles of disiloxane compound in the presence of the C moles of nitric acid as a reaction catalyst. The numbers of moles of A to C satisfy 1<C/(8×A)≤3 and 1≤(2×B)/(8×A)≤5 simultaneously. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a cage siloxane compound.

  The cage siloxane compound has a nanometer-scale inorganic siloxane skeleton, and is attracting attention as a nanomaterial. Introducing various organic substituents around the cage structure is also useful as a building block for organic-inorganic hybrid compounds. Recently, applications as a resist and a sealing material have been studied for electronic materials. As a method for producing a cage-type siloxane compound, several production methods are known, such as a method for producing a cage-type siloxane compound having a functional group using a cage-type silicate anion as a raw material and using a chlorosilane or a disiloxane compound ( For example, see Patent Documents 1 to 4).

However, in any of these production methods, since hydrochloric acid is used as the catalyst acid or chlorosilane is used as the raw material, halogen may remain in the product. The halogen remaining in the product causes fatal problems such as corrosion of the metal wiring or deterioration of the insulation performance when the product is used as an electronic material, so it is necessary to remove it by a high degree of purification. Further, the conventional production method is not economical because the chlorosilane or disiloxane compound is used in a large excess with respect to the cage silicate compound. Further, it is known to use nitric acid as a catalyst, and the use of nitric acid in excess of the anion equivalent is also known from the previously published patent documents.
JP-A-2-67290 JP-A-2-178291 Japanese Patent No. 2777058 Special table 2007-509177

  An object of the present invention is to provide a method for economically producing a cage-type siloxane compound containing no halogen component.

  As a result of intensive studies on the above problems, the inventors of the present invention economically produced a cage-type siloxane compound containing no halogen component by reacting a specific compound as a raw material in the presence of a specific amount of nitric acid as a reaction catalyst. The present invention has been found and the present invention has been completed.

That is, the present invention specifically includes the following embodiments [1] to [8].
[1]
A method for producing a cage siloxane compound represented by the following formula (1):

(Y in Formula (1) represents a trialkylsiloxy group represented by the following Formula (2).

(In Formula (2), R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a vinyl group,
R ² represents a methyl group, an ethyl group or a phenyl group. ) In the eight trialkylsiloxy groups, the same atom or group is selected as R ¹ , and the same group is selected as R ² . )
In the presence of nitric acid as a reaction catalyst,
The cage silicate compound represented by the following formula (3)

(In formula (3), each X independently represents a group represented by the following formula (4) or the following formula (5).

(In formula (5), each R ³ independently represents an alkyl group having 1 to 4 carbon atoms.))
Including a reaction step of reacting with a disiloxane compound represented by the following formula (6):

(In formula (6), R ¹ and R ² represent the same groups as R ¹ and R ^{2 in} formula (2), respectively).
When the mole number of the cage silicate compound is A mole, the mole number of the disiloxane compound is B mole, and the mole number of the nitric acid is C mole, the mole numbers A to C are
1 <C / (8 × A) ≦ 3 and 1 ≦ (2 × B) / (8 × A) ≦ 5
A method for producing a cage-type siloxane compound characterized by satisfying

[2]
The method for producing a cage siloxane compound according to [1], wherein, in the formulas (2) and (6), R ¹ is hydrogen and R ² is a methyl group.

[3]
The method for producing a cage siloxane compound according to [1], wherein in formulas (2) and (6), R ¹ and R ² are both methyl groups.

[4]
In the above formulas (2) and (6), the method for producing a cage siloxane compound according to [1], wherein R ¹ is a vinyl group and R ² is a methyl group.

[5]
[1] to [1], wherein the reaction step is carried out in the presence of at least one organic solvent selected from the group consisting of halogenated hydrocarbons, aliphatic hydrocarbons and aromatic hydrocarbons.
4] The method for producing a cage-type siloxane compound according to any one of [4].

[6]
After preparing the mixed solution containing the said disiloxane compound and alcohol, nitric acid as a catalyst is added to this mixed solution, The cage-type siloxane compound of any one of [1] thru | or [5] characterized by the above-mentioned Production method.

[7]
The method for producing a cage siloxane compound according to [6], wherein the amount of the alcohol is 10 to 100 parts by mass with respect to 100 parts by mass of the nitric acid.

[8]
A cage-type siloxane compound obtained by the production method according to any one of [1] to [7].

  According to the production method of the present invention, a cage-type siloxane compound in which no halogen remains can be produced economically. A cage-type siloxane compound in which no halogen remains is useful as an electronic material such as a resist material or a semiconductor sealing material.

Hereinafter, the method for producing the cage siloxane compound of the present invention will be described in detail.
The method for producing a cage-type siloxane compound of the present invention is a production method for obtaining a cage-type siloxane compound, which comprises a specific amount of a cage-type silicate compound and a specific amount of disiloxane in the presence of a specific amount of nitric acid as a reaction catalyst. It includes a reaction step of reacting with a compound.

  The cage siloxane compound is a compound represented by the following formula (1).

(Y in Formula (1) represents a trialkylsiloxy group represented by the following Formula (2).

(In Formula (2), R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a vinyl group,
R ² represents a methyl group, an ethyl group or a phenyl group. ) In the eight trialkylsiloxy groups, the same atom or group is selected as R ¹ , and the same group is selected as R ² . )
The said cage silicate compound is a compound represented by following formula (3).

(In formula (3), each X independently represents a group represented by the following formula (4) or the following formula (5).

(In formula (5), each R ³ independently represents an alkyl group having 1 to 4 carbon atoms.))
The counter cation of the cage silicate compound is preferably quaternary ammonium, and specific examples thereof include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, and choline. The cage silicate compound is disclosed in J. Org. Mol. Liq. , 34 307-315 (1987) or the like, or commercially available products may be used. The cage silicate compound is usually obtained as a hydrate solid, but can be used as it is in the reaction step when it is obtained as an alcohol solution at the time of manufacture, not as a hydrate solid.

  Specific examples of the cage silicate compound include octa (tetramethylammonium) silsesquioxane, octa (tetraethylammonium) silsesquioxane, octa (tetrapropylammonium) silsesquioxane, and the like. Is octa (tetramethylammonium) silsesquioxane. Such a compound is preferable because of its high solubility in methanol and high concentration during the reaction.

  The disiloxane compound is a compound represented by the following formula (6).

(In formula (6), R ¹ and R ² represent the same groups as R ¹ and R ^{2 in} formula (2), respectively).
In the formulas (2) and (6), R ¹ and R ² are preferably groups having a small number of carbon atoms. In the above formulas (2) and (6), R ¹ is preferably a vinyl group, R ² is preferably a methyl group, more preferably R ¹ and R ² are both methyl groups, and R ¹ is hydrogen. And R ² is particularly preferably a methyl group. The present inventors presume that when the number of carbon atoms of R ¹ and R ² is small, the solubility in water is high and the reactivity is therefore high.

In the method for producing a cage siloxane compound of the present invention, nitric acid is used as a reaction catalyst. Nitric acid is preferably used as a reaction catalyst in that the halogen content in the product can be suppressed.
Moreover, it is preferable to add nitric acid as a reaction catalyst to the mixed solution containing the disiloxane compound and alcohol. When nitric acid as a reaction catalyst is added to a mixture containing no alcohol, for example, a mixture of the disiloxane compound and an organic solvent described later, the mixture is colored. When the product obtained from such a colored mixture is used as a photo-curing resin for electronic materials, there is a problem that light absorption lowers the curing efficiency, and when it is used as an optical material, the light transmittance is poor. Become. The mixed solution containing alcohol in the mixture is not colored even when nitric acid as a reaction catalyst is added. In the prior art, hydrochloric acid is often used as a reaction catalyst. When hydrochloric acid having a concentration of about 35%, generally called concentrated hydrochloric acid, is used, it may be particularly colored yellow. If nitric acid is used as a catalyst and the nitric acid is added to the mixed solution containing the disiloxane compound and the alcohol, the reaction solution will not be colored and the product will not be adversely affected. Examples of the alcohol include methanol, ethanol,
1-propanol, 2-propanol and the like can be preferably used.

  The addition amount of the alcohol is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and particularly preferably 40 to 70 parts by mass with respect to 100 parts by mass of the nitric acid. It is preferable that the amount of the alcohol added be within the above range because coloring with nitric acid as a reaction catalyst can be prevented.

  In the method for producing a cage siloxane compound of the present invention, when the mole number of the cage silicate compound is A mole, the mole number of the disiloxane compound is B mole, and the mole number of nitric acid is C mole, The number of moles A to C is characterized by satisfying 1 <C / (8 × A) ≦ 3 and 1 ≦ (2 × B) / (8 × A) ≦ 5 at the same time.

  According to the knowledge so far, it is customary to use a disiloxane compound or a chlorosilane compound in a large excess with respect to the silicate compound as a raw material for the synthesis of the cage siloxane compound. However, in the method for producing a cage siloxane compound of the present invention, the reaction proceeds sufficiently even if the disiloxane compound and nitric acid are used in a small excess amount with respect to the cage silicate compound, and the efficiency is improved. Thus, a cage-type siloxane compound can be obtained.

  Although it is clear that the reaction will occur even when “C / (8 × A)” is larger than 3, it is not economical because more nitric acid than necessary is wasted and waste is increased. When “C / (8 × A)” is 1 or less, the acid is less than the amount of the base, that is, the ammonium salt, so that the function as a catalyst is not exhibited and the reaction does not proceed, which is not preferable. Further, since this reaction does not proceed unless the acid concentration is high, it is preferable to use one having a high concentration. In consideration of ease of handling, the concentration of nitric acid aqueous solution is preferably 50 to 75%, more preferably 60 to 75%, and generally around 68% circulating as concentrated nitric acid aqueous solution is used. Is particularly preferred.

  “(2 × B) / (8 × A)” is preferably 1 or more, more preferably greater than 1.1, and particularly preferably greater than 2. When “(2 × B) / (8 × A)” is less than 1, the reaction does not proceed sufficiently, and by-products which are reaction intermediates increase. On the other hand, if “((2 × B) / (8 × A)” is greater than 5, waste is increased, which is not economical.

In the method for producing a cage siloxane compound of the present invention, the reaction step is preferably performed in the presence of at least one organic solvent selected from the group consisting of halogenated hydrocarbons, aliphatic hydrocarbons and aromatic hydrocarbons. .

  The organic solvent is not particularly limited as long as it is a solvent that can be separated from water. Specific examples of the organic solvent include halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, chlorobenzene and dichlorobenzene, aliphatic hydrocarbons such as hexane and pentane, and aromatic hydrocarbons such as toluene and xylene. Of these, toluene is preferred. The mass of the organic solvent that separates from water is preferably 1/5 to 5 times, more preferably 1/2 to 3 times the mass of the cage silicate compound. When the amount is more than 5 times, the reaction becomes slow, and when the amount is less than 1/5 times, the product is hardly dissolved and the yield is lowered. The reaction temperature is preferably in the range of 5 to 40 ° C, and more preferably in the range of 10 to 30 ° C. When the reaction temperature is less than 5 ° C., the reaction rate is slow, and when it exceeds 40 ° C., side reactions increase and the yield decreases.

In the method for producing a cage siloxane compound of the present invention, the cage silicate compound is preferably added in a solution dissolved in alcohol. When this solution is added to the mixture of the disiloxane compound and the organic solvent, heat of neutralization is generated. Therefore, it is preferable to add the solution little by little. The cage silicate compound can be added as it is, but the solution is easier to control in consideration of the handling of the production. The alcohol is preferably methanol or ethanol. Alcohols having 3 or more carbon atoms are not suitable because of the low solubility of the cage silicate compound.

  In the method for producing a cage siloxane compound of the present invention, after adding nitric acid as a catalyst to the mixed solution of the disiloxane compound, the organic solvent and the alcohol, an alcohol solution of the cage silicate compound may be added. The disiloxane compound may be added after adding the alcohol solution of the cage silicate compound to the mixed solution of the organic solvent, alcohol and nitric acid.

  Usually, the reaction solution is separated into two phases, but an alcohol may be further added as a solvent if necessary in order to promote mass transfer between the phases. As such an alcohol, methanol, ethanol, 1-propanol, 2-propanol and the like are preferable.

The cage-type siloxane compound of the present invention is obtained by the above-described production method.
Moreover, since the cage siloxane compound of the present invention is obtained by reacting the cage silicate compound with the disiloxane compound in the presence of nitric acid as a reaction catalyst, it does not contain a halogen component. Such a cage-type siloxane compound not containing a halogen component is useful as an electronic material such as a resist material or a semiconductor sealing material.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples, and can be appropriately modified and implemented without departing from the scope of the present invention.
Example 1
A stirrer and a thermometer were installed in a three-necked glass flask, and tetramethyldisiloxane (12.8 g (95.1 mmol)), 150 g of toluene and 10 g of methanol were charged. The mixed solution was cooled to 5 ° C., and 69% nitric acid (17.4 g (190 mmol)) was added dropwise to the mixed solution while stirring. Thereafter, the mixed solution is returned to room temperature, and a cage silicate compound (formula (5) R ³ = methyl group 50.0 g (21.6 mm) is stirred into the mixed solution.
ol)) in 50.0 g of methanol was added dropwise over 1 hour. After stirring at room temperature for 4 hours, the aqueous layer was separated, and the organic layer was washed with 100 g of water three times. Thereafter, the organic layer was evaporated to dryness to obtain white crystals (formula (2) R ¹ = H, R ² = methyl group) (C / (8 × A) = 1.1, (2 × B). /(8×A)=1.1).

²⁹ Si-NMR of the obtained crystal was measured. The spectrum is shown in FIG. The signals of Si in the cage skeleton and Si in the side chain were detected, and it was judged that the desired cage siloxane compound was formed from the integrated value ( ²⁹ Si-NMR (acetone d6, 53.54 MHz) JNM-EX270: δ (ppm) -1.0 (Si in the side chain portion), -107 (Si in the cage skeleton)). Moreover, when the chlorine content contained in the obtained crystal was measured, it was below the lower limit of detection (≦ 5 ppm). The chlorine content was measured by burning the sample in an oxygen stream, collecting the generated gas with alkali, and analyzing it by ion chromatography.

(Example 2)
A stirrer and a thermometer were placed in a three-necked glass flask, and 1,3-bisdivinyltetramethyldisiloxane (32.2 g (173 mmol)), 150 g of toluene, and 10 g of methanol were charged. The mixed solution was cooled to 5 ° C., and 69% nitric acid (31.6 g (346 mmol)) was added dropwise to the mixed solution while stirring. Thereafter, the mixed solution was returned to room temperature, and a cage silicate compound (formula (5) R ³ = methyl group 50.0 g) was stirred into the mixed solution.
(21.6 mmol)) in 50.0 g of methanol was added dropwise over 1 hour. After continuing stirring at room temperature for 24 hours, the aqueous layer was separated, and the organic layer was washed with 100 g of water three times. The organic layer was evaporated to dryness to obtain white crystals (formula (2) R ¹ = vinyl group, R ² = methyl group) (C / (8 × A) = 2.0, (2 × B) / (8 × A) = 2.0). As a result of measuring ²⁹ Si-NMR of the obtained crystals in the same manner as in Example 1, it was judged that the target cage-type siloxane compound was produced. When the chlorine content contained in the obtained crystal was measured by the same method as in Example 1, it was below the lower limit of detection (≦ 5 ppm).

(Comparative Example 1)
A stirrer and a thermometer were installed in a three-necked glass flask, and tetramethyldisiloxane (12.8 g (95.1 mmol)), toluene 150 g, and methanol 10 g were charged. The mixed solution was cooled to 5 ° C., and 35% hydrochloric acid (19.3 g (190 mmol)) was added dropwise to the mixed solution while stirring. Thereafter, the mixed solution was returned to room temperature, and a cage silicate compound (formula (5) R ³ = methyl group 50.0 g (21.6 mmol) was stirred into the mixed solution.
)) Dissolved in 50.0 g of methanol was added dropwise over 1 hour. After stirring at room temperature for 4 hours, the aqueous layer was separated, and the organic layer was washed with 100 g of water three times. The organic layer was evaporated to dryness to obtain white crystals (formula (2) R ¹ = H, R ² = methyl group). When the chlorine content contained in the obtained crystal was measured by the same method as in Example 1, it was 140 ppm.

(Comparative Example 2)
A stirrer and a thermometer were installed in a three-necked glass flask, and tetramethyldisiloxane (12.8 g (95.1 mmol)), toluene 150 g, and methanol 10 g were charged. The mixed solution was cooled to 5 ° C., and 69% nitric acid (7.89 g (86.4 mmol)) was added dropwise to the mixed solution while stirring. Then, the mixed solution was returned to room temperature, and the cage silicate compound (formula (5) R ³ = methyl group 50.0 g (21.6 mmol) was stirred into the mixed solution.
A solution prepared by dissolving 1)) in 50.0 g of methanol was added dropwise over 1 hour. Stirring was continued for 4 hours at room temperature, but the aqueous layer was in an emulsion state. The upper organic layer was separated and washed 3 times with 100 g of water. When the solvent of the organic layer was removed under reduced pressure, a liquid material was obtained. Analysis by gas chromatography revealed almost no target product (C / (8 × A) = 0.5, (2 × B) / (8 × A) = 1.1).

(Comparative Example 3)
A stirrer and a thermometer were installed in a three-necked glass flask, and tetramethyldisiloxane (5.80 g (43.2 mmol)), toluene 150 g, and methanol 10 g were charged. The mixed solution was cooled to 5 ° C., and 69% nitric acid (17.4 g (190 mmol)) was added dropwise to the mixed solution while stirring. Thereafter, the mixed solution was returned to room temperature, and a cage silicate compound (formula (5) R ³ = methyl group 50.0 g (21.6 mmol) was stirred into the mixed solution.
)) Dissolved in 50.0 g of methanol was added dropwise over 1 hour. After stirring at room temperature for 4 hours, the aqueous layer was separated, and the organic layer was washed with 100 g of water three times. The organic layer was evaporated to dryness to obtain 5.5 g of white crystals (formula (2) R ¹ = H, R ² = methyl group). The yield was 25% based on the theoretical yield of 22.0 g (C / (8 × A) = 1.1, (2 × B) / (8 × A) = 0.5).

2 is a ²⁹ Si-NMR spectrum of the compound obtained in Example 1.

Claims (8)

A method for producing a cage siloxane compound represented by the following formula (1):
(Y in Formula (1) represents a trialkylsiloxy group represented by the following Formula (2).
(In Formula (2), R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a vinyl group,
R ² represents a methyl group, an ethyl group or a phenyl group. ) In the eight trialkylsiloxy groups, the same atom or group is selected as R ¹ , and the same group is selected as R ² . )
In the presence of nitric acid as a reaction catalyst,
The cage silicate compound represented by the following formula (3)
(In formula (3), each X independently represents a group represented by the following formula (4) or the following formula (5).
(In formula (5), each R ³ independently represents an alkyl group having 1 to 4 carbon atoms.))
Including a reaction step of reacting with a disiloxane compound represented by the following formula (6):
(In formula (6), R ¹ and R ² represent the same groups as R ¹ and R ^{2 in} formula (2), respectively).
When the mole number of the cage silicate compound is A mole, the mole number of the disiloxane compound is B mole, and the mole number of the nitric acid is C mole, the mole numbers A to C are
1 <C / (8 × A) ≦ 3 and 1 ≦ (2 × B) / (8 × A) ≦ 5
A method for producing a cage-type siloxane compound characterized by satisfying The method for producing a cage siloxane compound according to claim 1, wherein, in the formulas (2) and (6), R ¹ is hydrogen and R ² is a methyl group. The method for producing a cage siloxane compound according to claim 1, wherein in the formulas (2) and (6), R ¹ and R ² are both methyl groups. 2. The method for producing a cage siloxane compound according to claim 1, wherein, in the formulas (2) and (6), R ¹ is a vinyl group and R ² is a methyl group. 5. The reaction step according to claim 1, wherein the reaction step is performed in the presence of at least one organic solvent selected from the group consisting of halogenated hydrocarbons, aliphatic hydrocarbons, and aromatic hydrocarbons. The manufacturing method of the cage-type siloxane compound as described in 2.   6. The method for producing a cage-type siloxane compound according to claim 1, wherein after preparing a mixed solution containing the disiloxane compound and alcohol, nitric acid as a catalyst is added to the mixed solution. .   The method for producing a cage siloxane compound according to claim 6, wherein the amount of the alcohol is 10 to 100 parts by mass with respect to 100 parts by mass of the nitric acid.   A cage-type siloxane compound obtained by the production method according to any one of claims 1 to 7.