Method for producing silane compound

Abstract

Provided is a method for producing a silane compound, which does not produce corrosive substances such as acids, does not use organic solvents and which contributes to a reduction in environmental load. This method for producing a silane compound has D) a siloxane decomposition step for heating a mixture containing: a siloxane compound A), which is a cyclic siloxane compound A-1) represented by formula (1), a linear siloxane compound A-2) represented by formula (2) and / or a silsesquioxane compound that is represented by formula (3) and has a siloxane bond as a main chain skeleton; a carbonate compound B) including at least one of a diaryl carbonate, a dialkyl carbonate and a monoalkylmonoaryl carbonate; and a basic compound catalyst C). The step D) further includes subjecting the siloxane compound A) to alkoxylation and / or aryloxylation. (In the formulae, R1 to R5, X, n, m and p are as described in the description of the present application.)

Description

[Technical field]

[0001] The present invention relates to a method for producing a silane compound, in particular, a method for producing a silane compound such as an aryloxysilane compound or an alkoxysilane compound. [Background technology]

[0002] As a method for producing a silane compound such as a diaryloxysilane compound or a dialkoxysilane compound, a method in which a dihalogenated silane compound, such as a dichlorosilane compound, or a diacyloxysilane compound, such as a diacetoxysilane compound, is reacted with a phenol derivative or various alcohol compounds is generally known.

[0003] For example, Patent Document 1 discloses a method for producing dimethyldiphenoxysilane from dimethyldichlorosilane and phenol. This method requires various steps, such as a step of treating hydrogen chloride gas that is by-produced simultaneously with the production of dimethyldiphenoxysilane, a washing step of washing the product with a base before distillation and purification, and an extraction step using an organic solvent. Furthermore, the process described in Patent Document 1 requires a waste liquid treatment step, which places a large burden on the environment. Furthermore, Patent Document 2 discloses a production method for obtaining dimethyldiphenoxysilane from polydimethylsiloxane and phenol, but this reaction also uses a solvent and does not provide a sufficient yield.

[0004] As a method for producing a silane compound such as a triaryloxysilane compound or a trialkoxysilane compound, a method in which a trihalogenated silane compound, such as a trichlorosilane compound, is reacted with a phenol derivative or various alcohol compounds is generally known.

[0005] For example, Patent Document 3 discloses a method for producing methyltriphenoxysilane from methyltrichlorosilane and phenol. Since this reaction is an equilibrium reaction, the rate-determining step of the reaction is how to remove the by-product hydrogen chloride from the reaction system. Like the diaryloxysilane compounds described above, the target triaryloxysilane compounds are often unstable in acidic aqueous solutions, and a step of removing hydrogen chloride is required to suppress hydrolysis and condensation reactions. As described above, it has not necessarily been easy to produce a silane compound safely and efficiently using conventional production methods. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] US2012 / 184702 publication [Patent Document 2] JP 2008-297227 A [Patent Document 3] Japanese Patent Application Publication No. 10-218885 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention provides a method for producing silane compounds, such as diaryloxysilane compounds, dialkoxysilane compounds, triaryloxysilane compounds, and trialkoxysilane compounds, which does not involve the production of corrosive substances such as hydrochloric acid or acetic acid, does not use organic solvents, and leads to reduced environmental impact. [Means for solving the problem]

[0008] The present invention provides a method for producing a silane compound, which is described below, and which is capable of reducing the environmental load and efficiently producing a target compound.

[0009] [1] A) a siloxane compound which is A-1) a cyclic siloxane compound represented by the following formula (1), A-2) a linear siloxane compound represented by the following formula (2), and / or A-3) a silsesquioxane compound having a siloxane bond as a main chain skeleton represented by the following formula (3). B) a carbonate compound containing at least one of a diaryl carbonate, a dialkyl carbonate, and a monoalkyl monoaryl carbonate, and C) Basic compound catalyst D) a siloxane decomposition step of heating the mixture containing the above A) to alkoxylate and / or aryloxylate the siloxane compound; A method for producing a silane compound, comprising at least one of a diaryloxysilane compound, a dialkoxysilane compound, a monoaryloxymonoalkoxysilane compound, a triaryloxysilane compound, and a trialkoxysilane compound. [ka] (In the formula, R 1 and R 2 each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, n represents an integer between 3 and 30. [ka] (In the formula, R 3 and R 4 each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, m represents an integer between 2 and 10,000, X's each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having a total of 1 to 10 carbon atoms which may have a substituent and which may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent. [R 5 SiO 1.5 ]p (3) (In the formula, R 5represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may have a substituent; p is a number between 4 and 24.) [2] A) a cyclic siloxane compound A-1) represented by the following formula (1), and / or a linear siloxane compound A-2) represented by the following formula (2): B) a carbonate compound containing at least one of a diaryl carbonate, a dialkyl carbonate, and a monoalkyl monoaryl carbonate, and C) Basic compound catalyst D) a siloxane decomposition step of heating the mixture containing the above A) to alkoxylate and / or aryloxylate the siloxane compound; A method for producing a silane compound, comprising at least one of a diaryloxysilane compound, a dialkoxysilane compound, and a monoaryloxymonoalkoxysilane compound. [ka] (In the formula, R 1 and R 2 each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, n represents an integer between 3 and 30. [ka] (In the formula, R 3 and R 4 each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, m represents an integer between 2 and 10,000, X's each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having a total of 1 to 10 carbon atoms which may have a substituent and which may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent. [3] R 1 ~R 4The method for producing the silane compound according to the above [1] or [2], wherein each independently represents an alkyl group, an alkenyl group having 1 to 8 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms in total. [4] The above R 1 ~R 4 The method for producing the silane compound according to the above [3], wherein each independently is any one selected from the group consisting of a methyl group, a phenyl group, a vinyl group, and a propyl group. [5] The method for producing the silane compound according to any one of the above [1] to [4], wherein the B) diaryl carbonate contains diphenyl carbonate. [6] The method for producing the silane compound according to any one of the above [1] to [4], wherein the alkyl group in the B) dialkyl carbonate has 4 or less carbon atoms. [7] The method for producing the silane compound according to any one of the above [1] to [6], wherein the C) basic compound catalyst contains an alkali metal carbonate or an alkali metal hydroxide. [8] The method for producing the silane compound according to the above [7], wherein the C) basic compound catalyst contains at least one of cesium carbonate and potassium carbonate. [9] The method for producing the silane compound according to any one of the above [1] to [8], wherein in the D) siloxane decomposition step, the ratio x of the molar amount of the B) carbonate compound to the Si molar amount of the A) siloxane compound is x≧1.

[10] The method for producing the silane compound according to any one of the above [1] to [8], wherein in the D) siloxane decomposition step, the ratio x of the molar amount of the B) carbonate compound to the Si molar amount of the A) siloxane compound is 0.8 < x < 1.6.

[11] The method for producing the silane compound according to any one of the above [1] to

[10] , wherein in the D) siloxane decomposition step, the ratio y of the molar amount of the C) basic compound catalyst to the Si molar amount of the A) siloxane compound is 0.0001 mmol / mol ≦ y ≦ 20 mmol / mol.

[12] The method for producing a silane compound according to any one of the above [1] to

[11] , wherein in the D) siloxane decomposition step, the temperature at which the siloxane compound is decomposed is 50°C or higher and 300°C or lower.

[13] The method for producing a silane compound according to the above

[12] , wherein in the D) siloxane decomposition step, the temperature is 50°C or higher and 150°C or lower.

[14] The method for producing a silane compound according to the above [1], wherein the molecular weight of the A-1) cyclic siloxane compound represented by the formula (1) is 2,000 or less, the molecular weight of the A-2) linear siloxane compound represented by the formula (2) is 60,000 or less, and the molecular weight of the A-3) silsesquioxane compound represented by the formula (3) is 3,500 or less.

[15] The method for producing a silane compound according to any one of the above [1] to

[14] , further comprising at least one E) distillation step / recrystallization step of distilling the silane compound produced by the D) siloxane decomposition step, and a recrystallization step of recrystallizing the silane compound produced by the D) siloxane decomposition step.

[16] The method for producing a silane compound according to the above

[15] , wherein the pressure in the distillation step E) is 1 hPa or more and 20 hPa or less.

[17] The method for producing a silane compound according to any one of the above [1] to

[16] , further comprising F) a dropping step of dropping the A) siloxane compound into a mixture containing the B) carbonate compound and the C) basic compound catalyst. Effect of the Invention

[0010] According to the method for producing a silane compound of the present invention, a silane compound can be efficiently produced without producing corrosive substances such as acids as by-products and by reducing the number of steps required. Therefore, according to the present invention, a method for efficiently producing a target silane compound while reducing the environmental load can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The method for producing a silane compound according to the present invention comprises the steps of: A) A cyclic siloxane compound, a linear siloxane compound, and / or a silsesquioxane compound, which will be described in detail later; B) a carbonate compound containing at least one of a diaryl carbonate, a dialkyl carbonate, and a monoalkyl monoaryl carbonate, and C) Basic compound catalyst The method further comprises a siloxane decomposition step of heating a mixture containing the above-mentioned (A) to alkoxylate and / or aryloxylate the siloxane compound. According to the production method of the present invention, at least any one of silane compounds selected from diaryloxysilane compounds, dialkoxysilane compounds, monoaryloxymonoalkoxysilane compounds, triaryloxysilane compounds, and trialkoxysilane compounds is produced. The method for producing a silane compound according to the present invention will be described in detail below.

[0012] [A) Siloxane compound] A-1) Cyclic siloxane compound Among the siloxane compounds used in the siloxane decomposition step, the cyclic siloxane compound is represented by the following formula (1). [ka] In formula (1), R 1 and R 2 R in formula (1) each independently represents an alkyl group, an alkenyl group, or an aryl group, which may have a substituent. 1 and R 2 is preferably an alkyl group or alkenyl group having a total of 1 to 8 carbon atoms, or an aryl group having a total of 6 to 30 carbon atoms, each of which may have a substituent. R 1 and R 2 When is an alkyl group which may have a substituent, or an alkenyl group which may have a substituent, it preferably has a total of 1 to 6 carbon atoms, more preferably has a total of 1 to 4 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. Also, R 1and R 2 When the aryl group is an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8. Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in formula (1) 1 and R 2 Preferred specific examples of the alkyl group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0013] In formula (1), n ​​represents an integer of 3 or more and 30 or less. The value of n in formula (1) is preferably 3 or more and 15 or less, more preferably 3 or more and 10 or less, even more preferably 3 or more and 8 or less, and particularly preferably 3 or more and 5 or less. In addition, the cyclic siloxane compound represented by formula (1) may be a mixture of compounds having different n values, different molecular structures, or compounds having both different n values ​​and different molecular structures.

[0014] The molecular weight of the cyclic siloxane compound represented by formula (1) is preferably 2,000 or less, more preferably 1,600 or less, even more preferably 1,200 or less, and particularly preferably 1,000 or less. The molecular weight of the cyclic siloxane compound represented by formula (1) is, for example, 100 or more, preferably 150 or more, and more preferably 200 or more.

[0015] A-2) Linear siloxane compound Of the siloxane compounds used in the siloxane decomposition step, the linear siloxane compound is represented by the following formula (2). [ka] In formula (2), R 3 and R 4R in formula (2) each independently represents an alkyl group, an alkenyl group, or an aryl group, which may have a substituent. 3 and R 4 is preferably an alkyl group or alkenyl group having a total of 1 to 8 carbon atoms, or an aryl group having a total of 6 to 30 carbon atoms, each of which may have a substituent. R 3 and R 4 When is an alkyl group which may have a substituent, or an alkenyl group which may have a substituent, it preferably has a total of 1 to 6 carbon atoms, more preferably has a total of 1 to 4 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. Also, R 3 and R 4 When the aryl group is an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8. Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in Equation (2) 3 and R 4 Preferred specific examples of the alkyl group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0016] In formula (2), m represents an integer of 2 or more and 10,000 or less. The value of m in formula (2) is preferably 10 or more and 7,000 or less, more preferably 20 or more and 2,000 or less, even more preferably 30 or more and 1,000 or less, and particularly preferably 40 or more and 800 or less. In addition, the linear siloxane compound represented by formula (2) may be a mixture of compounds having different m values, different molecular structures, or compounds having both different m values ​​and different molecular structures.

[0017] In formula (2), X's each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having a total of 1 to 10 carbon atoms which may have a substituent and may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent. Preferably, X's each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, or an alkyl group having a total of 1 to 10 carbon atoms which may have a substituent and may have an oxygen atom or a nitrogen atom, more preferably a hydroxyl group or an alkyl group having a total of 1 to 10 carbon atoms which may have a substituent, and even more preferably a hydroxyl group or an alkyl group having a total of 1 to 5 carbon atoms. Examples of the substituent for X include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group.

[0018] The molecular weight of the linear siloxane compound represented by formula (2) is preferably 60,000 or less, more preferably 56,000 or less, even more preferably 50,000 or less, and particularly preferably 45,000 or less. The molecular weight of the linear siloxane compound represented by formula (2) is, for example, 1,000 or more, preferably 2,000 or more, and more preferably 3,000 or more.

[0019] A-3) Silsesquioxane compounds Among the siloxane compounds used in the siloxane decomposition step, the silsesquioxane compound is a siloxane-based compound having a siloxane bond (Si—O—Si bond) as the main chain skeleton, and is represented by the following formula (3). [R 5 SiO 1.5 ]p (or the formula [R 5 SiO 3 / 2 ]p) (3)

[0020] As the silsesquioxane of formula (3), for example, a ladder type, a net type, a cage type, a random type, etc. are used. Among these, a cage type silsesquioxane is preferable in terms of solubility in a carbonate compound. For example, a cage type silsesquioxane is represented by the following formula (3') (R in formula (3') is the following R 5 (which is the same substituent as [ka] In formula (3), R 5 represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may have a substituent. R in Equation (3) 5 are preferably an alkyl group having a total of 1 or 2 carbon atoms which may have a substituent, an alkenyl group having a total of 2 or 3 carbon atoms which may have a substituent, or an aryl group having a total of 6 to 10 carbon atoms. 5 When the aryl group is an aryl group which may have a substituent, it more preferably has 6 to 8 carbon atoms in total. Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in Equation (3) 5 Preferred specific examples of the alkyl group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0021] In formula (3), p represents an integer of 4 or more and 24 or less. The value of p in formula (3) is preferably 5 or more and 20 or less, more preferably 6 or more and 18 or less. The value of p is still more preferably 8 to 14, and particularly preferably 8, 10, 12, or 14. The silsesquioxane of formula (3) preferably has the above-mentioned values ​​of p and is a cage type. In addition, the silsesquioxane compound represented by formula (3) may be a mixture of compounds having different p values, compounds having different molecular structures, or compounds having both different p values ​​and molecular structures.

[0022] In the silsesquioxane compound of formula (3), R as a substituent 5 The type of and the molecular weight of the silsesquioxane compound have the relationship shown in the following table. As described above, since the silsesquioxane compound of formula (3) in which the value of p is 8 to 14 is preferable, a preferable range of the molecular weight of the silsesquioxane compound of formula (3) having a representative substituent is determined. That is, the molecular weight of the silsesquioxane compound represented by formula (3) is preferably 3,500 or less, more preferably 3,100 or less, even more preferably 1,900 or less, still more preferably 1,600 or less, and particularly preferably 1,300 or less. The molecular weight of the silsesquioxane compound represented by formula (3) is, for example, 100 or more, preferably 150 or more, more preferably 200 or more, and even more preferably 250 or more. [Table 1]

[0023] Among the cyclic siloxane compound of the above formula (1), the linear siloxane compound of the formula (2), and the silsesquioxane compound of the formula (3), only one of the siloxane compounds may be used, or any of the cyclic siloxane compound, the linear siloxane compound, and the silsesquioxane compound may be used as a mixture. These siloxane compounds can be synthesized by known methods, and commercially available ones may be used. The cyclic siloxane compound of formula (1) and the linear siloxane compound of formula (2) are preferably used to produce any one of the silane compounds, i.e., diaryloxysilane compounds, dialkoxysilane compounds, and monoaryloxymonoalkoxysilane compounds. The silsesquioxane compound of formula (3) is preferably used to produce at least any one of the silane compounds, i.e., triaryloxysilane compounds and trialkoxysilane compounds.

[0024] [B) Carbonate compounds] The carbonate compound used in the siloxane decomposition step is at least one of diaryl carbonate, dialkyl carbonate, and monoalkyl monoaryl carbonate. The diaryl carbonate and the monoalkyl monoaryl carbonate preferably have an aryl group having a total of 6 to 30 carbon atoms, and the aryl group preferably has a total of 6 to 20 carbon atoms, more preferably a total of 6 to 12 carbon atoms, and particularly preferably a total of 6 to 8 carbon atoms. A preferred specific example of the aryl group is a phenyl group. When a diaryl carbonate is used as the carbonate compound, it preferably contains at least diphenyl carbonate.

[0025] In addition, the dialkyl carbonate and monoalkyl monoaryl carbonate as carbonate compounds preferably have an alkyl group having a total of 1 to 8 carbon atoms, more preferably a total of 1 to 6 carbon atoms in the alkyl group, and even more preferably an alkyl group having a total of 1 to 4 carbon atoms, i.e., 4 or less. The above carbonate compounds can be synthesized by known methods, and commercially available compounds may also be used.

[0026] [C) Basic compound catalyst] Examples of the basic compound catalyst used in the siloxane decomposition step include alkali metal compounds and alkaline earth metal compounds, and examples of such compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals and alkaline earth metal compounds, quaternary ammonium hydroxides and their salts, amines, and the like, and these compounds can be used alone or in combination of a plurality of types. In order to improve the efficiency of the reaction in the siloxane decomposition step, it is more preferable that the basic compound catalyst contains an alkali metal carbonate or an alkali metal hydroxide. Preferred specific examples of the basic compound catalyst include cesium carbonate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, cesium hydroxide, potassium hydroxide, and sodium hydroxide. The basic compound catalyst can be prepared by a known method, and a commercially available product may be used. The basic compound catalyst may be added to the reaction system as an aqueous solution or as a powder.

[0027] [D) Siloxane decomposition process] In the siloxane decomposition step, a mixture containing the cyclic siloxane compound and / or linear siloxane compound of A) and the carbonate compound of B) is heated in the presence of the basic compound catalyst of C) to alkoxylate and / or aryloxylate the siloxane compound of A) and decompose the siloxane. In this way, the siloxane decomposition reaction of the siloxane compound of A) produces a silane compound having an aryl group and / or an alkyl group introduced from the carbonate compound of B).

[0028] In the siloxane decomposition step, when a diaryl carbonate is used as the carbonate compound in B) above, the silane compound generated is a diaryloxysilane compound, when a dialkyl carbonate is used as the carbonate compound in B) above, the silane compound generated is a dialkoxysilane compound, and when a monoalkyl monoaryl carbonate is used as the carbonate compound in B) above, the silane compound generated is a monoaryloxy monoalkoxysilane compound.

[0029] For example, when diphenyl carbonate is used as the carbonate compound B) above and decamethylcyclopentasiloxane is used as the cyclic siloxane compound A) above, the siloxane decomposition reaction is represented by the following formula (4), and the main product obtained is dimethyldiphenoxysilane (hereinafter also referred to as DMDPS). [ka]

[0030] Formula (4) schematically shows the siloxane decomposition reaction, with a small amount of by-products that may be generated omitted, and the molar ratios between the compounds of diphenyl carbonate, decamethylcyclopentasiloxane, and dimethyldiphenoxysilane are not adjusted.

[0031] In the siloxane decomposition step, it is preferable for promoting the decomposition reaction of the siloxane compound that the molar amount of the carbonate compound of B) used is equal to or more than the Si molar amount of the siloxane compound of A), that is, the molar amount of silicon atoms in the siloxane compound. That is, it is preferable that the ratio x of the molar amount of the carbonate compound of B) to the Si molar amount of the siloxane compound of A) (that is, the value of the Si molar amount of the siloxane compound of A) / the molar amount of the carbonate compound of B)) satisfies the relationship of x≥1. Further, the molar amount of the carbonate compound may be 1.1 times or more (x≥1.1), for example, about 1.5 times the Si molar amount of the siloxane compound. Also, for the purpose of improving the efficiency of the decomposition reaction of the siloxane compound, it is preferable that the ratio x is 0.8 < x < 2.0, more preferably 0.8 < x < 1.8, still more preferably 0.8 < x < 1.6, and particularly preferably 0.9 < x < 1.5. In this case, the remaining amount of the siloxane compound as a raw material that remains unreacted can be suppressed. Note that the value of the ratio x can be adjusted according to the type of the siloxane compound as a raw material. For example, when using the above-mentioned A-1) cyclic siloxane compound or A-2) linear siloxane compound as the raw material, since the ideal ratio of the molar amount of the carbonate compound to the Si molar amount of the siloxane compound is 1:1, the value of the ratio x may be about 0.8 < x < 1.2, and preferably about 0.9 < x < 1.1. Also, when using the above-mentioned A-3) silsesquioxane compound as the raw material, since the ideal ratio of the molar amount of the carbonate compound to the Si molar amount of the siloxane compound is 1:1.5, the value of the ratio x may be about 1.0 < x < 1.8, and preferably about 1.3 < x < 1.7.

[0032] In the siloxane decomposition step, the ratio y of the C) basic compound catalyst to the Si molar amount of the A) siloxane compound (i.e., the value of the C) basic compound catalyst molar amount / A) siloxane compound molar amount) is, from the viewpoint of improving the efficiency of the decomposition reaction and suppressing excessive catalyst use, preferably 0.0001 mmol / mol≦y≦20 mmol / mol (the value of y is 0.0001 mmol / mol or more and 20 mmol / mol or less), more preferably 0.001 mmol / mol≦y≦15 mmol / mol (the value of y is 0.001 mmol / mol or more and 15 mmol / mol or less), even more preferably 0.1 mmol / mol≦y≦8 mmol / mol (the value of y is 0.1 mmol / mol or more and 8 mmol / mol or less), and particularly preferably 1 mmol / mol≦y≦5 mmol / mol (the value of y is 1 mmol / mol or more and 5 mmol / mol or less).

[0033] The temperature of the siloxane decomposition reaction in the siloxane decomposition step, i.e., the temperature at which the siloxane compound A is decomposed, is preferably from 50° C. to 300° C., and may be from 50° C. to 150° C., from the viewpoint of efficiency of the decomposition reaction and yield. The temperature in the siloxane decomposition step is more preferably from 70° C. to 250° C., even more preferably from 80° C. to 240° C., and particularly preferably from 90° C. to 220° C.

[0034] The siloxane decomposition reaction in the siloxane decomposition step can proceed at normal pressure, and there is no need to adjust the pressure by increasing or decreasing the pressure.

[0035] [E) Distillation process / recrystallization process] In the method for producing a silane compound of the present invention, it is preferable to further include at least one of a distillation step of distilling the silane compound produced in the siloxane decomposition step and a recrystallization step of recrystallizing the silane compound produced in the siloxane decomposition step in order to improve the purity of the silane compound.

[0036] For efficient distillation, the pressure in the distillation step is preferably 1 hPa or more and 20 hPa or less, more preferably 2 hPa or more and 10 hPa or less, and even more preferably 3 hPa or more and 5 hPa or less. For efficient distillation, the temperature in the distillation step is preferably 50°C or higher and 300°C or lower, more preferably 70°C or higher and 250°C or lower, even more preferably 100°C or higher and 200°C or lower, and particularly preferably 120°C or higher and 180°C or lower.

[0037] In the recrystallization step, a recrystallization solvent is used that is selected according to the properties of the produced silane compound, particularly its solubility, etc. From the viewpoint of solubility with the product, the recrystallization solvent is preferably heptane, octane, toluene, benzene, cyclohexane, hexane, etc. In addition, it is preferable to dissolve the silane compound in the solvent at a temperature of 50° C. to 120° C., and to cool the solution at a rate of 0.5° C. / min to 1° C. / min.

[0038] [F) Dripping process] In the method for producing a silane compound, it is preferable to mix the raw materials other than A) the siloxane compound with the catalyst in advance, and drop the A) siloxane compound into the resulting mixture, mainly the mixed solution.In this way, by further providing F) dropping step of gradually dropping the A) siloxane compound into the mixture containing at least B) the carbonate compound and C) the basic compound catalyst, the safety of the method for producing a silane compound can be further improved. The dropping speed of the siloxane compound A) in the dropping step F) is adjusted depending on the reaction scale, but is generally 0.1 ml / min to 10 l (liters) / min, preferably 1.0 ml / min to 7.0 l / min, more preferably 10 ml / min to 5.0 l / min, and particularly preferably 100 ml / min to 1.0 l / min. The dropping speed of the siloxane compound A) may be, for example, about 1 to 100 ml / min. For example, when about 250 g of diphenyl carbonate is used, about 0.23 mol of the siloxane compound is added at a dropping speed of about 1 ml / min, and the total dropping time is preferably about 90 minutes. F) The optimal dropping speed in the dropping step varies depending on the reaction scale, but the preferred total time for dropping does not change much, and is preferably about 30 minutes to 3 hours, more preferably about 1 hour to 2 hours, for example, about 90 minutes. In addition, the siloxane compound (A) may be dissolved in a suitable solvent to facilitate adjustment of the dropping speed.

[0039] In this way, by gradually adding A) a siloxane compound to a mixture containing B) a carbonate compound and C) a basic compound catalyst, which is usually a solution further containing a solvent, the sudden generation of CO2 is suppressed and safety is improved. Also, in the industrial-scale production process of silane compounds, the adoption of a dropping process can prevent the sudden pressurization of the inside of the reaction vessel by the by-product CO2, thereby improving safety. EXAMPLES

[0040] <Evaluation items> NMR: 1 The chemical shifts in the H-NMR analysis were based on the CDCl3 peak at 7.24 ppm.

[0041] Example 1 7.5 g (20.2 mmol, Si molar amount: 101.0 mmol) of decamethylcyclopentasiloxane, 21.6 g (101.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 As a result of H-NMR analysis, no peaks for protons of methyl groups on silicon based on decamethylcyclopentasiloxane were observed, confirming that the conversion rate of decamethylcyclopentasiloxane was 100%. Subsequently, the reaction mixture was cooled to 40° C., and then vacuum distilled at a reduced pressure of 4 hPa and 150° C. to obtain 23.7 g of a colorless oily component.

[0042] The obtained oily component 1 Analysis by H-NMR revealed that the only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane (DMDPS) and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated to be 98.6:1.4 from the peak area ratio. The molar yield of dimethyldiphenoxysilane, calculated from the weight of the resulting oily component and the above molar ratio, was 96.0% based on the molar amount of silicon atoms contained in decamethylcyclopentasiloxane. Dimethyldiphenoxysilane ( 1 H-NMR(CDCl3,500MHz,δ;ppm)=0.378(s;6H), 6.942, 6.944(d;4H), 6.959, 6.961, 6.995(t;2H), 7.230, 7.245, 7.257(t;4H)).

[0043] The siloxane decomposition reaction in this example is represented by the following formula (4-1), and in addition to the main product DMDPS, 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was obtained as a by-product. [ka]

[0044] Example 2 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 23.6 g (110.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1As a result of H-NMR analysis, no peaks for protons of methyl groups on silicon based on decamethylcyclopentasiloxane were observed, confirming that the conversion rate of decamethylcyclopentasiloxane was 100%. The reaction mixture was then cooled to 40° C. and distilled under reduced pressure at 150° C. and a reduced pressure of 4 hPa to obtain 25.1 g of a colorless oily component.

[0045] The obtained oily component 1 Analysis by H-NMR revealed that the only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the peak area ratio to be 99.8:0.2. A peak of 7.406 ppm due to the carbonate group and the protons in the meta position based on diphenyl carbonate was also observed. The weight of diphenyl carbonate calculated from the peak area derived from the mixed diphenyl carbonate was subtracted from the weight of the oily component obtained, and the molar yield of dimethyldiphenoxysilane calculated from the above molar ratio was 97.7% relative to the molar amount of silicon atoms contained in decamethylcyclopentasiloxane.

[0046] Example 3 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 32.1 g (150.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 As a result of H-NMR analysis, no peaks for protons of methyl groups on silicon based on decamethylcyclopentasiloxane were observed, confirming that the conversion rate of decamethylcyclopentasiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the peak area ratio to be 98.8:1.2.

[0047] Example 4 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 19.3 g (90.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR showed that no peaks were observed for the protons of the methyl groups on the silicon atom in decamethylcyclopentasiloxane, and the conversion of decamethylcyclopentasiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the peak area ratio to be 93.2:6.8.

[0048] Example 5 14.9 g (18.8 mmol, Si molar amount: 75.0 mmol) of octaphenylcyclotetrasiloxane (melting point: 197°C, molecular weight: 793.17) represented by the following formula (5), 16.1 g (75.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200°C for 10 minutes under a nitrogen atmosphere. [ka]

[0049] The reaction mixture 1 As a result of H-NMR analysis, no peak of protons based on the para-position of octaphenylcyclotetrasiloxane was observed, and it was confirmed that the conversion rate of octaphenylcyclotetrasiloxane was 100%. After cooling to room temperature, 20 g of heptane was added to the solidified reaction mixture, and the mixture was heated to 90°C and filtered while still hot. The filtrate was left at room temperature for 3 days to precipitate white crystals. The mixture was filtered by adding 10 g of heptane cooled to 5°C, and the crystals on the filter paper were removed and dried at 40°C and a reduced pressure of 1 hPa for 45 hours to obtain 24.1 g of a white powder. The powder obtained was 1 Analysis by H-NMR revealed peaks derived from diphenyldiphenoxysilane and 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane was calculated to be 95.4:4.6 from the peak area ratio.

[0050] The molar yield of diphenyldiphenoxysilane calculated from the weight of the resulting white powder and the above molar ratio was 81.1% based on the molar amount of silicon atoms contained in octaphenylcyclotetrasiloxane. Diphenyldiphenoxysilane ( 1 H-NMR(CDCl3,500MHz,δ;ppm)=6.915, 6.927, 6.939, 6.952, 6.965(p;6H), 7.142, 7.155, 7. 169(t;4H), 7.354, 7.366, 7.379(t;4H), 7.425, 7.437, 7.449(t;2H)), 7.750, 7.762(d;4H) .

[0051] Example 6 Octaphenylcyclotetrasiloxane 14.9 g (18.8 mmol, Si molar amount: 75.0 mmol), diphenyl carbonate 16.9 g (78.8 mmol), and cesium carbonate 33 mg (0.1 mmol) as a catalyst were stirred at 200° C. for 10 minutes under a nitrogen atmosphere. The reaction mixture 1 As a result of H-NMR analysis, no peak of protons based on the para-position of octaphenylcyclotetrasiloxane was observed, and it was confirmed that the conversion rate of octaphenylcyclotetrasiloxane was 100%. After cooling to room temperature, 20 g of heptane was added to the solidified reaction mixture, and the mixture was heated to 90°C and then filtered while hot. The filtrate was left at room temperature for 3 days to precipitate white crystals. The mixture was filtered with 10 g of heptane cooled to 5°C, and the crystals on the filter paper were taken out and dried at 40°C and a reduced pressure of 1 hPa for 45 hours, yielding 24.4 g of white powder.

[0052] The resulting powder 1 Analysis by H-NMR revealed peaks derived from diphenyldiphenoxysilane and 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane was calculated to be 99.5:0.5 from the peak area ratio. The molar yield of diphenyldiphenoxysilane calculated from the weight of the resulting white powder and the above molar ratio was 87.6% based on the molar amount of silicon atoms contained in octaphenylcyclotetrasiloxane.

[0053] Example 7 Octaphenylcyclotetrasiloxane 14.9 g (18.8 mmol, Si molar amount: 75.0 mmol), diphenyl carbonate 17.7 g (82.6 mmol), and cesium carbonate 33 mg (0.1 mmol) as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 As a result of H-NMR analysis, no peak of protons based on the para-position of octaphenylcyclotetrasiloxane was observed, and it was confirmed that the conversion rate of octaphenylcyclotetrasiloxane was 100%. After cooling to room temperature, 20 g of heptane was added to the solidified reaction mixture, and the mixture was heated to 90°C and then filtered while hot. The filtrate was left at room temperature for 3 days to precipitate white crystals. The mixture was filtered with 10 g of heptane cooled to 5°C, and the crystals on the filter paper were taken out and dried at 40°C and a reduced pressure of 1 hPa for 45 hours, yielding 23.1 g of white powder.

[0054] The resulting powder 1 Analysis by H-NMR revealed peaks derived from diphenyldiphenoxysilane and 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane was calculated from the peak area ratio to be 99.6:0.4. The molar yield of diphenyldiphenoxysilane calculated from the weight of the resulting white powder and the above molar ratio was 83.1% based on the molar amount of silicon atoms contained in octaphenylcyclotetrasiloxane.

[0055] Example 8 7.4 g (1.8 mmol, Si molar amount: 100.0 mmol) of dimethylpolysiloxane (hydroxy-terminated, molecular weight: 4,200) represented by the following formula (6), 21.4 g (100.0 mmol) of diphenyl carbonate, and 65 mg (0.2 mmol) of cesium carbonate as a catalyst were placed in a nitrogen atmosphere and stirred at 220° C. for 30 minutes. [ka]

[0056] The reaction mixture 1 As a result of H-NMR analysis, no proton peaks due to dimethylpolysiloxane were observed, confirming that the conversion rate of dimethylpolysiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the peak area ratio to be 95.0:5.0.

[0057] Example 9 7.4 g (0.19 mmol, Si molar amount: 100.0 mmol) of dimethylpolysiloxane represented by the following formula (7) (Shin-Etsu Chemical Co., Ltd., KF-96-3000cs, trimethylsiloxy terminal, molecular weight: 40,000), 21.4 g (100.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. [ka] The reaction mixture 1 As a result of H-NMR analysis, no proton peaks due to dimethylpolysiloxane were observed, confirming that the conversion rate of dimethylpolysiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the peak area ratio to be 98.1:1.9.

[0058] Example 10 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 17.4 g (100.0 mmol) of dibutyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture1 Analysis by H-NMR revealed that the peaks of the protons of the methyl groups on silicon were 0.055 ppm for protons derived from decamethylcyclopentasiloxane and 0.070 ppm for protons derived from dimethyldibutoxysilane. The conversion rate of decamethylcyclopentasiloxane calculated from the ratio of the areas of these two peaks was 69%.

[0059] Example 11 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 150° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR revealed that the peaks of the protons of the methyl groups on silicon were 0.055 ppm for protons derived from decamethylcyclopentasiloxane and 0.378 ppm for protons derived from dimethyldiphenoxysilane. The conversion rate of decamethylcyclopentasiloxane calculated from the ratio of the areas of these two peaks was 71%. The peaks observed as protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the area ratio of these two peaks to be 78.7:21.3.

[0060] Example 12 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 65 mg (0.2 mmol) of cesium carbonate as a catalyst were stirred at 220° C. for 30 minutes under a nitrogen atmosphere. The reaction mixture 1As a result of H-NMR analysis, no peaks for protons of methyl groups on silicon based on decamethylcyclopentasiloxane were observed, confirming that the conversion rate of decamethylcyclopentasiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the peak area ratio to be 99.6:0.4.

[0061] Example 13 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 28 mg (0.2 mmol) of potassium carbonate as a catalyst were stirred at 220° C. for 30 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR showed that no peaks were observed for the protons of the methyl groups on the silicon atom in decamethylcyclopentasiloxane, and the conversion of decamethylcyclopentasiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the peak area ratio to be 99.7:0.3.

[0062] Example 14 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 21 mg (0.2 mmol) of sodium carbonate as a catalyst were stirred at 220° C. for 30 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR revealed that the peaks of the protons of the methyl groups on silicon were 0.055 ppm for protons derived from decamethylcyclopentasiloxane and 0.378 ppm for protons derived from dimethyldiphenoxysilane. The conversion rate of decamethylcyclopentasiloxane calculated from the ratio of the areas of these two peaks was 89%. The peaks observed as protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the area ratio of these two peaks to be 94.3:5.7.

[0063] Example 15 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 17 mg (0.2 mmol) of sodium hydrogen carbonate as a catalyst were stirred at 220° C. for 30 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR revealed that the peaks of the protons of the methyl groups on silicon were 0.055 ppm for protons derived from decamethylcyclopentasiloxane and 0.378 ppm for protons derived from dimethyldiphenoxysilane. The conversion rate of decamethylcyclopentasiloxane calculated from the ratio of the areas of these two peaks was 87%. The peaks of methyl group protons on silicon were observed to be a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the area ratio of these two peaks to be 97.4:2.6.

[0064] Example 16 7.4 g (33.3 mmol, Si molar amount: 100.0 mmol) of hexamethylcyclotrisiloxane represented by the following formula (8), 21.4 g (100.0 mmol) of diphenyl carbonate, and 65 mg (0.2 mmol) of cesium carbonate as a catalyst were stirred at 220° C. for 30 minutes under a nitrogen atmosphere. [ka]

[0065] The reaction mixture 1 H-NMR analysis showed that no peaks were observed for the protons of the methyl groups on the silicon in hexamethylcyclotrisiloxane, and the conversion of hexamethylcyclotrisiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the area ratio of these two peaks to be 99.3:0.7.

[0066] (Example 17) 7.4 g (25.0 mmol, Si molar amount: 100.0 mmol) of octamethylcyclotetrasiloxane represented by the following formula (9), 21.4 g (100.0 mmol) of diphenyl carbonate, and 65 mg (0.2 mmol) of cesium carbonate as a catalyst were stirred at 220° C. for 30 minutes under a nitrogen atmosphere. [ka]

[0067] The reaction mixture 1 Analysis by H-NMR showed that no peaks were observed for the protons of the methyl groups on the silicon atoms in octamethylcyclotetrasiloxane, and the conversion of octamethylcyclotetrasiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated to be 99.4:0.6 from the ratio of the areas of these two peaks.

[0068] (Example 18) 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 75 mg (0.5 mmol) of cesium hydroxide as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR showed that no peaks were observed for the protons of the methyl groups on the silicon atom in decamethylcyclopentasiloxane, and the conversion of decamethylcyclopentasiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated to be 98.2:1.8 from the area ratio of these two peaks.

[0069] (Example 19) 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 11 mg (0.2 mmol) of potassium hydroxide as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1Analysis by H-NMR showed that no peaks were observed for the protons of the methyl groups on the silicon atom in decamethylcyclopentasiloxane, and the conversion of decamethylcyclopentasiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated to be 97.6:2.4 from the ratio of the areas of these two peaks.

[0070] (Example 20) 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 12 mg (0.3 mmol) of sodium hydroxide as a catalyst were stirred at 200° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR revealed that the peaks of the protons of the methyl groups on silicon were the proton peak of decamethylcyclopentasiloxane at 0.055 ppm and the proton peak of dimethyldiphenoxysilane at 0.378 ppm. The conversion rate of decamethylcyclopentasiloxane calculated from the ratio of the areas of the two peaks was 66%. The peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the area ratio of these two peaks to be 94.4:5.6.

[0071] Example 21 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 120° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR revealed that the peaks of the protons of the methyl groups on silicon were 0.055 ppm for protons derived from decamethylcyclopentasiloxane and 0.378 ppm for protons derived from dimethyldiphenoxysilane. The conversion rate of decamethylcyclopentasiloxane calculated from the ratio of the areas of these two peaks was 67%. The peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the area ratio of these two peaks to be 82.0:18.0.

[0072] Example 22 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 90° C. for 60 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR revealed that the peaks of the protons of the methyl groups on silicon were 0.055 ppm for protons derived from decamethylcyclopentasiloxane and 0.378 ppm for protons derived from dimethyldiphenoxysilane. The conversion rate of decamethylcyclopentasiloxane calculated from the ratio of the areas of these two peaks was 2%. The peaks observed for the protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the area ratio of these two peaks to be 33.3:66.7.

[0073] (Example 23) 1,3,5,7,9,11,13,15-Octamethylpentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 2.06 g (3.83 mmol, Si molar amount: 30.7 mmol) of octasiloxane, 9.85 g (46.0 mmol) of diphenyl carbonate, and 15 mg (0.05 mmol) of cesium carbonate as a catalyst were stirred at 180° C. for 150 minutes under a nitrogen atmosphere. The reaction mixture 1 H-NMR analysis revealed that 1,3,5,7,9,11,13,15-octamethylpentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 ]Octasiloxane-based methyl group proton peaks were not observed, and 1,3,5,7,9,11,13,15-octamethylpentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 ] The conversion of octasiloxane was 100%. The only peaks observed for the protons of the methyl groups on silicon were a peak at 0.483 ppm due to methyltriphenoxysilane and a peak at 0.289 ppm due to 1,3-dimethyl-1,1,3,3-tetraphenoxydisiloxane. The molar ratio of methyltriphenoxysilane to 1,3-dimethyl-1,1,3,3-tetraphenoxydisiloxane was calculated to be 93.7:6.3 from the ratio of the areas of these two peaks. The chemical formulas of the products, such as triaryloxysilane compounds, are shown below. Formula (10) shows methyltriphenoxysilane, and formula (11) shows 1,3-dimethyl-1,1,3,3-tetraphenoxydisiloxane. [ka]

[0074] Example 24 1,3,5,7,9,11,13,15-Octaphenylpentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 3.96 g (3.83 mmol, Si molar amount: 30.6 mmol) of octasiloxane, 9.85 g (46.0 mmol) of diphenyl carbonate, and 15 mg (0.05 mmol) of cesium carbonate as a catalyst were stirred at 180° C. for 150 minutes under a nitrogen atmosphere. The reaction mixture 1 H-NMR analysis revealed that 1,3,5,7,9,11,13,15-octaphenylpentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 ]Octasilosiloxane para-position proton peak was not observed, and 1,3,5,7,9,11,13,15-octaphenylpentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 ] The conversion of octasiloxane was confirmed to be 100%. After cooling to room temperature, 10 g of heptane was added to the solidified reaction mixture, and the mixture was heated to 90°C and then filtered while hot. The filtrate was left at room temperature for 3 days to precipitate white crystals. The mixture was filtered with 5 g of heptane cooled to 5°C, and the crystals on the filter paper were taken out and dried at 40°C and a reduced pressure of 1 hPa for 45 hours, yielding 9.42 g of white powder. The resulting powder 1H-NMR analysis revealed peaks derived from phenyltriphenoxysilane and 1,3-diphenyl-1,1,3,3-tetraphenoxydisiloxane. The molar ratio of phenyltriphenoxysilane to 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane was calculated to be 96.0:4.0 from the peak area ratio. The molar yield of phenyltriphenoxysilane calculated from the weight of the resulting white powder and the above molar ratio was 76.8% based on the molar amount of silicon atoms contained in octaphenylcyclotetrasiloxane. The chemical formulas of the products, such as triaryloxysilane compounds, are shown below. Formula (12) below shows phenyltriphenoxysilane, and formula (13) below shows 1,3-diphenyl-1,1,3,3-tetraphenoxydisiloxane. [ka]

[0075] (Example 25) A 500 ml 4-neck flask was fitted with a dropping funnel, thermometer and condenser, and 246.35 g (1.15 mol) of diphenyl carbonate and 0.3748 g (1.15 mmol) of cesium carbonate as a catalyst were charged and heated to 180°C without stirring. The diphenyl carbonate dissolved at around 100°C. After reaching 180°C, 85.30 g (0.23 mol) of decamethylcyclopentasiloxane was added dropwise at a rate of 1 ml / min over 90 minutes. CO2 gas was generated immediately after the addition of decamethylcyclopentasiloxane. After the addition of decamethylcyclopentasiloxane was completed, the temperature was raised to 200°C, and after heating at 200°C for 90 minutes, heating was stopped and the reaction was terminated. Subsequently, the reaction mixture was cooled to 40° C. and then distilled under reduced pressure at a reduced pressure of 4 hPa and 150° C. to obtain 270 g of a colorless oily component similar to that in Example 1.

[0076] Comparative Example 1 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane, 21.4 g (100.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at room temperature for 60 minutes under a nitrogen atmosphere. The mixture 1 As a result of H-NMR analysis, only the proton peak based on decamethylcyclopentasiloxane was observed as the proton peak of the methyl group on silicon, and the conversion rate of decamethylcyclopentasiloxane was 0%.

[0077] Comparative Example 2 7.4 g (20.0 mmol, Si molar amount: 100.0 mmol) of decamethylcyclopentasiloxane and 21.4 g (100.0 mmol) of diphenyl carbonate were placed in a nitrogen atmosphere and stirred at 200° C. for 60 minutes. The mixture 1 As a result of H-NMR analysis, only the proton peak based on decamethylcyclopentasiloxane was observed as the proton peak of the methyl group on silicon, and the conversion rate of decamethylcyclopentasiloxane was 0%.

[0078] Comparative Example 3 0.37 g (1.0 mmol, Si molar amount: 5.0 mmol) of decamethylcyclopentasiloxane, 0.94 g (10.0 mmol) of phenol, and 3.3 mg (0.01 mmol) of cesium carbonate as a catalyst were stirred at 175° C. for 90 minutes under a nitrogen atmosphere. The reaction mixture 1 Analysis by H-NMR revealed that the peaks of the protons of the methyl groups on silicon were 0.055 ppm for protons derived from decamethylcyclopentasiloxane and 0.378 ppm for protons derived from dimethyldiphenoxysilane. The conversion rate of decamethylcyclopentasiloxane calculated from the ratio of the areas of these two peaks was 4%. The peaks observed as protons of the methyl groups on silicon were a peak at 0.378 ppm due to dimethyldiphenoxysilane and a peak at 0.222 ppm due to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane. The molar ratio of dimethyldiphenoxysilane to 1,1,3,3-tetramethyl-1,3-diphenoxydisiloxane was calculated from the area ratio of these two peaks to be 59.6:40.4.

[0079] The results of each of the examples and comparative examples are shown in Tables 2 and 3 below. [Table 2] [Table 3]

Claims

1. A) A-1) a cyclic siloxane compound represented by the following formula (1): A-2) a linear siloxane compound represented by the following formula (2) and / or A siloxane compound having a siloxane bond as a main chain skeleton, which is a silsesquioxane compound represented by the following formula (3): B) a carbonate compound containing at least one of a diaryl carbonate and a monoalkyl monoaryl carbonate, and C) Basic compound catalyst D) a siloxane decomposition step of heating the mixture containing A) to alkoxylate and / or aryloxylate the siloxane compound of A; A method for producing a silane compound containing at least one of a diaryloxysilane compound, a monoaryloxymonoalkoxysilane compound, and a triaryloxysilane compound. 【Chemistry 1】 (In the formula, R １ and R ２ each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, n represents an integer of 3 or more and 30 or less. 【Chemistry 2】 (In the formula, R ３ and R ４ each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, m represents an integer of 2 or more and 10,000 or less, Each X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having a total of 1 to 10 carbon atoms which may have a substituent and which may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent. [R ５ Yes １．５ ]p (3) (In the formula, R ５ represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may have a substituent; p is a number between 4 and 24.

2. A) A-1) a cyclic siloxane compound represented by the following formula (1), and / or A-2) a linear siloxane compound represented by the following formula (2): B) a carbonate compound containing at least one of a diaryl carbonate and a monoalkyl monoaryl carbonate, and C) Basic compound catalyst D) a siloxane decomposition step of heating the mixture containing A) to alkoxylate and / or aryloxylate the siloxane compound of A; A method for producing a silane compound containing at least one of a diaryloxysilane compound and a monoaryloxymonoalkoxysilane compound. 【Chemistry 3】 (In the formula, R １ and R ２ each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, n represents an integer of 3 or more and 30 or less. 【Chemistry 4】 (In the formula, R ３ and R ４ each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, m represents an integer of 2 or more and 10,000 or less, Each X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having a total of 1 to 10 carbon atoms which may have a substituent and which may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent.

3. The R １ ~R ４ each independently represents an alkyl group, an alkenyl group, or an aryl group having a total of 6 to 30 carbon atoms, each of which may have a substituent.

4. The R １ ~R ４ The method for producing a silane compound according to claim 3, wherein each of the groups independently represents any one selected from the group consisting of a methyl group, a phenyl group, a vinyl group, and a propyl group.

5. The method for producing a silane compound according to any one of claims 1 to 4, wherein the B) diaryl carbonate includes diphenyl carbonate.

6. The method for producing a silane compound according to any one of claims 1 to 5, wherein the C) basic compound catalyst contains an alkali metal carbonate or an alkali metal hydroxide.

7. A) A-1) a cyclic siloxane compound represented by the following formula (1): A-2) a linear siloxane compound represented by the following formula (2) and / or A siloxane compound having a siloxane bond as a main chain skeleton, which is a silsesquioxane compound represented by the following formula (3): B) a carbonate compound containing at least one of a diaryl carbonate, a dialkyl carbonate, and a monoalkyl monoaryl carbonate; and C) Basic compound catalyst D) a siloxane decomposition step of heating the mixture containing A) to alkoxylate and / or aryloxylate the siloxane compound of A; A method for producing a silane compound containing at least one of a diaryloxysilane compound, a dialkoxysilane compound, a monoaryloxymonoalkoxysilane compound, a triaryloxysilane compound, and a trialkoxysilane compound, comprising the steps of: 【Chemistry 5】 (In the formula, R １ and R ２ each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, n represents an integer of 3 or more and 30 or less. 【Chemistry 6】 (In the formula, R ３ and R ４ each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, m represents an integer of 2 or more and 10,000 or less, Each X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having a total of 1 to 10 carbon atoms which may have a substituent and which may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent. [R ５ Yes １．５ ]p (3) (In the formula, R ５ represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may have a substituent; p is a number between 4 and 24. The method for producing a silane compound, wherein the basic compound catalyst C) contains at least one of cesium carbonate and potassium carbonate.

8. A) A-1) a cyclic siloxane compound represented by the following formula (1), and / or A-2) a linear siloxane compound represented by the following formula (2): B) a carbonate compound containing at least one of a diaryl carbonate and a monoalkyl monoaryl carbonate, and C) Basic compound catalyst D) a siloxane decomposition step of heating the mixture containing A) to alkoxylate and / or aryloxylate the siloxane compound of A; A method for producing a silane compound including at least one of a diaryloxysilane compound, a dialkoxysilane compound, and a monoaryloxymonoalkoxysilane compound, comprising the steps of: 【Chemistry 7】 (In the formula, R １ and R ２ each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, n represents an integer of 3 or more and 30 or less. 【Chemistry 8】 (In the formula, R ３ and R ４ each independently represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent, m represents an integer of 2 or more and 10,000 or less, Each X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having a total of 1 to 10 carbon atoms which may have a substituent and which may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent. The method for producing a silane compound, wherein the basic compound catalyst C) contains at least one of cesium carbonate and potassium carbonate.

9. The method for producing a silane compound according to any one of claims 1 to 8, wherein in the siloxane decomposition step D), a ratio x of the molar amount of the carbonate compound B) to the molar amount of Si in the siloxane compound A) is x ≧ 1.

10. The method for producing a silane compound according to any one of claims 1 to 8, wherein in the siloxane decomposition step D), a ratio x of the molar amount of the carbonate compound B) to the molar amount of Si in the siloxane compound A) is 0.8<x<2.

0.

11. The method for producing a silane compound according to any one of claims 1 to 10, wherein in the siloxane decomposition step D), a ratio y of a molar amount of the basic compound catalyst C) to the molar amount of Si in the siloxane compound A) is 0.0001 mmol / mol≦y≦20 mmol / mol.

12. The method for producing a silane compound according to any one of claims 1 to 11, wherein in the siloxane decomposition step D), the temperature at which the siloxane compound A is decomposed is 50°C or higher and 300°C or lower.

13. The method for producing a silane compound according to claim 12, wherein in the siloxane decomposition step D), the temperature is 50° C. or higher and 150° C. or lower.

14. The method for producing a silane compound according to claim 1 or 7, wherein the molecular weight of the cyclic siloxane compound A-1) represented by formula (1) is 2,000 or less, the molecular weight of the linear siloxane compound A-2) represented by formula (2) is 60,000 or less, and the molecular weight of the silsesquioxane compound A-3) represented by formula (3) is 3,500 or less.

15. The method for producing a silane compound according to any one of claims 1 to 14, further comprising at least one of E) a distillation step / recrystallization step of distilling the silane compound produced by the D) siloxane decomposition step and D) a recrystallization step of recrystallizing the silane compound produced by the D) siloxane decomposition step.

16. The method for producing a silane compound according to claim 15, wherein the pressure in the distillation step of E) is 1 hPa or more and 20 hPa or less.

17. The method for producing a silane compound according to any one of claims 1 to 16, further comprising: F) a dropping step of dropping the siloxane compound A) into a mixture containing the carbonate compound B) and the basic compound catalyst C).

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