JPWO2017018543A1 - Method for producing silanol compound - Google Patents

Abstract

It aims at providing the manufacturing method of the silanol compound which can manufacture a silanol compound efficiently. Efficiently by performing the reaction which produces | generates a silanol compound by making water react with at least 1 sort (s) of the silane compound represented by following formula (A-1)-(A-4) in the solvent containing an amide compound. Silanol compounds can be produced.

(In formulas (A-1) to (A-4), each X independently represents an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom. R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom.

Description

  The present invention relates to a method for producing a silanol compound, and more particularly to a method for producing a silanol compound using an amide compound.

  Siloxane is a very important compound that is used in a wide range of fields such as automobiles, architecture, electronics, and medicine because of its unique properties. In recent years, it is indispensable in the environment and energy fields, such as LED sealing materials and eco-tire silane coupling agents, and it is no exaggeration to say that there are no fields that do not use siloxane compounds (2009 market scale: 115 100 million dollars, production: 1.23 million tons per year

  Most of the siloxane compounds are generally synthesized via silanol by hydrolysis such as sol-gel method using alkoxysilane, halogenated silane or the like as a raw material. This silanol (including silane diol, silane triol, and silane tetraol) is condensed at the same time as hydrolysis in the presence of water, except for some silane diols and silane triols having bulky substituents such as phenyl groups. Therefore, it is difficult to synthesize with good yield. Further, its stability (stability in the presence of water) is extremely low, and it is known that condensation occurs quickly (see Non-Patent Documents 1 and 2).

Fyfe, C. A .; Aroca, P. P. J. Phys. Chem. B 1997, 101, 9504. Kim, Y .; Jung, E. Chem. Lett. 2002, 992.

  An object of this invention is to provide the manufacturing method of the silanol compound which can manufacture a silanol compound efficiently.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have conducted a reaction of a silane compound and water in a solvent containing an amide compound, thereby increasing the yield of the silanol compound and efficiently producing silanol. The present inventors have found that a compound can be produced and completed the present invention.
That is, the present invention is as follows.

<1> A method for producing a silanol compound comprising a reaction step 1 in which at least one silane compound represented by the following formulas (A-1) to (A-4) is reacted with water to produce a silanol compound. ,
The method for producing a silanol compound, wherein the reaction step 1 is performed in a solvent containing an amide compound.

(In formulas (A-1) to (A-4), each X independently represents an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom. R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom.
<2> The amount of water used in the reaction step 1 is 0.25 to 150 times in terms of a substance amount with respect to the silane compound represented by the formulas (A-1) to (A-4). The manufacturing method of the silanol compound as described in <1>.
<3> The amount of the solvent used in the reaction step 1 is such that the concentration of the silane compound represented by the formulas (A-1) to (A-4) is 0.001 to 2.00 mol / L. A method for producing a silanol compound according to <1> or <2>.
<4> The method for producing a silanol compound according to any one of <1> to <3>, wherein the amide compound is at least one compound represented by the following formula (i) or (ii).

(In the formulas (i) and (ii), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are two or more. (When it has a hydrocarbon group in a molecule | numerator, hydrocarbon groups may connect and it may form the cyclic structure.)
<5> A method for producing a silanol compound comprising a reaction step 2 in which at least one silane compound represented by the following formulas (A-1) to (A-4) is reacted with water to produce a silanol compound. ,
The method for producing a silanol compound, wherein the reaction step 2 is performed in an aqueous solution containing a polymer compound having at least one amide bond.

(In formulas (A-1) to (A-4), each X independently represents an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom. R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom.
<6> The amount of water used in the reaction step 2 is such that the concentration of the silane compound represented by the formulas (A-1) to (A-4) is 0.01 to 2.00 mol / L. The manufacturing method of the silanol compound as described in <5>.
<7> The production of the silanol compound according to <5> or <6>, wherein the polymer compound is a polymer compound having at least one of repeating structures represented by the following formulas (iii) to (v): Method.

(In the formulas (iii) to (v), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are two or more. (When it has a hydrocarbon group in a molecule | numerator, hydrocarbon groups may connect and it may form the cyclic structure.)
<8> The method for producing a silanol compound according to any one of <1> to <7>, wherein the reaction step 1 or the reaction step 2 is a step performed in the presence of an acid.
<9> The method for producing a silanol compound according to <8>, including a base addition step of adding a base to the product obtained in the reaction step 1 or the reaction step 2.
<10> An ammonium salt addition step of adding an ammonium salt to the product obtained in the reaction step 1 or the reaction step 2 or the product obtained in the base addition step, <1> to <9> The manufacturing method of the silanol compound in any one of.
<11> Freeze the product obtained in the reaction step 1 or the reaction step 2, the product obtained in the base addition step, or the product obtained in the ammonium salt addition step under reduced pressure. The manufacturing method of the silanol compound in any one of <1>-<10> including the freeze-drying process to expose.

  According to the present invention, a silanol compound can be produced efficiently.

It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 1. FIG. It is a ²⁹ Si-NMR measurement result after leaving the solution obtained in Example 1 to stand at room temperature for 1.5 hours. It is a measurement result of ²⁹ Si-NMR after allowing the solution obtained in Example 1 to stand at room temperature for 6 hours. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained by the comparative example. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 2. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 3. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 4. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 5. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 6. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 7. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 8. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 9. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 10. FIG. It is a ²⁹ Si-NMR measurement result immediately after completion | finish of reaction of the solution obtained in Example 11. FIG. It is a measurement result of IR of the composition obtained in Example 20. 2 is a measurement result of IR of the composition obtained in Example 21. FIG. 4 is a measurement result of IR of the composition obtained in Example 22. 4 is a measurement result of IR of the composition obtained in Example 23. 4 is a measurement result of IR of the composition obtained in Example 24. 4 is a measurement result of IR of the composition obtained in Example 25. 2 is a measurement result of IR of the composition obtained in Example 26. FIG. 4 is a measurement result of IR of the composition obtained in Example 27. 4 is a measurement result of IR of the composition obtained in Example 28. 4 is a measurement result of IR of the composition obtained in Example 29. 4 is a measurement result of IR of the composition obtained in Example 30. 2 is a measurement result of IR of the composition obtained in Example 31. FIG. 3 is a measurement result of IR of the composition obtained in Example 32. FIG. 4 is a measurement result of IR of the composition obtained in Example 33. 3 is a measurement result of IR of the composition obtained in Example 34. FIG.

  The details of the present invention will be described with specific examples. However, the present invention is not limited to the following contents without departing from the gist of the present invention, and can be implemented with appropriate modifications.

<Method for producing silanol compound>
The manufacturing method of the silanol compound which is 1 aspect of this invention is the reaction process of making at least 1 sort (s) of the silane compound represented by following formula (A-1)-(A-4), and water produce | generate a silanol compound. (Hereinafter, it may be abbreviated as “reaction step 1”.), Wherein the reaction step 1 is performed in a solvent containing an amide compound.

(In formulas (A-1) to (A-4), each X independently represents an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom. R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom.
As mentioned above, even if alkoxysilane, halogenated silane, etc. are simply reacted with water to synthesize silanol, the generated silanol will condense to produce siloxane (see the following formula). It was difficult to synthesize itself with high yield.

The inventors have increased the yield of the silanol compound by performing the reaction of the silane compound represented by the formulas (A-1) to (A-4) and water in a solvent containing an amide compound, It has been found that a silanol compound can be produced efficiently. The reason why the silanol compound can be produced efficiently is not sufficiently clear, but it is because the amide bond of the amide compound contributes to stabilization through the hydrogen bond with the silanol compound formed, and is intended to suppress condensation between the silanols. it is conceivable that. Moreover, the production method of the silanol compound of the present invention is an industrially very suitable production method from the viewpoint of using inexpensive and readily available raw materials such as silane compound and water and the point that the reaction proceeds promptly under mild conditions. It can be said.
In the present invention, the “silanol compound” means a compound in which at least one hydroxyl group (—OH) is bonded to a silicon atom (Si), and the number of hydroxyl groups and other structures are not particularly limited. . Therefore, for example, the reaction of tetraethoxysilane with water is considered to produce a silanol compound represented by the following formula. However, when at least one of these is produced, it can be said that the production method of the silanol compound of the present invention is applicable.

In the present invention, the “amide compound” means a compound having at least one amide bond, and other structures are not particularly limited. However, when the “solvent containing an amide compound” is composed of one kind of amide compound, the “amide compound” is liquid under the conditions of the reaction step.

The manufacturing method of the silanol compound which is another one aspect | mode of this invention similarly produces | generates a silanol compound by making water react with at least 1 sort (s) of the silane compound represented by following formula (A-1)-(A-4). In which the reaction step 2 is carried out in an aqueous solution containing a polymer compound having at least one amide bond. It is characterized by that.

(In formulas (A-1) to (A-4), each X independently represents an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom. R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom.
By using a polymer compound having at least one amide bond, the present inventors can use water not only as a reactant but also as a solvent, and a large amount of water is present. It has been found that a silanol compound can be produced efficiently in an aqueous solution. The reason why the silanol compound can be produced efficiently is the same as described above, in order to contribute to stabilization through the silanol compound in which the amide bond of the polymer compound is formed and the hydrogen bond, and to suppress the condensation between the silanols. it is conceivable that. In addition, a polymer compound having at least one amide bond has an advantage that it can be used as a stabilizer for a silanol compound as it is, and can be said to be an industrially very suitable production method.
Hereinafter, the “silane compound represented by formulas (A-1) to (A-4)”, “amide compound”, and “polymer having at least one amide bond” in “reaction step 1” and “reaction step 2”. The “compound” and other reaction conditions will be described in detail.

(Reaction Step 1 / Reaction Step 2)
The reaction step 1 and the reaction step 2 are steps in which at least one silane compound represented by the following formulas (A-1) to (A-4) is reacted with water to form a silanol compound. Specific types of the silane compounds represented by A-1) to (A-4), the amount of water used, and the like are not particularly limited, and can be appropriately selected according to the purpose. Hereinafter, a specific example will be described.

(In formulas (A-1) to (A-4), each X independently represents an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom. R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom.
X represents each independently an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom, and the hydrocarbon group of the alkoxy group is linear It is not limited to the saturated hydrocarbon group, and each of them may have a branched structure, a cyclic structure, or an aromatic ring.
The carbon number of the hydrocarbon group when X is an alkoxy group is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. Within the above range, it becomes easy to produce a silanol compound efficiently.
The carbon number of the hydrocarbon group when X is an amino group is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. Within the above range, it becomes easy to produce a silanol compound efficiently.
X includes methoxy group (—OMe), ethoxy group (—OEt), n-propoxy group ( ^—n Pr), phenoxy group (—OPh), amino group (—NH ₂ ), dimethylamino group (—NMe _2). ), Chlorine atom, bromine atom, iodine atom and the like, methoxy group (—OMe) and ethoxy group (—OEt) are preferable.
R each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom. "It may contain at least one atom selected from the group consisting of an atom, an oxygen atom, and a halogen atom" may include a functional group containing a nitrogen atom, an oxygen atom, a halogen atom, etc. It is meant that a linking group containing a nitrogen atom, an oxygen atom, etc. may be contained inside or at the end of the carbon skeleton. The “hydrocarbon group” is not limited to a linear saturated hydrocarbon group, and may have a carbon-carbon unsaturated bond, a branched structure, a cyclic structure, or an aromatic ring.
The functional group and linking group contained in the hydrocarbon group of R include an amide group (—NHCO—), an ether group (—O—), a fluorine atom (fluoro group, —F), a chlorine atom (chloro group, —Cl). ), A bromine atom (bromo group, —Br), an iodine atom (iodo group, —I), and the like.
As R, a methyl group (-Me), an ethyl group (-Et), an n-propyl group ( ^-n Pr), an i-propyl group ( ^-i Pr), an n-butyl group ( ^-n Bu), a cyclohexyl group , Phenyl group (-Ph), naphthyl group, anthryl group, fluorenyl group, hydrogen atom and the like.
Examples of the silane compounds represented by the formulas (A-1) to (A-4) include compounds represented by the following formulas.

  The amount of water used in the reaction step 1 is usually 0.25 times or more, preferably 0.3 times or more, in terms of the amount of substance relative to the silane compounds represented by the formulas (A-1) to (A-4). More preferably, it is 0.9 times or more, more preferably 2.5 times or more, and usually 150 times or less, preferably 100 times or less, more preferably 75 times or less, still more preferably 40 times or less. Within the above range, it becomes easy to produce a silanol compound efficiently.

Reaction step 1 is carried out in a solvent containing an amide compound, but the specific type of amide compound, the type of compound other than the amide compound contained in the solvent, the amount of solvent used, the amount of the amide compound in the solvent, A content ratio etc. are not specifically limited, According to the objective, it can select suitably. The amide compound contained in the solvent is not limited to one type, and two or more types may be combined. Hereinafter, a specific example will be described.
Examples of the amide compound include compounds represented by the following formula (i) or (ii). In addition, “polymer compound having at least one repeating structure represented by formulas (iii) to (v)” described later is also suitable as the amide compound.

(In the formulas (i) and (ii), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are two or more. (When it has a hydrocarbon group in a molecule | numerator, hydrocarbon groups may connect and it may form the cyclic structure.)
R ′ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, but a hydrogen atom, a methyl group (—Me), an ethyl group (—Et), an n-propyl group ( ^—n Pr). ), I-propyl group ( ^-i Pr), n-butyl group ( ^-n Bu), t-butyl group ( ^-t Bu), n-hexyl group ( ^-n Hex), cyclohexyl group ( ^-c Hex) ), A phenyl group (-Ph).
R ″ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, but a hydrogen atom, a methyl group (—Me), an ethyl group (—Et), an n-propyl group ( ^—n Pr) ), I-propyl group ( ^-i Pr), n-butyl group ( ^-n Bu), t-butyl group ( ^-t Bu), n-hexyl group ( ^-n Hex), cyclohexyl group ( ^-c Hex) ), A phenyl group (-Ph).
When R ′ and / or R ″ have two or more hydrocarbon groups in the molecule, the hydrocarbon groups may be linked to form a cyclic structure, but “form a cyclic structure”. For example, it means a structure such as an amide compound represented by the following formula.

Examples of the compound represented by the formula (i) include formamide, N, N-dimethylformamide (DMF), acetamide, N-methylacetamide, N, N-dimethylacetamide (DMAc), 2-pyrrolidone, N-methylpyrrolidone, Examples include 2-piperidone and ε-caprolactam.
Examples of the compound represented by the formula (ii) include urea, tetramethylurea (Me ₄ Urea), and tetraphenylurea.

  The solvent in the reaction step 1 may contain a compound other than an amide compound, and the types thereof include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, and n-octane, benzene, toluene, and xylene. Aromatic hydrocarbon compounds such as cyclohexane and decalin, alcohol compounds such as methanol, ethanol, n-propanol and i-propanol, tetrahydrofuran (THF), tetrahydropyran, dioxane, diethyl ether, dimethyl ether , Ether compounds such as diisopropyl ether, diphenyl ether, methyl ethyl ether, ester compounds such as ethyl acetate, n-amyl acetate, ethyl lactate, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, hexachloroethane, etc. Halogenated hydrocarbon compounds as acetone, methyl ethyl ketone, phenyl methyl ketone, aprotic polar solvents such as dimethyl sulfoxide (DMSO). In addition, compounds other than an amide compound are not restricted to one type, You may combine 2 or more types.

  The amount of the solvent used in the reaction step 1 is such that the concentration of the silane compound represented by the formulas (A-1) to (A-4) is usually 0.001 mol / L or more, preferably 0.010 mol / L. An amount that becomes above, more preferably an amount that becomes 0.10 mol / L or more, an amount that usually becomes 2.00 mol / L or less, preferably an amount that becomes 1.00 mol / L or less, more preferably 0.80 mol / L. The amount is L or less, more preferably 0.50 mol / L or less. Within the above range, it becomes easy to produce a silanol compound efficiently.

  The content ratio of the amide compound in the solvent of the reaction step 1 is usually 0.1% by volume or more, preferably 1% by volume or more, more preferably 50% by volume or more, and further preferably 70% by volume or more. Within the above range, it becomes easy to produce a silanol compound efficiently.

  The amount of water used in the reaction step 2 is such that the concentration of the silane compound represented by the formulas (A-1) to (A-4) is usually 0.01 mol / L or more, preferably 0.05 mol / L. An amount that becomes above, more preferably an amount that becomes 0.10 mol / L or more, usually an amount that becomes 2.00 mol / L or less, preferably an amount that becomes 1.00 mol / L or less, more preferably 0.50 mol / L. It is an amount that becomes L or less. Within the above range, it becomes easy to produce a silanol compound efficiently.

The reaction step 2 is performed in an aqueous solution containing a polymer compound having at least one amide bond, and the specific type of the polymer compound having at least one amide bond, the amount of water used, and the aqueous solution The content ratio of the polymer compound having at least one amide bond in is not particularly limited, and can be appropriately selected according to the purpose. The polymer compound having at least one amide bond contained in the aqueous solution is not limited to one type, and two or more types may be combined. Hereinafter, a specific example will be described.
The number average molecular weight (M _n ) of the polymer compound having at least one amide bond is usually 1,000 or more, preferably 3,000 or more, more preferably 5,000 or more, and usually 500,000 or less, preferably Is 300,000 or less, more preferably 200,000 or less.
The polymer compound having at least one amide bond has a weight average molecular weight (M _w ) of usually 1,000 or more, preferably 5,000 or more, more preferably 10,000 or more, and usually 1,000,000 or less. , Preferably 500,000 or less, more preferably 200,000 or less.
The number of amide bonds of the polymer compound having at least one amide bond is usually 10 or more, preferably 50 or more, more preferably 100 or more, and usually 10,000 or less, preferably 5,000 or less, more preferably 2,000 or less.
Examples of the polymer compound having at least one amide bond include polymer compounds having at least one repeating structure represented by the following formulas (iii) to (v).

(In the formulas (iii) to (v), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are two or more. (When it has a hydrocarbon group in a molecule | numerator, hydrocarbon groups may connect and it may form the cyclic structure.)
Note that R ′ and R ″ are the same as those described above.
Examples of the polymer compound having only the repeating structure represented by the formula (iii) include polyvinyl pyrrolidone, polyvinyl polypyrrolidone, polyvinyl piperidone, and polyvinyl caprolactam.
Examples of the polymer compound having only a repeating structure represented by the formula (iv) include polyacrylamide, poly-N-methylacrylamide, poly-N-ethylacrylamide, poly-N-ethylmethacrylamide, and poly-N-propylacrylamide. , Poly-N-propylmethacrylamide, poly-N-isopropylacrylamide, poly-N-isopropylmethacrylamide, poly-N-ethylmethylacrylamide, poly-N-diethylacrylamide, poly-N-isopropylmethylacrylamide, poly-N -Methylpropylacrylamide, poly-N-cyclopropylacrylamide, poly-N-cyclopentynylacrylamide and the like.
Examples of the polymer compound consisting only of the repeating structure represented by the formula (v) include poly-2-methyloxazoline, poly-2-ethyloxazoline, poly-2-propyloxazoline and the like.

  The aqueous solution in the reaction step 2 may contain compounds other than water, and the types thereof include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, and n-octane, benzene, toluene, xylene, and the like. Aromatic hydrocarbon compounds such as cyclohexane and decalin, alcohol compounds such as methanol, ethanol, n-propanol and i-propanol, tetrahydrofuran (THF), tetrahydropyran, dioxane, diethyl ether, dimethyl ether, Ether compounds such as diisopropyl ether, diphenyl ether and methyl ethyl ether, ester compounds such as ethyl acetate, n-amyl acetate and ethyl lactate, halogens such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane and hexachloroethane Hydrocarbon compound, acetone, methyl ethyl ketone, phenyl methyl ketone, aprotic polar solvents such as dimethyl sulfoxide (DMSO). The compound other than water is not limited to one type, and two or more types may be combined.

  The content ratio of the polymer compound having at least one amide bond in the aqueous solution of reaction step 2 is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 1.0% by mass or more, and further preferably. Is 5.0% by mass or more, usually 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. It is. Within the above range, it becomes easy to produce a silanol compound efficiently.

Reaction step 1 and reaction step 2 are steps in which at least one silane compound represented by formulas (A-1) to (A-4) is reacted with water to form a silanol compound, but the reaction temperature, Reaction conditions such as reaction time are not particularly limited, and can be appropriately selected according to the purpose. Hereinafter, a specific example will be described.
Reaction step 1 and reaction step 2 are preferably performed in the presence of an acid. The acid serves as a catalyst for the reaction of the silane compound and water, and the reaction proceeds rapidly.
Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, trifluoroacetic acid, formic acid, carbonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.
The amount of acid used (in terms of hydrogen ion concentration) when reaction step 1 or reaction step 2 is carried out in the presence of an acid is relative to the silane compound represented by formulas (A-1) to (A-4). Usually, 0.0010 mol% or more, preferably 0.010 mol% or more, more preferably 0.10 mol% or more, and usually 10.0 mol% or less, preferably 8.0 mol% or less, more preferably 4.0 mol% or less. It is. Within the above range, it becomes easy to produce a silanol compound efficiently.

The reaction temperature in reaction step 1 and reaction step 2 is usually −78 ° C. or higher, preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and usually 80 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower. It is.
The reaction time in the reaction step 1 and the reaction step 2 is usually 0.1 minutes or more, preferably 0.5 minutes or more, more preferably 1 minute or more, usually 5 hours or less, preferably 1 hour or less, more preferably 0.5 hours or less.
Within the above range, it becomes easy to produce a silanol compound efficiently.

The manufacturing method of the silanol compound of this invention may include processes other than the reaction process 1 and the reaction process 2, and as a specific process, it is the product obtained by the reaction process 1 or the reaction process 2. A base addition step for adding a base (hereinafter sometimes abbreviated as “base addition step”), a product obtained in the reaction step 1 or the reaction step 2 or an ammonium salt in the product obtained in the base addition step. Ammonium salt addition step (hereinafter sometimes abbreviated as “ammonium salt addition step”), product obtained in reaction step 1 or reaction step 2, product obtained in base addition step, or ammonium Examples thereof include a freeze-drying step in which the product obtained in the salt addition step is frozen and exposed to a reduced pressure (hereinafter sometimes abbreviated as “freeze-drying step”).
Hereinafter, the “base addition step”, “ammonium salt addition step”, “freeze drying step” and the like will be described in detail.

(Base addition process)
The base addition step is a step of adding a base to the product obtained in the reaction step 1 or the reaction step 2, but the specific type of base, the amount of base used, etc. are not particularly limited, and is appropriately determined depending on the purpose. You can choose.
Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, and amine compounds such as ammonia and aniline.
The “amine compound” means a compound having an amino group (which may be any of primary amine, secondary amine, and tertiary amine), and other structures are not particularly limited. And The base is considered to neutralize the acid and suppress the condensation of the silanol compound. Hereinafter, a specific example will be described.
Examples of amine compounds include ammonia, aniline (NH ₂ Ph), diphenylamine (NHPh ₂ ), dimethylpyridine (Me ₂ Pyr), di-tert-butylpyridine ( ^t Bu ₂ Pyr), pyrazine (Pyraz), triphenylamine ( NPh ₃ ), triethylamine (Et ₃ N), di-isopropylethylamine ( ⁱ Pr ₂ EtN) and the like.

  The amount of the base used is usually 0.1 or more, preferably 0.25 or more, more preferably 0.5 or more, and usually 4.0 or less, preferably 2. 0 or less, more preferably 1.5 or less. Within the above range, it becomes easy to produce a silanol compound efficiently.

(Ammonium salt addition process)
The ammonium salt addition step is a step of adding an ammonium salt to the product obtained in the reaction step 1 or the reaction step 2 or the product obtained in the base addition step. There are no particular restrictions on the amount used, and it can be appropriately selected according to the purpose. The “ammonium salt” means a compound comprising an ammonium ion and a counter anion, and the structure of the ammonium ion and the counter anion is not particularly limited. The ammonium salt is considered to suppress the condensation of the silanol compound. Hereinafter, a specific example will be described.
As ammonium ions, tetrahydroammonium ions (NH ₄ ⁺ ), tetramethylammonium ions (NMe ₄ ⁺ ), tetraethylammonium ions (NEt ₄ ⁺ ), tetrapropylammonium ions (NPr ₄ ⁺ ), tetrabutylammonium ions (NBu _4). ^+), benzyl tributyl ammonium ions (NBnBu ₃ ^+), tributyl (methyl) ammonium _(NBu 3 Me ⁺⁾ ions, tetrapentylammonium ion (NPen ₄ ^+), hexyl ammonium ion to tetra (nhex ₄ ^+), tetra heptyl ammonium ion (NHep ₄ ^+), 1- butyl-l-methyl pyrrolidium ion (BuMePyr ^+), methyl trioctyl ammonium ion (NMeOct ₃ ^+), di Chill dioctadecyl ammonium ion and the like.
Counter anions include fluoride ion (F ⁻ ), chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodide ion (I ⁻ ), acetoxy ion (AcO ⁻ ), nitrate ion (NO ₃ ⁻ ). , Azide ion (N ₃ ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), perchlorate ion (ClO ₄ ⁻ ), sulfate ion (HSO ₄ ⁻ ) and the like.
As the ammonium salt, tetrabutylammonium chloride (NBu ₄ Cl) and tetrabutylammonium bromide (NBu ₄ Br) are particularly preferable. In addition, the ammonium salt contained in a composition is not restricted to one type, You may contain 2 or more types.

  The amount of ammonium salt used is usually greater than 0 times, preferably 1 times or more, usually 4 times or less, preferably 3 times or less, more preferably 2 times or less, in terms of the amount of substance with respect to the silanol compound. .

(Freeze drying process)
The lyophilization step is a step in which the product obtained in the reaction step 1 or the reaction step 2, the product obtained in the base addition step, or the product obtained in the ammonium salt addition step is frozen and exposed to reduced pressure. However, the freezing temperature, drying temperature, drying pressure, drying time and the like are not particularly limited, and can be appropriately selected according to the purpose. Hereinafter, a specific example will be described.
The freezing temperature is not particularly limited as long as the product obtained in the ammonium salt addition step is frozen, but is usually 10 ° C. or lower, preferably 0 ° C. or lower, more preferably −20 ° C. or lower, and usually −196. ° C or higher, preferably -150 ° C or higher, more preferably -100 ° C or higher.
The drying temperature is usually 10 ° C. or lower, preferably 0 ° C. or lower, more preferably −20 ° C. or lower, and usually −196 ° C. or higher, preferably −150 ° C. or higher, more preferably −100 ° C. or higher.
The drying pressure is usually 100 Pa or less, preferably 20 Pa or less, more preferably 3 Pa or less, and usually 10 ⁻⁵ Pa or more, preferably 0.01 Pa or more, more preferably 1 Pa or more.
The drying time is usually 200 hours or less, preferably 100 hours or less, more preferably 50 hours or less, and usually 1 hour or more, preferably 5 hours or more, more preferably 10 hours or more.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Example 1>
Into a two-necked flask equipped with a magnetic stirrer, was charged 28.3 mg (0.136 mmol) of tetraethoxysilane, 0.723 mL of N, N-dimethylacetamide, and 0.0014 mL (1.0 mol%) of 1N hydrochloric acid, and 0.270 mL (15.0 mmol) of water was added and reacted at room temperature for 4 hours. Thereafter, 0.005 mL (1.0 mol%) of an N, N-dimethylacetamide solution of triethylamine (concentration: 27.5 g / L) was added to terminate the reaction, tetramethylsilane was added as an internal standard, and ²⁹ Si-NMR was measured. The results are shown in FIG. It was confirmed that the solution contained silanetetraol at a concentration of 162 mM (yield: 100%).
In addition, ²⁹ Si-NMR of the solution after the reaction was allowed to stand at room temperature for 1.5 hours and after being allowed to stand for 6 hours was measured. The results are shown in FIGS.

<Comparative example>
The reaction was carried out in the same manner as in Example 1 except that 0.723 mL of N, N-dimethylacetamide was changed to 0.573 mL of acetone, and ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. Silane tetraol could not be confirmed in the solution. This is considered to be because the produced silanetetraol is condensed and modified to siloxane.

<Example 2>
Tetraethoxysilane 28.3 mg to 56.6 mg, N, N-dimethylacetamide 0.723 mL to 1.023 mL, 1N hydrochloric acid 0.0014 mL to 0.0028 mL, triethylamine in N, N-dimethylacetamide 0.005 mL The reaction was carried out in the same manner as in Example 1 except that the amount was changed to 0.010 mL, and ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. The yield of silanetetraol was 88.4%.

<Example 3>
Tetraethoxysilane 28.3mg to 70.0mg, N, N-dimethylacetamide 0.723mL to 1.123mL, 1N hydrochloric acid 0.0014mL to 0.0042mL, triethylamine in N, N-dimethylacetamide 0.005mL It was made to react by the method similar to Example 1 except having changed to 0.015 mL, and ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. The yield of silanetetraol was 60.0%.

<Example 4>
²⁹ Si-NMR of the solution was measured by reacting in the same manner as in Example 1 except that 28.3 mg of tetraethoxysilane was changed to 20.7 mg of tetramethoxysilane and the reaction time was changed to 30 minutes. The results are shown in FIG. The yield of silanetetraol was 94.8%.

<Example 5>
The same method as in Example 4 except that 20.7 mg of tetramethoxysilane was changed to 41.4 mg, 0.0014 mL of 1N hydrochloric acid was changed to 0.0028 mL, and 0.005 mL of an N, N-dimethylacetamide solution of triethylamine was changed to 0.010 mL. The ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. The yield of silanetetraol was 95.3%.

<Example 6>
The same method as in Example 4 except that 20.7 mg of tetramethoxysilane was changed to 62.1 mg, 0.0014 mL of 1N hydrochloric acid was changed to 0.0042 mL, and 0.005 mL of an N, N-dimethylacetamide solution of triethylamine was changed to 0.015 mL. The ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. The yield of silanetetraol was 89.0%.

<Example 7>
The same method as in Example 4 except that 20.7 mg of tetramethoxysilane was changed to 82.8 mg, 0.0014 mL of 1N hydrochloric acid was changed to 0.0056 mL, and 0.005 mL of an N, N-dimethylacetamide solution of triethylamine was changed to 0.020 mL. The ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. The yield of silanetetraol was 88.8%.

<Example 8>
The reaction was performed in the same manner as in Example 1 except that 28.3 mg of tetraethoxysilane was changed to 18.0 mg of trimethoxymethylsilane and the reaction time was changed to 2 minutes, and ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. The yield of methylsilanetriol was 100%.

<Example 9>
The reaction was performed in the same manner as in Example 1 except that 28.3 mg of tetraethoxysilane was changed to 24.2 mg of triethoxymethylsilane and the reaction time was changed to 30 minutes, and ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. The yield of methylsilanetriol was 99.3%.

<Example 10>
²⁹ Si-NMR of the solution was measured by reacting in the same manner as in Example 1 except that 28.3 mg of tetraethoxysilane was changed to 16.3 mg of dimethoxydimethylsilane and the reaction time was changed to 2 minutes. The results are shown in FIG. The yield of dimethylsilanediol was 95.5%.

<Example 11>
The reaction was performed in the same manner as in Example 1 except that 28.3 mg of tetraethoxysilane was changed to 18.0 mg of diethoxydimethylsilane and the reaction time was changed to 10 minutes, and ²⁹ Si-NMR of the solution was measured. The results are shown in FIG. The yield of dimethylsilanediol was 93.0%.

<Example 12>
In a two-necked flask equipped with a magnetic stirring bar, 15.2 mg (0.100 mmol) of tetramethoxysilane, 100.0 mg (0.900 mmol) of polyvinylpyrrolidone (polyvinylpyrrolidone 25 manufactured by Nacalai Tesque), 1.000 mL of water, and 1N 0.001 mL (1.0 mol%) of an aqueous hydrochloric acid solution was added and reacted at room temperature for 0.083 hours. Thereafter, 0.010 mL (1.0 mol%) of an aqueous solution of triethylamine (concentration: 27.5 g / L) was added to terminate the reaction, and ²⁹ Si-NMR of the solution was measured. The yield of silanetetraol was 70.4%.

<Example 13>
Tetramethoxysilane 30.4 mg (0.200 mmol), 1N aqueous hydrochloric acid solution 0.002 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.020 mL (1.0 mol%) ), And the reaction was carried out in the same manner as in Example 12 to measure ²⁹ Si-NMR of the solution. The yield of silanetetraol was 66.7%.

<Example 14>
45.7 mg (0.300 mmol) of tetramethoxysilane, 0.003 mL of 1N aqueous hydrochloric acid solution (1.0 mol%), and 0.030 mL (1.0 mol%) of an aqueous solution of triethylamine (concentration: 27.5 g / L) ), And the reaction was carried out in the same manner as in Example 12 to measure ²⁹ Si-NMR of the solution. The yield of silanetetraol was 58.1%.

<Example 15>
Tetramethoxysilane was added to 60.9 mg (0.400 mmol), 1N hydrochloric acid aqueous solution was added to 0.004 mL (1.0 mol%), and triethylamine aqueous solution (concentration: 27.5 g / L) was added to 0.040 mL (1.0 mol%). ), And the reaction was carried out in the same manner as in Example 12 to measure ²⁹ Si-NMR of the solution. The yield of silanetetraol was 51.5%.

<Example 16>
In a two-necked flask equipped with a magnetic stirring bar, 15.2 mg (0.100 mmol) of tetramethoxysilane, poly-N-isopropylacrylamide (poly (N-isopropylacrylamide) manufactured by Sigma-Aldrich, Mn: 20000 to 40000) 8 mg (0.802 mmol), 1.000 mL of water, and 0.001 mL (1.0 mol%) of 1N hydrochloric acid aqueous solution were added and reacted at room temperature for 0.083 hours. Thereafter, 0.010 mL (1.0 mol%) of an aqueous solution of triethylamine (concentration: 27.5 g / L) was added to terminate the reaction, and ²⁹ Si-NMR of the solution was measured. The yield of silanetetraol was 67.1%.

<Example 17>
Tetramethoxysilane 30.4 mg (0.200 mmol), 1N aqueous hydrochloric acid solution 0.002 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.020 mL (1.0 mol%) ), And the reaction was carried out in the same manner as in Example 16, and ²⁹ Si-NMR of the solution was measured. The yield of silanetetraol was 54.9%.

<Example 18>
Tetramethoxysilane was added to 45.7 mg (0.300 mmol), 1N aqueous hydrochloric acid solution was added to 0.003 mL (1.0 mol%), and triethylamine aqueous solution (concentration: 27.5 g / L) was added to 0.030 mL (1.0 mol%). ), And the reaction was carried out in the same manner as in Example 16, and ²⁹ Si-NMR of the solution was measured. The yield of silanetetraol was 52.4%.

<Example 19>
Tetramethoxysilane was added to 60.9 mg (0.400 mmol), 1N hydrochloric acid aqueous solution was added to 0.004 mL (1.0 mol%), and triethylamine aqueous solution (concentration: 27.5 g / L) was added to 0.040 mL (1.0 mol%). ), And the reaction was carried out in the same manner as in Example 16, and ²⁹ Si-NMR of the solution was measured. The yield of silanetetraol was 47.4%.

<Example 20>
To a two-necked flask equipped with a magnetic stirrer, 20.7 mg (0.136 mmol) of tetramethoxysilane, 1.200 mL of tetramethylurea, and 0.0014 mL (1.0 mol%) of 1N hydrochloric acid were added. 270 mL (15.0 mmol) was added and reacted at room temperature for 0.5 hour. Then, 0.005 mL (1.0 mol%) of a trimethylamine tetramethylurea solution (concentration: 27.5 g / L) was added to terminate the reaction. The composition containing tetrabutylammonium chloride (Bu ₄ NCl, 76.0 mg) and tetramethylurea (Me ₄ Urea) 15 ml, which is 2.0 times the amount of tetramethoxysilane, and containing silanetetraol and the like. A product (solution) was obtained.
This composition was frozen using liquid nitrogen (−196 ° C.) and vacuum freeze-dried to sublime tetramethylurea and the like under reduced pressure (freeze-drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature. -40 ° C, holding time 15 hours, freeze-drying step (2) degree of vacuum 1-3 Pa, shelf temperature -40 ° C to -15 ° C over 15 hours, freeze-drying step (3) degree of vacuum 1-3 Pa, −15 ° C., holding time 24 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 94.1 mg of a composition containing powdered silanetetraol and the like.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -69.8 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 1, and the results of IR analysis of the composition are shown in FIG.

<Example 21>
To a two-necked flask equipped with a magnetic stirrer, 103.5 mg (0.680 mmol) of tetramethoxysilane, 6.000 mL of tetramethylurea, and 0.007 mL (1.0 mol%) of 1N hydrochloric acid were added. 350 mL (75.0 mmol) was added and reacted at room temperature for 0.5 hour. Thereafter, 0.025 mL (1.0 mol%) of a triethylamine tetramethylurea solution (concentration: 27.5 g / L) was added to terminate the reaction. The composition containing tetrabutylammonium chloride (Bu ₄ NCl, 378.0 mg) and tetramethylurea (Me ₄ Urea) 75 ml, whose amount is 2.0 times the amount of tetramethoxysilane, and containing silanetetraol and the like A product (solution) was obtained.
This composition was frozen using liquid nitrogen (−196 ° C.) and vacuum freeze-dried to sublime tetramethylurea and the like under reduced pressure (freeze-drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature. −40 ° C., holding time 24 hours, freeze-drying step (2) Decompression degree 1 to 3 Pa, shelf temperature from −40 ° C. to −15 ° C. over 24 hours, freeze-drying step (3) Decompression degree 1 to 3 Pa, −15 ° C., retention time 96 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 485.0 mg of a composition containing powdered silanetetraol and the like.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -69.8 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 2, and the results of IR analysis of the composition are shown in FIG.

<Example 22>
To a two-necked flask equipped with a magnetic stirrer, 103.5 mg (0.680 mmol) of tetramethoxysilane, 6.000 mL of tetramethylurea, and 0.007 mL (1.0 mol%) of 1N hydrochloric acid were added. 350 mL (74.9 mmol) was added and reacted at room temperature for 0.5 hour. Thereafter, 0.025 mL (1.0 mol%) of a triethylamine tetramethylurea solution (concentration: 27.5 g / L) was added to terminate the reaction. To this, polyvinylpolypyrrolidone (500.0 mg) and 54 ml of tetramethylurea (Me ₄ Urea) were added to obtain a composition (solution) containing silanetetraol and the like.
This composition was frozen using liquid nitrogen (−196 ° C.) and subjected to vacuum freeze drying in which water or the like was sublimated under reduced pressure (freeze drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature −40. C, holding time 285 hours). After completion of the drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 998.6 mg of a composition containing powdered silanetetraol and the like.
When this composition was analyzed by ²⁹ Si-NMR (Me ₄ Urea / THF-d ₈ : -71.7 ppm) and IR, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 3, and the results of IR analysis of the composition are shown in FIG.

<Example 23>
In a two-necked flask equipped with a magnetic stirring bar, 15.2 mg (0.100 mmol) of tetramethoxysilane, 100.0 mg (0.900 mmol) of polyvinylpyrrolidone, 1.000 mL of water and 0.001 mL (1.0 mol%) of 1N hydrochloric acid aqueous solution. ) And reacted at room temperature for 0.083 hours. Thereafter, 0.010 mL (1.0 mol%) of an aqueous solution of triethylamine (concentration: 27.5 g / L) was added to terminate the reaction. 9 ml of water was added thereto to obtain a composition (solution) containing silanetetraol and the like.
This composition was frozen using liquid nitrogen (−196 ° C.) and subjected to vacuum freeze drying in which water or the like was sublimated under reduced pressure (freeze drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature −40. C, holding time 72 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 103.8 mg of a composition containing powdered silanetetraol and the like.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.9 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −71.3 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 4, and the results of IR analysis of the composition are shown in FIG.

<Example 24>
The amount of tetramethoxysilane added was 30.4 mg (0.200 mmol), 1N hydrochloric acid aqueous solution 0.002 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.020 mL (1.0 mol%) 110.5 mg of a composition containing powdered silanetetraol and the like was obtained in the same manner as in Example 23 except that the content was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.9 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −71.3 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 5, and the results of IR analysis of the composition are shown in FIG.

<Example 25>
The amount of tetramethoxysilane added was 45.7 mg (0.300 mmol), 1N hydrochloric acid aqueous solution 0.003 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.030 mL (1.0 mol%) 124.2 mg of a composition containing powdered silanetetraol and the like was obtained in the same manner as in Example 23 except that the composition was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −71.3 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 6, and the results of IR analysis of the composition are shown in FIG.

<Example 26>
The amount of tetramethoxysilane added was 60.9 mg (0.400 mmol), 1N hydrochloric acid aqueous solution 0.004 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.040 mL (1.0 mol%) 130.3 mg of a composition containing powdered silanetetraol and the like was obtained in the same manner as in Example 23 except that the composition was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −71.3 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 7, and the results of IR analysis of the composition are shown in FIG.

<Example 27>
The amount of tetramethoxysilane added was 76.1 mg (0.500 mmol), 1N hydrochloric acid aqueous solution 0.005 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.050 mL (1.0 mol%) 139.0 mg of a composition containing powdered silanetetraol and the like was obtained in the same manner as in Example 23 except that the composition was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −71.3 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 8, and the results of IR analysis of the composition are shown in FIG.

<Example 28>
In a two-necked flask equipped with a magnetic stirring bar, 15.2 mg (0.100 mmol) of tetramethoxysilane, 90.8 mg (0.802 mmol) of poly-N-isopropylacrylamide, 1.000 mL of water, and 0.001 mL of 1N aqueous hydrochloric acid ( 1.0 mol%) was added and reacted at room temperature for 0.083 hours. Thereafter, 0.010 mL (1.0 mol%) of an aqueous solution of triethylamine (concentration: 27.5 g / L) was added to terminate the reaction. 9 ml of water was added thereto to obtain a composition (solution) containing silanetetraol and the like.
This composition was frozen using liquid nitrogen (−196 ° C.) and subjected to vacuum freeze drying in which water or the like was sublimated under reduced pressure (freeze drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature −40. C, holding time 72 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 94.4 mg of a composition containing powdered silanetetraol and the like.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.9 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -71.5 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. The result of IR analysis of this composition is shown in FIG.

<Example 29>
The amount of tetramethoxysilane added was 30.4 mg (0.200 mmol), 1N hydrochloric acid aqueous solution 0.002 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.020 mL (1.0 mol%) 102.9 mg of a composition containing powdered silanetetraol and the like was obtained in the same manner as in Example 28 except that the composition was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.9 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -71.4 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. The result of IR analysis of this composition is shown in FIG.

<Example 30>
The amount of tetramethoxysilane added was 45.7 mg (0.300 mmol), 1N hydrochloric acid aqueous solution 0.003 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.030 mL (1.0 mol%) 110.4 mg of a composition containing powdered silanetetraol and the like was obtained in the same manner as in Example 28 except that the composition was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.9 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -71.4 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. The result of IR analysis of this composition is shown in FIG.

<Example 31>
The amount of tetramethoxysilane added was 60.9 mg (0.400 mmol), 1N hydrochloric acid aqueous solution 0.004 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.040 mL (1.0 mol%) 116.1 mg of a composition containing powdery silanetetraol and the like was obtained in the same manner as in Example 28 except that the composition was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.0 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -71.4 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. The result of IR analysis of this composition is shown in FIG.

<Example 32>
The amount of tetramethoxysilane added was 76.1 mg (0.500 mmol), 1N hydrochloric acid aqueous solution 0.005 mL (1.0 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.050 mL (1.0 mol%) 128.2 mg of a composition containing powdered silanetetraol and the like was obtained in the same manner as in Example 28 except that the composition was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.0 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -71.4 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. The result of IR analysis of this composition is shown in FIG.

<Example 33>
In a two-necked flask equipped with a magnetic stirrer, 15.2 mg (0.100 mmol) of tetramethoxysilane, poly-2-ethyloxazoline (poly (2-ethyl-2-oxazoline) manufactured by Sigma-Aldrich, Mw: ˜50000) 89.2 mg (0.900 mmol), 1.000 mL of water and 0.0025 mL (2.5 mol%) of 1N hydrochloric acid aqueous solution were added, and reacted at room temperature for 0.167 hours. Thereafter, 0.025 mL (2.5 mol%) of an aqueous solution of triethylamine (concentration: 27.5 g / L) was added to terminate the reaction. 9 ml of water was added thereto to obtain a composition (solution) containing silanetetraol and the like.
This composition was frozen using liquid nitrogen (−196 ° C.) and subjected to vacuum freeze drying in which water or the like was sublimated under reduced pressure (freeze drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature −40. C, holding time 72 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 95.0 mg of a composition containing powdered silanetetraol and the like.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −71.2 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. The result of IR analysis of this composition is shown in FIG.

<Example 34>
The amount of tetramethoxysilane added was 45.7 mg (0.300 mmol), 1N aqueous hydrochloric acid solution 0.0075 mL (2.5 mol%), triethylamine aqueous solution (concentration: 27.5 g / L) 0.075 mL (2.5 mol%) 114.5 mg of a composition containing powdered silanetetraol and the like was obtained in the same manner as in Example 33 except that the composition was changed to.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 5.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −71.2 ppm) and IR. As a result of analysis, it was confirmed that silanetetraol and the like were contained. This composition is shown in Table 9, and the results of IR analysis of the composition are shown in FIG.

  The silanol compound produced by the method for producing a silanol compound of the present invention is useful as a raw material for siloxane compounds that are used in a wide range of fields such as automobiles, architecture, electronics, and medicine.

Claims (11)

A method for producing a silanol compound comprising a reaction step 1 in which at least one silane compound represented by the following formulas (A-1) to (A-4) is reacted with water to produce a silanol compound,
The method for producing a silanol compound, wherein the reaction step 1 is performed in a solvent containing an amide compound.

(In formulas (A-1) to (A-4), each X independently represents an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom. R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom.   The usage-amount of the said water in the said reaction process 1 is 0.25-150 times in conversion of a substance amount with respect to the silane compound represented by said Formula (A-1)-(A-4). The manufacturing method of the silanol compound as described in any one of.   The amount of the solvent used in the reaction step 1 is such that the concentration of the silane compound represented by the formulas (A-1) to (A-4) is 0.001 to 2.00 mol / L. Item 3. A method for producing a silanol compound according to Item 1 or 2. The manufacturing method of the silanol compound of any one of Claims 1-3 whose said amide compound is at least 1 sort (s) of the compound represented by following formula (i) or (ii).

(In the formulas (i) and (ii), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are two or more. (When it has a hydrocarbon group in a molecule | numerator, hydrocarbon groups may connect and it may form the cyclic structure.) A method for producing a silanol compound comprising a reaction step 2 in which at least one silane compound represented by the following formulas (A-1) to (A-4) is reacted with water to produce a silanol compound,
The method for producing a silanol compound, wherein the reaction step 2 is performed in an aqueous solution containing a polymer compound having at least one amide bond.

(In formulas (A-1) to (A-4), each X independently represents an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 6 carbon atoms, a chlorine atom, a bromine atom, or an iodine atom. R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom.   The amount of water used in the reaction step 2 is such that the concentration of the silane compound represented by the formulas (A-1) to (A-4) is 0.01 to 2.00 mol / L. Item 6. A process for producing a silanol compound according to Item 5. The method for producing a silanol compound according to claim 5 or 6, wherein the polymer compound is a polymer compound having at least one of repeating structures represented by the following formulas (iii) to (v).

(In the formulas (iii) to (v), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are two or more. (When it has a hydrocarbon group in a molecule | numerator, hydrocarbon groups may connect and it may form the cyclic structure.)   The method for producing a silanol compound according to any one of claims 1 to 7, wherein the reaction step 1 or the reaction step 2 is a step performed in the presence of an acid.   The method for producing a silanol compound according to claim 8, comprising a base addition step of adding a base to the product obtained in the reaction step 1 or the reaction step 2.   10. The method according to claim 1, comprising an ammonium salt addition step of adding an ammonium salt to the product obtained in the reaction step 1 or the reaction step 2 or the product obtained in the base addition step. The manufacturing method of the silanol compound as described in any one of.   Freeze-drying by freezing the product obtained in the reaction step 1 or the reaction step 2, the product obtained in the base addition step, or the product obtained in the ammonium salt addition step and subjecting to a reduced pressure The manufacturing method of the silanol compound of any one of Claims 1-10 including a process.