JP2002088156A - Method for producing crystalline hydrogenated silsesquioxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply producing a crystalline hydrogenated silsesquioxane in high yield. SOLUTION: This method for producing the crystalline hydrogenated silsesquioxane comprises (a) preparing a two-phase system of an organic phase comprising a water-insoluble organic solvent and an aqueous phase prepared by dissolving a surfactant composed of an organic sulfonic acid or its salt (in which >=5 mass% is soluble in an aqueous solution of hydrochloric acid at 36 mass% concentration) in the aqueous solution of hydrochloric acid at >=25 mass% concentration, (b) adding trichlorosilane to the two-phase system under stirring, hydrolyzing and condensing the trichlorosilane in the aqueous phase or the organic phase and producing the hydrogenated silsesquioxane and (d) separating the crystalline hydrogenated silsesquioxane from the organic phase containing the resultant hydrogenated silsesquioxane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing crystalline hydrogenated silsesquioxane.

[0002]

It is known that halosilanes hydrolyze in the presence of water to form silanols, which condense into polysiloxanes. Among them, trichlorosilane was dropped into a system of a polar solvent, a non-polar solvent, an aqueous solution of hydrochloric acid, and ferric chloride, and the mixture was hydrolyzed by stirring. It has been reported to obtain sesquioxane (Agaskar, Inor.
Chem. 1991, 30, 2708-2708).

It is also known that when the halosilane is a trihalosilane, the above two reactions, hydrolysis and condensation, occur almost simultaneously to form a gel. Several methods have been proposed to prevent this gelation,
Some of them disclose a method of hydrolyzing methylchlorosilane or organotrichlorosilane with methylchlorosilane in the presence of a mixture of an aromatic hydrocarbon and a water-miscible solvent. Water-soluble cationic surfactants, such as amine hydrochloride, quaternary ammonium salts, and protonated carboxylic acids (SU (11) 1147723).

In addition, as a hydrolysis of zirgano cis xanth using a nonionic surfactant, cyclic dimethylpolysiloxane is formed by hydrolysis of dimethyldichlorosilane and an aqueous solution of hydrochloric acid in the presence of nC ₆ -C ₁₆ alkylsulfonic acid. Methods are also known (U.S. Pat.
0).

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing crystalline hydrogenated silsesquioxane easily and with a high yield, which is different from the prior art as described above. It is.

[0006]

SUMMARY OF THE INVENTION The present invention provides a simple (rapid) high yield of crystalline hydrogenated silsesquioxane by hydrolyzing trihalosilanes using a specific two-phase system. It has been found that the present invention is possible, and the present invention has been completed. That is, the present invention provides the following method.

A) the organic phase comprises a water-insoluble organic solvent,
The aqueous phase dissolves a surfactant consisting of an organic sulfonic acid or a salt thereof in an aqueous solution of hydrochloric acid having a concentration of 25% by mass or more (however, a surfactant capable of dissolving 5% by mass or more in an aqueous solution of hydrochloric acid having an HCl concentration of 36% by mass). B) adding trichlorosilane to said two-phase system with stirring and hydrolyzing and condensing it in the aqueous phase and / or in the organic phase. And c) separating the crystalline silsesquioxane hydride from the organic phase containing the silsesquioxane hydride thus obtained. For producing a reactive hydrogenated silsesquioxane.

The method for separating the crystalline hydrogenated silsesquioxane from the organic phase containing the hydrogenated silsesquioxane obtained in the step b) is as follows. Removing the solvent from the phase and adding to the resulting solid residue a solvent that is non-reactive with silicon-bonded hydrogen (-SiH) groups to dissolve other than the crystallized material in said residue;
Then, any of a method of removing the solvent to isolate the crystalline hydrogenated silsesquioxane as a solid, and a method of ii) reducing the amount of the solvent in the organic phase to precipitate a crystallized product may be used.

The surfactant is preferably an aromatic organic sulfonic acid or a salt thereof.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method for producing crystalline hydrogenated silsesquioxane. Hydrogenated silsesquioxane is a compound represented by the composition formula (HSiO _3/2 ) _n , that is, a silicon atom has three bonds out of its four bonds.
The compounds are bonded to each other via an oxygen atom and one of the four bonds of a silicon atom is a compound bonded to a hydrogen atom. When at least n is in the range of 8 to 14, Since the -Si-O-Si-O- bond is formed in a cage shape, it is called a cage compound (cage structure). In the present invention, these cage compounds, in particular, hydrogenated octasilsesquioxane and hydrogenated decasilsesquioxane having n = 8 or 10 can be easily (fastly) produced by the production method of the present invention.
It has been found that it can be produced in high yield.

This hydrogenated silsesquioxane can be produced by hydrolysis of trihalosilane.
The raw materials of the present invention are limited to trihalosilane and water. 1.5 moles of water are required to completely hydrolyze and condense 1 mole of the trihalosilane to form a hydrogenated silsesquioxane. The hydrogenated silsesquioxane produced by the method of the present invention is a crystalline hydrogenated silsesquioxane. Crystalline hydrogenated silsesquioxanes, particularly hydrogenated octasilsesquioxane and hydrogenated decasilsesquioxane, are compounds having a unique oligomer structure. Such crystalline hydrogenated silsesquioxane is considered to be a useful compound for various uses, but its production method is still required to be improved.

According to the method of the present invention, the organic phase comprises a water-insoluble organic solvent, and the aqueous phase comprises a surfactant dissolved in a hydrochloric acid aqueous solution having a concentration of 25% by mass or more. Is used. In the present invention, the two-phase system means that the aqueous phase and the organic phase do not show compatibility and miscibility. If a rapid hydrolysis and condensation reaction occurs in the aqueous phase, gelation occurs, and a two-phase system is used to suppress this. Therefore, the property that the aqueous phase and the organic phase are not compatible or miscible is considered. The two phases must be capable of being present as a separate, separate layer in order to utilize and recover the product. The gel product is considered to have a structurally irregular and dense crosslinked structure, which is different from the product aimed at in the present invention.

The two-phase organic phase used in the present invention is required to be capable of dissolving trichlorosilane but not water. As a specific organic solvent, a nonpolar solvent or a halogenated hydrocarbon solvent insoluble in water can be used. For example, dodecane, n-pentane, n-hexane, n-heptane, saturated aliphatic hydrocarbon solvents such as isooctane, benzene, toluene, aromatic hydrocarbon solvents such as xylene, cycloaliphatic hydrocarbon solvents such as cyclohexane, Trichlorethylene, perchlorethylene,
Examples thereof include halogenated aliphatic hydrocarbon solvents such as 3-chloropropane, and halogenated aliphatic hydrocarbon solvents such as bromobenzene and chlorobenzene.

As the two-phase aqueous phase used in the present invention, an aqueous hydrochloric acid solution having a concentration of 25% by mass or more is used. In the aqueous phase, the intermediate (HSi
O _3/2 ) _x is generated, and the following equilibrium relationship is established. 1.5H ₂ O + HSiCl ₃ = (HSiO _3/2 ) _x + 3HCl At this time, if the hydrochloric acid concentration in the aqueous phase is low, the equilibrium proceeds too far to the right and gelation occurs. Therefore, by adding a certain amount of hydrochloric acid to the aqueous phase from the beginning, the equilibrium is prevented from proceeding to the right, and gelation can be prevented. The hydrochloric acid concentration required for such a purpose is 25% by mass or more. If the concentration of hydrochloric acid falls below this, the rate of formation of crystalline hydrogenated celsquioxane decreases. The upper limit of the hydrochloric acid concentration is in accordance with the requirements from the temperature and pressure at the time of carrying out the method of the present invention.
% By weight corresponds to it.

[0015] The aqueous phase used in the present invention may further comprise a surfactant.
Is dissolved and contained. Surfactant is trichloride in hydrochloric acid aqueous solution.
Intermediate (HSiO_3/2)_xTo
By transporting to the organic phase by the action of surfactant,
In the aqueous phase, the reaction of the intermediate proceeds further to cause gelation.
And the intermediate transported to the organic phase (HSi
O_{Three / 2})_xIndicates that the condensation reaction proceeds in the organic phase
Octasilsesquio hydrogenated silsesquioxane
Produces xane or hydrogenated decasilsesquioxane
it is conceivable that. The action of such surfactants is possible.
In order to achieve this, the surfactant must be a 36% strength by weight aqueous hydrochloric acid solution.
Organic sulfonic acid that can be dissolved in liquid at a concentration of 5% by mass or more
Limited. Such a 36% by mass aqueous hydrochloric acid solution
An organic sulfonic acid soluble at a concentration of 5% by mass or more, or
As a surfactant composed of the salt, for example, benzene
Sulfonic acid hydrate, ethanesulfonic acid, chlorobenzene
Sulfonic acid and the like;
Fonic acid is preferred, but not limited to
No. The upper limit of the amount of surfactant added can maintain a two-phase system
As long as it is not specifically restricted.

To produce the crystalline hydrogenated silsesquioxane of the present invention, the organic phase comprises a water-insoluble organic solvent,
The aqueous phase is prepared by dissolving a surfactant in an aqueous solution of hydrochloric acid having a concentration of 25% by mass or more. A two-phase system of an organic phase and an aqueous phase is prepared, and trichlorosilane is added to the two-phase system with stirring. The crystalline hydrogenated silsesquioxane formed in the phase is separated and recovered.

In order to add trichlorosilane to a two-phase system of an organic phase and an aqueous phase, any method can be used as long as it can suppress gelation. However, if trichlorosilane is rapidly added, the reaction is intense. It is preferred to dilute and add the dilute solution intermittently. An organic solvent that is not soluble in water is used. In a laboratory, the solution may be dropped using a dropping funnel, but industrially, the method is not limited to dropping.

In the method of the present invention, the two-phase system is devised as described above, so that even if the addition rate of trichlorosilane to the two-phase system (aqueous phase) is higher than before, gelation does not occur and high yield is obtained. It is characterized in that a crystalline hydrogenated silsesquioxane can be produced at a high rate. That is, the present invention has an effect that a crystalline hydrogenated silsesquioxane can be produced in a shorter time than the conventional method.

The hydrogenated silsesquioxane formed in the organic phase by adding trichlorosilane to the two-phase system includes, in addition to crystalline hydrogenated silsesquioxane, a non-crystalline product in the form of a gel. In the present invention, crystalline hydrogenated silsesquioxane is isolated. Isolation methods include, but are not limited to, first separating the organic phase from the two-phase system and then i) removing the solvent from the organic phase to a solid residue obtained by
A method in which a non-reactive solvent is added to SiH (silicon-bonded hydrogen) to dissolve and remove substances other than the crystallized substance, or ii) a method in which the solvent in the organic phase separated from the aqueous phase is reduced to precipitate the crystallized substance It is.

When the stirring is stopped after the completion of the reaction, the organic layer separates upward and the aqueous layer separates downward. The hydrogenated silsesquioxane is dissolved in the organic phase. The organic phase is dehydrated and dried using a known method. Sulfuric acid can be exemplified as the dehydrating agent, and calcium carbide can be exemplified as the drying agent. Filtration of the dried and dried organic phase gives a solid. This solid (solid residue) is composed of crystalline hydrogenated silsesquioxane (mainly hydrogenated octasilsesquioxane and hydrogenated decasilsesquioxane) and a resinous material having a larger molecular weight than that (non-crystalline). Of hydrogenated silsesquioxane and impurities.

When a solvent is added to the solid residue, the non-crystallized substance (resin-like substance) has higher solubility than the crystallized substance, so that it is dissolved in the solvent and only the crystallized substance remains as a solid substance. Thus, a crystalline hydrogenated silsesquioxane can be obtained. The solvent used for this purpose may be any solvent that is non-reactive with -SiH (silicon-bonded hydrogen), capable of dissolving a resinous material, and containing no water. Such a solvent may be not only the non-polar solvent of the organic solvent used in the two-phase system but also a polar solvent as long as the above requirements are satisfied. Examples of solvents that cannot be used as this solvent include alcohols. Alcohols cannot be used because the hydroxyl groups are reactive with -SiH. For example, n-hexane or the like can be used.

Alternatively, when the solvent is gradually stripped from the dehydrated and dried organic phase, the concentration of hydrogen silsesquioxane increases, and a crystal having low solubility precipitates. This is filtered to separate the crystallized product from the liquid phase to obtain crystalline hydrogenated silsesquioxane. The crystalline hydrogenated silsesquioxane obtained by the method of the present invention is typically composed of hydrogenated octasilsesquioxane and hydrogenated decasilsesquioxane, but a small amount of hydrogenated dodecasilsesquioxane. May contain oxane and hydrogenated tetradecasilsesquioxane. Also, if the reaction conditions are selected, it is possible that relatively large amounts of hydrogenated dodecasilsesquioxane and hydrogenated tetradecasilsesquioxane can be produced. Decasilsesquioxane.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, in which the yield of crystalline hydrogenated silsesquioxane is as follows.
1 when the raw material trichlorosilane is completely hydrolyzed
The yield was calculated as 00%. To completely hydrolyze and condense 1 mol of trichlorosilane, 1.5 mol of water is required.

Example 1 50.0 g of benzenesulfonic acid hydrate, 150.0 g of a 35% hydrochloric acid aqueous solution, and 650.0 g of toluene were placed in a 1-liter three-necked flask, and the toluene of HSiCl ₃ was stirred at 400 rpm. Solution (HSiCl ₃ / toluene = 50.0 g / 15
0.0g) was added dropwise over 50 minutes, and the mixture was further stirred for 2 hours.

The reaction product was poured into a separating funnel, and the organic layer was separated. The separated organic phase was washed twice with 100 ml of 47% sulfuric acid and then twice with 100 ml of deionized water. Next, after adding about 20 g of calcium carbonate CaCO ₃ and stirring for 10 minutes, about 20 g of magnesium sulfate MgSO ₄
And stirred for 10 minutes. The solvent was stripped from the filtrate obtained by filtering the solution. 17.4 g of the obtained solid
N-hexane was added to the mixture to dissolve the resinous substance, and the remaining crystalline substance was separated and collected as a solid substance.

4.7 g of the crystalline material thus obtained has a yield of crystalline hydrogenated silsesquioxane of 24% and ²⁹ Si
-NMR, ¹ H-NMR and gas chromatography analysis (GCMS-QP1000EX manufactured by Shimadzu Corporation) (M-1 = 42)
From 3), it was confirmed that hydrogenated octasilsesquioxane and hydrogenated decasilsesquioxane were contained at a ratio of 92: 8 (mass ratio). FIG. 1 shows the ²⁹ Si-NMR identification data, and FIG.
¹ H-NMR identification data and FIG. 3 show GPC identification data.

Example 2 50.0 g of benzene sulfonic acid hydrate, 150.0 g of 35%
A hydrochloric acid aqueous solution and 600.0 g of toluene were added, and an HSiCl ₃ / toluene (50.0 g / 150.0 g) solution was added dropwise over 60 minutes while stirring at 400 rpm, and the mixture was further stirred for 10 minutes. The reaction product was poured into a separating funnel, and an acid layer formed below the organic layer was drained to obtain an organic layer. The organic phase was washed four times with 50 ml of deionized water. Then, after adding about 20 g of calcium carbonate and stirring for 10 minutes, about 20 g of magnesium sulfate was added and stirred for 10 minutes. The solvent was stripped from the filtrate obtained by filtering the solution. Obtained solid 1
N-Hexane was added to 7.6 g (yield 89.8%) to dissolve the resinous matter, and the crystalline substance was separated and collected as a solid substance.

4.7 g of the crystalline material thus obtained has a yield of crystalline hydrogenated silsesquioxane of 24% and ²⁹ Si
-NMR, from ¹ H-NMR and gas chromatography, and a hydrogenated octasilsesquioxane and hydrogenated dec silsesquioxane may include 90:10 (mass ratio) was confirmed. On the other hand, when the solvent was stripped from the n-hexane solution after removing the solid crystal, 11.6 g of a white solid was obtained. This white solid is an amorphous resinous material.

(Comparative Example 1) 50.0 g of FeCl ₃ , 20 ml of 36% HCl aqueous solution, 40 ml of methanol, 350 ml of hexane, and 50.0 g of toluene were placed in a 1-liter three-necked flask.
While stirring at 400 rpm, HSiCl ₃ / hexane (26.84 g / 150.0
g) The solution was added dropwise over 40 minutes and then stirred for another 30 minutes.

The upper organic layer of the reaction product was poured into a flask and separated, and about 14 g of potassium carbonate K _{2 was} added to the organic phase.
After adding CO ₃ and about 20 g of calcium chloride CaCl ₂
Stirred for hours. The solvent was stripped from the filtrate obtained by filtering the solution. To 4.56 g (yield 43%) of the obtained solid, 10 ml of pentane was added to dissolve the resinous substance, and the crystalline substance was separated and collected as a solid.

This crystalline substance weighed 1.1 g and had a purity of 95% according to the infrared detector of gas chromatography.
The yield was 10.0%. (Comparative Example 2) 50.0 g of Fe was placed in a 1-liter three-necked flask.
Cl ₃ , 20 ml of 36% HCl aqueous solution, 40 ml of methanol, 350 m
l of hexane and 50.0 g of toluene were added, and an HSiCl ₃ / hexane (26.84 g / 150.0 g) solution was added dropwise over 6 hours while stirring at 400 rpm, and the mixture was further stirred for 30 minutes.

The upper organic layer of the reaction product was poured into a flask and separated, and about 14 g of potassium carbonate and about 20 g of calcium chloride were added to the organic phase, followed by stirring for 17 hours. The solvent was stripped from the filtrate obtained by filtering the solution. Pentane (10 ml) is added to the obtained solid (7.1 g, yield 67%).
Was added to dissolve the resinous substance, and the crystalline substance was separated and collected as a solid substance.

This crystalline substance weighed 2.2 g and had a purity of 78% according to the infrared detector of gas chromatography.
The yield was 16%. Example 3 50.0 g of ethanesulfonic acid EtSO ₃ H, 150 g of
A 36% hydrochloric acid aqueous solution and 333.2 g of toluene were placed in a 1-liter three-necked flask, and an HSiCl ₃ / toluene (49.4 g / 55.5 g) solution was added dropwise over 55 minutes while stirring at 600 rpm, and further stirred for 2 hours. did.

The reaction product was poured into a separating funnel, and the acid layer below the organic layer was drained. Water was added to the organic layer in the separation funnel and shaken to form an emulsion. After further addition of saturated saline, the aqueous layer was drained. The remaining organic layer was transferred to a 500 ml flask and, as in Example 1,
Calcium carbonate was added, magnesium sulfate was further added, and the solvent was stripped from the filtrate obtained by filtering the solution.

The obtained white solid (12.6 g) had a yield of 63% as silsesquioxane hydride, of which the fraction of crystalline hydrogen silsesquioxane by gel chromatography was 45.1%. Example 4 120.0 g of benzene sulfonic acid hydrate, 60.0 g
g of a 36% hydrochloric acid aqueous solution and 600.0 g of toluene were placed in a one-liter three-necked flask, and stirred at 350 rpm to form HSiCl ₃ /
After a toluene (50.0 g / 150.0 g) solution was added dropwise over 50 minutes, the mixture was further stirred for 30 minutes.

The reaction product was poured into a separation funnel, and the acid layer formed below was drained. About 130 g of the remaining organic layer was drained.
After washing twice with 50 ml of 47% sulfuric acid, it was washed twice with 50 ml of deionized water. Then, after adding about 20 g of calcium carbonate and stirring for 10 minutes, about 20 g of magnesium sulfate was added and stirred for 10 minutes. The solvent was stripped from the filtrate obtained by filtering the solution. To 17.0 g (yield: 86.7%) of the obtained solid, n-hexane was added to dissolve the resinous matter, and the remaining crystalline substance was separated and collected as a solid.

4.6 g of the crystalline substance thus obtained has a yield of crystalline hydrogenated silsesquioxane of 23.5% and ²⁹ S
From i-NMR, ¹ H-NMR and gas chromatography analysis, it was confirmed that hydrogenated octasilsesquioxane and hydrogenated decasilsesquioxane were contained at a ratio of 92: 8 (mass ratio). When the solvent was stripped from the solution after removing the crystalline substance, 11.2 g of a white solid was obtained.

Comparative Example 3 1.0 g of sodium octylsulfonate, 200.0 g of a 36% hydrochloric acid aqueous solution, and 300.0 g of toluene were placed in a 1-liter three-necked flask, and stirred at 300 rpm with HSiCl ₃ / toluene (50.0 g). g / 50.0 g) The solution was added dropwise over 80 minutes, and the mixture was further stirred for 2 hours. The reaction product was poured into a separating funnel, the lower acid layer was drained, and the remaining organic layer was washed four times with 50 ml of deionized water. Then
After adding about 20 g of calcium carbonate and stirring for 10 minutes, about 20 g of magnesium sulfate was added and stirred for 10 minutes. The solvent was stripped from the filtrate obtained by filtering the solution. Hexane was added to 15.45 g (yield 79%) of the obtained solid to dissolve the resinous matter, and the remaining crystalline substance was separated and collected as 2.0 g of a solid.

When the solvent was stripped from the solution from which the solids had been removed, 11.5 g of a resinous substance was obtained as a white solid. Table 1 summarizes the results of Examples 1 to 4 and Comparative Examples 1 to 3.

[0040]

[Table 1]

In Table 1, the hydrochloric acid concentration is the ratio (%) of the mass of hydrochloric acid to the total mass of hydrochloric acid and water.
The concentration of the surfactant is a ratio (%) of the mass of the surfactant to the total mass of the surfactant, hydrochloric acid, and water. Dropping rate of a toluene solution of HSiCl ₃ represents a dropping rate of HSiCl ₃ per unit time. TH8 and TH10 represent hydrogenated octasilsesquioxane and hydrogenated decasilsesquioxane. Table 1 also shows the solubility (% by mass) of the surfactant in a 36% by mass aqueous hydrochloric acid solution. These are the same in Tables 2 and 3 below.

(Examples 5 to 8 and Comparative Examples 4 to 5) The same procedure as in Example 2 was repeated under the conditions shown in Table 2. Table 2 shows the analysis results of the obtained products.

[0043]

[Table 2]

(Examples 9 to 11 and Comparative Example 6) The same procedure as in Example 2 was repeated under the conditions shown in Table 3. Table 2 shows the analysis results of the obtained products.

[0045]

[Table 3]

[0046]

According to the method of the present invention, crystalline hydrogenated silsesquioxane can be obtained at a high yield and more reliably and at a higher speed than the conventional method. Thus, it becomes easier to separate crystalline hydrogenated silsesquioxane and utilize this useful compound for research and commercial purposes.

[Brief description of the drawings]

FIG. 1 shows the hydrogenated silsesquioxane product of Example 1.
^{It is a 29} Si-NMR chart.

FIG. 2 shows the hydrogenated silsesquioxane product of Example 1.
It is a < ¹ > H-NMR chart.

FIG. 3 is a GPC chart of a hydrogenated silsesquioxane product of Example 1.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Leslie Earl Carpenter Second United States, 48842, Michigan, Midland, Todd Street 3823 (72) Inventor Greg Alan Zunk 33-16 Oyamacho, Shibuya-ku, Tokyo F-term (reference) 4J035 BA12 CA021 EA00 EB08

Claims (3)

[Claims] A) The organic phase is composed of a water-insoluble organic solvent, and the aqueous phase is prepared by adding an aqueous solution of hydrochloric acid having a concentration of 25% by mass or more to a surfactant comprising an organic sulfonic acid or a salt thereof (however, HC
It is limited to those which can be dissolved in an aqueous hydrochloric acid solution having a concentration of 36% by mass of 5% by mass or more. A) a biphasic system comprising an organic phase and an aqueous phase prepared by dissolving); b) adding trichlorosilane to the biphasic system under stirring and adding it to the aqueous phase and / or the organic phase. Decomposing and condensing to produce a hydrogenated silsesquioxane; c) separating the crystalline hydrogenated silsesquioxane from the organic phase containing the hydrogenated silsesquioxane thus obtained. For producing a crystalline hydrogenated silsesquioxane. 2. The organic phase containing the hydrogenated silsesquioxane obtained in step b) is separated from the aqueous phase, the solvent is removed from the organic phase, and the resulting solid residue contains silicon-bonded hydrogen. A non-reactive solvent is added to the (-SiH) group to dissolve other than the crystallized substance in the residue, and the solvent is removed to isolate the crystalline silsesquioxane hydride as a solid. A method for producing a crystalline hydrogenated silsesquioxane according to claim 1. 3. The method according to claim 1, wherein the organic phase containing the silsesquioxane hydride obtained in the step b) is separated from the aqueous phase, and the amount of the solvent is reduced in the organic phase to precipitate a crystallized product. 2. The method for producing the crystalline hydrogenated silsesquioxane according to 1.