JPH0827162A - Method for producing cyclic organosilicon compound - Google Patents

Abstract

(57) [Summary] [Structure] General formula (In the formula, R ¹ and R ² are each 1 to 10 carbon atoms.
And R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms,
x represents an integer of 3 to 10. ) Hydrolyze cyclopolysilazane represented by (In the formula, R ¹ , R ² , R ³ and x are as described above. Y is 1
Represents an integer from 1 to x. ), A method for producing a cyclic organosilicon compound, wherein the hydrolysis is carried out in the presence of a carboxyl group-containing compound capable of forming a water-soluble salt by reacting with water-soluble or ammonia. It is a method for producing an organosilicon compound. [Effect] The desired cyclic organosilicon compound can be produced in extremely high yield by simple production equipment and operation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cyclic organosilicon compound by hydrolyzing cyclopolysilazane. More specifically, it relates to a method for producing a cyclic organosilicon compound by hydrolyzing cyclopolysilazane in the presence of a carboxyl group-containing compound which is water-soluble or can react with ammonia to form a water-soluble salt.

[0002]

PRIOR ART General formula

Embedded image (In the formula, R ¹ and R ² each represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, x Is an integer from 3 to 10, and y is an integer from 1 to x.) When the cyclic organosilicon compound contains a silazane unit in its molecule (in the formula of “Chemical Formula 3”,
(when y ≠ x), due to the hydrolyzability of the silazane unit, it is important as a surface treatment agent for imparting water repellency to fillers, fibers, or inorganic substrates, and as a raw material for diorganosiloxane-diorganosilazane copolymers. It is a compound.

Further, when no silazane unit is contained (y = x in the formula of "Chemical Formula 3"), that is, cyclopolysiloxane is a useful cyclic compound as a basic raw material for silicone oil.

The cyclic compound containing no silazane unit (when y = x in the formula of "Chemical Formula 3"), that is, the cyclopolysiloxane is produced by a hydrolysis method of diorganodihalosilane or diorganosilane. A thermal cracking method of polysiloxane and the like are known.

Further, as a method for producing the cyclic compound containing a silazane unit (when y ≠ x in the formula of "Chemical Formula 3"), the following production method has been proposed.

(1) A method of producing a cyclic compound of the above "Chemical Formula 3" by treating α, ω-dichloropolysiloxane or a mixture of α, ω-dichloropolysiloxane and diorganodichlorosilane with ammonia ( Helv.C
him. Acta, 51 , 1160 (1968)). (2) A method of producing a cyclic compound of the above "Chemical Formula 3" by reacting α, ω-dichloropolysiloxane with hexaorganosilazane (Zb.Obshc)
h. Khim. , 47 , 233 (1977)). (3) A method of reacting cyclopolysilazane and phenylboron oxide under heating to produce the cyclic compound of "Chemical Formula 3" (Izv. Akad. Nauk. SSSR, Se
r. Khim. , 1145 (1987)).

However, the method (1) has a problem in the manufacturing process because a large amount of salt is by-produced.
The method (2) has a problem that Me ₃ SiCl, which is a silicon-containing product other than the cyclic compound of Chemical formula ₃ , is produced as a by-product, and a disadvantage in the manufacturing process that toxic pyridine is used. . Further (1) and (2)
In the above method, since α, ω-dichloropolysiloxane, which is relatively difficult to obtain, is used as a raw material, it is not rational as a manufacturing process. In the method (3), 180-
Since the reaction is performed at a high temperature of 280 ° C., there is a problem in the manufacturing process, and cyclopolyborazane (PhBN)
H) There is a drawback that a large amount of _n is produced as a by-product.

[0008]

Therefore, in view of the problems of the above-mentioned production method, the present inventors have earnestly studied a new production method of the cyclic compound of the above "Chemical formula 3", and as a result,
Conventionally, cyclic organosilicon compounds have not been obtained in good yields by hydrolysis of cyclopolysilazanes, but surprisingly, in the presence of a carboxyl group-containing compound that is water-soluble or can react with ammonia to form a water-soluble salt. In the present invention, a new finding was found that cyclopolysilazane was hydrolyzed to produce a cyclic organosilicon compound in extremely high yield, and the present invention was completed.

The object of the present invention is to provide a cyclic organosilicon compound which is important as a raw material for a filler, a surface treatment agent for imparting water repellency for fibers or inorganic substrates, a diorganosiloxane / diorganosilazane copolymer or a silicone oil. The object of the present invention is to provide a method of manufacturing with extremely high yield by a conventional manufacturing process.

[0010]

That is, the present invention provides a general formula

[Chemical 4] (In the formula, R ¹ and R ² are each 1 to 10 carbon atoms.
And R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms,
x represents an integer of 3 to 10. ) Hydrolyze cyclopolysilazane represented by

Embedded image (In the formula, R ¹ , R ² , R ³ and x are as described above. Y is 1
Represents an integer from 1 to x. ), A method for producing a cyclic organosilicon compound, wherein the hydrolysis is carried out in the presence of a carboxyl group-containing compound capable of forming a water-soluble salt by reacting with water-soluble or ammonia. It is a method for producing an organosilicon compound.

In the present invention, the carboxyl group-containing compound is used in an equivalent ratio of 0.
005 to 2 is the method for producing a cyclic organosilicon compound.

Further, the present invention is the above-mentioned method for producing a cyclic organosilicon compound, characterized in that the amount of the carboxyl group-containing compound used is an equivalent ratio of 0.05 to 1.5 with respect to cyclopolysilazane.

Further, in the present invention, the amount of water used for the hydrolysis is 1 to 2 in terms of an equivalent ratio to cyclopolysilazane.
It is 0, It is a manufacturing method of the said cyclic organosilicon compound characterized by the above-mentioned.

Further, the present invention is the above-mentioned process for producing a cyclic organosilicon compound, characterized in that the reaction temperature during hydrolysis is in the range of 0 ° C to 60 ° C.

Next, the manufacturing method of the present invention will be described in detail. The cyclopolysilazane used in the production method of the present invention has the general formula

[Chemical 6] It is a cyclic organosilicon compound represented by.

In the above "Chemical Formula 6", R ¹ and R ² are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R
³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

Specific examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; vinyl group. , Alkenyl groups such as allyl group, butenyl group, hexenyl group, isopropenyl group; aryl groups such as phenyl group, tolyl group, xylyl group; aralkyl groups such as benzyl group, phenethyl group; chloroethyl group, 3,3,3 -A halogen atom-substituted alkyl group such as a trifluoropropyl group is exemplified.

In the above "Chemical formula 6", x is an integer from 3 to 10. As such a cyclopolysilazane, specifically, for example, 1,1,3,3,5,5-hexamethylcyclotrisilazane, 1,1,3,3,5,5-hexaethylcyclotrisilazane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisilazane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisilazane, 1,1,3,3,5, 5,7,7-octamethylcyclotetrasilazane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasilazane, 1,1,2,3,3,4,5 , 5,6-Nonamethylcyclotrisilazane, 1,1,3,3,5,5-hexamethyl-2,4,6-triethylcyclotrisilazane, 1,1,2,3,3,
Examples include 4,5,5,6,7,7,8-dodecamethylcyclotetrasilazane and the like. Note that particularly preferable Xs are 3 and 4.

In the production method of the present invention, the cyclopolysilazane represented by the general formula "Chemical Formula 6" is hydrolyzed. The carboxyl group-containing compound used at that time is water-soluble or reacts with ammonia. It must be a compound capable of forming a water-soluble salt.

Specifically, formic acid, acetic acid, propionic acid,
Butyric acid, isobutyric acid and other aliphatic monobasic acids; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and other aliphatic dibasic acids; crotonic acid, itaconic acid, glutaconic acid, fumaric acid, maleic acid and other Unsaturated carboxylic acid; glycolic acid,
Examples thereof include hydroxy group-containing carboxylic acids such as tartaric acid, glyceric acid, citric acid and lactic acid; aromatic carboxylic acids such as benzoic acid and salicylic acid; and halides of the above carboxylic acids. Particularly preferred is acetic acid.

The amount of the above-mentioned carboxyl group-containing compound used is 0.005 in equivalent ratio to cyclopolysilazane.
The range of 2 is preferable, and the range of 0.
It is in the range of 05 to 1.5.

The amount of water used in carrying out the hydrolysis reaction of the present invention is an equivalent ratio of 1 to cyclopolysilazane.
It suffices if the above is satisfied, and in practice it is preferable that the equivalence ratio is in the range of 1-20. When the equivalence ratio is lower than 1, the hydrolysis reaction takes a long time and most of the cyclopolysilazane as a raw material is not hydrolyzed, and when the equivalence ratio exceeds 20, the volume efficiency is significantly lowered. Become.

In the production method of the present invention, the conditions of the hydrolysis reaction are not particularly limited and should be appropriately selected depending on the organic group in the starting material, cyclopolysilazane. In the production method of the present invention, in order to obtain a good reaction rate, the reaction temperature is preferably in the range of -20 ° C to 100 ° C,
More preferably, it is in the range of 0 ° C to 60 ° C.

The hydrolysis reaction in the production method of the present invention can be carried out in a non-reactive organic solvent, if necessary. Specific examples of the non-reactive organic solvent that can be used include aliphatic organic solvents such as hexane, heptane, and octane; aromatic organic solvents such as toluene and xylene.

[0025]

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

Example 1 In a four-necked flask equipped with a stirrer, 1,1,3,3,5,5-hexamethylcyclotrisilazane 26 was added.
0.8 g (1.19 mol) and toluene 259.5 g
Was added, and acetic acid 73. was stirred while cooling in an ice-water bath.
A mixture of 5 g (1.23 mol) and 240.8 g (13.38 mol) of water (equivalent ratio of carboxyl group-containing compound and cyclopolysilazane: 0.345, equivalent ratio of water and cyclopolysilazane: 3.75) was added to 24 It dripped over minutes. At this time, the reaction system generated heat and the temperature was raised from 4 ° C to 58 ° C. After cooling, the upper organic phase was separated, washed with water, and then distilled under normal pressure to obtain a fraction 210.4 g at 150 ° C to 152 ° C and a fraction 44.2 g at 165 ° C to 168 ° C. These fractions were analyzed by gas chromatography / mass spectrometry (hereinafter G
It is abbreviated as C-MS. ) And infrared spectroscopy (hereinafter,
Abbreviated as IR. ),
It was a compound represented by the following structural formula.

[0027]

[Chemical 7] Fraction: Yield 80.3%, Purity 95.8%

Embedded image Fraction: Yield 16.8%, Purity 98.8%

Example 2 In a four-necked flask equipped with a stirrer, 1,1,3,3,5,5-hexaethylcyclotrisilazane 1 was added.
0.8 g (35.6 mmol) and toluene 10.6
g and charged with acetic acid of 0.
A mixture of 7 g (11.6 mmol) and 9.2 g (511.1 mmol) of water (equivalent ratio of carboxyl group-containing compound to cyclopolysilazane: 0.109, equivalent ratio of water to cyclopolysilazane: 4.79), It dripped over 11 minutes. The reaction temperature at this time was 4 ° C to 8 ° C. After the dropping was completed, the upper organic phase was separated and washed with water, and then the solvent was distilled off under reduced pressure with heating to obtain 11.3 g of a colorless transparent liquid. The colorless transparent liquid was a mixture of compounds represented by the following structural formulas as analyzed by gas chromatography (hereinafter abbreviated as GLC) and GC-MS.

[0029]

[Chemical 9] GLC area ratio: 70.4%

[Chemical 10] GLC area ratio: 18.6%

[Chemical 11] GLC area ratio: 5.7%

[Chemical 12] GLC area ratio: 4.9%

Comparative Example 1 1,1,3,3,5,5-hexaethylcyclotrisilazane 10.2 g (33.7 mmol), toluene 10.5 g and water 9.2 g (511.1 mmol) Was used, and the hydrolysis reaction was performed in the same manner as in Example 2 except that the reaction was performed without using acetic acid to obtain 10.4 g of a colorless transparent liquid. When analyzed by GLC and GC-MS, this colorless transparent liquid was a mixture of compounds represented by the following structural formulas, and the yield of the target cyclic organosilicon compound was low.

[0031]

[Chemical 13] GLC area ratio: 94.6%

Embedded image GLC area ratio: 4.2%

Comparative Example 2 1,1,3,3,5,5-hexaethylcyclotrisilazane 10.5 g (34.7 mmol), toluene 10.8 g and water 9.8 g (544.4 mmol) 1.2 g of concentrated hydrochloric acid (35% hydrochloric acid concentration product, 11.5 mmol as hydrochloric acid) was used instead of acetic acid (equivalent ratio of hydrochloric acid to cyclopolysilazane: 0.110, equivalent ratio of water to cyclopolysilazane). : 5.23) The hydrolysis reaction was performed in the same manner as in Example 2 except that the reaction was performed to obtain 9.9 g of a colorless transparent liquid. This colorless transparent liquid was a mixture of compounds represented by the following structural formulas as analyzed by GLC and gel permeation chromatography (hereinafter abbreviated as GPC), and the yield of the target cyclic organosilicon compound was Was very low.

[0033]

[Chemical 15] (N = 3 to 35)

Embedded image GLC area ratio: 8.2%

Example 3 In a four-necked flask equipped with a stirrer, 18.3 g (62.7 mmol) of 1,1,3,3,3,5,5,7,7-octamethylcyclotetrasilazane and 1 part of toluene were added.
0.7 g was added, and 8.0 g (65.6 mmol) of benzoic acid and 20.38 g of water were stirred while cooling in an ice-water bath.
A mixture of (1.13 mol) (equivalent ratio of carboxyl group-containing compound and cyclopolysilazane: 0.262, equivalent ratio of water and cyclopolysilazane: 4.51) was added dropwise over 15 minutes. The reaction temperature at this time was 3 ° C to 10 ° C.
After completion of the dropping, the upper organic phase was separated and washed with water, and then the solvent was distilled off under reduced pressure with heating to obtain 17.7 g of a colorless transparent liquid. This colorless transparent liquid was a mixture of compounds represented by the following structural formulas as analyzed by GLC.

[0035]

[Chemical 17] GLC area ratio: 62.5%

Embedded image GLC area ratio: 23.4%

[Chemical 19] GLC area ratio: 10.1%

Embedded image GLC area ratio: 2.5%

[0036]

According to the production method of the present invention, a cyclic organosilicon compound which is important as a raw material for a surface treatment agent for imparting water repellency, a diorganosiloxane / diorganosilazane copolymer and a silicone oil can be produced with a simple production facility and By the operation, the product can be produced in extremely high yield.

Claims (5)

[Claims] 1. A compound of the general formula (In the formula, R ¹ and R ² are each 1 to 10 carbon atoms.
And R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms,
x represents an integer of 3 to 10. ) Is hydrolyzed to give a compound of the general formula: (In the formula, R ¹ , R ² , R ³ and x are as described above. Y is 1
Represents an integer from 1 to x. ), A method for producing a cyclic organosilicon compound, wherein the hydrolysis is carried out in the presence of a carboxyl group-containing compound capable of forming a water-soluble salt by reacting with water-soluble or ammonia. Method for producing organosilicon compound. 2. The amount of the carboxyl group-containing compound used is
The method for producing a cyclic organosilicon compound according to claim 1, wherein the equivalent ratio to cyclopolysilazane is 0.005 to 2. 3. The amount of the carboxyl group-containing compound used is
Equivalent ratio to cyclopolysilazane 0.05 to 1.5
The method for producing a cyclic organosilicon compound according to claim 1, wherein 4. The method for producing a cyclic organosilicon compound according to claim 1, wherein the amount of water used in the hydrolysis is an equivalent ratio of 1 to 20 with respect to cyclopolysilazane. 5. The method for producing a cyclic organosilicon compound according to claim 1, wherein the reaction temperature during the hydrolysis is in the range of 0 ° C. to 60 ° C.