JP3453863B2 - α, ω-dialkoxyorganohydrogenpolysiloxane and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel α, ω useful as a basic raw material for organohydrogen silicone oil.
A dialkoxyorganohydrogenpolysiloxane and a method for producing the same.

[0002]

2. Description of the Related Art Organohydrogenpolysiloxanes contain Si--H in the molecule.
Since it is a siloxane compound having a bond, it is an important intermediate as a raw material for organically modified silicone oils such as fiber oils, resin modifiers, waxes, paint additives and the like. In order to obtain this organohydrogenpolysiloxane, a production method using an acid catalyst shown in the following equilibration reaction formula is known.

[0003]

[Chemical 5]

However, in such an acid-catalyzed equilibration reaction, (R ''' ₂ SiO) units and (R''''
There is no report on the regularity in the bonding between the units such that the (HSiO) units are bonded alternately.

Further, as the organohydrogenpolysiloxane having functional groups at both ends, Izvest.
Akad. Nauk S. S. S. R. , Otdel.
Khim. Examples of Nauk, 806 (1957) and the like are known, but (R ₂ SiO) unit and (RHSiO)
It does not describe the regularity of binding between units.

Further, both end groups of the organohydrogenpolysiloxane obtained by the following reaction formula are halogen atoms, but a dialkoxy derivative corresponding thereto is not known.

[0007]

[Chemical 6]

The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel α, ω-dialkoxyorganohydrogenpolysiloxane in which organic groups are regularly arranged, and a method for producing the same.

[0009]

MEANS TO SOLVE THE PROBLEMS The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, diorganosilanediol represented by the following general formula (2) and the following general formula (3) By the reaction with the dialkoxyorganosilane represented by the formula (1), a novel α, ω-dialkoxyorganohydrogenpolysiloxane represented by the following general formula (1) is obtained, and the α, ω-dialkoxyorganohydrogenpolysiloxane is obtained. The inventors have found that siloxane is useful as a basic raw material for organohydrogen silicone oil, and have completed the present invention.

[0010]

[Chemical 7] (In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² and R ³ are each a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. is there.)

Therefore, the present invention provides an α, ω-dialkoxyorganohydrogenpolysiloxane represented by the above general formula (1), preferably R ^{1 in the} above general formula (1) is a methyl group or an ethyl group, n is 1 or 2 α, ω-dialkoxyorganohydrogenpolysiloxane, and the above general formula comprising reacting the diorganosilanediol of formula (2) with the dialkoxyorganosilane of formula (3) Provided is a method for producing an α, ω-dialkoxyorganohydrogenpolysiloxane represented by (1).

The present invention will be described in more detail below. The α, ω-dialkoxyorganohydrogenpolysiloxane of the present invention is a siloxane compound represented by the following general formula (1).

[0013]

[Chemical 8]

In the general formula (1), R ¹ has 1 to 4 carbon atoms.
R ² and R ³ are each a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.
R ¹ is a methyl group, an ethyl group, a propyl group, and a butyl group, and R ² and R ³ are an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, a vinyl group, and an allyl group. Group, butenyl group, hexenyl group,
Alkenyl group such as isopropenyl group, phenyl group, tolyl group, aryl group such as xylyl group, aralkyl group such as benzyl group and phenethyl group, chloroethyl group, 3,3,3
Examples thereof include halogen atom-substituted alkyl groups such as trifluoropropyl group. Here, R ¹ is a synthetic method,
A methyl group or an ethyl group is particularly preferable from the viewpoints of easiness of acquisition and handling of raw materials and cost. Also,
It is particularly preferable that each of R ² and R ³ is a methyl group. n is an integer of 1 to 3, preferably 1 or 2.

The α, ω-dialkoxyorganohydrogenpolysiloxane represented by the above general formula (1) is obtained by reacting a diorganosilanediol of the following general formula (2) with a dialkoxyorganosilane of the following general formula (3). Can be obtained.

[0016]

[Chemical 9] (However, R ¹ , R ² , and R ³ have the same meanings as above.)

In order to obtain the diorganosilanediol of the formula (2), it can be produced by a conventionally known method, specifically, hydrolysis of dialkoxydiorganosilane, diorganodihalosilane, etc. A method of hydrolyzing the organic organosilicon compound or the like can be adopted. Further, as the dialkoxyorganosilane of the formula (3), a commercially available product can be used.

When the diorganosilanediol and the dialkoxyorganosilane are reacted with each other, the use ratio thereof is not particularly limited, but one molar ratio of the dialkoxyorganosilane to the diorganosilanediol is used.
It is preferable to use it within the range of 10 to 10, especially 1.5 to 5. When the molar ratio of dialkoxyorganosilane to diorganosilanediol is less than 1, the production amount of dihydroxyorganohydrogenpolysiloxane having both terminals and cyclic [(R ³ HSiO) (R ² ₂ SiO)] _n increases. Then, the selectivity of the reaction is lowered, and if the molar ratio exceeds 10, the selectivity of the reaction is improved, but the amount of unreacted dialkoxyorganosilane is increased, which causes a decrease in the yield. , There may be an economic disadvantage.

The reaction between the diorganosilanediol and the dialkoxyorganosilane of the present invention is a dealcoholization reaction and can be carried out at room temperature without using a catalyst.
In order to accelerate the reaction, heating or a metal salt or halide may be used as a catalyst. In this case, the heating method is used at a reaction temperature of 20 to 100 ° C., particularly 20 to 6 ° C.
0 ° C is preferred. Examples of the metal salt or halide used as a catalyst include zinc carbonate, potassium carbonate, tin carbonate, zinc chloride and the like.

Further, this reaction can be carried out without solvent, but it is particularly preferable to carry out in the presence of a solvent. Examples of usable solvents include non-polar solvents such as hexane, heptane, benzene and toluene, tetrahydrofuran, diethyl ether, acetone, ethyl acetate, dimethyl sulfoxide, dimethylformamide, methanol,
Examples thereof include polar solvents such as ethanol and isopropanol, and chlorinated hydrocarbon solvents such as carbon tetrachloride, chloroform and dichloromethane.

As a method for producing α, ω-dialkoxyorganohydrogenpolysiloxane,
(1) Co-hydrolysis of diorganodihalosilane and dihaloorganosilane to obtain α, ω-dihaloorganohydrogenpolysiloxane, and then the α, ω-dihaloorganohydrogenpolysiloxane with alcohol There may be a method of reacting; and (2) a method of reacting diorganodihalosilane and dialkoxyorganosilane in the presence of a metal chloride such as iron chloride. In these methods,
There is a drawback that the yield of the α, ω-dialkoxyorganohydrogenpolysiloxane of the present invention is low, or the productivity is low. That is, in the method (1), (R
Regularity cannot be expected in the bond between the ( ² ₂ SiO) unit and the (R ³ HSiO) unit. Therefore, α, in which the (R ² ₂ SiO) unit and the (R ³ HSiO) unit are alternately bonded,
The yield of ω-dialkoxy organohydrogenpolysiloxane decreases. Furthermore, since this reaction involves the risk of gelation, it is necessary to use a large amount of solvent. Also,
In the method (2), the metal chloride as the catalyst also promotes the disproportionation reaction of the desired α, ω-dialkoxyorganohydrogenpolysiloxane, resulting in (R ² ₂ Si
The regularity of the bonding sequence of the (O) unit and the (R ³ HSiO) unit is lost. Therefore, since the yield and productivity of the desired α, ω-dialkoxyorganohydrogenpolysiloxane are high, the above-mentioned diorganosilane is used as a method for producing the α, ω-dialkoxyorganohydrogenpolysiloxane. A method by a reaction of a diol and a dialkoxyorganosilane is adopted.

The α, ω-of the present invention thus obtained
The dialkoxyorganohydrogenpolysiloxane has organic groups bonded regularly and, like the known organohydrogenpolysiloxane, has a Si-
Since it is a siloxane compound having an H bond, it can be suitably used as a raw material for an organically modified silicone oil such as a fiber oil agent, a resin modifier, a wax, and a paint additive. Further, α, ω-dialkoxyorganohydrogenpolysiloxane alone or mixed with a hydrolyzable group-containing silane such as dimethoxydimethylsilane or trimethylchlorosilane and thermally decomposed in the presence of an acid catalyst gives an organohydrogenpolysiloxane. It can be easily converted.

[0023]

EFFECTS OF THE INVENTION The α, ω-dialkoxyorganohydrogenpolysiloxane of the present invention comprises organically modified silicone oils such as fiber oils, resin modifiers, waxes and coating additives, in which organic groups are regularly bonded. It is a novel siloxane compound useful as a raw material, and according to the production method of the present invention, the above α, ω-dialkoxyorganohydrogenpolysiloxane can be produced in high yield and high purity.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the formula, Me is a methyl group, Et is an ethyl group, Ph
Represents a phenyl group.

Example 1 108.5 g (1.02 m) of dimethoxymethylsilane was placed in a four-necked flask equipped with a stirrer.
ol) and 46.5 g (0.51) of dimethylsilanediol.
(mol) was added and the mixture was stirred at room temperature for 12 hours. Then
The reaction mixture was distilled under normal pressure to obtain a colorless and transparent fraction having a temperature of 121 to 122 ° C. This product was analyzed by mass spectrometry (GC-M
S), ¹ H-nuclear magnetic resonance analysis (NMR), and infrared spectroscopic analysis (IR), the following structural formula (4)
Was 1,5-dimethoxy-1,3,3,5-tetramethyltrisiloxane. The yield of 1,5-dimethoxy-1,3,3,5-tetramethyltrisiloxane was 80.3% and the purity was 98.2%. It is to be noted that FIG. 1 shows an NMR spectrum chart (the signal marked with * in the figure is an internal standard benzene), and FIG. 2 shows I.
An R spectrum chart is shown.

[0026]

[Chemical 10]

[Example 2] 134.3 g (1.00 m) of diethoxymethylsilane was placed in a four-necked flask equipped with a stirrer.
ol), and while stirring at room temperature, 46.1 g (0.50 mol) of dimethylsilanediol and 6 parts of ethanol.
3.4 g of the mixture was added dropwise. After completion of dropping, 10 at room temperature
Stir for hours. The reaction mixture is then distilled under normal pressure,
A colorless and transparent fraction having a temperature of 145 to 146 ° C. was obtained. As a result of analysis by GC-MS, NMR, and IR, this product was 1,5-diethoxy-1, represented by the following structural formula (5).
It was 3,3,5-tetramethyltrisiloxane. The yield of 1,5-diethoxy-1,3,3,5-tetramethyltrisiloxane was 87.3%, and the purity was 9%.
It was 9.1%. An NMR spectrum chart (* in the figure has the same meaning as above) is shown in FIG.
A spectrum chart is shown.

[0028]

[Chemical 11]

Example 3 2.15 g (20.3 mm) of dimethoxymethylsilane was placed in a four-necked flask equipped with a stirrer.
ol), and a mixture of 2.81 g (13.0 mmol) of diphenylsilanediol and 2.58 g of methanol was added dropwise with stirring at room temperature. After the dropping, 60 ℃
And stirred for 8 hours. After distilling off the low-boiling substance, the reaction mixture was analyzed by GC-MS. As a result, 1,5-dimethoxy-1,5-dimethyl-3,3-diphenyltrisiloxane represented by the following structural formula (6) and 1,9-Dimethoxy-1,5,9-trimethyl-3,3,7,7-tetraphenylpentasiloxane represented by Structural Formula (7) and 1,13-dimethoxy-1 represented by Structural Formula (8) , 5,9,13-tetramethyl-3,3,7,
7,11,11-hexaphenylheptasiloxane
The content was 65.7%, 19.4%, and 10.8%, respectively.

[0030]

[Chemical 12]

[Brief description of drawings]

1 is the 1,5-dimethoxy-1, obtained in Example 1.
3 is an NMR spectrum chart of 3,3,5-tetramethyltrisiloxane.

2 is the 1,5-dimethoxy-1, obtained in Example 1.
3 is an IR spectrum chart of 3,3,5-tetramethyltrisiloxane.

FIG. 3 1,5-diethoxy-1, obtained in Example 2,
3 is an NMR spectrum chart of 3,3,5-tetramethyltrisiloxane.

FIG. 4 1,5-diethoxy-1, obtained in Example 2,
3 is an IR spectrum chart of 3,3,5-tetramethyltrisiloxane.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Ichinohe No. 1 Hitomi, Osamu Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) (JP, A) JP-A-60-76536 (JP, A) Tokuhyo 5-507101 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 77/00-77 / 62 C07F 7/18 CAPLUS (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. An α, ω-dialkoxyorganohydrogenpolysiloxane represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² and R ³ are each a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. is there.) 2. R ¹ is a methyl group or an ethyl group,
The α, ω-dialkoxyorganohydrogenpolysiloxane according to claim 1, wherein n is 1 or 2. 3. The following general formula (2): A diorganosilanediol represented by the following general formula (3) And a dialkoxyorganosilane represented by the following general formula (1) (In the above formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² and R
Each of ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. The manufacturing method of the (alpha), (omega)-dialkoxy organohydrogen polysiloxane shown by these.