JPH032188A - Production of monohydrogen (triorganisiloxy) organosilane - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the subject compound in high purity and yield by co-hydrolyzing a monohydrogenorganochlorosilane and an organosilazane in the presence of a carbonate or hydrogencarbonate. CONSTITUTION:One mol compound expressed by formula I (R<1> represents monovalent hydrocarbon group; n is an integer of 1-3) (example; dimethylchlorosilane) and a compound expressed by formula II (R<2> represents monovalent hydrocarbon group; m is 1 or 2) (example; trimethylsilazane) in an amount to provide 1.0-1.2 triorganosilyl group in 1 Cl in the component of the compound expressed by formula I are separately or as a mixture dripped in small portions into water containing a carbonate or hydrogencarbonate (preferably 0.1-2 equivalents based on the compound expressed by formula I are used), whereby a reaction is carried out at 0 deg.C to refluxing temperature of the raw material used and the organic solvent (mixed in water as necessary) to afford the objective compound expressed by formula III.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to polyorganosiloxanes having silicon-hydrogen bonds (Si-H bonds), particularly polyorganosiloxanes having 1 to 3 triorganosiloxy atoms on a silicon atom to which a hydrogen atom is bonded. The present invention relates to a method for producing a monohydrodiene (triorganosiloxy) organosilane having a group.

[Technical background of the invention and its problems]

Various reactions for forming siloxane bonds have been known in the past, but in the reaction for forming polysiloxanes having 5i-H bonds, the 5i-H bonds are easily decomposed by basic compounds, certain Lewis acids, strong acids, etc. However, it has only been practiced to a limited extent due to the disadvantages of oxidation and substituent exchange reactions. Therefore, the main formation reactions of this type were those shown by the following reaction formula.

The siloxane forming reaction represented by formula (1) is the most commonly used method. However, in this method, for example, dimethylchlorosilane [H(CH3) 2sic1] and trimethylchlorosilane [:(CH3) 3SiC1]
Three products obtained by cohydrolysis reaction with 1,1.3.3-tetramethyldisiloxane (b, p
, 70.5t) 1,1.3.3.3-pentamethyldisiloxane (b, p, 85°C) Hexamethyldisiloxane (1:+, p.

The boiling point difference between 1 and 5 degrees Celsius is only about 15 degrees Celsius, making it difficult to purify by distillation, as well as making it difficult to purify by distillation.
．． There were disadvantages such as the theoretical yield of L3.3.3-pentamethyldisiloxane was about 50% and the yield was poor.

The reaction represented by the following formula (2) is described in U.S. Patent No. 3.462.
．． Although this method is described in the specification of No. 386, the yield inevitably decreases due to the condensation reaction of raw material silanol due to the action of generated hydrogen chloride. On the other hand, a method using amines such as pyridine as a scavenger for hydrogen chloride prevents the condensation reaction between silanols caused by hydrogen chloride, and produces pottery with a higher yield than the above method, but the resulting hydrochloride can be removed. Due to these needs, there was a problem in terms of final yield. Furthermore, there are problems with the difficulty in synthesizing the raw material triorganosilanol and its instability, making it unsuitable as an industrial production method.

Next, the reaction represented by formula (3) is
68, in the presence of catalytic amounts of metal salts and/or metal oxides. This reaction, unlike the siloxane formation reaction by hydrolysis, is carried out without the use of water and has been shown to have a high yield. However, this reaction also uses triorganosilanol as a starting material, and as shown in the section of equation (2) above, there are drawbacks in its synthesis and instability, and the overall yield considering the starting material is low. and still have problems in terms of industrialization.

The reaction represented by the following equation (4) is (tl(CH3
)Sin]s By the equilibrium reaction between cyclopentasiloxane and hexamethyldisiloxane with an acid,
A method for obtaining bis(trimethylsiloxy)methylsilane is known [J, Org.

Chem, 30, 1651 (1965)]. Although a yield of 55.3% is shown in the literature, the yield of the target substance is extremely low on an actual industrial scale, and purification is difficult due to a large amount of by-products. Moreover, the reaction also requires a long time. Therefore, this reaction has many drawbacks and is currently hardly carried out industrially.

Thus, a method for industrially obtaining monohydrodiene (triorganosiloxy)organosilane in high yield has hitherto been an extremely difficult problem.

[Purpose of the invention]

An object of the present invention is to eliminate such drawbacks and provide a manufacturing method for obtaining monohydrodiene (triorganosiloxy) organosilane in high yield using industrially advantageous raw materials.

[Structure of the invention]

As a result of intensive studies to achieve such an objective, the present inventor found that when organochlorosilane and organosilazane having a 5i-H bond are used as starting materials and co-hydrolyzed in the presence of carbonate or hydrogen carbonate, Monohydrogen (
It has been discovered that triorganosiloxy)organosilane can be obtained in high yield, and the present invention has been completed.

That is, the present invention has the following features: (A) general formula % formula % (wherein R1 is a substituted or unsubstituted monovalent hydrocarbon group;
n is a number of 1.2 or 3) and (B) a monohydrodiene organochlorosilane represented by the general formula % formula % (wherein R2 is a substituted or unsubstituted monovalent hydrocarbon group,
m is a number of 1 or 2) by cohydrolyzing organosilazane represented by (C) the general formula % formula %:) (wherein R1, R2 and n are the same as above). In the method for producing a monohydrodiene (triorganosiloxy)organosilane, 1 mole of monohydrodiene organochlorosilane of (A) and 1.0 to 1.2 chlorosilanes per chlorine in component (A). The present invention relates to a method for producing a monohydrodiene (triorganosiloxy) organosilane, which comprises cohydrolyzing an organosilazane to give an amount of triorganosilyl groups in the presence of a carbonate or a hydrogen carbonate.

(A) used in the present invention has the above general formula H3+RA
It is a monohydrodiene organochlorosilane represented by -nCI- (wherein R' and n are the same as above).

The organic group R1 bonded to the silicon atom is a substituted or unsubstituted monovalent hydrocarbon group.

For example, as R1, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a 2-phenylethyl L 2-phenylpropyl group Aralkyl groups such as phenyl group, aryl group such as tolyl group; alkenyl group such as vinyl group, allyl group: and chloromethyl group, chlorophenyl L3
．． Examples include substituted hydrocarbon groups such as 3.3-trifluoropropyl group, but examples include methyl group, phenyl group, and vinyl L3.3.3-)trifluoropropyl group due to ease of synthesis of raw materials. preferable. n is an integer represented by 1, 2 or 3.

Specific examples of such lorosilanes include dimethylchlorosilane, methyldichlorosilane, trichlorosilane, diphenylchlorosilane, phenyldichlorosilane, vinylmethylchlorosilane, 3.3.3-trifluoropropylmethylchlorosilane, and the like. .

Component (8) used in the present invention has the general formula (RSi)
, NH3- (in the formula, R2 is the same as above), and its organic group R2 is exemplified by the same group as R1, but the types of organic groups in R1 and R2 are the same as each other. , or may be different from each other. Specific examples of such organosilazanes include trimethylsilazane, dimethylvinylsilazane, dimethylphenylsilazane, methyldichlorosilane, 3゜3.3-)
Lifluoropropyldimethylsilazane, dimethylchlorosilane, hexamethyldisilazane, 1.1.3.3-tetramethyl-1,3-divinyldisilazane, 1.1.3
．． 3-tetramethyl-1,3-diphenyldisilazane,
1.1,3.3-tetramethyl-1,3-(3,3,3
-) lifluoropropyl) disilazane, etc.

Component (B) of the present invention is easily obtained industrially from the reaction of the corresponding organochlorosilane, which is easily available industrially, and ammonia. Therefore, in the method for obtaining the desired monohydrodiene (triorganosiloxy)organosilane, even if organosilazane, which is component (B), is used as one of the starting materials, the selective yield is lower than that obtained by already known methods. Since it has been confirmed that the results are equivalent or higher, the present invention can be considered to be an extremely industrially advantageous method when viewed as a whole.

In the present invention, the ratio of component (A) and component (B) used is 1 mole of chlorosilane as component (^) to 1 mole of component (B).
The components are preferably adjusted in amounts such that the number of triorganosilyl groups in (B) is 1.0 to 1.2 per chlor in (A). Furthermore, considering that the products obtained by cohydrolysis are difficult to purify by distillation etc.
More preferably, the amount is such that the number of triorganosilyl groups in component (B) to be used per one chloro in component (A) is substantially 1.0.

Carbonates used in carrying out the method of the present invention include, for example, sodium carbonate, potassium carbonate, sodium potassium carbonate, ammonium carbonate, calcium carbonate, etc., and examples of hydrogen carbonates include, for example, hydrogen carbonate.
Examples include ammonium hydrogen carbonate, calcium hydrogen carbonate, ammonium hydrogen carbonate, magnesium hydrogen carbonate, and nickel hydrogen carbonate. Among them, IJum (hydrogen carbonate) is the easiest to use industrially. The amount used is not particularly limited, but - for boat fishing, it is preferable to use an amount that can neutralize the hydrogen chloride generated from the chlorosilane (A).
) It is preferable to use 0.1 to 2 equivalents of carbonate per mole of component.

Furthermore, the amount of water used in the present invention is not particularly limited within the range that can be used industrially; It is desirable that the amount is in the range of ~1000% by weight, preferably 50-300% by weight.

Although the organic solvent is not essential in the present invention,
When using it, alcohols such as methyl alcohol and ethyl alcohol; ketones such as acetone;
Aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; ethers such as ethyl ether; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as 1,2-dichloroethane Hydrogens and the like are preferred.

Although the reaction of the present invention can proceed in a wide temperature range, the range is practically selected from 0° C. to the reflux temperature of the raw material or organic solvent used.

In the present invention, by co-hydrolyzing the above-mentioned (A) component and (B>component) in the presence of a carbonate or hydrogen carbonate (for example, sodium hydrogen carbonate) and water, the objective can be easily achieved. Monohydrogenctriorganosiloxy)organosilane can be obtained in high yield.

In addition, in terms of reaction control, it is preferable to carry out the reaction by dropping component (A) and component (B), either alone or as a mixture, little by little into water containing carbonate or hydrogen carbonate.

〔Effect of the invention〕

The method of the present invention is capable of producing monohydrogenes (triorganosiloxy) with high purity and high yield due to the high selectivity of the reaction, and is industrially advantageous due to the ease of obtaining starting materials.
Can produce organosilane. Therefore, the silane of the present invention is advantageous when used as a reactive oligomer for modifying other organic materials, and a material that is reliable in terms of molecular design can be obtained. That is, when organic monomers or their polymers are reacted and modified with the silane of the present invention, excellent properties such as heat resistance, weather resistance, Hashimoto properties, gas permeability, etc. can be imparted to conventional organic materials.

〔Example〕

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the scope of the present invention is not limited only to the following examples. Note that parts in the text represent parts by weight.

Example 1 In a four-hole flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 504 parts of hydrogen carbonate and 2.100 parts of water were charged, and stirring was started. A mixed solution consisting of 1.134 parts of dimethylchlorosilane and 966 parts of hexamethyldisilazane was added dropwise to this dispersion mixture from the dropping funnel.

The dropwise addition was carried out while cooling in a water bath so as to maintain the liquid temperature at 30 to 40° C. during the reaction period, and took about 1 hour. After the addition was completed, stirring was continued for 30 minutes, and the upper layer of the reaction solution was separated using a separating funnel, thoroughly washed with water until neutral, and then dried over anhydrous sodium sulfate. Separate Glauber's salt by filtration,
The weight of the resulting crude product was 1.750 parts (98% of theoretical yield). The composition ratio of this product was determined by gas chromatography and was found to be 1.1.3°3-
Tetramethyldisiloxane 9.1%, pentamethyldisiloxane 72.7%, hexamethyldisiloxane 14.
2% and other impurities 4.0%. When calculating the reaction selectivity from the former champion siloxane, the reaction selectivity to the target substance, pentamethyldisiloxane, was 76%, making it clear that the reaction proceeds preferentially to the target substance. . This crude product was distilled in a distillation column with an inner diameter of 30 mm and a height of 1.000 mm packed with a Raschig ring with a diameter of 5 mm, and a fraction with a boiling point of 84 to 87°C was collected.
A high yield of 1.243 parts (yield 71%) was obtained.

This component is determined by gas chromatography analysis.
It was confirmed that pentamethyldisiloxane was contained at a high purity of 95%.

Comparative Example 1 In the same manner as in Example 1, a mixed solution of 1,134 parts of dimethylchlorosilane and 1.302B of trimethylchlorosilane was mixed in 2.100 parts of water while maintaining the temperature at 0 to 10°C.
The mixture was added dropwise over a period of time to obtain 1.687 parts of a crude product (yield: 95%). According to gas chromatography, the composition ratio of this product was 22.5% of 1.1,3.3-tetramethyldisiloxane, 46.0% of pentamethyldisiloxane, 24.6% of hexamethyldisiloxane, and impurities. 6.9
%Met. The reaction selectivity of pentamethyldisiloxane from the former champion siloxane was 49%. This is almost equal to the theoretical reaction rate of 50%, and it is clear that there is almost no selectivity in the reaction. When this crude product was distilled using the distillation column of Example 1, 532 parts of pentamethyldisiloxane with a purity of 70% (yield 30%) was obtained.

Comparative Example 2 Same as Example 1, hydrogen carbonate) IJum 1.008
A mixed solution of 567 parts of dimethylchlorosilane and 651 parts of trimethylchlorosilane was added dropwise to a dispersion mixture of 567 parts of dimethylchlorosilane and 2.100 parts of water while maintaining the temperature at 30 to 40°C, and 817 parts of a crude product was obtained in the same manner as in Example 1. (yield 92%). As a result of the gas chromatography analysis, the reaction selectivity of pentamethyldisiloxane was 54%, and almost no improvement in the selectivity was observed.

Comparative Example 3 A mixed solution of 2.500 parts of xylene, 270 parts of trimethylsilanol, and 238 parts of pyridine was heated to a temperature of 0 to 10°C.
While maintaining the temperature, 284 parts of dimethylchlorosilane was added dropwise over 2 hours. After the addition was completed, stirring was continued for 3 hours at room temperature, and the resulting salt was filtered off, washed with water, and dried over anhydrous sodium sulfate. As a result of gas chromatography analysis of this xylene solution, 1.1.3.3-tetramethyldisiloxane:/10.1%, pentamethyldisiloxane 46
．． 5%, hexamethyldisiloxane 43.4% and other products 9%? there were. The reaction selectivity of pentamethyldisiloxane was 46.5%, and no selectivity was observed. The distillation resulted in 148 parts of pentamethyldisiloxane with a purity of 77% as determined by gas chromatography, with a yield of only 33%.

Comparative Example 4 900 parts of trimethylsilanol, 1.040 parts of dimethylethoxysilane, and dibutyltin dilaurate IB were placed in a flask similar to Example 1 except that it was equipped with a mantle heater and a Dean-Stark separation tube, and the liquid temperature was raised to 80°C while stirring. The mixture was kept for 8 hours and allowed to react. Ethanol produced as a by-product at this time was removed using a Dean-Stark separation tube. The weight of the crude product obtained after cooling was 1.300 parts. The results of the gas chromatography analysis were 1
．． 1,3.3-tetramethyldisiloxane 14.8%,
Pentamethyldisiloxane was 40.0%, hexamethyldisiloxane was 20.0%, and other products were 25.2%, and the reaction selectivity for pentamethyldisiloxane was 52%, and the selectivity was hardly observed. Ta. In addition, this reaction resulted in the formation of many impurities, confirming the instability of the 5i-H bond and the instability of silanol (Si-H).

Example 2 The same operation as in Example 1 was performed except that 690 parts of methyldichlorosilane was used instead of dimethylchlorosilane in Example 1, and finally bis(trimethylsiloxy) with a purity of 94% was obtained by gas chromatography. Methylsilane 8T4nWjpri.

Example 3 The same procedure as in Example 1 was performed except that 542 parts of trichlorosilane was used instead of dimethylchlorosilane in Example 1, and the final purity was 95% as determined by gas chromatography.
680 parts of tris(trimethylsiloxy)silane was obtained.

Example 4 Using the same apparatus as in Example 1, 106 parts of sodium carbonate, 1.500 parts of water, and 1.200 parts of ethyl ether were charged, and then stirring was started and methylphenylchlorosilane was added while maintaining the temperature at 20 to 30°C. 626 copies and 1.1.
3.3-tetramethyl-1,3-divinyldisilazane 3
A mixed solution of 62 parts was added dropwise over 2 hours. After the dropwise addition, the reaction was completed by keeping the ether at the reflux temperature for an additional hour. After cooling, the layers were separated, thoroughly washed with water until the ether layer became neutral, and then dried with anhydrous sodium sulfate. Gas chromatography analysis of the obtained crude product revealed that 1.3-dimethyl-1,3-diphenyldisiloxane was 10.1%;
3.3-trimethyl-1-phenyl-3-vinyldisiloxane 77.2%, 1,1.3.3-tetramethyl-1
, 3-divinyldisiloxane 9.7% and other products 3.0%. 1.3.3 of target substance
-) The reaction selectivity of IJ methyl-1-phenyl-3-vinyldisiloxane was 79%, indicating high selectivity.

This crude product was subjected to vacuum distillation using the same distillation column as in Example 1, and 650 parts of a fraction containing the target substance with a purity of 97% (
A yield of 74% was obtained.

Claims (1)

[Claims] 1 (A) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R^1 is a substituted or unsubstituted monovalent hydrocarbon group, and n is 1, 2 or 3. monohydrodiene organochlorosilane represented by the general formula (R^2_3Si)_mNH_3_-_m (where R^2 is a substituted or unsubstituted monovalent hydrocarbon group, m is 1 or (C) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, R^2 and n are 1 mol of the monohydrodiene organochlorosilane of (A) and 1.0 to 1 mol of the monohydrodiene organochlorosilane of component (A) .A method for producing a monohydrodiene (triorganosiloxy) organosilane, which comprises cohydrolyzing an organosilazane that provides two triorganosilyl groups in the presence of a carbonate or a hydrogen carbonate. . 2. The monohydrodiene organochlorosilane (A) and the organosilazane (B) are co-hydrolyzed while being dropped into water containing carbonate or hydrogen carbonate, either alone or as a mixture. 2. The manufacturing method described in 2.