JP4513285B2 - Method for producing chlorosilane compound - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a chlorosilane compound from a disiloxane compound. Chlorosilane compounds are suitably used as main intermediates such as silicone rubber, silicone oil and silicone resin, and as raw materials for organic chemicals such as pharmaceuticals, agricultural chemicals and dyes.
[0002]
[Prior art]
Conventionally, as a method for producing a chlorosilane compound from a disiloxane compound, for example, JP-A 63-192789 (Patent Document 1) proposes to react a disiloxane compound with phosgene. JP-A-63-192788 (Patent Document 2) proposes reacting a disiloxane compound with a chlorinating agent such as phosgene in the presence of an N, N-disubstituted carboxylic acid amide. Yes.
[0003]
[Patent Document 1]
JP 63-192789 A [Patent Document 2]
Japanese Patent Laid-Open No. Sho 63-192788
[Problems to be solved by the invention]
However, in these conventional methods, the conversion rate of the disiloxane compound may not always be sufficient. Accordingly, an object of the present invention is to provide a method capable of producing a chlorosilane compound with high productivity by reacting a disiloxane compound with a high conversion rate.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above object can be achieved by carrying out the reaction in the presence of hydrogen chloride, and have completed the present invention. That is, the present invention relates to a method for producing a chlorosilane compound by reacting a disiloxane compound and phosgene in the presence of hydrogen chloride.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The disiloxane compound used as a raw material in the present invention has a silicon-oxygen-silicon bond in the molecule, and an organic group or a halogen atom is bonded to each silicon atom. As a suitable example, the following formula (1)
R ¹ R ² R ³ Si—O—SiR ⁴ R ⁵ R ⁶ (1)
(In the formula, R ^{1 to} R ⁶ each independently represents an alkyl group, an aryl group, or a halogen atom.)
Can be mentioned.
[0007]
In the formula, examples of the alkyl group represented by R ^{1 to} R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. The aryl group represented by R ^{1 to} R ⁶ can be an aryl group having about 6 to 12 carbon atoms such as a phenyl group, a tolyl group, or a naphthyl group. Can be. Moreover, the halogen atom represented by R < ¹ > -R < ⁶ > can be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
[0008]
Two or more kinds of disiloxane compounds may be used as necessary.
[0009]
In the present invention, the reaction of the disiloxane compound and phosgene is performed in the presence of hydrogen chloride. Thus, by making hydrogen chloride exist, reaction can be advanced smoothly and productivity of the chlorosilane compound which is a target object can be improved.
[0010]
In order to completely convert the disiloxane compound to the chlorosilane compound, 1 mol or more of phosgene is required with respect to 1 mol of the disiloxane compound, but in order to avoid excessive phosgene remaining, the amount of phosgene used should be reduced. The disiloxane compound may be allowed to remain. Usually, 0.5 to 2 mol of phosgene is used per 1 mol of the disiloxane compound. As the phosgene, a gaseous one or a liquid one may be used.
[0011]
The amount of hydrogen chloride used is usually 0.01 mol or more, preferably 0.1 mol or more, and usually 10 mol or less with respect to 1 mol of the disiloxane compound.
[0012]
In addition to hydrogen chloride, the presence of an N, N-disubstituted carboxylic acid amide allows the reaction to proceed more smoothly. As the N, N-disubstituted carboxylic acid amide, the following formula (2)
^{R 7 -CO-NR 8 R 9} (2)
(Wherein R ⁷ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁸ and R ⁹ each independently represents an alkyl group or an aryl group.)
Those represented by can be typically used.
[0013]
Examples of the alkyl group in the formula, represented by an alkyl group and R ⁸ and R ⁹ represented by R ⁷ is the same as the examples of alkyl groups represented by R ¹ to R ^6, Table with R ⁷ Examples of the aryl group represented by R ⁸ and R ⁹ are the same as the examples of the aryl group represented by R ^{1 to} R ⁶ .
[0014]
The amount of the N, N-disubstituted carboxylic acid amide to be used is usually 0.001 mol or more, preferably 0.01 mol or more, and usually 0.1 mol or less with respect to 1 mol of the disiloxane compound. As for N, N-disubstituted carboxylic acid amides, two or more of them can be used as necessary.
[0015]
The reaction is usually carried out in a solvent. Examples of the reaction solvent include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene; hexane, Aliphatic hydrocarbons such as cyclohexane, heptane and octane; ethers such as diethyl ether and dibutyl ether, esters such as ethyl acetate and butyl acetate; halogenation such as dichloromethane, chloroform and 1,2-dichloroethane Aliphatic hydrocarbons and the like can be mentioned, and two or more of them can be used as necessary.
[0016]
When using a solvent having a low substance-dissolving ability, such as aromatic hydrocarbons and aliphatic hydrocarbons, as the reaction solvent, it is difficult for the reaction to proceed smoothly by conventional methods. Even if a solvent is used, the conversion of the disiloxane compound can be sufficiently increased. In particular, when an aromatic hydrocarbon such as toluene is used as a reaction solvent, the effect of the present invention is more remarkably exhibited.
[0017]
The reaction temperature is usually 0 to 100 ° C., preferably 20 to 70 ° C., more preferably 30 to 70 ° C. Moreover, although reaction is normally implemented by the normal pressure vicinity, you may carry out under pressure or pressure reduction as needed. As the reaction system, any of a continuous system, a semi-continuous system, and a batch system can be employed.
[0018]
The reaction is preferably carried out while introducing hydrogen chloride into the reaction system. In this case, the disiloxane compound, phosgene, and the N, N-disubstituted carboxylic acid amide used as required are each of hydrogen chloride. It may be introduced before introduction or may be introduced together with the introduction of hydrogen chloride. The reaction solvent can be used to dilute one or more of these compounds.
[0019]
For the post-treatment operation of the reaction, a known method can be appropriately employed. Separation and purification of the target chlorosilane compound is usually carried out by distillation or crystallization. Unreacted disiloxane compounds, phosgene, hydrogen chloride, N, N-disubstituted carboxylic acid amides, reaction solvents, and the like can be recovered and reused.
[0020]
According to the present invention, theoretically, 2 mol of a chlorosilane compound can be produced from 1 mol of a disiloxane compound. For example, when 1 mol of one symmetric disiloxane compound, that is, a compound having the same two silyl groups bonded to an oxygen atom is used as a disiloxane compound, theoretically, 2 mol of one chlorosilane compound is produced. When 1 mol of one asymmetric disiloxane compound, that is, a compound having two different silyl groups bonded to an oxygen atom is used as a disiloxane compound, theoretically, 1 mol of each of two chlorosilane compounds is produced. be able to.
[0021]
For example, when the compound represented by the formula (1) is used as the disiloxane compound, the following formula (3) is used as the chlorosilane compound.
R ¹ R ² R ³ Si-Cl (3)
(Wherein R ^{1 to} R ³ represent the same meaning as described above.)
And a compound represented by the following formula (4)
R ⁴ R ⁵ R ⁶ Si-Cl (4)
(Wherein R ^{4 to} R ⁶ represent the same meaning as described above.)
Wherein the compound represented by the formula (1) is a symmetric disiloxane compound, that is, the R ¹ R ² R ³ Si group and the R ⁴ R ⁵ R ⁶ Si group are the same. If so, the compound represented by the above formula (3) and the compound represented by the above formula (4) are the same.
[0022]
The method of the present invention is also suitably employed, for example, when a chlorosilane compound is regenerated from a disiloxane compound that is by-produced when the chlorosilane compound is used in the production of organic chemicals.
[0023]
【Example】
Examples of the present invention will be described below, but the present invention is not limited thereto. In each case, the reaction solution was analyzed by gas chromatography equipped with a thermal conductivity detector (TCD), and the content of each component was calculated by a modified area percentage method with the sensitivity ratio corrected. The conversion rate of siloxane and the yield of chlorotrimethylsilane based on hexamethyldisiloxane were determined.
[0024]
Example 1
To a glass reactor equipped with a phosgene gas introduction tube, a hydrogen chloride gas introduction tube, a reflux condenser, a thermometer, and a stirrer, 23.66 g (0.146 mol) of hexamethyldisiloxane, 191.35 g of toluene, and N, 0.42 g (0.006 mol) of N-dimethylformamide was added and stirred. The inside of the reactor was set to a slightly reduced pressure of a gauge pressure of −400 to −200 mmH ₂ O (−4 to −2 kPa), and nitrogen was introduced into the gas phase portion at 8 ml / min under a nitrogen stream, and 19.87 g of phosgene ( 0.201 mol) and 2.84 g (0.078 mol) of hydrogen chloride were introduced into the liquid at 58-60 ° C. over 6 hours. Subsequently, the temperature is kept at 58 to 58.5 ° C. for 2 hours. During this time, in order to remove unreacted phosgene, 0.21 g at the start of the heat insulation, 0.24 g after 0.5 hours from the start of the heat insulation, and 1 hour from the start of the heat insulation Later 0.11 g of water was added. As a result of analyzing the resulting reaction solution (212.55 g), the conversion of hexamethyldisiloxane was 92.4%, and the yield of chlorotrimethylsilane was 84.7%.
[0025]
Comparative Example 1
In the same reactor as in Example 1, 23.65 g (0.146 mol) of hexamethyldisiloxane, 191.37 g of toluene, and 1.08 g (0.015 mol) of N, N-dimethylformamide were added and stirred. . The inside of the reactor was slightly reduced in pressure and under a nitrogen stream as in Example 1. 14.13 g (0.143 mol) of phosgene was introduced into the solution at 60 ° C. over 4 hours, and then kept at 60 ° C. for 2 hours. did. As a result of analyzing the obtained reaction liquid (222.15 g), the conversion of hexamethyldisiloxane was 15.3%, and the yield of chlorotrimethylsilane was 11.9%.
[0026]
Comparative Example 2
In the same reactor as in Example 1, 23.65 g (0.146 mol) of hexamethyldisiloxane and 191.35 g of toluene were added and stirred. The inside of the reactor was slightly reduced in pressure and under a nitrogen stream in the same manner as in Example 1, and 6.65 g (0.182 mol) of hydrogen chloride was introduced into the liquid at 60 ° C. over 5 hours. As a result of analyzing the obtained reaction liquid (215.11 g), the conversion of hexamethyldisiloxane was 12.6%, and the yield of chlorotrimethylsilane was 9.8%.
[0027]
Example 2
In a reactor similar to that of Example 1, 23.65 g (0.146 mol) of hexamethyldisiloxane, 191.35 g of toluene, and 0.43 g (0.006 mol) of N, N-dimethylformamide were added and stirred. . The inside of the reactor was slightly reduced pressure and nitrogen flow as in Example 1, and 19.66 g (0.199 mol) of phosgene and 4.95 g (0.136 mol) of hydrogen chloride were added at 58 to 60 ° C. over 6 hours. And introduced into the liquid. Subsequently, the mixture was kept at 59 ° C. for 2 hours. During this time, in order to remove unreacted phosgene, 0.20 g at the start of the incubation, 0.18 g after 0.5 hours from the start of the incubation, and 0 after 1.5 hours from the start of the incubation. 0.06 g of water was added. As a result of analyzing the resulting reaction solution (213.12 g), the conversion of hexamethyldisiloxane was 94.3%, and the yield of chlorotrimethylsilane was 87.7%.
[0028]
Example 3
In the same reactor as in Example 1, 23.66 g (0.146 mol) of hexamethyldisiloxane, 191.37 g of toluene, and 0.45 g (0.006 mol) of N, N-dimethylformamide were added and stirred. . The inside of the reactor was slightly reduced in pressure and under a nitrogen stream in the same manner as in Example 1, and 19.51 g (0.197 mol) of phosgene and 9.29 g (0.255 mol) of hydrogen chloride were added at 58 to 60.5 ° C. for 6 minutes. It was introduced into the liquid over time. Next, the mixture was kept at 57-61 ° C. for 2 hours. During this time, in order to remove unreacted phosgene, 0.21 g at the start of the incubation, 0.17 g after 1 hour from the start of the incubation, and 0 after 1.5 hours from the start of the incubation. .04 g of water was added. As a result of analyzing the resulting reaction solution (212.17 g), the conversion of hexamethyldisiloxane was 92.8%, and the yield of chlorotrimethylsilane was 84.6%.
[0029]
Example 4
In a reactor similar to that of Example 1, 23.65 g (0.146 mol) of hexamethyldisiloxane, 191.35 g of toluene, and 0.43 g (0.006 mol) of N, N-dimethylformamide were added and stirred. . The inside of the reactor was slightly reduced in pressure and under a nitrogen stream in the same manner as in Example 1, and 19.80 g (0.200 mol) of phosgene and 10.99 g (0.301 mol) of hydrogen chloride were added at 59.5 to 61 ° C. for 6 minutes. It was introduced into the liquid over time. Subsequently, the mixture was kept at 59 to 60 ° C. for 2 hours. During this period, 0.24 g of water was added 0.5 hours after the start of the incubation and 0.09 g of water was added 1 hour after the start of the incubation in order to remove unreacted phosgene. . As a result of analyzing the resulting reaction solution (210.34 g), the conversion of hexamethyldisiloxane was 91.1%, and the yield of chlorotrimethylsilane was 75.3%.
[0030]
Example 5
In a reactor similar to that of Example 1, 23.67 g (0.146 mol) of hexamethyldisiloxane, 191.36 g of toluene, and 0.44 g (0.006 mol) of N, N-dimethylformamide were added and stirred. . The inside of the reactor was slightly reduced in pressure and under a nitrogen stream in the same manner as in Example 1. 13.03 g (0.132 mol) of phosgene and 8.97 g (0.246 mol) of hydrogen chloride were added at 58-60 ° C. over 6 hours. And introduced into the liquid. Subsequently, the temperature was kept at 58.5 to 60 ° C. for 2 hours. During this time, 0.14 g of water was added 0.5 hours after the start of the temperature keeping in order to remove unreacted phosgene. As a result of analyzing the resulting reaction solution (210.78 g), the conversion of hexamethyldisiloxane was 79.7%, and the yield of chlorotrimethylsilane was 69.2%.
[0031]
Example 6
In a reactor similar to that of Example 1, 23.65 g (0.146 mol) of hexamethyldisiloxane, 191.35 g of toluene, and 0.43 g (0.006 mol) of N, N-dimethylformamide were added and stirred. . The inside of the reactor was slightly reduced pressure and under a nitrogen stream as in Example 1, and 12.92 g (0.131 mol) of phosgene and 2.90 g (0.080 mol) of hydrogen chloride were added at 59.5 to 61 ° C. for 6 minutes. It was introduced into the liquid over time. Next, the mixture was kept at 59-60 ° C. for 2 hours. During this period, 0.12 g of water was added 0.5 hours after the start of the incubation in order to remove unreacted phosgene. As a result of analyzing the resulting reaction solution (211.17 g), the conversion of hexamethyldisiloxane was 80.4%, and the yield of chlorotrimethylsilane was 71.2%.
[0032]
Example 7
In the same reactor as in Example 1, 23.65 g (0.146 mol) of hexamethyldisiloxane, 191.39 g of toluene, and 0.43 g (0.006 mol) of N, N-dimethylformamide were added and stirred. . The inside of the reactor was slightly reduced pressure and under a nitrogen stream as in Example 1. 16.27 g (0.164 mol) of phosgene and 4.87 g (0.133 mol) of hydrogen chloride were added at 61 to 61.5 ° C. It was introduced into the liquid over time. Next, the mixture was kept at 59-61 ° C. for 2 hours. During this period, 0.24 g of water was added 0.5 hours after the start of the incubation and 0.28 g of water was added 1 hour after the start of the incubation in order to remove unreacted phosgene. . As a result of analyzing the obtained reaction liquid (212.17 g), the conversion of hexamethyldisiloxane was 81.3%, and the yield of chlorotrimethylsilane was 72.2%.
[0033]
Example 8
In a reactor similar to that in Example 1, 23.66 g (0.146 mol) of hexamethyldisiloxane, 191.35 g of toluene, and 0.32 g (0.004 mol) of N, N-dimethylformamide were added and stirred. . The inside of the reactor was slightly reduced in pressure and under a nitrogen stream as in Example 1, and 13.31 g (0.135 mol) of phosgene and 5.04 g (0.138 mol) of hydrogen chloride were added at 49.5 to 52 ° C. for 6 minutes. After introducing into the liquid over time, 2.52 g (0.069 mol) of hydrogen chloride was further introduced into the liquid at 49-51 ° C. over 2 hours. As a result of analyzing the obtained reaction liquid (211.34 g), the conversion of hexamethyldisiloxane was 87.1%, and the yield of chlorotrimethylsilane was 77.9%.
[0034]
Example 9
714.00 g of toluene solution containing 69.90 g (0.430 mol) of hexamethyldisiloxane in a glass reactor equipped with a phosgene gas introduction pipe, hydrogen chloride gas introduction pipe, reflux condenser, thermometer, stirrer and baffle And 0.96 g (0.013 mol) of N, N-dimethylformamide were added and stirred. The inside of the reactor was set to a slight depressurization with a gauge pressure of −400 to −200 mmH ₂ O (−4 to −2 kPa), and nitrogen was introduced into the gas phase portion at 16 ml / min. At 2 ° C., 39.83 g (0.403 mol) of phosgene was introduced into the liquid over 6 hours, and 16.48 g (0.452 mol) of hydrogen chloride was added to the gas phase portion over 6 hours. After the introduction, 5.49 g of hydrogen chloride was further introduced into the gas phase part over 2 hours. As a result of analyzing the resulting reaction solution (732.76 g), the conversion of hexamethyldisiloxane was 94.1%, and the yield of chlorotrimethylsilane was 91.0%.
[0035]
Example 10
In a reactor similar to Example 9, 714.43 g of a toluene solution containing 69.91 g (0.431 mol) of hexamethyldisiloxane and 0.95 g (0.013 mol) of N, N-dimethylformamide were added. Stir. The inside of the reactor was slightly reduced pressure and nitrogen flow as in Example 9, and 49.05 g (0.496 mol) of phosgene was introduced into the liquid at 47 to 49 ° C. over 2.5 hours. Then, 394.73 g (10.826 mol) of hydrogen chloride was introduced into the gas phase portion over 2.5 hours, and then 394.73 g (10.826 mol) of hydrogen chloride was added to the gas phase portion over 2.5 hours. Introduced. As a result of analyzing the obtained reaction solution (700.59 g), the conversion of hexamethyldisiloxane was 85.2%, and the yield of chlorotrimethylsilane was 47.5%.
[0036]
Example 11
In a reactor similar to Example 9, 714.02 g of a toluene solution containing 69.87 g (0.430 mol) of hexamethyldisiloxane and 0.94 g (0.013 mol) of N, N-dimethylformamide were added. Stir. The inside of the reactor was slightly reduced pressure and under a nitrogen stream as in Example 9, and 39.96 g (0.404 mol) of phosgene was introduced into the solution over 2 hours at 48 to 51 ° C. After 103.33 g (2.834 mol) of hydrogen was introduced into the gas phase portion over 2 hours, 206.65 g (5.668 mol) of hydrogen chloride was further introduced into the gas phase portion over 3 hours. As a result of analyzing the resulting reaction solution (723.86 g), the conversion of hexamethyldisiloxane was 75.6%, and the yield of chlorotrimethylsilane was 61.2%.
[0037]
Example 12
In a reactor similar to Example 9, 714.00 g of a toluene solution containing 69.86 g (0.430 mol) of hexamethyldisiloxane and 0.94 g (0.013 mol) of N, N-dimethylformamide were added. Stir. The inside of the reactor was slightly reduced pressure and nitrogen flow as in Example 9, and 40.05 g (0.405 mol) of phosgene was introduced into the liquid at 50 to 54 ° C. over 1.5 hours. Then, 11.59 g (0.318 mol) of hydrogen chloride was introduced into the gas phase portion over 1.5 hours, and then 27.05 g (0.742 mol) of hydrogen chloride was added to the gas phase portion over 3.5 hours. Introduced. As a result of analyzing the resulting reaction solution (730.02 g), the conversion of hexamethyldisiloxane was 93.4%, and the yield of chlorotrimethylsilane was 89.2%.
[0038]
【The invention's effect】
According to the present invention, the raw material disiloxane compound can be reacted with a high conversion rate, and the target chlorosilane compound can be produced with high productivity.

Claims (3)

A process for producing a chlorosilane compound, comprising reacting a disiloxane compound and phosgene in toluene in the presence of hydrogen chloride.   Furthermore, the manufacturing method of Claim 1 which reacts in the presence of N, N- disubstituted carboxylic acid amide. The production method according to claim 1 or 2 , wherein the reaction is carried out while introducing hydrogen chloride into the reaction system.