JP2004292409A - Method for producing chlorosilane compound - Google Patents

Abstract

A method for producing a chlorosilane compound with high productivity by reacting a disiloxane compound with a high conversion rate is provided.
An N, N-disubstituted carboxylic acid amide and a compound represented by the following formula (1):
R ¹ O- (R ³ O) _n -R ² (1)
(In the formula, R ¹ and R ² each independently represent an alkyl group or an aryl group, R ³ represents an alkylene group, and n represents an integer of 1 to 10.)
A chlorosilane compound is produced by reacting a disiloxane compound and phosgene in the presence of an oxyalkylene compound represented by
[Selection diagram] None

Description

[0001]
TECHNICAL FIELD 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 reacting 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. I have.
[0003]
[Patent Document 1] JP-A-63-192789 [Patent Document 2] JP-A-63-192788
[Problems to be solved by the invention]
However, in these conventional methods, the conversion of the disiloxane compound may not always be sufficient. Therefore, an object of the present invention is to provide a method capable of producing a chlorosilane compound with good 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 reacting a disiloxane compound with phosgene in the presence of a specific compound, and have completed the present invention.
[0006]
That is, the present invention provides an N, N-disubstituted carboxylic acid amide and the following formula (1)
R ¹ O- (R ³ O) _n -R ² (1)
(In the formula, R ¹ and R ² each independently represent an alkyl group or an aryl group, R ³ represents an alkylene group, and n represents an integer of 1 to 10.)
The present invention relates to a method for producing a chlorosilane compound by reacting a disiloxane compound and phosgene in the presence of an oxyalkylene compound represented by
[0007]
BEST MODE FOR CARRYING OUT 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, a halogen atom, and the like are bonded to each silicon atom. A preferred example is the following formula (2)
^{R 4 R 5 R 6 Si-} O-SiR 7 R 8 R 9 (2)
(In the formula, R ^{4 to} R ⁹ each independently represent an alkyl group, an aryl group, or a halogen atom.)
Can be mentioned.
[0008]
In the formula, the alkyl group represented by R ^{4 to} R ⁹ is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, or the like. And an aryl group represented by R ^{4 to} R ⁹ , for example, an aryl group having about 6 to 12 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. Can be. Further, the halogen atom represented by R ^{4 to} R ⁹ can be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
[0009]
If necessary, two or more of these disiloxane compounds can be used.
[0010]
In the present invention, the disiloxane compound and phosgene are reacted in the presence of the N, N-disubstituted carboxylic acid amide and the oxyalkylene compound represented by the formula (1). As described above, by allowing a specific compound to be present in the reaction between the disiloxane compound and phosgene, the reaction can proceed smoothly, and the productivity of the target chlorosilane compound can be increased.
[0011]
In order to completely convert the disiloxane compound into a chlorosilane compound, one mole or more of phosgene is required for 1 mole of the disiloxane compound, but in order to avoid the residual phosgene, the amount of phosgene must be reduced. Alternatively, the disiloxane compound may be left. Usually, 0.5 to 2 mol of phosgene is used per 1 mol of the disiloxane compound. Phosgene may be used in gaseous form or in liquid form.
[0012]
As the N, N-disubstituted carboxylic acid amide, the following formula (3)
R ¹⁰ -CO-NR ¹¹ R ¹² (3)
(In the formula, R ¹⁰ represents a hydrogen atom, an alkyl group or an aryl group, and R ¹¹ and R ¹² each independently represent an alkyl group or an aryl group.)
Can be typically used.
[0013]
Examples of the alkyl group in the ^formula, represented by an alkyl group and ^{R 11} and ^{R 12} represented by ^{R 10} is the same as the examples of the alkyl group represented by ^R 4 to R ^9, Table with ^{R 10} Examples of the aryl group represented by and the aryl groups represented by R ¹¹ and R ¹² are the same as the examples of the aryl group represented by R ^{4 to} R ⁹ .
[0014]
The amount of the N, N-disubstituted carboxylic acid amide to be used is generally 0.001 mol or more, preferably 0.01 mol or more, and usually 0.1 mol or less, per 1 mol of the disiloxane compound. Two or more N, N-disubstituted carboxylic acid amides can be used as necessary.
[0015]
In the formula (1) showing the oxyalkylene compound, examples of the alkyl group represented by R ¹ and R ² are the same as the examples of the alkyl group represented by R ^{4 to} R ⁹ , and R ¹ and R Examples of the aryl group represented by ² are the same as the examples of the aryl group represented by R ^{4 to} R ⁹ . Further, the alkylene group represented by R ³ can be an alkylene group having 2 to 6 carbon atoms such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and n is 1 to 4 Preferably, it is an integer.
[0016]
This oxyalkylene compound is, in particular, a dialkyl ether of mono, di, tri or tetraethylene glycol [in the formula (1), a compound of R ¹ = alkyl, R ² = alkyl, R ³ = ethylene, n = 1 to 4 Or a diaryl ether [in the formula (1), a compound of R ¹ = aryl, R ² = aryl, R ³ = ethylene, n = 1 to 4]. Specific examples of the former include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol dimer ether, and the like. Specific examples of the latter include ethylene glycol diphenyl ether, diethylene glycol diphenyl ether, triethylene glycol diphenyl ether, and tetraethylene glycol diphenyl ether.
[0017]
The amount of the oxyalkylene compound to be used is generally 0.05 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the total amount of the disiloxane compound and the reaction solvent described below. As the oxyalkylene compound, if necessary, two or more of them can be used.
[0018]
Examples of the reaction solvent that can be used for the reaction of the disiloxane compound and phosgene include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene; Aliphatic hydrocarbons such as hexane, cyclohexane, heptane and octane; ethers such as diethyl ether and dibutyl ether; esters such as ethyl acetate and butyl acetate; such as dichloromethane, chloroform and 1,2-dichloroethane Examples thereof include halogenated aliphatic hydrocarbons, and two or more of them can be used as necessary.
[0019]
When a solvent having a low ability to dissolve substances such as aromatic hydrocarbons and aliphatic hydrocarbons is used as the reaction solvent, the reaction cannot proceed smoothly in the conventional method. Even when 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 effects of the present invention are more remarkably exhibited.
[0020]
In addition, the presence of water in the reaction system can further increase the conversion of the disiloxane compound. It is thought that the reason why the conversion is improved by the addition of water is that phosgene is consumed in the presence of water, but hydrogen chloride is generated instead, which contributes to the improvement of the reaction rate. The amount of water to be used is generally 0.05 to 5 mol, preferably 0.1 to 2 mol, more preferably 0.1 to 1 mol, per 1 mol of the disiloxane compound. Also, the amount of phosgene used when water is present is generally increased by about equimolar to water as compared to the case where no water is present. If too much water is used, a large amount of phosgene is required, which is not preferable.
[0021]
The reaction temperature is usually 0 to 100 ° C, preferably 20 to 70 ° C, and the reaction is usually carried out at about normal pressure, but may be carried out under increased or reduced pressure as necessary. As a reaction system, any of a continuous system, a semi-continuous system, and a batch system can be adopted.
[0022]
The supply method of the disiloxane compound, phosgene, N, N-disubstituted carboxylic acid amide, and the oxyalkylene compound represented by the formula (1) can be appropriately selected. , And an oxyalkylene compound are first mixed, and phosgene may be introduced therein, or an amide, phosgene and an oxyalkylene compound may be first mixed, and a disiloxane compound may be introduced therein, or amide and The oxyalkylene compound may be mixed first, into which the disiloxane compound and phosgene may be co-injected. The reaction solvent can be used to dilute each of these compounds, and when water is present, it may be added to the reaction system before the start of the reaction or may be introduced during the reaction. Good.
[0023]
For the post-treatment operation of the reaction, a known method can be appropriately adopted. The separation and purification of the target chlorosilane compound is usually performed by distillation or crystallization. Unreacted disiloxane compounds, phosgene, N, N-disubstituted carboxylic acid amides, oxyalkylene compounds, reaction solvents, and the like can be recovered and reused.
[0024]
According to the present invention, theoretically, 2 mol of the chlorosilane compound can be produced from 1 mol of the disiloxane compound. For example, when one kind of symmetric disiloxane compound, that is, one mole of a compound in which two silyl groups bonded to an oxygen atom are the same is used as a disiloxane compound, theoretically, two moles of one kind of chlorosilane compound are produced. When one kind of asymmetric disiloxane compound, that is, a compound having two different silyl groups bonded to oxygen atoms, is used as one mole of a disiloxane compound, theoretically, two moles of two kinds of chlorosilane compounds are produced. be able to.
[0025]
For example, when the compound represented by the formula (2) is used as the disiloxane compound, the following formula (4) is used as the chlorosilane compound.
R ⁴ R ⁵ R ⁶ Si-Cl (4)
(In the formula, R ^{4 to} R ⁶ represent the same meaning as described above.)
And a compound represented by the following formula (5)
R ⁷ R ⁸ R ⁹ Si-Cl (5)
(In the formula, R ^{7 to} R ⁹ represent the same meaning as described above.)
Wherein the compound represented by the formula (2) is a symmetric disiloxane compound, that is, a compound having the same R ⁴ R ⁵ R ⁶ Si group and the same R ⁷ R ⁸ R ⁹ Si group. Then, the compound represented by the above formula (4) and the compound represented by the above formula (5) are the same.
[0026]
The method of the present invention is also suitably employed, for example, when regenerating a chlorosilane compound from a disiloxane compound by-produced when the chlorosilane compound is used for producing an organic chemical.
[0027]
【Example】
Hereinafter, examples of the present invention will be described, 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 weight ratio of chlorotrimethylsilane as the target substance and hexamethyldisiloxane as the unreacted raw material was determined. It was calculated by the modified area percentage method in which the sensitivity ratio was corrected.
[0028]
Example 1
In a glass reactor equipped with a gas inlet tube, a reflux condenser, a thermometer and a stirrer, 23.65 g (0.146 mol) of hexamethyldisiloxane, 191.35 g of toluene, 90.03 g of tetraethylene glycol dimethyl ether, and 0.43 g (0.006 mol) of N, N-dimethylformamide was added and stirred. Slightly reduced pressure [gauge pressure _{-400~-200mmH 2 O (-4~-} 2kPa). The same shall apply hereinafter), in which 14.42 g (0.146 mol) of phosgene was introduced from a gas inlet tube at a temperature of 58 to 60.5 ° C over 4 hours, and then kept at 60 ° C for 0.5 hour. did. Next, 1.59 g (0.016 mol) of phosgene was additionally introduced from the gas inlet tube at a temperature of 60 ° C. over 0.5 hours, and the temperature was maintained at 60 for 2 hours. As a result of analyzing the obtained reaction solution (306.80 g), the weight ratio of chlorotrimethylsilane / hexamethyldisiloxane was 56.3 / 43.7.
[0029]
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 stirred and stirred. . Under a slightly reduced pressure, 14.13 g (0.143 mol) of phosgene was introduced from the gas introduction tube at a temperature of 60 ° C. over 4 hours, and the mixture was kept at 60 ° C. for 2 hours. As a result of analyzing the obtained reaction liquid (222.15 g), the weight ratio of chlorotrimethylsilane / hexamethyldisiloxane was 3.3 / 96.7.
[0030]
Example 2
In the same reactor as in Example 1, 23.66 g (0.146 mol) of hexamethyldisiloxane, 191.35 g of toluene, 90.04 g of tetraethylene glycol dimethyl ether, 0.44 g of N, N-dimethylformamide (0.006 g) Mol) and 1.25 g (0.069 mol) of water were added and stirred. Under a slightly reduced pressure, 23.36 g (0.236 mol) of phosgene was introduced from the gas inlet tube at a temperature of 57 to 61 ° C over 4.5 hours, and then kept at 58 to 60 ° C for 1 hour. . At the time of 0.5 hour from the start of the heat retention, 0.23 g of water was added. As a result of analyzing the obtained reaction solution (308.50 g), the weight ratio of chlorotrimethylsilane / hexamethyldisiloxane was 99.3 / 0.7.
[0031]
Example 3
In the same reactor as in Example 1, 23.67 g (0.146 mol) of hexamethyldisiloxane, 191.36 g of toluene, 90.03 g of triethylene glycol dimethyl ether, 0.45 g of N, N-dimethylformamide (0.006 g) Mol), and 1.26 g (0.070 mol) of water. Under a slightly reduced pressure, 23.61 g (0.239 mol) of phosgene was introduced from the gas introduction tube at a temperature of 57 to 61 ° C over 5 hours, and then the temperature was maintained at 60 ° C for 1 hour. As a result of analyzing the obtained reaction liquid (307.59 g), the weight ratio of chlorotrimethylsilane / hexamethyldisiloxane was 97.3 / 2.7.
[0032]
Example 4
In the same reactor as in Example 1, 23.64 g (0.146 mol) of hexamethyldisiloxane, 191.41 g of toluene, 90.03 g of diethylene glycol dimethyl ether, 0.46 g (0.006 mol) of N, N-dimethylformamide And 1.30 g (0.072 mol) of water were added and stirred. Under a slightly reduced pressure, 23.61 g (0.239 mol) of phosgene was introduced therein from the gas inlet tube at a temperature of 57.5 to 60.5 ° C. over 5 hours, and then kept at 60 ° C. for 2 hours. . At 0.5 hour and 1 hour after the start of the heat retention, 0.16 g (0.009 mol) of water was added. As a result of analyzing the obtained reaction solution (306.21 g), the weight ratio of chlorotrimethylsilane / hexamethyldisiloxane was 99.5 / 0.5.
[0033]
Example 5
In a reactor similar to that of Example 1, 23.65 g (0.146 mol) of hexamethyldisiloxane, 191.35 g of toluene, 45.05 g of tetraethylene glycol dimethyl ether, 0.43 g of N, N-dimethylformamide (0.006 mol) Mol) and 1.30 g (0.072 mol) of water were added and stirred. Under a slightly reduced pressure, 25.97 g (0.263 mol) of phosgene was introduced from the gas inlet tube at a temperature of 57 to 59 ° C. over 4.5 hours, and then kept at 60 ° C. for 2 hours. One hour after the start of the heat retention, 0.22 g (0.012 mol) of water was added. As a result of analyzing the obtained reaction solution (260.95 g), the weight ratio of chlorotrimethylsilane / hexamethyldisiloxane was 99.2 / 0.8.
[0034]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the disiloxane compound of a raw material can be made to react with good conversion, and the chlorosilane compound of an object can be manufactured with high productivity.

Claims (3)

N, N-disubstituted carboxylic acid amide and the following formula (1)
R ¹ O- (R ³ O) _n -R ² (1)
(In the formula, R ¹ and R ² each independently represent an alkyl group or an aryl group, R ³ represents an alkylene group, and n represents an integer of 1 to 10.)
A method for producing a chlorosilane compound, comprising reacting a disiloxane compound and phosgene in the presence of an oxyalkylene compound represented by the formula: The method according to claim 1, wherein the reaction is performed in an aromatic hydrocarbon solvent. 3. The method according to claim 1, wherein water is further present in the reaction system.