[go: up one dir, main page]

WO2025244039A1 - Procédé de production de tétraalcoxysilane à l'aide de carbonate d'alkyle, et composition contenant du tétraalcoxysilane - Google Patents

Procédé de production de tétraalcoxysilane à l'aide de carbonate d'alkyle, et composition contenant du tétraalcoxysilane

Info

Publication number
WO2025244039A1
WO2025244039A1 PCT/JP2025/018268 JP2025018268W WO2025244039A1 WO 2025244039 A1 WO2025244039 A1 WO 2025244039A1 JP 2025018268 W JP2025018268 W JP 2025018268W WO 2025244039 A1 WO2025244039 A1 WO 2025244039A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
represented
tetraalkoxysilane
composition
following formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/018268
Other languages
English (en)
Japanese (ja)
Inventor
一浩 山内
ブディアント 西山
知紘 菅原
久成 米田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Corp, Asahi Chemical Industry Co Ltd filed Critical Asahi Kasei Corp
Publication of WO2025244039A1 publication Critical patent/WO2025244039A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Definitions

  • the present invention relates to a method for producing tetraalkoxysilanes using alkyl carbonates and compositions containing tetraalkoxysilanes.
  • Tetraalkoxysilanes are industrially important silicon compounds used in protective films, insulating and space-filling films between elements and wiring, etching-resistant films for forming holes and wiring patterns, insulating films between wiring layers and space-filling films for shielding, fixing, and absorbing impurities, and cross-linking agents.
  • alkyl carbonates have recently been synthesized using carbon dioxide and alcohol as raw materials, and are environmentally friendly compounds used as intermediates in the synthesis of diphenyl carbonate, a raw material for polycarbonate.
  • Non-Patent Document 1 discloses a method for synthesizing tetramethoxysilane or tetraethoxysilane by reacting dimethyl carbonate or diethyl carbonate with silica.
  • Patent Document 1 discloses a manufacturing method for synthesizing tetraethoxysilane from ethanol, silica, and carbon dioxide present in a single reaction system.
  • Patent Document 2 discloses a manufacturing method for synthesizing tetraethoxysilane from ethanol, silica, and tetraethoxytitanium.
  • Non-Patent Document 1 requires a high-temperature reaction at 400°C to obtain alkoxysilanes in high yield.
  • Patent Document 1 uses dimethoxypropane as a raw material, which generates by-products.
  • Patent Document 2 adds tetraethoxytitanium, which makes it difficult to separate from tetraethoxysilane. Therefore, conventional technology has not been able to produce alkoxysilanes under low-temperature conditions suitable for industrial mass production.
  • moisture accelerates the hydrolysis reaction of alkoxysilanes, reducing yield, so conventional processes for dehydrating and drying raw materials have been required.
  • the present invention therefore aims to provide a method for producing alkoxysilanes that is less affected by the moisture content of the raw materials than conventional methods and that can be produced industrially using a low-temperature production process.
  • the present invention is as follows.
  • a method for producing tetraalkoxysilane comprising the step of mixing a dialkyl carbonate, silicon oxide, an alcohol, and a base catalyst to form a mixture.
  • a composition comprising: ( ⁇ ) the tetraalkoxysilane; and ( ⁇ ) at least one compound selected from the group consisting of an ether represented by the following formula (1), an ester represented by the following formula (2), and an acetal represented by the following formula (3),
  • the method for producing tetraalkoxysilane according to any one of the above [1] to [7], wherein the content of the ether represented by the following formula (1), the ester represented by the following formula (2), or the acetal represented by the following formula (3) relative to the tetraalkoxysilane in the composition is 0.001 ppm or more based on the peak area ratio in a gas chromatograph when the composition is subjected to gas chromatography analysis.
  • a composition comprising: ( ⁇ ) a tetraalkoxysilane; and ( ⁇ ) at least one compound selected from the group consisting of an ether represented by the following formula (1), an ester represented by the following formula (2), and an acetal represented by the following formula (3), A composition in which the content of an ether represented by the following formula (1), an ester represented by the following formula (2), or an acetal represented by the following formula (3) relative to the tetraalkoxysilane in the composition is 0.001 ppm or more based on the peak area ratio in a gas chromatograph when the composition is subjected to gas chromatography analysis.
  • R1 's may be the same or different and each represent a linear or branched alkyl group, and R2 's represent a hydrogen atom or a linear or branched alkyl group.
  • the content ratio of the ester represented by the formula (2) to the ether represented by the formula (1) in the composition is 0.5 to 2.0 based on the area intensity ratio of a gas chromatograph when the composition is subjected to gas chromatography analysis;
  • the composition according to [11] above, wherein the content ratio of the acetal represented by the formula (3) to the ether represented by the formula (1) in the composition is 0.5 to 2.0 based on the peak area ratio in a gas chromatograph when the composition is subjected to gas chromatography analysis.
  • the present invention provides a method for producing alkoxysilanes that can be produced industrially using a low-temperature production process that is less affected by the moisture content of the raw materials than conventional methods.
  • the method for producing tetraalkoxysilane of this embodiment includes a step of mixing an alcohol, a dialkyl carbonate, silicon oxide, and a base catalyst to form a mixture (hereinafter referred to as the "reaction step").
  • a reaction step By forming a mixture of the dialkyl carbonate, silicon oxide, alcohol, and base catalyst, a reaction between the dialkyl carbonate and silicon oxide proceeds.
  • the alcohol improves the compatibility of the base catalyst with the silicon oxide and the alkyl carbonate, which has high reactivity, making it possible to carry out the reaction at a low temperature.
  • the weight of water contained in a mixture obtained by mixing alcohol, dialkyl carbonate, silicon oxide, and a base catalyst (especially alcohol and dialkyl carbonate) is 0.001 g/mol or more, 0.003 g/mol or more, 0.005 g/mol or more, 0.007 g/mol or more, 0.01 g/mol or more, 0.03 g/mol or more, 0.05 g/mol or more, 0.07 g/mol or more, 0.1 g/mol or more, based on the number of moles of silicon oxide in the mixture.
  • the water content may be 0.2 g/mol or more, 0.3 g/mol or more, 0.4 g/mol or more, 0.5 g/mol or more, 0.6 g/mol or more, 0.7 g/mol or more, 0.8 g/mol or more, 0.9 g/mol or more, 1.0 g/mol or more, 1.1 g/mol or more, 1.2 g/mol or more, 1.3 g/mol or more, 1.4 g/mol or more, or 1.5 g/mol or more, and the upper limit is not particularly limited, but is, for example, 20 g/mol or less.
  • the weight of water contained in the mixture can be measured and calculated using the Karl Fischer measurement method.
  • the lower limit of the heating temperature (reaction temperature) for the mixture is preferably 150°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, and particularly preferably 240°C or higher, from the viewpoint of reaction rate.
  • the upper limit of the heating temperature (reaction temperature) for the mixture is preferably 350°C or lower, more preferably 300°C or lower, and particularly preferably 290°C or lower, from the viewpoint of a decrease in yield due to the occurrence of side reactions.
  • the time (reaction time) for which the mixture is heated within the above-mentioned heating temperature (reaction temperature) range is, for example, 1 hour or more, preferably 6 hours or more, and more preferably 12 hours or more, and for example, 96 hours or less, preferably 48 hours or less, and more preferably 24 hours or less.
  • the internal temperature of the mixture is preferably 140°C or higher, more preferably 170°C or higher, even more preferably 190°C or higher, and particularly preferably 220°C or higher, with the upper limit being preferably 340°C or lower, more preferably 290°C or lower, and particularly preferably 280°C or lower.
  • the reaction step it is preferable to apply pressure to the mixture.
  • the upper limit of the pressure on the mixture is preferably 10 MPa or less, from the viewpoint of allowing the reaction to proceed at low pressure, more preferably 7 MPa or less, even more preferably 5 MPa or less, and particularly preferably 3 MPa or less.
  • the lower limit of the pressure on the mixture is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, and particularly preferably 0.5 MPa or more.
  • the mixture is preferably refluxed, for example, within the pressure range mentioned above.
  • Refluxing refers to the process of cooling and liquefying the vaporized components of the mixture by contacting them with a cooling means, and returning them to the mixture.
  • the method for bringing the vaporized components of the mixture into contact with the cooling means during refluxing is not particularly limited and can be selected appropriately depending on the purpose.
  • a method using a known cooling device used for refluxing and equipped with a cooling means can be used.
  • the cooling device is not particularly limited, but for example, a double-tube heat exchanger with a thin tube inside a thick tube to form two flow paths can be used.
  • Such a heat exchanger is used by passing a refrigerant (cooling chiller) through one flow path as the cooling means, and passing the vaporized components of the mixture through the other flow path.
  • the heat exchanger may be made of glass or stainless steel.
  • the temperature of the cooling means during reflux is preferably below the reaction temperature, for example, 290°C or below, preferably 200°C or below, more preferably 100°C or below, and for example, -60°C or above, preferably -20°C or above.
  • the reaction can be carried out without excessively increasing the internal pressure due to vaporized alcohol.
  • refluxing suppresses the production of by-products derived from carbonates and alcohol, further improving the yield of alkoxysilane.
  • a pressure-maintaining valve back pressure valve
  • a pressure-maintaining valve may be used to reduce the internal pressure and carry out the reaction at a constant pressure.
  • the liquefiable components of the gas generated in the reactor are condensed in the condenser, and the unliquefied gas is then discharged through the pressure-maintaining valve.
  • carbon dioxide which is difficult to liquefy, is generated
  • the gas released from the pressure-maintaining valve during venting can also be separated and/or recovered using a cooling trap, seal pot, scrubber, adsorption tower containing adsorbent, etc.
  • the vaporized components of the mixture may be dehydrated.
  • a method of dehydration may involve contacting the vaporized components of the mixture with a dehydration means.
  • a dehydration means for example, an adsorbent such as molecular sieves or zeolite may be used as the dehydration means.
  • a method may be used in which a refrigerant (cooling chiller) flows through one flow path, and the other flow path is filled with a dehydration means and the vaporized components flow through it.
  • the alcohol is preferably an alcohol having 1 to 8 carbon atoms, more preferably an alcohol having 1 to 4 carbon atoms, or more preferably an alcohol having 2 or more carbon atoms, more preferably an alcohol having 2 to 6 carbon atoms, even more preferably an alcohol having 2 to 5 carbon atoms, and particularly preferably an alcohol having 2 to 4 carbon atoms.
  • Specific alcohols include methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and tert-butyl alcohol.
  • ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and tert-butyl alcohol are preferred, and from the viewpoint of purification and separation of the reaction product, isobutyl alcohol is preferred.
  • isobutyl alcohol is preferred. Because there is a possibility that a very small amount of alcohol may react with silica to form an alkoxysilane bond, it is preferable that the carbon chain of the alcohol and the carbon chain of the carbonate are the same in order to improve the yield of the obtained alkoxysilane.
  • the dialkyl carbonate is preferably a dialkyl carbonate in which each of the two alkyl chains has 1 to 8 carbon atoms, more preferably a dialkyl carbonate in which each has 1 to 4 carbon atoms, or alternatively, a dialkyl carbonate in which each has 2 or more carbon atoms, more preferably a dialkyl carbonate in which each has 2 to 6 carbon atoms, even more preferably a dialkyl carbonate in which each has 2 to 5 carbon atoms, and particularly preferably a dialkyl carbonate in which each has 2 to 4 carbon atoms.
  • dialkyl carbonates include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-sec-butyl carbonate, and di-tert-butyl carbonate.
  • diisobutyl carbonate is preferred.
  • the chain lengths of the two carbon chains of the dialkyl carbonate may be different, but if one wishes to produce a single alkoxysilane in good yield, it is preferable that the chain lengths be the same.
  • Silicon oxide refers to a compound containing silicon atoms (Si) and oxygen atoms (O) as the main constituent elements, and may be silicon monoxide (SiO), silicon dioxide (SiO 2 ), or a composite oxide with other metals such as zeolite.
  • silicon oxide include natural minerals such as silica stone, silica sand, diatomaceous earth, and quartz, as well as burned ash of silicon-containing plants, volcanic ash, silicates, silica gel derived from silica sol, fumed silica, silica alumina, and zeolite.
  • the molar ratio of dialkyl carbonate/silicon oxide is preferably 0.001 or more, more preferably 0.01 or more, and even more preferably 0.1 or more. Furthermore, from the viewpoint of improving the yield of tetraalkoxysilane, the molar ratio of dialkyl carbonate/silicon oxide is preferably 100 or less, more preferably 50 or less, and even more preferably 10 or less, and from the viewpoint of yield per charged amount, it is preferably 5 or less.
  • the molar ratio of base catalyst/silicon oxide is preferably 0.001 or more, more preferably 0.01 or more, and particularly preferably 0.1 or more. Furthermore, from the viewpoint of improving the yield per charged amount of tetraalkoxysilane, the molar ratio of base catalyst/silicon oxide is preferably 100 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 1 or less.
  • the alcohol/dialkyl carbonate mass ratio is preferably 0.01 or more, more preferably 0.05 or more, and from the viewpoint of yield, it is particularly preferable that it be 0.1 or more. Furthermore, from the viewpoint of being able to react with tetraalkoxysilane at low temperature and pressure, the alcohol/dialkyl carbonate mass ratio is preferably 100 or less, more preferably 15 or less, and from the viewpoint of yield per charged amount, it is particularly preferable that it be 10 or less.
  • the base catalyst is preferably an alkali metal compound and/or an alkaline earth metal compound.
  • the presence of an alkali metal compound or an alkaline earth metal compound promotes the cleavage of the silicon-oxygen bond in silicon oxide, resulting in a higher yield of tetramethoxysilane.
  • alkali metals and alkaline earth metals in the alkali metal compounds and alkaline earth metal compounds include lithium (Li), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), and cesium (Cs).
  • Counterions include hydroxides, halides, oxides, carbonates, bicarbonates, alkoxides, silicates, aluminates, phosphates, organic acid salts, sulfates, and nitrates. Among these, hydroxides, halides, carbonates, and bicarbonates are preferred, with alkali metal hydroxides, alkali metal halides, alkali metal carbonates, and alkali metal bicarbonates being more preferred.
  • alkali metal compounds and alkaline earth metal compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium fluoride, potassium fluoride, and cesium fluoride.
  • the alkali metal compounds and alkaline earth metal compounds may be used singly or in combination of two or more.
  • the reactor, operating procedures, reaction conditions, etc. used to react the alcohol and dialkyl carbonate with silicon oxide and the base catalyst are not particularly limited and can be selected appropriately depending on the purpose.
  • the reactor is preferably a pressure-resistant reactor such as an autoclave.
  • One example of an operating procedure is to charge the alcohol, alkyl carbonate, silicon oxide, base, etc. into the reactor and then heat the reactor to the reaction temperature.
  • the process for producing alkoxysilanes which includes the reaction step, can be carried out as either a batch process or a continuous process.
  • R1 's may be the same or different and each represent a linear or branched alkyl group.
  • a side reaction of the raw material alcohol or alkyl carbonate tends to produce at least one compound selected from the group consisting of an ether represented by formula (1) below, an ester represented by formula (2) below, and an acetal represented by formula (3) below.
  • R1 's may be the same or different and each represent a linear or branched alkyl group, and R2 's represent a hydrogen atom or a linear or branched alkyl group.
  • the R1 of the alcohol represented by formula (B) used as a raw material and the two R1 of the dialkyl carbonate represented by formula (C) used as a raw material are all the same, at least one compound selected from the group consisting of an ether represented by formula ( 1 ) in which the two R1 in the molecule are the same as the R1 of the raw material, an ester represented by formula (2) in which the R1 in the molecule is the same as the R1 of the raw material, and an acetal represented by formula (3) in which the two R1 in the molecule are the same as the R1 of the raw material is produced.
  • tetraethoxysilane (formula (1-A) below) is produced as the tetraalkoxysilane, and at least one compound selected from the group consisting of diethyl ether (formula (1-1) below) as the ether, ethyl acetate (formula (1-2) below) as the ester, and 1,1-diethoxyethane (formula (1-3) below) as the acetal is produced.
  • tetrapropoxysilane (formula (2-A) below) is produced as the tetraalkoxysilane, and at least one compound selected from the group consisting of dipropyl ether (formula (2-1) below) as the ether, propyl propionate (formula (2-2) below) as the ester, and 1,1-dipropoxypropane (formula (2-3) below) as the acetal is produced.
  • tetraisopropylsilane (formula (3-A) below) is produced as the tetraalkoxysilane, and at least one compound selected from the group consisting of diisopropyl ether (formula (3-1) below) as the ether and 2,2-diisopropoxypropane (formula (3-3) below) as the acetal is produced.
  • tetrabutylsilane (formula (4-A) below) is produced as the tetraalkoxysilane, and at least one compound selected from the group consisting of dibutyl ether (formula (4-1) below) as the ether, butyl butyrate (formula (4-2) below) as the ester, and 1,1-dibutoxybutane (formula (4-3) below) as the acetal is produced.
  • tetraisobutylsilane (formula (5-A) below) is produced as the tetraalkoxysilane, and at least one compound selected from the group consisting of diisobutyl ether (formula (5-1) below) as the ether, isobutyl isobutyrate (formula (5-2) below) as the ester, and 1,1-diisobutoxy-2-methylpropane (formula (5-3) below) as the acetal is produced.
  • diisobutyl ether (formula (5-1) below) as the ether
  • isobutyl isobutyrate (formula (5-2) below) as the ester
  • 1,1-diisobutoxy-2-methylpropane (formula (5-3) below) as the acetal
  • the content ratio of the ether represented by formula (1), the ester represented by formula (2), or the acetal represented by formula (3) relative to the tetraalkoxysilane in the mixture (composition) obtained in the reaction step (before the purification step) is 0.001 ppm or more, based on the peak area ratio in the gas chromatograph when the mixture (composition) is subjected to gas chromatography analysis.
  • the content of the ether represented by formula (1), the ester represented by formula (2), or the acetal represented by formula (3) relative to the tetraalkoxysilane in the mixture (composition) obtained in the reaction step (before the purification step) varies depending on the reaction conditions, but in a preferred specific embodiment, based on the peak area ratio in the gas chromatograph when the mixture (composition) is analyzed by gas chromatography, the content is 0.001 ppm or more, 0.01 ppm or more, 0.1 ppm or more, 1 ppm or more, 0.001% or more (10 ppm or more), 0.01% or more, 0.1% or more, 1% or more, 2% or more, 3% or more, 4% or more, or 5% or more, with the upper limit being 20% or less, 18% or less, 16% or less, 14% or less, 12% or less, 10% or less, 9% or less, 8% or less, or 7% or less.
  • the total content of the ether represented by formula (1), the ester represented by formula (2), and the acetal represented by formula (3) relative to the tetraalkoxysilane in the mixture (composition) (before the purification step) obtained in the reaction step varies depending on the reaction conditions, but in a preferred specific embodiment, based on the peak area ratio in the gas chromatograph when the mixture (composition) is analyzed by gas chromatography, the total content is 0.001 ppm or more, 0.01 ppm or more, 0.1 ppm or more, 1 ppm or more, 0.001% or more (10 ppm or more), 0.01% or more, 0.1% or more, 1% or more, 5% or more, 10% or more, 13% or more, or 15% or more, with the upper limit being 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, or 20% or less.
  • the mixture (composition) obtained in the reaction step (before the purification step) preferably contains at least two of the ether represented by formula (1), the ester represented by formula (2), and the acetal represented by formula (3), and more preferably contains all of the ether represented by formula (1), the ester represented by formula (2), and the acetal represented by formula (3).
  • the content ratio of the ester represented by formula (2) to the ether represented by formula (1) in the mixture (composition) obtained in the reaction step (before the purification step) is 0.01 or more, 0.05 or more, 0.1 or more, 0.3 or more, or 0.5 or more, based on the area intensity ratio of the gas chromatograph when gas chromatography analysis of the mixture (composition) is performed, and the upper limit is 10.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, or 2.0 or less.
  • the ratio of the acetal represented by formula (3) to the ether represented by formula (1) in the mixture (composition) obtained in the reaction step (before the purification step) is 0.01 or more, 0.05 or more, 0.1 or more, 0.3 or more, or 0.5 or more, based on the peak area ratio in the gas chromatograph when the mixture (composition) is subjected to gas chromatography analysis, while the upper limit is 10.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, or 2.0 or less.
  • the method for producing tetraalkoxysilane of this embodiment may include, in addition to the reaction step, a step of purifying tetraalkoxysilane from the mixture after the reaction step (hereinafter referred to as the "purification step").
  • the method for purifying tetraalkoxysilane in the purification step is not particularly limited, but examples include distillation.
  • the purification step can achieve a purity of tetraalkoxysilane of preferably 95% or more, more preferably 98% or more, and particularly preferably 99% or more.
  • residue containing one or more of dialkyl carbonate, silicon oxide, alcohol, and base catalyst may be recovered and reused in the reaction step.
  • the content ratio of the ether represented by formula (1), the ester represented by formula (2), or the acetal represented by formula (3) relative to the tetraalkoxysilane in the mixture (composition) after a purification step varies depending on the purification method, but in a preferred specific embodiment, when the mixture (composition) is subjected to gas chromatography analysis, the content ratio is, based on the peak area ratio in the gas chromatograph, 0.001 ppm or more, 0.01 ppm or more, 0.1 ppm or more, 1 ppm or more, 0.001% or more (10 ppm or more), 0.01% or more, 0.1% or more, or 1% or more, with the upper limit being 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, 1.5% or less, 1.0% or less, 0.5% or less, 0.1% or less, or 0.01% or less.
  • a 14 cm3 stainless steel pipe running a -5°C chiller was connected to the autoclave. Thereafter, the autoclave was stirred at 150 rpm while the mixture was reacted for 12 hours in an oil bath heated to 260°C.
  • the surface temperature of the SUS piping was 10 to 20°C.
  • the internal temperature of the reactor was 240°C, and the pressure was 2.2 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) to calculate the yield using the absolute calibration curve method. The yield of tetraisobutoxysilane based on silicon dioxide was 15%.
  • the total weight of water contained in the raw material reagents of isobutyl alcohol and diisobutyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.57 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm 3 stainless steel pipe running a -5°C chiller was connected to the autoclave.
  • the autoclave was then stirred at 150 rpm while the mixture was reacted for 12 hours in an oil bath heated to 260°C.
  • the surface temperature of the SUS piping was 10-20°C.
  • the internal temperature of the reactor was 236°C, and the pressure was 2.2 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) using the absolute calibration curve method to calculate the yield.
  • the yield of tetraisobutoxysilane based on silicon dioxide was 61%.
  • the content ratios of ether, ester, and acetal relative to the tetraalkoxysilane in the reaction mixture were calculated from the peak area ratios of the gas chromatograph from the analysis results of the reaction mixture by gas chromatography (Shimadzu Corporation, GC-2030).
  • the proportions of ether, ester, and acetal relative to the tetraalkoxysilane were 5.4%, 5.7%, and 6.6%, respectively, based on the peak area ratios of the gas chromatograph.
  • the reaction liquid was distilled to obtain a target product with a purity of 99% or more relative to the tetraisobutoxysilane (manufactured by Kojundo Chemical Laboratory, product name SIR05LB) used as a standard.
  • the content ratios of ether, ester, and acetal relative to the tetraalkoxysilane in the target product were calculated from the peak area ratios in the gas chromatograph based on the results of gas chromatography (Shimadzu Corporation, "GC-2030") of the target product.
  • the proportions of ether, ester, and acetal relative to the tetraalkoxysilane were 10 ppm, 0.19%, and 1.1%, respectively, based on the peak area ratios in the gas chromatograph.
  • the total weight of water contained in the raw material reagents of isobutyl alcohol and diisobutyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.67 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm3 stainless steel pipe running a -5°C chiller was connected to the autoclave. Thereafter, the autoclave was stirred at 150 rpm while the mixture was reacted for 12 hours in an oil bath heated to 260°C.
  • the surface temperature of the SUS piping was 10 to 20°C.
  • the internal temperature of the reactor was 236°C, and the pressure was 2.7 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) to calculate the yield using the absolute calibration curve method.
  • the yield of tetraisobutoxysilane based on silicon dioxide was 65%.
  • the total weight of water contained in the raw material reagents of isobutyl alcohol and diisobutyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.26 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm 3 stainless steel pipe running a -5°C chiller was connected to the autoclave. Thereafter, the autoclave was stirred at 150 rpm while the mixture was reacted for 12 hours in an oil bath heated to 210°C.
  • the surface temperature of the SUS piping was 10 to 20°C.
  • the internal temperature of the reactor was 200°C, and the pressure was 1.1 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) to calculate the yield using the absolute calibration curve method.
  • the yield of tetraisobutoxysilane based on silicon dioxide was 15%.
  • the total weight of water contained in the raw material reagents of isobutyl alcohol and diisobutyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.70 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm 3 stainless steel pipe running a -5°C chiller was connected to the autoclave. Thereafter, the autoclave was stirred at 150 rpm while the mixture was reacted for 12 hours in an oil bath heated to 290°C.
  • the surface temperature of the SUS piping was 10 to 20°C.
  • the internal temperature of the reactor was 270°C, and the pressure was 4.0 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) to calculate the yield using the absolute calibration curve method.
  • the yield of tetraisobutoxysilane based on silicon dioxide was 60%.
  • the total weight of water contained in the raw material reagents of isobutyl alcohol and diisobutyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.70 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm3 stainless steel pipe running a -5°C chiller was connected to the autoclave. Thereafter, the autoclave was stirred at 150 rpm while the mixture was reacted for 12 hours in an oil bath heated to 260°C.
  • the surface temperature of the SUS piping was 10 to 20°C.
  • the internal temperature of the reactor was 255°C, and the pressure was 1.9 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) to calculate the yield using the absolute calibration curve method. The yield of tetraethoxysilane based on silicon dioxide was 98%.
  • the total weight of water contained in the raw material reagents of ethanol and diethyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 1.59 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm3 stainless steel pipe running a -5°C chiller was connected to the autoclave.
  • the autoclave was then stirred at 150 rpm while the mixture was reacted for 12 hours in an oil bath heated to 260°C.
  • the surface temperature of the SUS piping was 10-20°C.
  • the internal temperature of the reactor was 251°C, and the pressure was 1.9 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) using the absolute calibration curve method to calculate the yield.
  • the yield of tetraethoxysilane based on silicon dioxide was 60%.
  • the reaction solution was distilled to obtain the target product with a purity of 99% or more relative to the tetraethoxysilane (manufactured by Kojundo Chemical Laboratory, product name SIR02LB) used as a standard. Furthermore, the total weight of water contained in the raw material reagents of ethanol and diethyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.26 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm 3 SUS pipe with a -5 ° C cooling chiller was connected to the autoclave. The mixture was then stirred at 150 rpm in an oil bath heated to 260 ° C and reacted for 12 hours. At the end of the reaction, the internal temperature of the reactor was 224°C and the pressure was 0.5 MPa. The surface temperature of the SUS piping was 10 to 20°C.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) using the absolute calibration curve method to calculate the yield. The yield of tetraethoxysilane based on silicon dioxide was 51%.
  • the total weight of water contained in the raw material reagents of ethanol and diethyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.11 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm 3 SUS pipe with an internal volume through which a -5 ° C. cooling chiller was flowing was connected to the autoclave.
  • the mixture was then stirred at 150 rpm in an oil bath heated to 260 ° C. and reacted for 12 hours.
  • the internal temperature of the reactor was 225°C and the pressure was 0.4 MPa.
  • the surface temperature of the SUS piping was 10 to 20°C.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) using the absolute calibration curve method to calculate the yield.
  • the yield of tetraethoxysilane based on silicon dioxide was 25%.
  • the total weight of water contained in the raw material reagents of ethanol and diethyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.032 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm 3 SUS pipe with an internal volume through which a -5 ° C. cooling chiller was flowing was connected to the autoclave.
  • the mixture was then stirred at 150 rpm in an oil bath heated to 260 ° C. and reacted for 12 hours.
  • the surface temperature of the SUS piping was 10 to 20°C.
  • the internal temperature of the reactor was 224°C, and the pressure was 0.5 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) using the absolute calibration curve method to calculate the yield.
  • the yield of tetraethoxysilane based on silicon dioxide was 25%.
  • the total weight of water contained in the raw material reagents of ethanol and ethyl methyl carbonate used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.073 g/mol based on the number of moles of silicon dioxide.
  • a 14 cm 3 SUS pipe with an internal volume through which a -5 ° C. cooling chiller flows was connected to the autoclave, and a pressure-holding valve (manufactured by TESCOM) set to 1 MPa was attached to the end of the SUS pipe. Thereafter, the autoclave was stirred at 150 rpm while the mixture was reacted for 12 hours in an oil bath heated to 260°C. The temperature of the SUS piping surface was 10 to 20°C. At the end of the reaction, the internal temperature of the reactor was 240°C, and the pressure was 1.0 MPa. The reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) to calculate the yield using the absolute calibration curve method.
  • silicon dioxide manufactured by Fujifilm Wa
  • the autoclave was stirred at 150 rpm in an oil bath heated to 260 °C and the mixture was allowed to react for 12 hours.
  • the surface temperature of the SUS piping was 10 to 20°C.
  • the internal temperature of the reactor was 254°C, and the pressure was 2.6 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) using the absolute calibration curve method to calculate the yield.
  • the yield of tetraisobutoxysilane based on silicon dioxide was 31%.
  • the weight of water contained in the raw material reagent of isobutyl alcohol used above was calculated based on the amount charged from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.14 g/mol based on the number of moles of silicon dioxide.
  • the internal temperature of the reactor at the end of the reaction was 213°C, and the pressure was 1.5 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation "GC-2030") using the absolute calibration curve method to calculate the yield.
  • the yield of tetraisobutoxysilane based on silicon dioxide was 1%.
  • the weight of water contained in the raw material reagent of isobutyl alcohol used above was calculated based on the amount charged from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.14 g/mol based on the number of moles of silicon dioxide.
  • the contents were then stirred at 150 rpm in an oil bath heated to 260°C and reacted for 12 hours.
  • the surface temperature of the SUS pipe was 10-20°C.
  • the internal temperature of the reactor was 250°C and the pressure was 0.5 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation, GC-2030) using the absolute calibration curve method to calculate the yield.
  • the yield of tetraisobutoxysilane based on silicon dioxide was less than 0.1%.
  • the weight of water contained in the diethyl carbonate raw material reagent used above was calculated based on the charged amounts from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm's "899 Coulometer,” catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K,” anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”), and the weight of water was found to be 0.090 g/mol based on the number of moles of silicon dioxide.
  • the surface temperature of the stainless steel pipe was 10-20°C. At the end of the reaction, the internal temperature of the reactor was 248°C, and the pressure was 0.9 MPa.
  • the reaction mixture was analyzed by gas chromatography (Shimadzu Corporation "GC-2030") using an absolute calibration curve method to calculate the yield. The yield of tetraisobutoxysilane based on silicon dioxide was less than 0.1%.
  • the weight of water contained in the raw ethanol reagent used above was calculated based on the amount charged from the measurement results using a Karl Fischer trace moisture analyzer (Metrohm "899 Coulometer", catholyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat CG-K", anolyte: Honeywell-Fluka (registered trademark) "HYDRANAL (registered trademark) Coulomat AK”).
  • the weight of water was calculated based on the number of moles of silicon dioxide and was 0.022 g/mol.
  • alkoxysilanes can be produced in high yields by mixing dialkyl carbonate, silicon oxide, alcohol, and a base catalyst and reacting the mixture.

Abstract

La présente invention aborde le problème de la fourniture d'un procédé de production d'un alcoxysilane, le procédé étant moins susceptible d'être affecté par la teneur en eau de matières premières que les procédés classiques et permettant de produire industriellement de l'alcoxysilane par l'intermédiaire d'un procédé de production à basse température. L'invention concerne un procédé de production d'un tétraalcoxysilane qui comprend une étape consistant à mélanger un carbonate de dialkyle, de l'oxyde de silicium, un alcool et un catalyseur de base afin d'obtenir un mélange.
PCT/JP2025/018268 2024-05-23 2025-05-20 Procédé de production de tétraalcoxysilane à l'aide de carbonate d'alkyle, et composition contenant du tétraalcoxysilane Pending WO2025244039A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024083841 2024-05-23
JP2024-083841 2024-05-23

Publications (1)

Publication Number Publication Date
WO2025244039A1 true WO2025244039A1 (fr) 2025-11-27

Family

ID=97795505

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/018268 Pending WO2025244039A1 (fr) 2024-05-23 2025-05-20 Procédé de production de tétraalcoxysilane à l'aide de carbonate d'alkyle, et composition contenant du tétraalcoxysilane

Country Status (1)

Country Link
WO (1) WO2025244039A1 (fr)

Similar Documents

Publication Publication Date Title
JP3543352B2 (ja) 含硫黄有機珪素化合物の製造方法
WO2006025226A1 (fr) Monoéthers de polyglycérol et processus de production
EP3424896B1 (fr) Procédé de production d'une composition liquide contenant un monoéthérate, composition liquide et procédé de production d'un composé polymérisable
JP5423039B2 (ja) 高純度トリアルキルガリウム及びその製造方法
KR102044434B1 (ko) 불포화 결합 함유 실란 화합물의 정제 방법 및 제조 방법
EP3363779B1 (fr) Procédé de production de carbonate à chaîne asymétrique
WO2025244039A1 (fr) Procédé de production de tétraalcoxysilane à l'aide de carbonate d'alkyle, et composition contenant du tétraalcoxysilane
JP6555385B1 (ja) ケチミン構造を有する有機ケイ素化合物の製造方法
KR102513651B1 (ko) 에테르 화합물 제조 방법
JP5657465B2 (ja) アリルアルコール化合物の製造方法
CN110128273B (zh) 一种二(缩乙二醇碳酸甲酯)碳酸酯的合成方法
JP2010037286A (ja) 酢酸−ｎ−プロピルの製造方法
EP0146886B1 (fr) Compositions de solvant pour l'enlèvement de gaz acides de mélanges de gaz
JP2017088498A (ja) テトラメトキシシランの製造方法
JP4884982B2 (ja) ビニルシランの製造方法
US2801267A (en) Production of vinyl sulfones
JP3752530B2 (ja) アルコールおよび炭酸エステルの混合物を用いるケイ素のアルコキシドの製造方法
CN103732576B (zh) 氟代烷磺酸的制备方法
US2246545A (en) Isoprene pbopionate and method fob
JP4797449B2 (ja) 含ヨウ素フルオロポリエーテルおよびその製造法
JP6341040B2 (ja) １，１，１，５，５，５−ヘキサフルオロアセチルアセトンの製造方法
JP7375519B2 (ja) ハロゲン化アクリル酸エステルの製造方法
RU2417228C1 (ru) Способ получения алкоксисиланов
JP5373259B2 (ja) Ｎ−アルキルボラジンの製造方法
JP2024081363A (ja) シリコーンモノマーの製造方法