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WO2018173993A1 - Procédé de production d'alcoxyhydrosilane et procédé de production d'alkoxyhalosilane - Google Patents

Procédé de production d'alcoxyhydrosilane et procédé de production d'alkoxyhalosilane Download PDF

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Publication number
WO2018173993A1
WO2018173993A1 PCT/JP2018/010720 JP2018010720W WO2018173993A1 WO 2018173993 A1 WO2018173993 A1 WO 2018173993A1 JP 2018010720 W JP2018010720 W JP 2018010720W WO 2018173993 A1 WO2018173993 A1 WO 2018173993A1
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Prior art keywords
alkoxyhalosilane
producing
group
alkoxyhydrosilane
formula
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PCT/JP2018/010720
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English (en)
Japanese (ja)
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章徳 佐藤
誠 安田
能弘 西本
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株式会社カネカ
国立大学法人大阪大学
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Application filed by 株式会社カネカ, 国立大学法人大阪大学 filed Critical 株式会社カネカ
Priority to JP2019507654A priority Critical patent/JPWO2018173993A1/ja
Priority to CN201880020434.4A priority patent/CN110461856B/zh
Publication of WO2018173993A1 publication Critical patent/WO2018173993A1/fr

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  • the present invention relates to a method for producing alkoxyhydrosilane, a method for producing alkoxyhalosilane suitably used as a raw material compound in the production method, and an alkoxyhalosilane having a specific structure.
  • alkoxyhydrosilane having a specific substituent on a carbon atom bonded to a silicon atom is also known, and it is known that a curable composition having a high curing rate can be obtained from a polymer produced therefrom.
  • Patent Document 1 alkoxyhydrosilane having a specific substituent on a carbon atom bonded to a silicon atom is also known, and it is known that a curable composition having a high curing rate can be obtained from a polymer produced therefrom.
  • a method for producing alkoxyhydrosilane a method of selectively hydrogenating a part of alkoxy groups of the corresponding trialkoxysilane in a plurality of steps can be considered.
  • methoxymethyltrimethoxysilane is reacted with acetyl chloride in the presence of a catalyst to obtain methoxymethyltrichlorosilane, then methoxymethyltrichlorosilane and methyldichlorosilane are reacted to obtain methoxymethyldichlorosilane
  • a method for producing methoxymethyldimethoxysilane (H—Si (CH 2 OCH 3 ) (OCH 3 ) 2 ) by reacting methoxymethyldichlorosilane with trimethyl orthoacetate or methanol and trimethyl orthoacetate has been proposed.
  • Patent Document 2 Synthesis Example 1
  • Patent Document 3 Example 6
  • Patent Document 4 Example 3
  • Patent Document 1 has a large number of steps and a low yield when selectively hydrogenating one or two of the three halogen atoms of organotrihalosilane. As a result, there is still room for improvement in the desired yield of alkoxyhydrosilane based on the amount of organotrimethoxysilane as a raw material.
  • the present invention has been made in view of the above problems, and a method for producing an alkoxyhydrosilane capable of producing a target product in a high yield and a method for producing an alkoxyhalosilane suitably used as a raw material in the method for producing an alkoxyhydrosilane.
  • the object is to provide a method and a novel alkoxyhalosilane of a specific structure.
  • the inventors of the present invention produce an alkoxyhalosilane having a predetermined structure by halogenating an alkoxysilane having a predetermined structure with a halogenating agent under specific conditions, and converting the alkoxyhalosilane having the predetermined structure into an ether.
  • the present inventors have found that the above problems can be solved by producing an alkoxyhydrosilane having a desired structure by hydrogenation using a hydrogenating agent in a solvent containing an aprotic organic solvent having a bond. It was.
  • H-SiR 1 a (OR 2 ) 3-a (1)
  • R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is 1 or 2.
  • R For each of 1 and OR 2 when there are a plurality of them, they may be the same or different.
  • a halogenating agent E
  • halogenating agent (E) when 1 mole equivalent of stoichiometric halogenating agent (E) is used to form 1 mol of alkoxyhalosilane (B) from 1 mol of alkoxysilane (C) The manufacturing method whose quantity is 1.5 molar equivalent or less.
  • X is a chlorine atom
  • the halogenating agent (E) is acetyl chloride.
  • R 3 is an alkyl group having 1 to 20 carbon atoms, and the alkyl group as R 3 may be substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms.
  • R 4 is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom, and for two OR 4 , they may be the same or different.
  • R 3 is an alkyl group having 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms
  • R 4 is an alkyl group having 1 to 3 carbon atoms.
  • (22) The alkoxyhalosilane compound according to (21), wherein R 3 is a methoxymethyl group and R 4 is a methyl group. About.
  • the manufacturing method of the alkoxyhydrosilane which can manufacture a target object with a high yield, the manufacturing method of the alkoxyhalosilane used suitably as a raw material in the manufacturing method of the said alkoxyhydrosilane, and novel of a specific structure And alkoxyhalosilanes can be provided.
  • the alkoxyhydrosilane (A) produced by the method according to the present invention has the following formula (1): H-SiR 1 a (OR 2 ) 3-a (1)
  • R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is 1 or 2.
  • It is a compound represented by these.
  • R 1 and R 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • the substituent that the hydrocarbon group as R 1 and R 2 may have is not particularly limited as long as it is a group that does not inhibit the good production of alkoxyhydrosilane. Specific examples include an alkoxy group, a cycloalkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, and a halogen atom.
  • an alkoxy group and a halogen atom are preferable from the usefulness of the resulting hydrosilane.
  • the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, still more preferably a methoxy group and an ethoxy group, and particularly preferably a methoxy group.
  • An alkoxy group having a small number of carbon atoms and a small stericity tends to favorably advance the hydrogenation reaction.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable in that a side reaction with the hydrogenating agent (D) hardly occurs.
  • the total number of carbon atoms of the hydrocarbon group which may have a substituent as R 1 and R 2 is smaller as the reactive functional group when the total number of carbon atoms is smaller when introduced into the polymer molecular chain. Since reactivity tends to be high, 1 to 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable.
  • the unsubstituted hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, 2 -Alkyl groups such as ethylhexyl group, n-dodecyl group and n-icosyl group; cycloalkyl groups such as cyclopropyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and isopropenyl group; phenyl group Aromatic hydrocarbon groups such as o-tolyl group, m-tolyl group, p-tolyl group and naphthalen-1-yl group; and aralkyl groups such as benzyl group, phenethyl group and naphthalen-1-ylmethyl group It is done. Among them,
  • R 1 is preferably a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent from the viewpoint of easy availability and production of the raw material of alkoxyhydrosilane (A). Further, R 1 is either substituted by a chlorine atom, that an ether bond preferable from the viewpoint of reactivity.
  • Suitable groups for R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 1-chloropropyl group, 2-chloropropyl group, Examples include 3-chloropropyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-methoxypropyl group, 2-methoxypropyl group, and 3-methoxypropyl group. Among these, a methoxymethyl group is preferable because the hydrogenation reaction proceeds well.
  • R 2 is preferably a methyl group or an ethyl group, and more preferably a methyl group. That is, the alkoxyhydrosilane (A) is preferably methoxyhydrosilane or ethoxyhydrosilane, and more preferably methoxyhydrosilane.
  • the plurality of groups when there are a plurality of R 1 or (OR 2 ), the plurality of groups may be the same or different from each other, and are preferably the same from the viewpoint of ease of raw material production. .
  • a is 1 or 2. From the viewpoint of availability of raw materials, a is preferably 1. On the other hand, the reactivity of the alkoxysilyl group of the alkoxyhydrosilane (A) can be adjusted and further chemical modification can be performed by the substituent of the organic group on the silicon group. For this reason, a is preferably 2. In producing various chemical products using the obtained alkoxyhydrosilane (A), the number of alkoxy groups contained in the alkoxysilyl group is determined from the reactivity of the alkoxysilyl group derived from the alkoxyhydrosilane (A). Is more preferable. For this reason, a is more preferably 1.
  • alkoxyhydrosilane (A) represented by the formula (1) obtained by the method for producing an alkoxyhydrosilane according to the present invention include methyldimethoxysilane (HSi (CH 3 ) (OCH 3 ) 2 ), methyl diethoxy silane (HSi (CH 3) (OC 2 H 5) 2), ethyl dimethoxy silane (HSi (C 2 H 5) (OCH 3) 2), ethyldiethoxysilane (HSi (C 2 H 5) (OC 2 H 5) 2), n- propyl dimethoxy silane (HSi (n-C 3 H 7) (OCH 3) 2), n- propyl diethoxy silane (HSi (n-C 3 H 7) (OC 2 H 5 2 ), n-hexyldimethoxysilane (HSi (n-C 6 H 13 ) (OCH 3 ) 2 ), n-hexyldiethoxysilane
  • the alkoxy hydrosilane (A) is represented by the following formula (2): X-SiR 1 a (OR 2 ) 3-a (2) (In Formula (2), R 1 , R 2 , and a are the same as in Formula (1), and X is a halogen atom.) It is manufactured using the alkoxyhalosilane (B) represented by these.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a chlorine atom and a bromine atom are preferable from the viewpoint of availability of raw materials, and a chlorine atom is more preferable in terms of ease of handling.
  • a preferred method for producing the alkoxyhalosilane (B) will be described later.
  • a hydrogen atom bonded to a silicon atom in the compound exemplified as a preferable specific example of the alkoxyhydrosilane (A) represented by the formula (1) is a chlorine atom.
  • the compound substituted by is mentioned.
  • the alkoxyhydrosilane (A) is produced by hydrogenating the halogen atom (X) contained in the alkoxyhalosilane (B) with the hydrogenating agent (D).
  • the type of the hydrogenating agent (D) is not particularly limited as long as the halogen atom (X) in the alkoxyhalosilane (B) can be hydrogenated well, and is appropriately selected from the known hydrogenating agents (D).
  • the hydrogenating agent (D) may be used in combination of two or more.
  • the following formula (D1) MBH 4 ... (D1) (In the formula (D1), M is lithium, sodium, or potassium.)
  • M is lithium, sodium, or potassium.
  • the compound represented by these is mentioned.
  • sodium borohydride, in which M is sodium, is preferable because the alkoxyhydrosilane (A) can be easily produced from the alkoxyhalosilane (B) with a high yield.
  • the amount of hydrogenating agent (D) used is not particularly limited as long as alkoxyhydrosilane (A) can be produced in a desired yield.
  • the amount of the hydrogenating agent (D) used is preferably 0.5 to 10 times the stoichiometric amount capable of hydrogenating 1 mol of the halogen atom (X) contained in the alkoxyhalosilane (B).
  • An amount of 0.0 to 5.0 times is more preferable, and an amount of 1.2 to 3.0 times is particularly preferable.
  • Suitable aprotic organic solvents having an ether bond include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; dialkyl ethers such as diethyl ether, di-n-butyl ether, and cyclopentyl methyl ether; Alkoxybenzenes such as anisole; alkoxyalkanoic acid esters such as methyl methoxyacetate and ethyl methoxyacetate; 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol dimethyl ether, diethylene glycol dimethyl ether (diglyme), dipropylene glycol Dimethyl ether, triethylene glycol dimethyl ether (triglyme), tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether (Tetraglyme), glycol dialkyl ethers such as tetraethylene glycol dimethyl ether, ethylene glycol
  • alkoxyhydrosilane (A) can be easily produced in a good yield, and recovery and purification after handling and reaction. 1,2-dimethoxyethane is more preferable.
  • the content of the aprotic organic solvent having an ether bond in the solvent (S) is not particularly limited as long as it is 50% by mass or more, but is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass. preferable. As the content of the aprotic organic solvent having an ether bond in the solvent (S) is larger, the hydrogenation reactivity tends to be improved.
  • the type of the other solvent is a hydrogenating agent (D) of the halogen atom (X) contained in the alkoxyhalosilane (B).
  • D hydrogenating agent
  • X halogen atom
  • the other solvent typically, a hydrocarbon organic solvent is preferable in that it hardly reacts with the hydrogenating agent (D).
  • a solvent that is miscible with an aprotic organic solvent having an ether bond is more preferable.
  • the amount of the solvent (S) used is not particularly limited as long as the alkoxyhydrosilane (A) can be produced in a desired yield.
  • the amount of the solvent (S) used is typically preferably 50 to 1000 parts by weight, more preferably 70 to 800 parts by weight, and more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the alkoxyhalosilane (B). Particularly preferred.
  • solvent (S) When there is too little solvent (S), there exists a tendency for progress of hydrogenation to become slow, and when there is too much solvent (S), the removal after reaction becomes complicated.
  • the conditions for reacting the alkoxyhalosilane (B) with the hydrogenating agent (D) described above are not particularly limited as long as the reaction proceeds well.
  • the hydrogenating agent (D) may be added to the alkoxyhalosilane (B), and conversely, the alkoxyhalosilane (B) may be added to the hydrogenating agent (D).
  • the solvent (S) is preferably present in the reaction system.
  • the method for adding the alkoxyhalosilane (B) or the hydrogenating agent (D) is not particularly limited, and the alkoxyhalosilane (B) or the hydrogenating agent (D) may be added alone to the reaction system.
  • a solution or suspension of B) or hydrogenating agent (D) may be added to the reaction system.
  • Alkoxyhalosilane (B) or hydrogenating agent (D) may be added to the reaction system by dividing it once or several times, or may be continuously added to the reaction system by a method such as dropping.
  • the time for adding the alkoxyhalosilane (B) or the hydrogenating agent (D) to the reaction system is not particularly limited, and is appropriately selected according to the progress of the reaction.
  • the temperature at which the alkoxyhalosilane (B) and the hydrogenating agent (D) are reacted is not particularly limited as long as the reaction proceeds well. Typically, it is 0 to 40 ° C.
  • the atmosphere in which the alkoxyhalosilane (B) and the hydrogenating agent (D) are reacted is not particularly limited, but the reaction is preferably performed in an inert gas atmosphere such as nitrogen gas.
  • the reaction between the alkoxyhalosilane (B) and the hydrogenating agent (D) may be carried out under atmospheric pressure, under reduced pressure, or under pressure.
  • the reaction between the alkoxyhalosilane (B) and the hydrogenating agent (D) can be carried out by either a batch method or a continuous method.
  • the time for reacting the alkoxyhalosilane (B) and the hydrogenating agent (D) is not particularly limited as long as the reaction proceeds well. Including the addition time of alkoxyhalosilane (B) or hydrogenating agent (D), it is typically 1 hour to 24 hours, preferably 1 hour 30 minutes to 10 hours, more preferably 2 hours to 5 hours. . If the reaction time is short, there is a concern that the temperature of the reaction system rapidly rises due to heat generated by the reaction. If the reaction time is long, the product may be decomposed. However, when the number of carbon atoms of R 1 in the alkoxyhalosilane (B) represented by the formula (2) is large, the hydrogenation reaction may take a long time. In consideration of this point, the reaction time is preferably appropriately determined while analyzing the progress of the reaction as necessary.
  • the alkoxyhydrosilane (A) produced by the method described above is recovered from the reaction system by a well-known method such as filtration or collection under reduced pressure, and then purified by a method such as distillation, if necessary.
  • the alkoxyhydrosilane (A) produced by such a method is, for example, as proposed in WO2011 / 161915, hydrosilylation reaction using Si—H, hydrolysis and condensation reaction using Si—OR 2. It can be used as a raw material for producing various compounds.
  • the production method of the alkoxyhalosilane (B) represented by the above formula (2) used for the production of the alkoxyhydrosilane is not particularly limited. Since the yield is good, the production method of alkoxyhalosilane (B) is represented by the following formula (3): SiR 1 a (OR 2 ) 4-a (3) (In formula (3), R 1 , R 2 , and a are the same as in formula (2).)
  • a method comprising reacting the alkoxysilane (C) represented by formula (I) with a halogenating agent (E) at a temperature of ⁇ 30 ° C. or higher and 80 ° C.
  • alkoxysilane (C) is SiR 1 a (OR 2 ) 4-a (3) (In formula (3), R 1 , R 2 , and a are the same as in formula (2).) It is a compound represented by these.
  • alkoxysilane (C) As a suitable specific example of alkoxysilane (C), the hydrogen atom couple
  • the halogenating agent is not particularly limited as long as it is a compound that can halogenate one of the alkoxy groups represented by 4-a OR 2 contained in the alkoxysilane (C) with a desired high selectivity. Not.
  • a carboxylic acid halide is preferable because post-treatment after the reaction is easy.
  • a halogen atom (X) a chlorine atom or a bromine atom is preferable in terms of reactivity, and a chlorine atom is more preferable in terms of availability of raw materials and price.
  • a carboxylic acid halide a carboxylic acid chloride or a carboxylic acid bromide is preferable, and a carboxylic acid chloride is more preferable.
  • carboxylic acid halides include monochlorides such as acetyl chloride, propionyl chloride, butanoyl chloride, acryloyl chloride, methacryloyl chloride, benzoyl chloride, oxalyl chloride, adipoyl chloride, succinic acid chloride, sebacic acid chloride, and the like.
  • Examples thereof include dichlorides, trichlorides such as 1,3,5-benzenetricarboxylic acid trichloride, and bromides such as acetyl bromide.
  • acetyl chloride, benzoyl chloride, and acetyl bromide are more preferable in terms of yield of the reaction, and acetyl chloride is particularly preferable in terms of cost.
  • the amount of the halogenating agent (E) used is 1 molar equivalent of the stoichiometric amount of the halogenating agent (E) that generates 1 mol of alkoxyhalosilane (B) from 1 mol of alkoxysilane (C). In some cases, the amount is 1.5 molar equivalents or less, preferably 0.5 to 1.2 molar equivalents, and more preferably 0.7 to 1.1 molar equivalents. If the amount of the halogenating agent (E) used decreases, the halogenation rate decreases, which ultimately leads to a decrease in the yield of the desired hydrosilane. If the amount used increases, the amount of by-produced dihalogenated compounds and trihalogenated compounds increases. Resulting in.
  • the metal salt (F) is preferably a salt composed of a metal cation and an anion.
  • Preferred examples of the metal in the metal salt (F) include alkaline earth metals, transition metals, zinc, aluminum, and boron.
  • Preferred examples of the anion constituting the metal salt (F) include halide ions, BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , ClO 4 ⁇ , CF 3 CO 2 ⁇ , and CF 3 SO 3 ⁇ .
  • Halide ions are more preferable in that by-products other than halosilane can be suppressed.
  • Preferred examples of the metal salt (F) exhibiting Lewis acidity include magnesium chloride (MgCl 2 ), magnesium bromide (MgBr 2 ), boron trifluoride ether complex (BF 3 .O (C 2 H 5 ) 2 ), Boron trichloride (BCl 3 ), aluminum chloride (AlCl 3 ), aluminum bromide (AlBr 3 ), zinc chloride (ZnCl 2 ), zinc bromide (ZnBr 2 ), tin tetrachloride (SnCl 4 ), tin tetrabromide (SnBr 4 ), iron trichloride (FeCl 3 ), iron tribromide (FeBr 3 ), titanium tetrachloride (TiCl 4 ), titanium tetrabromide (TiBr 4 ), and the like.
  • MgCl 2 magnesium chloride
  • MgBr 2 magnesium bromide
  • zinc chloride is preferable in terms of reactivity and ease of handling. For this reason, it is preferable to use the metal salt (F) containing zinc chloride for the reaction between the alkoxysilane (C) and the halogenating agent (E).
  • the amount of the metal salt (F) used is not particularly limited as long as the reaction between the alkoxysilane (C) and the halogenating agent (E) proceeds well.
  • the amount of the metal salt (F) used is typically preferably 0.01 to 20 mol%, more preferably 0.05 to 10 mol%, relative to the amount of the alkoxysilane (C) substance. 1 to 2.0 mol% is particularly preferred. If the amount of the metal salt (F) used is small, the reaction rate is slow, and if it is too large, it is economically disadvantageous.
  • a solvent can be used as necessary.
  • the solvent is not particularly limited as long as the halogenation of the alkoxysilane (C) is not inhibited by reaction with the halogenating agent (E) or the like.
  • Suitable solvents include, for example, aprotic ether solvents such as 1,2-dimethoxyethane, hydrocarbon solvents such as hexane, and aprotic ester solvents such as methyl acetate.
  • a solvent may be used independently or may be used in mixture of multiple.
  • the solvent (S) described above as the solvent used for the production of the alkoxyhalosilane (B) can also be used.
  • the amount of the solvent used is not particularly limited as long as the alkoxyhalosilane (B) can be produced in a desired yield.
  • the amount of the solvent used is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, and particularly preferably 500 parts by mass or less with respect to 100 parts by mass of the alkoxysilane (C).
  • the removal after the reaction becomes complicated, and it is disadvantageous economically.
  • the reaction between the alkoxysilane (C) and the halogenating agent (E) is performed at a temperature of ⁇ 30 ° C. or higher and 100 ° C. or lower.
  • the reaction temperature may be constant during the reaction or may vary.
  • the temperature at which the alkoxysilane (C) and the halogenating agent (E) are reacted may be at least partially -30 ° C to 100 ° C, and the average temperature during the reaction is -30 ° C to 100 ° C.
  • the temperature during the reaction is preferably within the range of ⁇ 30 ° C. or more and 100 ° C. or less. When the temperatures during the reaction are all lower than ⁇ 30 ° C., the reaction hardly proceeds. If the reaction temperature exceeds 100 ° C. for a long time, the amount of by-produced dihalides and trihalides increases.
  • the temperature at which the alkoxysilane (C) and the halogenating agent (E) are reacted is preferably at least partly ⁇ 10 ° C. or higher and 90 ° C. or lower, and the average temperature during the reaction is ⁇ 10 ° C. It is more preferable that the temperature is 90 ° C. or lower, and it is particularly preferable that all the temperatures during the reaction are within a range of ⁇ 10 ° C. or higher and 90 ° C. or lower. If the reaction temperature is within such a range, the reaction temperature can be adjusted using a commonly used heat medium or refrigerant such as hot water, cold water, or brine, which is economically advantageous.
  • a commonly used heat medium or refrigerant such as hot water, cold water, or brine
  • At least a part of the reaction between the alkoxysilane (C) and the halogenating agent (E) is 0 ° C. or higher and 20 ° C. or lower, and the average temperature during the reaction is 0 ° C. or higher and 20 ° C. or lower. It is more preferable that all the temperatures during the reaction are in the range of 0 ° C. or higher and 20 ° C. or lower. Sufficient reactivity can be secured by setting the temperature during the reaction to 0 ° C. or higher. In addition, when the reaction temperature is 20 ° C. or less, the amount of by-produced dihalides and trihalogenated substances can be sufficiently suppressed.
  • the method for adding the halogenating agent (E) and the metal salt (F) is not particularly limited, and the halogenating agent (E) or the metal salt (F) may be added to the reaction system alone. Alternatively, a solution or suspension of the metal salt (F) may be added to the reaction system. The halogenating agent (E) and the metal salt (F) may be added to the reaction system by dividing it once or several times, or may be continuously added to the reaction system by a method such as dropping.
  • the time for adding the halogenating agent (E) and the metal salt (F) to the reaction system is not particularly limited, and is appropriately selected according to the progress of the reaction.
  • the order of addition of the halogenating agent (E) and the metal salt (F) is not particularly limited, but the metal salt (F) is added first, and then the halogenating agent (E) is added to suppress the temperature increase during the reaction. It is preferably added continuously to the reaction system by a method such as dropping.
  • the atmosphere in which the alkoxysilane (C) and the halogenating agent (E) are reacted is not particularly limited, but the reaction is preferably performed in an inert gas atmosphere such as nitrogen gas.
  • the reaction between the alkoxysilane (C) and the halogenating agent (E) may be carried out under atmospheric pressure, under reduced pressure, or under pressure.
  • the reaction of the alkoxysilane (C) and the halogenating agent (E) can be carried out by either a batch method or a continuous method.
  • the time for reacting the alkoxysilane (C) and the halogenating agent (E) is not particularly limited. Including the time for dropping the halogenating agent (E) and the subsequent reaction time, it is typically 10 minutes to 24 hours, preferably 30 minutes to 10 hours, and more preferably 1 hour to 5 hours. If the reaction time is short, there is a concern that the temperature of the reaction system rapidly rises due to heat generated by the reaction. Although there is no particular influence on the reaction system due to the long reaction time, it is economically disadvantageous.
  • the alkoxyhalosilane (B) thus produced is directly or purified, preferably purified, and used as a production raw material in the method for producing alkoxyhydrosilane (E) by the above-described method.
  • it can be used for hydrolysis, condensation reaction, etc. using Si—X or Si—OR 2 and is suitably used as a raw material for producing various compounds.
  • the alkoxy halosilane compound (B) represented by the said Formula (2) which is a manufacturing raw material of alkoxy hydrosilane (A) is manufactured.
  • the alkoxyhalosilane compounds (B) the following formula (4): X-SiR 3 (OR 4 ) 2 (4)
  • R 3 is an alkyl group having 1 to 20 carbon atoms, and the alkyl group as R 3 may be substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms
  • R 4 is a hydrocarbon group having 1 to 20 carbon atoms
  • X is a halogen atom, and for two OR 4 , they may be the same or different.
  • the alkoxyhalosilane compound represented by these is preferable.
  • the halogen atom as X and the halogen atom as a substituent on the alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable for ease of production, From the availability of raw materials, a chlorine atom is preferable.
  • Specific examples of the alkyl group having 1 to 20 carbon atoms for R 3 and specific examples of the hydrocarbon group having 1 to 20 carbon atoms for R 4 include those described for R 1 and R 2 . This is the same as the specific example of the alkyl group and the specific example of the hydrocarbon group having 1 to 20 carbon atoms.
  • R 3 is an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom (preferably a chlorine atom) from the viewpoint of reactivity when used as a raw material for producing various compounds. It is preferably an alkyl group having 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms, and R 4 is preferably an alkyl group having 1 to 3 carbon atoms.
  • R 3 is preferably a methoxymethyl group
  • R 4 is preferably a methyl group.
  • alkoxyhalosilane (A) represented by the formula (4) include methyldimethoxychlorosilane (ClSi (CH 3 ) (OCH 3 ) 2 ), methyldiethoxychlorosilane (ClSi (CH 3 ) (OC) 2 H 5) 2), ethyl dimethoxy chlorosilane (ClSi (C 2 H 5) (OCH 3) 2), ethyl diethoxy chlorosilane (ClSi (C 2 H 5) (OC 2 H 5) 2), n- propyl dimethoxy Chlorosilane (ClSi (n—C 3 H 7 ) (OCH 3 ) 2 ), n-propyldiethoxychlorosilane (ClSi (n—C 3 H 7 ) (OC 2 H 5 ) 2 ), n-hexyldimethoxychlorosilane (ClSi) (NC 6 H 13
  • Example 1 Methoxymethyltrimethoxysilane was used as the aforementioned alkoxysilane (C) (silane (C)).
  • the amount of silane (C) is as described in Table 1.
  • Zinc chloride (ZnCl 2 ) was added as a metal salt (F) at a ratio shown in Table 1 (mol%, number of moles of silane (C)) with respect to silane (C).
  • Acetyl chloride as the halogenating agent (E) was added dropwise to the mixture of silane (C) and metal salt (F) in the amount shown in Table 1.
  • Table 1 shows the initial temperature at the start of dropping and the maximum temperature from the start of dropping to the end of reaction.
  • Example 6 to 13 As the aforementioned alkoxysilane (C) (silane (C)), the types of silane compounds described in Table 2 were used. The amount of silane (C) is as described in Table 2. Zinc chloride (ZnCl 2 ) was added as a metal salt (F) at a ratio shown in Table 2 (mol%, moles of silane (C)) with respect to silane (C). However, in Example 13, the metal salt (F) was not used. In the mixture of silane (C) and metal salt (F), the types and amounts of halogenating agents (E) listed in Table 2 were added dropwise.
  • Zinc chloride (ZnCl 2 ) Zinc chloride (ZnCl 2 ) was added as a metal salt (F) at a ratio shown in Table 2 (mol%, moles of silane (C)) with respect to silane (C). However, in Example 13, the metal salt (F) was not used.
  • the initial temperature at the start of dropping was 5 ° C., and the maximum temperature from the start of dropping to the end of the reaction was less than 20 ° C.
  • the reaction was carried out for 30 minutes while maintaining the temperature after completion of dropping.
  • the composition of the reaction solution after completion of the reaction was analyzed to determine the consumption rate of the halogenating agent and the production ratio of the monohalo form (X 1 ) and dihalo form (X 2 ). These results are shown in Table 2.
  • the measurement results of 1 H-NMR (CDCl 3 ) of the product are shown in Table 3.
  • the 1 H-NMR measurement was performed using JNM-AL400 manufactured by JEOL Ltd.
  • Example 14 As the alkoxyhalosilane (B) (halosilane (B)), 26.83 mmol of the silanes described in Table 4 were used. 1.73 g (44.67 mmol, 1.67 equivalents based on halosilane (B)) of NaBH 4 as the hydrogenating agent (D) was suspended in 14.7 g of the solvent (S) of the type described in Table 4. Thereafter, the halosilane (B) was added dropwise to the suspension of the hydrogenating agent (D) at 20 ° C. over 30 to 90 minutes. After completion of dropping, the reaction was carried out at 20 ° C. for 2 hours. The yield of alkoxyhydrosilane (A) (methoxymethyldimethoxysilane) after the reaction was determined from 1 H-NMR (CDCl 3 ). The obtained yield is shown in Table 4.
  • Example 18 and Comparative Example 4 Changing the solvent (S) to the solvent shown in Table 4, changing the dropping time of the halosilane (B) to 13 hours, and changing the reaction time after the dropping of the halosilane (B) to 6 hours The others were reacted in the same manner as in Example 14. The yield of alkoxyhydrosilane (A) (methoxymethyldimethoxysilane) after the reaction was determined in the same manner as in Example 14. The obtained yield is shown in Table 4.
  • MMDMCS represents methoxymethyldimethoxychlorosilane
  • MMDMBS represents methoxymethyldimethoxybromosilane
  • a desired structure is obtained by reacting an alkoxyhalosilane (B) having a predetermined structure with a hydrogenating agent (D) in a solvent (S) containing 50% by mass or more of an aprotic organic solvent having an ether bond. It can be seen that the alkoxyhydrosilane (A) having the structure as described above is favorably produced.
  • Example 14 and Examples 20 to 24 Type and amount of use of alkoxyhalosilane (B) (halosilane (B)) (mmol), amount of use of hydrogenating agent (D) (equivalent), amount of use of solvent (S) (g), and reaction time And alkoxyhydrosilane (A) (hydrosilane (A)) were synthesized in the same manner as in Example 14 except that they were changed as described in Table 5. The yield of hydrosilane (A) measured in the same manner as in Example 14 is shown in Table 5.
  • MMDMCS Methoxymethyldimethoxychlorosilane
  • MDECS Methyldiethoxychlorosilane
  • nPrDMCS n-propyldimethoxychlorosilane
  • HexDMCS n-hexyldimethoxychlorosilane
  • PhDMCS phenyldimethoxychlorosilane 3-ClC3DMCS: 3-chloropropyldimethoxychlorosilane
  • Example 25 With respect to methoxymethyltrimethoxysilane, 0.011 mol% of zinc chloride was used as a catalyst, and addition of 0.92 mol equivalent of acetyl chloride at 5 ° C. was started. The addition was completed over 1.5 hours while adjusting the addition rate so that the temperature of the reaction system did not exceed 20 ° C. The reaction was further continued for 0.5 hours to obtain methoxymethyldimethoxychlorosilane. To the purified methoxymethyldimethoxychlorosilane, 1.67 molar equivalents of NaBH 4 and 3 times the mass of 1,2-dimethoxyethane were charged into the reaction vessel.
  • Example 25 is a method having only two steps according to the present invention, the monochloroation reaction of methoxymethyltrimethoxysilane and the monohydrolysis reaction of methoxymethyldimethoxychlorosilane.
  • the yield of methoxymethyldimethoxysilane based on the amount of methoxymethyltrimethoxysilane used was as high as 60%.
  • methoxymethyldichlorosilane To the purified methoxymethyldichlorosilane, 2.5 molar equivalents of trimethyl orthoacetate were charged into the reaction vessel. While stirring the contents of the reaction vessel, methoxymethyldimethoxysilane was obtained by slowly adding methoxymethyldichlorosilane so that the internal temperature of the reaction vessel did not exceed 50 ° C.
  • the method of Comparative Example 5 is a method having three steps: a trichlorination reaction of methoxymethyltrimethoxysilane, a monohydrolysis reaction of methoxymethyltrichlorosilane, and a dimethoxylation reaction of methoxymethyldichlorosilane described in Patent Document 2. It is. As a result, in Comparative Example 5, the yield of methoxymethyldimethoxysilane based on the amount of methoxymethyltrimethoxysilane used was as low as 30%.

Abstract

L'invention concerne : un procédé de production d'un alcoxyhydrosilane à partir duquel une substance objective peut être produite avec un rendement élevé ; un procédé de production d'un alcoxyhalosilane qui est approprié pour être utilisé en tant que matériau de départ dans le procédé de production d'un alcoxyhydrosilane ; et un nouvel alcoxyhalosilane ayant une structure spécifique. Un alcoxysilane ayant une structure donnée est halogéné avec un agent d'halogénation dans des conditions spécifiques pour produire un alcoxyhalosilane ayant une structure donnée. L'alcoxyhalosilane ayant une structure donnée est hydrogéné avec un agent d'hydrogénation dans un solvant comprenant un solvant organique aprotique ayant une liaison éther, ce qui permet de produire un alcoxyhydrosilane ayant une structure souhaitée.
PCT/JP2018/010720 2017-03-23 2018-03-19 Procédé de production d'alcoxyhydrosilane et procédé de production d'alkoxyhalosilane WO2018173993A1 (fr)

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CN114181243B (zh) * 2021-12-01 2024-04-02 浙江皇马科技股份有限公司 一种甲基二甲氧基氢硅烷的制备方法
CN114213450A (zh) * 2021-12-29 2022-03-22 南京杰运医药科技有限公司 一种甲氧基甲基二甲氧基硅烷的合成方法

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