Method for producing carbosilanes and / or hydrosilanes

Abstract

To provide an efficient method for the production of carbosilane and / or hydrosilane.SOLUTION: There is provided a method for producing carbosilane having an Si-R bond and / or hydrosilane having an Si-H bond, which comprises a step of reacting acyloxysilane having an Si-OCOR (wherein, OCO represents O-C(=O) of an oxycarbonyl group; R is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom in which part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group may be substituted with a group not involved in the reaction) in the presence of a carbon-based catalyst, wherein the carbon-based catalyst is a carbon-based compound containing 90 mass% or more carbon.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an efficient method for producing carbosilanes and / or hydrosilanes. [Background technology]

[0002] Carbosilanes containing Si-C bonds and hydrosilanes containing Si-H bonds are important compounds used as reagents and intermediates for precision synthesis in the production of various functional chemicals and materials, including pharmaceuticals, agricultural chemicals, and optoelectronic materials.

[0003] Well-known common methods for producing carbosilanes or hydrosilanes include a method of producing carbosilanes by reacting a chlorosilane, alkoxysilane, or the like with an organometallic compound such as a Grignard reagent or an organolithium reagent (Patent Document 1, Non-Patent Document 1), and a method of producing hydrosilanes by reacting a chlorosilane, alkoxysilane, or the like with a metal hydride such as lithium aluminum hydride (Non-Patent Document 1) (Method A).

[0004] Meanwhile, a method (Method B) has been reported for producing carbosilanes having an Si-R' bond by decarboxylation (hereinafter, "decarboxylation" refers to the elimination reaction of carbon dioxide (CO2)) from acyloxysilanes having a specific Si-O-C-R' bond (hereinafter, O-CO represents an oxycarbonyl group, O-C (=O), where R' is a trichloromethyl group (CCl3), a pentafluorophenyl group (CF5), a trifluoromethyl group (CF3), an alkynyl group (R"C≡C), or the like; R" represents a siloxycarbonyl group or an aryl group) using a catalytic reaction promoter (Non-Patent Documents 2-4, Patent Documents 2-4). In these methods, organic bases (Non-Patent Documents 2 and 3, Patent Document 4), quaternary ammonium salts (Non-Patent Document 4), alkali metal salts (Patent Documents 2 and 3), or copper salts (Non-Patent Document 5) have been used as catalytic reaction promoters. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 6,160,151 [Patent Document 2] Russian Patent Application Publication No. 2013111741 [Patent Document 3] French Patent Application Publication No. 2862972 [Patent Document 4] Japanese Patent Publication No. 2021-155337 [Non-patent literature]

[0006] [Non-Patent Document 1] Chemical Society of Japan, "Experimental Chemistry Course (Vol. 24) Organic Synthesis VI", 4th edition, Maruzen Publishing, September 1992, pp. 122, 157 [Non-patent document 2] Synthesis, 1980, 8, 626-627 [Non-patent document 3] Chimia, 1985, 39, 53 [Non-patent document 4] Russ. Chem. Bull., 1995, 44, 145-148 [Non-patent document 5] Organometallics, 2020, 39, 16, 2947-2950 Summary of the Invention [Problem to be solved by the invention]

[0007] However, Method A has the following problems: (1) it is necessary to use organometallic compounds, which are highly reactive to water and moisture and therefore difficult and dangerous to handle; (2) the production costs of organometallic compounds are generally high; and (3) a large amount of metal chlorides is produced as a by-product. In addition, in Method B, (1) the activity of previously known reaction accelerators is insufficient, so the acyloxysilanes that can be used as raw materials are limited to specific types, and acetoxysilanes are not suitable. There are problems such as (1) it is difficult to produce carbosilane from acyloxysilane, which has low reactivity like silane, and (2) because the reaction accelerator is a homogeneous system, it is difficult to separate and recover the reaction accelerator. For these reasons, there is a need for an industrially advantageous method that can solve the problems of the prior art.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a carbosilane having a Si-C bond and / or a hydrosilane having a Si-H bond more safely and efficiently than conventional methods. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that even in the case of low-reactivity acyloxysilanes such as acetoxysilane, a carbosilane having a Si-C bond and / or a hydrosilane having a Si-H bond can be efficiently produced by reacting the acyloxysilane in the presence of a carbon-based catalyst containing 90 mass % or more of carbon, which has led to the completion of the present invention.

[0010] That is, this application provides the following inventions. <1> The method includes a reaction step of reacting an acyloxysilane having a Si-OCOR bond (hereinafter, OCO represents an oxycarbonyl group, O-C(=O); R represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction) in the presence of a carbon-based catalyst, The carbon-based catalyst is a carbon-based compound containing 90 mass % or more of carbon, and the method for producing a carbosilane having an Si-R bond and / or a hydrosilane having an Si-H bond is also included. <2> The carbon-based compound is a porous carbon-based compound. <1> The manufacturing method described in <3> The porous carbon-based compound is at least one selected from activated carbon, graphene, mesoporous carbon, carbon nanotubes, and carbon black. <2> The manufacturing method described in <4> The reaction step is carried out at a temperature of 100 to 800°C. <1> ~ <3> 1. The manufacturing method according to any one of the preceding claims. <5> The acyloxysilane having a Si-OCOR bond is an acyloxysilane represented by the following general formula (I): <1> ~ <4> 1. The manufacturing method according to any one of the preceding claims. R 1 a R 2 b R 3 c Si(OCOR) d (I) (In the formula, a, b, and c each independently represent 0 or 1; d represents an integer of 1 or greater and 3 or less; a+b+c+d=4; R has the same meaning as defined above; and R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom, and some or all of the hydrogen atoms bonded to carbon atoms of the hydrocarbon group and alkoxy group may be substituted with groups that do not participate in the reaction. <6> The method includes a pre-step of producing an acyloxysilane having the Si-OCOR bond prior to the reaction step, The preceding step is any one of the following steps (1) to (3): <1> ~ <5> 1. The manufacturing method according to any one of the preceding claims. (1) Si-OR 4 Join(R 4 is a hydrocarbon group having 1 to 3 carbon atoms.) is reacted with an alkoxysilane having the formula (RCO)2O (R is as defined above) to form a carboxylic acid anhydride. a step of reacting the above-mentioned compounds to produce an acyloxysilane having the Si-OCOR bond. (2)Si-R 5 Join(R 5is an allyl group.) with a carboxylic acid represented by RCO2H (R has the same meaning as above), thereby producing an acyloxysilane having the Si-OCOR bond. (3) A step of producing an acyloxysilane having a Si-O—C—R bond by reacting a halosilane having a Si—X bond with a carboxylic acid represented by RCOH (R is as defined above; X is a halogen atom). [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a method for producing a carbosilane having an Si—C bond and / or a hydrosilane having an Si—H bond more safely and efficiently than conventional methods. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below. One embodiment of the present invention is a method for producing a carbosilane having an Si-R bond (R has the same meaning as defined above) and / or a hydrosilane having an Si-H bond, comprising a reaction step of reacting an acyloxysilane having an Si-O-C-R bond (hereinafter, O-C-O represents an oxycarbonyl group, O-C (=O); R represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction) in the presence of a carbon-based catalyst. Hereinafter, alkoxysilanes having an Si-O—C—R bond, carbosilanes having an Si—R bond, and hydrosilanes having an Si—H bond may be simply referred to as "acyloxysilanes," "carbosilanes," and "hydrosilanes," respectively.

[0013] Specifically, the method for producing carbosilane and / or hydrosilane according to this embodiment has the following features. (1) It is highly safe because it does not require the use of organometallic compounds, which are difficult to handle and dangerous. (2) The catalyst is readily available, low cost, and easy to separate and recover. (3) The reaction system does not produce large amounts of waste materials such as salts. The manufacturing method according to this embodiment enables the safety and efficiency of the manufacturing process to be improved, and has great advantages over conventional techniques in terms of economy and low environmental impact.

[0014] 1.Reaction process <Acyloxysilane> In this embodiment, the acyloxysilane used in the reaction step includes, for example, an acyloxysilane represented by the following general formula (I). R 1 a R 2 b R 3 c Si(OCOR) d (I)

[0015] (R 1 , R 2 and R 3 ) R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom, and some or all of the hydrogen atoms bonded to carbon atoms of the hydrocarbon group and alkoxy group may be substituted with groups that do not participate in the reaction. In this specification, the term "group not involved in the reaction" refers to a group that does not directly participate in the target reaction as a reactive group and does not inhibit the reaction.

[0016] R 1 , R 2 and R 3 Examples of the hydrocarbon group represented by the formula include an alkyl group, an aryl group, an aralkyl group, and an alkenyl group.

[0017] When the hydrocarbon group is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 16, more preferably 1 to 12, even more preferably 1 to 10, and particularly preferably 1 to 4. Some or all of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted with groups that do not participate in the reaction.

[0018] Examples of the group that does not participate in the reaction include an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a halogen atom, etc. More specifically, examples of the alkoxy group, alkoxycarbonyl group, and halogen atom include a methoxy group, an ethoxy group, and a hexoxy group; examples of the alkoxycarbonyl group having 1 to 6 carbon atoms include a methoxycarbonyl group and a propoxycarbonyl group; and examples of the halogen atom include a fluorine atom and a chlorine atom.

[0019] Specific examples of the alkyl group which may be substituted with a group which does not participate in the reaction include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, a 2-methoxyethyl group, a 3-ethoxypropyl group, a 2-methoxycarbonylethyl group, a trifluoromethyl group, and a 3-chloropropyl group.

[0020] Furthermore, when the hydrocarbon group is an aryl group, the aryl group can be a monovalent aromatic organic group of a hydrocarbon ring system or a heterocyclic ring system. When the aryl group is a monovalent aromatic organic group of a hydrocarbon ring system, the number of carbon atoms therein is preferably 6 to 18, more preferably 6 to 14. Specific examples of the monovalent aromatic organic group of a hydrocarbon ring system include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. When the aryl group is a monovalent aromatic organic group of a heterocyclic ring system, the heteroatom in the heterocyclic ring is a sulfur atom, an oxygen atom, or the like. The number of carbon atoms in the monovalent aromatic organic group of a heterocyclic ring system is preferably 4 to 12, more preferably 4 to 8. Specific examples of the monovalent aromatic organic group of a heterocyclic ring system include a thienyl group, a benzothienyl group, a dibenzothienyl group, a furyl group, a benzofuryl group, and a dibenzofuryl group.

[0021] Some or all of the hydrogen atoms bonded to the carbon atoms of the aryl group may be substituted with groups that do not participate in the reaction. Examples of groups that do not participate in the reaction include those listed above as groups that may be substituted on the alkyl group. Other groups that do not participate in the reaction include oxyethylene groups and oxyethyleneoxy groups, which are divalent groups that bond two carbon atoms on a ring.

[0022] Specific examples of the aryl group which may be substituted with a group which does not participate in the reaction include a methylphenyl group, an ethylphenyl group, a hexylphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, an octoxyphenyl group, a methyl(methoxy)phenyl group, a fluoro(methyl)phenyl group, a chloro(methoxy)phenyl group, a bromo(methoxy)phenyl group, a 2,3-dihydrobenzofuranyl group, and a 1,4-benzodioxanyl group.

[0023] Furthermore, when the hydrocarbon group is an aralkyl group, the number of carbon atoms in the aralkyl group is preferably 7 to 19, more preferably 7 to 15. In addition, some or all of the hydrogen atoms bonded to the carbon atoms of the aralkyl group may be substituted with a group that does not participate in the reaction. Examples of the group that does not participate in the reaction include those exemplified above as the group that may be substituted on the alkyl group.

[0024] Specific examples of the aralkyl group which may be substituted with a group which does not participate in the reaction include benzyl group, a phenethyl group, a 2-naphthylmethyl group, a 9-anthrylmethyl group, a (4-chlorophenyl)methyl group, a 1-(4-methoxyphenyl)ethyl group, and the like.

[0025] Furthermore, when the hydrocarbon group is an alkenyl group, the number of carbon atoms in the alkenyl group is preferably 2 to 18, more preferably 2 to 14. Furthermore, some or all of the hydrogen atoms bonded to the carbon atoms of the alkenyl group may be substituted with groups that do not participate in the reaction. Examples of the groups that do not participate in the reaction include those exemplified above as groups that may substitute on the alkyl group, as well as the aryl groups exemplified above.

[0026] Specific examples of the alkenyl group which may be substituted with a group which does not participate in the reaction include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 5-hexenyl group, a 9-decenyl group, a 2-phenylethenyl group, a 2-(methoxyphenyl)ethenyl group, a 2-naphthylethenyl group, and a 2-anthrylethenyl group.

[0027] R 1 , R 2 , or R 3 However, in the case of an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 16, more preferably 1 to 12. Some or all of the hydrogen atoms bonded to the carbon atoms of the alkoxy group may be substituted with a group that does not participate in the reaction. Examples of the group that does not participate in the reaction include those exemplified above as groups that may be substituted on an alkyl group.

[0028] Specific examples of the alkoxy group which may be substituted with a group which does not participate in the reaction include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a tert-butoxy group, and a cyclohexoxy group.

[0029] Also, R 1 , R 2 or R 3 is a halogen atom, the halogen atom is a fluorine atom, a chlorine atom, or a bromine atom.

[0030] (R) R is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction. When R is a hydrocarbon group, the number of carbon atoms in the hydrocarbon group is preferably 1 to 16, more preferably 1 to 12, even more preferably 1 to 10, and particularly preferably 1 to 4. The hydrogen atoms may be substituted with groups that do not participate in the reaction. Specific examples of groups that do not participate in the reaction include R 1 , R 2 and R 3 Examples of the groups that may be substituted on the alkyl group represented by the formula (I) and do not participate in the reaction include those shown above.

[0031] Specific examples of R as a hydrocarbon group include alkyl groups, aryl groups, aralkyl groups, alkenyl groups, and alkynyl groups. Specific examples of these groups include R 1 , R 2 , and R 3 Examples include those shown in the explanation of .

[0032] (a, b, c, and d) a, b, and c each independently represent 0 or 1. d is an integer of 1 or more and 3 or less, preferably 1 or 2, and more preferably 1. Furthermore, a, b, c, and d satisfy a+b+c+d=4.

[0033] Specific examples of acyloxysilanes represented by general formula (I) include acetoxytrimethylsilane ((MeCO2)SiMe3), diacetoxydimethylsilane ((MeCO2)2SiMe2), triacetoxy(methyl)silane ((MeCO2)3SiMe), acetoxytriethylsilane ((MeCO2)SiEt3), acetoxytributylsilane ((MeCO2)SiBu3), acetoxytrimethoxysilane ((MeCO2)Si(OMe )3), diacetoxydimethoxysilane ((MeCO2)2Si(OMe)2), acetoxytriethoxysilane ((MeCO2)Si(OEt)3), diacetoxydiethoxysilane ((MeCO2)2Si(OEt)2), acetoxytripropoxysilane ((MeCO2)Si(OPr)3), acetoxytributoxysilane ((MeCO2)Si(OBu)3), acetoxytrichlorosilane ((MeCO2)SiCl3), diacetoxydichlorosilane ((MeCO2)2SiCl2), triacetoxychlorosilane ((MeCO2)3SiCl), (benzoyloxy)trimethylsilane ((PhCO2)SiMe3), bis(benzoyloxy)dimethylsilane ((PhCO2)2SiMe2), (benzoyloxy)trimethoxysilane ((PhCO2)Si(OMe)3), bis(benzoyloxy)dimethoxysilane ((PhCO2)2Si(OMe)2), (benzoyloxy)trichlorosilane ((PhCO2)SiCl3), bis(benzoyloxy)dichlorosilane ((PhCO2)2SiCl2), acetoxydi(methyl)silane (Vinyl)silane ((MeCO2)SiMe2(CH=CH2)), diacetoxy(methyl)(vinyl)silane ((MeCO2)2SiMe(CH=CH2)), triacetoxy(vinyl)silane ((MeCO2)3Si(CH=CH2)), trimethyl[(2-phenylethenyl)carbonyloxy]silane ((PhCH=CHCO2)SiMe3), tetraacetoxysilane ((MeCO2)4Si), trimethyl(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)SiMe3), dimethylbis(pentafluorophenyl)silane tris(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)2SiMe2), methyltris(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)3SiMe), triethoxy(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)Si(OEt)3), diethoxybis(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)2Si(OEt)2), trimethoxy(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)Si(OMe)3),Dimethoxybis(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)2Si(OMe)2), trichloro(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)SiCl3), dichlorobis(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)2SiCl2), dimethylphenyl(pentafluorophenylcarbonyloxy)silane ((C6F5CO2)SiMe2Ph), dimethyl(pentafluorophenylcarbonyloxy)(vinyl)silane ((C6F5CO2)S iMe2(CH=CH2)), trimethyl(trifluoroacetyloxy)silane ((CF3CO2)SiMe3), dimethylbis(trifluoroacetyloxy)silane ((CF3CO2)2SiMe2), triethoxy(trifluoroacetyloxy)silane ((CF3CO2)Si(OEt)3), dimethoxybis(trifluoroacetyloxy)silane ((CF3CO2)2Si(OMe)2), trichloro(trifluoroacetyloxy)silane ((CF3CO2)SiCl3), trimethyl(pentafluoropropionyloxy)silane oxy)trimethylsilane ((CF3CF2CO2)SiMe3), trimethyl(trichloroacetyloxy)silane ((CCl3CO2)SiMe3), ethoxydimethyl(trichloroacetyloxy)silane ((CCl3CO2)SiMe2(OEt)), diethoxymethyl(trichloroacetyloxy)silane ((CCl3CO2)SiMe(OEt)2), triethoxy(trichloroacetyloxy)silane ((CCl3CO2)Si(OEt)3), trichloro(trichloroacetyloxy)silane ((CCl3CO2)SiC l3), dichlorobis(trichloroacetyloxy)silane ((CCl3CO2)2SiCl2), trimethyl(phenylethynylcarbonyloxy)silane ((PhC≡CCO2)SiMe3), triethoxy(phenylethynylcarbonyloxy)silane ((PhC≡CCO2)Si(OEt)3), trimethyl(1-propynylcarbonyloxy)silane ((MeC≡CCO2)SiMe3), formyloxytrimethylsilane ((HCO2)SiMe3), formyloxytrimethoxysilane ((HCO2)Si(OMe)3),Examples include formyloxytrichlorosilane ((HCO2)SiCl3).

[0034] <Carbosilanes and hydrosilanes> According to the production method of this embodiment, a carbosilane having an Si-C bond and / or a hydrosilane having an Si-H bond can be produced by reacting an acyloxysilane having at least one acyloxy group in the presence of a specific carbon-based catalyst.

[0035] The reaction step in this embodiment is a step in which carbosilanes and / or hydrosilanes are produced by reaction of the acyloxy groups of acyloxysilane. When the acyloxysilane is monoacetoxysilane, the reaction mechanism may be, for example, the following reaction mechanism shown in Scheme 1 or 2.

[0036] [ka]

[0037] [ka]

[0038] In Scheme 1, which gives carbosilanes, the methyl group of the acetoxy group transfers to the silicon atom, and CO2 is eliminated to produce methylsilanes. On the other hand, in Scheme 2, which produces hydrosilanes, the hydrogen atom of the acetoxy group moves to the silicon atom and a CH2CO2 unit is eliminated to produce hydrosilane. The hydrosilane production pathway according to Scheme 2 can occur not only with acetoxy groups but also with other acyloxy groups that have a hydrogen atom on the carbon atom adjacent to the carbonyl group. Furthermore, if the acetoxy group (OCOCH3 group) is replaced with a formyloxy group (OCOH group) in Scheme 1, the hydrogen atom of the formyloxy group moves to the silicon atom, resulting in the elimination of CO2, which may lead to the production of hydrosilane.

[0039] The reaction pathways in Schemes 1 and 2 include a substituent R on the silicon atom. 1 , R 2 , and R 3 It is believed that factors such as reaction conditions have a significant impact. For example, in monoacetoxysilane, when the substituent on the silicon atom is relatively bulky, the migration of the hydrogen atom tends to proceed more easily than the migration of the methyl group, which is sterically larger than the hydrogen atom. It is also possible that these reaction pathways proceed radically, and that carbon-based catalysts such as activated carbon may be involved in the generation of radical intermediates from acyloxysilanes and the promotion of these reactions.

[0040] When the acyloxysilane has a plurality of acyloxy groups, the carbosilane and / or hydrosilane obtained by the production method according to this embodiment may contain some of the acyloxy groups. Alternatively, the carbosilane and / or hydrosilane produced by the reaction of all of them is included.

[0041] In the reaction step of this embodiment, side reactions may produce silanol, disiloxane, etc. When the acyloxysilane is monoacetoxysilane, it is thought that there is a possibility that silanol and ketene are produced from the monoacetoxysilane, and disiloxane is produced from the silanol, for example, according to a reaction mechanism such as that shown in Scheme 3 below.

[0042] [ka]

[0043] According to the production method of this embodiment, for example, tetramethylsilane (MeSi) and / or trimethylsilane (MeSiH) can be produced from acetoxytrimethylsilane ((MeCO)SiMe); triethyl(methyl)silane (EtSiMe) and / or triethylsilane (EtSiH) can be produced from acetoxytriethylsilane ((MeCO)SiEt); trimethoxy(methyl)silane ((MeCO)Si(OMe)) can be produced from acetoxytrimethoxysilane ((MeCO)Si(OMe)). Silane (MeSi(OMe)3) and / or trimethoxysilane (HSi(OMe)3); acetoxytriethoxysilane ((MeCO2)Si(OEt)3) to give triethoxy(methyl)silane (MeSi(OEt)3) and / or triethoxysilane (HSi(OEt)3); acetoxytrichlorosilane ((MeCO2)SiCl3) to give trichloro(methyl)silane (MeSiCl3) and / or trichlorosilane (HSiCl3); (benzoyloxy) (Me)trimethylsilane ((PhCO2)SiMe3) to give trimethyl(phenyl)silane (Me3SiPh) and / or trimethylsilane (Me3SiH); diacetoxydimethylsilane ((MeCO2)2SiMe2) to give (acetoxy)trimethylsilane ((MeCO2)SiMe3), tetramethylsilane (Me4Si), acetoxydimethylsilane ((MeCO2)SiMe2H), dimethylsilane (Me2SiH2), and / or trimethylsilane ( MeSiH; diacetoxydimethoxysilane ((MeCO)Si(OMe)Me), (acetoxy)dimethoxy(methyl)silane ((MeCO)Si(OMe)Me), dimethoxydi(methyl)silane (MeSi(OMe)), (acetoxy)dimethoxysilane ((MeCO)Si(OMe)H), dimethoxysilane (HSi(OMe)), and / or dimethoxy(methyl)silane (HMeSi(OMe)); can be produced.

[0044] In the reaction step, in the carbosilane and / or hydrosilane produced, isomerization of the R structure or disproportionation of the substituent on the silicon atom may occur depending on the type of R in the acyloxy group (OCOR), the reaction conditions, etc. The carbosilane and / or hydrosilane obtained by the production method according to this embodiment includes Mixtures of these isomers and / or disproportionates are also included. For example, in Scheme 1 above, R of the carbosilane 1 R 2 R 3 SiCH3 is produced, but its disproportionate, R 1 R 2 Si(CH3)2, R 2 R 3 Si(CH3)2, R 1 R 3 Compounds such as Si(CH3)2 are also included in the carbosilanes obtained by the production method according to this embodiment. In Scheme 2, R of the hydrosilane 1 R 2 R 3 SiH is generated, but its disproportionate, R 1 R 2 SiH2, R 2 R 3 SiH2, R 1 R 3 Compounds such as SiH2 are also included in the hydrosilanes obtained by the production method according to this embodiment.

[0045] <Carbon-based catalyst> In the reaction step of this embodiment, a carbon-based compound containing 90 mass % or more of carbon is used as a carbon-based catalyst in order to promote the reaction. A preferred example of such a carbonaceous compound is a porous carbonaceous compound. As the porous carbon-based compound, various known compounds can be used, and a representative example is activated carbon.

[0046] The activated carbon may be produced by any of various conventionally known methods (for example, the method described in Chapter 2 of "New Edition of Activated Carbon: Fundamentals and Applications" (edited by Sanada Yuzo, Suzuki Motoyuki, and Fujimoto Kaoru, Kodansha, 1997), or the method described in Chapter 2 of the Basics section of "Application Technology of Activated Carbon" (edited by Tatemoto Hideki and Abe Ikuo, Techno System, 2000). Examples of raw materials for activated carbon include plant-based, mineral-based, and polymer-based materials. Plant-based raw materials include rice husks, coconut shells, wood, and charcoal. Mineral-based raw materials include peat charcoal, turf, lignite, and coke. Polymer-based raw materials include rayon, acrylic polymers, and phenolic compounds. Methods for increasing the specific surface area of ​​activated carbon for activation include gas activation and chemical activation. Gas activation methods include methods using steam, carbon dioxide, oxygen, etc. Chemical activation methods include methods using zinc chloride, phosphoric acid, or salts thereof; alkali metal hydroxides; alkali metal carbonates; etc. Regarding the nature of the activated carbon, any of basic, neutral and acidic activated carbon can be used, but basic or neutral activated carbon is preferably used. The activated carbon may be in various forms such as powder, granules, or fibers.

[0047] Examples of carbon-based compounds other than activated carbon include graphene, carbon nanotubes, mesoporous carbon, and carbon black. Of these, the carbon-based compound is preferably selected from graphene, carbon nanotubes, and mesoporous carbon, which have a relatively large specific surface area.

[0048] The carbon-based compound may contain or support less than 10 mass % of other elements in addition to carbon. Examples of the other elements include elements of Groups 1 to 14, and more specifically, examples include lithium, sodium, potassium, calcium, magnesium, iron, ruthenium, rhodium, nickel, palladium, platinum, copper, zinc, aluminum, silicon, etc. Of these, the other elements are preferably selected from ruthenium, rhodium, palladium, platinum, and copper.

[0049] The specific surface area of ​​carbonaceous compounds is usually 50 to 4000 m 2 / g, preferably 100 to 3000m 2 / g, more preferably 150 to 2500m2 / g. On the other hand, the pore size of porous carbon compounds is divided into macropores (pore diameter > 50 nm), mesopores (pore diameter > 50 nm), and Porous carbon-based compounds having various pore sizes such as pores (pore diameter 2 to 50 nm) and micropores (pore diameter < 2 nm) can be used. Specifically, the average pore diameter of the porous carbon-based compound is usually 0.5 to 100 nm, preferably 1 to 50 nm, and more preferably 1 to 10 nm. The carbon-based compounds may be used alone or in any combination of two or more in any ratio.

[0050] Examples of commercially available carbon-based compounds that can be used in this embodiment include activated carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number 032-18091, powder), activated carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number 037-02115, powder), activated carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number 034-02125, granular), activated carbon (manufactured by Merck & Co., Ltd., product number 242276, powder), and graphene (manufactured by Merck & Co., Ltd., product number 9 00407, nanoplatelets, powder), 5% palladium-loaded activated carbon (Merck & Co., product number 205680, powder), 5% platinum-loaded activated carbon (Merck & Co., product number 205931, powder), 3% copper-loaded activated carbon (Merck & Co., product number 709107, powder), 5% ruthenium-loaded activated carbon (Merck & Co., product number 206180, powder), 5% platinum-loaded activated carbon (Merck & Co., product number 206164, powder), and the like.

[0051] The amount of the carbon-based catalyst relative to the acyloxysilane can be determined arbitrarily, but the weight ratio of the carbon-based catalyst relative to the acyloxysilane is usually 0.001-100, preferably 0.01-50, and more preferably 0.01-20.

[0052] <Reaction conditions> The reaction of the present invention can be carried out in a liquid phase system or a gas phase system depending on the reaction temperature and reaction pressure. The reaction can be carried out in various conventional reactor configurations such as a batch system or a flow system. The reaction temperature in a liquid phase system is usually 100 to 300°C, and in a gas phase system is usually 100 to 800°C, preferably 300 to 800°C, and more preferably 500 to 750°C. In consideration of reaction efficiency, productivity, etc., the production method according to this embodiment is preferably a flow reaction mode, in which the reaction temperature is preferably 300 to 750°C, more preferably 350 to 750°C. Furthermore, the reaction pressure is usually 0.001 to 10 atmospheres, preferably 0.001 to 5 atmospheres, and more preferably 0.001 to 3 atmospheres. The reaction time depends on the amount of raw materials, the amount of catalyst, the reaction temperature, the shape of the reaction apparatus, etc., but taking into consideration efficiency, productivity, etc., it is usually 1 minute to 12 hours, preferably 1 minute to 6 hours, more preferably 1 minute to 3 hours, even more preferably 5 minutes to 1 hour, and particularly preferably 5 minutes to 30 minutes.

[0053] In the reaction step of this embodiment, the reaction can be made to proceed more efficiently by using an open or reduced pressure reactor and continuously releasing the reaction product, co-product carbon dioxide, etc. outside the reaction system.

[0054] When the reaction is carried out in a liquid phase, it can be carried out with or without a solvent. When a solvent is used, various solvents that do not react with the raw materials, catalyst, or product can be used, such as hydrocarbons such as decalin (decahydronaphthalene) and decane; halogenated hydrocarbons such as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene; and ethers such as tert-butyl methyl ether, dibutyl ether, and tetrahydrofuran. The solvents may be used alone or in any combination and ratio of two or more.

[0055] When the reaction is carried out in a gas phase system, the carrier gas is mixed with the acyloxysilane gas to carry out the reaction. As the carrier gas, an inert gas such as nitrogen, argon, or helium can be used. The amount of carrier gas used can be determined arbitrarily, but the volume ratio of the carrier gas to the volume of vaporized acyloxysilane is usually 0.1-200, preferably 0.1-100, and more preferably 0.1-50. In a gas-phase flow reaction, when liquid acyloxysilane is injected using a syringe pump or the like at an injection rate of 1 to 1000 μL / min, the flow rate of the carrier gas is usually 0.1 to 100 mL / min, preferably 0.5 to 70 mL / min, and more preferably 0.5 to 40 mL / min. The gas-phase flow reaction can be carried out not only by vaporizing liquid acyloxysilane in a vaporization unit and then reacting it, but also by a simpler method in which the vaporization unit is omitted and the reaction is carried out by vaporizing the acyloxysilane in a heating furnace in the presence of a carbon-based catalyst. When the reaction is carried out in a gas-phase flow system, in order to increase the collection efficiency of the product, the collection vessel may be cooled to room temperature or below, or a carrier gas containing the product may be bubbled through an appropriate solvent to dissolve the product in the solvent and collect it. As the type of solvent, various solvents can be used except those that react with acyloxysilane and the product, and the solvent used in product analysis (for example, a heavy solvent such as deuterated chloroform in nuclear magnetic resonance spectroscopy) may also be used.

[0056] 2.Pre-process The production method according to this embodiment may include a pre-step for producing an acyloxysilane. Suitable pre-steps include the following (1) to (3). Carbosilane and / or hydrosilane can be produced more efficiently by continuously carrying out any one of the pre-steps (1) to (3) and the subsequent reaction step. (1) Si-OR 4 Join(R 4 is a hydrocarbon group having 1 to 3 carbon atoms.) with a carboxylic acid anhydride represented by (RCO)2O (R is as defined above), to produce an acyloxysilane having the Si-OCOR bond. (2)Si-R 5 Join(R 5is an allyl group.) with a carboxylic acid represented by RCO2H (R has the same meaning as above), thereby producing an acyloxysilane having the Si-OCOR bond. (3) A step of producing an acyloxysilane having an Si-O—C—R bond by reacting a halosilane having an Si—X bond with a carboxylic acid represented by RCOH (R is as defined above; X is a halogen atom). Examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferred.

[0057] For example, when the acyloxysilane is a monoacyloxysilane, it can be produced from a monoalkoxysilane, a monoallylsilane, or a monohalosilane in a pre-step, as shown in the following Scheme 4. The monoacyloxysilane produced in the pre-step can be converted to a carbosilane and / or a hydrosilane in a subsequent reaction step.

[0058] [ka]

[0059] These pre-step reactions do not necessarily require a reaction accelerator such as a catalyst, but the reactions can also be carried out using various reaction accelerators. For example, in the reaction of monoalkoxysilane with carboxylic acid anhydride in the previous step (1) and the reaction of monoallylsilane with carboxylic acid in the previous step (2), an acid catalyst such as an inorganic or organic solid acid or Lewis acid can be used. In the reaction of halosilane with carboxylic acid in the previous step (3), an organic or inorganic base catalyst can be used.

[0060] In the pre-step, it is not necessary to isolate and purify the acyloxysilane, and it is possible to combine the pre-step and the subsequent reaction step in a one-pot manner. Another feature of the production method according to this embodiment is that carbosilanes and / or hydrosilanes can be efficiently produced from alkoxysilanes or the like by continuously carrying out the pre-process and the subsequent reaction process.

[0061] 3. Other processes The production method according to this embodiment may include other steps in addition to the pre-step. Examples of such other steps include a catalyst recovery step in which the carbon-based catalyst used in the reaction step is separated and recovered from the reaction system. In a flow reaction system, the catalyst recovery step simply involves separating the column or reaction tube packed with the carbon-based catalyst. Also, in a batch reaction system, the catalyst can be easily separated and recovered by methods such as filtration and centrifugation.

[0062] Other steps include a purification step of purifying the produced carbosilanes and / or hydrosilanes. The produced carbosilanes and / or hydrosilanes can be easily purified by means commonly used in organic chemistry, such as distillation, recrystallization, and column chromatography. [Example]

[0063] Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples. The main analytical devices used in the following examples are as follows: Nuclear magnetic resonance spectroscopy (hereinafter sometimes referred to as NMR): Bruker AVANCE III HD 600MHz (with cryoprobe) Gas chromatograph analysis (hereinafter sometimes referred to as GC): Shimadzu GC-2014 Gas chromatograph mass spectrometry (hereinafter sometimes referred to as GC-MS): Shimadzu GCMS-QP2010Plus

[0064] Example 1 A quartz tube (7 mm inner diameter, 40 cm long) was filled with 100 mg of activated carbon (Fujifilm Wako, product number 032-18091, lot number PTE1918, powder), a carbon-based catalyst, with 50 mg of quartz wool on each side. The tube was then placed in a small vertical electric furnace (Furutech FT-01P, modified model with 10 mm holes at the top and bottom). The catalyst was then calcined at 700 °C for approximately 1 hour while nitrogen was flowed through the top of the quartz tube at a rate of 8 mL / min. The carrier gas flow rate was then changed to 4 mL / min, and the starting material, acetoxytrimethylsilane ((MeCO2)SiMe3), was introduced into the furnace through a stainless steel needle at a rate of 10 μL / min using a syringe pump. The reaction mixture (unreacted raw materials and reaction products) was collected in a glass collection vessel (cooled to -40°C using an aluminum block cryostat (Tokyo Rika PSL-2500)) placed at the bottom of the quartz tube. To improve collection efficiency, a solvent (1 mL of deuterated chloroform) was placed in the collection vessel, and the carrier gas containing the reaction mixture, which was flowing out from the end of the quartz tube, was bubbled through the solvent to collect the product. Five, six, eight, and ten minutes after the start of the acetoxytrimethylsilane flow, aliquots of the solution containing the dissolved reaction mixture were taken and analyzed by NMR, GC, and GC-MS.

[0065] As a result, the products confirmed to be tetramethylsilane (Me4Si), trimethylsilane (Me3SiH), trimethylsilanol (Me3SiOH), hexamethyldisiloxane (Me3SiOSiMe3), octamethyltrisiloxane (Me3SiOSiMe2OSiMe3), and hexamethylcyclotrisiloxane ((SiMe2O)3). The raw material conversion and the yield of the above products (calculated based on the composition ratios at each collection time) were 100%, 66%, 4%, 0%, 23%, 2%, and 2%, respectively, at 5 minutes; 100%, 58%, 3%, 0%, 30%, 4%, and 3%, respectively, at 6 minutes; 100%, 43%, 3%, 0%, 40%, 6%, and 4%, respectively, at 8 minutes; and 100%, 33%, 3%, 1%, 47%, 6%, and 5%, respectively, at 10 minutes (see Table 1-1). Among the products, Me4Si and Me3SiH correspond to carbosilane and hydrosilane, respectively, which are the targets of the production method of the present invention. The NMR and GC-MS measurement results of the obtained product are shown in Table 2.

[0066] Examples 2 to 21 The reaction conditions (catalyst, reaction temperature, etc.) were changed, and the reaction and analysis were carried out in the same manner as in Example 1. The results are shown in Tables 1-1 to 1-3 and 2. The catalyst calcination temperature before the flow of acetoxytrimethylsilane was set to the same temperature as the reaction temperature. In Examples 17 to 21, the collecting glass vessel was cooled with ice water.

[0067] The manufacturing method of the present invention may include a pre-step of manufacturing an acyloxysilane, as shown in the following examples.

[0068] Example 22 [Pre-process] 10 mmol of ethoxytrimethylsilane (MeSiOEt), 10 mmol of acetic anhydride ((MeCO)O), and catalyst H +A mixture of 25 mg of cation exchange resin (Amberlyst 15) and 25 mg of methyl methyl silane was heated at 110°C for 30 minutes in a sealed reaction vessel while stirring. After the catalyst was removed by centrifugation, the reaction solution was analyzed by NMR, which revealed that 9.6 mmol (96% yield) of acetoxytrimethylsilane ((MeCO2)SiMe3), an acyloxysilane, had been produced.

[0069] [Reaction process] The acetoxytrimethylsilane solution obtained in the previous step was used as is to carry out the reaction and analysis under the same reaction conditions as in Example 2.

[0070] As a result, the products confirmed to be tetramethylsilane (Me4Si), trimethylsilane (Me3SiH), trimethylsilanol (Me3SiOH), hexamethyldisiloxane (Me3SiOSiMe3), octamethyltrisiloxane (Me3SiOSiMe2OSiMe3), and hexamethylcyclotrisiloxane ((SiMe2O)3). The raw material conversion and the yields of the above products (calculated based on the composition ratios at each collection time) were 100%, 26%, 4%, 13%, 42%, 4%, and 7% at 5 minutes; 100%, 25%, 4%, 14%, 41%, 5%, and 7% at 6 minutes; 100%, 23%, 2%, 18%, 41%, 4%, and 7% at 8 minutes; and 99%, 21%, 3%, 19%, 41%, 6%, and 7% at 10 minutes, respectively (see Tables 1-3).

[0071] Example 23 The reaction and analysis were carried out in the same manner as in Example 2, except that the solution of acetoxytrimethylsilane ((MeCO2)SiMe3) obtained in the previous step under the same reaction conditions as in Example 22 was used, the injection rate using a syringe pump was set to 5 μL / min, and the solution trapping the reaction mixture was sampled 8, 12, 16, and 20 minutes after the start of the flow of acetoxytrimethylsilane.

[0072] As a result, the products confirmed to be tetramethylsilane (Me4Si), trimethylsilane (Me3SiH), trimethylsilanol (Me3SiOH), hexamethyldisiloxane (Me3SiOSiMe3), octamethyltrisiloxane (Me3SiOSiMe2OSiMe3), and hexamethylcyclotrisiloxane ((SiMe2O)3). The raw material conversion and the yields of the above products (calculated based on the composition ratios at each collection time) were 100%, 48%, 0%, 6%, 46%, 0%, and 0% at 8 minutes; 100%, 41%, 0%, 8%, 48%, 0%, and 2% at 12 minutes; 100%, 37%, 0%, 11%, 48%, 0%, and 4% at 16 minutes; and 100%, 32%, 2%, 12%, 46%, 3%, and 3% at 20 minutes, respectively (see Tables 1-3).

[0073] In the production method of the present invention, when a carbon-based catalyst was not used in the reaction step, the yields of carbosilane and hydrosilane were significantly reduced, as shown in the following comparative example.

[0074] (Comparative Example 1) Instead of 100 mg of activated carbon, 100 mg of quartz wool was packed into the quartz tube, and the reaction and analysis were carried out in the same manner as in Example 1.

[0075] As a result, the yield of tetramethylsilane (calculated based on the composition ratio at each time) was 1% at 5, 6, 8, and 10 minutes after starting the flow of acetoxytrimethylsilane, and the yield of trimethylsilane was 0% at 5, 6, 8, and 10 minutes after starting the flow of acetoxytrimethylsilane (see Table 1-3).

[0076] In Example 1, which used a carbon-based catalyst, carbosilane was 66-33% and hydrosilane was 4%. On the other hand, in Comparative Example 1, in which no carbon-based catalyst was used, the yields of carbosilane and hydrosilane were 1% and 0%, respectively, which were significantly lower than in Example 1. This result indicates that the carbon-based catalyst is involved in the production of carbosilanes and hydrosilanes.

[0077] [Table 1-1]

[0078] [Table 1-2]

[0079] [Table 1-3]

[0080] The notes in Tables 1-1 to 1-3 are as follows: 1) In Examples 22 and 23, the pre-processing step and the reaction step were carried out continuously. 2) (MeCO2)SiMe3: Acetoxytrimethylsilane (MeCO2)SiEt3: Acetoxytriethylsilane. 3) AC1: Activated carbon (Fujifilm Wako Pure Chemical Industries, Ltd., product number 032-18091, lot number PTE1918, powder) AC2: Activated carbon (Fujifilm Wako Pure Chemical Industries, Ltd., product number 037-02115, lot number LEK0442, powder) AC3: Activated carbon (Fujifilm Wako Pure Chemical Industries, Ltd., product number 037-02115, lot number PAM0181, powder) AC4: Activated carbon (Fujifilm Wako Pure Chemical Industries, Ltd., product number 037-02115, lot number WTK0788) powder) AC5: Activated carbon (Fujifilm Wako Pure Chemical Industries, Ltd., product number 034-02125, lot number LEM6266, crushed granules) AC6: Activated carbon (Merck, product number 242276, lot number SHBM8130, powder) GR1: Graphene (Merck, product number 900407, lot number MKCP4989, nanoplatelets, powder) Pd / C: 5% palladium-loaded activated carbon (Merck, product number 205680, lot number MKCN6878 , powder) Pt / C: 5% platinum-loaded activated carbon (Merck, product number 205931, lot number MKCN3581, powder) ) Cu / C: 3% copper-loaded activated carbon (Merck, product number 709107, lot number SHBC9181V, powder) Ru / C: 5% ruthenium-loaded activated carbon (Merck, product number 206180, lot number MKCN4206 , powder) Rh / C: 5% rhodium-loaded activated carbon (Merck, product number 206164, lot number MKCH2780, powder). 4) Nitrogen gas was used as the carrier gas. 5) The components collected from the start of acyloxysilane flow until sampling (unreacted The conversion rate of acyloxysilane and the yield of each product were calculated from the composition ratio of acyloxysilane and the product. The composition ratio of the collected components is as follows: When the acyloxysilane is (MeCO2)SiMe3, 1 Calculation was made from the integrated intensity ratio of each component peak in H NMR. In the case of acyloxysilane (MeCO2)SiEt3, the area ratio of each component peak in GC was calculated. 29 It was calculated from the integrated intensity ratio of each component peak in Si NMR. 6) Si-R and Si-H are carbosilane and hydrosilane, respectively, obtained by the production method of the present invention. It is. When the acylosilane is Me3Si(OCOMe), the various products are as follows: Si-R: Me4Si (tetramethylsilane) Si-H: Me3SiH (trimethylsilane) Si-OH: Me3SiOH (trimethylsilanol) Si-O-Si:Me3SiOSiMe3 (hexamethyldisiloxane) Si-O-Si-O-Si:Me3SiOSiMe2OSiMe3 (octamethyltrisiloxane) (SiO)3:(SiMe2O)3 (hexamethylcyclotrisiloxane) When the acyloxysilane is Et3Si(OCOMe), the various products are as follows: Si-R: Et3SiMe (triethyl(methyl)silane) Si-H: Et3SiH (triethylsilane) Si-OH: Et3SiOH (triethylsilanol) Si-O-Si:Et3SiOSiEt3(hexaethyldisiloxane) Si-O-Si-O-Si:Et3SiOSiEt2OSiEt3 (octaethyltrisiloxane) (SiO)3:(SiEt2O)3 (hexaethylcyclotrisiloxane) 7) 50 mg of quartz wool was placed on both sides of 100 mg of quartz wool for fixing, and the quartz tube was filled with the quartz wool.

[0081] [Table 2]

[0082] The notes in Table 2 are as follows: 1) For the names of the reaction products, see Note 6 in Tables 1-1 to 1-3. 2) Measurements in deuterated chloroform. The relaxation reagent Cr(acac)3 (chromium(III) acetylacetonate) The values ​​in parentheses indicate the integrated intensity ratio of each peak. 3) GC-MS (EI, 70 eV). 4) Low production 29 The peak intensity was weak in Si NMR, so the peak position could not be clearly determined. I couldn't recognize it. [Industrial Applicability]

[0083] The production method of the present invention enables more efficient and safe production of carbosilanes and / or hydrosilanes that are useful as functional chemicals, functional materials, and the like, and therefore the present invention has great utility value and is of great industrial significance.

Claims

1. The method includes a reaction step of reacting an acyloxysilane having a Si-OCOR bond (hereinafter, OCO represents an oxycarbonyl group, O-C(=O); R represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction) in the presence of a carbon-based catalyst, The carbon-based catalyst is a carbon-based compound containing 90 mass % or more of carbon.

2. The method according to claim 1 , wherein the carbon-based compound is a porous carbon-based compound.

3. The method according to claim 2, wherein the porous carbon-based compound is at least one selected from the group consisting of activated carbon, graphene, mesoporous carbon, carbon nanotubes, and carbon black.

4. The method according to any one of claims 1 to 3, wherein the reaction step is carried out at a temperature of 100 to 800°C.

5. The method according to any one of claims 1 to 4, wherein the acyloxysilane having an Si-OCOR bond is an acyloxysilane represented by the following general formula (I): R １ ａ R ２ ｂ R ３ ｃ Si(OCOR) ｄ (I) (In the formula, a, b, and c each independently represent 0 or 1; d represents an integer of 1 or greater and 3 or less; a + b + c + d = 4; R has the same meaning as defined above; R １ , R ２ and R ３ are each independently a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom, and some or all of the hydrogen atoms bonded to carbon atoms of the hydrocarbon group and alkoxy group may be substituted with groups that do not participate in the reaction.

6. a pre-step of producing an acyloxysilane having the Si—OCOR bond prior to the reaction step, The manufacturing method according to any one of claims 1 to 5, wherein the pre-process is any one of the following (1) to (3): (1) Si—OR ４ Bond (R ４ is a hydrocarbon group having 1 to 3 carbon atoms. ２ a step of reacting a carboxylic acid anhydride represented by the formula (I) with a carboxylic acid anhydride represented by the formula (I) and the formula (II) to produce an acyloxysilane having the Si—OCOR bond. (2) Si-R ５ Bond (R ５ is an allyl group. ２ a step of reacting a carboxylic acid represented by H (wherein R has the same meaning as above) with the acyloxysilane having the Si—OCOR bond. (3) A halosilane having an Si—X bond is reacted with RCO ２ a step of reacting a carboxylic acid represented by the formula (I) with a carboxylic acid represented by the formula (I) and ...

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