Method for producing organosilicon compounds having (meth)acryloxy groups and organosilicon compounds having acryloxy groups

Abstract

Provided is a production method comprising subjecting a siloxyalkylhalosilane compound represented by general formula (1) (R1 represents a monovalent hydrocarbon group, R2 represents a divalent hydrocarbon group, R3 represents a hydrogen atom or a monovalent hydrocarbon group, R4 represents a monovalent hydrocarbon group, X represents a chlorine atom or a bromine atom, m represents 0, 1, or 2, and n represents 0, 1, 2, or 3) and a carboxylic acid halide represented by general formula (2) (R5 represents a hydrogen atom, a chlorine atom, or a monovalent hydrocarbon, and X is the same as above) to a siloxy-(meth)acryloxy exchange reaction in the presence of at least one metal compound selected from the group consisting of zinc, copper, and iron, to obtain an organosilicon compound having a (meth)acryloxy group, represented by general formula (3) (R2-R5, X, and m are the same as above). In principle, the production method does not produce a (meth)acrylic adduct or a bis-adduct, and stably provides an organosilicon compound having a (meth)acryloxy group in high yield and high purity.

Description

[Technical Field]

[0001] The present invention relates to a method for producing an organosilicon compound having a (meth)acryloxy group, and to an organosilicon compound having an acryloxy group. [Background technology]

[0002] Organosilicon compounds containing hydrolyzable silyl groups and organic groups can bond organic and inorganic materials that would normally be difficult to bond together by hydrolysis of the hydrolyzable silyl groups to form silanol groups that form covalent bonds with hydroxyl groups on the surface of inorganic materials, and the organic groups then react with the organic materials, thereby imparting properties such as heat resistance, water resistance, weather resistance, improved mechanical strength, adhesion, dispersibility, hydrophobicity, and rust resistance to organic-inorganic composite materials. By utilizing these properties, the organosilicon compounds are used in a wide range of fields and applications, such as silane coupling agents, resin additives, surface treatment agents, fiber treatment agents, adhesives, paint additives, and polymer modifiers.

[0003] Among the above organosilicon compounds, organosilicon compounds having a (meth)acryloxy group are useful compounds as radical polymerizable monomers for obtaining silicon-containing polymers, since the (meth)acryloxy group, which is a polymerizable functional group, copolymerizes with various radical polymerizable monomers.

[0004] Examples of such organosilicon compounds having a (meth)acryloxy group include 3-acryloxypropyltrichlorosilane, 3-acryloxypropyldimethylchlorosilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyldimethylchlorosilane, etc. In particular, (meth)acryloxyalkylmonochlorosilane compounds such as 3-acryloxypropyldimethylchlorosilane and 3-methacryloxypropyldimethylchlorosilane are also used as modifiers for anionic polymerization terminals.

[0005] A common method for producing the organosilicon compound having a (meth)acryloxy group is to synthesize the compound by subjecting a hydrohalosilane compound and a (meth)acrylate compound having an alkenyl group to a hydrosilylation reaction using a transition metal catalyst (Patent Document 1). It has also been reported that a (meth)acryloxyalkylmonochlorosilane compound such as 4-methacryloxybutyldimethylchlorosilane can be produced by reacting a cyclic organoxysilane compound with methacrylic acid chloride in the presence of zinc chloride (Non-Patent Document 1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 9-202791 [Non-patent literature]

[0007] [Non-Patent Document 1] Zhurnal Obshchei Khimii,58(9),pp.2145-2148,1988 Summary of the Invention [Problem to be solved by the invention]

[0008] In Patent Document 1, the allyl group and (meth)acryloxy group of the allyl (meth)acrylate having an allyl group are each functional groups capable of reacting with a hydrohalosilane compound. Therefore, in addition to the target (meth)acryloxyalkylhalosilane compound produced by the reaction of the allyl group of the allyl (meth)acrylate having an allyl group with the hydrohalosilane compound, a compound produced by the reaction of the (meth)acryloxy group of the allyl (meth)acrylate with the hydrohalosilane compound (hereinafter also referred to as a "(meth)acryloxy adduct") and a compound produced by the reaction of both the allyl group and the (meth)acryloxy group of the allyl (meth)acrylate with the hydrohalosilane compound (hereinafter also referred to as a "bis-adduct") are also produced. The production of these compounds reduces the yield of the target (meth)acryloxyalkylhalosilane compound. In particular, compounds having an acryloxy group have low steric hindrance and are highly reactive, making them prone to the formation of undesired acrylic adducts and bis-adducts. Furthermore, in these compounds, the (meth)acryloxy groups in the organosilicon compounds having (meth)acryloxy groups are reduced, resulting in the loss of the (meth)acryloxy groups from the molecules, making it impossible to obtain the desired performance when used in various applications.

[0009] Furthermore, because the boiling points of the (meth)acrylic adducts and bis-adducts are close to those of the target (meth)acryloxyalkylhalosilane compound, separating them by distillation requires long periods of time or multiple operations. However, because the (meth)acryloxy group is a polymerizable functional group, prolonged exposure to high temperatures is undesirable because it can lead to polymerization of the target compound. Multiple distillations are not only time-consuming but also result in a corresponding decrease in the yield of the target compound.

[0010] On the other hand, while the method of Non-Patent Document 1 can produce the target product in high yield, the raw material, a cyclic organoxysilane compound, is self-reactive. Therefore, if undesired self-polymerization occurs during the reaction on an industrial scale, the viscosity of the reaction solution increases significantly, not only failing to produce the target product but also potentially making it impossible to recover the reaction solution from the reaction vessel. For these reasons, it is difficult to use a cyclic organoxysilane compound as a raw material.

[0011] The present invention has been made in view of the above circumstances, and aims to provide a method for producing an organosilicon compound having a (meth)acryloxy group in a stable manner with high yield and high purity, without, in principle, producing (meth)acrylic adducts or bis-adducts, and to provide an organosilicon compound having an acryloxy group. [Means for solving the problem]

[0012] As a result of extensive research conducted by the present inventors in order to achieve the above-mentioned object, they discovered that by reacting a siloxyalkylhalosilane compound with a (meth)acrylic acid halide in the presence of a specific metal compound, it is possible to produce a (meth)acryloxyalkylhalosilane compound in high yield and high purity without producing a (meth)acrylic adduct or a bis-adduct and without using a compound that is self-reactive, thereby completing the present invention.

[0013] That is, the present invention provides: 1. The following general formula (1) [ka] (In the formula, R 1 represents an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 each independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one atom selected from the group consisting of O, S, and Si; R 3 each independently represents a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R 4 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X represents a chlorine atom or a bromine atom, m represents 0, 1, or 2, and n represents 0, 1, 2, or 3. and a siloxyalkylhalosilane compound represented by the following general formula (2): [ka] (In the formula, R 5represents a hydrogen atom, a chlorine atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and X has the same meaning as above. in the presence of at least one metal compound selected from the group consisting of zinc, copper, and iron, to undergo a siloxy-(meth)acryloxy exchange reaction, [ka] (In the formula, R 2 ~R 5 , X and m have the same meanings as above. a method for producing an organosilicon compound having a (meth)acryloxy group, the method comprising the step of obtaining an organosilicon compound having a (meth)acryloxy group represented by the formula: 2. The following general formula (4) [ka] (In the formula, R 1 ~R 3 and n have the same meaning as above. and an unsaturated bond-containing organoxysilane compound represented by the following general formula (5): H-SiR 4 m X 3-m (5) (In the formula, R 4 , X and m have the same meanings as above. a method for producing an organosilicon compound having a (meth)acryloxy group according to claim 1, further comprising a step of subjecting a hydrohalosilane compound represented by the following formula (1) to a hydrosilylation reaction in the presence of a platinum catalyst to obtain a siloxyalkylhalosilane compound represented by the following formula (1): 3. An organosilicon compound having an acryloxy group represented by the following general formula (6): [ka] (In the formula, R 6 each independently represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom, or an acryloxy group; R 7represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain O or S, and R 3 represents a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 4 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X represents a chlorine atom or a bromine atom, and m represents 0, 1, or 2. to provide. [Effects of the Invention]

[0014] According to the present invention, (meth)acryloxyalkylhalosilane compounds can be stably produced in high yield and with high purity without producing (meth)acrylic adducts or bis-adducts and without using compounds that have self-reactivity. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a diagram showing the H-NMR spectrum of (4-chlorodimethylsilylpropyl-2-methoxy-)phenyl acrylate obtained in Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be specifically described below. The method for producing an organosilicon compound having a (meth)acryloxy group of the present invention comprises the step of subjecting a siloxyalkylhalosilane compound represented by the following general formula (1) (hereinafter referred to as "compound (1)") and a carboxylic acid halide represented by the following general formula (2) (hereinafter referred to as "compound (2)") to a siloxy-(meth)acryloxy exchange reaction in the presence of at least one metal compound selected from the group consisting of zinc, copper, and iron, to obtain an organosilicon compound having a (meth)acryloxy group represented by the following general formula (3) (hereinafter referred to as "compound (3)").

[0017] [ka]

[0018] In the above general formula (1), R 1 represents an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. R 1 The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, thexyl, and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl (2-propenyl), 1-propenyl, butenyl, pentenyl, and octenyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl. Among these, linear or branched alkyl groups are preferred from the viewpoint of ease of procurement of raw materials.

[0019] In the above general formula (1), R 2 each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms, which may contain at least one atom selected from the group consisting of O, S, and Si. R 2The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, and octamethylene; branched alkylene groups such as methylethylene (propylene) and methyltrimethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as propenylene, butenylene, hexenylene, and octenylene; branched alkenylene groups such as isopropenylene and isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene and methylenephenylenemethylene. Among these, linear alkylene groups and aralkylene groups are preferred from the viewpoint of ease of procurement of raw materials.

[0020] Also, R 2 Some or all of the hydrogen atoms in the divalent hydrocarbon group may be substituted, and examples of the substituent include an alkoxy group having 1 to 3 carbon atoms; a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom; an aryl group having 6 to 10 carbon atoms; an aralkyl group having 7 to 10 carbon atoms; a cyano group, an amino group, an acyl group, and a carboxy group.

[0021] R 2 Examples of the divalent hydrocarbon group containing at least one atom selected from the group consisting of O, S, and Si include oxyalkylene, alkyleneoxyalkylene, oxyarylene, oxyaralkylene, thioalkylene, alkylenethioalkylene, thioarylene, thioaralkylene, alkylenedialkylsilylalkylene, alkylenedialkylsilylarylene, alkylenedialkylsilylaralkylene groups, etc. Examples of these alkylene groups, arylene groups, and aralkylene groups include the same as those described above. Among these, oxyalkylene groups and oxyaralkylene groups are preferred from the viewpoint of ease of procurement of raw materials. 。

[0022] In the above general formula (1), R 3each independently represents a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. R 3 The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, thexyl, and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl (2-propenyl), 1-propenyl, butenyl, pentenyl, and octenyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl. Among these, methyl, ethyl, isopropyl, tert-butyl, and phenyl groups are preferred from the viewpoint of ease of raw material procurement.

[0023] In the above general formula (1), R 4 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and R 4 The monovalent hydrocarbon group of R 3 However, from the viewpoint of ease of procurement of raw materials, a methyl group is preferred. In the general formula (1), each X independently represents a chlorine atom or a bromine atom, and from the viewpoints of ease of procurement of raw materials and safety, a chlorine atom is preferred. In the above general formula (1), m is 0, 1 or 2, and is preferably 2. In the above general formula (1), n ​​is 0, 1, 2 or 3, and is preferably 3.

[0024] Specific examples of compound (1) include trimethylsiloxypropyldimethylchlorosilane, triethylsiloxypropyldimethylchlorosilane, tert-butyldimethylsiloxypropyldimethylchlorosilane, triisopropylsiloxypropyldimethylchlorosilane, dimethylhexylsiloxypropyldimethylchlorosilane, dimethyloctylsiloxypropyldimethylchlorosilane, dimethyldecylsiloxypropyldimethylchlorosilane, dimethyldodecylsiloxypropyldimethylchlorosilane, and dimethyltetradecylsiloxypropyldimethylchlorosilane. Silylchlorosilane, dimethylhexadecylsiloxypropyldimethylchlorosilane, dimethyloctadecylsiloxypropyldimethylchlorosilane, diphenylmethylsiloxypropyldimethylchlorosilane, trimethylsiloxyoctyldimethylchlorosilane, triethylsiloxyoctyldimethylchlorosilane, tert-butyldimethylsiloxyoctyldimethylchlorosilane, triisopropylsiloxyoctyldimethylchlorosilane, (4-chlorodimethylsilylpropyl-2-methoxy-1-trimethylsiloxy)benzene, (2-chlorodimethylsilylpropyl)benzene Thilsilylpropyl-1-trimethylsiloxy)benzene, (1,2-bis(trimethylsiloxy)-3-chlorodimethylsilylpropyl)benzene, (1,2-bis(trimethylsiloxy)-4-chlorodimethylsilylpropyl)benzene, (1,2-bis(trimethylsiloxy)-5-chlorodimethylsilylpropyl)benzene, (1,3-bis(trimethylsiloxy)-2-chlorodimethylsilylpropyl)benzene, (1,3-bis(trimethylsiloxy)-4-chlorodimethylsilylpropyl)benzene, (1,3-bis(trimethylsiloxy) )-5-chlorodimethylsilylpropyl)benzene, (1,4-bis(trimethylsiloxy)-2-chlorodimethylsilylpropyl)benzene, trimethylsiloxypropyldimethylbromosilane, triethylsiloxypropyldimethylbromosilane, tert-butyldimethylsiloxypropyldimethylbromosilane, triisopropylsiloxypropyldimethylbromosilane, trimethylsiloxyoctyldimethylbromosilane, triethylsiloxyoctyldimethylbromosilane, tert-butyldimethylsiloxyoctyldimethylbromosilane,Monohalosilane compounds having a trialkylsiloxy group, such as triisopropylsiloxyoctyldimethylbromosilane, (4-bromodimethylsilylpropyl-2-methoxy-1-trimethylsiloxy)benzene, (2-bromodimethylsilylpropyl-1-trimethylsiloxy)benzene; trimethylsiloxypropylmethyldichlorosilane, triethylsiloxypropylmethyldichlorosilane, tert-butyldimethylsiloxypropylmethyldichlorosilane, triisopropylsiloxypropylmethyldichlorosilane, trimethylsiloxypropylmethyldichlorosilane, Siloxyoctylmethyldichlorosilane, triethylsiloxyoctylmethyldichlorosilane, tert-butyldimethylsiloxyoctylmethyldichlorosilane, triisopropylsiloxyoctylmethyldichlorosilane, (4-dichloromethylsilylpropyl-2-methoxy-1-trimethylsiloxy)benzene, (2-dichloromethylsilylpropyl-1-trimethylsiloxy)benzene, (1,2-bis(trimethylsiloxy)-3-dichloromethylsilylpropyl)benzene, (1,2-bis(trimethylsiloxy)-4-dichloro alkyldihalides having a trialkylsiloxy group, such as (1,2-bis(trimethylsiloxy)-5-dichloromethylsilylpropyl)benzene, (1,3-bis(trimethylsiloxy)-2-dichloromethylsilylpropyl)benzene, (1,3-bis(trimethylsiloxy)-4-dichloromethylsilylpropyl)benzene, (1,3-bis(trimethylsiloxy)-5-dichloromethylsilylpropyl)benzene, and (1,4-bis(trimethylsiloxy)-2-dichloromethylsilylpropyl)benzene Silane compounds: trimethylsiloxypropyltrichlorosilane, triethylsiloxypropyltrichlorosilane, tert-butyldimethylsiloxypropyltrichlorosilane, triisopropylsiloxypropyltrichlorosilane, trimethylsiloxyoctyltrichlorosilane, triethylsiloxyoctyltrichlorosilane, tert-butyldimethylsiloxyoctyltrichlorosilane, triisopropylsiloxyoctyltrichlorosilane, (4-trichlorosilylpropyl-2-methoxy-1-trimethylsiloxy)benzene,(2-trichlorosilylpropyl-1-trimethylsiloxy)benzene, (1,2-bis(trimethylsiloxy)-3-trichlorosilylpropyl)benzene, (1,2-bis(trimethylsiloxy)-4-trichlorosilylpropyl)benzene, (1,2-bis(trimethylsiloxy)-5-trichlorosilylpropyl)benzene, (1,3-bis(trimethylsiloxy)-2-trichlorosilylpropyl)benzene, (1,3-bis(trimethylsiloxy)-4-trichlorosilylpropyl)benzene, (1,3-bis(trimethylsiloxy) Trihalosilane compounds having a trialkylsiloxy group, such as (1,4-bis(trimethylsiloxy)-2-trichlorosilylpropyl)benzene; bis(chlorodimethylsilylpropoxy)dimethylsilane, bis(chlorodimethylsilylpropoxy)ethylmethylsilane, bis(chlorodimethylsilylpropoxy)dipropylsilane, bis(chlorodimethylsilylpropoxy)dibutylsilane, bis(chlorodimethylsilylpropoxy)phenylmethylsilane, bis(chlorodimethylsilylpropoxy) )diphenylsilane, bis(chlorodimethylsilyloctoxy)dimethylsilane, bis(chlorodimethylsilyloctoxy)ethylmethylsilane, bis(chlorodimethylsilyloctoxy)dipropylsilane, bis(chlorodimethylsilyloctoxy)dibutylsilane, bis(chlorodimethylsilyloctoxy)phenylmethylsilane, bis(chlorodimethylsilyloctoxy)diphenylsilane, and other bis(monochlorodialkylsilylalkoxy)dialkylsilane compounds; bis(dichloromethylsilylpropoxy)dimethylsilane, bis(dic bis(dichloromethylsilylpropoxy)ethyl methylsilane, bis(dichloromethylsilylpropoxy)dipropyl silane, bis(dichloromethylsilylpropoxy)dibutyl silane, bis(dichloromethylsilylpropoxy)phenyl methylsilane, bis(dichloromethylsilylpropoxy)diphenyl silane, bis(dichloromethylsilyloctoxy)dimethyl silane, bis(dichloromethylsilyloctoxy)ethyl methylsilane, bis(dichloromethylsilyloctoxy)dipropyl silane, bis(dichloromethylsilyloctoxy)dibutyl silaneBis(dichloroalkylsilylalkoxy)dialkylsilane compounds such as bis(dichloromethylsilyloctoxy)phenylmethylsilane and bis(dichloromethylsilyloctoxy)diphenylsilane; bis(trichlorosilylpropoxy)dimethylsilane, bis(trichlorosilylpropoxy)ethylmethylsilane, bis(trichlorosilylpropoxy)dipropylsilane, bis(trichlorosilylpropoxy)dibutylsilane, bis(trichlorosilylpropoxy)phenylmethylsilane, and bis(trichlorosilylpropoxy) Bis(trihalosilylalkoxy)dialkylsilane compounds such as diphenylsilane, bis(trichlorosilyloctoxy)dimethylsilane, bis(trichlorosilyloctoxy)ethylmethylsilane, bis(trichlorosilyloctoxy)dipropylsilane, bis(trichlorosilyloctoxy)dibutylsilane, bis(trichlorosilyloctoxy)phenylmethylsilane, and bis(trichlorosilyloctoxy)diphenylsilane; tris(chlorodimethylsilylpropoxy)methylsilane, tris(chlorodimethylsilylpropoxy) tris(halodialkylsilylalkoxy)alkylsilane compounds such as tris(dichloromethylsilylpropoxy)hexylsilane, tris(chlorodimethylsilylpropoxy)octylsilane, and tris(chlorodimethylsilylpropoxy)phenylsilane; tris(dihaloalkylsilylalkoxy)alkylsilane compounds such as tris(dichloromethylsilylpropoxy)methylsilane, tris(dichloromethylsilylpropoxy)hexylsilane, tris(dichloromethylsilylpropoxy)octylsilane, and tris(dichloromethylsilylpropoxy)phenylsilane; tris(trihalosilylalkoxy)alkylsilane compounds such as tris(trichlorosilylpropoxy)methylsilane, tris(trichlorosilylpropoxy)hexylsilane, tris(trichlorosilylpropoxy)octylsilane, and tris(trichlorosilylpropoxy)phenylsilane; and tetrakis(halosilylpropoxy)silane compounds such as tetrakis(chlorodimethylsilylpropoxy)silane, tetrakis(dihalomethylsilylpropoxy)silane, and tetrakis(trihalosilylpropoxy)silane.

[0025] In the above general formula (2), R 5 represents a hydrogen atom, a chlorine atom, or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 carbon atom. R 5 The monovalent hydrocarbon group of R 3 or R 4 However, from the viewpoints of ease of procurement of raw materials and usefulness of the product, a hydrogen atom and a methyl group are preferred. In addition, in the above general formula (2), X has the same meaning as in the above general formula (1).

[0026] Specific examples of compound (2) include acrylic acid chloride, methacrylic acid chloride, chloroacrylic acid chloride, (trifluoromethyl)acrylic acid chloride, itaconic acid chloride, acrylic acid bromide, methacrylic acid bromide, chloroacrylic acid bromide, (trifluoromethyl)acrylic acid bromide, and itaconic acid bromide.

[0027] In the production method of the present invention, the compounding ratio of compound (1) to compound (2) is not particularly limited, but the amount of compound (2) relative to the number of moles of siloxy groups contained in compound (1) is preferably 1 to 1.5 moles, more preferably 1 to 1.2 moles, and even more preferably 1 to 1.05 moles.

[0028] The production method of the present invention is carried out in the presence of at least one metal compound selected from the group consisting of zinc, copper and iron. Specific examples of metal compounds include zinc compounds such as zinc oxide, zinc chloride, zinc bromide, zinc iodide, zinc acetate, and zinc trifluoromethanesulfonate; copper compounds such as copper oxide (II), copper oxide (I), copper chloride (II), copper chloride (I), copper bromide (II), copper bromide (I), copper iodide (II), copper iodide (I), copper acetate (II), copper acetate (I), and copper trifluoromethanesulfonate; and iron compounds such as iron oxide (III), iron oxide (II), iron chloride (III), iron chloride (II), iron bromide (III), iron bromide (II), iron acetate (III), iron acetate (II), iron trifluoromethanesulfonate, and iron trifluoromethanesulfonate (II). Among these, zinc oxide, copper bromide, and iron (III) chloride are preferred from the viewpoint of reactivity and ease of handling, zinc compounds are more preferred, and zinc oxide is even more preferred. The amount of the metal compound used is not particularly limited, but is preferably 0.01 to 10 mol %, more preferably 0.05 to 5 mol %, and even more preferably 0.1 to 2 mol %, relative to the number of moles of siloxy groups contained in compound (1).

[0029] The reaction temperature in the siloxy-(meth)acryloxy exchange reaction is not particularly limited, but is preferably 40 to 120°C, more preferably 60 to 100°C, and even more preferably 80 to 100°C. The reaction time for the siloxy-(meth)acryloxy exchange reaction is not particularly limited, but is preferably 0.5 to 10 hours, more preferably 0.5 to 4 hours.

[0030] The siloxy-(meth)acryloxy exchange reaction proceeds without a solvent, but can also be carried out in the presence of a solvent. Examples of solvents that can be used include (iso)paraffin compounds such as hexane, octane, isooctane, decane, dodecane, and isododecane; aromatic hydrocarbon compounds such as toluene and xylene; ether compounds such as tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, cyclopentyl methyl ether, dioxane, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether; and nitrile compounds such as acetonitrile, propionitrile, and butyronitrile. These can be used alone or in combination of two or more.

[0031] Furthermore, the siloxy-(meth)acryloxy exchange reaction is preferably carried out in the presence of a polymerization inhibitor in order to inhibit polymerization of the target compound (3) and the substrate compound (2). Examples of the polymerization inhibitor include commonly used methoxyphenol compounds, hydroxyphenol compounds, hindered phenol compounds, and phenothiazine compounds.

[0032] Among these, particularly from the viewpoint of availability, 4-methoxyphenol, 2-methyl-4-methoxyphenol, 2-tert-butyl-4-methoxyphenol, 4-hydroxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), 4,4-methylenebis(2,6-di-tert-butylphenol), 2,2-methylenebis(6-tert-butyl-4-methylphenol), 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-hydroxyphenol, 3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-1-benzopyran-6-ol, phenothiazine, and 3,7-dioctylphenothiazine are preferred. The polymerization inhibitor may be used singly or in combination of two or more from each group. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, and even more preferably 0.01 to 1% by mass, based on the compound (2).

[0033] In the above general formula (3), R 2 ~R 5 , X and m have the same meanings as above. Specific examples of the compound (3) obtained by the present invention include acryloxypropyldimethylchlorosilane, acryloxypentyldimethylchlorosilane, acryloxyoctyldimethylchlorosilane, acryloxyethoxypropylmethyldichlorosilane, (4-chlorodimethylsilylpropyl-2-methoxy)phenyl acrylate, (2-chlorodimethylsilylpropyl-1-acryloxy)phenyl acrylate, (1,2-bis(acryloxy)-3-chlorodimethylsilylpropyl)benzene, (1,2-bis( (acryloxy)-4-chlorodimethylsilylpropyl)benzene, (1,2-bis(acryloxy)-5-chlorodimethylsilylpropyl)benzene, (1,3-bis(acryloxy)-2-chlorodimethylsilylpropyl)benzene, (1,3-bis(acryloxy)-4-chlorodimethylsilylpropyl)benzene, (1,3-bis(acryloxy)-5-chlorodimethylsilylpropyl)benzene, (1,4-bis(acryloxy)-2-chlorodimethylsilylpropyl)benzene, methacryloxypropyl Methacryloxypentyldimethylchlorosilane, Methacryloxyoctyldimethylchlorosilane, Methacryloxyethoxypropylmethyldichlorosilane, (4-chlorodimethylsilylpropyl-2-methoxy)phenyl methacrylate, (2-chlorodimethylsilylpropyl-1-acryloxy)phenyl methacrylate, (1,2-bis(methacryloxy)-3-chlorodimethylsilylpropyl)benzene, (1,2-bis(methacryloxy)-4-chlorodimethylsilylpropyl)benzene dialkylchlorosilane compounds having a (meth)acryloxy group, such as benzene, (1,2-bis(methacryloxy)-5-chlorodimethylsilylpropyl)benzene, (1,3-bis(methacryloxy)-2-chlorodimethylsilylpropyl)benzene, (1,3-bis(methacryloxy)-4-chlorodimethylsilylpropyl)benzene, (1,3-bis(methacryloxy)-5-chlorodimethylsilylpropyl)benzene, and (1,4-bis(methacryloxy)-2-chlorodimethylsilylpropyl)benzene;Acryloxypropylmethyldichlorosilane, acryloxypentylmethyldichlorosilane, acryloxyoctylmethyldichlorosilane, acryloxyethoxypropylmethyldichlorosilane, (4-dichloromethylsilylpropyl-2-methoxy)phenyl acrylate, (2-dichloromethylsilylpropyl-1-acryloxy)phenyl acrylate, (1,2-bis(acryloxy)-3-dichloromethylsilylpropyl)benzene, (1,2-bis(acryloxy)-4-dichloromethylsilylpropyl)benzene, (1,2-bis(acryloxy)-3-dichloromethylsilylpropyl)benzene, (acryloxy)-5-dichloromethylsilylpropyl)benzene, (1,3-bis(acryloxy)-2-dichloromethylsilylpropyl)benzene, (1,3-bis(acryloxy)-4-dichloromethylsilylpropyl)benzene, (1,3-bis(acryloxy)-5-dichloromethylsilylpropyl)benzene, (1,4-bis(acryloxy)-2-dichloromethylsilylpropyl)benzene, methacryloxypropylmethyldichlorosilane, methacryloxypentylmethyldichlorosilane, methacryloxyoctylmethyldichlorosilane Chlorosilanes, methacryloxyethoxypropylmethyldichlorosilane, (4-dichloromethylsilylpropyl-2-methoxy)phenyl methacrylate, (2-dichloromethylsilylpropyl-1-acryloxy)phenyl methacrylate, (1,2-bis(methacryloxy)-3-dichloromethylsilylpropyl)benzene, (1,2-bis(methacryloxy)-4-dichloromethylsilylpropyl)benzene, (1,2-bis(methacryloxy)-5-dichloromethylsilylpropyl)benzene, (1,3-bis(methacryloxy)-2- alkyldichlorosilane compounds having a (meth)acryloxy group, such as (1,3-bis(methacryloxy)-4-dichloromethylsilylpropyl)benzene, (1,3-bis(methacryloxy)-5-dichloromethylsilylpropyl)benzene, and (1,4-bis(methacryloxy)-2-dichloromethylsilylpropyl)benzene; acryloxypropyltrichlorosilane, acryloxypentyltrichlorosilane, acryloxyoctyltrichlorosilane, and acryloxyethoxypropylmethyl; BirdChlorosilanes, (4-trichlorosilylpropyl-2-methoxy)phenyl acrylate, (2-trichlorosilylpropyl-1-acryloxy)phenyl acrylate, (1,2-bis(acryloxy)-3-trichlorosilylpropyl)benzene, (1,2-bis(acryloxy)-4-trichlorosilylpropyl)benzene, (1,2-bis(acryloxy)-5-trichlorosilylpropyl)benzene, (1,3-bis(acryloxy)-2-trichlorosilylpropyl)benzene, (1,3-bis(acryloxy)-4-trichlorosilylpropyl)benzene, (1,3-bis(acryloxy)-5-trichlorosilylpropyl)benzene, (1,4-bis(acryloxy)-2-trichlorosilylpropyl)benzene, methacryloxypropyltrichlorosilane, methacryloxypentyltrichlorosilane, methacryloxyoctyltrichlorosilane, methacryloxyethoxypropylmethyl Bird Examples of the compound include trichlorosilane compounds having a (meth)acryloxy group, such as chlorosilane, (4-trichlorosilylpropyl-2-methoxy)phenyl methacrylate, (2-trichlorosilylpropyl-1-acryloxy)phenyl methacrylate, (1,2-bis(methacryloxy)-3-trichlorosilylpropyl)benzene, (1,2-bis(methacryloxy)-4-trichlorosilylpropyl)benzene, (1,2-bis(methacryloxy)-5-trichlorosilylpropyl)benzene, (1,3-bis(methacryloxy)-2-trichlorosilylpropyl)benzene, (1,3-bis(methacryloxy)-4-trichlorosilylpropyl)benzene, (1,3-bis(methacryloxy)-5-trichlorosilylpropyl)benzene, and (1,4-bis(methacryloxy)-2-trichlorosilylpropyl)benzene.

[0034] Among these, acryloxypropyldimethylchlorosilane, acryloxypentyldimethylchlorosilane, acryloxyoctyldimethylchlorosilane, (4-chlorodimethylsilylpropyl-2-methoxy)phenyl acrylate, and (2-chlorodimethylsilylpropyl-1-acryloxy)phenyl acrylate are preferred in terms of the usefulness of the product.

[0035] Furthermore, among the organosilicon compounds having a (meth)acryloxy group included in compound (3), the organosilicon compound having an acryloxy group represented by the following general formula (6) (hereinafter referred to as "compound (6)") has a benzene ring in the molecule, is highly soluble, and is a compound that is expected to be applied to various resin-modifying materials.

[0036] [ka] (In the formula, R 3 , R 4 , X and m have the same meanings as above.)

[0037] In the above general formula (6), R 6 each independently represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms, which may contain a heteroatom, or an acryloxy group. R 6 The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, thexyl, and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl (2-propenyl), 1-propenyl, butenyl, pentenyl, and octenyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl.

[0038] Also, R 6 The monovalent hydrocarbon group may have one or more hetero atoms such as an ether group (-O-) or a thioether group (-S-) present in the molecular chain. Furthermore, R 6In the monovalent hydrocarbon group, some or all of the hydrogen atoms may be substituted with other substituents, and specific examples of the substituents include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, and (iso)propoxy groups; halogen atoms, such as fluorine, chlorine, bromine, and iodine atoms; aryl groups having 6 to 10 carbon atoms, such as phenyl and tolyl groups; and aralkyl groups having 7 to 10 carbon atoms, such as benzyl and phenethyl groups.

[0039] In the above formula (6), R 7 represents a single bond or a divalent hydrocarbon group which may contain O or S and has 1 to 10 carbon atoms, preferably 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms. R 7 The divalent hydrocarbon group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, and decylene; branched alkylene groups such as propylene (methylethylene) and methyltrimethylene; cyclic alkylene groups such as cyclohexylene; alkenylene groups such as propenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene and methylenephenylenemethylene. Among these, linear alkylene groups and aralkylene groups are preferred from the viewpoint of ease of procurement of raw materials.

[0040] R 7 Specific examples of the divalent hydrocarbon group containing O or S include an alkyleneoxyalkylene group, an alkylenethioalkylene group, and the like. 7 Examples of the straight-chain, branched, and cyclic alkylene groups include the same groups as those exemplified above for the straight-chain, branched, and cyclic alkylene groups. The number of acryloxy groups contained in compound (6) is at least 1, preferably 1 to 4, and more preferably 1 or 2. By containing an acryloxy group in compound (6), the acryloxy group can be copolymerized with various radical polymerizable monomers.

[0041] Specific examples of compound (6) include (4-chlorodimethylsilylethyl)phenyl acrylate, (1,2-bis(acryloxy)-4-chlorodimethylsilylethyl)benzene, (1,3-bis(acryloxy)-4-chlorodimethylsilylethyl)benzene, (4-chlorodimethylsilylethyl)phenyl methacrylate, (1,2-bis(methacryloxy)-4-chlorodimethylsilylethyl)benzene, (1,3-bis(methacryloxy)-4-chlorodimethylsilylethyl)benzene, and (4-chlorodimethylsilylpropyl-2- dialkylchlorosilane compounds having a (meth)acryloxy group, such as (4-chlorodimethylsilylpropyl-2-methoxy)phenyl methacrylate, (1,2-bis(methacryloxy)-4-chlorodimethylsilylpropyl)benzene, (1,3-bis(acryloxy)-4-chlorodimethylsilylpropyl)benzene, (4-chlorodimethylsilylpropyl-2-methoxy)phenyl methacrylate, (1,2-bis(methacryloxy)-4-chlorodimethylsilylpropyl)benzene, and (1,3-bis(methacryloxy)-4-chlorodimethylsilylpropyl)benzene; alkyldichlorosilane compounds having a (meth)acryloxy group, such as (1,2-bis(acryloxy)-4-dichloromethylsilylpropyl-2-methoxy)phenyl, (1,2-bis(acryloxy)-4-dichloromethylsilylpropyl)benzene, (1,3-bis(acryloxy)-4-dichloromethylsilylpropyl)benzene, methacrylate (4-dichloromethylsilylpropyl-2-methoxy)phenyl, (1,2-bis(methacryloxy)-4-dichloromethylsilylpropyl)benzene, and (1,3-bis(methacryloxy)-4-dichloromethylsilylpropyl)benzene; and trichlorosilane compounds having a (meth)acryloxy group, such as (4-trichlorosilylpropyl-2-methoxy)phenyl acrylate, (1,2-bis(acryloxy)-4-trichlorosilylpropyl)benzene, (1,3-bis(acryloxy)-4-trichlorosilylpropyl)benzene, (4-trichlorosilylpropyl-2-methoxy)phenyl methacrylate, (1,2-bis(methacryloxy)-4-trichlorosilylpropyl)benzene, and (1,3-bis(methacryloxy)-4-trichlorosilylpropyl)benzene. Among these, (4-chlorodimethylsilylpropyl-2-methoxy)phenyl acrylate and (1,2-bis(acryloxy)-4-chlorodimethylsilylpropyl)benzene are preferred in terms of the usefulness of the product and ease of synthesis.

[0042] To isolate the target compound (3) or compound (6) from the reaction mixture obtained in the above series of reactions, an appropriate purification method can be selected from those commonly used in organic synthesis, such as filtration, distillation, vacuum stripping, various types of chromatography, and treatment with an adsorbent. Among these, purification by distillation is preferred from the viewpoint of achieving high purity of the target product. Furthermore, since compound (3) has a polymerizable (meth)acryloxy group, it is preferable to shorten the thermal history as much as possible. For this reason, it is preferable to reduce the number of theoretical plates of the distillation apparatus, and purification by thin film distillation is preferred. If necessary, the above-mentioned polymerization inhibitor may also be added in the purification step.

[0043] The compound (1) used in the present invention can be obtained by subjecting an unsaturated bond-containing organoxysilane compound represented by the following general formula (4) (hereinafter referred to as "compound (4)") to a hydrosilylation reaction with a hydrohalosilane compound represented by the following general formula (5) (hereinafter referred to as "compound (5)") in the presence of a platinum catalyst.

[0044] [ka] (In the formula, R 1 ~R 3 , X, n, and m have the same meanings as above.)

[0045] Specific examples of compound (4) include allyloxytrimethylsilane, allyloxytriethylsilane, allyloxytert-butyldimethylsilane, allyloxytriisopropylsilane, allyloxydimethylhexylsilane, allyloxydimethyloctylsilane, allyloxydimethyldecylsilane, allyloxydimethyldodecylsilane, allyloxydimethyltetradecylsilane, allyloxydimethylhexadecylsilane, allyloxydimethyloctadecylsilane, allyloxydiphenylmethylsilane, and pentenoxytrimethylsilane. Silane, pentenoxytriethylsilane, pentenoxytert-butyldimethylsilane, pentenoxytriisopropylsilane, octenoxytrimethylsilane, octenoxytriethylsilane, octenoxytert-butyldimethylsilane, octenoxytriisopropylsilane, (4-allyl-2-methoxy-1-trimethylsiloxy)benzene, (2-allyl-1-trimethylsiloxy)benzene, (1,2-bis(trimethylsiloxy)-3-allyl)benzene, (1,2-bis(trimethylsiloxy)- Trialkylsilane compounds having an alkenyl(oxy) group, such as (1,3-bis(trimethylsiloxy)-2-allyl)benzene, (1,3-bis(trimethylsiloxy)-4-allyl)benzene, (1,3-bis(trimethylsiloxy)-5-allyl)benzene, and (1,4-bis(trimethylsiloxy)-2-allyl)benzene; diallyloxydimethylsilane, diallyloxyethylmethylsilane, diallyloxydipropylsilane, diallyloxydibutylsilane, diallyloxyphenylmethylsilane; dialkenyloxydialkylsilane compounds such as silane, diallyloxydiphenylsilane, dipentenoxydimethylsilane, dipentenoxyethylmethylsilane, dipentenoxydipropylsilane, dipentenoxydibutylsilane, dipentenoxyphenylmethylsilane, dipentenoxydiphenylsilane, dioctenoxydimethylsilane, dioctenoxyethylmethylsilane, dioctenoxydipropylsilane, dioctenoxydibutylsilane, dioctenoxyphenylmethylsilane, and dioctenoxydiphenylsilane;Examples of such trialkenyloxyalkylsilane compounds include triallyloxymethylsilane, triallyloxyhexylsilane, triallyloxyoctylsilane, triallyloxyphenylsilane, tripentenoxymethylsilane, tripentenoxyhexylsilane, tripentenoxyoctylsilane, tripentenoxyphenylsilane, trioctenoxymethylsilane, trioctenoxyhexylsilane, trioctenoxyoctylsilane, and trioctenoxyphenylsilane; and tetraalkenyloxysilane compounds such as tetraallyloxysilane, tetrapentenoxysilane, and tetraoctenoxysilane.

[0046] Specific examples of compound (5) include dialkylchlorosilane compounds such as dimethylchlorosilane and diphenylchlorosilane; alkyldichlorosilane compounds such as methyldichlorosilane and phenyldichlorosilane; and trichlorosilane.

[0047] The compounding ratio of compound (4) to compound (5) is not particularly limited, but from the viewpoint of productivity, the amount of compound (5) is preferably 0.8 to 2.0 mol, more preferably 0.8 to 1.5 mol, and even more preferably 0.9 to 1.1 mol per 1 mol of unsaturated bonds contained in compound (4).

[0048] In the hydrosilylation reaction, a platinum compound is used as a catalyst. Specific examples of platinum compounds include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and platinum-activated carbon. The amount of the platinum compound used is not particularly limited, but from the viewpoint of productivity, it is preferably 0.000001 to 0.2 mol, more preferably 0.00001 to 0.1 mol per 1 mol of unsaturated bonds contained in compound (4).

[0049] The reaction temperature in the hydrosilylation reaction is not particularly limited, but is preferably 0 to 200°C, more preferably 20 to 150°C, from the viewpoint of the stability of the product. The reaction time for the hydrosilylation reaction is not particularly limited, but from the viewpoint of the stability of the product, it is preferably 1 to 40 hours, more preferably 1 to 20 hours. The hydrosilylation reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon to prevent deactivation of the catalyst and hydrolysis of compound (4) and compound (5).

[0050] The hydrosilylation reaction can proceed without a solvent, but can also be carried out in the presence of a solvent, such as the same solvents used in the siloxy-(meth)acryloxy exchange reaction. [Example]

[0051] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples and comparative examples, the production rates (area %) of the target product (A), the (meth)acryloxy adduct (B), and the bis-adduct (C) were determined by gas chromatography analysis (hereinafter also referred to as "GC analysis") using the following calculation.

[0052] Object (A): (area value of A) / (area value of A + area value of B + area value of C) x 100 [ka]

[0053] (Meth)acryloxy adduct (B): (area value of B) / (area value of A + area value of B + area value of C) x 100 [ka]

[0054] Bis-adduct (C): (area value of C) / (area value of A + area value of B + area value of C) x 100 [ka]

[0055] [Example 1] Synthesis of 3-acryloxypropyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 266.9 g (1.000 mol) of triethylsiloxypropyldimethylchlorosilane, 0.083 g (0.0010 mol) of zinc oxide, and 0.1 g of 2,6-di-tert-butyl-4-methylphenol (di(tert-butyl)hydroxytoluene (hereinafter also referred to as "BHT")) were charged and heated to 70°C. 91.4 g (1.01 mol) of acrylic acid chloride was added, and the mixture was stirred at the same temperature for 3 hours. GC analysis of the reaction solution confirmed that triethylsiloxypropyldimethylchlorosilane had disappeared and 3-acryloxypropyldimethylchlorosilane had been produced. The production rates of each product are shown in Table 1. The reaction mixture was distilled to obtain 176.9 g of 95% pure 3-acryloxypropyldimethylchlorosilane (yield 86%).

[0056] [Example 2] Synthesis of 8-acryloxyoctyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 129 g (0.384 mol) of triethylsiloxyoctyldimethylchlorosilane, 0.302 g (0.00371 mol) of zinc oxide, and 0.06 g of BHT were charged and heated to 70°C. 35.7 g (0.394 mol) of acrylic acid chloride was added and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed that triethylsiloxyoctyldimethylchlorosilane had disappeared and 8-acryloxyoctyldimethylchlorosilane had formed. The yields of each product are shown in Table 1. The reaction mixture was distilled to obtain 93.8 g of 8-acryloxyoctyldimethylchlorosilane with a purity of 95% (yield: 85%).

[0057] [Example 3] Synthesis of (4-chlorodimethylsilylpropyl-2-methoxy-)phenyl acrylate A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen and charged with 193 g (0.583 mol) of (4-chlorodimethylsilylpropyl-2-methoxy-1-trimethylsiloxy)benzene, 0.048 g (0.00059 mol) of zinc oxide, and 0.09 g of BHT. The mixture was heated to 80°C. 53.9 g (0.596 mol) of acrylic acid chloride was added and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed that (4-chlorodimethylsilylpropyl-2-methoxy-1-trimethylsiloxy)benzene had disappeared and (4-chlorodimethylsilylpropyl-2-methoxy-)phenyl acrylate had been produced. The yields of each product are shown in Table 1. The reaction mixture was distilled to obtain 119 g of (4-chlorodimethylsilylpropyl-2-methoxy-)phenyl acrylate with a purity of 99% or more (yield: 61%). 1 The H-NMR chart is shown in Figure 1.

[0058] [Example 4] Synthesis of (2-chlorodimethylsilylpropyl)phenyl acrylate A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen and charged with 272 g (0.904 mol) of (2-chlorodimethylsilylpropyl-1-trimethylsiloxy)benzene, 0.75 g (0.00922 mol) of zinc oxide, and 0.12 g of BHT, heated to 80°C. 83.0 g (0.922 mol) of acrylic acid chloride was added and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed that (2-chlorodimethylsilylpropyl-1-trimethylsiloxy)benzene had disappeared and (2-chlorodimethylsilylpropyl)phenyl acrylate had been produced. The yields of each product are shown in Table 1. The reaction mixture is distilled to obtain acrylic acid ( 2-Chlorodimethylsilylpropyl 166 g of phenyl was obtained (yield 61%).

[0059] [Example 5] Synthesis of 3-acryloxyethoxypropyldimethylchlorosilane The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was replaced with nitrogen, and 31.0 g (0.0997 mol) of triethylsiloxyethoxypropyldimethylchlorosilane, 0.184 g (0.00226 mol) of zinc oxide, and 0.01 g of BHT were charged and heated to 70°C. 9.5 g (0.105 mol) of acrylic acid chloride was added and stirred at the same temperature for 3 hours. The reaction solution was analyzed by GC to determine the triethylsiloxyethoxypropyldimethylchlorosilane content. Ethoxy It was confirmed that propyldimethylchlorosilane had disappeared and 3-acryloxyethoxypropyldimethylchlorosilane had been produced. The production rates of each product are shown in Table 1.

[0060] [Example 6] Synthesis of 3-acryloxypropyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 130.4 g (1.001 mol) of allyloxytrimethylsilane and 0.975 g (0.0001 mol of platinum atom) of a 2-ethylhexanol solution of chloroplatinic(IV) acid were charged and heated to 80°C. 81.4 g (0.860 mol) of dimethylchlorosilane was added dropwise over 3 hours and stirred at the same temperature for 1 hour. GC analysis of the reaction solution confirmed the formation of trimethylsiloxypropyldimethylchlorosilane. After cooling the reaction mixture to room temperature, 0.814 g (0.0100 mol) of zinc oxide and 0.1 g of BHT were added and the temperature was adjusted to 80°C. 90.5 g (1.00 mol) of acrylic acid chloride was added and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed that trimethylsiloxypropyldimethylchlorosilane had disappeared and 3-acryloxypropyldimethylchlorosilane had been produced. The production rates of each product are shown in Table 1. The reaction mixture was distilled to obtain 133.1 g of 3-acryloxypropyldimethylchlorosilane with a purity of 95% (yield: 64%).

[0061] [Example 7] Synthesis of 3-acryloxypropyldimethylchlorosilane The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was replaced with nitrogen, and 135.6 g (0.7829 mol) of allyloxytriethylsilane and 0.383 g (0.000393 mol as platinum atoms) of a 2-ethylhexanol solution of chloroplatinic (IV) acid were charged and heated to 80°C. 64.2 g (0.679 mol) of dimethylchlorosilane was added dropwise over 3 hours, and the mixture was stirred at the same temperature for 1 hour. The reaction solution was analyzed by GC, and Triethylsiloxypropyldimethylchlorosilane was confirmed to have been produced. After cooling the reaction mixture to room temperature, 1.38 g (0.0170 mol) of zinc oxide and 0.08 g of BHT were added and the temperature was adjusted to 80°C. 72.7 g (0.803 mol) of acrylic acid chloride was added and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed that triethylsiloxypropyldimethylchlorosilane had disappeared and 3-acryloxypropyldimethylchlorosilane had been produced. The production rates of each product are shown in Table 1. The reaction mixture was distilled to obtain 99.0 g of 3-acryloxypropyldimethylchlorosilane with a purity of 95% (yield: 61%).

[0062] [Example 8] Synthesis of 3-acryloxypropyldimethylchlorosilane The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was replaced with nitrogen, and 17.1 g (0.0992 mol) of allyloxy tert-butyldimethylsilane and 0.0914 g (0.00000937 mol as platinum atoms) of a 2-ethylhexanol solution of chloroplatinic (IV) acid were charged and heated to 80°C. 8.6 g (0.091 mol) of dimethylchlorosilane was added dropwise over 3 hours, and the mixture was stirred at the same temperature for 1 hour. The reaction solution was analyzed by GC, and tert-Butyldimethylsiloxypropyldimethylchlorosilane was confirmed to have been produced. After the reaction mixture was cooled to room temperature, 0.0814 g (0.00100 mol) of zinc chloride and 0.01 g of BHT were added, and the temperature was adjusted to 100°C. 9.2 g (0.10 mol) of acrylic acid chloride was added thereto, and the mixture was stirred at the same temperature for 1 hour. The reaction mixture was analyzed by GC, and tert-butyldimethylsiloxypropyldimethylchlorosilane was detected. NgaIt was confirmed that the product had disappeared and that 3-acryloxypropyldimethylchlorosilane had been produced. The production rates of each product are shown in Table 1.

[0063] [Example 9] Synthesis of 3-acryloxypropyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 17.2 g (0.100 mol) of diallyloxydimethylsilane and 0.082 g (0.000084 mol of platinum atoms) of a 2-ethylhexanol solution of chloroplatinic(IV) acid were charged and heated to 60°C. 17.0 g (0.18 mol) of dimethylchlorosilane was added dropwise over 3 hours and stirred at the same temperature for 1 hour. GC analysis of the reaction solution confirmed the formation of bis(chlorodimethylpropoxy)dimethylsilane. After cooling the reaction mixture to room temperature, 0.337 g (0.00414 mol) of zinc oxide and 0.01 g of BHT were added and the temperature was adjusted to 80°C. 18.5 g (0.204 mol) of acrylic acid chloride was added and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed that bis(chlorodimethylpropoxy)dimethylsilane had disappeared and 3-acryloxypropyldimethylchlorosilane had been produced. The production rates of each product are shown in Table 1.

[0064] [Example 10] Synthesis of 5-acryloxypentyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 40.1 g (0.200 mol) of pentenoxytriethylsilane and 0.099 g (0.000010 mol of platinum atom) of a 2-ethylhexanol solution of chloroplatinic(IV) acid were charged and heated to 80°C. 17.2 g (0.181 mol) of dimethylchlorosilane was added dropwise over 3 hours and stirred at the same temperature for 1 hour. GC analysis of the reaction solution confirmed the formation of triethylsiloxypentyldimethylchlorosilane. After cooling the reaction mixture to room temperature, 0.343 g (0.00421 mol) of zinc oxide and 0.02 g of BHT were added and the temperature was adjusted to 80°C. 19.0 g (0.210 mol) of acrylic acid chloride was added and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed that triethylsiloxypentyldimethylchlorosilane had disappeared and 5-acryloxypentyldimethylchlorosilane had been produced. The production rates of each product are shown in Table 1. The reaction mixture was distilled to obtain 32.0 g (yield 68%) of 5-acryloxypentyldimethylchlorosilane with a purity of 98%.

[0065] [Example 11] Synthesis of 3-methacryloxypropyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 266.9 g (1.000 mol) of triethylsiloxypropyldimethylchlorosilane, 0.083 g (0.0010 mol) of zinc oxide, and 0.1 g of BHT were charged and heated to 70°C. 107 g (1.02 mol) of methacrylic acid chloride was added and stirred at the same temperature for 3 hours. GC analysis of the reaction mixture confirmed that triethylsiloxypropyldimethylchlorosilane had disappeared and 3-methacryloxypropyldimethylchlorosilane had been produced. The production yields of each product are shown in Table 1.

[0066] [Example 12] Synthesis of 8-acryloxyoctyltrichlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 209 g (0.554 mol) of triethylsiloxyoctyltrichlorosilane, 0.90 g (0.011 mol) of zinc oxide, and 0.08 g of BHT were charged and heated to 70°C. 51.1 g (0.565 mol) of acrylic acid chloride was added and stirred at the same temperature for 3 hours. GC analysis of the reaction solution confirmed that triethylsiloxyoctyltrichlorosilane had disappeared and 8-acryloxyoctyltrichlorosilane had been produced. The production yields of each product are shown in Table 1.

[0067] [Example 13] Synthesis of 3-acryloxypropyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen and charged with 266.9 g (1.000 mol) of triethylsiloxypropyldimethylchlorosilane, 2.2 g (0.0098 mol) of copper(II) bromide, and 0.1 g of BHT, heated to 70°C. 91.4 g (1.01 mol) of acrylic acid chloride was added and stirred at the same temperature for 3 hours. GC analysis of the reaction mixture confirmed that triethylsiloxypropyldimethylchlorosilane had disappeared and 3-acryloxypropyldimethylchlorosilane had formed. The yields of each product are shown in Table 1.

[0068] [Example 14] Synthesis of 3-acryloxypropyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 631 g (1.711 mol) of allyloxydimethyloctadecylsilane and 0.55 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.000085 mol of platinum atoms) were charged and heated to 60°C. 146 g (1.54 mol) of dimethylchlorosilane was added dropwise over 3 hours and stirred at the same temperature for 1 hour. GC analysis of the reaction solution confirmed the formation of dimethyloctadecylsiloxypropyldimethylchlorosilane. After cooling the reaction mixture to room temperature, 2.79 g (0.0342 mol) of zinc oxide and 0.1 g of BHT were added and the temperature was adjusted to 80°C. 163 g (1.80 mol) of acrylic acid chloride was added and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed that dimethyloctadecylsiloxypropyldimethylchlorosilane had disappeared and 3-acryloxypropyldimethylchlorosilane had been produced. The production rates of each product are shown in Table 1. The reaction mixture was distilled to obtain 197 g of 3-acryloxypropyldimethylchlorosilane with a purity of 98% (yield: 62%).

[0069] [Comparative Example 1] Synthesis of 3-acryloxypropyldimethylchlorosilane A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 224.2 g (2.000 mol) of allyl acrylate, 0.975 g of a 2-ethylhexanol solution of chloroplatinic(IV) acid (0.000100 mol of platinum atoms), and 0.2 g of BHT were charged and heated to 80°C. 208.1 g (2.200 mol) of dimethylchlorosilane was added dropwise over 3 hours and stirred at the same temperature for 1 hour. GC analysis of the reaction mixture confirmed the formation of 3-acryloxypropyldimethylchlorosilane. The yields of each product are shown in Table 1. The reaction mixture was distilled to obtain 3-acryloxypropyldimethylchlorosilane with a purity of 75%, which was then distilled again to obtain 74.4 g of 3-acryloxypropyldimethylchlorosilane with a purity of 97% (yield: 18%).

[0070] [Table 1]

[0071] As shown in Table 1, Examples 1 to 14, which are the production methods of the present invention, can selectively produce the target (meth)acryloxyhalosilane compound (A) without using a self-reactive compound and without producing the (meth)acryloxy adduct (B) or bis-adduct (C). Thus, the production method of the present invention can stably produce the target product with high yield and high purity.

Claims

1. The following general formula (1) 【Chemistry 1】 (In the formula, R 1 represents an unsubstituted linear alkyl group having 1 to 20 carbon atoms, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, or a phenyl group; R 2 represents an unsubstituted linear alkylene group or oxyalkylene group having 1 to 20 carbon atoms, or an unsubstituted or alkoxy-substituted phenylene group having 1 to 3 carbon atoms; R 3 each independently represents a hydrogen atom or a methyl group, R 4 each independently represents an unsubstituted linear alkyl group having 1 to 10 carbon atoms, X represents a chlorine atom or a bromine atom, m represents 0, 1 or 2, and n represents 0, 1, 2 or 3. and a siloxyalkylhalosilane compound represented by the following general formula (2): 【Chemistry 2】 (In the formula, R 5 represents a hydrogen atom or a methyl group, and X has the same meaning as above. in the presence of at least one metal compound selected from the group consisting of zinc, copper, and iron, to undergo a siloxy-(meth)acryloxy exchange reaction, 【Transformation 3】 (In the formula, R 2 ~R 5 , X and m have the same meanings as above. The present invention relates to a method for producing an organosilicon compound having a (meth)acryloxy group, the method comprising the step of obtaining an organosilicon compound having a (meth)acryloxy group represented by the formula:

2. The following general formula (4) 【Chemistry 4】 (In the formula, R 1 ~R 3 and n have the same meaning as above. and an unsaturated bond-containing organoxysilane compound represented by the following general formula (5): H-SiR 4 m X 3-m (5) (In the formula, R 4 , X and m have the same meanings as above.

2. The method for producing an organosilicon compound having a (meth)acryloxy group according to claim 1, further comprising a step of subjecting a hydrohalosilane compound represented by the following formula (1) to a hydrosilylation reaction in the presence of a platinum catalyst to obtain a siloxyalkylhalosilane compound represented by the following formula (1):

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