Method for producing organosilicon compound

Abstract

To provide a method for producing a blocked isocyanate group-containing organic silicon compound that facilitates temperature control, has high safety, and has a low content of by-products.SOLUTION: A method for producing an organic silicon compound represented by formula (1) includes the steps of: (I) reacting a compound represented by formula (2) with a compound represented by formula (3) to give the compound represented by formula (1); (II) feeding the compound represented by formula (2) to a mixture including the compound represented by formula (1), prepared in step (I), and an unreacted compound represented by formula (3), reacting the same with the unreacted compound represented by formula (3), to give the compound represented by formula (1).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an organosilicon compound.

Background Art

[0002] A silane coupling agent has two or more different functional groups in one molecule and acts as an intermediary for connecting organic materials and inorganic materials that are usually difficult to bond. One of the functional groups of the silane coupling agent is a hydrolyzable silyl group, which generates a silanol group in the presence of water, and this silanol group reacts with the hydroxyl group on the surface of the inorganic material to form a chemical bond with the surface of the inorganic material. Further, the other functional groups are organic reaction groups such as vinyl groups, epoxy groups, amino groups, (meth)acrylic groups, and mercapto groups that form chemical bonds with organic materials such as various synthetic resins. Silane coupling agents are widely used as modifiers for organic resins and inorganic resins, adhesion aids, various additives, etc. by utilizing the characteristics of these reaction groups.

[0003] Among the uses of silane coupling agents, organosilicon compounds having blocked isocyanate groups have attracted attention as additives to coating compositions, adhesive compositions, and bonding agent compositions, and as treating agents for fillers such as silica (Patent Documents 1 to 3).

[0004] An organosilicon compound having a blocked isocyanate group can be obtained by the reaction of an organosilicon compound having an isocyanate group with a blocking agent. The organosilicon compound having an isocyanate group is a liquid, and the blocking agent is a solid, resulting in a solid-liquid reaction. In Patent Document 3, an organic silicon compound having an isocyanate group and 3,5-dimethylpyrazole as a blocking agent are reacted together. When the reaction scale becomes large, it is difficult to control the heat generation. When the reaction temperature becomes high, side reactions proceed and there is a problem that the purity decreases. Further, due to the solid-liquid reaction, if stirring is insufficient, there is a risk that solids will remain. Furthermore, when charging solids first, it is difficult to check the temperature in the reaction system. In Patent Document 4, since a solvent is used, it is difficult for stirring to be insufficient, but there is a problem such as a low productivity because a step of removing the solvent after the reaction is required.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a blocked isocyanate group-containing organic silicon compound that is easy to control temperature, has high safety, and has a low by-product content.

Means for Solving the Problems

[0007] As a result of extensive research aimed at solving the above problems, the present inventors have discovered that safety and productivity can be improved when producing blocked isocyanate group-containing organosilicon compounds by first reacting a small amount of an isocyanate group-containing organosilicon compound with a blocking agent and then reacting the remaining isocyanate group-containing organosilicon compound with a blocking agent, or by carrying out the reaction of the isocyanate group-containing organosilicon compound with the blocking agent in the presence of a separately prepared blocked isocyanate group-containing organosilicon compound, and have completed the present invention.

[0008] That is, the present invention is 1. The following formula (1) [ka] (In the formula, R 1 each independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, and X represents -O- or -NR 2 -, Z represents a hydrogen atom or a monovalent organic group, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group capable of forming a ring structure by bonding with Z, and m represents an integer of 1 to 3. A method for producing an organosilicon compound represented by the formula: (I): Formula (2) below [ka] (In the formula, R 1 , L and m are the same as above. and a compound represented by the following formula (3): [ka] (wherein X and Z are the same as above.) to obtain an organosilicon compound represented by formula (1), and (II): To the mixture containing the compound represented by the formula (1) obtained in step (I) and the unreacted compound represented by the formula (3), supply the compound represented by the formula (2), react the compound represented by the formula (2) with the unreacted compound represented by the formula (3), and obtain the organosilicon compound represented by the formula (1). A method for producing an organosilicon compound containing 2. The method for producing an organosilicon compound according to claim 1, wherein in the step (II), the mixture containing the compound represented by the formula (1) obtained in the step (I) and the unreacted compound represented by the formula (3) is a solution. 3. The method for producing an organosilicon compound according to claim 1 or 2, wherein in the step (I), the addition amount of the compound represented by the formula (2) is 1 to 80 mol% of the total amount of steps (I) and (II). 4. The following formula (1)

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] According to the production method of the present invention, in the production of a blocked isocyanate group-containing organosilicon compound, even on a large production scale, temperature control is possible, safety is high, and the generation of side reaction products can be suppressed, so that the productivity is high.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be specifically described. 〔First Production Method〕 The first production method of the organosilicon compound represented by the following formula (1) of the present invention includes the following steps (I) and (II). (I): A step of reacting (a part of) the compound represented by the following formula (2) with the compound represented by the following formula (3) to obtain the organosilicon compound represented by the following formula (1). (II): To a mixture containing the compound represented by the following formula (1) obtained in step (I) and the unreacted compound represented by the following formula (3), the compound (the remainder) represented by the following formula (2) is supplied, and the compound represented by this formula (2) is reacted with the unreacted compound represented by the following formula (3) to obtain the organosilicon compound represented by the following formula (1).

[0011]

Chemical Formula

[0012] In formula (1), R 1 each independently represents an alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms; L represents a divalent linking group; X represents -O- or -NR 2 -, Z represents a hydrogen atom or a monovalent organic group, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group capable of bonding with Z to form a ring structure; m represents an integer of 1 to 3, preferably 3;

[0013] R 1 The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl groups. Among these, R 1 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

[0014] Specific examples of the divalent linking group for L include alkylene groups, -O-, -S-, -NR-, -C(=O)-, -C(=O)-O-, -NRCO-, -SO2-, and combinations thereof. Here, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. The alkyl group may be any of the alkyl groups exemplified above, but having 1 to 4 carbon atoms. Among these, the divalent linking group for L is preferably -(CH2) because of the availability of raw materials when producing organosilicon compounds. n - (n is an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 4), or this -(CH2) n Among the -, groups in which one or more methylene units are replaced by -O-, -S-, -NH-, -C(=O)- and -C(=O)-O- are preferred, and -(CH2)3- (trimethylene group) is more preferred.

[0015] In formula (1), X is -O- or -NR 2 -, but it is a group that forms part of the protecting group of the blocked isocyanate silane compound and is not particularly limited because it is eliminated by heating. In -NR 2 - of X, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group capable of combining with Z to form a ring structure. As the alkyl group having 1 to 8 carbon atoms of R 2 , those similar to the groups exemplified above for R 1 can be mentioned. Among them, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. In -NR 2 -, when R 2 represents a group capable of combining with Z to form a ring structure, -NR 2 - preferably forms a heterocyclic structure with X in formula (1). As the heteroatom in such a heterocyclic structure, it is preferable to contain 2 or more nitrogen atoms, and more preferably to contain 2 nitrogen atoms. As the heterocyclic structure, a 5-membered ring or 6-membered ring structure is preferable, and a 5-membered ring structure is more preferable.

[0016] In formula (1), Z is a hydrogen atom or a monovalent organic group, but it is a group that forms part of the protecting group of the blocked isocyanate silane compound and is not particularly limited because it is eliminated by heating. Specific examples of the monovalent organic group of Z may have a substituent and may contain an ether bond or an ester bond (however, excluding those containing O at the bonding end with an oxygen atom and generating an -O-O- bond), a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group (however, excluding the case where X is -O-), -N=R 5 (R 5 represents an alkylidene group having 1 to 10 carbon atoms which may be substituted with an aryl group or a heteroaryl group having 6 to 20 carbon atoms.) and the like can be mentioned. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include linear, branched, and cyclic groups, and examples thereof include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Specific examples of the alkyl group include those exemplified by R 1 In addition to the groups exemplified above, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-icosyl groups and the like can be mentioned. Specific examples of the aryl group include phenyl, naphthyl groups and the like. Specific examples of the aralkyl group include benzyl, phenylethyl groups and the like. In addition, at least a part of the hydrogen atoms of these groups may be substituted with other substituents, and examples of the other substituents include a carboxyl group, a hydroxyl group, an oxo group (=O), a thioxo group (=S) and the like. In the above formula -N=R 5 wherein R 5 The alkylidene group having 1 to 10 carbon atoms which may be substituted with an aryl group or a heteroaryl group having 6 to 20 carbon atoms may be linear, branched, or cyclic. Specific examples thereof include methylidene, ethylidene, propylidene, propane-2-ylidene, butylidene, butane-2-ylidene, pentylidene, 4-methylpentane-2-ylidene, hexylidene, cyclohexylidene, heptylidene, octylidene, nonylidene, decylidene groups and the like. Specific examples of the aryl group having 6 to 20 carbon atoms include the same groups as those exemplified for the monovalent hydrocarbon group above. Specific examples of the heteroaryl group having 6 to 20 carbon atoms include pyrrol-1-yl, 1H-pyrrol-2-yl, imidazol-1-yl, imidazol-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyridin-2-yl, pyridin-3-yl groups and the like. Specific examples of the substituted alkylidene group include phenylmethylene, diphenylmethylene groups and the like.

[0017] The organosilicon compound represented by the above formula (1) is particularly preferably the one represented by the following formula (4).

[0018] [Chemical formula] (In the formula, R 1 , R 2 , Z and m are the same as those described above.)

[0019] R 2 and Z are the same as those described above. Among them, it is preferable that they are bonded to each other to form a ring structure together with the nitrogen atom to which R 2 and Z are bonded. Specific examples of the ring structure include an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, and a 1,2,4-triazole ring, with the pyrazole ring being more preferable. Note that the above ring structure may have a substituent such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a carboxyl group, a hydroxyl group, an ester group, an oxo group (=O), a halogen group such as chlorine or bromine, or a nitro group. Preferable ring structures include the following, but are not limited thereto.

[0020] [Chemical formula] (In the formula, the wavy line represents the bonding position.)

[0021] Preferable specific examples of the organosilicon compound represented by formula (1) include the following, but are not limited thereto.

[0022] [Chemical formula] (In the formula, Me represents a methyl group and Et represents an ethyl group.)

[0023] Specific examples of the organosilicon compound represented by the formula (2) used in the production method of the present invention include, for example, 1-isocyanatomethyltrimethoxysilane, 1-isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 6-isocyanatohexyltrimethoxysilane, 6-isocyanatohexyltriethoxysilane, 8-isocyanatooctyltrimethoxysilane, 8-isocyanatooctyltriethoxysilane, and the like.

[0024] Specific examples of the compound represented by formula (3) include, for example, oxime compounds such as acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc.; phenolic compounds such as phenol, para-tert-butylphenol, cresol, etc.; alcohol compounds such as n-butanol, 2-ethylhexanol, phenyl carbinol, methyl phenyl carbinol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, methoxymethanol, etc.; lactam compounds such as ε-caprolactam, γ-butyrolactam, etc.; pyrrole compounds such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.; indole compounds such as indole, N-methylindole, 2-methylindole, etc., pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-benzyl-3,5-dimethylpyrazole, methyl-5-methylpyrazole-3-carboxylate, 3-methyl-5-phenylpyrazole, 3,5-dimethylpyrazole-4-carboxyanilide and other pyrazole compounds; acid amide compounds such as acetanilide, acetanisidide, acetotoluidide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide, benzamide, etc.; imide compounds such as succinimide, phthalimide, maleimide, etc.; amine compounds such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, butylphenylamine, etc.; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, benzimidazole, etc.; triazole compounds such as 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole, etc.; piperidine compounds such as piperidine, N-methylpiperidine, 4-methylpiperidine, etc.;Urea compounds such as urea, thiourea, ethylene urea, ethylene thiourea, diphenyl urea; carbamate compounds such as phenyl N-phenylcarbamate; imine compounds such as ethyleneimine and propyleneimine, etc. can be mentioned.; In addition to the above compounds, active methylene compounds such as dimethyl malonate, diethyl malonate, diisopropyl malonate, ethyl acetoacetate, isopropyl acetoacetate, methyl acetoacetate, isopropyl acetoacetate, acetylacetone, etc.; mercaptan compounds such as n-butyl mercaptan, tert-butyl mercaptan, n-hexyl mercaptan, tert-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, ethylthiophenol, etc.; sulfite compounds such as sodium bisulfite and potassium bisulfite can also be used.; These may be used alone or in combination of two or more. Among these, as the compound represented by formula (3), lactam compounds, pyrazole compounds, pyrrole compounds, indole compounds, imidazole compounds, triazole compounds, and piperidine compounds are preferred, and the following compounds are more preferred.;

[0025]

Chemical formula

[0026] The first production method of the organosilicon compound of the present invention is different from the method of reacting the compound represented by the above formula (2) (isocyanate group-containing organosilicon compound) and the compound represented by the above formula (3) (blocking agent) at once. After performing step (I) of producing an organosilicon compound represented by formula (1) (blocked isocyanate group-containing organosilicon compound) by reacting a part of the compound represented by formula (2) with the compound represented by formula (3), a mixture (preferably a solution) containing the compound represented by formula (1) obtained and the unreacted compound represented by formula (3) is further supplied with the compound represented by formula (2), and this is reacted with the unreacted compound represented by formula (3) to perform step (II) of producing an organosilicon compound represented by formula (1). If necessary, a method having two or more steps of further supplying the compound represented by formula (2) and reacting it with the unreacted compound represented by formula (3) is provided. In the present invention, it is preferable to perform the reaction in two steps of step (I) and step (II).

[0027] [1] First step Step (I) is a step of reacting an isocyanate group-containing organosilicon compound represented by the above formula (2) with a blocking agent represented by the above formula (3) to obtain a blocked isocyanate group-containing organic compound represented by the above formula (1). In the reaction between the isocyanate group-containing organosilicon compound represented by formula (2) and the blocking agent represented by formula (3), since the solid blocking agent represented by formula (3) hardly dissolves in the isocyanate group-containing organosilicon compound represented by formula (2), it is difficult to control the heat generated by this exothermic reaction. Therefore, in this step, a reaction between a part of the isocyanate group-containing organosilicon compound represented by formula (2) and the blocking agent represented by formula (3) is performed in advance to generate a blocked isocyanate group-containing organosilicon compound represented by formula (1), so that the compound represented by formula (1) acts as a compatibilizing agent, dissolves the blocking agent represented by formula (3), and the temperature in the reaction system can be easily controlled in step (II).

[0028] In step (I), the method of mixing the isocyanate group-containing organosilicon compound represented by formula (2) and the blocking agent represented by formula (3) is not particularly limited. However, in the air or an inert gas atmosphere such as nitrogen or argon, while stirring the liquid isocyanate group-containing organosilicon compound represented by formula (2), it is preferable to add the solid blocking agent represented by formula (3). By such a method, since the reaction can be carried out while measuring the temperature of the reaction system, higher safety can be ensured. In this case, from the viewpoints of improving productivity and suppressing side reactions, the time required for supplying the blocking agent represented by the above formula (3) is preferably 0.5 to 30 hours, more preferably 0.5 to 10 hours, and even more preferably 0.5 to 5 hours.

[0029] From the viewpoints of improving productivity and suppressing side reactions, the reaction temperature in step (I) is preferably 0 to 150 °C, more preferably 20 to 130 °C, and even more preferably 30 to 90 °C.

[0030] In the first production method of the present invention, the usage ratio of the isocyanate group-containing organosilicon compound represented by the above formula (2) and the blocking agent represented by the above formula (3) is, as the total amount of all steps, 0.7 to 1.3 moles of the compound represented by the above formula (3) per 1 mole of the isocyanate group-containing organosilicon compound represented by the above formula (2) is preferable, and 0.8 to 1.2 moles is even more preferable.

[0031] In step (I), the usage amount of the isocyanate group-containing organosilicon compound represented by the above formula (2) is preferably 1 to 80 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 45 mol% of the total amount of all steps, particularly the total amount of steps (I) and (II). Within such a range, the heat generated by the reaction in step (I) will not become excessive, and the temperature in the reaction system can be easily controlled in step (II).

[0032] In step (I), an organic solvent can be used as necessary, but it is preferable to carry out the reaction without a solvent. If there is no solvent, there is no need for a step of removing the organic solvent, so productivity can be further enhanced.

[0033] [2] Second step Step (II) is a step of supplying the remaining isocyanate group-containing organosilicon compound represented by the above formula (2) to a mixture containing the blocked isocyanate group-containing organic compound represented by the above formula (1) obtained in step (I) and the unreacted blocking agent represented by the above formula (3), and reacting this with the blocking agent represented by the above formula (3). Step (II) is preferably carried out after 50 mol% or more of the reaction has proceeded among the isocyanate group-containing organosilicon compounds represented by the above formula (2) used in step (I), and more preferably after 80 mol% or more of the reaction has proceeded, step (II) is carried out. Also, after step (I), the mixture may be taken out from the reaction vessel and transferred to another vessel, and step (II) may be carried out, but it is preferable to continuously carry out step (II) in the same reaction vessel after step (I).

[0034] The method for supplying the isocyanate group-containing organosilicon compound represented by the formula (2) is not particularly limited, but from the viewpoint of temperature control, a method of continuously supplying at a constant rate by in-liquid insertion, dropping, etc., or a method of adding in multiple portions is preferable.

[0035] Also, in step (II), from the viewpoints of improving productivity and suppressing side reactions, the time required for supplying the isocyanate group-containing organosilicon compound represented by the above formula (2) is preferably 1 to 30 hours, more preferably 1 to 10 hours, and even more preferably 2 to 5 hours. The reaction temperature of step (II) is preferably 0 to 150°C, more preferably 20 to 130°C, and even more preferably 30 to 90°C from the viewpoints of improving productivity and suppressing side reactions, similar to the above step (I).

[0036] In step (II), an organic solvent can be used if necessary, but it is preferable to carry out the reaction without a solvent. If there is no solvent, since there is no need for a step of removing the organic solvent, productivity can be further enhanced.

[0037] 〔Second production method〕 Moreover, the method for producing the organosilicon compound represented by the above formula (1) of the present invention may be one in which the isocyanate group-containing organosilicon compound represented by the above formula (2) and the blocking agent represented by the above formula (3) are reacted in the presence of the organosilicon compound represented by the above formula (1) prepared separately. The above reaction is carried out, for example, by adding the organosilicon compound represented by formula (1) prepared separately to the reaction system when reacting the compound represented by formula (2) and the blocking agent represented by formula (3) in the air or in an inert gas atmosphere such as nitrogen or argon (reacting the above respective compounds in the presence of a blocked isocyanate group-containing organic compound). Since the compound represented by formula (1) acts as a compatibilizer to dissolve the blocking agent represented by formula (3) and the liquid compound represented by formula (1) is added, temperature control is easy and temperature control during the reaction can be easily carried out. The above reaction is preferably carried out by a method of mixing a solution in which the blocking agent represented by formula (3) is dissolved in the organosilicon compound represented by formula (1) and the compound represented by formula (2).

[0038] As the organosilicon compound represented by the above formula (1) to be added, the same as the target organosilicon compound is preferable, and one prepared in advance from the isocyanate group-containing organosilicon compound represented by the above formula (2) and the blocking agent represented by the above formula (3) may be used, or a commercially available product may be used. The addition amount is not particularly limited, but is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total amount of the reaction raw materials.

[0039] In the second production method of the present invention, the usage ratio of the isocyanate group-containing organosilicon compound represented by the above formula (2) and the blocking agent represented by the above formula (3) is the same as that in the first production method. From the viewpoints of improving productivity and suppressing side reactions, the reaction temperature is preferably 0 to 150°C, more preferably 20 to 130°C, and even more preferably 30 to 90°C.

[0040] The organosilicon compound represented by the above formula (1) is preferably present in the reaction system from the start of the reaction between the isocyanate group-containing organosilicon compound represented by the above formula (2) and the blocking agent represented by the above formula (3). In particular, after mixing the blocking agent represented by the formula (3) and the organosilicon compound represented by the formula (1), it is preferable to add the isocyanate group-containing organosilicon compound represented by the formula (2) and carry out the reaction. At this time, as the method of adding the isocyanate group-containing organosilicon compound represented by the formula (2), a method of continuously supplying it at a constant rate by dropping or the like is preferable. From the viewpoints of improving productivity and suppressing side reactions, the time required for supplying the isocyanate group-containing organosilicon compound represented by the above formula (2) is preferably 1 to 30 hours, more preferably 1 to 10 hours, and even more preferably 2 to 5 hours.

[0041] In the above production method, an organic solvent can be used as necessary, but it is preferable to carry out the reaction without a solvent. If there is no solvent, a step of removing the organic solvent is not required, so productivity can be further increased.

Examples

[0042] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The content of each organosilicon compound is the value of the area percentage determined by gel permeation chromatography (GPC) measurement. The viscosity is the value at 25°C measured using a rotational viscometer. The GPC measurement conditions are as follows. Apparatus: HLC-8220 GPC (manufactured by Tosoh Corporation) Column: TSKgel GMHXL-L (manufactured by Tosoh Corporation) TSKgel SuperH4000 (manufactured by Tosoh Corporation) TSKgel SuperH2000 (manufactured by Tosoh Corporation) Solvent: THF Flow rate: 0.6 ml / min In the following examples, Me represents a methyl group and Et represents an ethyl group.

[0043] [Example 1] 2474 g (10 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 12000 mL pressurized reaction vessel purged with nitrogen, and while stirring, 2463 g (30 mol) of 2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added over 1 hour while controlling the internal temperature to be 30 to 60°C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. The 2-methylimidazole dissolved and the system became homogeneous. Thereafter, 4948 g (20 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was added over 3 hours while controlling the internal temperature to be 30 to 60°C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. As a result of GPC analysis, the content of the organosilicon compound represented by the following formula (5) was 99.7%, and the content of the side reaction product represented by the following formula (6) was 0.0%.

[0044] [Chemical formula]

[0045] [Example 2] Into a nitrogen-substituted 12000 mL pressure reaction vessel, 2474 g (10 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed, and while stirring, 3543 g (30 mol) of benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added over 1 hour while controlling the internal temperature to be 30 to 60 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. Benzimidazole dissolved and the system became homogeneous. Thereafter, further, 4948 g (20 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was added over 3 hours while controlling the internal temperature to be 30 to 60 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. As a result of GPC analysis, the content of the organosilicon compound represented by the following formula (7) was 99.7%, and the content of the by-product represented by the following formula (6) was 0.0%.

[0046] [Chemical formula]

[0047] [Example 3] Into a nitrogen-substituted 12000 mL pressure reaction vessel, 2474 g (10 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed, and while stirring, 2884 g (30 mol) of 3,5-dimethylpyrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added over 1 hour while controlling the internal temperature to be 30 to 60 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. 3,5-Dimethylpyrazole dissolved and the system became homogeneous. Thereafter, further, 4948 g (20 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was added over 3 hours while controlling the internal temperature to be 30 to 60 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. As a result of GPC analysis, the content of the organosilicon compound represented by the following formula (8) was 99.8%, and the content of the side reaction product represented by the following formula (6) was 0.0%.

[0048]

Chemical formula

[0049] [Example 4] Into a 12000 mL pressure reaction vessel purged with nitrogen, 2474 g (10 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged, and while stirring, 3574 g (30 mol) of benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added over 1 hour while controlling the internal temperature to be 30 to 60 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. Benzotriazole dissolved and the system became homogeneous. Thereafter, further, 4948 g (20 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was added over 3 hours while controlling the internal temperature to be 30 to 60 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. As a result of GPC analysis, the content of the organosilicon compound represented by the following formula (9) was 99.8%, and the content of the side reaction product represented by the following formula (6) was 0.0%.

[0050]

Chemical formula

[0051] [Example 5] Into a 12000 mL pressure reaction vessel purged with nitrogen, 2474 g (10 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed, and while stirring, 3395 g (30 mol) of caprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.) was added over 1 hour while controlling the internal temperature to be 70 to 90 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. The caprolactam dissolved and the system became homogeneous. Thereafter, further, 4948 g (20 mol) of 3-isocyanatopropyltriethoxysilane (KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd.) was added over 3 hours while controlling the internal temperature to be 70 to 90 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. As a result of GPC analysis, the content of the organosilicon compound represented by the following formula (10) was 99.8%, and the content of the side reaction product represented by the following formula (6) was 0.0%.

[0052] [Chemical formula]

[0053] [Example 6] Into a 12000 mL pressure reaction vessel purged with nitrogen, 2053 g (10 mol) of 3-isocyanatopropyltrimethoxysilane (KBM-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed, and while stirring, 2463 g (30 mol) of 2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added over 1 hour while controlling the internal temperature to be 30 to 60 °C. The 2-methylimidazole dissolved and the system became homogeneous. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. Thereafter, further, 4106 g (20 mol) of 3-isocyanatopropyltrimethoxysilane (KBM-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) was added over 3 hours while controlling the internal temperature to be 30 to 60 °C. Thereafter, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. As a result of GPC analysis, the content of the organosilicon compound represented by the following formula (11) was 99.7%, and the content of the side reaction product represented by the following formula (12) was 0.0%.

[0054] [Chemical formula]

[0055] [Example 7] Into a 12000 mL pressure reaction vessel purged with nitrogen, 2874 g of the product obtained in Example 6 above and 1642 g (20 mol) of 2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed, and after stirring to dissolve 2-methylimidazole, 4106 g (20 mol) of 3-isocyanatopropyltrimethoxysilane (KBM-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) was added over 3 hours while controlling the internal temperature to 30 - 60°C. Then, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. As a result of GPC analysis, the content of the organosilicon compound represented by the following formula (11) was 99.7%, and the content of the side reaction product represented by the following formula (12) was 0.0%.

[0056] [Chemical formula]

[0057] [Comparative Example 1] Into a 12000 mL pressure reaction vessel purged with nitrogen, 2463 g (30 mol) of 2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed, and while stirring the suspension, 4516 g (30 mol) of 3-isocyanatopropyltrimethoxysilane (KBM-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour. The internal temperature was 30 - 140°C. Then, stirring was carried out for 1 hour, and disappearance of the isocyanate group was confirmed by IR measurement. As a result of GPC analysis, the content of the organosilicon compound represented by the following formula (11) was 97.5%, and the content of the side reaction product represented by the following formula (12) was 1.2%.

[0058] [Chemical formula]

[0059] In the production methods of the above Examples 1 to 7, it is possible to easily control the temperature and obtain a high-purity product. On the other hand, in the production method of Comparative Example 1, since temperature control is difficult, the reaction system becomes high temperature, and a decrease in purity due to by-products was observed.

Claims

1. A method for producing an organosilicon compound represented by the following formula (1), 【Chemical 1】 (In the formula, R 1 each independently represents an alkyl group having 1 to 8 carbon atoms; L represents a divalent linking group; X represents —O— or —NR 2 -, Z represents a monovalent organic group, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group capable of forming a ring structure by bonding with Z, and m represents an integer of 1 to 3. comprising: (I): reacting a compound represented by the following formula (2) [Chemical 2] (wherein R 1 , L and m are the same as defined above.) with a compound represented by the following formula (3) 【Chemical Formula 3】 (wherein Z represents a monovalent organic group and X is the same as defined above) to obtain the organosilicon compound represented by the formula (1); and (II): supplying the compound represented by the formula (2) to a mixture containing the compound represented by the formula (1) obtained in step (I) and the unreacted compound represented by the formula (3), and reacting the compound represented by the formula (2) with the unreacted compound represented by the formula (3) to obtain the organosilicon compound represented by the formula (1). The method for producing an organosilicon compound according to claim 1, wherein in step (I), the addition amount of the compound represented by the formula (2) is 1 to 80 mol% of the total amount of steps (I) and (II).

2. The method for producing an organosilicon compound according to claim 1, wherein in step (II), the mixture containing the compound represented by the formula (1) obtained in step (I) and the unreacted compound represented by the formula (3) is a solution.

3. 【Chemical Formula 4】 (In the formula, R 1 each independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, X represents -O- or -NR 2 -, Z represents a monovalent organic group, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a group capable of combining with Z to form a ring structure, and m represents an integer of 1 to 3.) A method for producing an organosilicon compound represented by the following formula (1), comprising reacting a compound represented by the following formula (2) 【Chemical Formula 5】 (wherein R 1 , L and m are the same as defined above.) with a compound represented by the following formula (3) [Chemical Formula 6] (wherein Z represents a monovalent organic group and X is the same as defined above) in the presence of a separately prepared organosilicon compound represented by the formula (1).

4. The method for producing an organosilicon compound according to claim 3, wherein the reaction is carried out by mixing a solution in which the compound represented by the formula (3) is dissolved in a separately prepared organosilicon compound represented by the formula (1) with the compound represented by the formula (2).

5. wherein L is a trimethylene group and X is -NR 2 -(R 2 is the same as defined above). The method for producing an organosilicon compound according to any one of claims 1 to 4

Images