TWI680980B - Sulfur-containing amine-based organic oxysilane compound and manufacturing method thereof - Google Patents

Abstract

The purpose of the present invention is to provide a sulfur-containing amine-based organic oxygen The silane compound and its manufacturing method can fully exert the effects of the amine group and the organic oxysilane group when used as a paint additive, etc., and can be set as a one-component hardenable composition.

(式中，R¹，R²係氫原子或可含有雜原子的取代或非取代之1價烴基，各自可相同或相異，但R¹及R²並非同時為氫原子。另外，R¹與R²係亦可相互鍵結而與此等所鍵結的氮原子一起形成環。R³係亦可含有雜原子的直鏈狀或分支狀之2價烴基，R⁴係直鏈狀或分支狀之2價烴基，R⁵、R⁶係1價烴基，n為0、1或2)。 Sulfur-containing amine organooxysilane compound represented by the following general formula (I)

(In the formula, R ¹ and R ² are hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups which may contain hetero atoms, and each may be the same or different, but R ¹ and R ^{2 are} not both hydrogen atoms. In addition, R ¹ It can also be bonded to R ² system to form a ring together with the nitrogen atoms to which they are bonded. R ³ system can also contain a linear or branched divalent hydrocarbon group containing a heteroatom, R ⁴ system can be linear or Branched divalent hydrocarbon group, R ⁵ and R ⁶ are monovalent hydrocarbon groups, and n is 0, 1 or 2).

Description

Sulfur-containing amine-based organic oxysilane compound and manufacturing method thereof

The present invention relates to a sulfur-containing amine-based organic oxysilane compound useful as a silane coupling agent, surface treatment agent, resin additive, paint additive, adhesive, etc., and a method for manufacturing the same.

Aminoalkoxysilane compounds have amine groups with polar functional groups and hydrolyzable alkoxysilane groups, so they are useful as silane coupling agents, surface treatment agents, resin additives, paint additives, adhesives, etc. Use case. As a specific example of such an aminoalkoxysilane compound, 3-aminopropyltrimethoxysilane or 3-ethylenediaminopropyltrimethoxysilane, etc., especially sulfur-containing amine organic oxygen Specific examples of the silane compound include 1-amino-4-thio-heptyltrimethoxysilane (Patent Document 1: International Publication No. 2009/056778).

[Prior Technical Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2009/056778

However, the above-mentioned sulfur-containing amine-based organooxysilane compound has a first-level amine group, and when added to a resin containing a specific functional group, especially when added to an epoxy resin or a carbonate resin, it may not perform as expected. Possibility of effect. For example, when added to an epoxy resin, the epoxy group undergoes ring-opening polymerization through an amine group, and the resin may be hardened. In addition, when added to a carbonate resin, the amine group of the sulfur-containing amine group organic oxysilane compound is converted to an amide group, and the effect of the amine group may not be fully exerted. Therefore, it is desirable to have amine-based organooxysilane compounds that are stable to various functional groups (which can be used in one-component hardenable compositions).

The present invention is made in view of the above circumstances, and its object is to provide a sulfur-containing amine-based organooxysilane compound and a method for producing the same, which can fully utilize amine groups and alkoxy groups when used as paint additives, adhesives, etc. The effect of organic oxysilyl groups such as silane groups can also be set as a one-component hardening composition.

In order to achieve the above object, the present inventors have repeatedly devoted themselves to the results of research, and found that the sulfur-containing amino-organooxysilane compound represented by the general formula (1) has a higher degree of freedom than the previous amino-alkoxy group Silane compounds are higher, so they are used as paint additives or adhesives In addition, the effects of organic oxysilyl groups such as amine groups and alkoxysilyl groups can be fully exerted, and it can be set as a one-component composition, thereby completing the present invention.

Therefore, the present invention provides a sulfur-containing amine-based organic oxysilane compound shown below and a method for producing the same.

[1] A sulfur-containing amine organic oxysilane compound, which is represented by the following general formula (1)

(In the formula, R ¹ and R ² are hydrogen atoms or C 1-20 substituted or unsubstituted monovalent hydrocarbon groups which may contain hetero atoms, and each may be the same or different, but R ¹ and R ^{2 are} not both hydrogen. Atoms. In addition, R ¹ and R ² can also be bonded to each other to form a ring with these bonded nitrogen atoms. R ³ can contain a hetero atom of 1 to 20 linear or branched carbon 2 The valent hydrocarbon group, R ⁴ is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ and R ⁶ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and n is 0, 1 or 2).

[2] The sulfur-containing amine organooxysilane compound as described in [1], wherein the aforementioned R ³ is represented by [-CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -] or [-CH ₂ CH ₂ OCH ₂ CH(CH ₃ )-].

[3] A method for producing a sulfur-containing amine-based organooxysilane compound represented by the following general formula (1'), characterized in that the amine-based compound represented by the following general formula (2)

(In the formula, R ¹ and R ² are hydrogen atoms or C 1-20 substituted or unsubstituted monovalent hydrocarbon groups which may contain hetero atoms, and each may be the same or different, but R ¹ and R ^{2 are} not both hydrogen. atoms. Further, R ¹ and R ² may be bonded to each other to form a ring .R ^{3 'may} contain a carbon-based number of heteroatoms linear or branched of 1 to 18 of these are bonded together with a nitrogen atom Bivalent hydrocarbon group, R ⁷ is a hydrogen atom or a methyl group, when R ⁷ is a hydrogen atom, R ^3′ is a divalent hydrocarbon group having 1 to 18 carbon atoms, and when R ⁷ is a methyl group, R ^3′ is a carbon (Number 1~17 of divalent hydrocarbon group)

With the organooxysilane compound containing mercapto group represented by the following general formula (3)

(In the formula, R ⁴ is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ and R ⁶ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and n is 0, 1 or 2)

React

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and n are the same as above, R ^3" is a linear or branched divalent hydrocarbon group of 3 to 20 carbon atoms which may contain hetero atoms ).

[4] The method for producing a sulfur-containing amine-based organic oxysilane compound as described in [3], wherein the obtained sulfur-containing amine-based organic oxysilane compound is R ^3" in the general formula (1') It is a mixture containing those represented by [-CH ₂ CH ₂ CH ₂ -] and those represented by [-CH ₂ CH(CH ₃ )-].

According to the present invention, a sulfur-containing amine-based organic oxysilane compound can be provided, which can exert the effect of amine groups to the previous level when used, and can be set as a one-component hardening composition, which can be used as Silane coupling agent, surface treatment agent, resin additive, paint additive, adhesive, etc. are used.

[Figure 1] 1-Dimethylamino-4-thio-heptyltrimethoxysilane obtained in Example 1 and 1-dimethylamino-2-methyl-3-thio-hexyltrimethoxy ¹ H-NMR spectrum of a mixture of silanes.

[Figure 2] 1-Dimethylamino-4-thio-heptyltrimethoxysilane obtained in Example 1 and 1-dimethylamino-2-methyl-3-thio-hexyltrimethoxy IR spectrum of a mixture of silanes.

[Figure 3] 1-Dimethylamino-4-sulfo-heptylmethyldimethoxysilane and 1-dimethylamino-2-methyl-3-sulfide obtained in Example 2 ¹ H-NMR spectrum of a mixture of hexylmethyldimethoxysilane.

[Figure 4] 1-Dimethylamino-4-thio-heptylmethyldimethoxysilane and 1-dimethylamino-2-methyl-3-sulfide obtained in Example 2 IR spectrum of a mixture of hexylmethyldimethoxysilane.

[Figure 5] 1-Dimethylamino-3- pendant-7-thio-decyltrimethoxysilane and 1-dimethylamino-5-methyl-3 obtained in Example 3 ^-1 H-NMR spectrum of a mixture of pendant-6-sulfur-nonyltrimethoxysilane.

[Figure 6] 1-Dimethylamino-3- pendant-7-thio-decyltrimethoxysilane and 1-dimethylamino-5-methyl-3 obtained in Example 3 -IR spectrum of a mixture of pendant-6-sulfur-nonyltrimethoxysilane.

[Figure 7] 1-Dimethylamino-3-pentoxy-7-thio-decylmethyldimethoxysilane and 1-dimethylamino-5-methyl obtained in Example 4 ¹ H-NMR spectrum of a mixture of phenyl-3-oxo-6-thio-nonylmethyldimethoxysilane.

[Figure 8] The 1-dimethylamino-3-pentoxy-7-thio-decylmethyldimethoxysilane and 1-dimethylamino-5-methyl obtained in Example 4 IR spectrum of the mixture of -3--3-oxo-6-thio-nonylmethyldimethoxysilane.

The sulfur-containing amine organooxysilane compound of the present invention is a compound represented by the following general formula (1).

(In the formula, R ¹ and R ² are hydrogen atoms or C 1-20 substituted or unsubstituted monovalent hydrocarbon groups which may contain hetero atoms, and each may be the same or different, but R ¹ and R ^{2 are} not both hydrogen. In addition, R ¹ and R ² can also be bonded to each other to form a ring with these bonded nitrogen atoms. R ³ can contain heteroatoms with a linear or branched carbon number of 1 to 20 Divalent hydrocarbon group, R ⁴ is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ and R ⁶ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and n is 0, 1 or 2).

Here, R ¹ and R ² are hydrogen atoms or heteroatoms which may contain oxygen atoms, nitrogen atoms, sulfur atoms, etc. The carbon number is 1-20, especially 1-10 substituted or unsubstituted monovalent hydrocarbon groups, each of which may be The same or different, but R ¹ and R ^{2 are} not simultaneously hydrogen atoms. In addition, R ¹ and R ² systems may be bonded to each other to form a ring together with these bonded nitrogen atoms. Specific examples of R ¹ and R ² include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups, isopropyl groups, and isopropyl groups. Branched alkyl such as butyl, second butyl, third butyl, third hexyl, 2-ethylhexyl, cyclic alkyl such as cyclopentyl, cyclohexyl, vinyl, allyl, propylene Alkenyl groups such as aryl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, phenethyl groups, etc. Especially in terms of ease of raising raw materials and usefulness of products, methyl and ethyl groups are ideal . In addition, some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Specific examples of the substituent include alkoxy groups such as methoxy, ethoxy, and (iso)propoxy. ; Fluorine atom, chlorine atom, bromine atom, iodine atom and other halogen atoms; cyano group; amine group; phenyl group, tolyl group, etc. C 6-10 aryl group, benzyl group, phenethyl group, etc. carbon number 7 ~10 aralkyl group, C 2-10 acyl group; each alkyl group and each alkoxy group are C 1~5 trialkyl silane group, trialkoxy silane group, dialkyl mono Alkoxy silane groups, monoalkyl dialkoxy silane groups, etc., between which there are further ester groups (-COO-), ether groups (-O-), thioether groups (-S-), etc., These components may be used in combination.

可例示哌啶基、吡咯啶基、哌嗪基、甲基哌嗪基、嗎啉基等。 In addition, the case where R ¹ and R ² combine to form a ring structure is represented as a group represented by the following formula

Examples include piperidinyl, pyrrolidinyl, piperazinyl, methylpiperazinyl, and morpholinyl.

R ³ is a divalent hydrocarbon group with 1 to 20 carbon atoms which may contain heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms, especially a linear or branched divalent hydrocarbon group with 1 to 10 carbon atoms. Hydrocarbyl groups, specifically, linear alkylene groups such as methylene, ethylidene, propylidene, butylidene, hexamethylene, octylene, decylidene, etc. , Branched alkylene such as methyl propyl, cyclic alkylene such as cyclohexyl, alkenyl such as propenyl, aryl such as phenyl, methyl phenyl, etc. The aralkylene groups such as the methylidene group and the phenylene group are particularly preferred in terms of ease of raising raw materials. In addition, examples of the bivalent hydrocarbon group having 1 to 20 carbon atoms which may contain heteroatoms include [-CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -], [-CH ₂ CH ₂ OCH ₂ CH(CH ₃ ) -] Represents the base etc. In addition, some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Specific examples of the substituent include alkoxy groups such as methoxy, ethoxy, and (iso)propoxy. ; Fluorine atom, chlorine atom, bromine atom, iodine atom and other halogen atoms; cyano group; amine group; phenyl group, tolyl group, etc. C 6-10 aryl group, benzyl group, phenethyl group, etc. carbon number 7 ~10 aralkyl group, C 2-10 acetyl group, each alkyl group, each alkoxy group is C 1-5 trialkyl silane group, trialkoxy silane group, dialkyl mono Alkoxy silane groups, monoalkyl dialkoxy silane groups, etc., furthermore, ester groups (-COO-), ether groups (-O-), thioether groups (-S-), etc. may be present, These components may be used in combination.

R ⁴ is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10, specifically, as exemplified as R ³ (as a divalent hydrocarbon group which may contain a hetero atom) The exceptions are the same.

R ⁵ and R ⁶ have a carbon number of 1 to 10, preferably 1 to 6, and more preferably 1 to 3 monovalent hydrocarbon group, specifically methyl, ethyl, propyl, butyl, pentyl , Linear alkyl groups such as hexyl, heptyl, octyl, decyl, branched alkyl groups such as isopropyl, isobutyl, and tertiary butyl, cyclic alkyl groups such as cyclopentyl, cyclohexyl, etc. Alkenyl groups such as vinyl, allyl, propenyl, aryl groups such as phenyl, tolyl, aralkyl groups such as benzyl, phenethyl, etc., from the point that the target object becomes a lower boiling point compound , Especially methyl and ethyl are ideal.

As a specific example of the sulfur-containing amine organooxysilane compound represented by the above general formula (1), 1-dimethylamino-4-sulfo-heptyltrimethoxysilane, 1-dimethyl Amino-4-thio-heptylmethyldimethoxysilane, 1-dimethylamino-4-thio-heptyldimethylmethoxysilane, 1-dimethylamino-4-sulfide -Heptyltriethoxysilane, 1-dimethylamino-4-thio-heptylmethyldiethoxysilane, 1-dimethylamino-4-thio-heptyldimethylethoxy Silane, 1-dimethylamino-2-methyl-3-sulfo-hexyltrimethoxysilane, 1-dimethylamino-2-methyl-3-sulfo-hexylmethyldimethoxy Silane, 1-dimethylamino-2-methyl-3-sulfo-hexyldimethylmethoxysilane, 1-dimethylamino-2-methyl-3-sulfo-hexyltriethoxy Silane, 1-Dimethylamino-2-methyl-3-thio-hexylmethyl diethoxysilane, 1-dimethylamino-2-methyl-3-thio-hexyldimethylethoxy Silane, 1-diethylamino-4-thio-heptyltrimethoxysilane, 1-diethylamino-4-thio-heptylmethyldimethoxysilane, 1-diethylamino -4-thio-heptyldimethylmethoxysilane, 1-diethylamino-4-thio-heptyltriethoxysilane, 1-diethylamino-4-thio-heptylmethyl Diethoxysilane, 1-diethylamino-4-thio-heptyldimethylethoxysilane, 1-diethylamino-2-methyl-3-thio-hexyltrimethoxy Silane, 1-diethylamino-2-methyl-3-sulfo-hexylmethyldimethoxysilane, 1-diethylamino-2-methyl-3-sulfo-hexyldimethylmethyl Oxysilane, 1-diethylamino-2-methyl-3-sulfo-hexyltriethoxysilane, 1-diethylamino-2-methyl-3-sulfo-hexylmethyldiethyl Oxysilane, 1-diethylamino-2-methyl-3-thio-hexyldimethylethoxysilane, 1-methylpiperazinyl-4-thio-heptyltrimethoxysilane, 1 -Methylpiperazinyl-4-thio-heptylmethyldimethoxysilane, 1-methylpiperazinyl-4-thio-heptyldimethylmethoxysilane, 1-methylpiperazinyl -4-thio-heptyltriethoxysilane, 1-methylpiperazinyl-4-thio-heptylmethyldiethoxysilane, 1-methylpiperazinyl-4-thio-heptyldi Methylethoxysilane, 1-methylpiperazinyl-2-methyl-3-sulfo-hexyltrimethoxysilane, 1-methylpiperazinyl-2-methyl-3-sulfo-hexylmethyl Dimethoxysilane, 1-methylpiperazinyl-2-methyl-3-sulfo-hexyldimethylmethoxysilane, 1-methylpiperazinyl-2-methyl-3-sulfo-hexyl Triethoxysilane, 1-methylpiperazinyl-2-methyl-3-sulfo-hexylmethyl diethoxysilane, 1-methylpiperazinyl-2-methyl-3-sulfo-hexyldimethylethoxy Silane, 1-benzylamino-4-thio-heptyltrimethoxysilane, 1-benzylamino-4-thio-heptylmethyldimethoxysilane, 1-benzylamino -4-thio-heptyldimethylmethoxysilane, 1-benzylamino-4-thio-heptyltriethoxysilane, 1-benzylamino-4-thio-heptylmethyl Diethoxysilane, 1-benzylamino-4-thio-heptyldimethylethoxysilane, 1-benzylamino-2-methyl-3-thio-hexyltrimethoxy Silane, 1-benzylamino-2-methyl-3-sulfo-hexylmethyldimethoxysilane, 1-benzylamino-2-methyl-3-sulfo-hexyldimethylform Oxysilane, 1-Benzylamino-2-methyl-3-sulfo-hexyltriethoxysilane, 1-Benzylamino-2-methyl-3-sulfo-hexylmethyldiethyl Oxysilane, 1-benzylamino-2-methyl-3-sulfo-hexyldimethylethoxysilane, 1-dimethylamino-3- pendant-7-sulfo-decyl Trimethoxysilane, 1-dimethylamino-3- pendant-7-thio-decylmethyldimethoxysilane, 1-dimethylamino-3- pendant-7-sulfur -Decyldimethylmethoxysilane, 1-dimethylamino-3- pendant-7-thio-decyltriethoxysilane, 1-dimethylamino-3- pendant -7-thio-decylmethyldiethoxysilane, 1-dimethylamino-3-pendantoxy-7-thio-decyldimethylethoxysilane, 1-dimethylamino -5-methyl-3-oxo-6-thio-nonyltrimethoxysilane, 1-dimethylamino-5-methyl-3-oxo-6-thio-nonylmethyl Dimethoxysilane, 1-dimethylamino-5-methyl-3- pendant-6-thio-nonyldimethylmethoxysilicone Alkanes, 1-dimethylamino-5-methyl-3-oxo-6-thio-nonyltriethoxysilane, 1-dimethylamino-5-methyl-3-oxo Yl-6-thio-nonylmethyldiethoxysilane, 1-dimethylamino-5-methyl-3- pendant-6-thio-nonyldimethylethoxysilane, 1 -Diethylamino-3-oxo-7-thio-decyltrimethoxysilane, 1-diethylamino-3-oxo-7-thio-decylmethyldimethoxy Silane, 1-diethylamino-3-oxo-7-thio-decyldimethylmethoxysilane, 1-diethylamino-3-oxo-7-sulfo-decyl Triethoxysilane, 1-diethylamino-3-oxo-7-thio-decylmethyl diethoxysilane, 1-diethylamino-3-oxo-7- Sulfur-decyldimethylethoxysilane, 1-diethylamino-5-methyl-3-pentoxy-6-thio-nonyltrimethoxysilane, 1-diethylamino- 5-methyl-3-oxo-6-thio-nonylmethyldimethoxysilane, 1-diethylamino-5-methyl-3-oxo-6-thio-nonyl Dimethylmethoxysilane, 1-diethylamino-5-methyl-3-oxo-6-thio-nonyltriethoxysilane, 1-diethylamino-5-methyl 3-Phenoxy-6-thio-nonylmethyl diethoxysilane, 1-diethylamino-5-methyl-3- pendoxy-6-thio-nonyldimethyl Ethoxysilane etc.

As a method for producing the sulfur-containing amine-based organic oxysilane compound of the present invention, for example, an amine-based compound represented by the following general formula (2) can be exemplified

(In the formula, R ¹ and R ² are hydrogen atoms or C 1-20 substituted or unsubstituted monovalent hydrocarbon groups which may contain hetero atoms, and each may be the same or different, but R ¹ and R ^{2 are} not both hydrogen. atoms. Further, R ¹ and R ² may be bonded to each other to form a ring .R ^{3 'may} contain a carbon-based number of heteroatoms linear or branched of 1 to 18 of these are bonded together with a nitrogen atom Bivalent hydrocarbon group, R ⁷ is a hydrogen atom or a methyl group, when R ⁷ is a hydrogen atom, R ^3′ is a divalent hydrocarbon group having 1 to 18 carbon atoms, and when R ⁷ is a methyl group, R ^3′ is a carbon (Number 1~17 of divalent hydrocarbon group)

The organooxysilane compound containing mercapto group represented by the following general formula (3)

(In the formula, R ⁴ is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ and R ⁶ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and n is 0, 1 or 2)

The method of reaction.

Here, R ³ may contain a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, and the like, having a carbon number of 1 to 18, especially a linear or branched divalent hydrocarbon group of 1 to 8, as a carbon number of 1 to 18. The bivalent hydrocarbon group is specifically a linear alkylene group such as methylene, ethylidene, propylidene, butylidene, hexamethylene, octylene, etc. Branched alkylene such as methyl propyl, cyclic alkylene such as cyclohexyl, alkenyl such as propenyl, aryl such as phenyl, methyl phenyl, etc. The aralkylene group such as methyl phenyl phenyl methyl group is particularly preferred in terms of ease of raising raw materials, and the methylene group is preferred. In addition, examples of the divalent hydrocarbon group having 1 to 18 carbon atoms which may contain a hetero atom include a group represented by [-CH ₂ CH ₂ OCH ₂ -]. In addition, some or all of the hydrogen atoms of the hydrocarbon group of these components may be substituted. Specific examples of the substituent include alkoxy groups such as methoxy, ethoxy, and (iso)propoxy groups. Group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; cyano group; amine group; phenyl group, tolyl group, etc. C 6-10 aryl group, benzyl group, phenethyl group, etc. 7-10 aralkyl groups, etc., in which there are further ester groups (-COO-), ether groups (-O-), thioether groups (-S-), etc., can also be used in combination with these components .

R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n are as described above.

The amino compound represented by the general formula (2), specifically, exemplified dimethylallylamine, diethylallylamine, allylmethylaniline, allylpyrrolidine, allylpiperidine , Allyl piperazine, methallyl piperazine, allyl morpholine and so on.

As the mercapto group-containing organooxysilane compound represented by the general formula (3), specifically, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyldimethylmethyl Oxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyldimethylethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Methyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyl Dimethyl ethoxy silane and so on.

The amine compound represented by the above general formula (2), and The compounding ratio of the mercapto group-containing organic oxysilane compound represented by the general formula (3) is not particularly limited, but from the viewpoint of reactivity and productivity, it is less than the compound 1 represented by the general formula (2). For the ear, it is desirable to set the compound represented by the general formula (3) to 0.1 to 4 moles, particularly 0.2 to 2 moles.

In order to increase the reaction rate of the above reaction, a free radical generator may also be used as a catalyst. As the radical generator used, peroxides such as t-butyl peroxide, di-t-butyl peroxide, benzoyl peroxide, azobisisobutyronitrile, 2,2' can be exemplified. -Azo compounds such as azobis-(2-methylbutyronitrile), etc.

The amount of catalyst used is not particularly limited, but from the viewpoint of reactivity and productivity, it is 0.0001 to 0.2 mol, especially 0.001 to 1 mol of the compound represented by the above general formula (2) The range of 0.1 mole is ideal.

The reaction temperature of the above reaction is not particularly limited, but is preferably 0 to 200°C, especially 20 to 150°C, and the reaction time is not particularly limited, but is preferably 1 to 40 hours, especially 1 to 20 hours. The reaction environment is preferably an inert gas environment such as nitrogen or argon.

Still, the above reaction can be carried out without a solvent, but a solvent can also be used. Examples of the solvent used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene, and ether solvents such as diethyl ether, tetrahydrofuran, and dioxane. , Ethyl acetate, butyl acetate and other ester solvents, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone and other aprotic polar solvents, methylene chloride, chloroform and other chlorine Hydrocarbon Department of solvents. These solvent systems may be used alone or in combination of two or more.

(式中，R¹、R²、R⁴~R⁶及n係與上述相同，R^3"係可含有雜原子的碳數3~20之直鏈狀或分支狀之2價烴基)。 From the above reaction, for example, a sulfur-containing amine-based organooxysilane compound represented by the following general formula (1') can be obtained

(In the formula, R ¹ , R ² , R ⁴ to R ⁶ and n are the same as above, and R ^3" is a linear or branched divalent hydrocarbon group having 3 to 20 carbon atoms which may contain a heteroatom).

R ^3" series may also contain heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms and the like, having a carbon number of 3 to 20, especially a linear or branched divalent hydrocarbon group of 3 to 10, specifically, it can be exemplified by Straight-chain alkylene such as propyl, butylene, hexamethylene, octylene, decylene, etc., branched alkylene such as methylpropylene, combined ethylene, propylene, etc. Straight-chain alkylene groups and cyclic alkylene groups such as cyclohexyl groups, alkenyl groups such as butyl groups, ethylene groups such as ethyl groups, phenylene groups such as methyl groups In particular, the propyl group is preferable in terms of the ease of raising raw materials. In addition, examples of the heteroatom-containing system include [-CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -], [-CH ₂ The group represented by CH ₂ OCH ₂ CH(CH ₃ )-], etc. Furthermore, a part or all of the hydrogen atoms of the hydrocarbon group of these components may be substituted, and specific examples thereof include, for example, a Alkoxy groups such as oxy, ethoxy, (iso) propoxy, etc.; halogen atoms such as fluorine, chlorine, bromine, iodine; cyano; amine; phenyl, tolyl, etc. 6 to 10 aryl groups, benzyl groups, phenethyl groups, etc., having 7 to 10 carbon atoms, 2 to 10 carbon atoms, each alkyl group, and each alkoxy group have 1 to 5 carbon atoms Trialkylsilyl, trialkoxysilyl, dialkylmonoalkoxysilyl or monoalkyldialkoxysilyl, there are further ester groups (-COO-), ether groups (-O-), thioether group (-S-), etc. may be used in combination.

As the sulfur-containing amine-based organooxysilane compound of the present invention obtained by the above reaction, specifically, it can be exemplified as the same as the specific example of the general formula (1), but particularly as In the general formula (1'), R ^3" is a group containing a group represented by [-CH ₂ CH ₂ CH ₂ -] and a group containing a group represented by [-CH ₂ CH(CH ₃ )-] The mixture is obtained, for example, by the following formula (4) [Chem 10] (H ₃ C) ₂ N-CH ₂ CH ₂ CH ₂ -S-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ (4) 1-dimethylamino-4-thio-heptyltrimethoxysilane and the following formula (5) [Chem. 11] (H ₃ C) ₂ N-CH ₂ CH(CH ₃ )-S-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ A mixture of 1-dimethylamino-2-methyl-3-thio-hexyltrimethoxysilane represented by (5); or by the following formula (6) [Chemical 12] 1-dimethylamine represented by (H ₃ C) ₂ N-CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -S-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ (6) 3-Phenoxy-7-thio-decyltrimethoxysilane, and the following formula (7) [Chem. 13] (H ₃ C) ₂ N-CH ₂ CH ₂ OCH ₂ CH(CH ₃ )- S-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ (7) 1-dimethylamino-5-methyl-3-oxo-6-thio-nonyltrimethoxysilane represented by (7) Of mixtures, etc.

In this case, R ^3" of the general formula (1') is represented by [-CH ₂ CH ₂ CH ₂ -], and represented by [-CH ₂ CH(CH ₃ )-] The ratio (mass %) of the base is usually 50:50~95:5, especially 65:35~90:10.

In addition, in the sulfur-containing amine-based organooxysilane compound represented by the general formula (1) of the present invention, R ³ is a hydrocarbon group having a carbon number of 1 or 2, the production method may be, for example, A method in which a thiolate produced by mixing bases such as 3-mercaptopropyltrimethoxysilane and potassium carbonate with dialkylaminoethyl chloride reacts.

[Example]

Hereinafter, the present invention will be specifically described by showing examples, but the present invention is not limited to the following examples.

[Example 1]

In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 78.5g (0.400 mol) of 3-mercaptopropyltrimethoxysilane was filled and heated to 80°C. After stabilization at the internal temperature, a mixture of 42.5 g (0.499 mol) of dimethylallylamine and 3.9 g (0.019 mol) of 2,2′-azobis(2-methylbutyronitrile) was dropped over 2 hours And stirred at 85°C for 1 hour. The reaction solution was distilled to obtain 12.4 g of distillate having a boiling point of 121 to 122° C./0.4 kPa.

The mass spectrum, ¹ H-NMR spectrum and IR spectrum of the obtained distillate were measured.

Mass spectrometry

m/z 204,179,121,91,58

¹ H-NMR spectrum (heavy chloroform solvent)

The first figure is represented by a graph.

IR spectrum

The graph is shown in Figure 2.

From the above results, it was confirmed that the obtained compound was 1-dimethylamino-4-sulfo-heptyltrimethoxysilane 55% by mass and 1-dimethylamino-2-methyl-3-sulfide- 45% by mass of hexyltrimethoxysilane.

[Example 2]

In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 72.0 g (0.400 mol) of 3-mercaptopropylmethyldimethoxysilane was filled, and heated to 80°C. After stabilization at the internal temperature, a mixture of 34.0 g (0.399 mol) of dimethylallylamine and 3.9 g (0.019 mol) of 2,2′-azobis(2-methylbutyronitrile) was dropped in 1 hour And stirred at 85°C for 2 hours. The reaction liquid was distilled to obtain 15.9 g of distillate having a boiling point of 107 to 108° C./0.4 kPa.

The mass spectrum, ¹ H-NMR spectrum and IR spectrum of the obtained distillate were measured.

Mass spectrometry

m/z 188,119,105,75,58

¹ H-NMR spectrum (heavy chloroform solvent)

It is represented by a graph in Figure 3.

IR spectrum

The graph is shown in Figure 4.

From the above results, it was confirmed that the obtained compound was 1-dimethylamino-4-thio-heptylmethyldimethoxysilane 51% by mass and 1-dimethylamino-2-methyl-3 -49% by mass of sulfur-hexylmethyldimethoxysilane.

[Example 3]

In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 56.0 g (0.285 mole) of 3-mercaptopropyltrimethoxysilane was filled, and the temperature was raised to 80°C. After stabilization at internal temperature, 36.6 g (0.283 mol) of dimethylaminoethyl allyl ether and 0.556 g (0.00289 mol) of 2,2'-azobis(2-methylbutyronitrile) The mixture was dropped in 1 hour and stirred at 95°C for 2 hours. The reaction solution was distilled to obtain 70.1 g of distillate with a boiling point of 135 to 140° C./0.4 kPa.

The mass spectrum, ¹ H-NMR spectrum and IR spectrum of the obtained distillate were measured.

Mass spectrometry

m/z 280,162,121,91,58

¹ H-NMR spectrum (heavy chloroform solvent)

The graph is shown in Figure 5.

IR spectrum

The graph is shown in Figure 6.

From the above results, it was confirmed that the obtained compound was 1-dimethylamino-3-pendoxy-7-thio-decyltrimethoxysilane 85% by mass and 1-dimethyl Amino-5-methyl-3- pendant-6-thio-nonyltrimethoxysilane 15% by mass.

[Example 4]

In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 51.8 g (0.287 mol) of 3-mercaptopropylmethyldimethoxysilane was filled and heated to 80°C. After stabilization at internal temperature, 37.2 g (0.288 mol) of dimethylaminoethyl allyl ether and 0.5814 g (0.003022 mol) of 2,2′-azobis(2-methylbutyronitrile) The mixture was dropped in 1 hour and stirred at 95°C for 2 hours. The reaction liquid was distilled to obtain 66.3 g of distillate having a boiling point of 154 to 156° C./0.4 kPa.

The mass spectrum, ¹ H-NMR spectrum and IR spectrum of the obtained distillate were measured.

Mass spectrometry

m/z 264,162,131,105,75,58

¹ H-NMR spectrum (heavy chloroform solvent)

The graph is shown in Figure 7.

IR spectrum

This is shown graphically in Figure 8.

From the above results, it was confirmed that the obtained compound was 1-dimethylamino-3-pendoxy-7-sulfo-decylmethyldimethoxysilane (10-dimethylamino-4-sulfide -8- pendant-decylmethyldimethoxysilane) 88% by mass with 1-dimethylamino-5-methyl-3- pendant-6-thio-nonylmethyl dimethyl 12% by mass of oxysilane.

Claims (4)

A sulfur-containing amine-based organooxysilane compound represented by the following general formula (1)

(In the formula, R ¹ and R ² are unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, each of which may be the same or different; in addition, R ¹ and R ² may also be bonded to each other and bonded to these Nitrogen atoms form a ring together; R ³ is a linear or branched divalent hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms, and R ⁴ is a linear or branched divalent hydrocarbon group with 1 to 20 carbon atoms , R ⁵ and R ⁶ are monovalent hydrocarbon groups with 1 to 10 carbon atoms, and n is 0, 1 or 2). The sulfur-containing amine-based organooxysilane compound according to claim 1, wherein the aforementioned R ³ is represented by [-CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -] or [-CH ₂ CH ₂ OCH ₂ CH(CH ₃ ) -] The base shown. A method for producing a sulfur-containing amine-based organic oxysilane compound represented by the following general formula (1'), characterized in that the amine-based compound represented by the following general formula (2)

(In the formula, R ¹ and R ² are unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, each of which may be the same or different; in addition, R ¹ and R ² may also be bonded to each other and to these. when R ^{3 'may} contain a divalent hydrocarbon-based carbon number of hetero atoms of 1 to 18 linear or branched chain of, R ⁷ a hydrogen atom or a methyl-based, R ⁷ is a hydrogen atom; together with the nitrogen atom form a ring , ^'when the case 1 to 18 carbon atoms of the divalent hydrocarbon group, R ⁷ is methyl, R ^3' R ³ is a 1 to 17 carbon atoms of the divalent hydrocarbon group) represented by containing (3) represented by the following general formula Mercapto-organooxysilane compound

(In the formula, R ⁴ is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ and R ⁶ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and n is 0, 1 or 2). ;

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and n are the same as above, R ^3" is a linear or branched divalent hydrocarbon group of 3 to 20 carbon atoms which may contain hetero atoms ). The method for producing a sulfur-containing amine-based organic oxysilane compound according to claim 3, wherein the obtained sulfur-containing amine-based organic oxysilane compound is represented by R ^3" in the general formula (1') as containing [- CH ₂ CH ₂ CH ₂ -], and a mixture containing a group represented by [-CH ₂ CH(CH ₃ )-].

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