JPH08134083A - Organic silicon compound and its production - Google Patents

Abstract

PURPOSE: To obtain the subject new compound having excellent solubility in water and storage stability in an aqueous solution, useful for a silane coupling agent, etc., by reacting a specific nitrogen-containing heterocyclic ring-containing alkoxysilane with a (meth)acryloyl halide. CONSTITUTION: This new organic silicon compound is expressed by formula I (R1 is a 1-2C monofunctional hydrocarbon; R2 is a 1-10C bifunctional hydrocarbon; R3 and R4 are each a 2-3C bifunctional hydrocarbon; R5 is H or methyl; (m) is an integer of 1-3) and has excellent solubility in water, exceedingly good storage stability in an aqueous solution and is useful as a silane coupling agent, etc. The compound is obtained by reacting an alkoxysilane expressed by formula II containing a nitrogen-containing heterocyclic ring such as piperazine with a (meth)acryloyl halide expressed by formula III (X is a halogen) (e.g.; methacrylic acid chloride) in the presence of a base such as triethylamine and a polymerization inhibitor such as p-methoxyphenol at <=60 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel organosilicon compound and a method for producing the same. More specifically, it relates to a novel silane coupling agent having excellent water solubility and extremely good stability in an aqueous solution, and a method for producing the same.

[0002]

2. Description of the Related Art As an organic functional group, acryloyl group or methacryloyl group (methacyl) which is a polymerizable group.
A silane coupling agent containing ryloyl) is widely used as a binder at the interface between the polymerizable group and the vinyl-based organic resin because the silane coupling agent makes a strong bond with the inorganic material.

As such an acryloyl group- or (meth) acryloyl group-containing alkoxysilane compound, γ
-Acryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc. are known. .

However, these compounds have a problem that they are poorly soluble in water and turbidity occurs in the aqueous solution in a short period of time.

[0005]

Therefore, in view of the above problems, the present inventors have considered an acryloyl group or a (meth) group.
As a result of diligent research to obtain a silane coupling agent having an acryloyl group, excellent in water solubility, and good in stability in an aqueous solution, a novel organosilicon compound having an amino group and an amide group in the molecule is The inventors have found that they have excellent properties and have extremely good stability in an aqueous solution, and have completed the present invention.

A formula containing an amide bond in the molecule,

Embedded image (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOC
_{(CH 3) = CH 2,} (CH 3 O) 3 SiCH 2 CH 2 CH 2 NHCOCH = amidosilane represented by CH ₂ is already known, as in the present invention, an amide bond and 3 in the molecule Organosilicon compounds containing both primary amino groups are not known.

[0007]

According to the present invention, there is provided a compound of the general formula

[Chemical 6](In the formula, R₁Is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R₂Represents a divalent hydrocarbon group having 1 to 10 carbon atoms
Then R₃And R_FourIs a divalent hydrocarbon having 2 or 3 carbon atoms
Represents a group, R_FiveIs a hydrogen atom or a methyl group And m is
Represents an integer from 1 to 3. ) Organosilicon represented by
It is a combination.

The present invention also has the general formula

[Chemical 7] (In the formula, R ₁ is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R ₂ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and m represents an integer of 1 to 3. ) And a general formula

[Chemical 8](In the formula, R_FiveIs a hydrogen atom or a methyl group Represents, and X is halo
Represents a gen atom. ) The compound represented by
General formula, characterized by

[Chemical 9](In the formula, R₁Is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R₂Represents a divalent hydrocarbon group having 1 to 10 carbon atoms
Then R₃And R_FourIs a divalent hydrocarbon having 2 or 3 carbon atoms
Represents a group, R_FiveIs a hydrogen atom or a methyl group And m is
Represents an integer from 1 to 3. ) Organosilicon represented by
It is a manufacturing method of a compound.

Next, the present invention will be described in detail. General formula of the invention

[Chemical 10] The organosilicon compound represented by is a novel compound containing both an amide bond and a tertiary amino group in the molecule and having an acryloyl group or a (meth) acryloyl group as a polymerizable group.

In the above "Chemical Formula 10", R ₁ represents a monovalent hydrocarbon group having 1 to 2 carbon atoms, and examples thereof include a methyl group and an ethyl group.

R ₂ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, for example, --CH _2- , --CH ₂ CH.
_{2 -, - CH 2 CH 2} CH 2 -, - CH (CH 3) CH 2 -,
_{- (CH 2) 4 -,} - (CH 2) 6 -, - (CH 2) 8 -, -
_{(CH 2) 9 -, -} (CH 2) 10 -,

[Chemical 11] Etc. are mentioned as specific examples.

R ₃ and R ₄ represent a divalent hydrocarbon group having 2 to 3 carbon atoms, for example, --CH ₂ CH _2- , --CH ₂ C.
Specific examples include H ₂ CH ₂ — and —CH (CH ₃ ) CH ₂ —.

Further, R_FiveIs a hydrogen atom or a methyl group The table
However, m represents an integer from 1 to 3.

The compound of the present invention represented by such a general formula is, for example,

[Chemical 12]

[Chemical 13]

Embedded image

[Chemical 15]

Embedded image

[Chemical 17]

Embedded image

[Chemical 19]

Embedded image

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

Embedded image

[Chemical 31] Is a specific example.

The above compounds of the present invention have the general formula

Embedded image (In the formula, R ₁ is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R ₂ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, m is an integer from 1 to 3 (preferably 2 or 3,
More preferably, it represents 3). ) A compound represented by
General formula

[Chemical 33](In the formula, R_FiveIs a hydrogen atom or a methyl group Represents, and X is halo
Examples include gen atom (chlorine, bromine, iodine, etc., especially salt)
Elemental and bromine are preferred. ) Represents. ) An unsaturated group represented by
The contained carboxylic acid halide is 3 at 20 to 150 ° C.
What can be obtained by reacting for about 0 minutes to 10 hours
I can do it.

In this reaction, a tertiary amine such as triethylamine or tributylamine, or an amine compound such as urea may be used as a hydrogen halide scavenger.

A solvent may be added during the reaction, and the solvent is not particularly limited. For example, aromatic hydrocarbons such as toluene, xylene and benzene; pentane, hexane, heptane, octane, nonane, decane and the like. Hydrocarbons of: dimethyl ether, diethyl ether,
Examples thereof include ethers such as methyl ethyl ether, tetrahydrofuran and dioxane.

The molar ratio in the above reaction is such that the alkoxysilane represented by "Chemical Formula 32" is 0.5 to 1.5 and the carboxylic acid halide represented by "Chemical Formula 33" is 0.5 to 1. 5 is preferable, and 1.0: 1.0 to 1.2 is more preferable.

The excess carboxylic acid halide may be separated by distillation after the reaction is completed, but it is preferable to separate it by distillation after forming an alkyl ester with an alcohol such as methanol or ethanol.

[0020]

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 483.3 g (5.61 mol) of piperazine and 227.1 g (2.24 mol) of triethylamine were placed in a 1 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel. Then, 450 g of toluene was charged and the mixture was heated and stirred at about 110 ° C. to completely dissolve the piperazine. There, the formula (CH ₃ 0) ₃ Si
Alkoxysilane 371.6 represented by (CH ₂ ) ₃ Cl
g (1.87 mol) was added dropwise over 30 minutes. After completion of dropping, the mixture was heated and stirred at 110 ° C. for 4 hours to be aged. After cooling, 28% methanol solution of sodium methoxide 3
42.6 g (sodium methoxide 95.9 g: 1.
(78 mol) was added for neutralization, and methanol was distilled off. Precipitated sodium chloride was filtered off, toluene was distilled off, and excess piperazine was distilled off. Then, when distilled, 221.4 g of a pale yellow liquid having a boiling point of 138 ° C./5 torr was obtained. This compound was identified by the formula from the results of infrared absorption spectrum, ¹ H-nuclear magnetic resonance spectrum analysis and elemental analysis.

Embedded image It was confirmed that the piperazine-containing alkoxysilane represented by The yield was 45%, and the purity by gas chromatography analysis was 99.4%.

Example 1 Next, in the same apparatus as in Synthesis Example 1, 108.1 g (0.44 mol) of the alkoxysilane of Chemical formula 28 and 66.1 g (0.65 mol) of triethylamine were placed in a 1 liter separable flask. Mol), toluene 8
0.0 g of P-methoxyphenol as a polymerization inhibitor was charged, and 50.0 g of methacrylic acid chloride (0.
(48 mol) was added dropwise while controlling the temperature in the reaction system not to exceed 60 ° C. After completion of dropping, stirring was continued at room temperature for 3 hours. Triethylamine hydrochloride was filtered, toluene was distilled off, and the mixture was distilled, and the boiling point was 166 ° C./0.
At 007 torr, 86.4 g (0.27 mol) of a pale yellow liquid was obtained. This compound has the formula based on the results of infrared absorption spectrum and elemental analysis of nuclear magnetic resonance spectrum analysis.

Embedded image Was confirmed. The purity by gas chromatography analysis was 99.2%, and the yield was 62.8%.

The infrared absorption spectrum is shown in FIG. As a result of analyzing the infrared absorption spectrum, an absorption spectrum based on the following characteristic groups was observed. ^{1088cm -1: Si-O-CH3} 1433cm -1: C-H 2839cm -1: C-H 2942cm -1: C-H 1624cm -1:> C = O stretching

Nuclear magnetic resonance spectrum (¹H-NMR)
As shown in FIG. As a result of analyzing the nuclear magnetic resonance spectrum,
A resonance spectrum based on the following characteristic groups was observed.
Was.  1H-NMR (60MHZ, CC1_Four) Si-CH ₂ -0.56ppm (t, 2H) Si-C₂H-CH ₂ -CH₂-1.5 to 2.0 ppm (m, 2H)

Embedded image 1.90ppm (s, 3H)

Embedded image 2.2~2.5ppm (m, 6H) C H 3 -O-Si 3.51ppm (s, 9H)

[Chemical 38] 3.4-3.5 ppm (m, 4H)

[Chemical Formula 39] 4.91ppm (s, 1H)

[Chemical 40] 5.07ppm (s, 1H)

[0025] In Synthesis Example 2] Synthesis Example 1, substituting piperazine homopiperazine 561.0g (5.61 moles), also represented by the formula _{(CH 3 0) 3 Si- (} CH 2) 3 -Cl the alkoxysilane _{(CH 3 CH 2 0) 3} Si-CH 2
-Cl, the reaction was performed in the same manner as in Synthesis Example 1 except that 397.3 g (1.87 mol) was used, and the same operation was performed and then distillation was performed, whereupon the boiling point was 152 ° C / 5 torr, 211 0.7 g (0.767 mol) of a pale yellow transparent liquid was obtained. This compound has an infrared absorption spectrum,
By nuclear magnetic resonance spectrum analysis and elemental analysis, the formula

Embedded image It was confirmed that the homosilane was a homopiperazine-containing alkoxysilane. The purity by gas chromatography analysis was 99.0%, and the yield was 41.0%.

[Example 2] Next, the same procedure as in Example 1 was performed except that the alkoxysilane "Chemical 41" obtained in Synthesis Example 2 was replaced with 121.4 g (0.44 mol) of the alkoxysilane. The reaction was performed in the same manner as in Example 1, and the same operation was performed and then distillation was performed. The boiling point was 184 ° C./0.007 t
At orr, 97.3 g of a pale yellow transparent liquid was obtained. This compound was identified by the formula from the results of infrared absorption spectrum, nuclear magnetic resonance spectrum analysis and elemental analysis.

Embedded image Was confirmed to be homopiperazine-containing methacrylsilane. The purity as determined by gas chromatography was 97.2%, and the yield was 64.3%.

[Synthesis Example 3] In Synthesis Example 1, the alkoxysilane was replaced with (CH ₃ 0) ₂ Si (CH ₃ ) -C (CH ₃ ).
HCH ₂ -Cl, except that the amount was changed to 341.2 g (1.87 mol), the reaction was performed in the same manner as in Synthesis Example 1, the same operation was performed, and then the distillation was performed to obtain 150 to 153 ° C / 5t.
At orr, 204.2 g (0.88 mol) of a pale yellow transparent liquid was obtained. This compound was identified by the formula from the results of infrared absorption spectrum, nuclear magnetic resonance spectrum analysis and elemental analysis.

[Chemical 43] It was confirmed that the piperazine-containing alkoxysilane represented by The purity by gas chromatographic analysis is
The 95.1% yield was 47.0%.

[Example 3] Next, in Example 1, except that the alkoxysilane of "Chemical Formula 37" obtained in Synthesis Example 3 was replaced with 102.1 g (0.44 mol) of the alkoxysilane. The same reaction as in Example 1 was carried out, the same operation was carried out, and then distillation was carried out. As a result, the boiling point was 151 ° C./0.0.
71.1 g of a pale yellow transparent liquid was obtained at 07 torr.
This compound was analyzed by infrared absorption spectrum, nuclear magnetic resonance spectrum analysis and elemental analysis.

[Chemical 44] It was confirmed that the piperazine-containing methacrylic silane represented by The purity by gas chromatography analysis was 96.2%, and the yield was 53.8%.

[Synthesis Example 4] 361.8 g (4.20 mol) of piperazine was placed in a 1 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel.
170.0 g (1.68 mol) of triethylamine and 350 g of toluene were charged and heated and stirred at about 110 ° C. to completely dissolve piperazine. There, the formula (CH ₃ 0) ₃ S
i- (CH ₂₎ alkoxysilane 4, represented by 10-Br
77.9 g (1.40 mol) was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at 110 ° C. for 4 hours and aged. After cooling
28% sodium methoxide solution in methanol
． 6 g (71.9 g, 1.33 mol) was added for neutralization, and methanol was distilled off. The sodium salt was filtered off, and the obtained liquid was concentrated under reduced pressure at 160 ° C./10 torr to obtain 193.8 g (0.56 mol) of a brown transparent liquid. This compound was identified by the formula from the results of nuclear magnetic resonance spectrum, infrared absorption spectrum analysis and elemental analysis.

Embedded image It was confirmed that the piperazine-containing alkoxysilane represented by The yield was 42.3%.

Example 4 Next, in the same apparatus as in Synthesis Example 4, a 1-liter separable flask was placed in Synthesis Example 4.
The piperazine-containing alkoxysilane obtained in 15.2.
g (10.44 mol), triethylamine 66.1 g
(0.65 mol), 80.0 g of toluene and P-methoxyphenol as a polymerization inhibitor were charged, and while stirring, 43.4 g (0.48 mol) of acrylic acid chloride was added at a temperature of 60 ° C or higher in the reaction system. It dripped while adjusting so that it might not become. After completion of dropping, the mixture was stirred at room temperature for 3 hours, triethylamine hydrochloride was filtered off, and the obtained liquid was 145 ° C / 10t.
Concentration under reduced pressure at orr gave a brown transparent liquid (0.
60 g) was obtained. This liquid has a formula based on the results of nuclear magnetic resonance spectrum, infrared absorption spectrum analysis and elemental analysis.

Embedded image It was confirmed that the piperazine-containing acrylic silane represented by The yield was 60.2%.

[Synthesis Example 5] In Synthesis Example 4, an alkoxysilane is represented by the formula

[Chemical 47] The same reaction as in Synthesis Example 4 was performed and the same operation was performed except that 384.7 g (1.40 mol) of the alkoxysilane represented by The obtained liquid is 160 ° C / 10 to
Concentration under reduced pressure with rr gave a brown transparent liquid 189.0
g was obtained. From the results of infrared absorption spectrum, nuclear magnetic resonance spectrum analysis and elemental analysis of this compound, the formula

Embedded image It was confirmed that the piperazine-containing alkoxysilane represented by The yield was 41.6%.

[Example 5] Next, in Example 4, the piperazine-containing alkoxysilane was replaced with the piperazine-containing alkoxysilane 142.
The same reaction as in Example 4 was carried out except that the amount of acrylic acid chloride was changed to 50.0 g (0.48 mol) instead of 8 g (0.44 mol), and the same operation was performed. . 118.0 g of the obtained liquid was obtained. From the results of infrared absorption spectrum, nuclear magnetic resonance spectrum analysis and elemental analysis of this compound, the formula

[Chemical 49] It was confirmed that the methacrylic silane containing piperazine represented by The yield was 68.3%.

[0037]

The compound of the present invention is a novel organosilicon compound having an amino group and an amide group in the molecule, has excellent water solubility, and has extremely good storage stability in an aqueous solution.

The conventional γ- (meth) acryloxypropylalkoxysilane does not dissolve in water unless acetic acid is added and the acidic condition is weak, whereas the compound of the present invention can be added without acetic acid. It is an alkoxysilane that is highly soluble in water and has excellent water solubility.

Further, the conventional γ- (meth) acryloxypropylalkoxysilane is insolubilized in a 1% weakly acidic aqueous solution after 1 day, whereas the compound of the present invention is It is an alkoxysilane that does not become insoluble at all even after 5 days and has extremely excellent storage stability in water. Therefore, the compound of the present invention is usually used in the form of a dilute aqueous solution used as a silane coupling agent.
It can be stored for more than a week. INDUSTRIAL APPLICABILITY The organosilicon compound of the present invention can be suitably applied to a composite material such as a primer for building materials, an adhesive, an additive for paints, a laminated plate, FRP, FRTP, a resin encapsulant, and a molding material.

[Brief description of drawings]

1 is an infrared absorption spectrum of the compound of the present invention obtained in Example 1. FIG.

2 is a nuclear magnetic resonance spectrum ( ¹ H-NMR) of the compound of the present invention obtained in Example 1. FIG.

Front Page Continuation (72) Inventor Shoji Ichinohe 1 Hitomi, Katsura, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (2)

[Claims] 1. A general formula:(In the formula, R₁Is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R₂ Represents a divalent hydrocarbon group having 1 to 10 carbon atoms
Then R₃ And R_Four Is a divalent hydrocarbon having 2 or 3 carbon atoms
Represents a group, R_FiveIs a hydrogen atom or a methyl group And m is
Represents an integer from 1 to 3. ) Organosilicon represented by
Compound 2. A general formula:(In the formula, R₁Is a monovalent hydrocarbon having 1 to 2 carbon atoms
Group, R₂Is a divalent hydrocarbon group having 1 to 10 carbon atoms
And m represents an integer from 1 to 3. )
The compound and the general formula:(In the formula, R_FiveIs a hydrogen atom or a methyl group Represents, and X is halo
Represents a gen atom. ) The compound represented by
And a general formula, characterized by(In the formula, R₁Is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R₂Represents a divalent hydrocarbon group having 1 to 10 carbon atoms
Then R₃And R_FourIs a divalent hydrocarbon having 2 or 3 carbon atoms
Represents a group, R_FiveIs a hydrogen atom or a methyl group And m is
Represents an integer from 1 to 3. ) Organosilicon represented by
Compound manufacturing method.