KR102067785B1 - Method for preparing aminoalkylsilane compound, and aminoalkylsilane compound produced thereby - Google Patents

Abstract

The present invention relates to a process for preparing high purity and high yield aminoalkylsilane compounds, and to aminoalkylsilane compounds produced by such methods.

Description

Method for preparing aminoalkylsilane compound and aminoalkylsilane compound prepared by the method TECHNICAL FIELD [0001] AND AMINOALKYLSILANE COMPOUND PRODUCED THEREBY}

The present invention relates to a process for preparing high purity and high yield aminoalkylsilane compounds and to aminoalkylsilane compounds produced by such methods.

Looking at recent trends in the automotive industry, there is a constant need for durability, stability and fuel savings, and efforts are being made to meet those demands.

In particular, several attempts have been made to reinforce the physical properties of rubber, which is the material of automobile tires, in particular tire treads in contact with the ground. As a rubber composition for automobile tires, a rubber composition containing a conjugated diene polymer such as polybutadiene or butadiene-styrene copolymer is used. In order to improve the performance of automobile tires, research is being conducted to mix various reinforcing materials with conjugated diene-based rubber compositions.

The inventors of the present invention have proposed the present invention to develop a rubber as a material of a tire tread, while having excellent exothermicity, and having tensile strength, wear resistance, low fuel consumption and wet road resistance.

US Patent No. 6,310,230 United States Patent Application Publication No. 9,096,622 Japanese Laid-Open Patent Publication JP 2008-143855

In order to solve the above problems, the present invention provides a method for producing an aminoalkylsilane compound used in a rubber composition with high purity and high yield.

The present invention also provides a high purity aminoalkylsilane compound prepared by the above method.

In one embodiment for achieving the above object,

Preparing a bromoalkyl imidazole compound represented by Formula 1; And

It provides a method for producing an aminoalkylsilane compound comprising; reacting the bromoalkyl imidazole compound and the amine compound represented by the following formula (2) in the presence of a catalyst.

[Formula 1]

[Formula 2]

Where

R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

R ₁ is hydrogen or an alkyl group having 1 to 3 carbon atoms,

R ₂ and R ₃ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

R ₄ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,

n and m are integers from 1 to 3.

In addition, the present invention provides an aminoalkylsilane compound represented by the following formula (3) prepared by the above method.

[Formula 3]

Where

R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

R ₂ and R ₃ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

R ₄ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,

n and m are integers from 1 to 3.

According to the method of the present invention, the aminoalkylsilane compound used in the rubber composition excellent in exothermicity, tensile strength, abrasion resistance, low fuel consumption and wet road resistance can be produced in high purity and high yield under mild reaction conditions.

Hereinafter, the present invention will be described in more detail.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

Aminosilane compounds containing tertiary imidazole, which are known to be prepared by conventional amine derivatives and chloropropylsilane compound derivatives, are excellent in compatibility with inorganic fillers and have excellent processability, so that rubber compositions containing them are exothermic. It is known to be excellent in properties, tensile strength, abrasion resistance, low fuel consumption and wet road resistance.

However, the reaction of preparing an aminoalkylsilane compound using a conventional chloropropylsilane compound has a disadvantage that the reaction conditions are not only difficult because of the high temperature reaction, and the reaction rate is slow. In addition, in the case of an amine derivative used in excess, a long chain has a high boiling point, and therefore, it takes a long time to remove it at a high temperature after the completion of the reaction, and it is difficult to completely remove it, which is difficult to obtain in high purity and high yield.

Accordingly, an object of the present invention is to provide a method for improving the reaction rate and producing an aminoalkylsilane compound with high purity and high yield.

Specifically, in one embodiment of the present invention

Preparing a bromoalkyl imidazole compound represented by Formula 1; And reacting the bromoalkyl imidazole compound with an amine compound represented by Formula 2 in the presence of a catalyst.

[Formula 1]

[Formula 2]

Where

R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

R ₁ is hydrogen or an alkyl group having 1 to 3 carbon atoms,

R ₂ and R ₃ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

R ₄ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,

n and m are integers from 1 to 3.

First, in the method of the present invention, the bromoalkyl imidazole compound represented by Chemical Formula 1 may be prepared by the following method.

Adding a reaction solvent to potassium hydroxide and cooling to 0 ° C;

Sequentially adding a dibromoalkane compound and imidazole represented by Formula 4 to the potassium hydroxide solution and stirring at 0 ° C .;

Diluting by adding ethyl acetate to the remaining reactants after removing the reaction solvent; And

Washing the diluted solution with an aqueous solution and then concentrating under reduced pressure to obtain a bromoalkyl imidazole compound represented by Chemical Formula 1.

[Formula 4]

Br-R ₅ -Br

Wherein R ₅ is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.

In the above method, it is preferable to react with stirring at 0 ° C. in order to prevent the temperature from rising due to the heat of reaction.

In the above method, potassium hydroxide is a strongly basic substance, and may be included in an amount of 1 to 2 mol based on 1 mol of the imidazole.

Moreover, as said reaction solvent, hydrocarbon solvents, such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, xylene, ether solvents, such as diethyl ether, tetrahydrofuran, dioxane, ethyl acetate, acetic acid Ester solvents such as butyl, aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform, and the like, and these solvents may be used alone. You may use it, or may mix and use 2 or more types. Among the solvents, aprotic polar solvents such as acetonitrile or N, N-dimethylformamide are preferable.

The reaction solvent may be included in an amount of 500 to 600 parts by weight based on 100 parts by weight of imidazole.

In addition, the dibromoalkane compound may be included in 2 mol to 3 mol with respect to 1 mol of imidazole. If the content of the dibromoalkane compound is 2 mol or less, there is a disadvantage in that the ratio of 1,3-di (1H-imidazol-1-yl) propane is increased, and if it exceeds 3 mol, the reaction effect is It is not greatly improved, so the economic effect is lowered.

The dibromoalkane compound may be at least one selected from the group consisting of dibromomethane, dibromoethane, dibromopropane, dibromobutane, and dibromohexane, among which dibromopropane may be used. have.

In addition, the method preferably comprises the step of removing all the reaction solvent after the reaction, and then adding and diluting ethyl acetate so as to increase a large amount of the final product relative to the amount of solvent.

Subsequently, in the method of the present invention, the dilute solution is washed with an aqueous solution and then concentrated under reduced pressure to obtain a bromoalkyl imidazole compound represented by Chemical Formula 1 in the form of an oil.

In addition, the method of the present invention may include the step of reacting the bromoalkyl imidazole compound represented by the formula (1) prepared in the step and the amine compound represented by the formula (2) in the presence of a catalyst.

In this case, in the amine compound represented by Formula 2, R ₁ may include hydrogen.

In addition, in the amine compound represented by Formula 2, R ₂ and R ₃ may each include at least one selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene. And specifically ethylene, propylene, or butylene.

In addition, in the amine compound represented by Formula 2, R ₄ may include at least one selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene, specifically Methylene, ethylene, or propylene is mentioned as an example.

In addition, in the method of the present invention, the reaction step of the bromoalkyl imidazole compound and the amine compound may be carried out in the following steps.

Dissolving the amine compound represented by Chemical Formula 2 in a reaction solvent;

Dissolving the bromoalkyl imidazole compound represented by Chemical Formula 1 in a reaction solvent;

Adding a basic compound to the amine compound reaction solution;

Heating the amine compound reaction solution and reacting the bromoalkyl imidazole compound reaction solution dropwise for 10 to 12 hours; And

After completion of the reaction, the reaction product is extracted and concentrated under reduced pressure.

In this case, as the reaction solvent, hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, xylene, ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate Ester solvents such as acetonitrile, aprotic polar solvents such as acetonitrile and N, N-dimethylformamide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform, and the like, and these solvents may be used alone. Or two or more types can also be mixed and used. Among the solvents, aprotic polar solvents such as acetonitrile or N, N-dimethylformamide are preferable.

In addition, in the method of the present invention, examples of the basic compound include a basic compound which can be used for dehydrogenation, and representative examples thereof include hydroxide, alcoholate, and N, N-diisopropylethylamine. It may include at least one selected from the group consisting of (Hunig's base), and among these, Hunig base may be used.

Although the amount of the basic compound is not particularly limited, 1 to 4 moles, specifically 3 moles, may be used per 1 mole of the amine compound represented by Formula 2 in consideration of reactivity and productivity. If the catalyst is less than 1 mole, a sufficient effect of the catalyst may not be expressed. If the catalyst is more than 4 mole, there is a possibility that a reaction promoting effect suitable for the amount of the catalyst is not seen.

In addition, in the method of the present invention, the bromoalkyl imidazole compound: the amine compound represented by Formula 2 may include 1 to 2: 1 equivalent. If the content of the bromoalkyl imidazole compound is less than 1, it is difficult to remove the amine compound of Formula 2 remaining after the reaction. That is, after the reaction, only the compound of formula 3 is obtained by separating hexane, and the compound of formula 2 may be obtained by dissolving in hexane. In addition, when the content of the bromoalkyl imidazole compound exceeds 2, the economic effect is low.

In addition, in the method of the present invention, the reaction temperature of the bromoalkyl imidazole compound: the amine compound represented by the formula (2) is preferably carried out after the temperature is raised to 60 ° C.

In detail, the reaction temperature may be, for example, 60 to 80 ° C., and the reaction may be performed for 4 hours to 6 hours after completion of the dropwise addition of the bromoalkyl imidazole compound solution.

On the other hand, the hydrochloride of an amine compound arises after completion | finish of reaction, but this can be removed by methods, such as adding and extracting hexane. From the reaction liquid from which the salt was removed as mentioned above, a product can be obtained by conventional methods, such as distillation.

As described above, in the method of the present invention, a bromoalkylimidazole which is highly reactive with secondary aminosilane in place of the chloropropylene compound is used in the preparation of the aminoalkylsilane compound represented by the formula (3). The reaction may proceed at temperature conditions. In particular, by using tertiary amine bases, it is possible to simply remove some of the remaining byproducts, such as secondary aminosilanes, in salt form to produce high purity and high yields of aminoalkylsilane compounds.

In addition, the present invention provides an aminoalkylsilane compound represented by the following formula (3) prepared by the above method.

[Formula 3]

Where

R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

R ₂ and R ₃ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

R ₄ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,

n and m are integers from 1 to 3.

In the present invention,

It provides a rubber composition comprising 100 parts by weight of the conjugated diene polymer modified by the aminoalkylsilane compound and 0.1 to 200 parts by weight of the inorganic filler.

The inorganic filler may be, for example, 10 to 150 parts by weight, or 50 to 100 parts by weight.

The inorganic filler may be at least one selected from the group consisting of silica-based fillers, carbon black, and mixtures thereof. In the case where the inorganic filler is a silica-based filler, dispersibility is greatly improved, and the hysteresis loss is greatly reduced by bonding the silica particles with the terminal of the aminoalkylsilane compound of the present invention.

In addition, in the rubber composition of the present invention, the terminal-modified conjugated diene-based polymer may be styrene-butadiene rubber (SBR), butadiene rubber (BR), natural rubber or a mixture thereof. The SBR may be, for example, solution styrene-butadiene rubber (SSBR).

In this case, the aminoalkylsilane compound may be included in an amount of 0.1 to 30 parts by weight, specifically 1 to 10 parts by weight, and more specifically 1 to 5 parts by weight, based on 100 parts by weight of the conjugated diene polymer.

In addition, the rubber composition of the present invention may further include 1 to 100 parts by weight, or 20 to 80 parts by weight of oil. The oil may be, for example, a mineral oil or a softener. The oil is good in the physical properties within this range, and also has an effect of excellent softening the rubber composition moderately.

Such, the rubber composition of the present invention can implement an improved effect of exothermicity, tensile strength, wear resistance, low fuel consumption and wet road resistance by including a high purity and high yield of aminoalkylsilane compound prepared by the method of the present invention .

According to another aspect of the present invention, there is provided a tire or tire tread using the modified conjugated diene-based polymer rubber composition described above.

The tire or tire tread is manufactured by using a rubber composition including a modified conjugated diene-based polymer having excellent compatibility with inorganic fillers and improved processability, thereby providing excellent tensile strength, wear resistance, and wet road resistance. There is this.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example

Example 1

(Stage 1)

After adding 150 ml of acetonitrile to 27 g (481 mmol) of potassium hydroxide, the mixture was cooled to 0 ° C. 162 g (802 mmol) of dibromopropane was added to the reaction, followed by 27.3 g (401 mmol) of imidazole. The reaction was stirred at 0 ° C. for 3 hours to terminate the reaction and then concentrated under reduced pressure to remove the solvent. 200 g of ethyl acetate was added, diluted, washed with a saturated aqueous solution (200 ml), and concentrated under reduced pressure to obtain 1- (3-bromopropyl) -1H-imidazole (60%) as a yellow oil (see Schemes 1 and 2 below). .

¹ H-NMR (CDCl ₃ ) δ: 7.52 (s, 1H), 7.08 (s, 1H), 6.94 (s, 1H), 4.16 (t, 2H), 3.31 (t, 2H), 2.28 (m, 2H )

Scheme 1

Scheme 2

(Step 2)

10 g (23.5 mmol) of bis (3- (triethoxysilyl) propyl) amine is dissolved in 10 ml of acetonitrile and 7.13 g (70.47 mmol) of diisopropylethylamine are added thereto. Acetonitrile (2.8M) in which 4.44 g (23.5 mmol) of 1- (3-bromopropyl) -1H-imidazole was dissolved at 60 ° C. was added dropwise for 12 hours, followed by stirring for 4 hours. After the reaction, the reaction product was extracted with hexane and concentrated under reduced pressure to give N- (3- (1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) -N- (3- (tri Ethoxysilyl) propyl) propan-1-amine (93% purity, 65% yield) was obtained (see Scheme 3 below).

¹ H-NMR (CDCl ₃ ) δ: 7.47 (s, 1H), 7.02 (s, 1H), 6.90 (s, 1H), 3.97 (t, 2H), 3.80 (q, 12H), 2.38 (m, 6H ), 1.87 (t, 2H), 1.50 (m, 4H), 0.56 (t, 4H)

Scheme 3

(Comparative Example 1)

3 g (24.0 mmol) of 1- (3-aminopropyl) imidazole are dissolved in 10 ml of acetonitrile, and 9.29 g (71.9 mmol) of diisopropylethylamine are added thereto. Acetonitrile (2.8M), in which 5.77 g (24.0 mmol) of (3-chloropropyl) triethoxysilane was dissolved at 60 ° C, was added dropwise for 12 hours, followed by stirring for 12 hours.

The reaction product obtained was analyzed by gas chromatography, and N- (3- (1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) -N- (2- (triethoxysilyl) ethyl N- (3- (1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) propan-1-amine and intermediate 1- (3-aminopropyl) It was found that imidazole was mixed at a ratio of 0.15: 0.1: 1.

(Comparative Example 2)

3 g (24.0 mmol) of 1- (3-aminopropyl) imidazole in 10 ml of acetonitrile and 5.77 g (24.0 mmol) of (3-chloropropyl) triethoxysilane at 60 ° C were dissolved in acetonitrile (2.8 M). To the reaction mixture was added dropwise for 12 hours and then stirred for 12 hours.

The reaction product was analyzed by gas chromatography, and N- (3- (1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) -N- (2- (triethoxysilyl) ethyl N- (3- (1H-imidazol-1-yl) propyl) -3- (triethoxysilyl) propan-1-amine as an intermediate and 1- (3-aminopropyl) as a raw material It was found that imidazole was mixed at a ratio of 0: 0.1: 1.

Example 1 Comparative Example 1 Comparative Example 2 Reactant 1 matter Bis (3- (triethoxysilyl) propyl) amine (3-chloropropyl) triethoxysilane (3-chloropropyl) triethoxysilane content 23.5mmol 24.0mmol 24.0mmol Reactant 2 matter 2- (3-bromopropyl)
-1H-imidazole 1- (3-aminopropyl) imidazole 1- (3-aminopropyl) imidazole content 23.5mmol 24.0mmol 24.0mmol Reactant 1: 2 content ratio 1: 1 1: 1 1: 1 catalyst Diisopropylethylamine Diisopropylethylamine - Reaction temperature 60 ℃ Reaction time 4 hours 12 hours 12 hours yield 65% 12% 0% water 93% - 0%

As shown in the results of Table 2 above, according to the present invention method of Example 1, it can be seen that the aminoalkylsilane compound with improved yield (65%) and purity (93%) can be obtained even under mild temperature conditions. there was.

On the other hand, it can be seen that the yield and purity of the aminoalkylsilane compound are low or hardly produced in the method of Comparative Examples 1 and 2 applying the same temperature conditions as the method of the present invention.

Claims (21)

Preparing a bromoalkyl imidazole compound represented by Formula 1; And
A method for producing an aminoalkylsilane compound represented by the following Chemical Formula 3, comprising: reacting the bromoalkyl imidazole compound and an amine compound represented by the following Chemical Formula 2 in the presence of a catalyst.
[Formula 1]

[Formula 2]

[Formula 3]

Where
R is an alkylene group having 1 to 10 carbon atoms.
R ₁ is hydrogen or an alkyl group having 1 to 3 carbon atoms,
R ₂ and R ₃ is an alkylene group having 1 to 10 carbon atoms,
R ₄ is an alkyl group having 1 to 5 carbon atoms,
n and m are integers from 1 to 3.
The method according to claim 1,
To prepare a bromoalkyl imidazole compound represented by Formula 1,
Adding a reaction solvent to potassium hydroxide and cooling to 0 ° C;
Sequentially adding a dibromoalkane compound and imidazole represented by Formula 4 to the potassium hydroxide solution and stirring at 0 ° C .;
Diluting by adding ethyl acetate to the remaining reactants after removing the reaction solvent; And
Washing the diluted solution with an aqueous solution and then concentrating under reduced pressure to obtain a bromoalkyl imidazole compound represented by Chemical Formula 1; a method for preparing an aminoalkylsilane compound, comprising:
[Formula 4]
Br-R ₅ -Br
Where
R ₅ is an alkylene group having 1 to 5 carbon atoms.
The method according to claim 2,
The potassium hydroxide is prepared in an amount of 1 to 2 moles per 1 mole of imidazole.
The method according to claim 2,
The reaction solvent is a single substance or a mixture of two or more selected from the group consisting of a hydrocarbon solvent, an ether solvent, an ester solvent, an aprotic polar solvent, and a chlorinated hydrocarbon solvent,
The hydrocarbon solvent is at least one selected from the group consisting of pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene,
The ether solvent is at least one selected from the group consisting of diethyl ether, tetrahydrofuran and dioxane,
The ester solvent is ethyl acetate or butyl acetate,
The chlorinated hydrocarbon solvent is a method for producing an aminoalkylsilane compound, characterized in that dichloromethane or chloroform.
The method according to claim 2,
The reaction solvent is a method for producing an aminoalkylsilane compound, characterized in that it comprises 500 to 600 parts by weight based on 100 parts by weight of imidazole.
The method according to claim 2,
The dibromoalkane compound is a method for producing an aminoalkylsilane compound, characterized in that it comprises 2 to 3 moles per mole of imidazole.
The method according to claim 2,
The dibromoalkane compound is a dibromomethane, dibromoethane, dibromopropane, dibromobutane, dibromobutane, and a method for producing an aminoalkylsilane compound, characterized in that it comprises at least one selected from the group consisting of dibromohexane.
The method according to claim 1,
In the amine compound represented by Formula 2, R ₁ is hydrogen,
R ₂ and R ₃ each independently include at least one selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene,
R ₄ is a method for producing an aminoalkylsilane compound, characterized in that it comprises at least one selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene.
The method according to claim 1,
The reaction step of the bromoalkyl imidazole compound and the amine compound is
Dissolving the amine compound represented by Chemical Formula 2 in a reaction solvent;
Dissolving the bromoalkyl imidazole compound represented by Chemical Formula 1 in a reaction solvent;
Adding a basic compound to the amine compound reaction solution;
Heating the amine compound reaction solution and reacting the bromoalkyl imidazole compound reaction solution dropwise for 10 to 12 hours; And
After the reaction is completed, extracting the reaction product and concentrating under reduced pressure.
The basic compound is at least one selected from the group consisting of hydroxide, alcoholate and Hunig base,
The said elevated temperature raises the reaction temperature so that it may become 60-80 degreeC, The manufacturing method of the aminoalkylsilane compound characterized by the above-mentioned.
The method according to claim 9,
The reaction solvent is a single substance or a mixture of two or more selected from the group consisting of a hydrocarbon solvent, an ether solvent, an ester solvent, an aprotic polar solvent, and a chlorinated hydrocarbon solvent,
The hydrocarbon solvent is at least one selected from the group consisting of pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene,
The ether solvent is at least one selected from the group consisting of diethyl ether, tetrahydrofuran and dioxane,
The ester solvent is ethyl acetate or butyl acetate,
The chlorinated hydrocarbon solvent is a method for producing an aminoalkylsilane compound, characterized in that dichloromethane or chloroform.
delete The method according to claim 9,
The basic compound is a method for producing an aminoalkylsilane compound, characterized in that contained in 1 to 4 moles per mole of the amine compound represented by the formula (2).
The method according to claim 9,
The bromoalkyl imidazole compound: the amine compound is 1 to 2: 1 equivalent Method for producing an aminoalkylsilane compound, characterized in that it comprises.
The method according to claim 9,
The reaction step of the bromoalkyl imidazole compound and the amine compound is a method for producing an aminoalkylsilane compound, characterized in that carried out for 4 to 6 hours at 60 to 80 ℃.
The method according to claim 9,
The method further comprises the step of removing the hydrochloride of the amine compound produced after completion of the reaction by the addition of hexane and extraction method, aminoalkylsilane compound.
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