KR20240033783A - Method for preparing aminoalkoxysilane compounds - Google Patents

Abstract

One embodiment of the present specification includes (a) preparing a mixture containing a chloroalkylalkoxysilane, an amine compound, and a metal halide; and (b) reacting the mixture. It provides a method for producing an aminoalkoxysilane compound, including the step of reacting the mixture.

Description

Method for producing aminoalkoxysilane compounds {METHOD FOR PREPARING AMINOALKOXYSILANE COMPOUNDS}

This specification relates to a method for producing aminoalkoxysilane compounds.

Aminoalkoxysilane is a representative compound used as an end-modifying agent in the production of rubber compositions for tire treads. Aminoalkoxysilane compounds are used to improve compatibility with fillers by bonding to the ends of conjugated diene polymers, and ultimately play a role in improving the wetting resistance and rolling resistance of tires.

Conventionally, aminoalkoxysilane compounds were manufactured using rare metals such as palladium, rhodium, and platinum as catalysts. However, reductive amination reaction using palladium has low yield and there is a risk of fire. Reductive elimination reaction using a rhodium catalyst has the disadvantage of low yield and expensive catalyst. In addition, it has been reported that the hydrosilylation reaction using platinum as a catalyst can reuse the catalyst, but the yield is low and the final material is poor due to the selection of alpha and beta positions during hydrosilylation reaction at the allyl position. A mixture is created, and there is a problem that requires an additional process to purify it.

A reaction that does not use a catalyst is the SN2 reaction between an amine and a halogen, but this method is also reported to have a low yield of less than 2%, and a high-pressure reaction is essential because it uses ammonia in a liquid state.

Another method for synthesizing aminoalkoxysilanes is the reaction of primary amines with chloroalkylalkoxysilanes, and is known to have a high yield of 90%, but has the problem of requiring a fairly long reaction time of 4 days.

Accordingly, there is an increasing demand for a process for producing aminoalkoxysilane compounds with a method that exhibits high selectivity and yield, while requiring a short reaction time and improved safety.

The description in this specification is intended to solve the problems of the prior art described above, and one purpose of this specification is to provide a method for producing aminoalkoxysilane compounds with improved selectivity, yield, reaction time, and safety.

According to one aspect, (a) preparing a mixture containing a chloroalkylalkoxysilane, an amine compound, and a metal halide; and (b) reacting the mixture. It provides a method for producing an aminoalkoxysilane compound, including the step of reacting the mixture.

In one embodiment, the chloroalkyl alkoxysilane may be a compound represented by Formula 1 below.

[Formula 1]

Cl-(R ¹ )-Si(R ² ) _m (OR ³ ) _3-m

In Formula 1, R ¹ is an alkylene group of C ₁ to C ₄ , R ² is an alkyl group of C ₁ to C ₂ , R ³ is an alkyl group of C ₁ to C ₄ , and m is 0, 1 or 2. .

In one embodiment, the amine compound may be a compound represented by the following formula (2).

[Formula 2]

NH(R ⁴ ) _p [(R ⁵ )-Si(R ⁶ ) _n (OR ⁷ ) _3-n ] _2-p

In Formula 2, R ⁴ is hydrogen, a C ₁ to C ₁₆ alkyl group or a C ₁ to C ₁₂ heteroalkyl group, R ⁵ is a C ₁ to C ₄ alkylene group, and R ⁶ is a C ₁ to C ₂ alkyl group. It is an alkyl group, R ⁷ is an alkyl group of C ₁ to C ₄ , n is 0, 1 or 2, and p is 0, 1 or 2.

In one embodiment, the metal halide may be a compound represented by Formula 3 below.

[Formula 3]

MX

In Formula 3, M is an alkali metal, and X is a halogen element.

In one embodiment, the metal halide may be a compound represented by Formula 4 below.

[Formula 4]

M'X ₂

In Formula 4, M' is an alkaline earth metal, and X is a halogen element.

In one embodiment, the content of the chloroalkylalkoxysilane contained in the mixture may be 1.1 to 10 moles per mole of the amine compound.

In one embodiment, the content of the metal halide contained in the mixture may be 0.01 to 5 moles per mole of the amine compound.

In one embodiment, the mixture may further include a base.

In one embodiment, the base is triethylamine (TEA), N,N-diisopropylethylamine (DIEA), 1,1,3,3-tetramethylguanidine (TMG), and a combination of two or more thereof. It may be one selected from a group consisting of

In one embodiment, step (b) may be performed at 60 to 200°C.

In one embodiment, step (b) may be performed for 1 to 50 hours.

In one embodiment, step (b) may be performed under a pressure of 0.1 to 10 bar.

The method for producing an aminoalkoxysilane compound according to one aspect of the present specification can exhibit high selectivity and yield despite a short reaction time.

The effect of one aspect of the present specification is not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration described in the detailed description or claims of the present specification.

Hereinafter, one aspect of the present specification will be described with reference to the attached drawings. However, the description in this specification may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In order to clearly explain one aspect of the specification in the drawings, parts that are not related to the description are omitted, and similar parts are given similar reference numerals throughout the specification.

Throughout the specification, when a part is said to be “connected” to another part, this includes not only cases where it is “directly connected,” but also cases where it is “indirectly connected” with another member in between. . Additionally, when a part is said to “include” a certain component, this does not mean that other components are excluded, but that other components can be added, unless specifically stated to the contrary.

When a range of numerical values is described herein, unless the specific range is stated otherwise, the value has the precision of significant figures given in accordance with the standard rules in chemistry for significant figures. For example, the number 10 includes the range 5.0 to 14.9, and the number 10.0 includes the range 9.50 to 10.49.

As used herein, the term “alkyl group” refers to a linear or branched hydrocarbon group “C _n H _2n+1 -“. Examples include methyl, ethyl, propyl, isopropyl, butyl, etc., but are not limited thereto.

As used herein, the term “heteroalkyl group” refers to an alkyl group in which one or more carbon atoms are replaced with a hetero atom.

The term “heteroatom” used in this specification refers to all atoms except carbon and hydrogen, and examples include, but are not limited to, oxygen, nitrogen, sulfur, phosphorus, and halogen atoms.

As used herein, the term “alkylene group” refers to a linear or branched hydrocarbon group “-C _n H _2n -“ having two valences. For example, methylene group (-CH ₂ -), ethylene group (-CH ₂ -CH ₂ -), etc. may be mentioned, but it is not limited thereto.

As used herein, the term “C _x ~C _y “means having x to y carbon atoms. For example, “an alkyl group of C _x to C _y ” means an alkyl group having x to y carbon atoms.

Hereinafter, an embodiment of the present specification will be described in detail.

Method for producing aminoalkoxysilane compounds

A method for producing an aminoalkoxysilane compound according to an aspect of the present specification includes the steps of (a) preparing a mixture containing a chloroalkylalkoxysilane, an amine compound, and a metal halide; and (b) reacting the mixture.

Step (a) is a step of mixing starting materials for synthesizing aminoalkoxysilane compounds. By using metal halides as additives along with chloroalkylalkoxysilane and amine compounds, the reaction time is shortened and high selectivity and yield are achieved. You can get it.

The chloroalkyl alkoxysilane may be a compound represented by the following formula (1).

[Formula 1]

Cl-(R ¹ )-Si(R ² ) _m (OR ³ ) _3-m

In Formula 1, R ¹ is a C ₁ to C ₂₀ alkylene group, R ² is a C ₁ to C ₂₀ alkyl group, R ³ is a C ₁ to C ₂₀ alkyl group, and m is 0, 1 or 2 days. You can. For example, R ¹ is an alkylene group of C ₁ ~ C ₄ , R ² is an alkyl group of C ₁ ~ C ₂ , R ³ is an alkyl group of C ₁ ~ C ₄ , and m may be 0, 1, or 2. However, it is not limited to this.

The chloroalkylalkoxysilane may be (3-Chloropropyl)trimethoxysilane (Cl(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ), but is not limited thereto.

The amine compound may be a compound represented by the following formula (2).

[Formula 2]

NH(R ⁴ ) _p [(R ⁵ )-Si(R ⁶ ) _n (OR ⁷ ) _3-n ] _2-p

In Formula 2, R ⁴ is hydrogen, a C ₁ to C ₃₀ alkyl group or a C ₁ to C ₂₀ heteroalkyl group, R ⁵ is a C ₁ to C ₂₀ alkylene group, and R ⁶ is a C ₁ to C ₂₀ alkyl group. It is an alkyl group, R ⁷ is an alkyl group of C ₁ to C ₂₀ , n is 0, 1 or 2, and p may be 0, 1 or 2. For example, R ⁴ is hydrogen, a C ₁ to C ₁₆ alkyl group, or a C ₁ to C ₁₂ heteroalkyl group, R ⁵ is a C ₁ to C ₄ alkylene group, and R ⁶ is a C ₁ to C ₂ alkyl group. , R ⁷ is an alkyl group of C ₁ to C ₄ , n is 0, 1 or 2, and p may be 0, 1 or 2, but is not limited thereto.

The amine compound may be a silylated amine, for example, 3-(Trimethoxysilyl)propylamine, H ₂ N(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ). , but is not limited to this.

The metal halide may be a compound represented by the following formula (3).

[Formula 3]

MX

In Formula 3, M is an alkali metal, and X is a halogen element.

The alkali metal may be Li, Na, K, Rb, Cs, or Fr, and the halogen element may be F, Cl, Br, or I. For example, the metal halide may be NaBr, NaI, or KBr, but is not limited thereto.

The metal halide may be a compound represented by the following formula (4).

[Formula 4]

M'X ₂

In Formula 4, M' is an alkaline earth metal, and X is a halogen element.

The alkaline earth metal may be Be, Mg, Ca, Sr, Ba, or Ra, and the halogen element may be F, Cl, Br, or I.

The content of the chloroalkyl alkoxysilane contained in the mixture may be 1.1 to 10 moles per mole of the amine compound. For example, 1.1 mol, 1.2 mol, 1.3 mol, 1.4 mol, 1.5 mol, 1.6 mol, 1.7 mol, 1.8 mol, 1.9 mol, 2.0 mol, 2.1 mol, 2.2 mol, 2.3 mol, 2.4 mol, 2.5 mol, 2.6 mol. mol, 2.7 mol, 2.8 mol, 2.9 mol, 3.0 mol, 3.1 mol, 3.2 mol, 3.3 mol, 3.4 mol, 3.5 mol, 3.6 mol, 3.7 mol, 3.8 mol, 3.9 mol, 4.0 mol, 4.1 mol, 4.2 mol, 4.3 mol, 4.4 mol, 4.5 mol, 4.6 mol, 4.7 mol, 4.8 mol, 4.9 mol, 5.0 mol, 5.1 mol, 5.2 mol, 5.3 mol, 5.4 mol, 5.5 mol, 5.6 mol, 5.7 mol, 5.8 mol, 5.9 mol. , 6.0 mol, 6.1 mol, 6.2 mol, 6.3 mol, 6.4 mol, 6.5 mol, 6.6 mol, 6.7 mol, 6.8 mol, 6.9 mol, 7.0 mol, 7.1 mol, 7.2 mol, 7.3 mol, 7.4 mol, 7.5 mol, 7.6 mol, 7.7 mol, 7.8 mol, 7.9 mol, 8.0 mol, 8.1 mol, 8.2 mol, 8.3 mol, 8.4 mol, 8.5 mol, 8.6 mol, 8.7 mol, 8.8 mol, 8.9 mol, 9.0 mol, 9.1 mol, 9.2 mol, It may be 9.3 mol, 9.4 mol, 9.5 mol, 9.6 mol, 9.7 mol, 9.8 mol, 9.9 mol, 10.0 mol, or a value between two of these values. If the content of the chloroalkylalkoxysilane is outside the above range, the yield of the product may decrease and the efficiency of the aminoalkoxysilane compound manufacturing process may decrease.

In one example, the content of the chloroalkylalkoxysilane contained in the mixture may be 1.3 to 4 moles per 1 mole of the amine compound, but is not limited thereto.

The content of the metal halide contained in the mixture may be 0.001 to 5 moles per 1 mole of the amine compound. For example, 0.001 mol, 0.01 mol, 0.1 mol, 0.2 mol, 0.3 mol, 0.4 mol, 0.5 mol, 0.6 mol, 0.7 mol, 0.8 mol, 0.9 mol, 1.0 mol, 1.1 mol, 1.2 mol, 1.3 mol, 1.4 mol. mol, 1.5 mol, 1.6 mol, 1.7 mol, 1.8 mol, 1.9 mol, 2.0 mol, 2.1 mol, 2.2 mol, 2.3 mol, 2.4 mol, 2.5 mol, 2.6 mol, 2.7 mol, 2.8 mol, 2.9 mol, 3.0 mol, 3.1 mol, 3.2 mol, 3.3 mol, 3.4 mol, 3.5 mol, 3.6 mol, 3.7 mol, 3.8 mol, 3.9 mol, 4.0 mol, 4.1 mol, 4.2 mol, 4.3 mol, 4.4 mol, 4.5 mol, 4.6 mol, 4.7 mol. , 4.8 mol, 4.9 mol, 5.0 mol, or a value between these two values. If the content of the metal halide is less than the above range, the reaction time may be prolonged and process efficiency may be reduced, and if the content of the metal halide is above the above range, the process economics may be reduced.

In one example, the content of the metal halide contained in the mixture may be 1 to 4 moles per mole of the amine compound, but is not limited thereto.

The mixture may further include a base. That is, step (a) may be a step of preparing a mixture containing a chloroalkyl alkoxysilane, an amine compound, a metal halide, and a base.

The base is one selected from the group consisting of triethylamine (TEA), N,N-diisopropylethylamine (DIEA), 1,1,3,3-tetramethylguanidine (TMG), and combinations of two or more of these. However, it is not limited to this.

In one example, the content of the base contained in the mixture may be 1 to 4 moles per 1 mole of the amine compound, but is not limited thereto.

Step (b) is a step of reacting the mixture prepared in step (a), and may be performed with stirring.

Step (b) may be performed at 60 to 200°C. For example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135 ℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, or a value between two of these values. . If the reaction temperature is below the above range, the reaction time may be prolonged or the yield of the product may be reduced, and if the reaction temperature is above the above range, the yield of the product and process safety may be reduced.

Step (b) may be performed for 1 to 50 hours. For example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16. Time, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours, 37 hours, 38 hours, 39 hours, 40 hours, 41 hours, 42 hours, 43 hours, 44 hours, 45 hours, 46 hours, 47 hours, 48 hours, 49 hours , 50 hours, or any time between these two values. In one example, the method for producing an aminoalkoxysilane compound according to the present specification uses a metal halide as an additive along with a chloroalkylalkoxysilane and an amine compound, thereby reducing the reaction time by more than 50% compared to the case where the metal halide is not used. It can be shortened and at the same time show high selectivity and yield.

In step (b), a S _N 1 substitution reaction may occur. The reaction may be endothermic. The metal halide can promote the reaction by improving the living property of the nucleophile. The halogen of the metal halide can be Cl, Br, or I, and Br can induce a faster reaction than Cl, and I can induce a faster reaction than Br. Additionally, when a metal halide containing Br is used, the ratio of aminoalkoxysilanes with three alkoxysilane branches may be higher compared to when a metal halide containing Cl is used. When a metal halide containing I is used, an aminoalkoxysilane having four or more alkoxysilane branches can be produced.

Step (b) may be performed under a pressure of 0.1 to 10 bar. For example, 0.1bar, 0.2bar, 0.3bar, 0.4bar, 0.5bar, 0.6bar, 0.7bar, 0.8bar, 0.9bar, 1bar, 2bar, 3bar, 4bar, 5bar, 6bar, 7bar, 8bar, 9bar, 10bar. Alternatively, it may be performed under a pressure between any two of these values.

The method for producing the aminoalkoxysilane compound may further include (c) obtaining an aminoalkoxysilane compound as a product. For example, step (c) may include post-treatment (work-up) processes such as extraction, filtration, drying, distillation, etc., but is not limited thereto.

The yield of the aminoalkoxysilane compound prepared by the above method may be 80% or more. For example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95. It may be %, 96%, 97%, 98%, 99%, 99.5%, 99.9%, or a value between two of these values.

Hereinafter, embodiments of the present specification will be described in more detail. However, the following experimental results describe only representative experimental results among the above examples, and the scope and content of the present specification cannot be interpreted as being reduced or limited by the examples. Each effect of various implementations of the present specification that are not explicitly presented below will be described in detail in the corresponding section.

Examples 1 to 9

(3-Chloropropyl)trimethoxysilane, Cl(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ), 3-(trimethoxysilyl)propylamine, H ₂ N(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ), base and metal halide were mixed according to Table 1 below. The mixture was reacted by stirring at a temperature and pressure of 133° C. and 2.1 bar, and then cooled to room temperature. Heptane (C ₇ H ₁₆ ) was added to precipitate the formed salt, then the suspension was filtered and the solvent was evaporated. The product was distilled under reduced pressure to obtain Tris(3-(trimethoxysilyl)propyl)amine (C ₁₈ H ₄₅ NO ₉ Si ₃ ) as a colorless liquid.

Comparative example

A mixture of 196 mmol of (3-chloropropyl)trimethoxysilane, 55.6 mmol of 3-(trimethoxysilyl)propylamine, and 224 mmol of N,N-diisopropylethylamine (DIEA) was stirred until the starting materials were completely consumed. It was heated to 115°C. After confirming that the starting material was completely consumed, it was cooled to room temperature. After adding 300 mL of pentane to precipitate the formed salt, the suspension was filtered and the solvent was evaporated. The crude product was distilled under reduced pressure to give tris(3-(trimethoxysilyl)propyl)amine as a yellow viscous liquid.

division Chloroalkylalkoxysilane content (mmol) Amine compound content (mmol) base Base content (mmol) metal halide Metal halide content (mmol) Example 1 162.6 50.8 TEAs 106.7 NaBr 106.7 Example 2 163.8 51.2 TEAs 107.5 NaI 105.0 Example 3 164.5 51.4 TEAs 107.9 KBr 106.9 Example 4 170.2 53.2 DIEA 111.7 NaBr 112.8 Example 5 178.6 55.8 DIEA 117.2 NaI 113.3 Example 6 159.7 49.9 DIEA 104.8 KBr 102.8 Example 7 173.4 54.2 TMG 113.8 NaBr 112.7 Example 8 169.9 53.1 TMG 111.5 NaI 112.6 Example 9 171.2 53.5 TMG 112.4 KBr 114.5 Comparative example 196 55.6 DIEA 224 - - - TEA: Triethylamine (C ₂ H ₅ ) ₃ N)
- DIEA: N,N-Diisopropylethylamine, [(CH ₃ ) ₂ CH] ₂ NC ₂ H ₅ )
- TMG: 1,1,3,3-Tetramethylguanidine (CH ₃ ) ₂ NC(=NH)N(CH ₃ ) ₂ )

Experiment example

In the manufacturing methods of Examples 1 to 9 and Comparative Examples, the reaction time and product yield were measured and shown in Table 2 below.

division reaction time (hr) transference number (%) Example 1 48 96 Example 2 24 85 Example 3 36 93 Example 4 43 96 Example 5 24 87 Example 6 36 92 Example 7 40 97 Example 8 20 86 Example 9 36 92 Comparative example 96 90

Referring to Table 2, the manufacturing methods of Examples 1 to 9 showed a high yield of 91.56% on average, and in particular, Examples 1, 4, and 7 using NaBr as an additive showed a yield of more than 96%.

In addition, the preparation methods of Examples 1 to 9 had a reaction time of 20 to 48 hours, and the reaction was completed within one to two days, whereas the comparative example in which no metal halide was added required a reaction time of 96 hours, that is, 4 days. It was confirmed that it was done. In particular, Examples 2, 5, and 8, which used NaI as an additive, completed the reaction within 24 hours, requiring a shorter reaction time of less than 25% compared to the comparative example.

The description of the present specification described above is for illustrative purposes, and a person skilled in the art to which an aspect of the present specification pertains can easily transform it into another specific form without changing the technical idea or essential features described in the present specification. You will be able to understand it. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present specification is indicated by the claims described below, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present specification.

Claims (12)

(a) preparing a mixture containing a chloroalkyl alkoxysilane, an amine compound, and a metal halide; and
(b) reacting the mixture; a method for producing an aminoalkoxysilane compound, comprising: According to paragraph 1,
The chloroalkyl alkoxysilane is a method of producing an aminoalkoxysilane compound, which is a compound represented by the following formula (1):
[Formula 1]
Cl-(R ¹ )-Si(R ² ) _m (OR ³ ) _3-m
In Formula 1,
R ¹ is an alkylene group of C ₁ to C ₄ ,
R ² is an alkyl group of C ₁ to C ₂ ,
R ³ is an alkyl group of C ₁ to C ₄ ,
m is 0, 1 or 2. According to paragraph 1,
The amine compound is a method of producing an aminoalkoxysilane compound, which is a compound represented by the following formula (2):
[Formula 2]
NH(R ⁴ ) _p [(R ⁵ )-Si(R ⁶ ) _n (OR ⁷ ) _3-n ] _2-p
In Formula 2,
R ⁴ is hydrogen, a C ₁ to C ₁₆ alkyl group, or a C ₁ to C ₁₂ heteroalkyl group,
R ⁵ is an alkylene group of C ₁ to C ₄ ,
R ⁶ is an alkyl group of C ₁ to C ₂ ,
R ⁷ is an alkyl group of C ₁ to C ₄ ,
n is 0, 1 or 2,
p is 0, 1 or 2. According to paragraph 1,
The metal halide is a method of producing an aminoalkoxysilane compound, which is a compound represented by the following formula (3):
[Formula 3]
MX
In Formula 3 above,
M is an alkali metal,
X is a halogen element. According to paragraph 1,
The metal halide is a method of producing an aminoalkoxysilane compound, which is a compound represented by the following formula (4):
[Formula 4]
M'X ₂
In Formula 4 above,
M' is an alkaline earth metal,
X is a halogen element. According to paragraph 1,
A method for producing an aminoalkoxysilane compound, wherein the content of the chloroalkylalkoxysilane contained in the mixture is 1.1 to 10 mol per 1 mol of the amine compound. According to paragraph 1,
A method for producing an aminoalkoxysilane compound, wherein the content of the metal halide contained in the mixture is 0.01 to 5 mol per 1 mol of the amine compound. According to paragraph 1,
A method for producing an aminoalkoxysilane compound, wherein the mixture further includes a base. According to clause 8,
The base is one selected from the group consisting of triethylamine (TEA), N,N-diisopropylethylamine (DIEA), 1,1,3,3-tetramethylguanidine (TMG), and combinations of two or more of these. , Method for producing aminoalkoxysilane compounds. According to paragraph 1,
Step (b) is a method for producing an aminoalkoxysilane compound, wherein the step is performed at 60 to 200°C. According to paragraph 1,
The method of producing an aminoalkoxysilane compound, wherein step (b) is performed for 1 to 50 hours. According to paragraph 1,
Step (b) is a method for producing an aminoalkoxysilane compound, wherein the step is performed under a pressure of 0.1 to 10 bar.