KR20170005345A

KR20170005345A - Method for the preparation of alkylaminosilane

Info

Publication number: KR20170005345A
Application number: KR1020150095448A
Authority: KR
Inventors: 조수동; 전진욱; 이상필; 이수진; 전용석; 강일; 최승구; 김자연; 남종원; 홍종태; 이상진; 정회선; 정현호
Original assignee: 주식회사 덕산유엠티
Priority date: 2015-07-03
Filing date: 2015-07-03
Publication date: 2017-01-12

Abstract

More particularly, the present invention relates to a process for producing alkylaminosilanes, which comprises reacting an alkylamine with at least two halosilane mixtures selected from the group consisting of dihalosilanes, trihalosilanes and tetrahalosilanes, The present invention relates to a process for producing an alkylaminosilane by preparing an intermediate and reducing it to a metal hydride. The method of producing alkylaminosilane according to the present invention can produce alkylaminosilane with high yield while lowering the manufacturing cost by using commercially available low cost raw material.

Description

METHOD FOR THE PREPARATION OF ALKYLAMINOSILANE < RTI ID = 0.0 >

The present invention relates to a process for the preparation of alkylaminosilanes. More specifically, the present invention relates to a process for producing an alkylaminosilane, which comprises reacting an amine with halosilane to obtain an alkylaminosilane intermediate which is halogenated, and reacting the intermediate with a reducing agent to obtain an alkylaminosilane

Aminosilane is a compound useful as a film-forming material for electronic materials. The aminosilane precursors may be formed by a chemical vapor deposition (CVD) or an atomic layer deposition (ALD) in a semiconductor manufacturing process, such as a silicon-containing film such as a silicon nitride film, a silicon carbonitride film, or a silicon oxynitride ) Thin films. &Lt; / RTI >

Silicon nitride thin films act as diffusion masks, oxidation barriers, trench isolation, intermetallic dielectric materials that exhibit high dielectric breakdown voltages, and passivation layers. Because of these properties, new semiconductor processes require dielectric films that exhibit very low etch rates or very high film stresses. In order to obtain a dielectric film satisfying such a demand, a silicon nitride constituent material having an excellent electrical insulating property and oxidation resistance is required.

Chemical vapor deposition must be performed at a temperature of 750 ° C or higher to obtain the best film characteristics by depositing a silicon nitride thin film having a proper growth rate and uniformity from a mixture of ammonia (NH ₃ ) and dichlorosilane (Cl ₂ SiH ₂ ). Submerged ammonium chloride (NH ₄ Cl) or other chlorides, which are byproducts produced by the chemical reaction between the two materials, can cause problems such as particle formation and cloudy film formation. Furthermore, they may cause particle formation and deposition in the back of the tubes, piping lines and pump systems, which may cause damage to the wafer and the pump.

A technique for forming a silicon nitride film by plasma chemical vapor deposition or thermochemical deposition of ammonia and an aminosilane derivative (general formula (R ₁ R ₂ N) _n SiH ₄ _-n ) in the presence of nitrogen has been reported in Japanese Patent Laid-Open No. H06-132284. U.S. Pat. No. 5,234,869 reports that a silicon nitride film is formed by chemical vapor deposition of Si (N (CH ₃ ) ₂ ) ₄ (TDMASi) and ammonia at a chamber temperature of 700 ° C. and a pressure of 0.5 torr. Under the addition of the combined gas of ammonia or nitrogen _{SiH (N (CH 3) 2} ) 3 (tDMASi), SiH 2 (N (CH 3) 2) 2 (BDMASi) , and _{SiH 3 (N (CH 3)} 2) ( MDMASi) have been proposed as alternative reactants.

In US Patent No. 5,874,368, bis (t-butylamino) silane was used as a precursor for depositing a silicon nitride thin film by low-pressure chemical vapor deposition (CVD) at 500 to 800 ° C. Also in U.S. Patent Nos. 5,874,368 and 6,153,261, a silicon nitride film was formed using bis (t-butylamino) silane. U.S. Patent No. 6,391,803 discloses a _{Si (N (CH 3) 2} ) 4, SiH (N (CH 3) 2) 3, SiH 2 (N (CH 3) 2) 2, SiH 3 (N (CH 3) 2) , A thin film was formed by atomic layer deposition using trisdimethylaminosilane as the first reactant.

Recently, as the use and use of aminosilane have been increasing commercially, a process for producing aminosilane with high yield and efficiency by various synthesis methods has been of interest. A typical method for producing an aminosilane derivative is to react the halosilane with a secondary amine, separate the formed ammonium chloride and aminosilane, and then distillate and purify to obtain high purity aminosilane.

The first method for preparing primary dialkylaminosilanes is the preparation and characterization of dimethylaminosilane and diethylaminosilane (The Preparatoin and Properties of Dimethylamino and Diethylamino Silane, Aylett and Emsley, J. Chem. Soc. (P) 652- 655, 1967) by reacting the corresponding amine with a monohalosilane.

XSiH ₃ + 2RR ¹ NH → RR ¹ N-SiH ₃ + RR ¹ NH · HX

In this reaction, amines are linear, cyclic and heterocyclic alkyl amines and preferred amines are lower alkyl amines such as ethylamine, isopropylamine, t-butylamine, cyclohexylamine, and the like. Amines also use primary or secondary amines, depending on the desired product.

However, the monochlorosilane has a low boiling point, and is highly pyrophoric, and is chemically unstable, and is likely to spontaneously decompose into silane (SiH ₄ ) and dichlorosilane (SiH ₂ Cl ₂ ). Also, when reacting with a secondary amine, the yield of primary dialkylaminosilane is very low due to decomposition reaction of silane and halosilane, and it is difficult to obtain commercially.

A method for solving this problem is to prepare alkylaminosilane using dichlorosilane, trichlorosilane or tetrachlorosilane having high volatility. Korean Patent Laid-Open Publication No. 10-2014-0093915 discloses a process for producing chlorodialkylaminosilane and ammonium chloride by adding 2 equivalents of a secondary amine to dichlorosilane and then reacting the resulting filtrate with a metal hydride to form a primary di Alkylaminosilane. In a similar manner, in Korean Patent No. 1040325, an intermediate of SiH (NR ¹ R ² ) Cl ₂ is produced by reacting trichlorosilane with a secondary amine, and a metal hydride such as LiAlH ₄ is added, Alkylaminosilane. This method is advantageous in that trichlorosilane is easier to obtain and commercially available than dichlorosilane, and thus the production cost can be lowered.

Korean Patent Laid-Open Publication No. 10-2012-0037902 discloses a method for producing a primary dialkylaminosilane from tetrachlorosilane having a boiling point of 58 ° C and the lowest price. However, the intermediate formed from tetrachlorosilane has a disadvantage in that a large amount of metal hydride must be used as a reducing agent. In this patent, NaH / LiAlH ₄ / NaBH ₄ (100: 1: 2.65, molar ratio) or NaH / NaBH ₄ / LiAlH ₄ (as a reducing agent) is added to trichlorodiisopropylaminosilane as an intermediate to reduce the amount of LiAlH ₄ in the metal hydride 100: 10.6: 0.22, molar ratio), and the like are used to prepare the primary diisopropylaminosilane.

However, it is difficult to produce alkylaminosilane with a low yield and a high production yield, and there are restrictions on the use of raw materials. Therefore, there is a need to develop a process for producing alkylaminosilanes which can produce alkylaminosilanes at a high yield while lowering the manufacturing cost by using various raw materials and low cost raw materials by overcoming restrictions on the use of raw materials.

Korean Patent Publication No. 10-2014-0093915 Korean Patent No. 1040325 Korean Patent Publication No. 10-2012-0037902

Articles: J. Chem. Soc. (A) p 652-655, 1967

It is an object of the present invention to provide a method for economically producing alkylaminosilanes using commercially available and inexpensive raw materials.

Another object of the present invention is to provide a method for producing alkylaminosilane in high yield while lowering the production cost by optimizing the reaction raw materials and reaction conditions.

The technical problem of the present invention described above

(a) reacting an amine represented by the formula R ¹ R ² NH with a mixture of at least two halosilanes represented by the formula SiH ₃ _- _n X _n ₊₁ to obtain a compound represented by the following formula (1); And

(b) reacting a compound of formula (1) with a metal hydride to obtain a compound of formula (2)

Alkylaminosilane. &Lt; / RTI >

[Chemical Formula 1]

(2)

Wherein R ¹ and R ² are each independently a straight, branched or cyclic alkyl group of 1 to 6 carbon atoms, n is an integer of 1 to 3, and X is fluoro, chloro, bromo or iodo .

Preferably, in step (a), a mixture of two or more compounds represented by formula (1) is obtained.

When the halosilane mixture contains two kinds of halosilanes, the mixing ratio thereof is 100-0: 0-100 in terms of mol%, wherein one of them is less than 100 mol%, the other one is more than 0 mol% It is preferable that the total amount does not exceed 100 mol%.

When the halosilane mixture contains three kinds of halosilanes, the mixing ratio thereof is 100: 100: 0: 100 0 in terms of mol%, wherein one of the halosilane is less than 100 mol% and the other two halosilanes are each more than 0 mol% It is preferable that the total of the three species does not exceed 100 mol%.

In the step (a), the mixing ratio of the amine and the halosilane is preferably 2.0 - 2.5: 1.0 in terms of the molar ratio.

The amount of the metal hydride used in the step (b) is preferably proportional to the number of moles of the secondary amine used in the step (a) and the number of halogen atoms of the halosilane. In the step (b) It is preferable that the metal hydride is reacted at a rate of 1.5 mol or less per 1 mol.

The metal hydride is preferably at least one selected from the group consisting of _{LiH, NaH, KH, NaBH 4} , KBH4, NaAlH 4 and LiAlH _4.

A process for the preparation of alkylaminosilanes according to the present invention is provided. In the present invention, a halomonilane intermediate is prepared by reacting an alkylamine with at least two halosilane mixtures selected from the group consisting of dihalosilane, trihalosilane and tetrahalosilane, and reducing the resulting halohydrosilane intermediate to a metal hydride to obtain an alkyl By making the aminosilane, it is possible to produce the alkylaminosilane in a high yield while lowering the production cost by using a commercially available and inexpensive raw material which is commercially available.

1 is a gas chromatographic (GC) analysis result of a mixture of dichlorodiisopropylaminosilane and trichlorodiisopropylaminosilane, which is a diisopropylaminosilane preparation intermediate according to Example 1.
2 is a mass spectrum (GC-MS) of a mixture of dichlorodiisopropylaminosilane and trichlorodisopropylaminosilane, which is a diisopropylaminosilane preparation intermediate according to Example 1, wherein (a) is dichlorodiisopropylamino (B) is the mass spectrum of trichlorodisopropylaminosilane.
3 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of the diisopropylaminosilane prepared in Example 1. Fig.
4 is a carbon nuclear magnetic resonance (C-NMR) spectrum of the diisopropylaminosilane prepared in Example 1. Fig.
5 is a silicon nuclear magnetic resonance (Si-NMR) spectrum of the diisopropylaminosilane prepared in Example 1. Fig.
6 is a thermogravimetric analysis (TG) analysis result of the diisopropylaminosilane prepared in Example 1. Fig.
7 shows the results of differential scanning calorimetry (DSC) analysis of the diisopropylaminosilane prepared in Example 1. Fig.
8 is a gas chromatographic (GC) analysis result of the diisopropylaminosilane prepared and purified in Example 1. Fig.

The present invention relates to a process for the preparation of alkylaminosilanes,

(b) reacting the compound of formula (1) with a metal hydride to obtain a compound of formula (2).

[Chemical Formula 1]

(2)

In the above-mentioned amine, halosilane, R ¹ and R 2 in formulas (1) and ( ²⁾ are each independently a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, preferably each independently methyl, ethyl, Propyl, n-butyl, t-butyl, pentyl, methylcyclopentyl, hexyl and cyclohexyl, more preferably isopropyl or t-butyl, n is an integer of 1 to 3, X Is preferably fluoro, chloro, bromo or iodo, more preferably chloro.

In the present invention, the halosilane is at least two selected from the group consisting of dihalosilane, trihalosilane and tetrahalosilane. In the present invention, a haloalkylaminosilane intermediate is prepared using a mixture of at least two commercially available low cost halosilanes as a reactant, and the intermediate is reduced with a reducing agent, It becomes possible to manufacture

When it is necessary to increase the purity of the final product, alkylaminosilane, the secondary amine and halosilane are preferably used with a purity of 99.5% or more, more preferably 99.99% or more, and most preferably, And a metal impurity component of several ppb or less is used.

When the reagent is introduced into the reactor, it is preferable to use an inert gas as a carrier gas to prevent exposure to air or moisture. The inert gas may be selected from nitrogen, argon, helium, and a mixed gas thereof.

Examples of the reaction solvent include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane or 2,2,4-trimethylpentane; Alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene, and xylene; Ketone solvents such as acetone and methyl ethyl ketone; Diethyl ether, di-n-propyl ether, diisopropyl ether, diglyme, dimethoxymethane, dimethoxyethane, dimethoxypropane, diethoxymethane, diethoxyethane or diethoxyethane Ether solvents such as diethoxypropane; Ester solvents such as methyl acetate and ethyl acetate; And a cyano solvent such as acetonitrile may be used. Most preferably, tetrahydrofuran can be used as the solvent. It is preferred that the solvent be added in an amount of 4 to 10 times the total volume of the halosilane mixed with the amine.

In the step (a), the mixing ratio of the amine and the halosilane is suitably in a stoichiometrically 2.0 2.5: 1.0 molar ratio, and preferably the molar ratio is 2.05: 1.0 in terms of the yield of the haloalkylaminosilane intermediate Do.

The reaction of step (a) is carried out at -30 to 80 캜, preferably -20 to 60 캜. If it is necessary to control the heat generated during the reaction, circulating refrigerant may be introduced into the jacket reactor or a cooling temperature control device may be installed.

In step (a) of the present invention, the removal of the by-product amine salt is closely related to the yield of the final product. Therefore, it is preferable to use at least one filter for the filtration process. In addition, when the salt is removed after the reaction with the metal hydride in step (b), it is appropriate to use a plurality of mini filters capable of filtering by a small amount. A suitable filtration medium is a 0.5-5 micron mesh filter, wherein the reduced pressure is suitably carried out at 500-750 torr. In order to effectively remove ammonium chloride, filtration is preferably carried out at a temperature in the range of 0-30 占 폚.

In the present invention, the step (b) is a reduction reaction in which the haloalkylaminosilane, which is an intermediate, is substituted with a halogen. As the reducing agent, it is preferable to use at least one metal hydride selected from the group consisting of LiH, NaH, KH, NaBH ₄ , KBH ₄ and LiAlH ₄ .

For example, the addition amount of the metal hydride in the step (b) can be expressed by the following equation (1).

[Equation 1]

(Number of moles of secondary amine used / number of halosilane A / 200) x (number of halogen atoms of halosilane A / 2)] + [(number of moles of secondary amine used x% of halosilane B / 200) x (the number of halogen atoms of halosilane B / 2)]

For example, when 4 mol of secondary amine, 1 mol of 50% trihalosilane and 1 mol of 50% dichlorosilane are used as starting materials, 2.5 mol of LiAlH ₄ is preferably added.

In the addition of the metal hydride, it is possible to add 2 mol or more of a metal hydride to 1 mol of the haloalkylaminosilane intermediate, but it is inefficient to add an excessive amount, and it is also easy to treat the remaining metal hydride in the filtration step Not desirable. Therefore, in the step (b), it is appropriate to add the metal hydride in a proportion of 1.5 mol or less based on 1 mol of the intermediate represented by the formula (1).

When the reaction of substituting the halogen with hydrogen in the reaction of step (b) is slow, refluxing when LAlH ₄ remains in the reactant, or adding about 1/10 of LAlH ₄ and refluxing the reaction mixture, You can let it go.

It is effective to keep the temperature at room temperature (about 20 ° C) during the addition of the metal hydride to the filtrate obtained by filtration after completing the reaction of step (a), and it is effective that the metal hydride is not to exceed 40 ° C as much as possible. However, after the addition of the metal hydride, the reaction is carried out at 20 to 100 캜, preferably 30 to 80 캜. When the reaction is carried out under such conditions for 4 to 24 hours, the reduction reaction is completed.

In the present invention, the final product can be obtained in a yield of 80% or more, and the alkylaminosilane can be obtained in a purity of 99.98% or more through a distillation purification process.

Synthetic example

1. Intermediate Haloalkylaminosilane Synthetic example

Illustratively, the compound represented by formula (1) can be produced by a reaction path as shown in the following reaction formula (1). In the following Reaction Scheme 1, the halosilane mixture reacting with the secondary amine is a halosilane mixture of dichlorosilane and trichlorosilane, which is a halosilane represented by SiH _3-n X _{n + 1} wherein n is 1 and 2 Lt; RTI ID = 0.0 > halosilane.

As shown in Scheme 1, monochloroalkylaminosilane and dichloroalkylaminosilane can be produced by reacting a chlorosilane mixture in which dichlorosilane and trichlorosilane are mixed under an anhydrous atmosphere or an inert gas with a secondary amine. Removal of the ammonium chloride precipitate from the product gives the intermediate filtrate of formula (1).

2. Alkylaminosilane Synthetic example

Illustratively, the alkylaminosilane, which is the final compound represented by Formula 2, can be produced by the following Reaction Scheme 2.

As shown in Reaction Scheme 2, when one or more metal hydrides are added to the intermediate filtrate in which the monochloroalkylaminosilane and dichloroalkylaminosilane produced in Scheme 1 are mixed, alkylaminosilane, which is the final product, is obtained .

Example

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the examples are merely examples of the present invention and the scope of the present invention should not be construed as being limited to these examples.

One. Chlorosilane Depending on type and mixing ratio Of diisopropylaminosilane Produce

Example 1 Preparation of diisopropylaminosilane from tetrachlorosilane and trichlorosilane mixed at 50:50

(1) Production example of haloalkylaminosilane which is an intermediate

A mechanical stirrer, a digital thermometer and a condenser were installed in a 5-necked 20 L round-bottomed flask, which was dried under a nitrogen stream, and diisopropylamine (1,086 g, 10.732 mol) was added. 6000 mL of tetrahydrofuran was added, Respectively. The solution was cooled to -20 ° C while stirring, and a mixed solution obtained by dissolving trichlorosilane (360 g, 2.658 mol) and tetrachlorosilane (451.6 g, 2.658 mol) in 1000 mL of tetrahydrofuran was maintained at -20 ° C. After slowly adding to the above reaction, the reaction solution was slowly warmed to room temperature. The reaction was stirred for 5 hours at room temperature and then for 2 hours at 35-40 < 0 > C for 2 hours. A sample of the reactant was sampled and analyzed by gas chromatography to determine the reaction conversion rate and end point.

The resulting white solid was then filtered and washed three times with 200 mL each of tetrahydrofuran. The white solid was removed from the filter, and a filtrate was obtained. The compounds were identified by GC data on the filtrate. As a result, the following GC data, the GC results shown in FIG. 1, and the MS results of the GC-MS shown in FIG. 2 were obtained.

Fig. 2 (a) shows the GC-MS results of the dichlorodiisopropylaminosilane as an intermediate, and Fig. 2 (b) shows the MS results of the GC-MS of the intermediate trichlorodiisopropylaminosilane.

Thus, it was confirmed that the filtrate contained dichlorodiisopropylaminosilane and trichlorodiisopropylaminosilane as intermediates.

(2) Production Example of alkylaminosilane as the final product

LiAlH ₄ (255 g, 6.708 mol) was gradually added while maintaining the filtrate obtained in the above (1) at room temperature. After the addition, the temperature was raised to 50 DEG C and refluxed for 6 hours. After refluxing, the reaction was cooled to room temperature, filtered and washed with 200 mL of tetrahydrofuran three times to give a clear filtrate. Samples were taken from the obtained filtrate and analyzed by gas chromatography to confirm the reaction conversion ratio and the end point.

The filtrate was transferred little by little to a 2 L flask in a fractionation distillation apparatus equipped with a distillation head, a column, a condenser and a diaphram pump, and concentrated and repeatedly worked to remove the solvent. The solvent was removed, and vacuum distillation was performed at 49 ° C to 50 ° C at 100 Torr to obtain 606 g (yield: 86%) of diisopropylaminosilane.

The finally obtained compound was analyzed for hydrogen nuclear magnetic resonance (H-NMR), carbon nuclear magnetic resonance (C-NMR), silicon nuclear magnetic resonance (Si-NMR), thermogravimetric analysis (TG) ), And gas chromatography (GC) analysis. As a result, it was confirmed that the final compound obtained was diisopropylaminosilane. Fig. 3 shows the nuclear magnetic resonance (H-NMR) spectrum, Fig. 4 shows the carbon nuclear magnetic resonance (C-NMR) spectrum, Fig. 5 shows the silicon nuclear magnetic resonance (TG) analysis, FIG. 7 shows differential scanning calorimetry (DSC) results, and FIG. 8 shows gas chromatography (GC) analysis.

< Example 2 > 50:50 Dichlorosilane and From trichlorosilane Of diisopropylaminosilane Produce

(1) Production example of haloalkylaminosilane which is an intermediate

A mechanical stirrer, a digital thermometer and a condenser were installed in a 5-necked 20 L round-bottomed flask, which was dried under a nitrogen stream, and diisopropylamine (1,086 g, 10.732 mol) was added. 6000 mL of tetrahydrofuran was added, Respectively. The solution was cooled to 20 ° C with stirring, and a mixed solution obtained by dissolving trichlorosilane (360 g, 2.658 mol) and dichlorosilane (268.5 g, 2.658 mol) in 1000 mL of tetrahydrofuran was maintained at -20 ° C. Was added slowly to the reaction mixture, and then the reaction solution was slowly warmed to room temperature. The reaction was stirred for 5 hours at room temperature and then for 2 hours at 35-40 < 0 > C for 2 hours. A sample of the reactant was sampled and analyzed by gas chromatography (GC) to determine the reaction conversion rate and end point.

The resulting white solid was then filtered and washed three times with 200 mL each of tetrahydrofuran. The white solid was removed from the filter and the filtered filtrate was obtained.

(2) Production Example of alkylaminosilane as the final product

LiAlH ₄ (153 g, 4.025 mol) was slowly added while maintaining the filtrate obtained in the above (1) at room temperature. After the addition was completed, the temperature was raised to 50 DEG C and refluxed for 5 hours. After refluxing, the reaction was cooled to room temperature, filtered and washed with 200 mL of tetrahydrofuran three times to give a clear filtrate. Samples were taken from the obtained filtrate and analyzed by gas chromatography to confirm the reaction conversion ratio and the end point.

The filtrate was transferred little by little to a 2 L flask in a fractionation distillation apparatus equipped with a distillation head, a column, a condenser and a diaphram pump, and concentrated and repeatedly worked to remove the solvent. After the solvent was removed, the product was vacuum distilled at 49 ° C to 50 ° C and 100 Torr to obtain 592 g (yield: 84%) of the final product

< Example 3 > 50:50 Tetrachlorosilane and From dichlorosilane Of diisopropylaminosilane Produce

(1) Production example of haloalkylaminosilane which is an intermediate

A mechanical stirrer, a digital thermometer and a condenser were installed in a 5-necked 20 L round-bottomed flask, which was dried under a nitrogen stream, and diisopropylamine (1,086 g, 10.732 mol) was added. 6000 mL of tetrahydrofuran was added, Respectively. The solution was cooled to -20 ° C while stirring, and a mixed solution obtained by dissolving tetrachlorosilane (451.6 g, 2.658 mol) and dichlorosilane (268.5 g, 2.658 mol) in 1000 mL of tetrahydrofuran was maintained at -20 ° C. Was slowly added to the reaction mixture, and the reaction solution was slowly warmed to room temperature. The reaction was stirred for 5 hours at room temperature and then for 2 hours at 35-40 < 0 > C for 2 hours. A sample of the reactant was sampled and analyzed by gas chromatography to determine the reaction conversion rate and end point.

The resulting white solid was then filtered and washed three times with 200 mL each of tetrahydrofuran. The white solid was removed from the filter, and a filtrate was obtained.

(2) Production Example of alkylaminosilane as the final product

LiAlH ₄ (204 g, 5.366 mol) was gradually added while maintaining the filtrate obtained in the above (1) at room temperature. After the addition, the temperature was raised to 50 DEG C and refluxed for 6 hours. After refluxing, the reaction was cooled to room temperature, filtered and washed with 200 mL of tetrahydrofuran three times to give a clear filtrate. Samples were taken from the obtained filtrate and analyzed by gas chromatography to confirm the reaction conversion ratio and the end point. The filtrate was transferred little by little to a 2 L flask in a fractionation distillation apparatus equipped with a distillation head, column, chiller and diaphram pump, and concentrated and repeatedly worked to remove the solvent. The solvent was removed, and vacuum distillation was performed at 49 ° C to 50 ° C at 100 Torr to obtain 599 g (yield: 85%) of diisopropylaminosilane.

< Example 4 > 90:10 Tetrachlorosilane and From trichlorosilane Of diisopropylaminosilane Produce

(1) Production example of haloalkylaminosilane which is an intermediate

A mechanical stirrer, a digital thermometer and a condenser were installed in a 5-necked 20 L round-bottomed flask, which was dried under a nitrogen stream, and diisopropylamine (1,086 g, 10.732 mol) was added. 6000 mL of tetrahydrofuran was added, Respectively. The solution was cooled to -20 ° C with stirring, and a mixed solution obtained by dissolving trichlorosilane (72.683 g, 0.5366 mol) and tetrachlorosilane (820.47 g, 4.8294 mol) in 1000 mL of tetrahydrofuran was maintained at -20 ° C. After slowly adding to the above reaction, the reaction solution was slowly warmed to room temperature. The reaction was stirred for 5 hours at room temperature and then for 2 hours at 35-40 < 0 > C for 2 hours. A sample of the reactant was sampled and analyzed by gas chromatography to determine the reaction conversion rate and end point.

(2) Production Example of alkylaminosilane as the final product

LiAlH ₄ (295.3 g, 7.781 mol) was gradually added while maintaining the filtrate obtained in the above (1) at room temperature. After the addition was completed, the temperature was raised to 50 DEG C and refluxed for 5 hours. After refluxing, the reaction was cooled to room temperature, filtered and washed with 200 mL of tetrahydrofuran three times to give a clear filtrate. Samples were taken from the obtained filtrate and analyzed by gas chromatography to confirm the reaction conversion ratio and the end point.

The filtrate was transferred little by little to a 2 L flask in a fractionation distillation apparatus equipped with a distillation head, a column, a condenser and a diaphram pump, and concentrated and repeatedly worked to remove the solvent. The solvent was removed and vacuum distillation was conducted at 49 ° C to 50 ° C at 100 Torr to obtain 595 g (yield: 84.5%) of diisopropylaminosilane.

2. Depending on the type of reducing agent Of diisopropylaminosilane Produce

< Example 5 > 50:50 Monochlorodiisopropylaminosilane and Of dichlorodiisopropylaminosilane By reduction Of diisopropylaminosilane Produce

NaH (54 g, 1.35 mol) was gradually added to the filtrate obtained in Example 2 (1) at room temperature, followed by the slow addition of LiAlH ₄ (100.87 g, 2.658 mol). After the addition of the reducing agent was completed, the temperature was raised to 50 DEG C and refluxed for 8 hours. After refluxing, the reaction was cooled to room temperature, filtered and washed with 200 mL of tetrahydrofuran three times to give a clear filtrate. Samples were taken from the obtained filtrate and analyzed by gas chromatography to confirm the reaction conversion ratio and the end point.

< Example 6 > 50:50 Monochlorodiisopropylaminosilane and Of dichlorodiisopropylaminosilane By reduction Of diisopropylaminosilane Produce

NaH (54 g, 1.35 mol) was slowly added to the filtrate obtained in Example 2 (1) at room temperature, followed by the slow addition of NaBH ₄ (100.6 g, 2.658 mol). After the addition of the reducing agent was completed, the temperature was raised to 50 DEG C and refluxed for 12 hours. After refluxing, the reaction was cooled to room temperature, filtered and washed with 200 mL of tetrahydrofuran three times to give a clear filtrate. Samples were taken from the obtained filtrate and analyzed by gas chromatography to confirm the reaction conversion ratio and the end point.

The filtrate was transferred little by little to a 2 L flask in a fractionation distillation apparatus equipped with a distillation head, a column, a condenser and a diaphram pump, and concentrated and repeatedly worked to remove the solvent. The solvent was removed, and vacuum distillation was performed at 49 ° C to 50 ° C at 100 Torr to obtain 599 g (yield: 85%) of diisopropylaminosilane.

< Example 7 > 50:50 Monochlorodiisopropylaminosilane and Of dichlorodiisopropylaminosilane By reduction Of diisopropylaminosilane Produce

LiAlH ₄ (25.81 g, 0.68 mol) was slowly added to the filtrate obtained in Example 2 (1) at room temperature, followed by slowly adding NaBH ₄ (100.6 g, 2.658 mol). After the addition of the reducing agent was completed, the temperature was raised to 50 DEG C and refluxed for 12 hours. After refluxing, the reaction was cooled to room temperature, filtered and washed with 200 mL of tetrahydrofuran three times to give a clear filtrate. Samples were taken from the obtained filtrate and analyzed by gas chromatography to confirm the reaction conversion ratio and the end point.

The filtrate was transferred little by little to a 2 L flask in a fractionation distillation apparatus equipped with a distillation head, a column, a condenser and a diaphram pump, and concentrated and repeatedly worked to remove the solvent. The solvent was removed, and vacuum distillation was conducted at 49 ° C to 50 ° C at 100 Torr to obtain 585 g (yield: 83%) of diisopropylaminosilane.

The present invention has been described above by way of examples. It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are only illustrative of the present invention and are not intended to limit the scope of the invention. The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.

Claims

(a) reacting an amine represented by the formula R ¹ R ² NH with a mixture of at least two halosilanes represented by the formula SiH ₃ _- _n X _n ₊₁ to obtain a compound represented by the following formula (1); And
(b) reacting a compound of formula (1) with a metal hydride to obtain a compound of formula (2): < EMI ID =
[Chemical Formula 1]

(2)

Wherein R ¹ and R ² are each independently a straight, branched or cyclic alkyl group of 1 to 6 carbon atoms, n is an integer of 1 to 3, and X is fluoro, chloro, bromo, or iodo to be.

The method according to claim 1,
Wherein a mixture of two or more compounds represented by the formula (1) is obtained in the step (a).

The method according to claim 1,
Wherein R ¹ and R ² are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, methylcyclopentyl, hexyl and cyclohexyl &Lt; / RTI >

4. The method according to any one of claims 1 to 3,
Wherein X is chloro.

The method according to claim 1,
When the halosilane mixture contains two kinds of halosilanes, the mixing ratio thereof is 100-0: 0-100 in terms of mol%, wherein one of them is less than 100 mol%, the other one is more than 0 mol% And the total amount does not exceed 100 mol%.

The method according to claim 1,
When the halosilane mixture contains three kinds of halosilanes, the mixing ratio thereof is 100: 100: 0: 100 0 in terms of mol%, wherein one of the halosilane is less than 100 mol% and the other two halosilanes are each more than 0 mol% And all three species do not exceed 100 mol%.

The method according to claim 1,
Wherein the molar ratio of amine to halosilane in the step (a) is 2.0 to 2.5: 1.0.

The method according to claim 1,
Wherein the amount of the metal hydride used in the step (b) is proportional to the number of moles of the secondary amine used in the step (a) and the number of halogen atoms of the halosilane.

The method according to claim 1,
Wherein the metal hydride is reacted in a ratio of 1.5 mol or less to 1 mol of the compound of the formula (1) in the step (b).

The method according to claim 1,
A method for producing a silane-alkylamino in that the metal hydride is _{LiH, NaH, KH, NaBH 4} , KBH4, NaAlH 4 and LiAlH ₄ is at least one selected from the group consisting of.