JPH0219385A - Production of aminoalkyl group-containing silicon compound - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the subject compound useful as a raw material, etc., for synthesis of various chemical substances in high purity by subjecting a specific compound and a hydrosilane compound to addition reaction in the presence of a catalyst. CONSTITUTION:For example, to 100pts.wt. compound expressed by formula I (Q represents divalent 2-6C hydrocarbon) (diallylamine derivative), are added 0.001-5.0pts. catalyst (preferably platinum black, etc.), which is heated at preferably 10-110 deg.C while stirring in a solvent (example; toluene), into which a compound expressed by formula II [R<1> represents monovalent (substituted) hydrocarbon; Y represents alkoxy; n is 0, 1 or 2] (example; trimethoxysilane) is dripped and the product is purified by distillation under a reduced pressure, etc., to afford the objective compound expressed by formula III. The compound expressed by formula II is preferably used at a molar ratio within the range of 2.0-4.0 based on the compound expressed by formula I.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention provides an aminoalkyl group-containing material useful as a synthetic raw material for various chemical substances, a modifier for polymer compounds, a coupling agent for organic resins and inorganic fillers, etc. The present invention relates to a method for producing a silicon compound.

[Technical background of the invention and its problems]

Organosilicon compounds having two types of functional groups in the same molecule are well known, and by taking advantage of the reactivity or difference in reactivity of each functional group, they can be used as silane coupling agents, raw materials for various chemical substances, and silicon-containing compounds. For example, an organosilicon compound used as a silane coupling agent, which is used as a monomer, crosslinking agent, or modifier for the production of polymeric compounds, contains a carbon functional group that binds to an organic material in the same molecule.
It has a silicon functional group that reacts with and bonds with inorganic materials, and plays the role of intervening at the interface between organic and inorganic materials to firmly bond them.

As such a substance, HJ-CFlzCHz-N [(CHI) ssi (
OCH*) 3)! The compound represented by
It is shown in the publication No.-12407. However, in the production method described in the publication, two types of reaction products, CI) and (n), are obtained according to the following formula.

HJC4hCIItNHz + 2CICIIzCHz
CHgSi C0CHs”) sThis publication does not contain any description of reaction yield or reaction selectivity, but when the reaction is actually carried out, the reaction product will be a mixture of (1) and (II), and the production ratio will be is (1): (n); 3: 7
It became.

A further problem is that (I) and (II) are structural isomers and have almost no difference in physical properties, making separation extremely difficult. Therefore, for industrial use, (1), (
There was no choice but to use the mixture as it was without performing the separation of II). In addition, (1) and (n) contain large differences in reactivity, such as primary and secondary amines, so they are insufficient as raw materials for the synthesis of organic compounds, and are not used as silane coupling agents. The effects were also uneven.

That is, the conventional method has a drawback of low reaction selectivity as a method for producing the target compound (I), and therefore, the application of the compound (1) is also limited.

[Purpose of the invention]

The purpose of the present invention is to eliminate such drawbacks and to produce an aminoalkylsilane compound containing a highly reactive primary amino group and a silyl group with two hydrolyzable groups, which is highly pure and industrially advantageous. The object of the present invention is to provide a method for manufacturing the same.

[Structure of the invention]

As a result of intensive studies to achieve the above object, the present inventors found that a compound represented by the general formula % (where Q is a divalent hydrocarbon group having 2 to 6 carbon atoms); A hydrosilane compound represented by the general formula % (where R' is a substituted or unsubstituted monovalent hydrocarbon group, Y is an alkoxy group, and n is 0.1 or 2) in the presence of a catalyst. An aminoalkyl group-containing silicon compound represented by the general formula % (where Q, R', Y, and n are as described above) is produced by the addition reaction, and
It has been discovered that the desired product can be easily purified by distillation under reduced pressure, and the present invention has been completed.

That is, the present invention relates to a method for producing an aminoalkyl group-containing silicon compound useful as a raw material for the synthesis of organic compounds and as a coupling agent between an organic phase and an inorganic phase.

A compound represented by the formula HJ-Q-N(CHzCH=CHz)z (where Q is as described above) has an allyl group of 2
It is a diamine compound that contains 1,000 ml of diamine, and is a substance that forms the composition of the present invention through an addition reaction with a hydrosilane compound. This substance is obtained by a dehydrohalogenation reaction between a halogenated alkylamine represented by XI (3N-Q-X' (X is a halogen atom) and diallylamine. Q of such a halogenated alkylamine is carbon Although it represents a divalent hydrocarbon group of number 2 to 6, -CI (zcH
z-, -CHzCHzCII□-, -C)12clI-
Such compounds, preferably selected from CH3, include 2-chloroethylamine hydrochloride, 2-bromoethylamine hydrobromide, 3-bromopropyl-1-amine hydrobromide, 1-amino-2
-bromopropane hydrobromide, 3-bromo-2
- Amitubukun hydrobromide and the like are exemplified.

In addition, if necessary, a known method (Org, 5ynthesis Co1. Vol.
, II+91 (1966), J, 8a+, ch.
em, Soc,, Dan3. 2374 (1941
).

J, Am, Chem, Soc,, 59.2252 (
The corresponding halogenated alkylamine salts can also be synthesized according to the method (1937)).

The charging molar ratio of diallylamine to halogenated alkylamine salt is set at 3. from the viewpoint of preventing side reactions such as reactions between halogenated alkylamine salts and from an economical point of view.
It is generally carried out in the range of 0 to 7.0.

The reaction temperature can be carried out in the range of 20 to 150"C, but preferably in the range of 70 to 110"C.

This reaction is generally carried out at normal pressure, but may be under increased or reduced pressure if necessary. Furthermore, the solvent used during the reaction is not particularly required, but may be used to enhance the solubility of the raw materials or to control the temperature. Examples of such solvents include water, toluene, xylene, cyclohexane, n-
Hydrocarbon solvents such as hexane, n-hebutane, naphtha, mineral spirits, petroleum benzine, halogenated hydrocarbons such as chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, 1,1.1-)lichloroethane Ether solvents such as ethyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; Ester solvents such as ethyl acetate, butyl acetate, and amyl acetate; acetone, methyl ethyl ketone,
Ketone solvents such as methyl isobutyl ketone; methanol, ethanol, isopropanol, butanol, 2
-methoxyethanol, 2-ethoxyethanol, 2-
Examples include alcohol solvents such as butoxethanol, ethylene glycol, and propylene glycol; and aprotic polar solvents such as dimethylformamide, dimethylacetamide, and dimethyl sulfoxide.

The reaction time is not particularly limited, as it varies depending on the raw materials, solvent, reaction temperature, etc. used. However, conditions are usually set so that the reaction is completed in 1.0 to 10 hours.

The reaction is carried out by mixing the halogenated alkylamine salt and diallylamine and heating and stirring the mixture at a predetermined temperature6.
After the reaction, hydrogen halide in the reaction system is removed by washing with water, and a diallylamine derivative can be obtained by distillation.

The hydrosilane compound that undergoes the addition reaction with the diallylamine derivative has the formula H5IR'+sY! -n (R', Y, n
is expressed as (as described above). Examples of the substituted or unsubstituted monovalent hydrocarbon group for R1 include alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; 2-phenyl; Aralkyl groups such as ethyl groups, phenyl groups, aryl groups such as tolyl groups;
and chloromethyl group, chlorophenyl group, 3.3.3
- Substituted hydrocarbon groups such as -trifluoropropyl group are exemplified, but methyl group is preferred from the viewpoint of easy availability. Further, as the alkoxy group of Y, methoxy group,
Examples include ethoxy group, propoxy group, butoxy group, and from the viewpoint of reactivity and availability, alkoxy groups having 1 to 3 carbon atoms, particularly methoxy group or ethoxy group, are more preferred.

Therefore, examples of such silanes include trimethoxysilane, triethoxysilane, tripropoxysilane, methyldimethoxysilane, methyljethoxysilane, dimethylmethoxysilane, and dimethylethoxysilane.

The catalyst used for the addition reaction between the diallylamine derivative and the hydrosilane compound is a catalyst commonly used in the so-called hydrosilylation reaction, such as platinum, palladium, nickel,
Examples include transition metals such as cobalt and ruthenium and their complexes, but platinum metals such as platinum black and chloroplatinic acid,
A platinum catalyst is preferred because it shortens the reaction time and provides the desired product in high yield. The amount of catalyst is preferably in the range of 0.001 to 5.0 parts by weight, more preferably 0.01 to 1.0 parts by weight, per 100 parts by weight of diallylamine derivative produced in the first step. If the amount of catalyst added is less than 0.001 parts by weight, the reaction rate will not be sufficient, and if it is added in excess of 5.0 parts by weight, not only will there be no improvement in the reaction rate, but it is also preferable from an economical point of view. do not have.

The molar ratio of the hydrosilane compound to the diallylamine derivative is 1.5 to 5.0, and 2.0 to 4.
A range of 0 is preferred. The reaction temperature of hydrosilylation is -3
It can be carried out in the range of 0 to 150"C, but preferably 10"C.
It is usually carried out in the range of ~110°C. This reaction is generally carried out at normal pressure, but may be under increased or reduced pressure if necessary.

Further, the solvent used in the reaction is not particularly required, but may be used to improve the solubility of the catalyst or to control the temperature. As such a solvent, a solvent without reactivity of an alkoxy group can be used, such as toluene, xylene, cyclohexane, n-hexane, n-hebutane, naphtha, mineral spirit,
Hydrocarbon solvents such as petroleum benzene; Chloroform:
Halogenated hydrocarbon solvents such as carbon tetrachloride, trichlorethylene, perchlorethylene, 1.1.1-trichloroethylene; ether solvents such as ethyl ether, tetrahydrofuran, ethylene glycol diethyl ether; ethyl acetate, butyl acetate, amyl acetate Examples include ester solvents such as; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and aprotic polar solvents such as dimethylformamide and dimethylacetamide.

The reaction time is not particularly limited because it varies depending on the raw materials, catalyst or solvent used, reaction temperature, etc.

However, conditions are usually set so that the reaction is completed in 0.5 to 6 hours. The reaction is carried out by conventional methods.

For example, this can be carried out by heating a mixture of a diallylamine derivative and a catalyst to a predetermined temperature while stirring, and adding a hydrosilane compound dropwise thereto.

Since the obtained compound was obtained through a highly selective reaction, it can be purified by known techniques such as distillation, gas chromatography, liquid chromatography, and column chromatography.

In order to increase the stability of the raw materials and products during the reaction and purification, there is no problem in adding known appropriate polymerization inhibitors and antioxidants in advance as a conventional method.

〔Effect of the invention〕

By the production method of the present invention described above, N can be produced with high yield and high purity.
, N-bis(silylpropyl)alkylene diamines were obtained, and N,N'-bis(silylpropyl)alkylene diamines, which are difficult to separate and interfere with subsequent reactions, could be removed. Organosilicon compounds containing such highly reactive primary amino groups are extremely useful in molecular design as various reaction raw materials and intermediates.

Thus, the aminoalkylsilane compound obtained by the production method of the present invention can be used as a raw material for the synthesis of various organic compounds, as a raw material for silicone modification of other organic polymers and as an intermediate, or as a raw material for silicone modification of other organic polymers or as an intermediate for the synthesis of organic resins and inorganic fillers. Numerous applications are possible, including use as a coupling agent.

〔Example〕

EXAMPLES In order to explain the present invention more specifically, Examples will be given below, but the present invention is not limited to these Examples. Note that all parts in the examples indicate parts by weight.

Synthesis Example 1 (Synthesis of N,N-diallylethylenediamine) In a three-bottle flask equipped with a cooling tube and a mechanical stirrer, 30% of 2-bromoethylamine hydrobromide was added.
8 parts and 300 parts of cold water were added and stirred. 728 parts of diallylamine suspended in 1050 parts of cold water were added thereto, and the reaction mixture was gradually heated to 70°C while stirring.

After heating and stirring at 70°C for 4 hours, the mixture was cooled to room temperature. Then, sodium hydroxide was added while stirring until the reaction mixture separated into two layers. Subsequently, the organic layer was separated, and the aqueous layer was extracted with ether twice.

After thoroughly drying the organic layer using potassium hydroxide, ether was removed, and unreacted diallylamine was recovered (428 parts, 74% recovery) and distilled under reduced pressure.

94.8 parts of a colorless and transparent liquid with a boiling point of 90-91'C/30 Torr was obtained. The yield was 45%.

Example 1 A dropping funnel, a thermometer, and a cooling tube with a drying tube were attached to a three-bottle flask, and the N produced in Synthesis Example 1 was added to the flask.
94.8 parts of N-diallylethylenediamine, 0.3 parts of phenothiazine, 1% chloroplatinic acid inpropatol solution 1
．． 0 parts and heated to 90°C. 173 parts of trimethoxysilane was added dropwise over 2.5 hours, and then
After heating and stirring for a period of time to react, vacuum distillation was performed to obtain 209 parts of a colorless and transparent liquid with a boiling point of 144 to 147' C10.5 Torr. This fraction was subjected to infrared absorption spectrum, nuclear magnetic resonance spectrum, mass spectrum, and elemental analysis measurements. The result is the first
Shown in the table. The resulting compound was found to be N,Nbis(3-methyldimethoxysilylpropyl)ethylenediamine. The yield was 88%. nMS=1.44
80. d=0.981° The infrared absorption spectrum and nuclear magnetic resonance spectrum are shown in FIGS. 1 and 2.

Synthesis Example 2 (Synthesis of N,N-diallylpropylene diamine) Reacted in the same manner as Synthesis Example 1 except that 329 parts of 3-bromopropyl-1-amine hydrobromide was used in place of 2-bromoethylamine hydrobromide in Synthesis Example 1. I let it happen. As a result, 59-61°C/3. OTorr
96.5 parts of a colorless and transparent liquid was obtained. Yield is 42%
Met.

Example 2 96.5 parts of N,N-diallylpropylene diamine obtained in Synthesis Example 2 and 184 parts of trimethoxysilane were added to Example 1.
After reacting under exactly the same conditions as , vacuum distillation was performed, and 2
24 parts of a colorless transparent liquid at 155-159°C 10,5
Obtained as a fraction of Torr. Example 1 about this item
The same measurements as above were carried out and the results are shown in Table 1. The resulting compound was found to be N,N-bis(3-trimethoxysilylpropyl)propylene diamine. The yield was 89%.

Comparative Example 1 A thermometer, a cooling tube with a drying tube, and a mechanical stirrer were attached to a three-bottle flask, and xylene 58 was added to the flask.
0 parts, 30 parts of ethylenediamine, 20 parts of triethylamine
2 parts, γ-chloropropylmethyldimethoxysilane 18
3 parts were added and heated and stirred at 100"C for 10 hours to react. After cooling, the generated salt was removed and vacuum distillation was performed.
98 parts of a colorless and transparent liquid was obtained as a 45-150'' C10.5 Torr fraction.

Gas chromatography of this fraction revealed that it was a mixture with a ratio of 3. Further investigation revealed that 3% of the 11th order was also produced in Example 1, and ? ,
: N,N-bis(3-methyldimethoxysilylpropyl)ethylenediamine, and the remaining 70% was revealed to be N,N'-bis(3-methyldimethoxysilylpropyl)ethylenediamine, which is a structural isomer. Ta.

1. When measuring GC-Mass, all peak compounds have a parent peak of M''=352.

2. In the gas chromatograph measurement, 30% of the minor products correspond to the peak of N,N-bis(3-methyldimethoxysilylpropyl)ethylenediamine produced in Example 1.

3. When NMR of the mixture obtained in Comparative Example 1 was measured,
Regarding the 30% minor product, all peaks matched the peaks of the compound prepared in Example 1. Regarding the major product that accounts for 70%, N of the ethylenediamine moiety is
-CHzCHz-N proton absorption was obtained as a singlet peak at δ = 2.70, indicating that the structure is symmetrical N,N'-bis(3-methyldimethoxysilylpropyl)ethylenediamine. There is. (In N,N-bis(3-methyldimethoxysilylpropyl)ethylenediamine, the peak at the N-CHzCHi-N portion does not form a singlet as shown in Table 1 and Figure 1.)

[Brief explanation of the drawing]

FIG. 1 is a chart of the infrared absorption spectrum of the compound produced in the example process, and FIG. 2 is a chart of the nuclear magnetic resonance spectrum.

Claims (1)

[Claims] 1. A compound represented by the general formula H_2N-Q-N(CH_2CH=CH_2)_2 (where Q is a divalent hydrocarbon group having 2 to 6 carbon atoms); A hydrosilane compound represented by HSiR^1_nY_3_-_n (where R^1 is a substituted or unsubstituted monovalent hydrocarbon group, Y is an alkoxy group, and n is 0, 1 or 2) in the presence of a catalyst. General formula H_2N-Q-N [-(CH_2)_3SiR^1_n
A method for producing an aminoalkyl group-containing silicon compound represented by Y_3_-_n]_2 (where Q, R^1, Y, and n are as described above). 2. The method for producing the compound according to claim 1, wherein R^1 is a methyl group. 3. Q is -CH_2CH_2-, -CH_2CH_2C
2. The method for producing the compound according to claim 1, wherein the compound is a group selected from H_2-, ▲ which has a mathematical formula, a chemical formula, a table, etc. 4. The method for producing a compound according to claim 1, wherein Y is a methoxy group or an ethoxy group. 5. The method for producing a compound according to claim 1, wherein the catalyst is a platinum-based catalyst.