JPH02304094A - Preparation of bis(aminopropyl)tetraorganodisiloxane - Google Patents

Abstract

PURPOSE:To prepare the subject organic silicon compound useful for improving the characteristics of synthetic resins by subjecting an allylamine and a diorganoalkoxysilane to an addition reaction in the presence of a platinum complex catalyst containing an olefin as a ligand and subsequently hydrolyzing the reaction product. CONSTITUTION:Allylamine and a diorganoalkoxysilane of formula I (R<1> is alkyl or aryl; R<2> is 1 to 4C alkyl) e.g. dimethylmethoxysilane are subjected to an addition reaction in the presence of a platinum complex catalyst containing an olefin, a derivative thereof or a siloxane derivative thereof as a ligand to prepare a 3-aminopropyldiorganoalkoxysilane of formula II, which is hydrolyzed in the presence of a basic hydroxide catalyst to provide the objective compound.

Description

Detailed Description of the Invention [Objective of the Invention] (Industrial Field of Application) The present invention relates to a method for producing an organosilicon compound used for modifying the properties of synthetic resins, and more specifically relates to a method for producing organosilicon compounds used for modifying the properties of synthetic resins.
Interfacial properties of synthetic resins that utilize the reactivity of amine groups such as polyamides and polyurethanes [! I.

This invention relates to a novel method for producing bis(aminopropyl)tetraorganodisiloxane, which is said to be useful for modifying.

(Prior art) Method for producing 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, which is conventionally considered the most useful among bis(aminopropyl)tetraorganodisiloxanes. The following methods are known.

For example, benzylideneallylamine is first produced by the dehydration reaction of allylamine and benzaldehyde, and then a mixture of this product and a catalytic amount of platinum is heated at 170-180°C.
1.3-bis[3-(benzylideneimino)propyl]-1. ], 3. A method for obtaining the target substance by producing 3-tetramethyldisiloxane, then hydrolyzing the compound with hydrochloric acid to obtain amine hydrochloride, and further neutralizing this with sulfur hydroxide. (Gre
ber, Jager: Macromolekula
re Chemje.

57, 150 f1962) l. Alternatively, in the above method, only the production part of 1,3-bis[3-(benzylidenimino)propyl], ], , 3.3-tetramedyldisylogysan, 1,1,3.3 - a mixture containing tetramethyldisiloxane, a platinum-based catalyst, and xylene;
A method (Japanese Unexamined Patent Publication No. 63-275591) is known in which benzylideneallylamine is added dropwise to react while maintaining the temperature at 0 to 150'C.

(Problems to be Solved by the Invention) However, the former method involves long, complicated, and time-consuming steps, and requires the use of benzylideneallylamine. ,l,3
．． 3-Te] Ramedyldisiloxy→None reaction, an undesirable addition reaction to the imino group also occurs. Furthermore, as pointed out in JP-A-63-27559, when benzylideneallylamine is reacted with 1,1,3,3-tetramethyldisiloxane, no polymerization reaction occurs (in some cases, no polymerization occurs). The disadvantage is that most of the products are polymerized.On the other hand, in the latter method, when benzylideneallylamine is reacted with 1.],]3.3-tetramethyldisiloxa, the product is polymerized. However, the disadvantages of long steps and simultaneous addition reactions to imino groups have not been completely eliminated, and there are concerns regarding industrialization, purity of the target substance, and overall Problems remain in terms of yield.

Thus, high purity], 3-bis(3-aminopropyl)-], 1. , 3,3-Tetramethyldisiloxane has hitherto been extremely difficult to obtain industrially in high yield.

The purpose of the present invention is to solve these problems of conventional methods and to produce high-purity bis(aminopropyl)tetraorganodisiloxane in large quantities with simple operations.
An object of the present invention is to provide an industrially advantageous method for producing bis(aminopropyl)tetraorganodisiloxane.

[Structure of the Invention] (Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors have determined that allylamine and diorganoalkoxysilane can be combined into olefins, derivatives thereof, or siloxane derivatives thereof. Bis(aminopropyl)
It has been discovered that de la organodisiloxane can be obtained in high yield and high purity, and the present invention has been completed based on this knowledge.

That is, the present invention relates to allylamine and a diorganoid represented by the general formula %) (wherein R1 represents the same or different alkyl group or aryl group, and R2 represents an alkyl group having 1 to 4 carbon atoms). An addition reaction is carried out with an alkoxysilane in the presence of a platinum complex catalyst whose ligand is an olefin, its derivative, or its siloxane derivative, and the general formula HJ-(CH2) 3-3t, -0R2(III) (
The general formula % consists of producing a 3-aminopropyldiorganoalkoxysilane represented by the formula (wherein R1 and R2 are the same as above) and then hydrolyzing it in the presence of a basic hydroxide catalyst. This is a method for producing bis(aminopropyl)tetraorganodisilogyzan represented by the formula % (wherein R1 is the same as above).

The method of the present invention can be expressed as a chemical reaction formula as follows. That is, reaction formula (]) is an addition reaction between allylamine and diorganoalkoxysilane (II), and reaction formula (2)
This is a hydrolysis reaction of 3-aminopropyldiorganoalkoxysilane (Ill), which is an addition reaction product.

H, NCH2CH-CH2+H3i-OR" (JJ) - t(2N-(CH2) 3-3], -0
R2 (1) (Ill) 2 (Ill) + R20→R' R
'H2N (C:Hz) 3-3j-0-3j, -fcH
213-NH2+2R"Oll (2) R' R
' (I) In the addition reaction of reaction formula (1), allylamine used as a raw material is commercially available and can be easily obtained.

Furthermore, in the formula of diorganoalkoxysilane (It), R1
Examples of the argyl group include methyl, ethyl, propyl, butyl, pentyl, hegysyl, and dodecyl, and examples of the aryl group include phenyl and tolyl. In addition, as the alkyl group of R2, 0'' methyl, ethyl, n-propyl,
Examples include isopropyl, n-butyl, and isobutyl.

Among these, R1 is preferably an alkyl group having 1 to 4 carbon atoms, especially a methyl group, and R2 is preferably a methyl, ethyl, or isopropyl group because of easy availability of raw materials and easy production. Such diorganoalkoxysilanes (
Specific examples of IT) include dimethylmethoxysilane, dimethylethoxysilane, and dimethylisopropoxysilane.

The ratio of allylamine and diorganoalkoxysilane (II) to be used is not particularly limited, but stoichiometric amounts are economically preferred.

In the addition reaction of reaction formula (1), platinum complexes having an olefin, a derivative thereof, or a siloxane derivative thereof as a ligand used as a catalyst include edi-1non, octene, cycloofoxyene, mesityl oxide, 1.3 −
Divinyl-1,1゜3.3-tetramethyldisiloxane, 1,3゜5.7-titravinyl-1.3.5.7-tetramethylvinylsiloxane, polymethylvinylsiloxane, etc. Examples include platinum complexes having as a ligand 1,3,5,7-te1-ravinyl-], ]3,5,7-titramedylcyclote]lasiloxane as a ligand. Platinum monomer is particularly preferred from the viewpoint of reactivity. On the other hand, platinum complexes that do not contain such olefins, their derivatives, or their sylogisan derivatives as ligands, such as chloroplatinic acid, have extremely low yields or do not react at all. The amount of platinum mirror to be used is not particularly limited, but it is 10 ppm or more as platinum atoms, 110 ppm or more as platinum atoms based on the total amount of allylamine and diorganoalkoxysilane (II).
A range of less than 00 pp is preferred. If it is less than 1.0 ppm, the reaction will be slow (and a good yield cannot be achieved in a short period of time).If it is used at more than 1.000 ppm, there will be no particular effect.

In the addition reaction of reaction formula (), organic solvents are not essential, but if used, alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone, and aliphatic carbonizations such as hexadi and heptane may be used. Preferred are hydrogens; alicyclic hydrocarbons such as cyclohexane; ethers such as ethylether; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as 2-dichloroethane.

In this reaction, it is preferable in terms of reaction control that allylamine and the platinum anchor catalyst described above are placed in a reaction vessel, heated to a predetermined temperature, and diorganoalkoxysilane (II) is reacted therewith little by little. Also, this reaction is 30 to 15
It is carried out at a temperature range of 0°C, preferably 40-120°C. Normal pressure is usually used during the reaction, but a pressurized state may also be used. The reaction time depends on the reaction conditions, but usually 3 to 15 hours, including the time for dropwise addition of diorganoalkoxysilane (II), is sufficient. Due to the above,
3-Aminopropyldiorganoalkoxysilane (II
I) is obtained.

Next, 3-aminopropyldiorganoalkoxysilane (III) is hydrolyzed in the presence of a basic hydroxide catalyst according to reaction formula (2). This hydrolysis reaction is carried out by adding an aqueous solution of a basic hydroxide to the reaction mixture obtained by reaction formula (1) or its purified product. Examples of the basic hydroxide used include sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like. The amount of basic hydroxide used is not particularly limited, but is usually 0.001% by weight or more based on 3-aminopropyldiorganoalkoxysilane (III),
A range of less than 5% by weight is preferred. If it is less than 0.001% by weight, the reaction will be slow and a good yield cannot be achieved in a short period of time. Even if it is used in an amount of 5% by weight or more, there is no particular effect.

In the hydrolysis reaction of Reaction Formula (2), an organic solvent is not essential, but if it is used as desired, it is preferable to use the same solvent as in Reaction Formula (1). Methanol or ethanol is preferable because it does not require troublesome operations such as liquid separation and extraction after the reaction. The amount of these organic solvents used is preferably in the range of 10% by weight or more and less than 500% by weight based on the 3-aminopropyldiorganoalkoxysilane (III').

The amount of water used in the hydrolysis reaction is usually 3-aminopropyldiorganoalkoxysilane (III).
The range is preferably 6% by weight or more and less than 100% by weight. If it is less than 6% by weight, the reaction may be delayed or may not be completed, making it impossible to achieve a good yield in a short period of time. ], Even if O is used in an amount of 0% by weight or more, not only will it not be particularly effective, but separation after the reaction may become troublesome.

This hydrolysis reaction is from 0 to 150°C, preferably from 20°C],
It is carried out in the temperature range of 00°C. The pressure during the reaction is not particularly limited, but it is usually carried out at normal pressure. Although the reaction time depends on the reaction conditions, 0.5 to 3 hours is usually sufficient. After the reaction, the desired bis(aminopropyl)tetraorganodisiloxane (I) is obtained by performing vacuum distillation.

[Effects of the Invention] According to the method of the present invention, bis(aminopropyl)tetraorganodisiloxane (I) with high purity (99% or more) can be produced in high yield using easily available raw materials and with simple operations. It is suitable as an industrial production method because it can be obtained at a high yield (70% or more).

Therefore, the bis(aminopropyl)tetraorganodisiloxane (1) obtained by the method of the present invention is advantageous when used as a reactive oligomer raw material for modifying organic materials, and is extremely reliable in terms of molecular design. A certain material can be obtained.

That is, when organic polymers or their polymers are reacted and modified with bis(aminopropyl)tetraorganodisiloxane (I) obtained by the method of the present invention, conventional organic materials have adhesion, adhesion, and It can provide excellent properties unique to silicone, such as heat resistance, weather resistance, water repellency, abrasion resistance, and gas permeability.

[Example code] The present invention will be explained in more detail below with reference to Examples.

Note that the scope of the present invention is not limited only to the following examples.

Example 1 Allylamine 1.1 was added to a 51 volume flask equipped with a stirrer, thermometer, addition funnel, reflux condenser and oil bath.
A platinum complex containing 40 g (20 mol) and 1,3,5.7-tetravinyl-1,3,5,fuchtramethylcyclotetrasyrogisan as a ligand containing 0.23 g as platinum atoms was charged, and stirring was started. Then, the solution was heated to a temperature of 50''C.

2080 g (20 mol) of dimethylethoxysilane was gradually added dropwise from a dropping funnel while maintaining the liquid temperature at 50 to 60°C. After 3 hours, the dropping was completed, and while stirring,
The liquid temperature was raised to 105°C over time. When a sample was taken out from the reaction vessel and analyzed by gas chromatography, it was confirmed that allylamine and dimethylethoxysilane were almost completely consumed and 3-aminobrobyldimethylethoxysilane was produced.

After cooling the reaction product, 2415 g of 3-aminobrobyldimethylethogysilane in the form of a transparent liquid with a color of 50-b was obtained by distillation under reduced pressure. This is 7 for allylamine.
The yield was 5%.

In the same flask as above, 2415 g (15 mol) of 3-aminopropyldimethylethoxysilane and 2000 g of methanol were charged, stirring was started, and the flask was heated to the liquid temperature of SO'C.

An aqueous solution prepared by dissolving 25 g of potassium hydroxide in 500 g of water was added dropwise from a dropping funnel over 30 minutes while maintaining the liquid temperature at 50 to 70°C. After the dropwise addition was completed, the mixture was heated and stirred at a liquid temperature of 70°C for 1 hour. When a sample was taken out from the reaction vessel and analyzed by gas chromatography, 3-aminopropyldimethylethogysilane was completely consumed and 1°3-bis(3-aminopropyl>1.1,3. 3
- It was confirmed that tetramethyldisiloxane was produced quantitatively.

After the reaction product was cooled, it was distilled under reduced pressure to obtain 59-b.
85 g was obtained. This is a 95% yield for 3-aminopropyldimethylethoxysilane, while
The yield was 71% based on allylamine, the starting material. 1,3-bis(3-aminopropyl) thus obtained = 1.1. ．． 3.3-Tetramethyldisiloxane is 99.8% as a result of gas chromatography analysis.
As a result of elemental analysis, infrared absorption spectrometry, H nuclear magnetic resonance absorption analysis and mass spectrometry, it was confirmed that the molecular structure was as follows:

H3CH3 112NICH□)3-3i-0-3j-(CH2)3
-Nl+2H3C13 Comparative Example 1 Synthesis of benzylideneallylamine In a flask with an internal volume of 51 mm equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser, and an ice bath, 1.0% benzaldehyde was added.
060 g (1.0.0 mol) was charged, stirring was started, and the liquid temperature was cooled to 10°C. Next, 570 g (100 mol) of allylamine was added dropwise from the dropping funnel over 10 hours while maintaining the liquid temperature at 10 to 30°C. After completion of the dropwise addition, the mixture was further stirred at room temperature for 14 hours until no change was observed by gas chromatography analysis.

Next, 2000 d of toluene and 1 g of activated clay were added,
A D2-Stark water separation tube was installed, and water was removed over 7 hours under toluene reflux. After removal, cool to room temperature and ? Activated clay was separated by filtration. Furthermore, as a result of fractionating a fraction with a boiling point of 63 to 65° C./3 Torr by vacuum distillation, 942 g of benzylideneallylamine was obtained. The purity of this product was determined to be 961% by gas chromatography analysis, and the yield was 65% based on allylamine.
．． It was confirmed that it was 0%.

1.3-bis(3-aminopropyl)-1゜1.3.3
- Synthesis of tetramethyldisiloxane Internal volume 5 with stirrer, thermometer, addition funnel, reflux condenser and oil bath
609 g (4.2 mol) of the benzylideneallylamine synthesized above and 0.2 mol of platinum atoms were placed in a flask of No. 1.
An isopropanol solution containing 12 g of chloroplatinic acid was charged, stirring was started, and the solution was heated to 170°C.

Next, 1,1,3,3-tetramethyldisiloxane was added dropwise from the dropping funnel over 5 hours while maintaining the temperature at 170 to 180°C. After the dropwise addition was completed, the mixture was stirred at a liquid temperature of 170 to 180'C for 24 hours until the peak of 1,1,3.3-tetramethyldisiloxane disappeared according to gas chromatography analysis. After the reaction, cool to room temperature and add 17% hydrochloric acid 9.
40 g was added and the hydrolysis reaction was carried out at room temperature for 10 hours.

Then, the two layers were separated, and the aqueous layer was washed with an equal volume of toluene. Furthermore, sodium hydroxide 16
2 g and 470 g of water were added to extract the organic layer, anhydrous sodium sulfate was added thereto, and the mixture was dried day and night. After drying, the desired 1,3-bis(3
-aminopropyl)-],,] 990 g of 1,3,3-tetramethyldisiloxane were obtained. The purity of this product was confirmed to be 95.0% by gas chromatography analysis, and the yields based on benzylideneallylamine and allylamine were 200% and 13.0%, respectively.

Claims (1)

[Claims] Allylamine and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R^1 represents the same or different alkyl group or aryl group, and R^2 has 1 to 1 carbon atoms. 4 (representing an alkyl group) in the presence of a platinum complex catalyst whose ligand is an olefin, a derivative thereof, or a siloxane derivative thereof, to obtain the general formula ▲ mathematical formula, chemical formula, table, etc. ▼(III) (In the formula, R^1 and R^2 are the same as above) 3-aminopropyldiorganoalkoxysilane is produced, and then it is reacted with a basic hydroxide catalyst in the presence of a basic hydroxide catalyst. Below, the general formula consisting of hydrolysis ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is the same as above) Bis (
A method for producing (aminopropyl)tetraorganodisiloxane.