JP2862977B2 - Method for producing siloxane compound having diaminoalkyl group - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing an organosilicon compound used for modifying the properties of a synthetic resin, and more particularly, to the application of the reactivity of amino groups such as polyimide, polyamide, and polyurethane. The present invention relates to a novel method for producing a siloxane compound having a diaminoalkyl group, which is useful for modifying the interface characteristics of a synthetic resin.

[Technical background of the invention and its problems]

The present inventors have previously found a novel siloxane compound having a diaminoalkyl group which is useful for improving the interface characteristics of a synthetic resin as described above, and filed a patent application (Japanese Patent Application No. 1-87).
No. 296). In this specification, it has been made clear that such a compound can be synthesized by, for example, a method of subjecting 1,3-diamino-2-methylenepropene or the like to a one-terminal hadrogen-modified diorganoschirosan by an addition reaction.

However, as a result of further research, it was found that such a synthesis method had some problems.

That is, this method has a drawback that undesirable addition of isomers and simultaneous dehydrogenation occur during the addition reaction.
Further, 1,3-diamino-methylenepropane, which is a reaction raw material, has a very high water solubility and hygroscopicity, and has a disadvantage that it is difficult to stably produce it in a high yield.

Thus, it has been difficult to industrially obtain a high-purity siloxane compound having a diaminoalkyl group in a high yield.

[Object of the invention]

An object of the present invention is to solve the above-mentioned problems of the conventional method, and to provide a method for producing a siloxane compound having a high-purity diaminoalkyl group in a high yield using easily available raw materials. That is.

[Configuration of the invention]

The present inventors have conducted intensive studies to achieve such an object, and as a result, by reacting a siloxane compound having a phthalimide group with hydrazine monohydrate, a siloxane compound having a diaminoalkyl group has high purity and high yield. The present invention was found to be obtained at a high rate, and based on this finding, the present invention was accomplished.

That is, the present invention provides a compound represented by the general formula (II): (In the formula, R represents the same or different alkyl group, aryl group or perfluoroalkyl group, and n represents 0 to 1,
Wherein the siloxane compound having a phthalimide group represented by an integer of 000) is reacted with hydrazine monohydrate. (Wherein, R and n are the same as described above).

When the method of the present invention is represented by a chemical reaction formula, the following formula (1) is obtained.

Wherein R and n are the same as defined above.
Indicates that the phthalimide group is decomposed by hydrazine to be converted to a diaminoalkyl group, and phthalhydrazide is produced as a by-product.

In the reaction formula (1), hydrazine monohydrate used as a reaction reagent is commercially available and easily available.

In the reaction formula (1), the siloxane compound having a phthalimide group (II) used as a reaction raw material is synthesized by the method described in the prior application specification (Japanese Patent Application No. 2-184259) proposed by the present inventors. It is possible to In the compound (II), R is the same or different alkyl group, aryl group or perfluoroalkyl group.
For example, as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a dodecyl group, an aryl group as a phenyl group, a tolyl group, and a perfluoroalkyl group as 3,3,3- Examples thereof include a trifluoropropyl group and a hepatadecafluorodecyl group. Among these, an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, is preferable because of easy availability of raw materials and easy synthesis. n is an integer of 0 to 1,000, preferably 1 to 200. If n exceeds 1,000, it is difficult to synthesize them with good control. Specific examples of such a compound (II) include the following compounds.

In the reaction formula (1), compound (II) and hydrazine 1
The ratio of use with the hydrate is not particularly limited, but stoichiometric use is economically preferable.

In the reaction formula (1), an organic solvent is not essential, but it is preferable to use an organic solvent in order to smoothly carry out the reaction. When used as desired, alcohols such as methanol and ethanol; ketones such as acetone; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; ethers such as ethyl ether; Aromatic hydrocarbons: and halogenated hydrocarbons such as 1,2-dichloroethane are preferred, and among these, the reaction controllability, smoothness, and reaction of the target compound (I) with by-produced phthalhydrazide. Use of ethanol is preferred because liquid-solid separation is easy. The usage of the organic solvent is not particularly limited, but is preferably in the range of 10% by weight or more and less than 2000% by weight based on the compound (II).

In addition, this reaction is preferably performed by charging compound (II) and an organic solvent into a reaction vessel and reacting hydrazine monohydrate dropwise at a predetermined temperature for reaction control. The reaction temperature ranges from -20 to 90C, preferably from 0 to 70C. The pressure at the time of the reaction is not particularly limited, but is usually performed at normal pressure. The reaction time depends on the reaction conditions, but usually 0.5 to 24 hours is sufficient.

The isolation and purification of the compound (I) from the reaction mixture thus obtained can be performed by a method usually used in the field of synthetic organic chemistry. For example, after the reaction, a precipitate of phthalhydrazide is separated by filtration, and low-boiling components are distilled off from the filtrate to obtain a siloxane compound (I) having a diaminoalkyl group.

〔The invention's effect〕

According to the method of the present invention, using readily available raw materials,
Since a siloxane compound (I) having a high-purity diaminoalkyl group can be obtained in a high yield, it is suitable as an industrial production method.

The siloxane compound (I) having a diaminoalkyl group obtained by the method of the present invention is advantageous when used as a raw material for a reactive oligomer for modifying an organic material, and a material having extremely high molecular design can be obtained. Can be That is, when modified by reacting an organic monomer or a polymer thereof with the siloxane compound (I) having a diaminoalkyl group obtained by the method of the present invention, it adheres to conventional organic materials, has low adhesion, heat resistance, and weather resistance. Excellent properties unique to silicone such as water resistance, water repellency, abrasion resistance and gas permeability can be imparted.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples. The scope of the present invention is not limited only to the following examples.

Example 1 A siloxane compound having a phthalimide group was placed in a 500-ml flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, and oil bath. 49.4 g (0.10 mol) and 75 g of ethanol were charged, and stirring was started at 20 ° C.

To this, 10.1 g (0.20 mol) of hydrazine monohydrate,
The solution was added dropwise over 10 minutes while maintaining the liquid temperature at 20 to 30 ° C. After completion of the dropwise addition, the mixture was stirred at a liquid temperature of 25 ° C for an hour, and further heated and stirred at a liquid temperature of 55 ° C for 1 hour.

A sample was taken out of the reaction vessel and subjected to liquid chromatography analysis, and it was confirmed that the peak of the siloxane compound having a phthalimide group, which was a reaction raw material, had disappeared.

After cooling the reaction mixture, a precipitate of phthalhydrazide was separated by suction filtration, and the filtrate was distilled under reduced pressure to a boiling point of 92%.
As a result of fractionating a fraction at ~ 93 ° C / 4 Torr, a colorless transparent liquid 1
-(2-aminomethyl-3-aminopropyl) -1,1,3,
21.1 g of 3,3-pentamethylcidyloxane was obtained. this is,
The yield was 90% based on the siloxane compound having a phthalimide group.

Gas chromatographic analysis, infrared absorption spectrum analysis, ¹ H nuclear magnetic resonance absorption of 1- (2-aminomethyl-3-aminopropyl) -1,1,3,3,3-pentamethyldisiloxane thus obtained The results of the analysis and the mass spectrum analysis are as follows, and it was confirmed that the molecular structure was represented by the following formula. 1 and 2 show charts of the ¹ H nuclear magnetic resonance absorption spectrum and the infrared absorption spectrum of the nuclear compound.

・ Gas chromatography analysis: 98.0% ・ Infrared absorption spectrum analysis (liquid film method): Wave number (cm ^-1 ) Attribution 3360 NH 3270 NH 1250 Si-CH ₃ 1100 to 1000 Si-O-Si · ¹ H nuclear magnetic resonance spectrum analysis (90 MHz, CDCl
₃ ): Position Chemical shift δ (ppm) Integrated intensity Multiplicity a 1.5 to 1.64 Hs b 2.6 to 2.74 H d c 1.4 to 1.7 1 H md 0.4 to 0.6 2 H de 0.16 Hs f 0.19 Hs Mass spectrum Analysis (m / e): 234 (M ⁺ ) Comparative Example 1 In a 100 ml flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and oil bath, 1,3-diamino-
1,3,5,7-tetravinyl-1,3,5,7-containing 17.2 g (0.20 mol) of 2-methylenepropane and 0.005 g of platinum atoms
A platinum complex having tetramethylcycltetrasiloxane as a ligand was charged, stirring was started, and the solution was heated to 70 ° C.

To this, 29.6 g (0.20 mol) of 1,1,3,3,3-pentamethyldisiloxane was added dropwise from a dropping funnel over 15 minutes while maintaining the liquid temperature at 70 to 90 ° C. After completion of the dropwise addition, the mixture was heated and stirred at a liquid temperature of 70 to 100 ° C. for 8 hours until the peak of 1,1,3,3,3-pentamethyldisiloxane disappeared by gas chromatography analysis.

After allowing to cool, the mixture was distilled under reduced pressure in the same manner as in Example 1 to give
1- (2-aminomethyl-3-aminopropyl) -1,1,1
32.7 g of 3,3,3-pentamethyldisiloxane was obtained. As a result of gas chromatography analysis, the purity of the product was 89.0%
And isomers of the target substance or the target substance as impurities,
It was confirmed that a dehydrogenation product with 1,3,3,3-pentamethyldisiloxane was contained. In addition, it was confirmed that the yield was 70% based on 1,3-diamino-2-methylenepropane.

[Brief description of the drawings]

FIG. 1 shows the ¹ H nuclear magnetic resonance absorption spectrum of 1- (2-aminomethyl-3-aminopropyl) -1,1,3,3,3-pentamethyldisiloxane obtained in Example 1. It is a chart. FIG. 2 is a chart showing an infrared absorption spectrum of 1- (2-aminomethyl-3-aminopropyl) -1,1,3,3,3-pentamethyldisiloxane obtained in Example 1. .

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-287786 (JP, A) JP-A-2-264782 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/10 C08G 77/26 C08G 77/388 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (II) (In the formula, R represents the same or different alkyl group, aryl group or perfluoroalkyl group, and n represents 0 to 1,
Wherein the siloxane compound having a phthalimide group represented by an integer of 000) is reacted with hydrazine monohydrate. (Wherein, R and n are the same as those described above).