JPH0755953B2 - Manufacturing method of diaminopropyldisiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Prior Art] An epoxy resin is generally used as a plastic molding compound used in the manufacture of electronic parts such as ICs and transistors. Since the flexibility of this epoxy resin is strongly required as the degree of integration of ICs increases, attempts have been made to impart flexibility to the epoxy resin by incorporating a soft segment into the molecule. Organosiloxane has features such as a large molecular volume, a long bonding distance of siloxane bonds, and a large degree of freedom of molecular rotation, and thus is highly expected as such a soft segment. A compound useful for introducing this organosiloxane structure into the epoxy resin as the soft segment is 1,3-di (γ-aminopropyl) tetramethyldisiloxane.

Conventionally, as a method for producing 1,3-di (γ-aminopropyl) tetramethyldisiloxane, after heating a mixture of benzylideneallylamine and a catalytic amount of platinum to 170 ° C to 180 ° C, 1,1,3, 3-Tetramethyldisiloxane was added dropwise to react and the formula: A bis (benzylideneiminopropyl) tetramethyldisiloxane represented by the following formula is synthesized, and then the compound is hydrolyzed with hydrochloric acid to form an amine hydrochloride and further neutralized with sodium hydroxide to obtain a free amine. Has been announced.

(Die Macromolekulare Chemie, 57 , 150 (1962)).

[Problems to be solved by the invention]

However, the above method was attempted by the present inventor, and when a mixture of benzylideneallylamine and platinum was heated to 170 to 180 ° C., a polymerization reaction occurred, and after 5 hours, most of the product was polymerized, The problem is that the target compound can be obtained only in a yield of several%.

Therefore, an object of the present invention is to synthesize the above-mentioned intermediate, bis (benzylideneiminopropyl) tetramethyldisiloxane, in high yield, and thus to obtain 1,3-di (aminopropyl) disiloxane in high yield. The object is to provide a manufacturing method capable of

[Means for solving problems]

MEANS TO SOLVE THE PROBLEM this invention solves said problem, General formula (I): [Wherein R ¹ may be the same or different and is an alkyl group such as methyl, ethyl or propyl, an alkyl group such as phenyl or tolyl, or an aralkyl group such as benzyl]. General formula (II): [Wherein R ¹ is as described above], while maintaining the mixture containing the disiloxane, the platinum-based catalyst and the nonpolar solvent at 90 to 150 ° C., the compound represented by the general formula (III): [Wherein, R ² is a monovalent hydrocarbon group and R ³ is a hydrogen atom or a monovalent hydrocarbon], and a Schiff base represented by the following formula is added dropwise to give a compound represented by the general formula (IV): [Wherein R ¹ , R ² and R ³ are as described above] is synthesized, and then the organic silicon compound is hydrolyzed under acidic conditions to neutralize the reaction mixture. The present invention provides a method for producing diaminopropyldisiloxane.

The disiloxane of the general formula (II) used as a raw material in the method of the present invention can be easily produced by a known method.

Further, in the Schiff base of the general formula (III), R ² or R ³
Examples of the monovalent hydrocarbon group represented by are methyl, ethyl,
Examples thereof include an alkyl group such as propyl, a cycloalkyl group such as cyclohexyl, methylcyclohexyl and cycloheptyl, an aryl group such as phenyl and tolyl, and a methyl group, an ethyl group, a phenyl group and the like are preferable.

Representative examples of the Schiff base takes the general formula _{(III), C 6 H 5} -CH = NCH 2 CH = CH 2, (CH 3) 2 C = NCH 2 CH = CH 2, Among them, C ₆ H ₅ —CH═NCH ₂ CH═CH ₂ is preferable from the viewpoint of good safety. It is preferable that the Schiff base of the general formula (III) is used in an approximately equivalent amount to the disiloxane of the general formula (II) and reacted.

Examples of the platinum-based catalyst used in the method of the present invention include chloroplatinic acid, chloroplatinic acid-alcohol solution, platinum black, platinum-olefin complex, and other known ones. Usually, 0.0001 to 0.005 parts by weight may be used per 100 parts by weight of disiloxane.

Examples of the non-polar solvent used in the method of the present invention include xylene, methoxytoluene, ethoxytoluene,
Examples thereof include ethyltoluene and t-butyltoluene. Usually, xylene is used because the addition reaction of disiloxane to Si—H progresses smoothly and the price is low.

The reaction between the sidiroxane of the general formula (II) and the Schiff base of the general formula (III) needs to be carried out at a temperature of 90 to 150 ° C, preferably 100 to 120 ° C. If the reaction temperature is lower than 90 ° C, the above-mentioned addition reaction becomes extremely slow, and if it exceeds 150 ° C, the product is polymerized to lower the yield of the desired diaminoalkyldisiloxane. The pressure for carrying out this reaction is not particularly limited, but is usually sufficient under normal pressure, in which case the type and amount of the solvent used are selected so that the boiling point of the reaction mixture is 90 to 150 ° C., and the mixture is refluxed. It is desirable to react. As the solvent suitable for such an embodiment, the above-exemplified non-polar solvent can be mentioned.

In the method of the present invention, first, the disiloxane of the general formula (II), the non-polar solvent and the platinum-based catalyst are placed in a reaction vessel, heated to a required reaction temperature and kept, while the Schiff base of the general formula (III) is added. It can be performed by dropping.

Next, the organosilicon compound represented by the general formula (IV) obtained by the above reaction is hydrolyzed and neutralized under acidic conditions. For the hydrolysis under acidic condition, for example, an aqueous acid solution may be added to the reaction mixture obtained in the above reaction, and examples of the acid used include hydrochloric acid and the like. The amount of the acid used at this time must be at least equivalent to the organosilicon compound of the general formula (IV), and hydrolysis with this acid produces a diaminopropyldisiloxane acid addition salt. Then, the solution containing the acid addition salt is neutralized with, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or the like to obtain the desired diaminopropyldisiloxane in a free state.

〔Example〕

 Next, the present invention will be specifically described with reference to examples.

Example 1 300 g of 1,1,3,3-tetramethyldisiloxane and 600 g of xylene were placed in a 2 liter reaction flask equipped with a thermometer, a stirrer and a reflux device, and a solution of chloroplatinic acid in isopropanol (platinum content 2 wt%) and heated to 100 ° C. Next, 690 g of benzylideneallylamine was added dropwise over 2 hours for reaction, and after completion of the addition, the reaction was continued at 150 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and hydrolyzed by adding 1100 g of 17% hydrochloric acid. The two layers were separated, an equal amount of toluene was added to the aqueous layer for washing, and 190 g of NaOH and 550 g of water were further added to the aqueous layer. Further, 1000 g of toluene was added to extract the organic layer, and N
After drying with a ₂ SO ₄ and distillation, 390 g of a colorless transparent liquid having a boiling point of 120 to 125 ° C./7 mmHg was obtained. The yield was 70.4%.

The obtained compound is represented by the formula below. Was confirmed to be 1,3-di (γ-aminopropyl) tetramethyldisiloxane.

NMR spectrum: shown in FIG.

IR spectrum: shown in FIG.

Elemental analysis value Theoretical value (%) Actual value (%) C: 48.33 48.52 H: 11.36 11.42 Si: 22.61 22.59 Comparative Example 1 In a 2 l reaction flask equipped with a thermometer, a stirrer and a reflux device, 690 g of benzylideneallylamine, Charge 170 g of chloroplatinic acid in isopropanol (platinum content 2 wt%) 0.6 g
Heat to 0 ° C to remove 1,1,3,3-tetramethyldisiloxane
Drop it over a period of time to react, and after finishing the dropping, add 170-1
The reaction was carried out at 80 ° C for 3 hours. After the completion of this reaction, the procedure after the hydrolysis with 17% hydrochloric acid was carried out in the same manner as in Example 1. 50 g of the target 1,3-di (γ-aminopropyl) tetramethyldisiloxane was obtained, and the yield was 9%.

Comparative Example 2 The same operation as in Example 1 was repeated except that 600 g of xylene was not used when charging 1,1,3,3-tetramethyldisiloxane, but 1,3-di (γ-amino) was used. No propyl) tetramethyldisiloxane was obtained.

Comparative Example 3 Heating temperature 100 when benzylideneallylamine was added dropwise
The same operation as in Example 1 was repeated except that the temperature was changed to 60 ° C. and the reaction temperature after the dropping was also changed to 60 ° C.
Di (γ-aminopropyl) tetramethyldisiloxane could not be obtained.

〔The invention's effect〕

According to the method of the present invention, diaminodisiloxane can be obtained in a high yield of 70 to 80%. Further, this diaminodisiloxane is useful as a basic raw material for amino-modified silicone used for modifying polyimide resins and epoxy resins.

[Brief description of drawings]

FIG. 1 shows the NMR spectrum of 1,3-di (γ-aminopropyl) tetramethyldisiloxane obtained in Example 1. FIG. 2 shows an IR spectrum of 1,3-di (γ-aminopropyl) tetramethyldisiloxane obtained in Example 1.

Claims (1)

[Claims] 1. General formula (I): [In the formula, R ¹ may be the same or different and is an alkyl group, an aryl group or an aralkyl group. ] A method for producing diaminopropyldisiloxane represented by the following general formula (II): [Wherein R ¹ is as described above] while maintaining the mixture containing the disiloxane represented by the formula, the platinum-based catalyst, and the nonpolar solvent at 90 to 150 ° C. [Wherein, R ² is a monovalent hydrocarbon group and R ³ is a hydrogen atom or a monovalent hydrocarbon group], and a Schiff base represented by the following formula is added dropwise to give a compound represented by the general formula (IV): [Wherein R ¹ , R ² and R ³ are as described above] is synthesized, and then the organic silicon compound is hydrolyzed under acidic conditions to neutralize the reaction mixture. A method for producing diaminopropyldisiloxane.