JPS61289094A - Purification of silicon-containing isocyanate compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound having high purity and stability, by reacting carbonyl chloride with a silicon-containing alkylamine, neutralizing the reaction liquid with a specific neutralizing liquid and purifying the product. CONSTITUTION:Carbonyl chloride is made to react with the silicon-containing alkylamine of formula I (R<1>-R<3> are hydrocarbon group, alkoxy or siloxy, at least one of them is alkoxy; n is 1-4) in an inert organic solvent in the presence of a tertiary amine to obtain a silicon-containing isocyanate compound of formula II. The reaction liquid containing the compound of formula II is neutralized with an alkali or alkaline earth metal slat of an unsaturated fatty acid, a higher saturated fatty acid or an aromatic carboxylic acid (e.g. calcium stearate), and the objective compound is separated from the system by conventional method. The purity, etc., of the objective compound can be improved further by adjusting the pH of the reaction liquid obtained by neutralization to 6-7 and distilling the liquid.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for purifying a silicon-containing isocyanate compound,
Particularly useful as a raw material for producing various siliμ group-containing compounds.
The present invention relates to a method for producing a silylated μ isocyanate compound containing an alkoxy-silicon bond.

[Conventional technology]

Conventionally, silylalkylamine containing an alkoxy-silicon bond and carpo chloride d+, which were previously discovered by the present inventors,
A silicon-containing isoanate compound obtained by reacting / with an inert solvent Nakatatsu tertiary amine (Japanese Patent Application No. 1983)
No. 265468), after the completion of the reaction, the crystals of the hydrochloride of a tertiary amine were separated from the reaction solution, and the solution was distilled to isolate them. However, if the product is simply distilled, the target product will contain trace amounts of tertiary amine hydrochloride dissolved in the r-liquid and/or hydrogen chloride generated due to dissociation or the like.

For this reason, when stored for a long period of one week or more, there were problems such as easy change over time and generation of turbidity.

[Problem that the invention seeks to solve]

Therefore, it is generally considered to neutralize trace amounts of tertiary amine hydrochloride and/or hydrogen chloride to stabilize the resulting silicon-containing isocyanate compound.

However, when hydroxides or carbonates of alkali metals or alkaline earth metals, such as sodium hydroxide, μsium hydroxide, magnesium hydroxide, calcium carbonate, etc., are used as neutralizing agents, the resulting water may not be used as a product. It was found that the salt used may react or dissolve in water, becoming strongly alkaline and having an adverse effect on the target product.

Therefore, it is necessary to search for the best neutralizing agent to stabilize the quality of the target product.

A feature of the present invention is to provide a method for obtaining a target highly pure and stable isocyanate compound by purifying it by adding a specific neutralizing agent.

[Means for solving problems]

To summarize the present invention, the present invention relates to a method for purifying a silicon-containing isocyanate compound, and the present invention relates to a method for purifying a silicon-containing isocyanate compound.
H2... [■] (In the formula, R1, R1 and R3 are the same or different υ, a hydrocarbon group, an alkoxy group or a siloxy group, at least one of which is an alkoxy group, and n
represents a number from 1 to 4) with a silicon-containing alkyl amine in the presence of a tertiary amine in an inert organic solvent. R1, R2, R3 and n are synonymous with the above formula One kind of power p
It is characterized in that it includes a step of treating with an alkali metal salt or an alkaline earth metal salt of a bonic acid.

The present inventors have prepared the reaction solution obtained by the above reaction, the R solution obtained by separating the tertiary amine hydrochloride with F, the residual solution obtained by distilling off the solvent, or the distillate obtained by distilling the same, using the above-mentioned method. It has been found that a highly pure and stable target isocyanate compound can be obtained by providing a step of treating p-acid with an alkali or alkaline earth metal salt. In addition, after this treatment, p
It has also been found that purification and stability can be further improved by distillation purification after adjustment to H6-7.

Among the alkali or alkaline earth metal salts of carboxylic acids used in the method of the present invention, examples of higher saturated fatty acids include:
Caprylic acid, lauric acid, myristic acid, stearic acid, etc., examples of unsaturated fatty acids include oleic acid, sorbic acid, etc., and examples of aromatic acids include benzoic acid, phthalic acid, etc. can be mentioned.

In addition, the alkali or alkaline earth metals include Na,
Examples include K, Mg5CaSBa, etc.

The amount of the alkali or alkaline earth metal salt of these carboxylic acids to be used is preferably equal to or more than the amount of hydrogen chloride present in the target product.

The treatment method is to remove tertiary amine hydrochloride from the reaction solution.
Either the residual liquid obtained by distilling off the solvent from the filtered F liquid or R liquid, or the distillate obtained by distilling this may be used, but add an alkali or alkaline earth metal salt of a bonic acid and stir thoroughly. After the pH reaches 6 to 7, the precipitated carboxylic acid, common salt and/or excess alkali or alkaline earth metal salt of the acid are filtered, and the liquid is preferably distilled to obtain high purity. A stable target product can be isolated.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Toluene 150wt chloride power μponi/1/9.9/
Dissolve i and add γ-triethoxyγsiliμpropy/
I/7mine 22.1g, gN-dimethylaniline 27,
A solution of 9 g dissolved in toluene 50-5 to -10
It was added dropwise at ℃ for 3 hours to react.

After the reaction, the crystals of N,N-dimethylaniline hydrochloride were separated and the liquid was distilled. After recovering toene, γ-triethoxysilyl was obtained as a fraction with a boiling point of 88-91°C/45 mg. 198 g of μpropyμ isocyanate was obtained.

When 2 g of calcium stearate is added to this and stirred for 4 hours, the pH becomes 7. Excess calcium stearate and precipitates were separated from P and the F solution was distilled, and the boiling point was 8.
178 g of r-)ethoxysiliμ propyl isocyanate were obtained as a fraction of 7-89° C./4 I (g).

When no stearic acid A/e7um was added, turbidity occurred after one week of storage, but the ice crystals remained stable even after six months of long-term storage.

Example 2 4.0 g of sodium myristate was added to the liquid from which toluene was recovered in Example 1, and the mixture was stirred until the pH reached 7.

Excess sodium myristate and precipitate were separated by F.
When the liquid was distilled, the boiling point was 93-95℃/6 WH
8 g of γ-triethoxysilylprobyl isocyanate 1a was obtained as a fraction of g. The ice crystals remained stable with no change over time even when stored for more than 6 months.

Example 5 The crystals of N,N-dimethylaniline hydrochloride in Example 1 were
Add 1 alg of sodium stearate to the separated solution f and stir until the pH reaches 7. Excess sodium stearate and precipitates were separated and the liquid f was distilled. As a result, γ-
1 and 9 g of triethoxysili-propyl isocyanate were obtained. The ice crystals were stable and did not become cloudy even when stored for more than 6 months.

Example 4 9.9 g of carbochloride/I/ was dissolved in 150 ml of toluene, and 19.1 g of γ-jetoxymethyμVsu propylamide and 24.2 g of N,N-dimethylaniline were dissolved in 150 ml of toluene.
A solution of fl dissolved in 50m of toluene is -5 to -10
It was added dropwise at ℃ for 3 hours to react. After the reaction, the crystals of dimethylaniline hydrochloride were separated, and toluene was recovered from the r liquid. A fraction with a boiling point of 80 to 85°C/6 tar Hg was taken, and 3 g of sorbic acid was added and stirred for 3 hours. When this liquid is distilled, the boiling point is 82-85℃/6■H.
17.6 g of γ-jethoxymethylsilylprobyl isocyanate was obtained as a fraction of g. The ice crystals were stable even when stored for more than 6 months.

Example 5 99 g of chlorinating power Honi/I was dissolved in 150 g of methylene chloride, and 19.1 g of γ-jethoxymethylsilylprobylamine and 25 g of ethylamine were added. A solution dissolved in imized methylene 50- was added dropwise at -5 to -10°C for 3 hours to react. After the reaction, the triethylamine hydrochloride crystals were separated by F, and methylene chloride was recovered from the F solution.
Take a fraction with a boiling point of 91-93°C/9 w Hg, add 9y of sodium oleate, and stir for 20 minutes, resulting in a pH of 7. Excess sodium oleate and precipitate were separated and the liquid was distilled, and the boiling point was 80-82.
γ-Dinitoxymethylsilylprobyl isocyanate) 15.7.9 was obtained as a fraction at °C/5 m Hg. The ice crystals were stable even when stored for more than 6 months.

Example 6 Chlorination power μboni/L/9.9 to 150Tnt of toluene
A solution of 2 & 3 g of γ-jethoxy(trimethylsiloxy)silylpropyl amine 29.5,9,1-liethy pamine 2 & 3 g dissolved in 50 d of toluene was added dropwise to this at -5 to -10°C over 3 hours. and reacted. After the reaction, the crystals of triethylamine hydrochloride were separated, and toluene was recovered from the r solution. 4.5 g of sodium caprylate was added to the residual liquid.
Add and stir for 20 minutes to reach a pH of 7. Excess sodium caprylate and precipitate were separated by f, and the r liquid was distilled to obtain γ-jethoxy(trimethylsiloxy)silylpropyl μ isocyanate 21.5 jii as a fraction with a boiling point of 84 to 86°C/8 w Hg. Ta. The crystals were stable when stored for more than 6 months.

Example 7 9.9 g of chlorination power Pony #9 was dissolved in 1 v 150 of ethyl ether, and 22-1 g of γ-triethoxysilylpropylamine and 1112 g of pyridine were dissolved in 50 g of ethyl ether.
A solution dissolved in 0.5° C. was added dropwise at −5 to −10° C. over 3 hours to cause a reaction. After the reaction, separate the crystals of pyridine hydrochloride,
The r liquid was distilled. After recovering the ethi μether p, γ-
Triethogysili μpropyl isocyanate 17,3
I got g.

Add 1.2 g of barium stearate to this and stir for 3 hours until the pH becomes 7. Excess barium stearate and precipitates were separated by F, and the F solution was distilled, and the boiling point was 90.
15.9 g of γ-triethoxy V-siliμ propi μ isocyanate was obtained as a fraction of ~93° C./5 m Hg. The crystal has a purity of 99% and is stable for a long time.

Example 8 Toluene 150tnt and chlorination power μPON/V 9.9g
Dissolve α-jethoxymethylsilylmethy~
Amine 11s, 59% N,N-dimethylaniline 24.
A solution of 29 dissolved in toluene 50°C was heated to -5 to -10°C.
, was added dropwise over 3 hours to react.

After the reaction, the crystals of N,N-dimethylaniline hydrochloride were separated by Fg! was distilled. When 59 g of sodium caprate is added to the residual liquid from which toluene has been recovered and stirred for 20 minutes, the pH becomes 7. When excess sodium caprate and precipitates were separated and the liquid f was distilled, the boiling point was 86-88℃/
11.0 g of α-jethoxymethyp-silylmethyp-isocyanate was obtained as a fraction of 20 μHg. The crystals were stable when stored for more than 6 months.

Example 9 Dissolve 9.9 g of chlorinating power μbony/l/l in 150 μm of toluene, and add 14.5 g of δ-dimethoxysilyl butyμamine and 27.9 f of KN-dimethylaniline.
A solution of i in toluene 50°C was heated to -5 to -10°C,
It was added dropwise over 3 hours to react.

After the reaction, the crystals of N,N-dimethylaniline hydrochloride were separated and the P solution was distilled. After recovering toluene, the boiling point was 95.
As a fraction of ~100°C/12 wi Hg, δ-dimethylmethoxysilibuty isocyanate 12.8.
I got a 9.

When 1 g of magnesium stearate is added to this and stirred, the pH becomes 7. Excess magnesium stearate and precipitates are separated and the P solution is distilled to give a boiling point of 98 to 100.
℃/12μHg distillation was carried out to obtain 11.5 g of δ-dimethylmethoxysilane isocyanate. The crystals were stable when stored for more than 6 months.

Example 10 Toluene 1501 nt was dissolved with 9.9 p of chloride, and 191 g of γ-jethoxymethylsilylprobylamine and 24.2 g of N,N-dimethylaniline were dissolved in 1501 nt of toluene.
Dissolve fi in toluene 50°C, -5 to -10°C, 3
The solution was added dropwise over time to react. After reaction, N, N
- After separating dimethylaniline hydrochloride with P and recovering υtoluene from the P solution, the boiling point was 91-93℃/9 wa Hg.
Distill the fraction, add 1 g of benzoic acid, and stir for 3 hours until the pH becomes 7. Excess sodium benzoate and precipitate were separated by F'g! When distilled, γ-
(Dietoxymethylsilylpropyl isocyanate)15.
6g was obtained. The ice crystals were stable even when stored for more than 6 months.

Example 11 Toluene 150-carbonychloride/l/9.9 fl
was dissolved, and 19.1 g of γ-jethoxymethylsiliμ propylamine and 24.1 g of N,N-dimethylaniline were dissolved therein.
29 was dissolved in 50°C of toluene, and the solution was added dropwise at -5 to -10°C for 3 hours to react. After the reaction, N-dimethyμ aniline hydrochloride was separated by F, and toluene was recovered from the F solution. Then, a fraction with a boiling point of 91 to 93°C/9 wm Hg was taken, and 8 g of dipotassium phthalate was added, followed by stirring for 3 hours. Then the pH becomes 7. Excess dipotassium phthalate and precipitates were separated and the liquid was distilled, and the boiling point was 80~
As a fraction at 82°C and 15mHg, γ-jethoxymethylsiliμpropy! 15.6 g of isocyanate'-) was obtained. The ice crystals were stable even when stored for more than 6 months.

〔Effect of the invention〕

As explained in detail above, according to the method of the present invention, a highly pure and stable silicon-containing isocyanate compound can be obtained.

Since the target compound of the method of the present invention has an isocyanate group and an apoxy group, it is useful for various purposes, and is used, for example, as a coupling agent for glass fibers, polyester films, etc., and as a coating agent for resins.

Claims (1)

[Claims] 1. Carbonyl chloride and the following general formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (In the formula, R^1, R^2 and R^3 are the same or Unlike,
a silicon-containing alkylamine represented by a hydrocarbon group, an alkoxy group, or a siloxy group, at least one of which is an alkoxy group, and n represents a number from 1 to 4) in an inert organic solvent, The following general formula I obtained by reacting in the presence of a tertiary amine: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R^1, R^2, R^3 and In the method for purifying a liquid containing a silicon-containing isocyanate compound represented by the formula II (n is the same as the formula II), one type of carboxylic acid selected from the group consisting of unsaturated fatty acids, higher saturated fatty acids, and aromatic carboxylic acids. 1. A method for purifying a silicon-containing isocyanate compound, comprising a step of treating with an alkali metal salt or an alkaline earth metal salt.