JP2000229919A - Production of aqueous solution of high-purity unsaturated quaternary ammonium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce the subject aqueous solution by directly introducing an alkyl halide into an acrylic or a methacrylic ester and starting the addition of water from the time when a specific amount of the alkyl halide is introduced. SOLUTION: (B) An alkyl halide (e.g. methyl chloride or ethyl chloride) is directly introduced into (A) an acrylic or a methacrylic ester represented by formula I (R1 is H or methyl; and (n) is 2 or 3) (e.g. dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate) preferably at 0-100 deg.C under 0.1-20 kg/cm2 for 3-24 hr. The addition of water is started from the time when the amount of the introduced alkyl halide attains 10-100% based on the total amount to thereby produce a compound represented by formula II (R2 is methyl or ethyl; and X is Cl, Br or I). In the above reaction, the molar amount of the charged components A and B is preferably 1.0-1.5 times based on the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aqueous solution of a high-purity unsaturated quaternary ammonium salt.
Unsaturated quaternary ammonium salts are cationic, conductive, water-soluble, by homopolymerization or copolymerization with other vinyl monomers, or by graft polymerization with other monomers.
Coagulants, antistatic agents, soil improvers, conductive processing agents, dye improvers, paper strength enhancers, paper drainage improvers, cosmetics, resin modification to easily provide polymers with functions such as adhesiveness It is a useful monomer that can be widely used as a raw material for agents and the like.

[0002]

2. Description of the Related Art Conventionally, many methods for producing an aqueous solution of an unsaturated quaternary ammonium salt have been reported.
A method for suppressing the hydrolysis of (meth) acrylic acid ester as a raw material has been reported. For example, Japanese Patent Application Laid-Open No. 8-268895 reports a method of introducing and reacting methyl chloride gas with dimethylaminoethyl (meth) acrylate in a mixed solvent of water and acetone, and then removing acetone under reduced pressure. Have been. in this way,
A water-acetone solution containing a polymerizable unsaturated quaternary ammonium salt is concentrated under reduced pressure, and a portion of the unsaturated quaternary ammonium salt is polymerized to remove acetone. The polymer is mixed into the aqueous solution of a quaternary ammonium salt, and the stability of the product is reduced. In addition, a large amount of a polymerization inhibitor needs to be added to the unsaturated quaternary ammonium salt aqueous solution in order to reduce the polymerization during the concentration. It is insufficient as an industrially inexpensive production method, for example, it causes deterioration in quality such as coloring of various polymer products used.

JP-A-52-31016 discloses that, when dimethylaminoethyl (meth) acrylate is reacted with methyl chloride, the reaction is carried out in the presence of (meth) acryloyloxyethyltrimethylammonium chloride in advance. How to do it has been reported. In this method, it is necessary to separately produce (meth) acryloyloxyethyltrimethylammonium chloride by a method using an organic solvent, and to add (meth) acryloyloxyethyltrimethylammonium chloride which is a target substance. This method is insufficient as an industrially inexpensive method of production, such as a decrease in production efficiency.

In Japanese Patent Application Laid-Open No. 3-135945, a predetermined amount of methyl chloride is charged into a pressurized container under pressure.
A method has been reported in which dimethylaminoethyl (meth) acrylate and water are simultaneously and continuously added. This method requires condensing methyl chloride at high pressure,
It is industrially expensive in terms of equipment, and is insufficient as an industrially inexpensive production method. Further, in any of the methods, since water coexists in the reaction system, it is not possible to completely suppress the hydrolysis of the raw material (meth) acrylic acid ester, and the hydrolysis product (meth) acrylic acid This method is insufficient for industrially producing a high-quality aqueous solution of an unsaturated quaternary ammonium salt, for example, such as contamination of the product with water or choline chloride.

[0005]

Generally, since unsaturated quaternary ammonium salts are homopolymerized or copolymerized with other vinyl monomers, they are generated by hydrolysis of (meth) acrylic acid and amino alcohols or amino alcohols. The graded product affects the polymerizability and the molecular weight of the polymer, and the expected polymer cannot be obtained. Therefore, a production method in which these impurities are controlled has been desired. In view of the above-mentioned problems of the prior art, an object of the present invention is to react an alkyl halide with a (meth) acrylic ester to produce an aqueous solution of an unsaturated quaternary ammonium salt. It is another object of the present invention to provide a method for obtaining a high-quality aqueous solution of an unsaturated quaternary ammonium salt with less unreacted (meth) acrylic acid ester easily and industrially at low cost.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that when an alkyl halide is directly introduced into a (meth) acrylate, the alkyl halide is dissolved in the (meth) acrylate. At the same time, it was found that a part of the reaction reacted to produce an aqueous solution of an unsaturated quaternary ammonium salt with high purity, and the present invention was completed.

That is, the present invention provides a compound represented by the following general formula (1)

Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a methyl group or an ethyl group, n represents 2 or 3, and X represents Cl, Br, or I). In producing an aqueous solution of a quaternary ammonium salt, the following general formula (2)

Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group, and n is 2
Or 3 is indicated. )), The alkyl halide is directly introduced into the (meth) acrylate, and the addition of water is started when the introduction amount of the alkyl halide reaches 10 to 100% of the total amount. A method for producing an aqueous solution of a high-purity unsaturated quaternary ammonium salt. ”.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention will be described below in detail. Examples of the (meth) acrylate used in the method of the present invention include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, and dimethylaminopropyl methacrylate. These (meth) acrylic acid esters may be of any quality as long as they can be obtained industrially, but from the viewpoint of improving product quality, those having as high a purity as possible are preferred.

The alkyl halide that can be used in the method of the present invention includes methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, benzyl chloride and the like. Particularly, methyl chloride and ethyl chloride are preferred. These alkyl halides may be of any quality as long as they can be obtained industrially, but from the viewpoint of improving product quality, those having as high a purity as possible are preferred.

In the method of the present invention, the reaction temperature is from 0 ° C. to 10 ° C.
A range of 0 ° C, preferably a range of 20 ° C to 70 ° C is good.
The temperature may be controlled before or after the introduction of the alkyl halide. The alkyl halide used in the method of the present invention may be introduced from the liquid surface of the reaction solution or from the liquid, but the liquid at room temperature may be dropped from the liquid surface as it is. Among the alkyl halides, those which are in a gaseous state at ordinary temperature may be used in a corresponding introduction tube, and preferably introduced into a liquid. The introduction of the alkyl halide may be carried out under normal pressure or under pressure. In order to increase the introduction efficiency of the alkyl halide, it is preferable to introduce the alkyl halide in a pressurized state. The introduction time of the alkyl halide is in the range of 3 hours to 24 hours, preferably in the range of 4 hours to 18 hours. Pressure introduction during and after the introduction of an alkyl ^{halide, 0.1kg / cm 2 ~20kg / cm} 2 range, preferably from a range of ^{0.5kg / cm 2 ~10kg / cm 2} .

The charge ratio of the (meth) acrylate to the alkyl halide in the method of the present invention is in the range of 1.0 to 1.5 moles of the alkyl halide to the (meth) acrylate, preferably 1.1-1.
The range of 3 moles is good. In the method of the present invention, the pressure in the reactor may be reduced before introducing the alkyl halide,
Range of vacuum degree can be determined arbitrarily between ^{-0.1kg / cm 2 ~-0.9kg /} cm 2.

In the method of the present invention, the addition of water is started when the amount of alkyl halide introduced is from 10% to 100% of the total amount. As for the method of adding water, the water may be added continuously or may be added in portions of a fixed amount. It is desirable to adjust the rate of addition of water at the same time as the introduction of the alkyl halide is completed, or so that the addition of water is completed after the introduction of the alkyl halide is completed. It is not preferable that the addition of water is completed earlier than the introduction of the alkyl halide. The amount of water to be added may be added during the reaction in an amount necessary to adjust the aqueous solution of the unsaturated quaternary ammonium salt having a desired concentration, or may be added while maintaining an amount capable of adjusting the concentration after the reaction. well. The amount can be arbitrarily determined.

In the method of the present invention, after completion of the introduction of the alkyl halide and water, a ripening time is allowed to complete the reaction. The aging conditions are as follows: temperature is in the range of 10 ° C to 90 ° C, preferably 20 ° C to 70 ° C, and pressure is 0.1 kg / cm ² to
20 kg / cm ² range, preferably 0.5 kg / cm ^{2 to} 10 kg
/ cm ² , the time is from 1 hour to 20 hours, preferably 2 hours.
The range of time to 15 hours is good. The concentration of the aqueous solution of the unsaturated quaternary ammonium salt that can be produced by the method of the present invention can be arbitrarily determined as long as the unsaturated quaternary ammonium salt does not crystallize. May be determined as the above-mentioned water addition amount.

In the method of the present invention, a polymerization inhibitor may be present in the reaction system. Examples of the polymerization inhibitor that can be used include monomethylhydroquinone, hydroquinone, and hydroquinone.
Examples include phenothiazine, cuperon, t-butylcatechol, copper sulfate and the like. The amount of the polymerization inhibitor to be used is 1,000 p in the obtained aqueous solution of unsaturated quaternary ammonium salt.
What is necessary is just to add so that it may become a pm-20,000 ppm concentration range.

[0015]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Acrylic acid dimethylaminoethyl ester 1 was placed in a 3 L pressurized reaction vessel equipped with a stirrer, thermometer, pressure gauge and gas inlet tube.
706 g was charged and the container was sealed. The pressure inside the container is set to -0.
After reducing the pressure to 5 kg / cm ² , the temperature in the vessel was increased to 25 ° C., and 700 g of methyl chloride gas was introduced over 6 hours.
Three hours after the start of the introduction of methyl chloride gas, 577 g of water was introduced over 6 hours. Pressure between Mechirugasu chloride introduction and water introduced rises from -0.5 kg / cm ² to 1.5 kg / cm ^2, the internal temperature rose to 30 ° C. to 37 ° C.. After completion of the introduction of water, the mixture was aged at 35 ° C. under a pressure of 15 kg / cm ² for 4 hours. The internal pressure of the container was released, excess methyl chloride gas was removed by aeration, and 2890 g of an 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride was used.
I got When this solution was analyzed by HPLC, the hydrolysis product of acrylic acid was 600 ppm, the choline chloride was 1000 ppm, and the raw material dimethylaminoethyl acrylate was 400 ppm.

Example 2 The same pressure reactor as in Example 1 was charged with 1614 g of dimethylaminoethyl methacrylate, and the vessel was sealed. After the pressure in the vessel was reduced to -0.5 kg / cm ² , the temperature in the vessel was heated to 25 ° C, and 570 g of methyl chloride gas was introduced over 8 hours. Two hours after the introduction of the methyl chloride gas, 533 g of water was introduced over 8 hours. Pressure between Mechirugasu chloride introduction and water introduced rises from -0.5 kg / cm ² to 1.4 kg / cm ^2, the internal temperature rose to 30 ° C. to 37 ° C.. After completion of the water introduction, the mixture was aged at 35 ° C. and a pressure of 15 kg / cm ² for 5 hours. After aging, the container was opened, and excess methyl chloride gas was removed by aeration to obtain 2660 g of an 80% aqueous solution of methacryloyloxyethyltrimethylammonium chloride. When this solution was analyzed using HPLC, the hydrolysis product methacrylic acid was 150 ppm, the same choline chloride was 600 ppm, and the raw material dimethyl methacrylic acid dimethylaminoethyl ester was 20 ppm.
It was 0 ppm.

Example 3 The same pressure reactor as in Example 1 was charged with 1640 g of dimethylaminopropyl acrylate, and the vessel was sealed. After the pressure in the vessel was reduced to -0.5 kg / cm ² , the temperature in the vessel was heated to 25 ° C., and 700 g of methyl chloride gas was introduced over 7 hours. Two hours after the introduction of the methyl chloride gas, 545 g of water was introduced over 7 hours. Pressure between Mechirugasu chloride introduction and water introduced rises from -0.5 kg / cm ² to 1.4 kg / cm ^2, the internal temperature rose to 30 ° C. to 38 DEG ° C.. After completion of the water introduction, the mixture was aged at 36 ° C. under a pressure of 15 kg / cm ² for 5 hours. After aging, the vessel was opened, and excess methyl chloride gas was removed by aeration to obtain 2720 g of an 80% aqueous solution of acryloyloxypropyltrimethylammonium chloride. When this solution was analyzed by HPLC, the hydrolysis product of acrylic acid was 600 ppm, the hydroxypropyltrimethylammonium chloride was 800 ppm, and the raw material dimethylaminopropyl acrylate was 500 ppm.

Example 4 The same pressure reactor as in Example 1 was charged with 1600 g of dimethylaminopropyl methacrylate, and the vessel was sealed. After reducing the pressure in the container to -0.5 kg / cm ² , the temperature in the container was increased to 25 ° C.
Introduced over time. Two hours after the introduction of the methyl chloride gas, 517 g of water was introduced over 7 hours. Pressure between Mechirugasu chloride introduction and water introduced rises from -0.5 kg / cm ² to 1.5 kg / cm ^2, the internal temperature rose to 30 ° C. to 45 ° C.. After completion of the introduction of water, the mixture was aged at 35 ° C. under a pressure of 15 kg / cm ² for 4 hours. After aging, the vessel was opened and excess methyl chloride gas was removed by aeration to obtain 2580 g of an 80% aqueous solution of methacryloyloxypropyltrimethylammonium chloride. When this solution was analyzed using HPLC, methacrylic acid as a hydrolysis product was 150 ppm, hydroxypropyltrimethylammonium chloride was 500 ppm, and dimethylaminopropyl methacrylate as a raw material was 200 ppm.
Met.

Examples 5 to 8 The same reactions as in Examples 1 to 4 were carried out using ethyl chloride instead of methyl chloride. The results are shown in Tables 1 and 2.

[0021]

[Table 1]

[Table 2]

Comparative Example 1 The apparatus of Example 1 was charged with 1706 g of dimethylaminoethyl acrylate and 581 g of water, and the vessel was sealed. After reducing the pressure in the container to -0.5 kg / cm ² , the temperature in the container was increased to 25 ° C.
Introduced over time. Pressure between Mechirugasu chloride introduction rises from -0.5 kg / cm ² to 1.5 kg / cm ^2, the internal temperature rose to 30 ° C. to 38 DEG ° C.. After completion of the introduction of the methyl chloride gas, the mixture was aged at 35 ° C. and a pressure of 15 kg / cm ² for 4 hours. The internal pressure of the container was released, excess methyl chloride gas was removed by aeration, and acryloyloxyethyltrimethylammonium chloride 80% aqueous solution 2880 was used.
g was obtained. When this solution was analyzed using HPLC, it was found that the hydrolysis product was 2,500 ppm of acrylic acid, similarly, choline chloride was 3,000 ppm, and dimethylaminoethyl acrylate, a raw material, was 1500 ppm.

Comparative Example 2 The apparatus of Example 1 was charged with 1614 g of dimethylaminoethyl methacrylate and 533 g of water, and the vessel was sealed. After depressurizing the internal pressure of the container up to -0.5 kg / cm ^2,
The temperature in the vessel was heated to 25 ° C., and 580 g of methyl chloride gas was introduced over 6 hours. Pressure between Mechirugasu chloride introduction rises from -0.5 kg / cm ² to 1.5 kg / cm ^2, the internal temperature rose to 30 ° C. ~ 39 ° C.. After completion of the introduction of the methyl chloride gas, the mixture was aged at 37 ° C. under a pressure of 15 kg / cm ² for 5 hours. The internal pressure of the container was released, excess methyl chloride gas was removed by aeration, and methacryloyloxyethyltrimethylammonium chloride 80% aqueous solution 266 was used.
0 g was obtained. When this solution was analyzed using HPLC,
Methacrylic acid as a hydrolysis product was 1500 ppm, choline chloride was 3000 ppm, and dimethylaminoethyl acrylate as a raw material was 2000 ppm.

[0024]

According to the method of the present invention, the amount of (meth) acrylic acid produced by hydrolysis of the raw material (meth) acrylic acid ester can be reduced to 100 to 1000 ppm, and a highly pure unsaturated methacrylic acid can be obtained. A quaternary ammonium salt aqueous solution can be easily obtained. In addition, the high-quality aqueous solution of unsaturated quaternary ammonium salt obtained by the method of the present invention has a low content of hydrolysis products (meth) acrylic acid, amino alcohol, and amino alcohol quaternary product. Not only reduces the effect on homopolymers or copolymers with other vinyl monomers using
The deterioration with the passage of time is extremely small.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Takashi Sato, Inventor 2-2 Miyashita, Joban Sekifune-cho, Iwaki, Fukushima Prefecture Inside of Toriken Industrial Co., Ltd. (72) Tetsuro Nakahama 2-2, Miyashita, Joban Sekifune-cho, Iwaki, Fukushima Nitto Riken Kogyo Co., Ltd. F-term (reference) 4H006 AA02 AC52 BB31 BD21 BE60 BT12 BU32 BU50

Claims (3)

[Claims] (1) The following general formula (1): (Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a methyl group or an ethyl group, n represents 2 or 3, and X represents Cl, Br, or I). In producing an aqueous solution of a quaternary ammonium salt, the following general formula (2): (Wherein, R ₁ represents a hydrogen atom or a methyl group, and n is 2
Or 3 is indicated. )), The alkyl halide is directly introduced into the (meth) acrylate, and the addition of water is started when the introduction amount of the alkyl halide reaches 10 to 100% of the total amount. A method for producing an aqueous solution of a highly pure unsaturated quaternary ammonium salt. 2. The method according to claim 1, wherein the (meth) acrylate is dimethylaminoethyl acrylate or dimethylamino methacrylate. 3. The method according to claim 1, wherein the alkyl halide is methyl chloride or ethyl chloride.