JP5809051B2 - Method for producing quaternary ammonium salt aqueous solution - Google Patents

Description

  The present invention relates to a method for producing an aqueous quaternary ammonium salt solution.

  The quaternary ammonium salt is used as a base for garment detergents, bactericides, antibacterial agents, softening agents such as fibers, hair treatment agents, antistatic agents, and the like. The quaternary ammonium salt is produced by a method of reacting a tertiary amine and a quaternizing agent using a solvent as necessary. However, the produced quaternary ammonium salt contains impurities such as lower amines produced as a by-product during the reaction and unreacted quaternizing agent. Even if these impurities are contained in a very small amount, they smell and preserve stably. There was a problem of worsening sex.

  Therefore, conventionally, for the purpose of improving odor and storage stability, removal using a carrier gas under normal pressure or reduced pressure and distillation under reduced pressure are performed after the reaction. For example, in Patent Document 1, the reaction solvent is quaternized using ethyl alcohol, isopropyl alcohol or the like, and the solvent used for the subsequent deodorization treatment is added with an antifoaming agent such as silicone to distill off the odor. It has improved. However, when water is used as the reaction solvent, the problem of flash point can be avoided, but impurities such as lower amines that cause odor deterioration are difficult to remove from the aqueous solution system, and effective odor improvement effects are achieved. Cannot be obtained. Further, as a method for improving the irritating odor, the prior art document 2 proposes a method of removing a volatile component by forming an aqueous solution having a pH of 7 to 12 into a thin film.

Japanese Patent Laid-Open No. 11-279132 JP-A-9-104661

  In Patent Document 1, since the quaternary ammonium salt to be produced is obtained as a mixture with a lower alcohol, it is flammable, so the cost of handling equipment is increased, and the odor effect and flash point of the lower alcohol as a product are increased. Detected and cannot be used. Also in Patent Document 2, the quaternary ammonium salt does not provide the effect of improving odor when stored under severe conditions for a long time, the production equipment is expensive, and the hue and the like deteriorate in storage stability. There was a problem such as.

  An object of the present invention is to provide a method for producing a high-quality quaternary ammonium salt aqueous solution that has a good odor and hue immediately after production and can maintain a good odor and hue even after being stored under harsh conditions. Is to provide.

The present invention provides a method for producing a quaternary ammonium salt aqueous solution having the following steps (I), (II) and (III).
Step (I): a tertiary amine having a C6-C30 linear or branched alkyl group or alkenyl group into which an ester group, an amide group or an ether group may be inserted, and a quaternizing agent Step (II) for preparing a reaction mixture containing quaternary ammonium salt (1) represented by the general formula (1) and water: reaction obtained in Step (I) Adjusting the pH of the mixture to 8.6 to 13.0 and introducing an inert gas into the reaction mixture in the presence of an antifoam agent Step (III): After step (II), the pH of the reaction mixture To obtain an aqueous solution containing the quaternary ammonium salt represented by the general formula (1)

(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms into which an ester group, an amide group or an ether group may be inserted, and R ² represents one carbon atom. ˜3 represents an alkyl group, and X ⁻ represents an anionic group.)

  According to the present invention, it is possible to produce a high-quality quaternary ammonium salt aqueous solution that has a good odor and hue immediately after production and can maintain a good odor and hue even after being stored under severe conditions. In the present invention, a high quality quaternary ammonium salt is prepared by introducing an inert gas into the reaction mixture in the presence of a specific pH and antifoaming agent after the quaternization reaction, and then adjusting to a specific pH. A production method capable of producing an aqueous solution can be provided. Furthermore, this aqueous solution of quaternary ammonium salt can be obtained in the form of an aqueous solution, and since it has no odor or flammability due to the solvent, it is easy to handle, and is a detergent for clothes, a bactericidal agent, an antibacterial agent, and a fiber. It is useful when used as a raw material for preparing softeners, hair treatment agents, antistatic agents and the like.

<Process (I)>
In step (I), a predetermined tertiary amine is reacted with a quaternizing agent in water to prepare a reaction mixture containing the quaternary ammonium salt (1) represented by the general formula (1) and water. It is a process to do.

  The tertiary amine as a raw material can be represented by the following general formula (1 ').

(In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 30 carbon atoms which may be interrupted by an ether group or an amide group.)

R ¹ of R ¹ and of the general formula (1) (1 ') in an ester group, an amide group or an ether group may be inserted, a straight-chain or branched-chain having 6 to 30 carbon atoms An alkyl group or an alkenyl group, preferably an ester group, an amide group, or an ether group into which a linear or branched alkyl group having 8 to 24 carbon atoms, more preferably 10 to 22 carbon atoms, may be inserted. A linear or branched alkyl group, more preferably a linear alkyl group having 10 to 18 carbon atoms.

Moreover, R < ² > in General formula (1) is a C1-C3 alkyl group, Preferably it is a methyl group, an ethyl group, More preferably, it is a methyl group.

In the general formula (1), X ⁻ is an anion group, specifically, halogen ions such as Cl ⁻ and Br ⁻ , short chain alkyl sulfate ions such as methyl sulfate ions and ethyl sulfate ions, acetic acid And anions of organic acids such as tartaric acid, lactic acid, malic acid and succinic acid, preferably halogen ions such as Cl ⁻ and Br ⁻ , and more preferably Cl ⁻ (chloride ion).

Although the quaternization reaction in the step (I) is not particularly limited, for example, a raw material tertiary amine is R ² -X in water (R ² is the same as described above, and X is a group that becomes an anion X ^−). And a quaternizing agent at a temperature of 25 to 120 ° C., followed by quaternization at a temperature of 25 to 120 ° C. for 0.1 to 20 hours.

  In step (I), a tertiary amine is quaternized in water to produce a quaternary ammonium salt (1). In addition to water, lower alcohols such as methanol, ethanol and isopropyl alcohol (1 to 3 carbon atoms), diols such as ethylene glycol and propylene glycol (2 to 5 carbon atoms), organic solvents such as acetone and acetonitrile. Can be added as appropriate within a range that does not affect the present reaction. As the range of the addition amount having no influence, for example, it can be added within the range where the flash point does not appear in the obtained aqueous solution of quaternary ammonium salt. Specifically, in the case of ethyl alcohol, it can be added at 5% by mass or less. In the present invention, since the quaternization is performed in water, the reaction solvent preferably contains 95% by mass or more of water, and more preferably 95-100% by mass.

  The ratio of the tertiary amine (1) to the water is the time before the first introduction of the quaternizing agent from the viewpoint of securing the fluidity of the resulting quaternary ammonium salt aqueous solution at room temperature and efficient productivity. It is preferable that it is 20-80 mass%, More preferably, it is 25-70 mass%, More preferably, it is 30-60 mass%. This ratio is obtained by [the amount of tertiary amine (1) charged / the amount of water charged] × 100.

  The amount of the quaternizing agent used is preferably 0.95 to 2.0 mol times based on the tertiary amine. From the viewpoint of reducing the burden on post-treatment such as reduction of unreacted tertiary amine content after quaternization, side reaction of quaternizing agent, disposal of quaternizing agent remaining after reaction, etc. The amount used is more preferably 0.98 to 1.5 mol times, more preferably 0.99 to 1.30 mol times, still more preferably 1.00 to 1.15 mol times with respect to the tertiary amine. .

  In the present invention, an inert gas is introduced into the reaction mixture in the presence of an antifoaming agent in the step (II), but as long as the antifoaming agent is included in the reaction mixture used in the step (II), The foaming agent may be added to the reaction system at a time such as step (I) [any time in step (I)] or between step (I) and step (II). In the present invention, it is preferable to add an antifoaming agent in the step (I) in order to improve productivity due to an increase in the amount of treatment during quaternization. Furthermore, it is preferable to perform a quaternization reaction in the presence of water and an antifoaming agent in step (I) to obtain a reaction mixture containing the quaternary ammonium salt (1), water and an antifoaming agent. In this case, the addition amount of the antifoaming agent is preferably 10 to 1,000 mg / kg, more preferably 25 to 500 mg / kg, and still more preferably 50 to 250 mg / kg with respect to the reaction system. This addition amount is the mass of the antifoaming agent (mg) / the mass of the reaction system (kg). In this case, the reaction system may be a mixture containing the tertiary amine (1) and water, and may further be a mixture containing a quaternizing agent. For example, the reaction system can be regarded as a mixture of the tertiary amine (1), the quaternizing agent and water, and in this case, the mass of the reaction system can be the sum of these three charges. .

  The reaction mixture obtained in the step (I) preferably contains 20 to 80% by mass, further 25 to 60% by mass, and more preferably 27 to 50% by mass of the quaternary ammonium salt (1).

<Process (II)>
In step (II), the pH of the reaction mixture obtained in step (I) is adjusted to 8.6 to 13.0, and an inert gas is introduced into the reaction mixture in the presence of an antifoaming agent. is there. By introducing the inert gas in step (II) under these conditions, a high-quality quaternary ammonium salt that has excellent odor and hue immediately after production and can maintain a good odor after storage under harsh conditions. An aqueous solution can be obtained. This is considered to be because components (for example, low-boiling organic compounds) that can cause odor or coloring immediately after production or after storage are efficiently distilled off from the reaction mixture.

  The pH of the reaction mixture at the time of introducing the inert gas is 8.6 to 13.0, and preferably 8.6 to 12.0, more preferably 8.6 to 11.0 from the viewpoint of improving odor. It is.

  The alkaline agent added for adjusting the pH is not particularly limited as long as the reaction mixture can be adjusted to the target pH, but is preferably an alkaline agent selected from alkali metal hydroxides and carbonates, More preferred is an alkali agent selected from sodium hydroxide, potassium hydroxide and carbonate, and still more preferred is an alkali agent selected from sodium carbonate and potassium carbonate. The alkaline agent can be used in the form of an aqueous solution.

Examples of the antifoaming agent include dimethylpolysiloxane, amino-modified silicone, polyether-modified silicone, and silicon dioxide. One or more of these can be used. Preferably, dimethylpolysiloxane, amino-modified silicone, polyether-modified silicone, more preferably polyether-modified silicone, still more preferably HLB 0.5-3 polyether-modified silicone, still more preferably, It is a polyether-modified silicone of HLB 0.5-3 having a polyoxyethylene group. By adding and mixing the antifoaming agent at the time of introducing the inert gas, the production can be performed smoothly, the processing amount can be increased, and the productivity can be greatly improved. In addition, what was previously emulsified can also be used for an antifoamer. The HLB for the polyether-modified silicone having a polyoxyethylene group is a value calculated by the following formula (Introduction to New Surfactant, p.129, Takehiko Fujimoto, published by Sanyo Chemical Industries, 1996) October).
HLB = E / 5
(E shows the ratio (mass%) of the mass of the oxyethylene group to the mass of the polyether-modified silicone having a polyoxyethylene group.)

  The addition amount of the antifoaming agent is preferably 10 to 1,000 mg / kg, more preferably 25 to 500 mg / kg, still more preferably 50 to 250 mg / kg with respect to the reaction mixture obtained in the step (I). is there. This addition amount is the mass of the antifoaming agent (mg) / the mass of the reaction mixture (kg).

  The antifoaming agent may be added before quaternization in step (I) or after quaternization, and after quaternization, either before or after adjusting the pH. As mentioned above, it is preferable to add before quaternization from the viewpoint of productivity improvement due to an increase in the amount of treatment during quaternization.

  The temperature of the reaction mixture at the time of introducing the inert gas is preferably 40 to 120 ° C., more preferably 50 to 100 ° C., and still more preferably, from the viewpoint of improving the odor and reducing side reactions of the aqueous quaternary ammonium salt solution. 60-90 ° C.

  The introduction of the inert gas can be performed under normal pressure or reduced pressure. The normal pressure is in the vicinity of 100 kPa, but may be 110 to 95 kPa. When performed under reduced pressure, the pressure is preferably 3 to 95 kPa, more preferably 6.7 to 90 kPa, and still more preferably 13 to 80 kPa. Preferably, it is under normal pressure.

  Examples of the inert gas include nitrogen gas and water vapor, and nitrogen gas is preferable. The inert gas is introduced in such a manner as to come into contact with the inside of the reaction mixture. For example, the inert gas can be introduced by blowing into the inside of the reaction mixture. More specifically, in a state where the inert gas introduction means is disposed inside the reaction mixture, for example, in a state where the tip (opening) of the inert gas introduction tube is immersed in the reaction mixture, / Or intermittently blowing inactive gas for a predetermined time (for example, bubbling).

  The introduction amount of the inert gas is preferably 0.05 to 500 L / kg with respect to the reaction mixture, more preferably 0.1 to 100 L / kg, more preferably from the viewpoints of odor improvement and economy and productivity. 0.5 to 50 L / kg, more preferably 1 to 20 L / kg. The amount introduced is volume of inert gas (L) / mass of reaction mixture (kg).

  In the step (II), the introduction of the inert gas can be performed in either a batch tank or a continuous apparatus (for example, a thin film evaporator). It is a tank.

  In the step (II), the time for introducing the inert gas is not particularly limited. However, in the case of the conditions of the present invention, it is usually within 20 hours, from the viewpoint of not deteriorating the hue and economical and productivity. 0.5 to 10 hours is preferable, and 1 to 8 hours is more preferable.

<Process (III)>
In step (III), after step (II), the pH of the reaction mixture is adjusted to 5.0 to 8.5 to obtain an aqueous solution containing a quaternary ammonium salt represented by general formula (1). It is.

  In step (III), an acid is added to the reaction mixture after the introduction of the inert gas is completed, and the pH is adjusted to 5.0 to 8.5. From the viewpoint of the storage stability of the quaternary ammonium salt aqueous solution, the pH is preferably adjusted to 5.5 to 8.5, more preferably 6.0 to 8.5. This pH is at the temperature at which step (III) is carried out, but it is preferable that the pH is in this range at 25 ° C.

  The acid added for adjusting the pH is not particularly limited as long as the quaternary ammonium salt aqueous solution can be adjusted to the target pH, and specifically, hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, 1 to 3 carbon atoms. Organic acids such as alkyl sulfuric acid, acetic acid, tartaric acid, lactic acid, malic acid, succinic acid, glutamic acid, and the like, preferably hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, lactic acid, more preferably hydrochloric acid, sulfuric acid, phosphoric acid, particularly preferable Is hydrochloric acid. These acids may be used in a dilution system such as water.

  The aqueous solution obtained in the step (III) preferably contains 20 to 80% by mass, further 25 to 60% by mass, and more preferably 27 to 50% by mass of the quaternary ammonium salt (1).

  The odor evaluation and hue evaluation of the quaternary ammonium salt aqueous solutions produced in Examples and Comparative Examples were performed as follows.

<Odor evaluation>
An aqueous solution immediately after production or an aqueous solution stored at 60 ° C. for 6 months was put in a 100 mL beaker, sensory evaluation was performed by five panelists at room temperature, and the suppression of off-flavors was evaluated according to the following criteria. The aqueous solution is stored in Kyodou Glass Co., Ltd. Hiroguchi Standard Bottle PS-No. 11 (cylinder diameter 51.5 mm, height 95.5 mm, caliber 39.5 mm, made of glass) was filled with 50 mL of an aqueous solution and sealed and shielded from light.
A: 5 people did not feel a bad odor B: 4 people did not feel a bad odor C: 3 people did not feel a bad odor D: 2 people did not feel a bad odor E: 0 people or 1 person had a bad smell Did not feel (4 or 5 people had a bad smell)

<Hue>
The aqueous solution immediately after production or the aqueous solution after being stored at 60 ° C. for 6 months in the same manner as in the method of odor evaluation, the hue (Hazen color) by the Hazen method (A. Hazen, Am. Chem. J. 14, 300 (1892)) Number).

Production Example 1
Step (I) was performed as follows.
In a 0.5 L autoclave equipped with a stirrer, a thermometer and a pressure gauge, 85.4 g (0.40 mol) of lauryldimethylamine (Farmin DM2098 manufactured by Kao Corporation), 177 g of ion-exchanged water, polyether-modified silicone [antifoaming] 0.029 g (100 mg / kg with respect to the reaction system)] of DOW CORNING TORAY FZ-2203, HLB1 (catalog value)] manufactured by Toray Dow Corning Co., Ltd. was added, and the atmosphere was replaced with nitrogen. Thereafter, 20.6 g of methyl chloride (1.02 mol times relative to lauryldimethylamine) was injected in 10 minutes and then reacted at 60 to 70 ° C. for 2 hours to obtain a quaternary ammonium salt concentration of 37.1 mass. %, A reaction rate of 99.4%, pH 6.1 quaternary ammonium salt aqueous solution 283g. This aqueous quaternary ammonium salt had an odor evaluation E immediately after production.

Production Example 2
Step (I) was performed as follows.
In a 0.5 L autoclave equipped with a stirrer, a thermometer, and a pressure gauge, 85.4 g (0.40 mol) of lauryldimethylamine (Farmin DM2098 manufactured by Kao Corporation) and 177 g of ion-exchanged water were substituted with nitrogen. Thereafter, 21.2 g of methyl chloride (1.05 mol times with respect to the tertiary amine) was injected in 10 minutes and then reacted at 60 to 70 ° C. for 2 hours to obtain a quaternary ammonium salt concentration of 37.0. %, Reaction rate 99.4%, pH 5.6 quaternary ammonium salt aqueous solution 283g. This aqueous quaternary ammonium salt had an odor evaluation E.

Production Example 3
Step (I) was performed as follows.
In a 0.5 L autoclave equipped with a stirrer, thermometer and pressure gauge, 67.4 g (0.25 mol) of hexadecyldimethylamine (Farmin DM6098 manufactured by Kao Corporation), 184 g of ion-exchanged water, polyether-modified silicone A foaming agent, DOW CORNING TORAY FZ-2203 manufactured by Toray Dow Corning Co., Ltd., HLB1 (catalog value)] 0.029 g (100 mg / kg for the reaction system) was added, and the atmosphere was replaced with nitrogen. Thereafter, 13.3 g of methyl chloride (1.05 mol times with respect to hexadecyldimethylamine) was injected in 10 minutes and then reacted at 60 to 70 ° C. for 2 hours to obtain a quaternary ammonium salt concentration of 30.0. %, Reaction rate 99.3%, pH 5.7 quaternary ammonium salt aqueous solution 264g was obtained. This aqueous quaternary ammonium salt had an odor evaluation E.

Example 1
Into a 0.5 L four-necked round bottom flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 250 g of the quaternary ammonium salt aqueous solution obtained in Production Example 1 was placed, and a 17% sodium carbonate aqueous solution at 80 ° C. 1 g was added to pH 9.7. Nitrogen gas (2 L) (8 L / kg with respect to the quaternary ammonium salt aqueous solution) was blown (bubbled) for 3 hours at 80 ° C. and normal pressure. At this time, nitrogen gas was blown (bubbled) with the tip of the nitrogen introduction tube (diameter 4 mm) immersed in the aqueous quaternary ammonium salt solution. Thereafter, 0.22 g of 35% hydrochloric acid aqueous solution was added and mixed and stirred at 60-80 ° C. for 1 hour to obtain 240 g of a quaternary ammonium salt aqueous solution having a pH of 7.1 and a quaternary ammonium salt concentration of 37.3 mass%. It was. The obtained quaternary ammonium salt aqueous solution was subjected to odor evaluation and hue evaluation by the above methods. The results are shown in Table 1. In addition, each process was performed, stirring a quaternary ammonium salt aqueous solution at a rotational speed of 350 rpm using a Teflon (registered trademark) crescent blade having a width of 6 cm. Moreover, Example 1 is a model test of a batch type tank.

Examples 2-8 and Comparative Examples 1-6
Step (I) is carried out in any one of Production Examples 1 to 3, and Step (II) is the same as in Example 1, except that the inert gas introduction conditions are as shown in Tables 1 and 2, and Tables 1 and 2 are used. A quaternary ammonium salt aqueous solution shown in FIG. Each quaternary ammonium salt aqueous solution was evaluated for odor and hue in the same manner as in Example 1. The results are shown in Tables 1 and 2. In addition, Examples 2-8 and Comparative Examples 1-6 are model tests of a batch type tank.

(note)
* 1 Per kg of reaction system (total of tertiary amine, quaternizing agent, and water charge) [when added in step (I)], or per kg of quaternary ammonium salt aqueous solution [step (II) Of defoaming agent (when added in 1 mg)
* 2 [] indicates the amount of inert gas blown per kg of quaternary ammonium salt aqueous solution (L).
* 3 In Comparative Example 6, the inert gas was not blown in, but the mixture was allowed to stand for 3 hours at 80 ° C. under normal pressure and 80 ° C. under stirring (a Teflon (registered trademark) crescent blade with a width of 6 cm, rotation speed: 350 rpm).

Claims (11)

A method for producing a quaternary ammonium salt aqueous solution having the following step (I), step (II) and step (III) , wherein step (I) is carried out in the presence of an antifoaming agent, and the reaction comprises an antifoaming agent. A method for producing a quaternary ammonium salt aqueous solution, wherein a mixture is obtained and used in step (II).
Step (I): a tertiary amine having a C6-C30 linear or branched alkyl group or alkenyl group into which an ester group, an amide group or an ether group may be inserted, and a quaternizing agent Step (II) for preparing a reaction mixture containing quaternary ammonium salt (1) represented by the general formula (1) and water: reaction obtained in Step (I) Adjusting the pH of the mixture to 8.6 to 13.0 and introducing an inert gas into the reaction mixture in the presence of an antifoam agent Step (III): After step (II), the pH of the reaction mixture To obtain an aqueous solution containing the quaternary ammonium salt represented by the general formula (1)

(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms into which an ester group, an amide group or an ether group may be inserted, and R ² represents one carbon atom. It indicates to 3 alkyl groups, X ^- represents an anion group). The method for producing an aqueous quaternary ammonium salt solution according to claim 1, wherein the quaternary ammonium salt (1) is a compound in which R ² in the general formula (1) is a methyl group and X ^- is a chloride ion.   In the step (II), the inert gas is introduced into the reaction mixture in the presence of 10 to 1,000 mg / kg of an antifoaming agent. Production method.   The method for producing an aqueous quaternary ammonium salt solution according to any one of claims 1 to 3, wherein in the step (II), an inert gas of 0.1 to 100 L / kg is introduced into the reaction mixture. The quaternary ammonium salt (1) is a quaternary compound according to any one of claims 1 to 4, wherein R ¹ in the general formula (1) is a compound having a linear alkyl group having 10 to 18 carbon atoms. A method for producing an aqueous ammonium salt solution.   The method for producing an aqueous quaternary ammonium salt solution according to any one of claims 1 to 5, wherein the quaternizing agent is methyl chloride. The method for producing an aqueous quaternary ammonium salt solution according to any one of claims 1 to 6 , wherein in the step (II), the inert gas is introduced under normal pressure. The method for producing an aqueous quaternary ammonium salt solution according to any one of claims 1 to 6 , wherein in the step (II), the inert gas is introduced under a reduced pressure of 6.7 to 90 kPa. The method for producing an aqueous quaternary ammonium salt solution according to any one of claims 1 to 8 , wherein in the step (II), the inert gas is introduced at a temperature of 50 to 100C. The aqueous quaternary ammonium salt solution according to any one of claims 1 to 9 , wherein the aqueous quaternary ammonium salt obtained in step (III) contains 25 to 60% by mass of the quaternary ammonium salt (1). Manufacturing method. The method for producing an aqueous quaternary ammonium salt solution according to any one of claims 1 to 10 , wherein in the step (II), the inert gas is introduced in a batch tank.