JP2639434B2 - Process for producing alkanol ammonium salt or ammonium salt of surfactant - Google Patents

Description

The present invention relates to a method for producing an alkanol ammonium salt or an ammonium salt of a surfactant, and more particularly to a method for producing an amino acid type surfactant or an acylated amino acid type surfactant. The present invention relates to a novel method for producing an alkanol ammonium salt or an ammonium salt by using a specific ion-exchange membrane to carry out a more efficient reaction when using an electrodialysis.

[Conventional technology]

In recent years, imidazoline-based amphoteric surfactants and amino acid-type surfactants have been widely used in shampoo bases and various detergents due to their low irritation, with increasing awareness of safety and low irritation. In particular, imidazoline amphoteric surfactants are widely used and studied because of their easy production method and low cost.

By the way, this imidazoline-based amphoteric surfactant is generally produced by a method in which an alkyl imidazoline is reacted with sodium monochloroacetate to amphoterate the same, but the imidazoline-based amphoteric surfactant obtained by this method has recently been studied. Has little imidazoline skeleton which has been considered for a long time in the past, and it has been found that imidazoline or a ring-opened amidoamine derivative, for example, as shown in the following formula (I).

(Wherein, R represents an alkyl group) Therefore, the imidazoline amphoteric surfactant can be produced not only by the above method but also by reacting amidoamine with sodium monochloroacetate.

When this alkali metal salt is replaced with an alkanol ammonium salt or an ammonium salt, the ionic strength of the surfactant is reduced, so that the surfactant has excellent compatibility with a water-soluble polymer and various additives, and has a low Krafft point. When this is done, the material has excellent low-temperature stability. Conventionally, as a method for producing the alkanol ammonium salt or ammonium salt of the imidazoline amphoteric surfactant, an alkali metal salt (eg, sodium salt) of the imidazoline amphoteric surfactant is treated with a mineral acid to form an acid form,
Then, a method of neutralizing with alkanolamine or ammonia has been adopted.

[Problems to be solved by the invention]

However, in this method, when treating with a mineral acid to obtain an acid form, a large amount of salt is formed and gelation occurs, or a mineral salt of an amine is formed, so that an alkanol ammonium salt or an ammonium salt is efficiently produced. Could not be manufactured. For example, using hydrochloric acid as a mineral acid for the imidazoline-based amphoteric surfactant of the formula (I) and neutralizing with triethanolamine, the desired high-purity (I)-as shown in the following reaction formula is obtained. a cannot be obtained, and (I) -a
Only a mixture of (I) -c and (I) was obtained.

Wherein R has the same meaning as described above. These phenomena occur for amino acid type surfactants and acylated amino acid type surfactants in general, so that a large amount of salt (eg, NaCl) is contained in the product. Therefore, such surfactants cannot exhibit sufficient compatibility with various alkanol ammonium salts or various additives, which are characteristics inherent to ammonium salts of these surfactants, and low-temperature stability.

[Means for solving the problem]

Thus, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by using electrodialysis, an alkanol ammonium salt or an ammonium salt of an amino acid type surfactant or an acylated amino acid type surfactant is easily prepared. And that it can be manufactured efficiently. That is, a method in which an alkali metal salt of an amino acid type surfactant or an acylated amino acid type surfactant is subjected to electrodialysis in the presence of an alkanolamine or ammonium mineral acid salt or an alkanolamine or ammonium and a mineral acid to exchange counter ions. It is. In this electrodialysis, when an ion-exchange membrane used in ordinary seawater desalination is used, alkanolamine or ammonium or a mineral salt thereof permeates the membrane, and a very large amount leaks. May be. As a result, the applied current is used not only for dialysis of metal ions but also for dialysis of these ammonium ions, and the current efficiency is reduced, making it difficult to obtain a counter ion exchange product of the desired purity. In order to obtain a counter ion exchange product of the desired purity, it is necessary to apply a current for a long time or to increase the area of the ion exchange membrane.
More than double. In addition, the loss amount increases, and a large amount of ammonium ions leak, which is very unfavorable in terms of manufacturing cost. Therefore, at the time of electrodialysis, it is very important industrially to set an ion exchange membrane in which the counter ion exchanged ammonium ions and the like are hardly dialyzed.

Therefore, the present inventors have further attempted to obtain an ion exchange membrane in which an amino acid type surfactant or an acylated amino acid type surfactant and an alkanol ammonium ion or an ammonium ion are hardly permeated and an alkali metal ion can be easily permeated. As a result of research, we used a cation exchange membrane as a base, which has the same ion exchange capacity as a normal membrane and a low water content. That the permeation speed of ions with low mobility is suppressed,
In addition, the inventors have found that by treating the surface or the surface layer with a condensate of an amine and an aldehyde, the permeability of a cation having a lower dissociation degree than that of an alkali metal ion is suppressed, and the present invention has been completed.

Accordingly, the present invention provides an electrodialysis of an alkali metal salt of an amino acid type surfactant or an acylated amino acid type surfactant in the presence of an alkanolamine or ammonium mineral salt or an alkanolamine or ammonia and a mineral acid. In a method for producing an alkanol ammonium salt or an ammonium salt of an amino acid type surfactant or an acylated amino acid type surfactant, an ion exchange membrane used in electrodialysis has an ion exchange capacity of 2.0 to 3.0 (milli equivalent / gram dry resin), Moisture content
Amino acid type surfactant characterized in that the surface or surface layer of a sulfonic acid type cation exchange membrane of 0.2 to 0.3 (gram water / gram wet resin) is treated with a condensate of amines and aldehydes. The present invention provides a method for producing an alkanol ammonium salt or an ammonium salt of an agent or an acylated amino acid type surfactant.

The sulfonic acid type cation exchange membrane (hereinafter abbreviated as “cation exchange membrane”) used in the present invention has an ion exchange amount of 2.0 to 3.0 (milliequivalent / gram dry weight) and a water content of 0.2 to 0.3. (Gram water / gram wet resin), for example, a hydrocarbon-based polymer film such as a sulfonated product of a styrene-divinylbenzene copolymer, a sulfonated product of a styrene-halomethylstyrene cross-linked copolymer, and tetrafluoroethylene. And fluorinated hydrocarbon-based polymer films such as -perfluorosulfonylethoxyvinyl ether copolymer. Here, the ion exchange capacity and the water content of the ion exchange membrane are those using the method described in “Ion Exchange Membrane (Kyoritsu Shuppan), pp. 123,124” by Yujiro Kosaka and Hiroshi Shimizu.

Examples of the condensate of an amine and an aldehyde used for treating the surface or the surface layer of the cation exchange membrane (hereinafter abbreviated as “amine-aldehyde condensate”) include, for example, an aliphatic or aromatic compound capable of reacting with the aldehyde. And condensates of aldehydes which react quickly with aliphatic amines and the like. Examples of preferred amines include one or more amino groups on the aromatic nucleus, such as aniline, metaphenylenediamine, metatoluidine, diphenylamine, and metaaminophenol. Preferred aldehydes include formaldehyde and acetaldehyde. And the like.

As a method of treating the surface or the surface layer of the cation exchange resin with an amine-aldehyde condensate, a mixed solution of amines and aldehydes or an initial condensate thereof is applied to the surface of the cation exchange membrane, or a mixture thereof. An appropriate method such as immersing the film in a resin and pulling it up and then converting it to resin, or applying or dipping amines to the film and then applying and dipping aldehydes and heating as necessary to generate a condensate Can be used. In this case, an acid, an alkali, preferably an acid catalyst is used as a catalyst for promoting the formation of a condensate. The condensate of an amine and an aldehyde may be applied to both surfaces of the cation exchange membrane, but is preferably applied only to the desalting chamber side, because the membrane resistance can be reduced. The ratio (as a molar ratio) of the amines and aldehydes used for the surface or surface treatment is preferably 1: 5 to 5: 1.

In the present invention, an alkali metal salt of an amino acid type surfactant is an aminocarboxylic acid having at least one primary, secondary, or tertiary amino group in a molecule and having at least one carboxyl group or a sulfonic acid group, or It refers to an alkali metal salt of aminosulfonic acid, and examples thereof include alkali metal salts of the following compounds (a) to (f).

Wherein R ₁ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group, an aralkyl group or a hydroxyalkyl group or a formula (R ₃ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an aralkyl group, or a hydroxyalkyl group wherein, R ₄
Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxyethyl group), and R ₂ represents a hydrogen atom,-
(CH ₂ CH ₂ O) _m- H, -(CH ₂ ) _n COOH (where m is an integer of 1 to 10, n is 1 to 5)
Or an alkyl group having 1 to 22 carbon atoms, an alkenyl group, an aralkyl group or a hydroxyalkyl group.] Wherein R ₅ is the same as R ₂ or Wherein R ₁ has the same meaning as described above) (Wherein, R ₁ and R ₂ have the same meaning as described above) [Wherein, R ₆ is a hydrogen atom,-(CH ₂ CH ₂ O) _m H, (Where m has the same meaning as above), Or an alkyl group having 1 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group or an aralkyl group] Wherein R ₇ is a hydrogen atom,-(CH ₂ CH ₂ O) _m H, — (CH ₂ ) _n SO ₃ H (where m and n have the same meanings as described above) or an alkyl group, alkenyl group, hydroxyalkyl group or aralkyl group having 1 to 22 carbon atoms] [Wherein R ₈ is a hydrogen atom,-(CH ₂ CH ₂ O) _m H, (Where m has the same meaning as above), Or an alkyl group, an alkenyl group, a hydroxyalkyl group or an aralkyl group having 1 to 22 carbon atoms.] The compound (a) includes an imidazoline amphoteric surfactant,
That is, those containing one or more compounds having the following three structures are included.

[Wherein R ₉ represents an alkyl group, an alkenyl group, a hydroxyalkyl group or an aralkyl group having 7 to 21 carbon atoms] Examples of the alkali metal salt of the acylated amino acid type surfactant include the following (g) to (g). And alkali metal salts of the compound (i).

[Wherein R ₁ , R ₂ and n have the same meaning as described above] [Wherein, R ₁ , R ₇ and n have the same meaning as described above] [In the formula, R ₁ and R ₈ have the same meanings as described above] An example of an electrodialysis tank used in the practice of the present invention is schematically shown in FIG. Next, the method of the present invention will be described with reference to this drawing.

An anion exchange membrane (A) and a cation exchange membrane (C) are alternately arranged, and an amino acid type surfactant or an acylated amino acid type surfactant is placed in a compartment (organic substance chamber) sandwiched between the two types of membranes. And an alkali metal salt of alkanolamine or ammonia, or a mineral acid and an alkanolamine or ammonia, and an electrolytic solution in an adjacent chamber (electrolyte chamber) via a membrane to generate a direct current. By conducting electricity, alkali metal ions are transferred from the organic substance chamber to the electrolyte chamber, and an alkanol ammonium salt or an ammonium salt of an amino acid type surfactant or an acylated amino acid type surfactant is generated in the organic substance chamber. . The ion exchange membrane used is a cation exchange membrane having the property of selectively transmitting alkali metal ions to various cations subjected to the above-described treatment, and selectively transmitting anions to the cations. It is a normal anion exchange membrane used for desalination of seawater having properties.

The mineral acid used in the present invention is not particularly limited, but hydrochloric acid, sulfuric acid, phosphoric acid, particularly hydrochloric acid is preferred. As the mineral salt of alkanolamine or ammonia, it is preferable to use a salt of alkanolamine or ammonia with the above-mentioned mineral acid.

The order of addition of the substances to be added to the organic substance is not particularly limited, but when a mineral acid and alkanolamine or ammonia are used, for example, after adding alkanolamine or ammonia to the alkali metal salt of the surfactant as a raw material , A mineral acid may be added, or vice versa. Further, one of these substances can be added continuously while performing electrodialysis.

The amount of the alkanolamine or ammonia used is preferably at least equimolar to the alkali metal salt of the surfactant. If the amount is less than the equimolar amount, the counter ion exchange is not sufficiently performed, and if the amount is excessive, the impurities remain in the system after the electrodialysis or the electrodialysis requires a long time. Therefore, the molar ratio is particularly preferably 1.0 to 3.0 times. The amount of the mineral acid used is 0.8 to 1.5 with respect to ammonia or alkanolamine.
The molar amount is preferably 1-fold, especially 1.0-1.5-fold. When alkanolamine or ammonia mineral salt is used, the amount used is the same as the above-mentioned alkanol or ammonia used amount.

The electrolyte to be used is not particularly limited, and any substance can be used as long as it dissociates in water or under a potential gradient. In general, salt, bow nitrate, potassium chloride, potassium sulfate, ammonium chloride And inorganic substances such as ammonium sulfate are preferably used. In the chamber in contact with the electrode plate, the above-mentioned electrolyte solution or the like may be used as the electrode solution.
Each of these solutions is preferably circulated through a pump or the like. The applied current value is preferably equal to or less than the limiting current density, but the limiting current density greatly varies depending on the type of solution, concentration, temperature, dialysis tank configuration and the like. Therefore, although the current density is not particularly specified, it is generally 0.1 to 10 amps / dm.
^{About 2} is appropriate.

The alkanol ammonium salt or ammonium salt of the amino acid type surfactant or the acylated amino acid type surfactant thus formed in the organic substance room can be used by collecting the liquid in the organic substance room and concentrating the liquid as it is or as necessary. it can.

〔The invention's effect〕

According to the present invention, it is possible to easily and efficiently produce an alkanol ammonium salt or an ammonium salt of an amino acid type surfactant or an acylated amino acid type surfactant which could not be produced with high purity in a conventional manner, and with high purity. In addition, loss due to permeation of alkanolamine or ammonia, which is a low molecular organic substance, through the membrane could be greatly reduced.

〔Example〕

 Hereinafter, the present invention will be further described with reference to examples.

Example 1 A 4-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer was charged with 268 g (1 mol) of 1-hydroxyethyl-2-laurylimidazoline, 90 g of water and 2 g of sodium hydroxide.
The mixture was heated to 80 ° C. while stirring, and stirring was continued at the same temperature for about 2 hours to open the ring of imidazoline. Next, 233 g (2 mol) of sodium monochloroacetate prepared separately
And a solution of 427.0 g of water were charged into the container. Next, 200 g of a 40% aqueous sodium hydroxide solution was added dropwise over 4 hours while maintaining the temperature of the solution at 70 to 80 ° C. After dropping, 75 ~
Aging was conducted at a temperature of 80 ° C., and N-lauroyl-N′-2-
An approximately 30% aqueous solution of hydroxyethyl-N'-sodium carboxymethylethylenediamine was obtained. To this solution was added 149.2 g (1 mol) of triethanolamine, and the solution was cooled. The solution was a light brown liquid with a pH of about 9.
The solution thus obtained was subjected to electrodialysis. In the electrodialysis, N-lauroyl-N'-2-hydroxyethyl-N'-sodium is placed in a compartment (organic material compartment) sandwiched between an anion exchange membrane (A) and a cation exchange membrane (C) in FIG. A mixed solution of carboxymethylethylenediamine and triethanolamine was circulated, and a 1% NaCl aqueous solution was circulated in an adjacent compartment (electrolyte compartment). The method was applied. At this time, electrodialysis was performed while uniformly adding 213.8 g (2.05 mol) of 35% HCl to the mixed solution over about 4 hours. The cation exchange membrane set in the electrodialysis apparatus used in this example had an ion exchange capacity of 2.75 (milli-equivalent /
Gram dry resin) and a water content of 0.275 (gram-water /
Gram wet resin), a sulfonic acid type cation exchange membrane (styrene-divinylbenzene copolymer sulfonated product) that has been subjected to a specialization process by condensation polymerization of metaphenylene diamine and formalin with an acidic catalyst on one side. is there. That is, as a treatment method, two cation exchange membranes to be treated are stacked or set one by one in a filter press type treatment apparatus and immersed in an alkaline solution having a pH of 10 ± 0.2 until a sufficient equilibrium is obtained. did. Thereafter, a liquid containing 1% of metaphenylenediamine and 0.2% of sodium sulfite was circulated at room temperature for 2 hours to be sufficiently impregnated. After draining the above solution, the solution was thoroughly drained, and a solution of 12% formalin and 2% sulfuric acid was circulated for 2 hours to cause condensation polymerization. After draining and washing, the treated ion-exchange membrane was removed from the treatment apparatus and the surface was wiped off, and then subjected to an electrodialysis experiment. On the other hand, as an anion exchange membrane, a standard membrane (Seremion AM manufactured by Asahi Glass Co., Ltd.) used in ordinary seawater desalination and the like is used.
V) was used. The cation exchange membrane was used such that the treated surface was on the desalination side. One of these two ion-exchange membranes, 0.02 m ² , was placed in each of 10 sheets (8 organic substance chambers), the current was an initial current density of 2 amps / dm ² , and electricity was supplied for 12 hours. The final current density after 12 hours was 0.1 amps / dm ² , and the integrated current value for 12 hours was 14.3 amps / hr. The current efficiency at this time was 93%. The current efficiency was calculated from the following equation.

At this time, the loss of triethanolamine was 8% of the added amount.

In this way, an approximately 35% solution of N-lauroyl-N'-2-hydroxyethyl-N'-triethanolaminocarboxymethylethylenediamine can be obtained with high current efficiency.
It could be obtained under electrodialysis conditions in which the loss of triethanolamine exchanged as a counter ion was reduced. Analysis of triethanolamine and nitrogen, Na ions, and Cl ions by liquid chromatography of this product confirmed that the product was the following ion.

Comparative Example 1 The same solution as in Example 1 was used, except that the cation exchange membrane subjected to the special treatment used in Example 1 was replaced with a general cation exchange membrane (Selemion CMV manufactured by Asahi Glass Co., Ltd.) without treatment. Was electrodialyzed. The applied current was an initial current density of 2 amps / dm ² , and energization was performed for 12 hours. The final current density after 12 hours was 0.2 amps / dm ² , and the integrated current value for 12 hours was 18.2 amps / hr. The current efficiency at this time was 70%. At this time, the loss of triethanolamine was 35% of the added amount. Triethanolamine and nitrogen, Na ion by liquid chromatography of this product,
From the analysis of Cl ions, the composition of the product is as follows:
Compared with Example 1, the amount of N-lauroyl-N'-2-hydroxyethyl-N'-triethanolaminocarboxymethylethylenediamine was significantly reduced, and N-lauroyl-N 'which had not undergone counterion exchange. −
It was found that a considerable amount of sodium carboxymethylethylenediamine remained.

Example 2 In a four-necked flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, 343 g (1 mol) of N-lauroyl-N-methyltaurine soda (NIKKOL LMT, manufactured by Nikko Chemicals Co., Ltd.) and water 1150 g was charged and dissolved at about 40 ° C. Next, 149.2 g (1 mol) of triethanolamine and 35
104.3 g (1 mol) of% HCl were added in this order with good stirring. The solution was a colorless transparent liquid having a pH of 6.4 and a viscosity of 15 cp / 25 ° C.

This solution was subjected to electrodialysis for 8 hours using an electrodialysis apparatus incorporating the same anion exchange membrane (A) as in Example 1 and a specially treated cation exchange membrane (C). The applied current was 0.4 amps / dm ^{2 at the} initial stage and 0.1 amps / dm ² at the final current density.
The integrated current value for 8 hours was 3.4 amp-hr. The current efficiency at this time was 91%. The loss of triethanolamine was 9% of the amount added.

In this manner, a solution of about 27% of triethanolamine salt of N-lauroyl-N'-methyltaurine can be obtained with high current efficiency under electrodialysis conditions in which the loss of triethanolamine exchanged as a counter ion is reduced. Was. Analysis of triethanolamine, nitrogen, Na ions and Cl ions of the product by liquid chromatography confirmed that the product had the following composition.

Comparative Example 2 The same solution as in Example 2 was subjected to electrodialysis, except that the cation exchange membrane subjected to the special treatment used in Example 2 was replaced with a general cation exchange membrane without treatment. The applied current was an initial current density of 0.4 amps / dm ² , and energization was performed for 8 hours. The final current density after 8 hours is 0.1 amp / dm
^2, integrated current value of 8 hours was 3.6 amps · hr. The current efficiency at this time was 67%. At this time, the loss of triethanolamine was 37% of the added amount. From the analysis of triethanolamine and nitrogen, Na ions and Cl ions by liquid chromatography of this product, the composition of the product was as follows. Compared with Example 2, tri-amine of N-lauroyl-N'-methyltaurine was It was found that the production amount of the ethanolamine salt was extremely small, and that N-lauroyl-N'-methyltaurine soda which had not undergone counterion exchange remained considerably.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing one example of an electrodialysis tank used in the present invention.

Claims (1)

(57) [Claims] An alkali metal salt of an amino acid type surfactant or an acylated amino acid type surfactant is subjected to electrodialysis in the presence of a alkanolamine or ammonia mineral acid salt or an alkanolamine or ammonia and a mineral acid. In a method for producing an alkanol ammonium salt or an ammonium salt of an amino acid type surfactant or an acylated amine acid type surfactant, an ion exchange membrane used in electrodialysis has an ion exchange capacity of 2.0.
~ 3.0 (meq / g dry resin), moisture content 0.2 ~ 0.3
Amino acid type surfactant or acyl, characterized in that the surface or surface layer of a sulfonic acid type cation exchange membrane (gram water / gram wet resin) is treated with a condensate of amines and aldehydes. For producing an alkanol ammonium salt or an ammonium salt of a functionalized amino acid type surfactant.