JPH04297436A - New carboxylic acid salt and production thereof - Google Patents

Abstract

PURPOSE:To provide a new carboxylic acid salt having excellent water solubility, biodegradability and safety and useful as a chelating agent having a high metal-dispersing ability. CONSTITUTION:A carboxylic acid salt of formula I [Y is H, but at least one of the Y groups is group of formula II; A is 1-5C alkylene, polyoxyalkylene (C number of alkylene is 1 to 5 and the average addition molar number of the oxyalkylene is 1-100); M is alkali metal, alkaline earth metal, ammonium, alkyl ammonium, alkanol ammonium; r is the valency of a cation represented by M; 4 < the average value of n<=100). The compound of formula I can be produced by reacting a compound of formula III with a compound of formula IV (X is halogen) or a salt thereof in the presence of an alkaline substance, or by reacting the compound of formula III with a compound of formula V or VI (R' is H, methyl, ethyl; Q is 1-5C alkyl) in the presence of an alkaline substance, hydrolyzing the product and, of necessary, further subjecting the reaction product to a salt-exchanging reaction.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel carboxylic acid salt and a method for producing the same, and more particularly to a water-soluble carboxylic acid salt useful as a metal dispersant and a method for producing the same. This substance is used as a chelating agent for domestic and industrial purposes.

0002

[Prior Art and Problems to be Solved by the Invention] Chelating agents are used in various fields for the purpose of sequestering metal ions and removing their harmful toxins, mainly for removing calcium and magnesium ions in hard water. ing.

[0003] In the textile and dyeing industry, natural fibers are contaminated with metals derived from insecticides and sterilization, and synthetic fibers are contaminated with metals from equipment. Therefore, chelating agents are used to prevent these metals from binding with soap and depositing within the fibers during the washing process. In addition, in the bleaching process, hydrogen peroxide is used to bleach the bleach, but trace amounts of metal ions (especially iron, copper, and manganese) cause the bleach to decompose, so chelating agents are added here as well to prevent this. are doing. Furthermore, during the dyeing process, trace metals that cause color changes and color unevenness are trapped using chelating agents.

[0004] In the metal and plating industry, a chelating agent is used for alkaline cleaning to clean metal surfaces. Also,
When plating steel with copper, called dip plating, Cu
When a (II)-chelating agent is used, the iron (I) produced in the reaction
I) It has the effect of binding ions, maintaining a dissolved state, and allowing fine and uniform plating.

[0005] In addition, various household cleaning agents are used to remove dirt from textiles, tableware, and the body, but the surfactants that have this effect react with calcium or magnesium in tap water, making cleaning difficult. to disturb. Therefore, detergents usually contain a builder as a chelating agent to efficiently disperse calcium and magnesium and bring out the performance of the surfactant.

Conventionally, sodium tripolyphosphate (STPP) and ethylenediaminetetraacetate (EDTA) have been used as these chelating agents, but STPP
The use of EDTA is being regulated due to the eutrophication of lake water, and the use of EDTA is due to toxic bacteria. Therefore, as alternatives, there are organic nitrogen-containing compounds, carbonates, zeolites, and acrylic acid oligomers. However, each of these substances has the following problems. There is concern that nitrogen-containing compounds have poor biodegradability. Carbonates also produce insoluble precipitates of insoluble calcium carbonate. Although zeolite is widely used, it has the disadvantage that it is a water-insoluble substance and can clog sewer pipes if used in excess. Furthermore, acrylic acid oligomers have a problem of low biodegradability.

[0007] Therefore, it is water-soluble and biodegradable;
There is a need for the development of chelating agents with excellent safety and high metal dispersion ability.

[0008]

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors discovered that a specific carboxylic acid salt can greatly achieve the above objects, and completed the present invention. .

That is, the present invention provides a carboxylic acid salt represented by the general formula (I) and a method for producing the same.

0010

[C6]

(wherein, Y is a hydrogen atom or the formula -A-C
A group represented by OO(M)1/r, in which at least one of the n+2 Y's is -A-COO(M)1/r
It is. Here, A has 1 to 1 carbon atoms, which may have a branched chain.
5 represents an alkylene group or a polyoxyalkylene group (the number of carbon atoms in the alkylene group is 1 to 5, the average number of added moles of oxyalkylene is 1 to 100), and M is the same or different alkali metal, alkaline earth metal, ammonium, represents an alkylammonium or alkanol ammonium group,
r indicates the valence of the cationic group represented by M. The average value of n is greater than 4 and less than 100. ) As the carboxylic acid salt represented by the general formula (I), n=1,2,3
, 4 has already been synthesized by Matsumura et al., and the study as a builder has been carried out in Oil Chemistry, 26.
Volume, No. 8, pages 458 to 463. However, the performance of mixtures of these compounds with a degree of condensation of 1 to 4 has not been investigated. From an industrial standpoint, it is difficult to obtain one with a single degree of condensation, and in practice it is desirable to evaluate a mixture of various degrees of condensation.

[0012] Furthermore, from the viewpoint of the performance of the chelating agent, it was found that it is desirable for the average degree of condensation of polyglycerin to be greater than 4, especially from the viewpoint of the degree of dispersion power, and this led to the completion of the present invention. . In the present invention, the average degree of condensation of polyglycerin is a value larger than 4, and 10
It is less than or equal to 0. More preferably, the value is greater than 4,
30 or less. Outside this range, the desired effects of the present invention cannot be obtained.

[0013] The carboxylic acid salt represented by the general formula (I) provided by the present invention is prepared by the following (a) for polyglycerin represented by the general formula (II) in the presence of an alkaline substance.
It is manufactured by performing any of the steps shown in ~(d).

[0014]

[C7]

(In the formula, n indicates the above meaning.) (a)
Formula (III)

[0016]

[Chemical formula 8]

A step of reacting with a compound represented by the formula (wherein X represents a halogen atom and A represents the meaning described above) or a salt thereof, and then, if necessary, performing salt exchange. (b) Formula (IV)

[0018]

[Chemical formula 9]

(In the formula, R' is a hydrogen atom or a carbon number of 1 to 2
represents an alkyl group, and Q represents an alkyl group having 1 to 5 carbon atoms. ), followed by hydrolysis of the resulting product, and further salt exchange if necessary. (c) Formula (V)

[0020]

[Chemical formula 10]

A step of reacting with a compound represented by the formula (wherein R' has the meaning defined above), then hydrolyzing the obtained product, and further salt-exchanging if necessary. (d) Addition of ethylene oxide followed by terminal -CH
A step in which the 2OH group is oxidized to form a carboxylic acid and, if necessary, salt exchanged.

The above steps (a) to (d) will be explained in more detail. Step (a) The compound represented by the general formula (II) and the compound represented by the general formula (III) or a salt thereof are combined into a hydroxide, oxide, carbonate, etc. of an alkali metal or alkaline earth metal. Alkaline substances (NaOH, KOH, Na2CO3, K
2CO3 etc.), and salt exchange is carried out if necessary to obtain a compound represented by general formula (I).

Examples of the salt of the compound represented by the general formula (III) include sodium ω-monochlorofatty acid and potassium ω-monobromofatty acid. The alkaline substance is prepared as an aqueous solution and dropped into a mixture (which may contain a solvent) of a compound represented by general formula (II) and a compound represented by general formula (III) or a salt thereof. go.

[0024] If too much water stays during dropping, it will accelerate the decomposition of the carboxyalkylating agent, so benzene, dioxane, ethylene glycol dimethyl ether, etc. are used as the solvent, and the mixed water is removed by azeotropic distillation. It is effective to carry out the reaction while removing the In order to carry out the reaction smoothly, the reaction rate can be further increased by using a phase transfer catalyst such as a tetrabutylammonium salt as a catalyst.

In addition, in this reaction, a portion of the salt of the compound represented by the general formula (III) usually has the formula HO-A-COOH.
It becomes a salt of the compound represented by, and sodium chloride is also produced as a by-product, so these must be removed after the reaction is completed. As a means for this purpose, electrodialysis or recrystallization in a water-alcohol system is promising.

Step (b) A compound represented by general formula (II) and a compound represented by general formula (IV) are reacted in the presence of an alkaline substance to form a compound represented by general formula (II) and a compound represented by general formula (IV). By obtaining an adduct with the compound represented by formula (IV), hydrolyzing the ester group in the adduct, and performing salt exchange if necessary, the general formula (
A compound represented by I) is obtained.

Step (c) Reacting the compound represented by the general formula (II) and the compound represented by the general formula (V) in the presence of an alkaline substance,
An adduct of the compound represented by the general formula (II) and the compound represented by the general formula (V) is obtained, the nitrile group in the adduct is hydrolyzed, and salt exchange is performed if necessary.
) is obtained.

Step (d) The compound represented by the general formula (II) and ethylene oxide are reacted in the presence of an alkaline or acidic substance, and then the -OCH2CH2OH group is reacted with oxygen or air in the presence of a noble metal catalyst such as Pd or Pt. Blow in to oxidize, -O
A compound represented by general formula (I) is obtained as the CH2COO(M)1/r group.

The polyglycerin represented by the general formula (II) used as a raw material for this reaction may have a single degree of condensation or a mixture of various degrees of condensation. From a manufacturing standpoint, the latter is more advantageous. Moreover, the polyglycerin used here is manufactured by a conventionally known method. That is, in the presence of an alkali catalyst, a nitrogen stream is passed through glycerin while maintaining the temperature at around 250° C., whereby a dehydration condensation reaction proceeds and polyglycerin is obtained.

[0030]

[Effect of the invention] The novel carboxylic acid salt of the present invention is water-soluble,
It has excellent biodegradability and dispersibility, and is useful as an unprecedented and innovative chelating agent.

[0031]

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

Example 1 8.376 g of polyglycerin with an average degree of condensation of 12.5 (0
．． 01 mol) and 46.40 g (1 mol) of sodium hydroxide
．． 16 mol), 65 cc of ethylene glycol dimethyl ether, and 40 cc of water were added and dissolved. After raising the temperature to 90°C, sodium monochloroacetate 81.08
g (0.696 mol) and 7.88 g (0.0232 mol) of tetrabutylammonium hydrogen sulfate were added over 2 hours. After distilling off the solvent and water, water
After adding 100 cc and making it uniform, it was heated to 100° C. or higher to evaporate water to dryness. Similarly, equal amounts of sodium monochloroacetate and tetrabutylammonium hydrogen sulfate were added at 90° C. over 4 hours, and then evaporated to dryness. After the reaction completed solid was cooled to room temperature, water was added while stirring until the inside of the system became almost transparent. After removing insoluble matter by filtration, ethanol in an amount of 6.2 times the volume of the added water was added dropwise to the filtrate over 15 minutes, and the mixture was allowed to stand for 1 hour. The mother liquor was removed from the resulting precipitate by filtration to obtain a crude product. After further purification in the same manner, the precipitate was dissolved in water and p
H was adjusted to 8.4. Lyophilize to obtain the desired product at 96.
Obtained with a yield of 0%. NMR confirmed that the OH groups in the raw material were completely replaced by OCH2COONa.

Example 2 9.25g (0.02g) of polyglycerin with a degree of condensation of 6.0
mol), sodium monochloroacetate 74.55 g (
0.64 mol), tetrabutylammonium bromide 0.77 g (0.0024 mol), dioxane 35
0 g was charged and the temperature was raised to 96°C. 53.33 g (0.64 mol) of 48% sodium hydroxide aqueous solution
It was added dropwise over 0 minutes. The temperature was further maintained to completely distill off water and dioxane. The reaction-completed solid was purified in the same manner as in Example 1 to obtain the desired product in a yield of 93.5%. From NMR, the OH group of the raw material is completely OCH2COON.
It was confirmed that it was replaced by a.

Comparative Example-1 6.91 g (0.075 mol) of glycerin, 104.83 g (0.9 mol) of sodium monochloroacetate,
Tetrabutylammonium bromide 1.21g (0.
00375 g), 350 g of dioxane was charged, 96
The temperature was raised to ℃. Then, at this temperature, 75.00 g (0.9 mol) of a 48% aqueous sodium hydroxide solution was added dropwise over 20 minutes. Furthermore, after water and dioxane were completely distilled off at the same temperature, the reaction-completed solid was purified in the same manner as in Example-1. The yield of the target product was 92.5%. From NMR, the three OH groups of the raw material are completely OCH2COONa.
It was confirmed that it was the basis.

Test Example The dispersibility of the carboxylic acid salts obtained in Examples 1 and 2 and Comparative Example 1 in mud and carbon black, Ca ion trapping ability, and Ca ion stability constant pK Ca2+ were investigated by the method shown below. Ta.

Dispersion effect measurement method for mud and carbon black All solutions were prepared using the following buffer solutions. Buffer; 0.01M NH4Cl-NH4OH buffer (pH 10) Prepare a solution with a concentration of 0.05 wt% of the builder (carboxylate salt obtained in Examples 1 and 2 and Comparative Example 1), put 50 ml into a sedimentation tube, and add it there. The mud is Kanuma gardening Akadama soil with 150 mesh (100μm) pass 0.1
wt%, and carbon black is added at 0.02 wt%. After shaking vigorously by hand for about 30 seconds, irradiate with ultrasound for 5 minutes. After standing for 2 hours in the case of mud and 8 hours in the case of carbon black, samples were taken from certain locations and the absorbance at 460 nm was measured. Table 1 shows the results.
Shown below.

[0037]

[Table 1]

[0038] Capture ability measurement method and chelate stability constant measurement method for calcium ions All solutions were prepared using the following buffer solutions. Buffer; 0.1M NH4Cl-NH4OH buffer (pH 10) (1) Creating a calibration curve Create a standard calcium ion solution and create a calibration curve showing the relationship between the logarithm of calcium ion concentration and potential as shown in Figure 1. .

(2) Measurement of calcium ion trapping ability 1
Weigh 0.1 g of sample into a 00 ml volumetric flask and make up to volume with the above buffer solution. 20,000 for this
A CaCl2 solution (pH 10) corresponding to ppm (calculated as CaCO3) is added dropwise from the burette (a blank is also measured). Drop the CaCl2 solution at a concentration of 0.1 to 0.
Add 2 ml at a time, read the potential at that time, and determine the calcium ion concentration from the calibration curve in Figure 1. The calcium ion concentration at the dripping amount A of the CaCl2 solution in FIG. 2 is the calcium ion trapping ability of the sample.

(3) Calculation of calcium ion chelate stability constant Calcium ion chelate stability constant (pK Ca2+
) uses the results when measuring Ca2+ trapping ability. It is calculated based on the assumption that a 1:1 complex is formed when an equimolar amount of calcium is added to the sample. The stability constant of the complex can be determined according to the following formula.

[0041]

[Math 1]

The results are shown in Table 2.

[0043]

[Table 2]

[Brief explanation of drawings]

FIG. 1 is a calibration curve showing the relationship between the logarithm of calcium ion concentration and potential.

[Figure 2] Ca during measurement of calcium ion trapping ability
A graph showing the relationship between the amount of Cl2 solution dropped and the calcium ion concentration.

Claims (2)

[Claims] Claim 1: A carboxylic acid salt represented by general formula (I). [Formula 1] (wherein, Y is a hydrogen atom or the formula -A-COO(M)1
/r, and at least one of the n+2 Y's is -A-COO(M)1/r. Here, A is an alkylene group having 1 to 5 carbon atoms, which may have a branched chain, or a polyoxyalkylene group (the number of carbon atoms in the alkylene group is 1 to 5, and the average number of added moles of oxyalkylene is 1 to 5.
100), M is the same or different alkali metal,
It represents an alkaline earth metal, ammonium, alkylammonium or alkanol ammonium group, and r represents the valence of the cationic group represented by M. The average value of n is greater than 4 and less than 100. ) 2. The polyglycerin represented by the general formula (II) is subjected to any of the following steps (a) to (d) in the presence of an alkaline substance. A method for producing a carboxylic acid salt represented by general formula (I). [Chemical formula 2] (In the formula, n shows the above meaning.) (a) Formula (III) [Chemical formula 3] (In the formula, X shows a halogen atom, and A shows the above meaning.) Represented by react with a compound or its salt,
Next, if necessary, there is a process of replacing the salt. (b) Formula (IV) [Chemical formula 4] (wherein, R' represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and Q represents an alkyl group having 1 to 5 carbon atoms.) a step of reacting with a compound, then hydrolyzing the resulting product and, if necessary, salt-exchanging it. (c) Formula (V) is reacted with a compound represented by [Chemical formula 5] (in the formula, R' has the above-mentioned meaning), and then the obtained product is hydrolyzed, and if necessary, a salt is added. The process of replacing. (d) Addition of ethylene oxide followed by terminal -CH
A step in which the 2OH group is oxidized to form a carboxylic acid and, if necessary, salt exchanged.