JPH0672941A - New polycarboxylic acid or its salt and their production - Google Patents

Abstract

PURPOSE:To provide a new compound useful as a chelating agent having excellent water-solubility, bio-degradability and dispersibility. CONSTITUTION:The compound of the formula (Y)p-(S)-(Z)q [S is residue obtained by removing (p+q) hydroxyl groups from mono or polypentaerythritol, etc., having a condensation degree of 1-20, etc.; (p) is positive number; (q) is 0 or positive number; (p+q) is total number of OH groups removed in S; Y is O-E- COOM, etc., (E is 1-5C alkylene, etc.; M is H ion, etc.); Z is group of formula, etc. (R is 1-22C alkyl, etc.; B is (CH2)mCOOM, etc.; (m) is 1-5], e.g. carboxymethylated dipentaerythritol. The subject compound can be produced by reacting a pentaerythritol with a compound of the formula X-E-COOM (X is halogen) in the presence of an alkali catalyst and optionally subjecting the reaction product to salt-exchange reaction.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polycarboxylic acid or a salt thereof and a method for producing the same, more specifically, a polycarboxylic acid useful as a water-soluble metal dispersant or a chelating agent for household and industry. The present invention relates to a salt and a method for producing the salt.

[0002]

BACKGROUND OF THE INVENTION Chelating agents are used in various fields for the purpose of sequestering metal ions mainly by removing calcium ions and magnesium ions in hard water and removing their harmful poisons. ing. In the textile and dyeing industry, natural fibers are mixed with metals derived from insecticides and bacteria, and synthetic fibers are mixed with metals from equipment. Therefore, in the washing process, these metals are combined with the soap and deposited in the fiber, and a chelating agent is used to prevent this. Also, in the bleaching process, bleaching is performed using hydrogen peroxide, etc., but a trace amount of metal ions (especially iron, copper, manganese) causes decomposition of the bleaching agent, so a chelating agent is added here to prevent this. is doing. Further, in the dyeing process, a trace metal that causes color change and color unevenness is trapped by a chelating agent.

In the metal / plating industry, alkali cleaning is performed using a chelating agent for cleaning the metal surface. Also, when plating the copper with dipping plating,
The use of the Cu (II) -chelating agent has the effect of binding the iron (II) ions generated by the reaction, maintaining the dissolved state, and enabling fine and uniform plating. In addition, in household use, various detergents are used to remove dirt from textiles, tableware, and the body, and the surfactant acting as this reacts with calcium or magnesium in tap water to interfere with washing. Therefore, a detergent is usually blended with a builder as a chelating agent to efficiently disperse calcium and magnesium and bring out the performance of a surfactant.

Conventionally, sodium tripolyphosphate (STPP) and ethylenediaminetetraacetate (EDTA) have been used as chelating agents for these, but STPP is in the direction of eutrophication in lake water, and EDTA is toxic because of its toxicity. Thus, alternatives include organic nitrogen-containing compounds, carbonates, zeolites and acrylic acid oligomers. However, each of these substances has the following problems. It is feared that the nitrogen-containing compound is inferior in biodegradability.
Carbonates also produce insoluble precipitates of insoluble calcium carbonate. Zeolites are widely used, but they are water-insoluble substances, and if they are used in excess, they have the drawback of clogging sewer pipes and the like. Further, the acrylic acid oligomer has a problem of low biodegradability. Therefore, it is required to develop a chelating agent which is water-soluble, has excellent biodegradability and safety, and has a high metal dispersing ability.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific novel polycarboxylic acid or a salt thereof can greatly achieve the above object, The present invention has been completed. That is, the present invention provides a novel polycarboxylic acid represented by the general formula (I) or a salt thereof, and a method for producing the same.

(Y) _p — (S) — (Z) _q (I) [wherein S: mono- or polypentaerythritol having a condensation degree of 1 to 20, or pentaerythritol and an ether group having two or more hydroxyl groups; A residue obtained by removing (p + q) hydroxyl groups from a cocondensation product with a polyhydric alcohol having 2 to 10 carbon atoms which may be contained is shown. Here, p is a positive number, q is 0 or a positive number, and (p + q) is a carbon which may include mono- or polypentaerythritol, or pentaerythritol and an ether group having two or more hydroxyl groups. It is the total number of hydroxyl groups in the cocondensation product with a polyhydric alcohol of several 2 to 10.

[0007]

[Chemical 11]

Or a hydroxyl group, p Y's may be the same or different, and at least one of Y's is

[0009]

[Chemical 12]

And the balance is a hydroxyl group. Where E
Represents an alkylene group having 1 to 5 carbon atoms which may have a branched chain or a polyoxyalkylene group having 2 to 5 carbon atoms and an added mole number of 1 to 100, and M represents a hydrogen ion or an alkali. Metal ion, alkaline earth metal ion, ammonium ion, alkanol group has 2 carbon atoms
To mono-, di-, or trialkanol ammonium ion of 3 to 3, an alkyl-substituted ammonium ion of 1 to 5 carbon atoms, or a basic amino acid group.

[0011]

[Chemical 13]

The q Zs may be the same or different.
Here, R represents an alkyl group or an alkenyl group having 1 to 22 carbon atoms, or a group represented by the formula —CH ₂ (OJ) _t OA or —CH ₂ OA. A represents an alkyl or alkenyl group having 1 to 22 carbon atoms, J represents an alkylene group having 2 to 3 carbon atoms, t is from 1 to 20 a positive number, the _{B - (CH 2) m COOM} ,

[0013]

[Chemical 14]

Alternatively, it represents a hydrogen atom. m is a number from 1 to 5, M
Indicates the above meaning. However, when S is monopentaerythritol having a degree of condensation of 1 and q is 0, E is a branched chain alkylene group having 4 to 5 carbon atoms or an oxyalkylene group having 2 to 2 carbon atoms. 5 to 1 to 100 moles added
Must be a polyoxyalkylene group of Also, S
Is mono- or dipentaerythritol having a condensation degree of 1, 2, and when q is not 0,

[0015]

[Chemical 15]

Alternatively, it is limited to hydroxyl groups. Examples of the polycarboxylic acid represented by the general formula (I) or a salt thereof provided by the present invention are as follows.

[0017]

[Chemical 16]

[0018]

[Chemical 17]

[0019]

[Chemical 18]

Compounds in which a part of the groups corresponding to Y in the above-exemplified compounds are replaced with hydroxyl groups can also be exemplified.

The polycarboxylic acid represented by the general formula (I) or a salt thereof provided by the present invention is obtained by performing the following steps (A) and (D) in this order, or by performing the following steps (A) and ( B) and step (D) are performed in this order, or the following step (A) and step
It is manufactured by performing (C) and step (D) in this order.

Step (A): A step of synthesizing pentaerythritol or a condensate thereof by any of the following methods i) to iv). i) reacting acetaldehyde with formaldehyde. ii) Condensing pentaerythritol. iii) Pentaerythritol is co-condensed with a polyhydric alcohol having 2 to 10 carbon atoms and optionally containing an ether group having two or more hydroxyl groups. iv) reacting pentaerythritol with glycidol. Step (B): Pentaerythritol or a condensate thereof is prepared according to the formula (II)

[0023]

[Chemical 19]

A step of reacting with a compound represented by Step (C): Pentaerythritol or a condensate thereof is represented by the formula
(III) A step of reacting with a fatty acid represented by ACOOH (III) (A has the same meaning as described above).

Step (D): Step (A), Step (B) or Step
The pentaerythritol, its condensate, its alkyl ether or its fatty acid ester obtained in (C) has the following i)
To the step of performing any one of vii).

I) A compound represented by the formula (IV) X-E-COOM (IV) (X represents halogen, E and M have the same meanings as described above) is reacted with an alkali catalyst, and if necessary, Exchange salt. ii) Formula (V)

[0027]

[Chemical 20]

(R 'represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and Q represents an alkyl group having 1 to 6 carbon atoms.)
After reacting with the compound represented by, the ester group is hydrolyzed and, if necessary, salt exchange is performed. iii) Formula (VI)

[0029]

[Chemical 21]

After reacting the compound represented by the formula (1) with an alkali catalyst, the nitrile group is hydrolyzed and, if necessary, salt exchange is performed. iv) React with ethylene oxide in the presence of an alkaline substance or an acidic substance, then oxidize the hydroxymethyl group in the product with air or oxygen in the presence of a noble metal catalyst, and if necessary salt exchange. v) Formula (VII)

[0031]

[Chemical formula 22]

(R "represents a hydrogen atom, -COOQ or -CH ₂ COOQ group, F represents an alkylene group having 1 to 4 carbon atoms, a represents 0 or 1, and Q has the same meaning as described above.) After reacting with a compound represented by the formula (1) in the presence of copper powder, the ester group is hydrolyzed and salt exchange is carried out if necessary.vi) Maleic acid or maleic anhydride and alkaline conditions
The reaction is carried out using calcium hydroxide as a catalyst, and salt exchange is carried out if necessary. vii) Formula (VIII)

[0033]

[Chemical formula 23]

The compound represented by the formula (1) is reacted in the presence of an acidic substance or a basic substance, and then the ester group is hydrolyzed and, if necessary, salt exchange is performed.

The above steps (A) to (D) will be described in more detail. Step (A): Synthesis of pentaerythritol or its condensate i) Synthesis of pentaerythritol Pentaerythritol is synthesized from acetaldehyde and formaldehyde, which are conventionally known methods. The polypentaerythritol produced as a by-product may be used in the next step as it is.

Ii) Synthesis of polypentaerythritol Condensation of pentaerythritol gives polypentaerythritol. This method has already been disclosed in Japanese Patent Laid-Open No. 63-
It is described in 202662.

Iii) Pentaerythritol and two hydroxyl groups
2 to 2 carbon atoms which may contain an ether group having the above
Synthesis of Copolycondensate with 10 Polyhydric Alcohol Pentaerythritol and polyhydric alcohol having 2 to 10 carbon atoms which may contain ether group having 2 or more hydroxyl groups at a temperature of 190 ° C or higher under a calcium oxide catalyst. , Reacting under flowing nitrogen. The amount of calcium oxide is preferably 0.5% by weight or more based on the total weight of the raw material.
As the polyhydric alcohol having 2 to 10 carbon atoms which may contain an ether group having two or more hydroxyl groups, glycerin,
Examples include trimethylolethane, trimethylolpropane, mannitol, sorbitan, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and the like.

Iv) of pentaerythritol and glycerin
Synthesis of Cocondensate Pentaerythritol and glycerin cocondensates are obtained from pentaerythritol and glycidol. This reaction is promoted in the presence of an acid such as boron trifluoride, p-toluenesulfonic acid or sulfuric acid, or an alkali catalyst such as sodium hydroxide or potassium hydroxide. Water-dioxane or the like may be used as the solvent. The reaction temperature is from room temperature
120 ° C, particularly 50 ° C to 100 ° C is preferable.

Step (B): Epoxy represented by the above formula (II)
The pentaerythritol or its condensate obtained in the side addition reaction step (A) is reacted with the epoxide represented by the above formula (II) in the presence of an acid or base catalyst to obtain an alkyl ether.
Here, the R group in the epoxide is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, dodecyl, myristyl, palmityl, stearyl, behenyl, 2-ethylhexyl, oleyl, linole, linolenyl, arachidyl. , An alkyl or alkenyl group having 1 to 22 carbon atoms such as an isostearyl group; a formula AO (JO) _t CH ₂ — (where A, J
, T represents the above meaning); or the formula AOCH ₂
Represents an alkyl (or alkenyl) oxymethylene group represented by-.

The acid catalyst used in this reaction is BF ₃
Lewis acids such as paratoluene sulfonic acid (PTs), H ₂ SO ₄
Bronsted acids such as Examples of the base catalyst include caustic alkalis such as potassium hydroxide and sodium hydroxide, and tertiary amines such as N, N, N ′, N′-tetramethyl-1,6-diaminohexane. If necessary, a solvent may be used, and the solvent may be tert.
Alcohol or ether solvents such as -butanol, 1,4-dioxane and tetrahydrofuran (THF) are preferable. In the case of a base catalyst, dimethyl sulfoxide (DMSO) is particularly preferable. The reaction temperature is 40 ° C to 160
C., preferably 60 to 140.degree. The molar ratio of pentaerythritol or its condensate to the epoxide represented by the formula (II) is preferably 100/1 to 1/1, more preferably 20/1 to 1/1. Excessive pentaerythritol or its condensate can be removed by extracting the product with an organic solvent and washing with water.

Step (C): fatty acid represented by the above formula (III)
The fatty acid ester represented by the formula (III) is reacted with the pentaerythritol or the condensate thereof obtained in the esterification reaction step (A). Here, as the fatty acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid. Acid, 2-ethylhexanoic acid,
Oleic acid, linoleic acid, linolenic acid, etc. 2 to 23 carbon atoms
Fatty acids of. This esterification reaction proceeds by being carried out by a conventionally known method. That is, a fatty acid ester is obtained by heating and dehydrating pentaerythritol or a condensate thereof and a fatty acid represented by the above formula (III) without a catalyst.

Step (D): Introducing reaction of carboxyl group Pentaerythritol obtained in step (A), step (B) or step (C), its condensate, its alkyl ether or its fatty acid ester (hereinafter referred to as pentaerythritol condensate) And the like) are introduced by any of the following steps i) to vii) to obtain a compound represented by the general formula (I) provided by the present invention.

I) A pentaerythritol condensate or the like and a compound represented by the above formula (IV) are treated with NaOH, KOH, Na ₂ CO ₃ ,
The compound represented by the general formula (I) is obtained by reacting in the presence of an alkaline substance such as K ₂ CO ₃ and, if necessary, by salt exchange. Here, examples of the compound represented by the formula (IV) include sodium ω-monochlorofatty acid and potassium ω-monobromofatty acid. The alkaline substance is prepared as an aqueous solution and added dropwise into a mixture (which may contain a solvent) of a pentaerythritol condensate or the like and a compound represented by the formula (IV). At the time of dropping, in order to accelerate the decomposition of the carboxyalkylating agent if too much water is retained, benzene, dioxane, ethylene glycol dimethyl ether, etc. are used as a solvent, while azeotropically distilling off water mixed with this. It is efficient to carry out the reaction. In order to carry out the reaction smoothly, a reaction rate is further increased by using a phase transfer catalyst such as tetrabutylammonium salt as a catalyst. Further, in this reaction, the compound represented by the formula (IV) is usually partially HO-E-COOM and MOOC-E-O-E-
It becomes a compound represented by COOM and halogen salts are also by-produced, so it is necessary to remove these after the reaction. As a means for this, electrodialysis, purification by a silica gel column, and the like are promising.

Ii) A pentaerythritol condensate or the like and a compound represented by the formula (V) are reacted in the presence of an alkaline substance such as potassium hydroxide or sodium hydroxide to obtain an adduct, and the addition thereof is obtained. The compound represented by the general formula (I) is obtained by hydrolyzing the ester group in the body and, if necessary, salt exchange. Examples of the compound represented by the formula (V) include ethyl acrylate and ethyl methacrylate.

Iii) A pentaerythritol condensate or the like and a compound represented by the above formula (VI) are reacted in the presence of an alkaline substance such as potassium hydroxide or sodium hydroxide to obtain an adduct, and the adduct is obtained. The compound represented by the general formula (I) can be obtained by hydrolyzing the nitrile group in, and if necessary, salt exchange.

Iv) The pentaerythritol condensate and the like are reacted with ethylene oxide in the presence of an alkaline substance such as potassium hydroxide or an acidic substance such as boron trifluoride, and then -OCH ₂ CH ₂ in the product. The OH group is oxidized by blowing O ₂ or air in the presence of a noble metal catalyst such as Pd or Pt to form a —OCH ₂ COOM group, and if necessary salt exchange, a compound represented by the general formula (I) is obtained. can get.

V) The pentaerythritol condensate and the like and the compound represented by the above formula (VII) are added in the presence of copper powder in an amount of 60 to 120.
A compound represented by the general formula (I) can be obtained by reacting at 0 ° C. to obtain an adduct, hydrolyzing the ester group in the adduct, and performing salt exchange if necessary. Where the formula (VII)
Examples of the compound represented by are diazoacetate methyl, ethyl diazoacetate, methyl diazosuccinate, ethyl diazosuccinate, methyl diazomalonate, ethyl diazomalonate and the like. In this reaction, in part, the formula

[0048]

[Chemical formula 24]

(Wherein R ", F, and a have the same meanings as described above) are by-produced, but if they need to be removed, they may be distilled by distillation at the stage of ester form or silica gel. It can be easily removed by column purification.

Vi) A compound represented by the general formula (I) can be obtained by adding pentaerythritol condensate or the like and maleic acid or maleic anhydride under alkaline conditions with calcium hydroxide as a catalyst and salt-exchange if necessary. Is obtained. Here, examples of the substance that makes the reaction system alkaline include hydroxides of alkali metals or alkaline earth metals.

Vii) A pentaerythritol condensate or the like and a compound represented by the above formula (VIII) are treated with BF ₃ .O (C ₂ H ₅ ) ₂ , p-
Toluenesulfonic acid (PTS), H ₂ SO ₄ , acidic substances such as cation exchange resins, or NaOC ₂ H ₅ , NaOCH ₃ , t-C ₄ H ₉ OK, Ca
When the compound is added in the presence of a basic substance such as (OH) ₂ , the ester group in the adduct is hydrolyzed, and if necessary salt exchange is performed, the compound represented by the general formula (I) is obtained.

[0052]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polycarboxylic acid or a salt thereof which is excellent in water solubility, biodegradability and dispersibility and is useful as an unprecedented epoch-making chelating agent.

[0053]

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

Example 1 Cal of dipentaerythritol
Synthesis of boxymethylated compounds

[0055]

[Chemical 25]

127.14 g of dipentaerythritol (0.5 mo
l) and 200.32 g (1.0 mol) of lauric acid were charged, and nitrogen was added.
While blowing at a flow rate of 9.5 liters / hour, the temperature was raised to 240 ° C. The dehydration reaction was carried out for 5 hours at 240 ° C. under the same nitrogen flow rate to obtain dipentaerythritol dilauroyl ester. The analytical values are as follows and were in good agreement with the theoretical values.

[0057]

[Table 1]

(B) Carboxymethylation (CMization)

[0059]

[Chemical formula 26]

Dipentaerythritol obtained in (a)
37.13 g (0.06 mol) of dilauroyl ester and 2.0 g of copper powder
Then, 41.08 g (0.36 mol) of ethyl diazoacetate was added dropwise over 6 hours at 90 ° C. with vigorous stirring.
After aging at 90 ° C. for 2 hours, 200 g of ethyl acetate and 10 g of activated carbon were added, and the mixture was treated with activated carbon for 1 hour under reflux. After filtration, concentrate the filtrate on a rotary evaporator and
4.17 g of tetra-ethoxycarboxymethyl dipentaerythritol dilauroyl ester were obtained. yield
93.7%. The analytical values were as follows.

[0061]

[Table 2]

[0062] ^{IR: 2930cm -1, 2850cm -1 (} C-H stretching vibration); 1750cm ^-1 (C = O stretching ^{vibration); 1130cm -1 (C-O} -C
Antisymmetric stretching vibration) ¹ H-NMR: 4.2 ppm (8H), 4.0 ppm (8H), 3.5 ppm (12H), 3.
4ppm (4H), 1.3ppm (40H), 0.8ppm (18H) (c) Saponification

[0063]

[Chemical 27]

48.16 g (0.05 mol) of tetra-ethoxycarboxymethyl dipentaerythritol dilauroyl ester obtained in (b), 32.22 g (0.38 g) of 48% NaOH aqueous solution.
7 mol), 175 g of water, and 300 g of ethanol were charged, and saponification of the ester was carried out under reflux for 3 hours.
After the reaction, ethanol was distilled off with a rotary evaporator, 400 g of water was added to the residue, and 39.16 g of concentrated hydrochloric acid (0.387
It was neutralized with (mol). Lauric acid once with 400 ml of hexane,
After extracting once with 100 ml, the aqueous phase was 48% NaOH 16.5 g (0.198
(mol) to pH 9. After removing sodium chloride by electrodialysis, the solution was concentrated with a rotary evaporator and dried under reduced pressure using a vacuum pump. Thus, 22.43 g of tetra-carboxymethyl dipentaerythritol tetrasodium salt (average CM conversion 4/6) was obtained. Yield 78.1%. The analytical values were as follows.

IR: 3500 cm ^-1 (OH stretching vibration); 2950c
m ^-1 , 2900cm ^-1 (C-H stretching vibration); 1620cm ^-1 , 1430cm
^-1 (C = O stretching ^{vibration); 1120cm -1 (C-O} -C stretching ^{vibration) 1 H-NMR: 3.9ppm (} 8H), 3.5ppm (12H), 3.4ppm (4H) Example 2 Pentaerythritol - Glycerin (1:
1) Synthesis of carboxymethylated condensate

[0066]

[Chemical 28]

68.08 g of pentaerythritol (0.5 mol)
, 85% potassium hydroxide 1.18g, and water 50g,
A solution of 7.41 g (0.1 mol) of glycidol and 40 g of dioxane was added dropwise thereto at 90 ° C. over 1 hour. Furthermore, at 96 ° C
Aged for 20 hours. 300 ml of methanol was added to the reaction mixture, and the insoluble material was removed by filtration. The filtrate was concentrated on a rotary evaporator, to which was also added 200 ml of methanol,
The insoluble material was removed by filtration. The filtrate was concentrated on a rotary evaporator to give 16.06 g of adduct. Yield 76.4%.
The analytical values were as follows.

[0068]

[Table 3]

¹³ C-NMR: 75 ppm, 73 ppm, 65 ppm (glycerin skeleton); 63 ppm, 47 ppm (pentaerythritol skeleton) (b) Carboxymethylation

[0070]

[Chemical 29]

9.46 g (0.045 mol) of the glycidol adduct of pentaerythritol obtained in (a) and 2.0 g of copper powder were charged, and 36.19 g (0.317 mol) of ethyl diazoacetate was added thereto.
It was added dropwise at 5 ° C over 5 hours. After further aging at 90 ° C. for 1 hour, 100 g of ethyl acetate and 5 g of activated carbon were added, and the mixture was treated with activated carbon for 1 hour under reflux. After filtration, concentrate the filtrate and
1.43 g of carboxymethylated product was obtained. The analytical values were as follows.

[0072]

[Table 4]

IR: 2970 cm ^-1 , 2940 cm ^-1 (C-H stretching vibration); 1740 cm ^-1 (C = O stretching vibration); 1120 cm ^-1 (C-O-C)
Stretching vibration) (c) Saponification

[0074]

[Chemical 30]

Carboxymethylated product obtained in (b) 15.2
7 g (0.0238 mol), 48% sodium hydroxide aqueous solution 13.26
g (0.159 mol), 180 g of water, and 180 g of ethanol were charged, and saponification of the ester was carried out under reflux for 3 hours. After distilling off ethanol with a rotary evaporator,
120 g was added, to this was added 2.90 g concentrated hydrochloric acid to adjust the pH to 9
Adjusted to. Then, it concentrated with the rotary evaporator and dried under reduced pressure with the vacuum pump. Thus the sodium salt
18.74 g was obtained. The content of sodium chloride was 8.49%. Further, 2960 cm from IR ^-1, C-H stretching vibration 2910cm ^-1, 1620cm ^-1, C sodium carboxylate salt 1440Cm ^-1
= O stretching vibration, C-O-C stretching vibration was observed at 1120 cm ^-1 .

Example 3 Tetracarboxymethyl dipe
Synthesis of nantaerythritol dilauroyl ester

[0077]

[Chemical 31]

(A) Carboxymethylation: 30.94 g (0.05 mol) of dipentaerythritol dilauroyl ester obtained in (a) of Example 1, 69.89 g (0.6 mol) of sodium monochloroacetate, and 0.806 g of tetrabutylammonium chloride. (0.0025mol), and dioxane
200 g was charged and the temperature was raised to 96 ° C. After raising the temperature, at the same temperature
50 g of 48% aqueous sodium hydroxide solution was added dropwise over 30 minutes. At this time, water in the system was distilled off azeotropically with dioxane.
Further, it was aged for 30 minutes, and dioxane was almost distilled off. After adding 500 g of water to the reaction solid and dissolving it, concentrated hydrochloric acid 60.7
7 g (0.6 mol) was added to neutralize the acid form. This is ether
Extract 3 times with 300 ml, wash 3 times with 1 liter of 5% sodium chloride solution, and dry with anhydrous sodium sulfate.
Finally, the ether was distilled off to obtain 45.0 g of the desired product. yield
95.8%. The analytical values are as shown below and were in good agreement with the theoretical values.

[0079]

[Table 5]

IR: 2960 cm ^-1 , 2900 cm ^-1 (CH stretching vibration);
1740cm ^-1 (ester C = O stretching vibration); 1600cm ^-1 , 1440cm
^-1 (carboxylic acid C = O stretching vibration); 1120 cm ^-1 (COC stretching vibration) Example 4 Octadecyl glyceryl pentaerythritol
Of sodium tetrasuccinate ether

[0081]

[Chemical 32]

163.38 g (1.2 mol) of pentaerythritol,
4.09 g (0.062 mol) of 85% potassium hydroxide and 490.14 g of dimethylsulfoxide were charged and dehydrated under reduced pressure at 110 ° C.-37 Torr for 20 minutes. At this time, an aqueous solution containing 60 cc of dimethyl sulfoxide was distilled. This was followed by 97.96 g of octadecyl glycidyl ether at 110 ° C for 2 hours.
(0.3 mol) was added dropwise. After aging at the same temperature for 4 hours, acetic acid
It was neutralized with 3.72 g (0.062 mol). After distilling off dimethyl sulfoxide with a rotary evaporator, 400 ml of hexane
It was extracted with a mixed solution of 400 ml of ethanol and ethanol. Insoluble pentaerythritol was removed by filtration, the filtrate was concentrated, then dissolved in 450 ml of ethyl acetate, and warmed with 300 ml of warm water.
In ml, a small amount of pentaerythritol was removed by washing. After drying over anhydrous sodium sulfate, ethyl acetate was distilled off by a rotary evaporator and recrystallization was performed with a mixed solvent of hexane 500 ml and ethanol 300 ml. The crystals are filtered,
Vacuum drying was performed with a vacuum pump to obtain 88.27 g of octadecyl glyceryl pentaerythritol. Yield 63.6%.
The purity by gas chromatography was 93.4%.
In addition, other analytical values are as follows, which were in good agreement with theoretical values.

[0083]

[Table 6]

(B) Addition of maleic acid

[0085]

[Chemical 33]

Octadecyl glyceryl pentaerythritol obtained in (a) 46.27 g (0.1 mol), calcium hydroxide 17.78 g (0.24 mol), sodium hydroxide 21.32 g
(0.533 mol) and 45 g of water were charged and the temperature was raised to 80 ° C. 47.07 g (0.48 mol) of maleic anhydride was added to this.
It was added over 30 minutes and aged at 90 ° C for 4 hours and 100 ° C for 5 hours. 26.82 g (0.253 mol) of sodium carbonate were added and insoluble calcium carbonate was removed by filtration. Then, the filtrate was concentrated and dried under vacuum to obtain 110.0 g of sodium salt of tetrasuccinic acid ether of octadecyl glyceryl pentaerythritol. Yield 99.7%. Hydroxyl value is 11.
Since it was 2, the average degree of etherification of the obtained target product was 3.8 / 4 (that is, 3.8 out of 4 hydroxyl groups were etherified). 1600 cm ^-1 and 1440 cm from IR analysis
^The absorption of sodium carboxylate by C = O stretching vibration was observed at ^-1, and the absorption of the ether by C-O-C stretching vibration at 1120 cm ^-1 , confirming that the obtained compound was the target compound.

Example 5 Octadecyl glyceryl penta
Nato, a tetraepoxysuccinic acid adduct of erythritol
Synthesis of selenium salt

[0088]

[Chemical 34]

(A) Epoxysuccinic acid addition trans-epoxysuccinic acid 25.3 g (0.19 mol), ethanol 523 g (11.4 mol), cation exchange resin NAFION (NR-5)
0) 13 g was charged and esterification was carried out at 80 ° C. for 16 hours.
The cation exchange resin was removed by filtration, and ethanol was distilled off with a rotary evaporator to obtain trans-epoxysuccinic acid diethyl ester in a yield of 92.5%. In a separate container, 13.88 g (0.03 mol) of octadecyl glyceryl pentaerythritol obtained in (a) of Example 4 and 1 part of toluene
00g, and boron trifluoride ether complex 0.7g (0.005mo
l) was added and the temperature was raised to 50 ° C. Next, 28.4 g (0.15 mol) of trans-epoxysuccinic acid diethyl ester synthesized above was added dropwise little by little. After aging at 50 ℃ for 2 hours, 10% Na
_The mixture was neutralized with a ₂ CO ₃ aqueous solution and the solvent was distilled off with a rotary evaporator. 50 g of water was added to the residue, and 80 ml of diethyl ether was added.
The extract was extracted 3 times with water, washed 3 times with 200 ml of a 5% aqueous sodium chloride solution, the ether phase was dried over anhydrous sodium sulfate, and the ether was distilled off with a rotary evaporator to obtain 37.0 g of a transparent oily product. 37.0 g of the obtained compound was added to ethanol 50
dissolved in 10 g of 10% aqueous sodium hydroxide solution
(0.15 mol) was added, and saponification of the ester was carried out for 4 hours under reflux. After cooling, water and ethanol were distilled off by a rotary evaporator and vacuum drying was carried out to obtain 35.05 g of a sodium salt of a tetraepoxysuccinic acid adduct of octadecyl glyceryl pentaerythritol. Yield 100%. IR analysis 1600 cm ^-1, of sodium carboxylate in 1440Cm ^-1
C = O Absorption due to stretching vibration, C of ether at 1120 cm ^-1
Absorption due to —O—C stretching vibration was confirmed, and it was confirmed that the obtained compound was the target compound.

Test Example The compounds obtained in Examples 1 and 2 had Ca ion-trapping ability and
The Ca ion stability constant pKCa ²⁺ was investigated by the method shown below. In addition, for the zeolite that has been conventionally used as a chelating agent for comparison, Ca ion trapping ability and
The Ca ion stability constant pK Ca ²⁺ was investigated. The results are shown in Table 7.

Method for measuring trapping ability for calcium ion
And chelate stability constant measurement methods All solutions were prepared using the following buffer solutions. _{Buffer; 0.1M NH 4 Cl-NH 4} OH buffer (pH 10) (1) Creating a calibration curve standard calcium ion solution to create a calibration curve showing the relationship between the logarithm and the potential of the calcium ion concentration such shown in FIG. 1 To create.

(2) Measurement of calcium ion-capturing ability 0.1 g of sample is weighed in a 100 ml volumetric flask, and the volume is adjusted with the above buffer solution. A CaCl ₂ solution (pH 10) equivalent to 20,000 ppm (calculated as CaCO ₃ ) is added dropwise to this from a buret (a blank is also measured). CaCl ₂ solution is dropped.
Add 0.1 to 0.2 ml each, read the potential at that time, and find the calcium ion concentration from the calibration curve in FIG.
The calcium ion concentration at the dropping amount A of the CaCl ₂ solution in FIG. 2 is the calcium ion trapping ability of the sample.

(3) Calculation of stability constant of calcium ion chelate Stability constant of calcium ion chelate (pK Ca ²⁺ ) is Ca
^Use the result of ²⁺ capture ability measurement. It is calculated as forming a 1: 1 complex when equimolar calcium is added to the sample. The stability constant of the complex can be calculated according to the following formula.

[0094]

[Equation 1]

[0095]

[Table 7]

[Brief description of drawings]

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

[Fig. 2] CaCl during measurement of calcium ion-capturing ability
₂ is a graph showing the relationship between the drop amount of _two solutions and the calcium ion concentration.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location D06M 13/192

Claims (2)

[Claims] 1. A novel polycarboxylic acid represented by the general formula (I) or a salt thereof. (Y) _p- (S)-(Z) _q (I) [wherein S is a mono- or polypentaerythritol having a condensation degree of 1 to 20, or pentaerythritol and an ether group having two or more hydroxyl groups. A residue obtained by removing (p + q) hydroxyl groups from a co-condensate with a polyhydric alcohol having 2 to 10 carbon atoms is also shown. Here, p is a positive number, q is 0 or a positive number, and (p + q) is a carbon which may include mono- or polypentaerythritol, or pentaerythritol and an ether group having two or more hydroxyl groups. It is the total number of hydroxyl groups in the cocondensation product with a polyhydric alcohol of several 2 to 10. [Chemical 1] Or a hydroxyl group, and p Y's may be the same or different, and at least one of Y's is And the balance is a hydroxyl group. Here, E represents an alkylene group having 1 to 5 carbon atoms which may have a branched chain or a polyoxyalkylene group having 2 to 5 carbon atoms and an added mole number of 1 to 100, and M is Hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, mono-, di- or trialkanol ammonium ion having 2 to 3 carbon atoms of alkanol group, alkyl-substituted ammonium ion having 1 to 5 carbon atoms, or basic amino acid Indicates a group. [Chemical 3] The q Zs may be the same or different. Here, R represents an alkyl group or an alkenyl group having 1 to 22 carbon atoms, or a group represented by the formula —CH ₂ (OJ) _t OA or —CH ₂ OA. A
Is an alkyl group or an alkenyl group having 1 to 22 carbon atoms, J is an alkylene group having 2 to 3 carbon atoms, t is a positive number of 1 to 20, B is-(CH ₂ ) _m COOM, and Or represents a hydrogen atom. m is a number from 1 to 5 and M is as defined above. However, when S is monopentaerythritol having a degree of condensation of 1 and q is 0, E is a branched chain alkylene group having 4 to 5 carbon atoms or an oxyalkylene group having 2 to 2 carbon atoms. 5 must be a polyoxyalkylene group having an addition mole number of 1 to 100. Also, S has a condensation degree of 1,
And monopentaerythritol of 2 and q is not 0, Or it is limited to hydroxyl groups. ] 2. The following step (A) and step (D) are performed in this order, or the following step (A), step (B) and step (D) are performed in this order, or the following step (A) The step (C) and the step (D) are performed in this order, and the method for producing a polycarboxylic acid represented by the general formula (I) or a salt thereof according to claim 1. Step (A): A step of synthesizing pentaerythritol or a condensate thereof by any one of the following methods i) to iv). i) reacting acetaldehyde with formaldehyde. ii) Condensing pentaerythritol. iii) Pentaerythritol is co-condensed with a polyhydric alcohol having 2 to 10 carbon atoms and optionally containing an ether group having two or more hydroxyl groups. iv) reacting pentaerythritol with glycidol. Step (B): Pentaerythritol or a condensate thereof is converted into the compound represented by the formula (II): The step of reacting with the compound represented by. Step (C): Pentaerythritol or a condensate thereof is represented by the formula
(III) A step of reacting with a fatty acid represented by ACOOH (III) (A has the same meaning as described above). Step (D): Pentaerythritol, its condensate, its alkyl ether or its fatty acid ester obtained in the step (A), the step (B) or the step (C) is reacted with any of the following i) to vii). Steps to perform. i) A compound represented by the formula (IV) X-E-COOM (IV) (X represents halogen, E and M have the same meanings as described above) is reacted with an alkali catalyst, and salt exchange is carried out if necessary. . ii) Formula (V): (R 'represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
Q represents an alkyl group having 1 to 6 carbon atoms. After the reaction with the compound represented by the formula (1), the ester group is hydrolyzed and, if necessary, salt exchange is performed. iii) Formula (VI) embedded image After reacting with the compound represented by the formula (1) in the presence of an alkali catalyst, the nitrile group is hydrolyzed and, if necessary, salt exchange is performed. iv) React with ethylene oxide in the presence of an alkaline substance or an acidic substance, then oxidize the hydroxymethyl group in the product with air or oxygen in the presence of a noble metal catalyst, and if necessary salt exchange. v) Formula (VII) (R "represents a hydrogen atom, -COOQ or -CH ₂ COOQ group, F represents an alkylene group having 1 to 4 carbon atoms, a represents 0 or 1, and Q
Has the same meaning as above. After reacting with the compound represented by the formula (1) in the presence of copper powder, the ester group is hydrolyzed and, if necessary, salt exchange is performed. vi) Maleic acid or maleic anhydride and alkaline conditions,
The reaction is carried out using calcium hydroxide as a catalyst, and salt exchange is carried out if necessary. vii) Formula (VIII) The compound represented by is reacted in the presence of an acidic substance or a basic substance, and then the ester group is hydrolyzed and, if necessary, salt exchange is performed.