JP3537550B2 - Carboxyl group-containing polyoxyalkylene compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyoxyalkylene compound having two or more carboxyl groups on the side chain of the skeleton of the polyoxyalkylene group.

[0002]

2. Description of the Related Art Hitherto, compounds in which a terminal hydroxyl group of a polyoxyalkylene group has been substituted with a carboxyl group are shown in lubricating oils (JP-B-63-4877) or synthetic resin additives (JP-A-63-182343). Has been
Widely used. In recent years, polyoxyalkylene compounds have attracted attention as important carriers for drug delivery systems (DDS), and active research has been conducted on compounds in which amino groups or carboxyl groups have been introduced into polyoxyalkylene groups. It has become to be. (For example, BIOCONJUGATE CHEM., 3 (4) 275-276)
A polyoxyalkylene compound having a large number of carboxyl groups on a side chain in the skeleton of the polyoxyalkylene group is not known.

[0003]

SUMMARY OF THE INVENTION Polyoxyalkylene compounds having a plurality of carboxyl groups on the side chains in the skeleton are:
The following advantages are conceivable because the carboxyl group content is higher than the molecular weight. In the field of synthetic resin additives, it is excellent in improving the compatibility effect. Excellent in heat resistance in lubricating oil field. Since DDS is used in the field of medicine and biochemistry and can transport many drugs at once, it is useful as a carrier for drug delivery systems. Useful as a surfactant for polycarboxylic acids. However, the polyoxyalkylene carboxylic acids provided so far are synthesized by replacing the terminal hydroxyl group of the polyoxyalkylene group with a carboxyl group, so that the number of carboxyl groups that can be introduced into the skeleton is limited. . Further, in order to improve the carboxyl group content, since there is no other way but to shorten the molecular weight of the polyoxyalkylene glycol, in the field of the synthetic resin additive, it is easy to bleed when added,
In the field of lubricating oils, there are problems such as difficulty in imparting the required viscosity to the product, or too high toxicity due to low molecular weight for use in DDS. Therefore,
Polyoxyalkylene compounds containing a plurality of carboxyl groups in the side chain in the skeleton of the compound are strongly desired. The compound is considered to have improved compatibility in the field of synthetic resin additives, improved heat resistance in the field of lubricating oils, increased number of drug-bonding groups and reduced toxicity in the field of DDS. An object of the present invention is to provide a compound having a carboxyl group on the side chain of a skeleton useful as a raw material for cosmetics, biomaterials, medicines, agricultural chemicals, additives for lubricating oil or synthetic resin, or a surfactant. . Another object of the present invention is to provide a manufacturing method thereof.

[0004]

Means for Solving the Problems The present inventors oxidize a copolymer having an alkenyl ether group in the side chain of a polyoxyalkylene group in the main chain with an oxidizing agent, without using a special reactor. It has been found that a polyoxyalkylene compound having a plurality of carboxyl groups in the side chain can be easily obtained, and the present invention has been completed. That is, the present invention is a carboxyl group-containing polyoxyalkylene compound represented by the formula (1).

[0005]

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Wherein Z is a residue of a compound having 2 to 8 hydroxyl groups, A ¹ O and A ² O are one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms, ¹ O, B ²
O represents one or a mixture of two or more groups represented by the formula (2):

[0007]

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(Where R ² is an unsaturated hydrocarbon group having 3 to 6 carbon atoms). C ¹ O and C ² O are one or a mixture of two or more groups represented by the formula (3):

[0009]

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(Where M is a hydrogen atom, an alkali metal,
Alkaline earth metals, ammonium, alkylammonium or hydrocarbon groups having 1 to 24 carbon atoms may be the same or different, and R ³ is an alkylene group having 1 to 4 carbon atoms. ) A ¹ O, B ¹ O, C ¹ O and A ² O, B ² O, C ² O
May be added in a block shape or a random shape, respectively, and R ¹ is a hydrocarbon group having 1 to 24 carbon atoms or an acyl group having 2 to 24 carbon atoms. Also, m is an integer of 0 to 8, n is an integer of 0 to 8, m + n = 2 to 8, 0
≦ a, 0 ≦ b, 0 ≦ i, 0 ≦ j, 0 ≦ p, 0 ≦ q, and am + bn = 1 to 1500, im + jn = 0 to 10
0, pm + qn = 2 to 100. Further, in the present invention, in the above formula (1), Z is one selected from ethylene glycol, propylene glycol and butylene glycol, R ¹ is a hydrogen atom, R ³ is a methylene group, an ethylene group, propylene It is preferable because a carboxyl group-containing polyoxyalkylene compound which is a group can be easily produced.

In the formula (1), 2 to 8 wherein Z is a residue
Compounds having one hydroxyl group include ethylene glycol, propylene glycol, butylene glycol, dodecylene glycol, octadecylene glycol, neopentyl glycol, glycerin, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, 3,5-pentanetriol, erythritol, pentaerythritol, dipentaerythritol,
Polyhydric alcohols such as sorbitol, sorbitan, sorbide, sorbitol-glycerin condensate, adonitol, arabitol, xylitol, mannitol; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose,
Saccharides such as trehalose, sucrose, raffinose, gentianose, and melezitose; their partially etherified and partially esterified products; polyhydric phenols such as catechol, resorcin, hydroquinone, and phloroglucin; and aromatic alcohols such as styrene glycol. can give.

The oxyalkylene groups represented by A ¹ O and A ² O include oxyethylene groups, oxypropylene groups,
Examples thereof include an oxytrimethylene group, an oxybutylene group, and an oxytetramethylene group. Examples of the unsaturated hydrocarbon group having 3 to 6 carbon atoms represented by R ² in the formula (2) include an allyl group, a 3-butenyl group, a 1-methyl-3-butenyl group, a 4-pentenyl group, and a 1-methyl- Some have a polymerizable unsaturated bond, such as a 4-pentenyl group, a 2-methyl-4-pentenyl group, and a 1,1-dimethyl-3-butenyl group. Examples of the hydrocarbon group having 1 to 24 carbon atoms represented by R ¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, and isoheptyl. Group,
2-ethylhexyl group, octyl group, isononyl group, decyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, isocetyl group, octadecyl group,
Isostearyl group, octyldodecyl group, docosyl group,
Decyltetradecyl group, a benzyl group, a phenyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctyl phenyl group, di- nonylphenyl group or the like, and further, represented by R ¹ Examples of the acyl group having 2 to 24 carbon atoms include acetic acid, propionic acid, butyric acid, isobutyric acid, caprylic acid, 2-ethylhexanoic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, isopalmitic acid, and stearic acid And acyl groups derived from isostearic acid, arachinic acid, behenic acid, palmitoleic acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, gallic acid and the like.

Formula (3) is a structure in the case where the unsaturated hydrocarbon group in Formula (2) is oxidized by an oxidizing agent to form a carboxyl group. Therefore, R ³ has 1 carbon atom.
And specific examples of the divalent hydrocarbon group represented by R ³ include a methylene group, an ethylene group, a propylene group, a trimethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, A dimethylethylene group. Among these, a methylene group, an ethylene group, and a propylene group are preferred as they are available.

In the formula (3), M represents a hydrocarbon group having 1 to 24 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,
Pentyl, isopentyl, hexyl, isoheptyl, 2-ethylhexyl, octyl, isononyl, decyl, dodecyl, isotridecyl, tetradecyl, hexadecyl, isocetyl, octadecyl, isostearyl, octyldodecyl Group, docosyl group, decyltetradecyl group, benzyl group, phenyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group,
Examples include a dioctylphenyl group and a dinonylphenyl group.
Further, an alkali metal, an alkaline earth metal represented by M,
As ammonium or alkyl ammonium salts,
Alkali metals such as lithium, sodium, potassium and rubidium; alkaline earth metals such as magnesium and calcium; ammonium salts, ethylamine salts, propylamine salts, butylamine salts, pentylamine salts, hexylamine salts, octylamine salts, 2-ethylhexyl Amine salt, decylamine salt, dodecylamine salt, isotridecylamine salt, tetradecylamine salt, hexadecylamine salt, isohexadecylamine salt, octadecylamine salt, isooctadecylamine salt, octyldodecylamine salt, docosylamine salt, decyl Aliphatic or aromatic monoamine salts such as tetradecylamine salt, oleylamine salt, linoleamine salt, dimethylamine salt, trimethylamine salt, aniline salt; ethylenediamine salt, tetramethylenediamine Polyamine salts such as salts, dodecyl-propylenediamine salts, tetradecyl-propylenediamine salts, octadecyl-propylenediamine salts, oleyl-propylenediamine salts, diethylenetriamine salts, triethylenetetramine salts, tetraethylenepentamine salts, pentaethylenehexamine salts, etc .; Alkanolamine salts such as ethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, triisopropanolamine salt and salts of alkylene oxide adducts thereof; amino acid salts such as lysine salt and arginine salt There is. Of these, a hydrogen atom, an alkali metal salt, and an alkanolamine salt are particularly preferred from the viewpoint of availability.

The compound of the formula (1) of the present invention can be obtained by reacting the compound of the formula (4) with an oxidizing agent.

[0016]

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Wherein Z is a residue of a compound having 2 to 8 hydroxyl groups; A ¹ O and A ² O are one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms; ¹ O, B ²
O is one or a mixture of two or more groups represented by the formula (2).

[0018]

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(However, R ² is an unsaturated hydrocarbon group having 3 to 6 carbon atoms.) A ¹ O and B ¹ O, and A ² O and B ² O may be added in a block shape. R ¹ may be a hydrocarbon group having 1 to 24 carbon atoms or an acyl group having 2 to 24 carbon atoms, m is an integer of 0 to 8, n is an integer of 0 to 8, m + n = 2-8, 0 ≦ a, 0 ≦ b, 0 ≦
i + p, 0 ≦ j + q, am + bn = 1 to 1500, im
+ Jn = 0 to 100 and pm + qn = 2 to 100. Specific examples of the oxidizing agent include alkali metal periodate and alkali metal permanganate. In particular, oxidation under mild conditions by a combination of sodium periodate and potassium permanganate is preferred.

In preparing the compound of the present invention, the compound of formula (4)
The reaction ratio between the compound of formula (I) and the oxidizing agent can be any ratio, and cannot be specified because the number of unsaturated groups varies according to i + p and j + q in formula (4). However, the number of unsaturated groups in the compound of formula (4) is preferably The equivalent ratio of the oxidizing agent of sodium periodate to the number of equivalents based on the above is in the range of 0.02 to 50, particularly preferably 0.2 to 20. As potassium permanganate, the equivalent ratio is 0 to 5, preferably 0.2 to 2. Potassium carbonate used as an oxidizing aid has an equivalent ratio of 0 to 30, preferably 0.1 to 10. is there.

If the equivalent ratio of the oxidizing agent to sodium periodate is less than 0.02, the content of the desired carboxyl group decreases, and if it exceeds 50, the cleavage of the polyoxyalkylene compound is liable to occur. Absent. If the equivalent ratio of potassium permanganate is more than 5, cleavage of the polyoxyalkylene compound is likely to occur, which is not preferable. The compound of the present invention can be obtained by adjusting the molecular weight and i + p, j + q of the compound of the formula (4), and the equivalent ratio of the oxidizing agent and the compound of the formula (4) to be charged. The number can be adjusted. That is, if the molecular weight of the compound of the formula (4) is reduced, the number of unsaturated groups is increased, and the charge ratio of the oxidizing agent is increased, a reaction product having a small molecular weight and a high carboxyl group content is obtained. If the molecular weight of the compound of formula (1) is increased, the number of unsaturated groups is reduced, and the charge ratio of the oxidizing agent is reduced, a reaction product having a high molecular weight and a low carboxyl group content can be obtained. If the ratio is small, the number of unsaturated groups is small, and the charge ratio of the oxidizing agent is low, a reaction product having a small carboxyl group content with a small molecular weight can be obtained, and the molecular weight of the compound of the formula (4) is increased,
By increasing the number of unsaturated groups and increasing the charge ratio of the oxidizing agent, a reaction product having a high molecular weight and a high carboxyl group content can be obtained.

The compound of the formula (4) is obtained by adding a compound having 2 to 8 hydroxyl groups to an alkali catalyst such as potassium hydroxide, sodium hydroxide or sodium methylate, or a Lewis acid catalyst such as boron trifluoride or tin tetrachloride. And alkenyl glycidyl ethers such as alkylene oxide and allyl glycidyl ether can be obtained by block- or random-addition polymerization. At this time, the number of unsaturated groups in the compound of the formula (4) can be adjusted by adjusting the mixing ratio between the alkylene oxide and the alkenyl glycidyl ether.
In the compound represented by the formula (4), at least two R ² are required to react with an oxidizing agent.

The solvent used for the oxidation reaction of the compound of the formula (4) is not particularly limited as long as it does not hinder the oxidation reaction. Specific examples thereof include water or ether solvents such as tetrahydrofuran and dioxane, acetone and methyl ethyl ketone. And ketone solvents such as methyl isobutyl ketone; carboxylic solvents such as acetic acid; ester solvents such as ethyl acetate and butyl acetate; and hydrocarbon solvents such as hexane and petroleum ether. The type and amount of the solvent used depends on the chemical structure, physical properties and reaction temperature of the compound of the formula (4). However, if the amount of the solvent is too large, it takes a long time for purification, which is not preferable. It is 0.01 to 1000 times, preferably 0.2 to 100 times the weight. Further, the reaction temperature is -20 to 1
At 20 ° C, preferably at 0-100 ° C, more preferably at 10-50 ° C. If the temperature is lower than −20 ° C., it is not preferable because the reaction time is too long.
If the temperature is higher, cleavage of the polyoxyalkylene compound tends to occur, which is not preferable. Still further, the reaction time is 0.5 to 120 hours. If the reaction time is less than 0.5 hour, the reaction hardly proceeds, and if the reaction time is longer than 120 hours, the reaction rate is not so improved, which is not preferable.

The compounds of the present invention, A ¹ in the formula (4)
O, A ² O, B ¹ O, B ² O, R ¹ , Z, m, n, i + p,
By appropriately changing the equivalent ratio of the oxidizing agent to j + q, a, b and the equivalent of the number of unsaturated groups of the compound of the formula (4), it is possible to obtain from a water-soluble liquid to a hardly water-soluble solid, and Since the number of carboxyl groups in the side chain in the medium can be arbitrarily adjusted, it can be used for various forms of use from water-soluble to fat-soluble and from liquid to solid.

[0025]

The compound of the present invention is a polyoxyalkylene compound having a plurality of carboxyl groups on the side chain in the skeleton, and a high molecular weight compound having a high carboxyl group content can be easily obtained. In order to make the resulting properties remarkable, it can be used as an additive in the lubricating oil field, an additive for a synthetic resin, or a compatibilizer. In addition, it easily reacts with amino groups and hydroxyl groups of pharmaceutical drugs, etc.,
It can also be used as a carrier for drug delivery systems. Further, it can be used as a polycarboxylic acid surfactant.
According to the synthesis method of the present invention, a carboxyl group-containing compound can be easily produced without using any special equipment.

[0026]

The present invention will be described in more detail with reference to the following examples. Production Example 1 A 5-liter autoclave was charged with 53 g (0.5 mol) of diethylene glycol and 4.0 g of potassium hydroxide, and the inside of the system was replaced with nitrogen gas.
Next, 1470 g of ethylene oxide (33.4 g)
Mol) and 673 g (5.9 mol) of allyl glycidyl ether were weighed into a measuring tank, and the mixed liquid was subjected to 100 to 15 mol.
Press-fitting was performed at 0 ° C. under 10 kg / cm ² for 8 hours. Thereafter, the reaction was continued for another hour. Next, unreacted ethylene oxide and allyl glycidyl ether were removed under a reduced pressure of 100 mmHg or less while passing nitrogen gas, and then cooled to 60 ° C. Thereafter, the pH was adjusted to 7.0 with a 10% hydrochloric acid aqueous solution, and dehydration was performed at 100 ° C. and 100 mmHg or less for 1 hour. Next, the mixture was cooled to 80 ° C., and the precipitate was separated by filtration to obtain 2072 g of a compound. (94% yield)
The hydroxyl value of the obtained compound was 26.8 mgKOH / g.
(Calculated value: 27.4), Unsaturation degree: 2.57 meq / g
(Calculated value was 2.68). Starting materials, reaction conditions,
No. shown in Table 1 from the analysis values This was identified as Compound 1. The analysis values are shown in Table 2.

[0027]

[Table 1]

[0028]

[Table 2]

The hydroxyl value is determined according to JIS K 1557.
The method was performed according to the method of 6.4 (1970), and the degree of unsaturation was performed according to the method of JIS K 1557 6.7 (1970). The measurement conditions of the gel permeation chromatography are as follows. <Measurement conditions of gel permeation chromatography> Model: Shodex GPC SYSTEM-1
1 developing solvent; tetrahydrofuran sample; 0.15% × 100 μl flow rate; 1.0 ml / min packed column; Shodex KF-801, KF-80
3, KF-804 column temperature; 40 ° C. column length; D 8 mm x 30 cm x 3 Detector; Differential refractive index detector Shodex RI-
71 The results of measurement by gel permeation chromatography are as follows. Number average molecular weight (Mn) = 3900 Weight average molecular weight (Mw) = 4100 Polydispersity (Mw) / (Mn) = 1.04 The measurement results of the infrared absorption spectrum are as follows. ^{1100cm -1 C-O-C 1640cm} -1 C = C 1 H-NMR measurement results of the spectrum are as follows. ¹ H-NMR (δ (ppm), CDCl ₃ ) δ = 5.2 (= CH 2) δ = 5.9 (-CH =)

Production Example 2 A 5-liter autoclave was charged with 53 g (0.5 mol) of diethylene glycol and 4.0 g of potassium hydroxide, and the inside of the system was replaced with nitrogen gas.
Then, 1681 g (38.2 mol) of ethylene oxide and 363 g (3.2 mol) of allyl glycidyl ether were weighed in a measuring tank in advance, and the mixed liquid was subjected to 100 to 15 g.
Press-fitting was performed at 0 ° C. under 10 kg / cm ² for 8 hours. The reaction was continued for another hour. Next, unreacted ethylene oxide and allyl glycidyl ether were removed under a reduced pressure of 100 mmHg or less while passing nitrogen gas.
Until cooled. Thereafter, the pH was adjusted to 7 with a 10% aqueous hydrochloric acid solution.
The temperature was adjusted to 0, and dehydration was performed at 100 ° C. and 100 mmHg or less for 1 hour. Next, the mixture was cooled to 80 ° C., and the precipitate was separated by filtration to obtain 2035 g of a compound. (Yield 97%) The hydroxyl value of the obtained compound was 27.2 mgKOH / g.
(Calculated value: 28.1), degree of unsaturation: 1.44 meq / g
(The calculated value is 1.51). Compound 2 was identified.

Example 1 No. 1 of Production Example 1 4.67 g of compound (1.1 ×
10 ^-3 mol, 1.2 × 10 ^-2 equivalents of unsaturated groups) and 75 ml of water are placed in a container and 25.7 g of sodium periodate (1.2 × 10 ^-1 mol, 10 equivalents / unsaturated) Base number), potassium permanganate 0.32 g (2.0 × 1
0 ^-3 mol, 0.17 equivalents / unsaturated groups) potassium carbonate 6.23g (4.5 × 10 ^-2 mol, 3.8 times equivalents / unsaturated groups), and water 225 ml of the solution was added, at room temperature For 24 hours. Then, the pH was adjusted to 2 to 3 with a 12N-HCl aqueous solution. Then, chloroform 1
Extraction was performed three times with 00 ml. The collected chloroform was washed twice with 100 ml of water, dehydrated using anhydrous sodium sulfate, and then the solvent chloroform was distilled off to obtain 2.7 g of a white solid. (Yield 57
%) The obtained compound has an acid value of 145.1 mgKOH / g,
The hydroxyl value is 25.7 mgKOH / g, and the degree of unsaturation is 0.5.
It was 00meq / g. As a result of infrared absorption spectrum analysis, it was confirmed that absorption of -COOH occurred at 1748 cm ^-1 . The oxidizing agents and the amounts used are shown in Table 3, the analytical values are shown in Table 4, and the structural formula of the product is shown in Table 5.

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

The acid value is measured according to JIS K155
7 According to the method of 6.6 (1970), the measurement conditions of gel permeation chromatography were as follows. <Measurement conditions for gel permeation chromatography> Model: Shimadzu High Performance Liquid Chromatograph LC-10
A System development solvent; 0.05 M NaNO ₃ aqueous solution sample; 0.5% × 20 μl Flow rate: 1.0 ml / min Packed column; Shodex OHPAK SB-80
M, column temperature; 30 ° C. column length; D 8mm × 30cm × 3 Detector; Differential refractive index detector Shodex RID
-6A

Example 2 The above Production Example No. 4.67 g of two compounds (1.2 × 10
^-3 mol, 6.7 × 10 ^-3 equivalents of unsaturated groups) and water 7
Take 5 ml into a container and add sodium periodate 1
4.3 g (6.7 × 10 ^-2 mol, 9.9 equivalents / number of unsaturated groups) 0.18 g of potassium permanganate (1.1 × 10
^-3 mol, 0.17 equivalent / number of unsaturated groups) 3.46 g of potassium carbonate (2.5 × 10 ^-2 mol, 3.7 equivalent / number of unsaturated groups) A solution of 225 ml of water was added thereto.
Stir for 4 hours. Then, p with an aqueous 12N-HCl solution
H was adjusted to 2-3. Then, extraction was performed three times with 100 ml of chloroform. The collected chloroform was washed twice with 100 ml of water, dehydrated using anhydrous sodium sulfate, and then chloroform as a solvent was distilled off to obtain 3.5 g of a white solid. (Yield: 71%) The obtained compound was analyzed by infrared analysis to have a concentration of 1746 cm ^-1 .
It was confirmed that COOH absorption had occurred. Further, the acid value was 82.6 mgKOH / g. The oxidizing agents and the amounts used are shown in Table 3, the analytical values are shown in Table 4, and the structural formula of the product is shown in Table 5.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akinori Suginaka 2-4-10 Murota, Chigasaki City, Kanagawa Prefecture (56) References JP-A-8-193128 (JP, A) JP-A-8-48763 (JP, A) JP-A-54-84523 (JP, A) JP-A-8-48764 (JP, A) JP-A-8-165349 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08G 65/32-65/338

Claims (2)

(57) [Claims] 1. A carboxyl group-containing polyoxyalkylene compound represented by the formula (1). Embedded image [Where Z is a residue of a compound having 2 to 8 hydroxyl groups,
A ¹ O and A ² O are one of oxyalkylene groups having 2 to 4 carbon atoms.
B ¹ O or B ² O is a species or a mixture of two or more species, and is represented by the formula (2)
A mixture of one or more of the groups represented by (Where R ² is an unsaturated hydrocarbon group having 3 to 6 carbon atoms) C ¹ O and C ² O are one or a mixture of two or more groups represented by the formula (3): (Where M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, alkylammonium or a hydrocarbon group having 1 to 24 carbon atoms which may be the same or different, and R ³ is an alkylene group having 1 to 4 carbon atoms) A ¹ O
And B ¹ O and C ¹ O and A ² O, B ² O and C ² O may be added in a block shape or in a random shape, respectively, and R ¹ has 1 to 24 carbon atoms. A hydrocarbon group or an acyl group having 2 to 24 carbon atoms, m is an integer of 0 to 8, n is 0 to
An integer of 8, m + n = 2-8, 0 ≦ a, 0 ≦ b, 0 ≦ i,
0 ≦ j, 0 ≦ p, 0 ≦ q, and am + bn = 1 to 15
00, im + jn = 0-100, pm + qn = 2-10
0 is satisfied. ] 2. In the formula (1) according to claim 1, Z is one kind of residue selected from ethylene glycol, propylene glycol and butylene glycol, R ¹ is a hydrogen atom, R ³ is a methylene group, The carboxyl group-containing polyoxyalkylene compound according to claim 1, which is an ethylene group or a propylene group.