JPH05140057A - New amino carboxylic acid or its salt, and surfactant thereof - Google Patents

Abstract

PURPOSE:To obtain the new amino carboxylic acid exceedingly useful for a surfactant, owing to having excellent surface activity and showing good resistance against hard water. CONSTITUTION:The objective compound is a compound of formula I [R<1> is C1-22 straight-chain alkyl or alkenyl; Y<1> and Y<2> are H or (CH2)m-COOM<3> (M<3> is H, alkali metal, etc.; (m) is 1-5); M<1> and M<2> are H, ammonium, etc.] or its salt, e.g. 3-(N-laurylamino)-2-hydroxy-propyl malonic acid.2 sodium salt. The compound of formula I having H for Y<1> and Y<2> is obtained by reaction of a compound of formula II (E is C1-5 alkyl; X is halogen) with a compound of formula R<1>-NH2 preferably at 80-120 deg.C to obtain a compound of formula III, which is hydrolyzed with NaOH preferably at >=80 deg.C and salt exchanged when needed.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel aminocarboxylic acid or a salt thereof useful as a surfactant.

[0002]

BACKGROUND OF THE INVENTION Surfactants consist of a hydrophobic part and a hydrophilic part, and efficiently disperse water into oil, water and dirt, and water and metals, and emulsify / suspend them. The state is used to obtain various industrial and domestic effects. However, conventional surfactants are susceptible to alkaline earth metal ions in hard water, particularly when hard water is used to disperse and wash dirt, and the foaming property and detergency are reduced. was there.

Therefore, it has been desired to develop a surfactant having good detergency as well as excellent hard water resistance and foamability.

[0004]

Under such circumstances, as a result of intensive studies by the present inventors, it was found that the novel aminocarboxylic acid represented by the following general formula (1) or a salt thereof solves the above problems. Heading, completed the present invention.

That is, the present invention has the following general formula (1):

[0006]

[Chemical 2]

[In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms. Y ^1, Y ^2: identical or different and each represents a hydrogen atom or a group - (C
H ₂ ) _m- COOM ³ (wherein M ³ is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, ammonium, an alkanol ammonium having a total carbon number of 2 to 9, an ammonium substituted by an alkyl group having a carbon number of 1 to 5). Or a basic amino acid group, and m represents a number of 1 to 5). M ¹ and M ² : the same or different, a hydrogen atom, an alkali metal atom, ammonium, an alkanolammonium having a total carbon number of 2 to 9, an ammonium substituted by an alkyl group having a carbon number of 1 to 5, or a basic amino acid group, M ¹ and M ² together represent an alkaline earth metal atom. ] The present invention provides an aminocarboxylic acid represented by: or a salt thereof, and a surfactant composed of these.

In the compound of the present invention represented by the general formula (1), the group represented by R ¹ is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. , Nonyl group, decyl group, undecyl group, lauryl group, myristyl group, palmityl group, stearyl group, arachidyl group, behenyl group, oleyl group, linole group, isostearyl group, 2-ethylhexyl group, 2-heptylundecanoyl group , Neodecanoyl group and the like.

The groups represented by M ¹ , M ² and M ³ include, for example, hydrogen atom; alkali metal atom such as sodium or potassium; alkaline earth metal atom such as calcium or magnesium; ammonium; trimethylammonium or triethyl. Ammonium substituted with an alkyl group having 1 to 5 carbon atoms such as ammonium;
Alkanol ammonium having a total carbon number of 2 to 9 such as monoethanol ammonium, diethanol ammonium or triethanol ammonium; or a basic amino acid group such as lysine or arginine.

Of the compounds (1) of the present invention, those in which Y ¹ and Y ² are both hydrogen atoms are subjected to amidoamination of the compound (2) with the compound (3) according to the following reaction formula A, and the compound (4) ), Followed by hydrolysis and, if necessary, salt exchange.

[0011]

[Chemical 3]

[Wherein R ¹ , M ¹ and M ² have the same meaning as described above. E: Shows an alkyl group having 1 to 5 carbon atoms. X: represents a halogen atom. ]

The compound (2) as a raw material here is a known compound, which is Chemische Berich.
te, 44, 1509 (1911). For example, when X is a chlorine atom and E is an ethyl group, it can be obtained by reacting diethyl malonate, epichlorohydrin and sodium ethylate in an ethanol solvent system. The reaction temperature of this reaction is 40 ° C.
The following is preferable, and the production of side reactions is increased at a temperature higher than that.

The compound (4) is obtained by amidating the compound (2) with the compound (3). This reaction is promoted by heating, and the reaction temperature is 40 to 15
0 ° C, preferably 60 to 140 ° C, more preferably 80
~ 120 ° C. If necessary, a solvent can be used. Examples of the solvent include methanol, ethanol, propanol, 1,4-dioxane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, benzene, toluene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride and the like. In this reaction, the compound (3) first reacts with the compound (2) to form an amide, and then reacts with a halogen atom to promote amination. Therefore, the reaction molar ratio of the compound (3) and the compound (2) is (3) / (2) = 100 to 3, preferably (3) / (2) = 20 to 3. After completion of the reaction, excess compound (3) and its HX salt (X has the same meaning as described above) can be removed by neutralizing with an alkaline substance and then dissolving and washing.

Then, the compound (4) thus obtained is hydrolyzed to produce the compound (1-i) of the present invention.
The hydrolysis reaction of the amide group proceeds by heating sodium hydroxide or potassium hydroxide in an equivalent amount to the amide and heating. The reaction temperature is preferably 80 ° C or higher. In this reaction, a solvent such as water-ethanol or water-propanol can be used. Further, R ¹ —NH ₂ (R ¹ has the same meaning as described above) generated by hydrolysis can be removed by distilling under reduced pressure or dissolving and washing after the reaction. Furthermore, if necessary, the compound of the present invention represented by the general formula (1-i) can be obtained by exchanging the desired salt with a conventional method.

Further, among the compounds of the present invention, those in which at least one of Y ¹ and Y ² is a group — (CH ₂ ) _m —COOM ³ (M ³ and m have the same meanings as described above) are, for example, Compound (4) obtained in the step in Reaction Formula A above is reacted with Compound (5) to carboxyalkylate to give Compound (6), which is then hydrolyzed and then, if necessary, a salt. It can be manufactured by exchanging.

[0017]

[Chemical 4]

[In the formula, R ¹ , M ¹ , M ² , m and X: have the same meanings as described above. E ′: a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a cationic group. Y ¹ ′, Y ² ′: the same or different, a hydrogen atom or a group — (C
Shows the H _{2) m} -COOE '. However, Y ¹ ′ and Y ² ′ do not simultaneously become hydrogen atoms. ]

The compound (4) obtained by the above-mentioned reaction formula A is NaOH, KOH, Na ₂ CO ₃ , K ₂
Compound (6) is derived by reacting with compound (5) in the presence of an alkaline substance such as CO ₃ . Here, as the compound (5), for example, ω-monochlorofatty acid sodium, ω-monochlorofatty acid methyl ester, ω
-Monobromofatty acid potassium, omega-monobromo fatty acid methyl ester, etc. are mentioned. In this reaction, as a solvent, methanol-water, ethanol-water, propanol-water,
1,4-dioxane-water or the like can be used.
The reaction temperature is 40 to 120 ° C, preferably 60 to 100 ° C
Is. The reaction molar ratio of the compound (5) to the compound (4) is (5) / (4) = 1-20, preferably 1-5.

Then, the obtained compound (6) is hydrolyzed by the same method as the compound (4) in the scheme represented by the above-mentioned reaction formula A, and further exchanged with a desired salt, if necessary. The compound of the present invention represented by the general formula (1-ii) can be obtained.

The thus-obtained aminocarboxylic acid of the present invention or its salt (1) is an organic salt and / or
Alternatively, although it contains an inorganic salt, it may be used as a surfactant while containing them depending on the purpose. Alternatively, the organic salt and / or the inorganic salt may be removed and purified by electrodialysis or the like, and then used as a surfactant.

Furthermore, the aminocarboxylic acid or its salt (1) of the present invention can be used in combination with a conventionally known anionic surfactant, cationic surfactant or nonionic surfactant.

[0023]

INDUSTRIAL APPLICABILITY The novel aminocarboxylic acid or a salt thereof of the present invention has an excellent surface-active effect and shows good hard water resistance, and is extremely useful as a surfactant.

[0024]

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

Example 1 Synthesis of 3- (N-laurylamino) -2-hydroxy-propylmalonic acid disodium salt (1-a): (1) 3-carboxy-5-chloromethyl-γ-butyrolactone Synthesis of ethyl ester (2-a): 160.17 g (1 mol) of diethyl malonate, 21% sodium ethylate (C ₂ H ₅ ONa) ethanol solution 324.0.
Charge 5 g (1 mol) and 200 g of ethanol, and add 92.52 g (1 mol) of epichlorohydrin at 40 ° C.
At 1 hour and 30 minutes. After aging at 40 ° C. for 3 hours, ethanol was distilled off with a rotary evaporator. To this, 450 g of water was added, and 50 g of concentrated sulfuric acid was gradually added to neutralize. After extraction with ether three times, the extract was washed with saturated saline three times. It was dried over anhydrous sodium sulfate, and the ether was distilled off with a rotary evaporator.
92.8 g of concentrate was obtained. Further distillation is performed, and 115.
8 g of 3-carboxy-5-chloromethyl-γ-butyrolactone ethyl ester (2-a) was obtained. Yield 5
6.0%. When the saponification value, chloride ion content and total chlorine content of the obtained compound (2-a) were measured, the values were in good agreement with the theoretical values.

[0026]

[Table 1]

(2) 3- (N-laurylamino) -2-
Hydroxy-propylmalonic acid / dilaurylamide (4
-A) Synthesis: 3-carboxy-5-chloromethyl-obtained in (1)
γ-butyrolactone ethyl ester (2-a) 35.
8 g (0.173 mol), laurylamine (C ₁₂H_{twenty five}N
H₂) 160.6 g (0.867 mol) and ethanol
161 g was charged and the mixture was refluxed for 5 hours. Rotary evaporator
After distilling off ethanol with a porator, 4% sodium hydroxide
173 g (0.173 mol) of an aqueous lithium solution was added. Ku
After extracting with 600 ml of Loloform, extract twice with 150 ml of water.
The effluent was washed. Dried over anhydrous sodium sulfate and
-Chloroform was distilled off with an evaporator. Solid content
After washing 3 times with 200 ml of methanol, dry under reduced pressure, and
8.9 g of 3- (N-laurylamino) -2-hydroxy
Si-propylmalonic acid / dilaurylamide (4-a)
Obtained. Yield 58.9%. The obtained compound (4-a)
The total amine value, chloride ion content and total chlorine content.
The value was in good agreement with the theoretical value.

[0028]

[Table 2]

(3) 3- (N-laurylamino) -2-
Hydroxy-propylmalonic acid disodium salt (1-
Synthesis of a): 3- (N-laurylamino) 2-hydroxy-propylmalonic acid / dilaurylamide (4-) obtained in (2)
a) 27.2 g (0.04 mol), 40.0% sodium hydroxide aqueous solution 80.0 g (0.08 mol) and ethanol 2
40 g was charged and refluxed for 5 hours and 20 minutes. While leaking nitrogen with a rotary evaporator, 1 at 90 ° C
Ethanol, water and laurylamine were distilled off over 1 hour. After washing with 20 g of ethanol, it was dissolved in 331 g of water, and the insoluble matter was filtered with a membrane filter. Water was distilled off, and the residue was dried under vacuum to obtain 11.9 g of 3- (laurylamino) -2-hydroxy-propylmalonic acid disodium salt (1-a). Yield 76.3%. When the total amine value, tertiary amine value, nitrogen content and sodium content of the obtained compound (1-a) were measured, the values were in good agreement with the theoretical values.

[0030]

[Table 3]

Example 2 3- (N-lauryl-N-carboxymethylamino)
Synthesis of 2-hydroxy-propylmalonic acid trisodium salt (1-b): (1) 3- (N-lauryl-N-carboethoxymethyl amino) -2-hydroxy-propionic acid dilaurylamide (6 Synthesis of -a): 1.70 g of 3- (N-laurylamino) -2-hydroxy-propylmalonic acid-dilaurylamide (4-a) obtained in (2) of Example 1.
(2.5 mmol), methyl bromoacetate (BrCH ₂ C
OOCH ₃ ) 0.459 g (3.0 mmol) and 1,
20 ml of 4-dioxane was charged, and 0.25 g (3.0 mmol) of 48% sodium hydroxide aqueous solution and ethanol 1 were added.
0 ml of solution was added dropwise at 80 ° C. over 1 hour. Then, the mixture was aged at 80 ° C. for 50 minutes, the solvent was distilled off with a rotary evaporator, and 3- (N-lauryl-N-carboethoxymethylamino) -2-hydroxy-propionic acid-dilaurylamide (6-a) was obtained. 2.23 g of a mixture of sodium bromide was obtained.

(2) Synthesis of 3- (N-lauryl-N-carboxymethylamino) -2-hydroxy-propylmalonic acid trisodium salt (1-b): Sodium bromide obtained in (1) Contain 3- (N-
Lauryl-N-carboethoxymethyl amino) -2-
Hydroxy-propionic acid / dilaurylamide (6-
a) 2.23 g (2.5 mmol), 4% sodium hydroxide 11.25 g (11.25 mmol) and 80 ml of ethanol were charged and refluxed for 10 hours. While leaking nitrogen with a rotary evaporator, 11 at 90 ° C
Ethanol, water and laurylamine were distilled off over time. Then, it was washed with ethanol, dissolved in water, and the insoluble matter was filtered through a membrane filter. The inorganic salt was removed from the filtrate by electrodialysis, water was distilled off, and the residue was vacuum dried to give 3- (N-lauryl-N-carboxymethylamino).
2-Hydroxy-propylmalonic acid trisodium salt (1-b) was obtained. FAB-mass spectrum of the obtained compound (1-b) was found to be M ⁺ (47
It was confirmed that there was a fragment of 0), and the compound was produced.

Claims (2)

[Claims] 1. The following general formula (1): [In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms. Y ^1, Y ^2: identical or different and each represents a hydrogen atom or a group - (C
H ₂ ) _m- COOM ³ (wherein M ³ is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, ammonium, an alkanol ammonium having a total carbon number of 2 to 9, an ammonium substituted by an alkyl group having a carbon number of 1 to 5). Or a basic amino acid group, and m represents a number of 1 to 5). M ¹ and M ² : the same or different, a hydrogen atom, an alkali metal atom, ammonium, an alkanolammonium having a total carbon number of 2 to 9, an ammonium or a basic amino acid group substituted by an alkyl group having a carbon number of 1 to 5, or ¹ and M ² together represent an alkaline earth metal atom. ] The aminocarboxylic acid or its salt represented by these. 2. A surfactant comprising the aminocarboxylic acid according to claim 1 or a salt thereof.