JPH05140055A - N-substituted diaminodicarcoxylic acid and its salt and surfactant comprising the same compound - Google Patents

Abstract

PURPOSE:To obtain the title new compound having excellent surface active ability, useful in a wide industrial field as a surfactant having high hard water resistance and foaming properties. CONSTITUTION:A compound of formula I [R is 8-22C chained alkyl or alkenyl; M<1> and M<2> are H, alkaline (earth) metal ion, ammonium ion, etc.; Y is OH or sulfonic group-substituted 1-10C alkyl; (m) is 1-9; (n) is 2 or 31 or its salt such as N-[3-(N'-lauryl-N'-carboxymethyl-amino)-propyl]-N-carboxymethyl-glucan di-sodium salt. The compound, for example, is obtained by reacting a diamine of the formula RNH(CH2)NH2 with a 3-halo-2-hydroxypropylsulfonic acid of formula II (M<3> is M<1>) in the presence of an alkali to give a compound of formula III and reacting the compound with a carboxylic acid halide derivative of the formula X(CH2)mCOOE (X is halogen; E is H, cation, etc.).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an N-substituted diaminodicarboxylic acid or a salt thereof useful as a surfactant.

[0002]

BACKGROUND OF THE INVENTION Surfactants are composed of a hydrophobic part and a hydrophilic part, and efficiently disperse water and oil, water and dirt, and water and metal, and emulsify and suspend these. The state is used to obtain various industrial and domestic effects.

However, in particular, in the case of cleaning by dispersing dirt, there is a problem that the foaming property and the cleaning power of the surfactant are lowered due to the influence of alkaline earth metal in hard water.

Therefore, a compound which is useful as a surfactant and is superior in hard water resistance and foaming property to conventional surfactants even in hard water has been desired.

[0005]

Under such circumstances, the inventors of the present invention have conducted extensive studies and as a result, as a result, a specific N-substituted diaminodicarboxylic acid or a salt thereof has excellent hard water resistance and foaming property as a surfactant. Therefore, the present invention has been completed.

That is, the present invention is based on the general formula (1)

[0007]

[Chemical 3]

(In the formula, R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms; M ¹ and M ²
Are the same or different and are hydrogen atom, alkali metal ion, alkaline earth metal ion, ammonium ion, carbon number 1
~ 5 alkylammonium ion, total carbon number 2-9 alkanolammonium ion or basic amino acid group; Y represents a C1-10 alkyl group substituted with a hydroxyl group or a sulfonic acid group; m is 1 Indicates a number from ~ 9;
(n is a number of 2 or 3) provides an N-substituted diaminodicarboxylic acid or a salt thereof and a surfactant comprising the compound.

The N-substituted diaminodicarboxylic acid or salt thereof of the present invention is represented by the above-mentioned general formula (1), wherein in the formula, R 8 is a straight chain or branched chain having 8 to 22 carbon atoms. As the chain alkyl group or alkenyl group, for example, octyl group, decyl group, lauryl group, myristyl group, palmityl group, stearyl group, arachidyl group, behenyl group, oleyl group, linole group, isostearyl group, 2-ethylhexyl group, Examples include 2-heptylundecyl group and neodecyl group.

As M ¹ and M ² , hydrogen atom; alkali metal ion such as sodium and potassium; alkaline earth metal ion such as calcium and magnesium; ammonium ion; trimethylammonium ion, triethylammonium ion and the like having 1 carbon atom Alkyl ammonium ion of 5 to 5; alkanol ammonium ion of total carbon number 2 to 9 such as mono, di or triethanol ammonium ion; and basic amino acid groups such as lysine and arginine.

Further, Y represents an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group or a sulfonic acid group, and among these, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group is, for example, generally Formula (2) -CH ₂ (CHOR ') _p CH ₂ OR' (2) (In the formula, R'represents a hydrogen atom or, of (p + 1) R ', one is a glycosyl hydroxyl group rather than a sugar. Is a residue remaining after the removal of p, and the other p R's represent a hydrogen atom. P represents a number of 3 or 4).

[0012]

[Chemical 4]

And the like. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a sulfonic acid group in Y include a 2-hydroxy-3-sulfonopropyl group and the like.

The N-substituted diaminodicarboxylic acid (1) of the present invention can be produced, for example, by the following method. [Production method 1]

[0015]

[Chemical 5]

(First Step) First, a compound (5) is produced by reacting a diamine (3) with a sugar aldehyde (4) in a hydrogen atmosphere in the presence of a metal catalyst. here,
Examples of the sugar aldehyde (4) include three monosaccharides such as glyceraldehyde, four monosaccharides such as erythrose, five monosaccharides such as arabinose, six monosaccharides such as glucose and mannose, and two monosaccharides such as maltose, lactose and sucrose. Examples include sugars to oligosaccharides. Examples of the metal catalyst include nickel-based catalysts such as Raney nickel and stabilized nickel; precious metal catalysts such as platinum, palladium, ruthenium, and rhodium. These are supported on a carrier such as carbon, silica, or alumina. It may be one. These metal catalysts are preferably used in an amount of 0.05 to 5% by weight based on the total amount of diamine (3) and sugar aldehyde (4). The molar ratio of diamine (3) and sugar aldehyde (4) is 1
/0.8 to 0.8 / 1 is preferable. The reaction is preferably carried out at room temperature to 140 ° C., particularly from the viewpoint of activity and coloring.
The range of 40-80 ° C is preferred. Further, the pressure of hydrogen is preferably normal pressure to 150 atm, particularly 30 to 80 atm. Further, it is preferable to use alcohols such as methanol, ethanol, propanol and butanol; ethers such as tetrahydrofuran and dioxane as the solvent.

(Step 2-1) The compound (5) obtained in the first step is reacted with the halogenated carboxylic acid derivative (6) in the presence of an alkali to give the compound (1) of the present invention.
-1) can be obtained. Examples of the halogenated carboxylic acid derivative (6) include ω-monochlorofatty acid sodium, ω-monobromofatty acid potassium, ω-monochlorofatty acid ethyl ester, ω-monobromofatty acid methyl ester, and the like. Examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. These alkalis are charged as an aqueous solution in the reaction system in advance and added dropwise to a mixture (which may contain a solvent) of the compound (5) and the halogenated carboxylic acid derivative (6). The reaction is
As the solvent, water, water-methanol, water-ethanol, water-propanol or the like can be used, and it is preferably carried out in the range of 50 to 110 ° C. After the reaction, the inorganic salt by-produced is
It can be removed by electrodialysis or the like.

(Step 2-2) The compound (5) obtained in the first step is reacted with the acryl derivative (7), and then the nitrile group or ester group is hydrolyzed.
This invention compound (1-1) can be obtained. The reaction is
The hydrolysis may be performed under the same conditions as in the step 2-1 and the nitrile group or the ester group may be hydrolyzed according to a usual method.

[Manufacturing Method 2]

[0020]

[Chemical 6]

(First Step) First, diamine (3) and 3
By reacting -halo-2-hydroxypropylsulfonic acid or a salt thereof (8) in the presence of an alkali,
A compound (9) having a —hydroxy-3-sulfonopropyl group introduced therein is produced. Here, in the compound (8),
Examples of the halogen atom represented by X include chlorine, bromine, iodine and the like. Examples of the alkali include sodium hydroxide and potassium hydroxide. The diamine (3) is preferably used in an amount of 1 to 10 equivalents, particularly 2 to 5 equivalents based on the compound (8). When the excess amount becomes small, a diamine (3) with 2 mol of the compound (8) added as a by-product. The excess diamine (3) can be removed by washing with a solvent such as diethyl ether after the reaction. The reaction is preferably carried out at room temperature to 120 ° C, particularly 40 to 90 ° C. Further, as a solvent, methanol-
Water, ethanol-water, propanol-water, etc. can be used. The inorganic salt produced as a by-product after the reaction can be removed by electrodialysis or the like.

(Second Step) The 2-1 step and the 2-2 step are the 2-1 step and the 2-2 step in the manufacturing method 1.
It can be performed under the same conditions as in the process.

The N-substituted diaminodicarboxylic acid of the present invention or the salt thereof (1) thus obtained contains an organic salt or an inorganic salt in the production process, and these are purified by electrodialysis or the like and used. However, depending on the purpose, it may be used while containing them. Further, the N-substituted diaminodicarboxylic acid or its salt (1) of the present invention can be used as a surfactant alone or in combination with a conventionally known anion, cation or nonionic surfactant.

[0024]

INDUSTRIAL APPLICABILITY The N-substituted diaminodicarboxylic acid or its salt (1) of the present invention is a novel compound, which has excellent surface-active ability and high hard water resistance and foaming resistance.
It is useful in a wide range of industrial fields.

[0025]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Synthesis of 3- (lauryl-amino) -propyl-glucamine 3- (lauryl-amino) -propylamine 97.0 g (
0.4 mol), 72.1 g (0.4 mol) of glucose, 250 g of ethanol and 5.8 g of 5% palladium carbon were charged into an autoclave and reacted at 60 ° C. for 7 hours at a hydrogen pressure of 40 kg / cmG. After completion of the reaction, the solution was extracted and 2 l of ethanol was added to carry out recrystallization. The crystals were filtered, washed with acetone, and dried under reduced pressure at room temperature overnight to give 3- (lauryl-
Amino) -propyl-glucamine 96.7 g (yield 58.1%)
Got The analytical values are shown in Table 1 and were in good agreement with the theoretical values. Further, when gas chromatography was performed after trimethylsilylation, a single peak was found.

[0026]

[Table 1]

(2) Carboxymethylated 3- (lauryl-amino) -propyl-glucamine 41.6
g (0.1 mol), sodium monochloroacetate 121.1 g
(1.04 mol), 38 g of ethanol and 61 g of water were charged, and 80
48% aqueous sodium hydroxide solution for 8 hours at 8 ° C
6.7 g (1.04 mol) was added dropwise and then aged at 80 ° C. for 60 hours. After filtering to remove unnecessary parts, dilute with water,
By-product sodium chloride and sodium glycolate were removed by electrodialysis. Finally, freeze-drying is performed to obtain N- [3-
(N'-lauryl-N'-carboxymethyl-amino)
45.3 g (yield 80.0%) of -propyl] -N-carboxymethyl-glucan disodium salt was obtained. The analytical values are shown in Table 2.
, Which is in good agreement with the theoretical value.

[0028]

[Table 2]

Example 2 (1) Synthesis of N- [3- (N'-lauryl-amino) -propyl] -N- (2-hydroxy-3-sulfono-propyl) -amine sodium salt 3- (lauryl -Amino) -propylamine 52.5 g (
0.217 mol) and 200 ml of ethanol are charged, and
A solution of 10.6 g (0.054 mol) of sodium 3-chloro-2-hydroxypropyl sulfonate and 200 ml of water at 80 ° C.
Dropped over time. Next, a solution of 2.16 g (0.054 mol) of sodium hydroxide and 20 ml of water was added dropwise at the same temperature over 30 minutes. After aging for 2 hours and 30 minutes at 80 ° C, concentrate the reaction mixture,
The solid content was washed with ether to remove excess starting amine. After vacuum drying, the mixture was extracted with methanol, the extract was dissolved in water, and electrodialysis was performed to remove salt. By concentrating the water and drying under reduced pressure, N- [3- (N'-lauryl-amino) -propyl] -N- (2-hydroxy-
3-Sulfono-propyl) -amine sodium salt 10.6
g (yield 38.5%) was obtained. Total amine value (KOH mg / g) is 2
76.6, which was in good agreement with the theoretical value of 278.9.

(2) Carboxymethylated N- [3- (N'-lauryl-amino) -propyl]-
N- (2-hydroxy-3-sulfono-propyl) -amine sodium salt 9.0g (0.0177mol) and water 200ml
A solution of 7.2 g (0.0470 mol) of methyl bromoacetate and 200 ml of methanol was added dropwise thereto at 65 ° C. for 1 hour. Next, add 3.8 g (0.09
A solution of 40 mol) and 20 ml of water was added dropwise at the same temperature for 1 hour and further aged at the same temperature for 24 hours. After the reaction, concentrate and
The solid content was washed with methanol, dissolved in water, and desalted by electrodialysis. After concentrating the water, it was vacuum dried to give N- [3- (N'-lauryl-N'-carboxymethyl-amino) -propyl] -N- (2-hydroxy-3-sulfono-propyl) -N. 9.0 g (yield 60.8%) of carboxymethyl-amine trisodium salt was obtained. Total amine number (KOH mg / g) is 397.8, theoretical 3
Good agreement with 99.0.

The surface tension, the critical micelle concentration (CMC) and the Kraft point of the calcium salt of the N-substituted diaminodicarboxylic acid of the present invention obtained in Examples 1 and 2 were measured.
The results are shown in Table 3.

[0032]

[Table 3]

As is clear from Table 3, the N-substituted diaminodicarboxylic acid of the present invention was found to be a surfactant having high water solubility of calcium salt and excellent hard water resistance.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms; M ¹ and M ² are the same or different and each is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, or ammonium. An ion, an alkyl ammonium ion having 1 to 5 carbon atoms, an alkanol ammonium ion having 2 to 9 carbon atoms or a basic amino acid group; Y represents an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group or a sulfonic acid group. Shown; m is a number from 1 to 9; n is 2 or 3
N-substituted diaminodicarboxylic acid or a salt thereof. 2. The general formula (1): (In the formula, R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms; M ¹ and M ² are the same or different and each is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, or ammonium. An ion, an alkyl ammonium ion having 1 to 5 carbon atoms, an alkanol ammonium ion having 2 to 9 carbon atoms or a basic amino acid group; Y represents an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group or a sulfonic acid group. Shown; m is a number from 1 to 9; n is 2 or 3
Of N-substituted diaminodicarboxylic acid or a salt thereof.