DE19806583A1 - Process for the production of surfactants containing amido groups - Google Patents

Description

This invention relates to a method for producing surface active agents containing amido groups. More accurate expressed it relates to a process for the production of surfactants or surfactants that a Amido group (amido amino acid, betaine, etc.) contain the have a high storage stability and therefore with regard on the color and smell after a long period of storage stay excellent.

In recent years it has been required that surfactants that used in detergents, etc., various excellent properties in addition to the Surface activity, e.g. B. high biodegradability, high Have security and minor irritation to the skin. Good Known examples of surfactants that meet these requirements meet include surfactants containing amido groups such as Imidazoline surfactants, also with amido amino acid surfactants and betaine surfactants.

These amido group-containing surfactants such as imidazoline surfactants and Betaine surfactants are characterized in that they are for eyes and skin are not very irritating, and additionally have one excellent foaming and cleaning effect. In  In recent years, these surfactants containing amido groups increasingly in less irritating shampoos etc. than Main component due to the properties mentioned above used.

One of the requirements for the qualities of this surfactants containing amido groups, a good color and Maintain smell.

Surfactants containing amido groups can by Dehydrate / condense a fatty acid or ester of which with polyamine and subsequent addition reaction Monohaloalkylcarboxylic acid or salt thereof made will.

The fatty acids in the above reaction in general used are those that are natural Starting materials such as coconut oil or palm kernel oil occur and contain impurities such as unsaturated components. If they are stored for a long time, they will surfactants containing amido groups sometimes with regard to the Color or smell due to the oxidation of the impurities, etc. deteriorated. So it is necessary to do this Solve a problem.

To avoid the impurities like unsaturated components eliminated, the unsaturated became conventional Components saturated by hydrogenation. However, one must complicated equipment used in this process which makes this economically disadvantageous. Furthermore can not completely unsaturated components be saturated.

Accordingly, an object of this invention is a method for the economical and efficient production of to specify surfactant-containing surfactants, the one excellent color and smell even after a long time Can maintain storage time.

Under these circumstances, these inventors have intensive studies carried out and as a result a method of manufacture developed a surfactant containing amido groups, whereby the problems mentioned above can be solved.

Accordingly, this invention proposes a process for producing an amido group-containing surfactant, which comprises condensing a fatty acid or an ester thereof with a polyamine to produce an amino group-containing fatty acid derivative, and then reacting the obtained derivative with a monohaloalkyl carboxylic acid represented by the formula (I), or a salt thereof by adding an antioxidant, to prepare an amido group-containing surfactant:

XR ¹ COOY (I)

wherein X is a halogen atom, R ^{1 is} a linear or branched alkylene group having 1 to 4 carbon atoms and Y is a hydrogen atom or an alkali metal.

The fatty acid or ester thereof used in the present invention is illustrated by higher fatty acids having the formula (II) or esters thereof:

R ² COOR ³ (II)

wherein R ^{2 is} a linear or branched alkyl, alkenyl or hydroxyalkyl group having 7 to 23 carbon atoms; and R ^{3 represents} a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or the residue obtained by eliminating an acyloxy group from a glyceride.

Concrete examples thereof include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid and vegetable or animal oil fatty acids such as coconut oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, beef tallow, Babassuölfettsäure, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and whale oil fatty acid or methyl ester, ethyl ester and glycerides thereof and mixtures thereof. Among them, higher fatty acids or lower alkyl esters thereof, wherein R ^{3 is} a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, are preferred. Particularly preferred are fatty acids or esters thereof which occur in natural fats, in particular coconut oil, in which R ^{2 is} a linear alkyl group with 9 to 17 carbon atoms and R ^{3 is} a hydrogen atom or a methyl group.

Examples of the polyamine used in the present invention include alkylene polyamines, hydroxyalkyl polyamines and N- (Hydroxy lower alkyl) alkanolamines. Examples of Alkylene polyamines include ethylene diamine, diethylene triamine, Triethylenetetramine, dimethylaminopropylamine, Dimethylaminoethylamine, diethylaminopropylamine and Diethylaminoethylamine. Examples of the hydroxyalkyl polyamines include aminoethylethanolamine, aminoethylpropanolamine, Aminoethylbutanolamine, N-β-hydroxypropylpropylenediamine,  Hydroxyethyldiethylenetriamine and Hydroxyethyltriethylene tetramine. Examples of N- (Hydroxy-lower alkyl) alkanolamines include N-β Hydroxyethyl ethanolamine.

Among these polyamines, diamines represented by the formulas (III) and (IV) are preferred.

H ₂ NC ₂ H ₄ NHZ (III)

wherein Z is an alkylol group having 2 to 4 carbon atoms.

wherein R ⁴ and R ^{5 may be the} same or different and each an alkyl group having 1 to 3 carbon atoms; and a is a number from 2 to 3.

Among the diamines represented by the formula (III), it is preferred to use aminoethylethanolamine (H ₂ NC ₂ H ₄ NHC ₂ H ₄ OH), and it is particularly preferred to use dimethylaminopropylamine among the diamines represented by the formula (IV ), to use.

In the invention, a fatty acid or an ester thereof is first subjected to a condensation reaction with a polyamine to produce an amino group-containing fatty acid derivative. Examples of the amino group-containing fatty acid derivative include imidazoline compounds obtained by reacting fatty acids or esters thereof with hydroxyalkyl polyamines or hydroxyalkyl alkylene polyamines; Oxazoline compounds obtained by reacting fatty acids or esters thereof with N-β- (hydroxy-lower alkyl) alkanolamines; and amidoamines obtained by reacting fatty acids or esters thereof with dialkylaminoalkylene amines. Among these compounds, preferred compounds include imidazoline compounds represented by the formula (V):

wherein R ² and z each have the same meaning as defined above; and amidoamines represented by formula (VI):

wherein R ² , R ⁴ , R ⁵ and a each have the same meaning as above.

In the process, the fatty acid or ester thereof and the polyamine usually at a molar ratio from 1: 1 to 1: 2, preferably 1: 1 to 1: 1.5.

Next, the amino group-containing thus obtained Fatty acid derivative of an addition reaction with a Monohaloalkyl carboxylic acid represented by the formula (I), or subjected to a salt thereof to produce a surfactants containing amido groups.  

Examples of the monohaloalkyl carboxylic acids represented by the formula (I) used in the invention, or the salts thereof include monochloroacetic acid, Monobromacetic acid, monochloropropionic acid and Monobromopropionic acid and sodium salts and potassium salts thereof. Among these compounds are monochloroacetic acid and salts of which particularly preferred. It is preferred that Monohaloalkyl carboxylic acid or the salt thereof in a 1 to 3 times the molar amount, more preferably 1 to 1.15 times molar amount compared to the amino group-containing To use fatty acid derivative.

According to the present invention, for example, an imidazoline compound represented by the formula (V) is reacted with a monohaloalkylcarboxylic acid represented by the formula (I) or a salt thereof to produce an amido amino acid represented by the formula (VII):

wherein R ¹ , R ² , Y and z each have the same meaning as defined above.

Alternatively, an amidoamine represented by the formula (VI) is reacted with a monohaloalkylcarboxylic acid represented by the formula (I), or a salt thereof, to prepare a betaine compound having the formula (VIII)

wherein R ¹ , R ² , R ⁴ , R ⁵ and a each have the same meaning as above.

According to the addition reaction between the amino group-containing fatty acid derivative and Monohaloalkyl carboxylic acid represented by the formula (I) or the salt thereof through a well known system be performed.

For example, if the fatty acid derivative containing amino groups is an imidazoline compound occurs with the imidazoline using an aqueous alkali solution Ring opening and then a reaction with the Monohaloalkyl carboxylic acid or the salt thereof. It is preferred that the pH of the reaction mixture in one Range is kept from 8 to 11. The reaction temperature is preferably 50 to 90 ° C. The reaction can take place under atmospheric or elevated pressure.

If the amino group containing fatty acid derivative the above Amidoamine mentioned, the pH of the mixture from the Amidoamine with the monohaloalkyl carboxylic acid or salt of which held at 8 to 10 until the conversion to betaine is completed. Then it is preferred to adjust the pH upright within a range of 11.5 to 13 obtained so as to hydrolysis of the remaining Accelerate monohaloalkyl carboxylic acid salt. The The reaction temperature is preferably 50 to 100 ° C. The  Reaction can take place under atmospheric or elevated pressure be performed.

In the production of an amido group-containing surfactant the above process becomes an antioxidant to improve the Storage stability of the color and smell added. Although the antioxidant is fundamentally involved in any step can be added in the process, it is preferred that Antioxidant in the step of the addition reaction of the Monohaloalkyl carboxylic acid represented by the formula (I) or the salt thereof, to the amino group-containing one Fatty acid derivative or after completion Add addition reaction.

Examples of the antioxidant used in the present invention include hindered phenolic compounds such as dibutylhydroxytoluene and butylhydroxyanisole; Isoascorbic acid or alkali metal salts thereof, Isopropyl citrate, dl-α-tocopherol, nordihydroguajaretic acid and Propyl gallate. One of these connections or a combination of which can be used for this. Under these Antioxidants are preferred to be sterically hindered Phenolic compounds such as dibutylhydroxytoluene and Butylated hydroxyanisole to use and dibutylated hydroxytoluene particularly preferred.

If the antioxidant in the condensation reaction of the Fatty acid or its ester added with the polyamine it is preferred to add the antioxidant in an amount of 0.001 to 5% by weight, more preferably from 0.01 to 1.0% by weight, based on the fatty acid or ester thereof. If the antioxidant in the addition reaction of Monohaloalkyl carboxylic acid represented by the formula (I),  or the salt thereof to the amino group-containing one Fatty acid derivative or after completion of the addition reaction it is preferred to add this in an amount of 0.001 to 5% by weight, more preferably from 0.01 to 1.0% by weight, based on the amino acid-containing fatty acid derivative to admit.

This invention is discussed in more detail below Reference to the following embodiments described.

Unless otherwise stated, all refer Percentages by weight.

example 1 (Amidation)

In a five-necked flask (1 liter), which is equipped with a stirrer, Provide thermometer, reflux condenser and pressure gauge 207 g (molecular weight: 207) of coconut oil fatty acid given. Then it was heated to 180 ° C with Nitrogen gas heated through a capillary at 100 ml / h. As next 102 g (molecular weight: 102) Dimethylaminopropylamine added dropwise over 3 h and the Reaction mixture under the same conditions for 2 hours held. After confirmation that the acid value (AV) is no longer when 10 was, the reaction mixture was cooled to 50 ° C and taken out.

(Ampholysation)

The amidoamine obtained in the amidation step above was transferred to a four-necked flask (2 liters), which with  a stirrer, thermometer and reflux condenser was. Then 740 g of deionized water and 116.5 g Sodium monochloroacetate is fed and the resulting Mixture heated to 80 ° C. The pH in the reaction system was made up with a 40% aqueous solution of sodium hydroxide 10 and the reaction was carried out for 5 h. Then the reaction mixture was cooled to 50 ° C and its pH adjusted to 7 with 35% HCl. Next, 0.2 g Dibutylhydroxytoluene added. So one Reaction mixture comprising 30% N-cocoylaminopropyl-N, N-di Get methylglycine betaine.

Example 2 (Amidation)

Using the same reaction device as in Example 1 was the amidation by the same Reaction conditions carried out as in Example 1, with the Exception that a coconut oil fatty acid methyl ester in one Amount of 220.5 g (molecular weight: 220.5, 1 mole) instead the coconut oil fatty acid was used.

(Ampholysation)

Using the same reaction device as in Example 1 underwent the same reaction and treatment as in Example 1 performed, except that N- Cocoylaminopropyl-N, N-dimethylamine was used, which the above amidation step. Thus was receive a reaction mixture containing 30% N-cocoylaminopropyl Contained N, N-dimethylglycine betaine.  

Example 3 (Amidation)

Using the same reaction vessel as in Example 1 was the amidation by the same Reaction conditions carried out as in Example 1, with the Exception that a refined coconut oil in an amount of 220.5 g (molecular weight: 657.5) instead of the Coconut oil fatty acid was used.

(Ampholysation)

Using the same reaction device as in Example 1 underwent the same reaction and treatment as in Example 1 performed, except that N- Cocoylaminopropyl-N, N-dimethylamine described in the above Amidation step was obtained was used. Consequently a reaction mixture was obtained, the 30% N- Contained cocoylaminopropyl-N, N-dimethylglycine betaine.

Example 4 (Imidazolinization)

In a five-necked flask (1 liter), which is equipped with a stirrer, Thermometer, reflux condenser and pressure meter equipped 207 g (molecular weight: 207.1 mol) Given coconut oil fatty acid. Then nitrogen gas was over a capillary was blown in at 100 ml / h. Next 109.2 g (molecular weight 104, 1.05 mol) Aminoethylethanolamine added.  

As the reaction temperature due to the exothermic heat 100 ° C was increased, the reaction pressure to 400 mmHg adjusted and the reaction mixture at 200 ° C over 1 h warmed up. When the reaction temperature reached 200 ° C the pressure is reduced to 200 mmHg and the mixture at these Conditions held for 2 hours. Then the pressure further reduced to 5 mmHg over 3 h and the reaction was then accomplished. After cooling to 50 ° C Reaction mixture removed. By measuring the amine value it was found that the reaction mixture was 94% Contained imidazoline ring.

(Conversion to amido amino acid)

The imidazolinized reaction mixture obtained above was placed in a four-necked flask (2 liters) which with a stirrer, thermometer and reflux condenser was provided. Then 18 g of deionized water and 0.54 g Sodium hydroxide is added and the resulting mixture heated to 80 ° C and at the same temperature for 1 h held.

Next were 720 g of deionized water and 116.5 g Sodium monochloroacetate added at the same time. After 100 g of a 40% strength were obtained at a temperature of 70 ° C aqueous solution of NaOH was added over 2 h and then the resulting mixture aged 6 h. After cooling to 50 ° C the pH of the mixture was reduced to 7 with 35% HCl set. Then 0.3 g of dibutylhydroxytoluene added. The product thus obtained was one Reaction mixture comprising 30% [N-cocoyl-N'- (2-hydroxyethyl) -n'-sodium carboxymethyl] ethylenediamine.  

Example 5 (Amidation)

Using the same reaction device as in Example 1, the amidation was carried out under the same Reaction conditions carried out as in Example 1, with the Exception that a fatty acid obtained by dry Distillation of palm kernel oil, in an amount of 220 g (Molecular weight: 220) instead of coconut oil fatty acid was used.

(Ampholysation)

Using the same reaction device as in Example 1 underwent the same reaction and treatment as in Example 1 performed, except that N- (Palm kernel oil fatty acid) amidopropyl-N, N-dimethylamine, which in the the above amidation step was used. Thus, a reaction mixture was obtained, the 30% N- (Palm kernel oil fatty acid) amidopropyl-N, N-dimethylglycine betaine contained.

Example 6

The same reaction and treatment as in Example 1 were carried out carried out, with the exception that butylated hydroxyanisole as Antioxidant used in place of dibutylhydroxytoluene has been. There was thus obtained a reaction mixture comprising Obtained 30% N-cocoylaminopropyl-N, N-dimethylglycine betaine.  

Example 7

The reaction was carried out under the same conditions as in Example 1 performed, except that 0.1 g Dibutylhydroxytoluene as an antioxidant in the Amidation reaction was added. So one Obtained reaction mixture containing 30% N-cocoylaminopropyl-N, N-di contained methylglycine betaine.

Comparative Examples 1 to 3

The reaction was carried out in the same manner as in Examples 1 to 3, except that none Dibutylhydroxytoluene was added as an antioxidant. Consequently a reaction mixture was obtained which contained 30% [N- Contained cocoylaminopropyl-N, N-dimethylglycine betaine.

Comparative Example 4

The reaction was carried out in the same manner as in Example 4 with the exception that no dibutylhydroxytoluene was added as an antioxidant. So one Receive reaction mixture containing 30% [N-Cocoyl-N '- (2-hydroxy contained ethyl) -N'-sodium carboxymethyl] ethylenediamine.

Comparative Example 5

The reaction was carried out in the same manner as in Example 1 performed, except that a citric acid, the is a chelating agent as an antioxidant instead of Dibutylhydroxytoluene was added. So one Obtained reaction mixture containing 30% N-cocoylaminopropyl-N, N-di contained methylglycine betaine.  

Comparative Example 6

The reaction was carried out in the same manner as in Example 1 with the exception that instead of Dibutylhydroxtoluene 0.6 g sodium borohydride (SBH) as Antioxidant in ampholysis immediately after Regulate the pH of the reaction system to 10 with a 40% aqueous solution of sodium hydroxide were. A reaction mixture was thus obtained which was 30% N-Cocoylaminopropyl-N, N-dimethylglycine betaine contained.

The in Examples 1 to 7 above and Comparative Examples 1 to 6 obtained reaction mixtures regarding color and smell immediately after the Production and after storage in a thermostat at 50 ° C evaluated for 1 month according to the following criteria.

hue

The hue of each reaction mixture was reduced to Use of color comparison tubes immediately after the Manufactured and measured after storage at 50 ° C for 1 month.

Procedure for evaluating the smell

Immediately after preparation and after storage at 50 ° C for 1 month, each reaction mixture containing the amido group-containing surfactant was diluted with deionized water to obtain a 10% concentration. Then a 30 g portion of it was placed in a 100 ml Meyer flask equipped with a stopper and stored in a thermostat at 40 ° C for 30 minutes. Next, the stopper was removed and the smell was evaluated by 5 subjects according to the following criteria. The mean of the ratings was expressed by the four criteria described below.

criteria
4: no smell
3: slight smell
2: relatively strong smell
1: strong and irritating smell
E: Average from 3 to 4
G: 2 ≦ mean <3
M: 1.5 ≦ mean <2
B: 1 ≦ mean <1.5

Table 1

Claims (8)

1. A process for producing an amido group-containing surface active agent comprising condensing a fatty acid or an ester thereof with a polyamine to produce an amino group-containing fatty acid derivative, and then reacting the obtained derivative with a monohaloalkyl carboxylic acid represented by the formula (I), or one Salt thereof, by adding an antioxidant, to prepare an amido group-containing surface-active agent:
XR ¹ COOY (I)
wherein X is a halogen atom; R ^{1 represents} a linear or branched alkylene group having 1 to 4 carbon atoms and Y represents a hydrogen atom or an alkali metal. 2. The method of claim 1, wherein the fatty acid or ester thereof is a higher fatty acid having formula (II) or an ester thereof:
R ² COOR ³ (II)
wherein R ^{2 is} a linear or branched alkyl, alkenyl or hydroxyalkyl group having 7 to 23 carbon atoms and R ^{3 is} a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or the rest obtained by eliminating an acyloxy group from a glyceride. 3. The method according to claim 1 or 2, wherein the polyamine is an alkylene polyamine Hydroxyalkyl polyamine or a Is N- (hydroxy lower alkyl) alkanolamine. 4. The method according to any one of claims 1 to 3, wherein the monohaloalkyl carboxylic acid represented by the Formula (I), or the salt thereof monochloroacetic acid or the Salt of it is. 5. The method according to any one of claims 1 to 4, wherein the antioxidant is at least one compound selected from the group consisting of Dibutylhydroxytoluene, butylhydroxyanisole, isoascorbic acid or the alkali metal salt thereof, isopropyl citrate, dl-α- Tocopherol, nordihydroguajaretic acid and propyl gallate. 6. The method according to any one of claims 1 to 5, wherein the antioxidant in an amount of 0.001 to 5 wt .-%, based on the fatty acid or ester thereof or amino group-containing fatty acid derivative is added. 7. The method of claim 1, wherein the antioxidant Is dibutylhydroxytoluene. 8. The method of claim 1, wherein the antioxidant in the Step of the addition reaction of the monohaloalkyl carboxylic acid or the salt thereof or after completion of the Addition reaction is added.