GB2278848A - 70% cleansing compositions containing solutions of glycinate compounds - Google Patents

70% cleansing compositions containing solutions of glycinate compounds Download PDF

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GB2278848A
GB2278848A GB9404740A GB9404740A GB2278848A GB 2278848 A GB2278848 A GB 2278848A GB 9404740 A GB9404740 A GB 9404740A GB 9404740 A GB9404740 A GB 9404740A GB 2278848 A GB2278848 A GB 2278848A
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solution
process according
acid
weight
water
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Guenter Hiller
Axel Holstein
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Rewo Chemische Werke GmbH
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/02Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00Carboxylic acid amides
    • C07C233/01Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/36Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds

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Description

2278848 91 Solutions of qlvcine compounds and process for their
Preparation The invention relates to solutions of amphoteric glycine compounds and, more particularly, to solutions of glycine compounds in organic solvents and to processes for their preparation.
Among the various surface-active amphoteric surfactants, the so-called glycine derivatives or glycinates have found particular interest because of their particularly good environmental compatibility, allround applicability and tolerability. As a result of their excellent skin tolerabilities and low eye irritations, combined with good cleaning properties, they are finding a growing market in personal hygiene and body cleaning compositions.
The preparation of the glycinates is the subject of a multiplicity of patents and general specialist publications such as, for example, US Patents 2 781 354, 3 231 580, 3 408 361, 3 941 817; H. Hoffmann, Seifen 6le - Fette - Wachse, 95, 3 [1969]; H. Hein, Fette Seifen Anstrichsmittel, 448 [1978]; U. Ploog, Fette Seifen - Anstrichsmittel, 154 [1979].
According to this literature, the preparation is carried out in two reaction stages:
1. The preparation of the 2-alkylimidazoline and 2. The preparation of the glycinate by further reaction with sodium chloroacetate.
In the first stage, the fatty acids are reacted with aminoethylethanolamine (AEEA) at temperatures of 170 to 220C and pressures of 10 to 50 mbar to give the corresponding imidazoline compounds.
In the second stage, the glycinates are prepared by addition of aqueous alkaline chloroacetic acid or alkali metal chloroacetate solution at 80 to 9WC with ring opening.
These solutions, which mainly contain the compounds 10 of the general formulae I and II R-COM-CH2-CH2-N-CH2-COO-K+ I 1 -;n2--;"2-OH R-CO-N-CH2-CH2-NH-CH2-COO-N+ II 1 CH2-CH2-OH and at the same time still contain small amounts of diamides and ester amides, come onto the market as 20 to 40% strength by weight solutions without further preparation, that is to say containing the alkali metal salts formed during the reaction.
These solutions no longer meet the requirements in practice in respect of their low concentration and their high water content and their content of inorganic salts.
Their low concentration increase both storage and transport costs; their high water content is undesirable in a multiplicity of cosmetic care products and in particular their content of inorganic salts in some cases drastically restricts the possibilities of use.
The latter is the case in e.g. viscous hair - 3 shampoos, in which the content of sodium chloride decreases the viscosity to an undesired extent or in bath oils, in which the natural oils can be salted out, and in wax-containing formulations such as in wax floor finishes, in which the stability of the final product is unfavourably affected.
As a result of the known corrosive properties, in particular of sodium chloride, these solutions are not suitable for aluminium cleaners, car shampoos and other metal cleaners and polishes.
Besides the disadvantageous effects mentioned, the combinability with other active ingredients is also affected, as the content of inorganic salts can have a demulsifying effect.
There was therefore a need for glycinates which do not have these disadvantages and meet the increased requirements in practice, that is to say which can be both stored and transported cost- effectively and which can be combined with a multiplicity of additional components to give utilizable formulations in the desired application areas.
An object of the present invention was therefore to make available glycine compounds with appropriate properties and to find a process for their preparation.
The present invention provides solutions of glycine compounds in organic solvents having contents of glycine compounds of at least 70% by weight, the solutions in general having contents of inorganic salts of not more than 1-9.- by weight.
The invention therefore relates to highly concentrated solutions having contents of at least 70% by weight, relative to the total solution, of glycine compounds of the general formulae R-CONH-CH2-CH2-N-CH2-COO_M+ I R-CO-N-CH2-CH2-NH-CH2-COO_M+ II I -;n2_';ft2-OH in which R has 5 to 19, preferably 11 to 17, carbon atoms and is the alkyl radical of a natural or synthetic monobasic fatty acid or of a fatty acid mixture and M+ represents the cation of an alkali metal or alkaline earth metal, in organic solvents and optionally small amounts of water. One or more alcohols selected from mono- and polyhydric alcohols may be present as solvent. The content of inorganic salts may be less than 1% by weight, preferably less than about 0.5% by weight, based on to the total mixture. The metal may advantageously be sodium or calcium.
According to-the invention there is provided a process for the preparation of solutions including at least 70% by weight based on the total solution, of glycine compounds of the general formulae R-CONH-CH2-CH2-N-CH2-COO_M+ -;n2-;n2-OH R-CO-N-CH2-CH2-NH-CH2-COO_M+ I ;n2--;n2-OH I II 1 in which R has 5 to 19 carbon atoms and is the alkyl radical of a natural or synthetic monobasic fatty acid or of a fatty acid ester and M represents an alkali metal or alkaline earth metal, the process comprising a first step in which one or more compounds selected from monobasic fatty acids having 6 to 20 carbon atoms and the esters of said acids is reacted with aminoethylethanolamine (AEEA) at a temperature of 150c to 2500C and continuous removal of the resulting condensate, and removal of the residual condensate and of unreacted AEEA; a second step in which the product of the first step is diluted with organic solvent and is treated with water; 15 a third step in which anydrous halocarboxylic acids or their salts are added to the reaction mixture of the second step and the mixture is then heated, the pH is kept in the range of 8 to 11 by the addition of bases; and 20 a fourth step in which inorganic salt which precipitates from the mixture is removed, and the content of glycine compounds in the solution is adjusted, if necessary, to at least 70% by weight by the removal of solvents present in the mixture. 25 According to a further aspect of the invention there is provided a process for the preparation of highly concentrated solutions having contents of at least 70% by weight, based on the total solution, of glycine C compounds of the general formulae R-CONH-CH2-CH2-N-CH2-COO-N+ R-CO-N-CH2-CH2-NH-CH2-COO-N+ 1 I ;'2-';'2-OH in which R has 5 to 19 carbon atoms and is the alkyl radical of a natural or synthetic monobasic fatty acid or of a fatty acid ester, and M+ represents the cation of an alkali metal or alkaline earth metal, comprising a first step in which monobasic fatty acids having 6 to 20 carbon atoms, preferably 12 to 18 carbon atoms, or their esters with lower monofunctional alcohols or triglycerides thereof or mixtures thereof are reacted, with stirring and in an inert gas atmosphere, with 0.5 to 2 molar excesses of aminoethyl- athanolamine (AEEA), if appropriate with additional use of catalysts, at 150 to 2500C, preferably 170 to 2300C, the resulting condensate and the excess AEEA being distilled off continuously, optionally at reduced pressures of 10 to 50 mbar, a second step in which the reaction product is cooled to not more than 1000C, is diluted to about 30 to 60% by weight, preferably about 40 to 50% by weight, with organic solvents, in particular short-chain mono- and/or polyfunctional alcohols and hydrolyzed with the stoichiometric amount of water needed for ring opening, if appropriate with additional use of basic catalysts, a third step in which a halocarboxylic acid or its salt is added to the reaction mixture at about 20 to 500C in equivalent amounts, the reaction mixture is heated to about 50 to 1OCC, preferably about 60 to 800C, and kept at this temperature for about 6 to 12 hours and the pH of the reaction mixture is kept in the range from about 8 to 5 11, preferably around about 10, by continuous or batchwise addition of bases in solid form or as alcoholic solutions, and then the inorganic salt precipitating from the reaction solution is separated off by customary technical separation processes.
Following this, the low-boiling solvents which may be present can be removed, if necessary, by distillation. In this case, relatively high-boiling solvents such as, in particular, glycerol and/or propylene glycol are added to begin with in amounts which correspond to a 70 to 95%, preferably 80 to 90% strength by weight final solution of the glycine compound.
Where M+ represents the cation of an alkali earth metal, it will be understood that each metal ion is associated with two glycinate ions and M+ represents one metal cation equivalent rather than one metal cation.
The concentrated solutions of the invention can be stored or transported without problems and, depending on the desired area of use, adjusted to the required concentration directly on site using the customary solvents and mixed with the customary additives and auxiliaries. The solutions may contain small amounts of water.
The glycine compounds prepared by means of the process according to the invention are industrial mixtures which, in addition to the compounds of the general formulae I and II, can contain further compounds. These may be, inter alia, small amounts of fatty acids or their derivatives, MEA, diamides and ester amides as well as reaction products thereof with the halocarboxylic acids or salts thereof.
If these reaction products remain homogeneously in the concentrated organic solution, they are likewise the subject of the present invention.
The reaction of the fatty acids (1 mol) with the aminoethylethanolamine (1 to 2.5, preferably 1.8 to 2.2 mol) in the first step is carried out by processes known per ge. The first step may, at least in part, be conducted at reduced pressure, for example, at a pressure in the range of from 10 to 50 mbar. In one suitable process, the components are heated to 150 to 180C, under an inert gas atmosphere, optionally additionally using a catalyst, and the liberated condensate such as water or alcohol is continously removed. By further heating of the resultant monoamide to 180 to 2500C, preferably 180 to 2300C, the imidazoline compound is formed with ring closure with liberation of a further mole of water. At constant temperature, the pressure is gradually reduced to 10 to 50 mbar in order to remove all the water of reaction and excess amine in the course of 14 to 20 hours.
In addition to the imidazoline compound (about 64 to C1 94% by weight), the reaction mixture can still contain, depending on the reaction conditions, relatively large amounts of secondary monoamide (about 30 to 3% by weight) as well as small amounts of tertiary monoamide, diamide, ester amide and free aminoethylethanolamine. In accordance with the invention, the reaction conditions may be so adjusted that degrees of cyclization of at least 90% by weight are achieved.
The fatty acids employed can be the commercially available natural or synthetic monobasic acids having 6 to 20, preferably 12 to 18, carbon atoms. The fatty acids may be used in the form of an ester. Examples of suitable fatty acids are caproic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid. Examples of suitable esters are the methyl, ethyl, propyl or butyl esters of those acids. Preferred according to the invention are the naturally occurring vegetable and animal glycerol esters such as coconut oils, castor oil, palm kernel oil, palm oil, olive oil, groundnut oil, rape oil and corn oil. The fatty acid or ester may be used alone or in with one or more further suitable fatty acids or esters. It-will be appreciated that, where mixtures of fatty acids or esters are used, the solutions of the invention may include, as the glycine component, mixtures of two or more compounds of the general formula I in which the nature of the radical R differs, and corresponding mixtures of compounds of general formual II.
- 10 c Aminoethylethanolamine (AEEA) is one of the normal commercially available products.
Undesired constituents can be removed from the reaction mixture of the first stage by the customary purification methods; as a rule, however, the mixture is directly hydrolyzed in a second stage by cooling to temperatures of not more than 1000C. Preferably, the product is diluted with organic solvent to about 30 to 60% by weight. Expediently, the solvents chosen are such that at least a proportion, and preferably a major proportion, of the solvents added have a boiling point, under normal pressure or vacuum, lower than 1000C using short-chain alcohols such as ethanol, propanol, isopropanol and/or glycerol, ethylene glycol or propylene glycol and then hydrolyzing the imidazoline compound to the corresponding open-chain amides using the stoichionetric amount, preferably at most twice the amount, of water needed for purification, optionally additionally using basic catalysts such as alkoxides, alkali metal hydroxides or alkali metal carbonates, at temperatures of 20 to 900C, preferably 50 to 80C.
Mainly formed in this process are the compounds of the general formulae III and IV R-CONH-CH2-CH2-NH-CH2-CH2-OH CH2-CH2-OH R-CO-N CH2-CH2-NH2 in which R is the radical of the monocarboxylic acid III IV C.
employed.
Anhydrous halocarboxylic acids or alkali metal salts thereof are added to this mixture and the pH of the mixture is kept in the range 8 to 11, preferably 9 to 10, for 6 to 12 hours at 50 to 1000C, preferably 60 to 800C, with good stirring with additions of bases - in anhydrous solid form or as alcohol solutions - and then the inorganic salt precipitating from the reaction mixture is removed by the customary technical separation processes such as centrifugation and/or filtration.
The use of ion exchangers on their own or in combination with a customary separation process is likewise possible. Ion exchangers which can be used are the commercially available products.
When using excess water in the ring cleavage and technical alcohols which can contain small amounts of water, this must be removed by distillation by means of suitable azeotropic mixtures before salt separation. If desired, suitable molecular sieves can also be employed.
The hydrolysis of the second step may be carried out in one or more alcohols selected from mono- and polyhydric alcohols having 2 to 10 carbon atoms in the chain, optionally interrupted by one or more oxygen atoms. The or each said alcohol may advantageously be selected from ethanol, isopropanol, n-propanol, ethylene glycol, propylene glycol, diethylene glycol and glycerol.
The halocarboxylic acids which can additionally be employed according to the invention are in particular - 12 nonochloracetic acid, nonobronoacetic acid, sodium monochloroacetate, potassium monochloroacetate, sodium monobromoacetate and potassium monobromoacetate.
The halocarboxylic acids or their salts are employed in at least stoichionetric amounts, relative to reactive amine groups, customarily in amounts of 1 to 3 mol, according to the invention preferably in amounts of 1.0 to 1.1 mol.
The bases which may additionally be used are, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide in solid form or as alcoholic solutions and sodium or potassium alkoxides such as sodium ethoxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
If desired, the low-boiling solvents which may be present are removed completely or partially from the reaction mixture by distillation. In this case, relatively high-boiling solvents which are desired in terms of application technology and physiologically acceptable, such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol or mono- and diethers thereof and in particular glycerol can be added to start with. The amounts are advantageously so selected that the content of glycine compound in the total mixture is 70 to 97% by weight. To establish a lower viscosity, water can optionally be additionally used, for example, in amounts up to about 10% by weight. The salt content, determined by the customary t potentiometric method for chloride determination (DGF (Deutsche Gesellschaft ftr Fettwissenschaften e.V.l Mfinster) method H-III 9), may be less than 1% by weight, mainly less than 0.5% by weight.
This high concentrate, which can contain, for example, about 70 to 95% by weight of glycine compound, to 25% by weight of organic solvent and 0 to 10% by weight of water and traces of inorganic salts can be stored without problems and is cost-effective to transport. Its viscosity corresponds to the requirements in practice with respect to further processing using the customary industrial pumps, apparatus and auxiliaries.
It will be appreciated that where reference is made herein to solutions of the compounds of formulae I and 11, those compounds may be in dissociated or undissociated form.
The following Examples will illustrate the invention. In the Examples, references to percentages are to percentages by weight, based on the total solution, except where indicated to the contrary.
Examples
A) Imidazoline DreDaration Exami:)1e 650 g (2.98 mol) of palm kernel oil (or the equivalent amount of another fat as an ester, glyceride C or fatty acid), 1 g of phosphoric acid (85% strength) and 650 g (6.25 mol) of aminoethylethanolamine are heated to 170C with stirring and under N2 and reacted until an ester band is no longer to be detected in the IR spectrum. Water or alcohol distill off during the course of this.
The excess amine is then distilled off at 170C and 5 mbar.
906 g of imidazoline (Overall amine number (OAN) 185 to 230. Tertiary amine number (TAN) 175) and 394 g of distilled AEEA with water of reaction are formed. TAN content: at least 90% (relative to molecular weight).
B) Preparation of the glycine compounds ExanDle 1 is 518 g (1.7 mol) of imidazoline according to Example A, 35 g (1.9 mol) of water and 400 g of isopropanol are treated with stirring with 260 g (2.2 mol) of Na monochloroacetate (100% strength) and the mixture is heated to 700C. About 68 g (1.7 mol) of NaOH (100% strength) are then introduced at 700C. The reaction material is then stirred at 700C until the alkalinity of the mixture remains constant and the analytical values saponifiable chloride: <0.05% free monochloroacetic acid <20 ppm are fallen short of. The reaction material is stirred until homogenous - is - with 300 g of isopropanol, then the resulting sodium Ir chloride is filtered off and the filter residue is washed 3 times with 100 ml of ispropanol. The combined filtrates are mixed with 130 g of propylene glycol. The isopropanol is then distilled off under vacuum (5 mbar) at 68 to 72C. Residual traces of isopropanol are removed by steam distillation corresponding to 30 g of water. After breaking the vacuum, 77 g of water are added.
During the course of the reaction, 131 g of sodium chloride and 922 g of product are formed having the following analytical data:
Nitrogen content 5.5% 72% active content as sodium salt is NaCl 0.2 to 0.4% Soap 0.1% Water 8.5% Propylene glycol 14% Glycerol 5.5% viscosity 4000 to 7000 mPa.s/200C Appearance yellow, clear liquid ExanDle 2 518 g (1.7 mol) of imidazoline according to Example A, 35 g of water and 400 g of butanol are treated with 260 g (2.20 mol) of monochloroacetic acid (80% strength) in H20 and the mixture is neutralized with 178 g (2.20 mol) of NaOH (50% strength) at 68 to 700C. Only about 136 g (1.7 mol) of NaOH (50% strength) in H20 are then metered in under vacuum (5 mbar) at 68 to 70'C and the mixture is stirred at 68 to 700C until the alkalinity of the mixture remains constant and H20 no longer distills and the analytical data saponifiable chloride: <0.05% free monochloroacetic acid: <20 ppm water <0.1% are fallen short of.
The reaction material is stirred until homogenous with 100 to 400 g of butanol, then the resultant sodium chloride is filtered off and the filter residue is washed with butanol. The combined filtrates are treated with 130 g of propylene glycol. The butanol is then distilled off under a vacuum of 5 mbar. Residual traces of butanol are removed by steam distillation corresponding to 30 g of water. After breaking the vacuum, 77 g of water or the desired solvent are added.
0 During the course of the reaction, 131 g of NaCl and 922 g of product are formed with the following analytical data:
2 Nitrogen content NaCl Soap Water Propylene glycol 5.5% by weight = 72% active content 0.2 to 0.4% 0.1% 8.5% 14% - 17 Ir Glycerol viscosity Appearance 5.5% 6000 to 7000 mPa.s/20'C yellow, clear liquid ExamDle 3 518 g of imidazoline, 35 g of H20, 400 g of isopropanol, 260 g of sodium salt of MCA, 68 g of NaOH (100% strength) are reacted as in Example B 1 and the reaction material is stirred until homogeneous with 100 to 400 g of isopropanol; 63 g of HCl gas are then passed in and the resulting sodium chloride is then filtered off and washed and the combined filtrates are further processed as in Example B 1.
230 g of sodium chloride and 869 g of product having the following analytical data are formed:
Nitrogen content 5.5% = 72% active content NaCl 0.2 to 0.4% Soap 0.1% Water or solvent 7% Propylene glycol Glycerol viscosity 15% 6% 30,000 mPa.s/200C ExamDle 4 The procedure is as in Example 3, but instead of 63 g of HCl gas, 193 g of aqueous 30% strength HCl are 25 used and the water produced is removed by azeotropic distillation with butanol before the precipitated salt is f iltered.
After filtration, the combined filtrates are further processed as in Example B 1.
230 g of sodium chloride and 869 g of product having 5 the following analytical data are formed:
Nitrogen content 5.5% NaCl 0.2 to 0.4% 0.1% Soap Water or solvent Propylene glycol Glycerol viscosity 7% 15% 6% 30,000 mPa.s/20C Examnle 5 518 g (1.7 mol) of imidazoline according to Example A, 35 g (1.9 mol) of water and 400 g of isopropanol are treated with 450 g (3.86 mol) of Na monochloroacetate (100% strength) with stirring and the mixture is heated to 700C. About 126 g (3.15 mol) of NaOH (100% strength) are then introduced at 70C. The reaction material is stirred at 70C until the alkalinity of the mixture remains constant and the analytical values saponifiable chloride: <0.05% free monochloroacetic acid <20 ppm are fallen short of.
The reaction material is stirred with 300 g of isopropanol until homogenous, then the resultant sodium chloride is filtered off and the filter residue is washed 1 Ir 3 times with 100 ml of isopropanol.
The combined filtrates are treated with 255 g of propylene glycol. The isopropanol is then distilled off under vacuum (5 mbar) at 70C (68 to 72). Residual traces of ispropanol are removed by steam distillation corresponding to 30 g of water. After breaking the vacuum, no water is added.
During the course of the reaction 225 g of sodium chloride and 1094 g of product having the following 10 analytical data are formed:
Nitrogen content 5.2% = 72% active content as the sodium salt 0.2 to 0.4% 0.1% 0.2% 23.3% 4.7% 10,000 to 40,000 mPa.s/200C 1000 to 2000 mPa.s/450C.
Viscous, yellow, clear liquid NaCl Soap Water Propylene glycol Glycerol viscosity Appearance 200C Example 6 518 g (1.7 mol) of imidazoline according to Example A, 35 g of water and 400 g of butanol are treated with 460 g (3.86 mol) of monochloroacetic acid (80% strength) 25 in H20. The mixture is neutralized at 68 to 70'C with 312 g (3.86 mol) of NaOH (50% strength). About 252 g (3.15 mol) of NaOH (50% strength) in H20 are then metered - 20 in at 68 to 70C under vacuum and the mixture is stirred at 68 to 700C until the alkalinity remains constant and H20 no longer distills and the analytical data saponifiable chloride 5 free monochloroacetic acid water content are fallen short of.
<O. 05% <20 ppm <O. 1% The reaction material is stirred with 100 to 400 g of butanol until homogeneous, then the resultant sodium chloride is filtered off and the filter residue is washed with butanol.
The combined filtrates are treated with 225 g of propylene glycol. The butanol is then distilled off under a vacuum of 5 mbar. Residual traces of butanol are removed by steam distillation corresponding to 30 g of water. After breaking the vacuum, no water is added.
During the course of the reaction, 226 g of NaCl and 1094 g of product having the following analytical data are formed:
Nitrogen content 4.7% = 72% active content as the sodium salt 0.2 to 0.4% 0.1% 0.2% 23.3% 4.7% 10,000 to 40,000 mPa.s/20C 1000 to 2000 mPa.s/450C NaCl Soap Water Propylene glycol Glycerol viscosity i Appearance viscous, yellow, clear liquid ExanDle 7 According to Example 5 or 6, a glycinate solution is prepared, the sodium chloride is filtered off and the filter residue is washed 3 times with 100 ml of the corresponding solvent.
The combined filtrates are treated with 30 g of propylene glycol. The isopropanol is then distilled off under vacuum (5 mbar) at 68 to 720C. Residual traces of isopropanol are removed by steam distillation corresponding to 30 g of water. After breaking the vacuum, 225 g of water are added.
During the course of the reaction, 225 g of sodium chloride and 1094 g of product having the following analytical data are formed:
Nitrogen content 4.7% = 72% active content as the sodium salt 0.2 to 0.4% 0.1% 20.6% 2.7% 4.7% 7,000 to 9,000 mPa.s/200C yellow, clear liquid Example 8
NaCl Soap Water Propylene glycol Glycerol viscosity Appearance 200C 518 g (2.13 mol, relative to OAN 230) of imidazoline n according to Example A, 35 g (1.9 mol) of water and 400 g of isopropanol are treated with stirring with 360 g (2.62 mol) of Na monochloroacetate (100% strength) and the mixture is heated to 700C. About 80 g (2.05 mol) of NaOH (100% strength) are then introduced at 700C. The reaction material is then stirred at 70cC until the alkalinity of the mixture remains constant and the analytical values saponifiable chloride <0.05% free monochloroacetic acid <20 ppm are not fallen short of.
The reaction material is stirred with 300 g of isopropanol until homogenous, then the resultant sodium chloride is filtered off and the filter residue is washed 3 times with 100 ml of isopropanol.
The combined filtrates are treated with 120 g of propylene glycol. The isopropanol is then distilled off under vacuum (5 mbar) at 68 to 720C. Residual traces of isopropanol are removed by steam distillation corresponding to 30 g of water. After breaking the vacuum, 100 g of water are added.
During the course of the reaction, 154 g of sodium chloride and 969 g of product having the following analytical data are formed:
Nitrogen content NaCl Soap 5.4% = 72% active content as the sodium salt 0.2 to 0.4% 0.1% i fl Water Propylene glycol Glycerol viscosity Appearance 10.3% 12.4% 5.3% 6,000 to 8,000 mPa.s/200C yellow, clear liquid Example 9
518 g (1.7 mol) of imidazoline according to Example A and 129 g of propylene glycol are mixed with stirring with 165 g (2.06 mol) of aqueous, 50% strength sodium hydroxide solution and neutralized with 243 g (2.06 mol) of aqueous, 80% strength monochloroacetic acid at 30 to 700C, preferably 480C.
After neutralization is complete, evacuation is carried out and 137 g (1. 71 mol) of aqueous, 50% strength sodium hydroxide solution are simultaneously metered in, it being intended for the acid number in the mixture to vary between -2 and +2. During the addition of sodium hydroxide solution 211 g of water distill; the vacuum is between 5 and 120 mbar. The vacuum distillation (at an acid number of -2 to +2 in the bottom) is continued, for about 6 hours, until analyses reveal that the monochloroacetic acid content is <20 ppm dichloroacetic acid content <50 ppm water content <3% Further treatment as Example 1.
ExamDle 10 518 g (1.7 mol) of imidazoline according to Example A and 119 g of propylene glycol are evacuated to 150 mbar with stirring. At the sametime, 302 g (3.77 mol) of aqueous, 50% strength sodium hydroxide solution and 243 g (2.06 mol) of aqueous, 80% strength monochloracetic acid are metered in alternately, the acid number in the distillation bottom being 2 and +2 - in about 6 hours. Water distills off and the vacuum is increased stepwise to 5 to 40 mbar; the bottom temperature is 30 to 50C. This distillation is continued until an analysis shows that the monochloroacetic acid content is <20 ppm dichloroacetic acid content <50 ppm water content <3% by weigh Further treatment as Example 1.
i A -.a-- ' - 25 claims 1. A solution containing at least 70% by weight, based on the total solution, of glycine compounds of the general formulae:
E.
R-COM-CH2-CH2-N-CH2-COO-M+ 1 ;n2-'"2-OH R-CO-N-CH2-CH2-M-CH2-COO-M+ 1 CH2-CH2-OH I II in which R has 5 to 19 carbon atoms and is an alkyl radical of a natural or synthetic monobasic fatty acid, and M+ represents the cation of an alkali metal or alkaline earth metal, in organic solvents.

Claims (1)

  1. 2. A solution according to Claim 1, wherein one or more alcohols selected
    from mono- and polyhydric alcohols are present as solvent.
    3. /A solution according to Claim-1 or claim 2, wherein the solution contAdns not more than 1% by weight, 20 based on the total solution, of inorganic salts.
    4. A solution according to claim 3, wherein the solution contains less than 0.5% by weight, based on the total solution, of inorganic salts.
    5. A solution according to any one of claims 1 to 25 4, wherein the solution also contaIns water.
    6. A solution according to anyone of claims 1 to 5, wherein R has 11 to 17 carbon atoms.
    7. A solution according to any one of claims 1 to t, 0 6, wherein M is sodium or calcium.
    8. A solution according to any one of claims 1 to 7, wherein R is the alkyl radical of a fatty-acid selected from caproic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid.
    9. A solution according to any of claims 1 to 7, wherein R is the alkyl radical of a naturally occurring vegetable or animal glycerol ester.
    10. A solution according to claim 9, wherein R is an alkyl radical derived from coconut oil, castor oil, palm kernel oil, palm oil, olive oil, groundnut oil, rape oil or corn oil.
    11. A solution containing at least 70% by weight based on the total solution of glycine compounds of the general formulae R-CONH-CH2-CH2-N-CH2-COO-M+ 1 ;n2--;"2-OH R-CO-N-CH2-CH2-NH-CH2-COO-M+ 1 .;12-'-;n2-OH the solutions being substantially as herein described.
    12. A process for the preparation of solutions including at least 70% by weight based on the total solution, of glycine compounds of the general formulae I II i (---1 1 R-CONH-CH2-CH2-N-CH2-COO-14+ 1 CH2-CH2-OH R-CO-N-CH2-CH2-NH-CH2-COO-N+ 1 "2-CH2-0H I II in which R has 5 to 19 carbon atoms and is the alkyl radical of a natural or synthetic monobasic fatty acid and M represents an alkali metal or alkaline earth metal, the process comprising a first step in which one or more compounds selected from monobasic fatty acids having 6 to 20 carbon atoms and the esters of said acids is reacted with aminoethylethanolamine (AEEA) at a temperature of 150C to 250'C and continuous removal of the resulting condensate, and removal of the residual condensate and of unreacted AEEA; a second step in which the product of the first step is diluted with organic solvent and is treated with water; a third step in which anydrous halocarboxylic acids or their salts are added to the reaction mixture of the second step and the mixture is then heated, the pH is kept in the range of 8 to 11 by the addition of bases; and a fourth step in which inorganic salt which precipitates from the mixture is removed, and the content of glycine compounds in the solution is adjusted, if necessary, to at least 70% by weight by the removal of n solvents present in the mixture.
    13. A process according to claim 12, wherein in the first step the fatty acid or its ester is reacted with 0.5 to 2.5 molar excesses of MEA.
    14. A process according to claim 12 or claim 13, wherein in the first step a catalyst is used.
    15. A process according to any of claims 12 to 14, wherein the first step is carried out at reduced pressure.
    16. A process according to claim 15, wherein the first step is carried out at a pressure of 10 to 50 mbar.
    17. A process according to any of claims 12 to 16, wherein in the second step the dilution with organic solvent is at a temperature below 1000C.
    18. A process according to any of claims 12 to 17, wherein in the second step the product is diluted with organic solvent to about 30 to 60% by weight.
    19. A process according to any of claims 12 to 18, wherein in the second step basic catalysts are also added.
    20. A process according to any of claims.12 to 19, wherein in the second step the diluted product is treated with water at a temperature of 20 to 900C.
    21. A process according to any of claims 12 to 20, wherein the amount of water added is not more than twice the stoichiometric amount required for ring opening.
    22. A process according to claim 21, wherein the amount of water added is substantially the stoichiometric i r amount required for ring opening.
    23. A process according to any of claims 12 to 22, wherein the third step is carried out at a temperature of to 1000C.
    24. A process according to any of claims 12 to 23, wherein the third step is continued for 4 to 12 hours.
    25. A process according to any of claims 12 to 24, wherein in the third step the bases added are in the form of anhydrous solid or are alcoholic solutions.
    26. A process according to any of claims 12 to 25, wherein in the fourth step, solvents present in the reaction mixture are distilled off after or simultaneously with the addition to the mixture of higher boiling point solvents.
    27. A process according to any of claims 12 to 26, wherein the hydrolysis of the second step is carried out in one or more alcohols selected from mono- and polyhydric alcohols having 2 to 10 carbon atoms in the chain, optionally interrupted by one or more oxygen atoms.
    28. A process according to claim 27, wherein the or each alcohol employed is selected from ethanol, isopropanol, n-propanol, ethylene glycol, propylene glycol, diethylene glycol and glycerol.
    29. A process according to any of claims 12 to 28, wherein the halocarboxylic acid employed is chloroacetic acid or sodium chloroacetate.
    30. A process according to any of claims 12 to 29, r wherein the reaction in the first step is carried out using one or more of the naturally occurring triglycerides and a 2-molar excess of aminoethylethanolamine, the hydrolysis of the second step is carried out in a 30 to 60% strength alcoholic solution using equinolar amounts of water and in a third step the pH during the reaction is kept at 9.5 to 10.5 using solid sodium hydroxide.
    31. A process according to any of claims 12 to 30, wherein after the removal of the inorganic salt, the reaction mixtures are adjusted to the desired final concentration with propylene glycol and/or glycerol and the contents of low-boiling organic solvents are removed by distillation.
    32. A process for the preparation of highly concentrated solutions having contents of at least 70% by weight, based on the total solution, of glycine compounds of the general formulae R-CONH-CH2-CH2-N-CH2-COO-14+ 1 k;n2-k;n2-OH R-CO-N-CH2-CH2-NH-CH2-COO-N+ 1 CH2-CH2-OH I II in which R has 5 to 19 carbon atoms and is the alkyl radical of a natural or synthetic monobasic fatty acid or of a fatty acid ester and M+ represents the cation of an alkali metal or alkaline earth metal, by reaction in a first step of monobasic fatty acids having 6 to 20 carbon atoms with 0. 5 to 2 molar excesses of aminoethylethanolamine (AEEA), optionally additionally using catalysts, at temperatures of 150 to 2500C and continuous removal of the resulting condensate, and removal of the residual condensate and of the excess AEEA at optionally reduced pressures of 10 to 50 mbar and in which in a second step the reaction product cooled to a temperature of below 1000C, is diluted with organic solvents to 30 to 60% by weight, treated with the stoichiometric amount of water and, if desired, basic catalysts needed for ring opening and at temperatures of 20 to 900C the imidazoline compounds are hydrolyzed to the corresponding open-chain amides and in which in a third step anhydrous halocarboxylic acids or their salts are added to the reaction mixture, the reaction is continued for 4 to 12 hours at 50 to 1000C and the pH is kept in the range from 8 to 11 by addition of bases - in anhydrous solid form or as alcoholic solutions, and in a fourth step the inorganic salt precipitating from the reaction mixture is removed, low- boiling organic solvents are if necessary distilled off to the desired extent and, prior to or simultaneously with their removal, the content of the glycine compounds in the highly concentrated solution is adjusted to at least 70% by weight, based on the total solution, by addition of desired relatively high-boiling solvents.
    33. A process for the preparation of solutions of the general formulae R-COM-CH2-CH2-N-CH2-COO-M+ 1 "2--;"2-OH R-CO-N-CH2-CH2-M-CH2-COO-M+ 1 CH2-CH2-OH I II the process substantially as herein described.
    34. A process for the preparation of highly concentrated glycine solutions, said process being substantially as described in any of Examples 1 to 10 herein.
    35. A solution of glycine compounds which has been prepared according to a process as claimed in any of claims 1 to 32.
    36. A solution according to claim 35, which contains from 70 to 95% by weight of glycine compounds, from 5 to 25% by weight of organic solvents and from 0 to 10% by weight of water.
    37. The use of a solution according to any one of claims 1 to 11, 35 and 36 in the manufacture of a cosmetic care product.
    0
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US5744063A (en) * 1993-10-12 1998-04-28 Rhone-Poulenc Inc. Higher purity imidazoline based amphoacetate surfactants and processes for the preparation thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1317863B1 (en) * 2000-02-29 2003-07-15 Vama Farmacosmetica S R L MANUFACTURE AND USE OF AMPHOGLICINATES FROM VEGETABLE OILS AND BUTTERS.
US7122690B1 (en) 2006-02-14 2006-10-17 E. I. Du Pont De Nemours And Company Process to prepare metal complex of N,N-bis(2-hydroxyethyl)glycine

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US3408361A (en) * 1967-04-05 1968-10-29 Hans S. Mannheimer Methods for producing imidazolines and derivatives thereof
EP0160507A2 (en) * 1984-04-25 1985-11-06 Eric Graham Fishlock-Lomax Shampoo compositions

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US2781354A (en) * 1956-03-26 1957-02-12 John J Mccabe Jr Imidazoline derivatives and process
WO1986002549A1 (en) * 1984-11-01 1986-05-09 FARRISH, Bryan, Harold (legal representative of FA Disinfectant and cleansing compositions

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US3408361A (en) * 1967-04-05 1968-10-29 Hans S. Mannheimer Methods for producing imidazolines and derivatives thereof
EP0160507A2 (en) * 1984-04-25 1985-11-06 Eric Graham Fishlock-Lomax Shampoo compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5744063A (en) * 1993-10-12 1998-04-28 Rhone-Poulenc Inc. Higher purity imidazoline based amphoacetate surfactants and processes for the preparation thereof
US5952291A (en) * 1993-10-12 1999-09-14 Rhodia Inc. Process for the preparation of high purity imidazoline based amphoacetate surfactants
US6057282A (en) * 1993-10-12 2000-05-02 Rhodia Inc. High purity imidazoline-based amphoacetate surfactants

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GB9404740D0 (en) 1994-04-27
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ES2077534B1 (en) 1996-07-01
DE4307709A1 (en) 1994-09-15
DE4307709C2 (en) 1998-04-09

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