Abstract:
An aqueous composition comprising solution of a betaine of the following general Formula I is disclosed Formula I 
                                 
in which R is an alkyl group of coconut fatty acids, preferably hydrogenated coconut fatty acids, or a fatty acid mixture which, on the average, corresponds to coconut fatty acids, wherein the solution has a solids content of at least 45% by weight, a pH of 4.5 to 8, an amidoamine content of not more than 1% by weight, and a free fatty acid content less than 1% by weight, an N-acyl α-aminoacids content between 0.5 to 3% by weight and 0 to 4% by weight of glycerin, based on the solution.

Description:
BACKGROUND OF THE INVENTION 
     Alkyl amidopropyl betaines in general and cocoamidopropylbetaine (CAPB, CAS 61789-40-0) in particular are known for their mildness and hence are very widely used in personal care and consumer products [“ Encyclopedia of conditioning rinse ingredients ” ed. A. L. L. Hunting, Micelle Press, London (1987), p. 125]. 
     As a result of their superior performance, biodegradability and low toxicology profile, they are used on huge scale in cosmetic industry [X. Domingo, “ Amphoteric Surfactants ” ed. E. G. Lomax, Surfactant Science Series, Marcel Dekker Inc., New York, (1996), Vol. 59, p. 75 and J. G. Weers, J. F. Rathman, F. U. Axe, C. A. Crichlow, L. D. Foland, D. R. Scheuing, R. J. Wiersema and A. G. Zielske, Langmuir, 7, 854-867, (1991)]. 
     A conventional commercial betaine composition typically has the following compositions: 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Water 
                 64% 
                 by weight 
               
               
                   
                 Betaine 
                 28-29% 
                 by weight 
               
               
                   
                 NaCl 
                 5-6% 
                 by weight 
               
               
                   
                 Glycerin 
                 0.3% 
                 by weight 
               
               
                   
                 Fatty acid 
                 0.5% 
                 by weight 
               
               
                   
                 Amidoamine 
                 ca. 0.3% 
                 by weight 
               
               
                   
                 Total solids content 
                 ca. 36% 
                 by weight 
               
               
                   
                   
               
             
          
         
       
     
     The solids content represents the sum of the components other than water. The proportions of betaine and sodium chloride arise out of the stoichiometry of the reaction of the fatty amide with tertiary amino group (amidoamine) and sodium chloroacetate according to the equation given below. 
     
       
                 
         
             
             
         
      
     
     A small amount of amidoamine normally remains in the product because the quaternization reaction is incomplete. This proportion can, however, be further reduced by an adapted stoichiometry and reaction procedure. The further typical components like glycerin and fatty acids listed originate from the synthesis of the amidoamine. Small amounts of fatty acids (0.5%) in the betaine composition results from synthesis of amidoamine from the corresponding fatty acid and 3-N,N-dimethylaminopropylamine. Glycerin is present in the betaine composition if the amidoamine is synthesized from triglycerides (coconut or palm oil) and 3-N,N-dimethylaminopropylamine. 
     It is well known that composition of betaines of the aforementioned type is liquid only below a particular concentration of total solids. For example, at ambient temperature a composition of a betaine of Formula I derived from coconut fatty acids solidifies at a solids content of about 40% by weight. For this reason, conventional, commercial, aqueous solutions of coconut amidopropylbetaine, derived from coconut fatty acids, have total solids concentrations below 40% by weight and in most cases about 35-36% by weight. The maximum achievable concentration of a flowable solution of a betaine decreases as the number of carbon atoms is increased. If the fatty acid mixture contains a higher proportion of unsaturated fatty acids, the concentrations achievable frequently are comparatively higher than those achievable with saturated fatty acids. 
     Several attempts have been made to create betaines (Formula I) of higher concentration primarily because it has been shown that aqueous betaine composition of higher concentrations is self-preserving. The second obvious motive for preparing betaines of higher concentration is low cost of transportation. U.S. Pat. No. 4,243,549 (1981) describes preparation of high active betaines (33.5% by weight) by blending equivalent amount of ethoxylated alkyl sulphate, the anionic surfactant. Flowable and pumpable high active betaines are reported in German patent DE 3613944. The synthesis described in this patent involves use of solvent and azeotropic removal of water. Another German patent DE 3726322 reveals use of highly acidic pH to create betaines of higher concentration. Use of 3 to 20% by weight of nonionic surfactant is taught by German patent DE 3826654 for making betaines of higher concentration. Reference is made to U.S. Pat. No. 5,354,906 (1994) according to which upto 36% by weight active betaines are produced by addition of 1 to 3% by weight of fatty acids. This results in overall solids content of at least 40% by weight [DE 4207386 (1993); EP 560114 (1993)]. DE 19523477 reports the process of making betaines with active content of 40 to 45% by weight using quaternised salts of tertiary amidoamines that are synthesized from 3-N,N-dimethylaminopropylamine and polycarboxylic acids. Flowable betaines of total solids content of 40-55% by weight are made by incorporation of 1 to 10% by weight of hydroxy carboxylic acids [DE 4408183]. Finally, inclusion of mixture of fatty acids and ethoxylated cocomono glycerides also result in achieving betaines of high activity [DE 4408228]. 
     Thus, it makes sense to create industrially feasible alkylamidopropylbetaines (Formula I) of higher concentration to save on freight charges and to render them self-preserving. The self-preserving nature of high active betaines has been established by performing ‘preservation loading test’ using various types of micro organisms [U.S. Pat. No. 5,354,906 (1994)]. It is an object of the present invention to provide a high active aqueous betaine composition comprising a betaine of the general Formula I with less than 5.0 ppm of free sodium monochloroacetate, a totally undesirable impurity. 
     It is an object of the present invention to provide a process for preparing a high active aqueous betaine composition comprising a betaine of the general Formula I which obviates steps like filtration, concentration and use of organic solvents for making high active betaines. 
     It is a further object of the present invention to provide an aqueous betaine composition comprising a betaine of the general Formula I which is self-preserving. 
     SUMMARY OF THE INVENTION 
     The present invention provides an aqueous betaine composition comprising a betaine of the general Formula I, 
     
       
                 
         
             
             
         
      
     
     in which R is an alkyl group of coconut fatty acids, preferably hydrogenated coconut fatty acids, or a fatty acid mixture which, on the average, corresponds to coconut fatty acids,
     an amidoamine of not more than 1% by weight,   a free fatty acid less than 1% by weight,   0 to 4% by weight of glycerin, based on composition,   less than 5 ppm of free sodium monochloroacetate and,   0.5 to 3% by weight of N-acyl α-amino acids of Formula III wherein R′ is selected from saturated or unsaturated alkyl group with carbon atoms from 8 to 20 and R″ is selected from H, methyl, ethyl or phenyl,
 
wherein the composition has a solids content of at least 45% by weight and a pH of 4.5 to 8.
   

     More particularly, the invention relates to aqueous betaine composition comprise a betaine of the aforementioned type with a solids content of at least 45% by weight, 0.5 to 3% by weight of N-acyl α-amino acids and free sodium monochloroacetate content of less than 5.0 ppm. The solids content is defined as the weight which is determined by evaporating sample on a flat glass dish for 2 hours at 105° C. 
     In the present invention, the high active betaines with solids content of at least 45% by weight are obtained by addition of N-acyl α-amino acids of Formula III to the extent of 0.5 to 3% by weight based on the composition. 
     
       
                 
         
             
             
         
      
     
     N-Acyl α-aminoacids of Formula III, wherein R′ is selected from saturated or unsaturated alkyl group with carbon atoms from 8 to 20 and R″ is selected from H, methyl, ethyl or phenyl. 
     The high active, self-preserving betaine composition of the present invention is a clear aqueous solution that is pourable and flowable at ambient temperatures. The trace level impurities of 3-N,N-dimethylaminopropylamine and sodium monochloroacetate are less than 5.0 ppm. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Alkylamidopropylbetaines are produced by quaternizing the alkylamindopropylamine of Formula II with stoichiometric quantity of sodium monochloro acetate in aqueous medium. The alkylamidopropylamine can be obtained by reacting stoichiometric amounts of fatty acids with 3-N,N-dimethylaminopropylamine or aminolysis of triglycerides with the same amine. Either route works very well and the amidification is normally done at 130-140° C. Depending upon the fatty raw material used the amidoamine of Formula II may contain small amounts of unreacted triglyceride or fatty acids usually around 1% by weight. The amidoamine generated from triglyceride obviously has stoichiometric quantities of glycerin liberated. In the present invention the quaternization of amidoamine of Formula II is done by reacting 1.0 mole with amidoamine with 1.05 to 1.08 mole of sodium monochloroacetate at the temperature of 80-85° C. while maintaining pH between 7.5-8.0 by adding sodium hydroxide solution (45%). The progress of the reaction is monitored by estimating the chloride ion liberated as well as by estimating the unreacted amidoamine. Both analytical parameters ensure the completion of quaternization with free amidoamine around 0.5% by weight. Determination of free amidoamine from aqueous betaine composition is done by extracting and then titrating it against standard acid using potentiometry. The amidoamine is extracted from aqueous betaine composition and then it is determined by titrating against acid using potentiometry. N-acyl α-aminoacid (0.5 to 3% by weight) is added to the reaction mass with the solids content above 45% by weight at 85° C. and the pH is raised to 10-10.5 at 95° C. for four hours. This step is essential for destruction of unreacted sodium monochloraceate and to ensure that free sodium monochloroacetate is less than 5.0 ppm. Free sodium monochloroacetate content was determined by ion chromatography of the solid phase extracted betaine composition using anion exchange column. Finally, the pH of the reaction mass is adjusted to 4.5 to 6.5 by mineral acid and is then cooled while stirring. Adjustment of solids content to at least 45% gives clear, flowable betaine composition. The betaine composition thus obtained has 0.5 to 3% of N-acyl α-aminoacid by weight and betaine content of minimum 35% by weight. The betaine composition thus obtained has cloud point above 40° C. and solidification point ranges between 5 to −10° C. The significance of cloud point is that the product remains clear liquid over a wide range of temperatures that covers the entire globe. 
     The N-acyl α-aminoacids that are used in the present invention to obtain high active betaines are of Formula III, wherein R′ is selected from saturated or unsaturated alkyl group with carbon atoms from 8 to 20 and R″ is selected from H, methyl, ethyl or phenyl. N-acyl α-aminoacids, particularly in the form of their sodium salts, are widely used because of their outstanding mildness to skin and eyes and biodegradability. They are compatible with cationic as well as amphoteric surfactants and find applications in shampoos, mouth washes and medicated skin cleansers [Spivack, J. D., ‘Anionic Surfactants’ edited by Linfield, W. A., Marcel Dekker New York, 1976, 561-617 and technical literature titled ‘Hamposyl Surfactants’ by Hampshire, Organic Chemicals Division, Texas, USA]. Hence N-acyl α-aminoacids are useful additives compared to the additives that are mentioned in the prior art to achieve flowable high active betaine solutions. 
     Thus, the process described herein generates high active aqueous betaine composition of Formula I with a composition characterized by solids content of minimum 45% by weight, clear flowing liquid, active betaine content of 35% minimum, sodium chloride content of 6% minimum, free fatty acid content less than 1%, free amidoamine content less than 1% and free sodium monochloroacetate and 3-N,N-dimethylaminopropylamine content less than 5 ppm, solidification point less than 5° C. and cloud point above 35° C. 
     The betaine composition of the present invention with minimum of 45% solids were subjected to microbial ‘challenge test’ using following microorganisms.
     A]  Staphylococcus aureus      B]  Escherichia coli      C]  Pseudomonas aeruginosa      D]  Candida albicans      E]  Aspergillus niger      

     The high active betaine samples with solids content of 45% minimum were inoculated by 1.0×10 5 -1.0×10 6  cfu/ml organisms of each of the above mentioned. The microbial counts of all the composition of betaines having solids content of at least 45% by weight were found to be less than 10 cfu/ml after 7 days. 
     
       
         
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Microbial count cfu/ml 
               
             
          
           
               
                 Microorganism 
                 0 hours 
                 24 hours 
                 7 days 
                 14 days 
               
               
                   
               
               
                 
                   Staphylococcus 
                 
                 2.0 × 10 6   
                 &lt;400 
                 &lt;10 
                 &lt;10 
               
               
                   aureus  ATCC 6538 
               
               
                 
                   Escherichia coli 
                 
                 5.0 × 10 5   
                 &lt;400 
                 &lt;10 
                 &lt;10 
               
               
                 ATCC 10148 
               
               
                 
                   Pseudomonas 
                 
                 &lt;400 
                  &lt;20 
                 &lt;10 
                 &lt;10 
               
               
                 
                   aeruginosa 
                 
               
               
                 (In-house isolate) 
               
               
                 
                   Candida albicans 
                 
                 1.28 × 10 6    
                 1.04 × 10 5   
                 &lt;10 
                 &lt;10 
               
               
                 ATCC 10231 
               
               
                 
                   Aspergillus niger 
                 
                 5.7 × 10 4   
                  5.6 × 10 3   
                 &lt;10 
                 &lt;10 
               
               
                 ATCC 16404 
               
               
                   
               
             
          
         
       
     
     The high active betaine composition of the present invention has the following advantages 
     As described in the background, N-acyl α-amino acid of Formula III is much more useful additive than those described in the prior art. 
     The process of the present invention circumvents steps like filtration, concentration and use of organic solvents for making high active betaines. 
     High active betaine composition of the present invention are self-preserving. 
     The process yields high active betaine composition with less than 5.0 ppm of free sodium monochloroacetate, a totally undesirable impurity. 
     The following examples describe in detail the process and the betaine composition of the present invention. These examples are by way of illustrations only and in no way restrict the scope of the invention. 
     EXAMPLES 
     Cocofatty acid amidoamine was prepared from cocofatty acid and 3-N,N-dimethylaminopropylamine. 3-N,N-Dimethylaminopropylamine was procured from BASF and sodium monochloroacetate was purchased from Clariant. 
     Example I 
     To a stirred mixture of cocofatty acid amidoamine (300 g, 1.0 mole, tertiary nitrogen content of 4.79%, acid value 7.3), glycerin (31.5 g) and water (320 ml) under nitrogen at 65° C., an aqueous solution of sodium monochloroacetate (311.6 g, 40%, 1.07 moles) was added over the period of half an hour. The reaction mixture was stirred for 8 hours at 80-85° C. by maintaining the pH between 7.5 to 8.2 with sodium hydroxide (47% aqueous solution). Cocoyl glycine (6 g) was then added to the reaction mixture and stirring was continued for 8 hours at 95° C. while maintaining pH between 10-10.5. The reaction mass was cooled and the pH was adjusted to 4.5 to 5.5 with hydrochloric acid. The clear product (982 g) so formed had the following composition. 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Solids 
                 47.2%  
               
               
                   
                 Betaine 
                 35.2%  
               
               
                   
                 NaCl 
                 6.9% 
               
               
                   
                 Fatty acids 
                 0.8% 
               
               
                   
                 Cocoyl glycine 
                 0.6% 
               
               
                   
                 Glycerin 
                 3.2% 
               
               
                   
                 Amidoamine 
                 0.1% 
               
               
                   
                 Sodium monochloroacetate 
                 &lt;5.0 ppm 
               
               
                   
                 pH 
                 5.2 
               
               
                   
                 Cloud point 
                 &gt;40° C. 
               
               
                   
                 Solidification point 
                 &lt;−7° C. 
               
               
                   
                   
               
             
          
         
       
     
     Example II 
     To a stirred mixture of cocofatty acid amidoamine (298 g, 1.0 mole, tertiary nitrogen content of 4.85%, acid value 4.6), glycerin (32.6 g) and water (341 ml) under nitrogen at 65° C., an aqueous solution of sodium monochloroacetate (311.6 g, 40%, 1.07 moles) was added over the period of half an hour. The reaction mixture was stirred for 8 hours at 80-85° C. by maintaining the pH between 7.5 to 8.2 with sodium hydroxide (47% aqueous solution). Lauroyl glycine (9.7 g) was then added to the reaction mixture and stirring was continued for 8 hours at 95° C. while maintaining pH between 10-10.5. The reaction mass was cooled and the pH was adjusted to 4.5 to 5.5 with phosphoric acid. The clear product (991 g) so formed had the following composition. 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Solids 
                  47% 
               
               
                   
                 Betaine 
                 35.04%  
               
               
                   
                 NaCl 
                 6.46%  
               
               
                   
                 Fatty acids 
                 0.5% 
               
               
                   
                 Lauroyl glycine 
                 1.0% 
               
               
                   
                 Glycerin 
                 3.3% 
               
               
                   
                 Amidoamine 
                 0.3% 
               
               
                   
                 Sodium monochloroacetate 
                 &lt;5.0 ppm 
               
               
                   
                 PH 
                 5.1 
               
               
                   
                 Cloud point 
                 &gt;40° C. 
               
               
                   
                 Solidification point 
                  &lt;3° C. 
               
               
                   
                   
               
             
          
         
       
     
     Example III 
     To a stirred mixture of cocofatty acid amidoamine (298 g, 1.0 mole, tertiary nitrogen content of 4.85%, acid value 4.6), glycerin (31.5 g) and water (331 ml) under nitrogen at 65° C., an aqueous solution of sodium monochloroacetate (311.6 g, 40%, 1.07 moles) was added over the period of half an hour. The reaction mixture was stirred for 8 hours at 80-85° C. by maintaining the pH between 7.5 to 8.2 with sodium hydroxide (47% aqueous solution). Oleoyl glycine (9.7 g) was then added to the reaction mixture and stirring was continued for 8 hours at 95° C. while maintaining pH between 10-10.5. The reaction mass was cooled and the pH was adjusted to 4.5 to 5.5 with phosphoric acid. The clear product (987 g) so formed had the following composition. 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Solids 
                 47.0% 
               
               
                   
                 Betaine 
                 35.23%  
               
               
                   
                 NaCl 
                 6.44% 
               
               
                   
                 Fatty acids 
                 0.48% 
               
               
                   
                 Oleoyl glycine 
                  1.0% 
               
               
                   
                 Glycerin 
                  3.2% 
               
               
                   
                 Amidoamine 
                 0.25% 
               
               
                   
                 Sodium monochloroacetate 
                 &lt;5.0 ppm 
               
               
                   
                 PH 
                 5.11 
               
               
                   
                 Cloud point 
                 &gt;40° C. 
               
               
                   
                   
               
             
          
         
       
     
     Example IV 
     To a stirred mixture of cocofatty acid amidoamine (300 g, 1.0 mole, tertiary nitrogen content of 4.79%, acid value 7.3), glycerin (32.5 g) and water (365 ml) under nitrogen at 65° C., an aqueous solution of sodium monochloroacetate (311.6 g, 40%, 1.07 moles) was added over the period of half an hour. The reaction mixture was stirred for 8 hours at 80-85° C. by maintaining the pH between 7.5 to 8.2 with sodium hydroxide (47% aqueous solution). Lauroyl sarcosine (6.1 g) was then added to the reaction mixture and stirring was continued for 8 hours at 95° C. while maintaining pH between 10 −10.5 . The reaction mass was cooled and the pH was adjusted to 4.5 to 5.5 with phosphoric acid. The clear product (1020 g) so formed had the following composition. 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Solids 
                 45.4% 
               
               
                   
                 Betaine 
                 34.21%  
               
               
                   
                 NaCl 
                 6.34% 
               
               
                   
                 Fatty acids 
                  0.8% 
               
               
                   
                 Lauroyl sarcosine 
                  0.6% 
               
               
                   
                 Glycerin 
                  3.2% 
               
               
                   
                 Amidoamine 
                 0.25% 
               
               
                   
                 Sodium monochloroacetate 
                 &lt;5.0 ppm 
               
               
                   
                 PH 
                 4.9 
               
               
                   
                 Cloud point 
                 &gt;40° C. 
               
               
                   
                 Solidification point 
                  &lt;5° C. 
               
               
                   
                   
               
             
          
         
       
     
     Example V 
     To a stirred mixture of cocofatty acid amidoamine (300 g, 1.0 mole, tertiary nitrogen content of 4.79%, acid value 7.3), glycerin (30.7 g) and water (300 ml) under nitrogen at 65° C., an aqueous solution of sodium monochloroacetate (311.6 g, 40%, 1.07 moles) was added over the period of half an hour. The reaction mixture was stirred for 8 hours at 80-85° C. by maintaining the pH between 7.5 to 8.2 with sodium hydroxide (47% aqueous solution). Cocoyl glycine (6 g) was then added to the reaction mixture and stirring was continued for 8 hours at 95° C. while maintaining pH between 10-10.5. The reaction mass was cooled and the pH was adjusted to 4.5 to 5.5 with phosphoric acid. The clear product (961 g) so formed had the following composition. 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Solids 
                 48.28% 
               
               
                   
                 Betaine 
                 35.93% 
               
               
                   
                 NaCl 
                  7.0% 
               
               
                   
                 Fatty acids 
                  0.8% 
               
               
                   
                 Cocoyl glycine 
                  0.6% 
               
               
                   
                 Glycerin 
                  3.2% 
               
               
                   
                 Amidoamine 
                  0.25% 
               
               
                   
                 Sodium monochloroacetate 
                 &lt;5.0 ppm 
               
               
                   
                 PH 
                 4.8 
               
               
                   
                 Cloud point 
                 &gt;40° C. 
               
               
                   
                 Solidification point 
                 &lt;−3° C.