Lactylate synthesis methods using dilactides

Abstract

The present invention involves a new synthesis route for the formation of lactylates. The method comprises reacting a dilactide with a compound comprising a hydroxy group. This reaction is preferably carried out in the presence of a cation or other source of alkalinity. Preferred compounds comprising a hydroxy group include any fatty acid and fatty acid alcohol (particularly C 1 -C 26 fatty acid chains). Preferred cations include cations of Group I and II metals, with sodium, calcium, and potassium cations being particularly preferred. The inventive reactions proceed much more rapidly than prior art lactylate synthesis reactions, and can be used to form 1-, 2-, 3-, 4-, and 5-lactylates.

We claim: 
     
       1. A method of forming a lactylate, said method comprising reacting a dilactide with a compound comprising an —OH a —COOH group to form a lactylate, wherein the molar ratio of dilactide to the compound comprising an —OH a —COOH group is of from about 1:0.25 to about 1:4. 
     
     
       2. The method of  claim 1 , wherein said compound comprises a —COOH group. 
     
     
       3. The method of  claim 1 , wherein said reacting is carried out in the presence of a source of alkalinity. 
     
     
       4. The method of  claim 1 , wherein said reacting is carried out in the presence of a cation. 
     
     
       5. The method of claim  4  1, wherein said reacting is carried out in the presence of a cation, and said cation is selected from the group consisting of cations of Group I, II, and III metals and ammonium. 
     
     
       6. The method of claim  4  1, wherein said reacting is carried out in the presence of a cation, and said cation is selected from the group consisting of cations of sodium, potassium, calcium, magnesium, aluminum, ammonium, and lithium. 
     
     
       7. The method of claim  4  1, wherein reacting is carried out in the presence of a cation, and the source of said cation is selected from the group consisting of sodium stearate, potassium stearate, calcium stearate, sodium palmitate, potassium palmitate, calcium palmitate, sodium behenate, potassium behenate, calcium behenate, sodium oleate, potassium oleate, calcium oleate, sodium caprate, potassium caprate, calcium caprate, sodium isostearate, potassium isostearate, calcium isostearate, sodium caprylate, potassium caprylate, calcium caprylate, sodium laurate, potassium laurate, calcium laurate, sodium myristate, potassium myristate, calcium myristate, aluminum stearate, sodium hydroxide, calcium hydroxide, and tetramethylammonium hydroxide. 
     
     
       8. The method of claim  4  1, wherein said reacting is carried out in the presence of a cation, and further comprising generating said cation in situ prior to, during, or prior to and during, said reacting. 
     
     
       9. The method of  claim 1 , wherein said compound comprising an —OH a —COOH group has a formula selected from the group consisting of 
       
         
           
           
               
               
           
         
         where each R is individually selected from the group consisting of —H, substituted and unsubstituted and saturated and unsaturated alkyl groups, substituted and unsubstituted aromatic groups, and silicon-containing groups. 
       
     
     
       10. The method of  claim 9 , wherein said compound is selected from the group consisting of stearic acid, palmitic acid, behenic acid, oleic acid, capric acid, caprylic acid, isostearic acid, lauric acid, and myristic acid, glycerine, propylene glycol, monoglycerides, diglycerides, and propylene glycol monoester. 
     
     
       11. The method of  claim 1 , wherein said dilactide has the formula 
       
         
           
           
               
               
           
         
         where each R 1  is individually selected from the group consisting of —H, substituted and unsubstituted and saturated and unsaturated alkyl groups, substituted and unsubstituted aromatic groups, halogens, and moieties including S, P, N, and/or Si atoms. 
       
     
     
       12. The method of  claim 1 , wherein said reacting forms a mixture of lactylates. 
     
     
       13. The method of  claim 1 , wherein said lactylate is selected from the group consisting of 1-lactylates, 2-lactylates, 3-lactylates, 4-lactylates, 5-lactylates, and mixtures thereof. 
     
     
       14. The method of  claim 13 , wherein said lactylate is selected from the group consisting of palmitoyl-n-lactylate, stearoyl-n-lactylate, behenoyl-n-lactylate, oleoyl-n-lactylate, caproyl-n-lactylate, capryloyl-n-lactylate, lauroyl-n-lactylate, myristoyl-n-lactylate, and mixtures thereof, where each n is individually selected from the group consisting of 1, 2, 3, 4, and 5. 
     
     
       15. The method of  claim 1 , wherein said reacting is carried out at a temperature of from about 100° C. to about 200° C. 
     
     
       16. The method of  claim 1 , wherein said reacting is carried out for a time period of less than about 90 minutes. 
     
     
       17. The method of  claim 15 , wherein said reacting is carried out for a time period of less than about 90 minutes. 
     
     
       18. A method of forming a lactylate, said method comprising reacting, in the presence of a cation, a reactant mixture to form the lactylate, said reactant mixture consisting essentially of a dilactide and a compound comprising an —OH group selected from the group consisting of glycerine, propylene glycol, monoglycerides, diglycerides, and propylene glycol monoester, and having a molar ratio of lactic acid to dilactide of less than about 0.5:1. 
     
     
       19. The method of  claim 18 , wherein said compound comprises a —COOH group. 
     
     
       20. The method of  claim 18 , wherein said reacting is carried out in the presence of a source of alkalinity. 
     
     
       21. The method of  claim 18 , wherein said reacting is carried out in the presence of a cation. 
     
     
       22. The method of  claim 18 , wherein said compound comprising an —OH group has a formula selected from the group consisting of 
       
         
           
           
               
               
           
         
         where each R is individually selected from the group consisting of —H, substituted and unsubstituted and saturated and unsaturated alkyl groups, substituted and unsubstituted aromatic groups, and silicon-containing groups. 
       
     
     
       23. The method of  claim 18 , wherein said dilactide has the formula 
       
         
           
           
               
               
           
         
         where each R 1  is individually selected from the group consisting of —H, substituted and unsubstituted and saturated and unsaturated alkyl groups, substituted and unsubstituted aromatic groups, halogens, and moieties including S, P, N, and/or Si atoms. 
       
     
     
       24. The method of  claim 18 , wherein said reacting forms a mixture of lactylates. 
     
     
       25. The method of  claim 18 , wherein said reacting is carried out at a temperature of from about 100° C. to about 200° C. 
     
     
       26. The method of  claim 18 , wherein said reacting is carried out for a time period of less than about 90 minutes. 
     
     
       27. A method of forming a lactylate, said method comprising reacting, in the presence of a cation, a reactant mixture to form the lactylate, said reactant mixture comprising a dilactide and a compound comprising an —OH group selected from the group consisting of glycerine, propylene glycol, monoglycerides, diglycerides, and propylene glycol monoester, said reactant mixture having a molar ratio of lactic acid to dilactide of less than about 0.5:1. 
     
     
       28. The method of  claim 27 , wherein said compound comprises a —COOH group. 
     
     
       29. The method of  claim 27 , wherein said reacting is carried out in the presence of a source of alkalinity said cation is selected from the group consisting of cations of Group I, II, and III metals, aluminum, and ammonium. 
     
     
       30. The method of  claim 29 , wherein said source of alkalinity is a cation. 
     
     
       31. The method of  claim 27 , wherein said compound comprising an —OH group has a formula selected from the group consisting of 
       
         
           
           
               
               
           
         
         where each R is individually selected from the group consisting of —H, substituted and unsubstituted and saturated and unsaturated alkyl groups, substituted and unsubstituted aromatic groups, and silicon-containing groups. 
       
     
     
       32. The method of  claim 27 , wherein said dilactide has the formula 
       
         
           
           
               
               
           
         
         where each R 1  is individually selected from the group consisting of —H, substituted and unsubstituted and saturated and unsaturated alkyl groups, substituted and unsubstituted aromatic groups, halogens, and moieties including S, P, N, and/or Si atoms. 
       
     
     
       33. The method of  claim 27 , wherein said reacting forms a mixture of lactylates. 
     
     
       34. The method of  claim 27 , wherein said reacting is carried out at a temperature of from about 100° C. to about 200° C. 
     
     
       35. The method of  claim 27 , wherein said reacting is carried out for a time period of less than about 90 minutes. 
     
     
       36. The method of claim 18, wherein said cation is selected from the group consisting of cations of sodium, potassium, calcium, magnesium, aluminum, ammonium, and lithium. 
     
     
       37. The method of claim 27, wherein said cation is selected from the group consisting of cations of sodium, potassium, calcium, magnesium, aluminum, ammonium, and lithium. 
     
     
       38. The method of claim 24, wherein said lactylate is selected from the group consisting of 1-lactylates, 2-lactylates, 3-lactylates, 4-lactylates, 5-lactylates, and mixtures thereof. 
     
     
       39. The method of claim 33, wherein said lactylate is selected from the group consisting of 1-lactylates, 2-lactylates, 3-lactylates, 4-lactylates, 5-lactylates, and mixtures thereof. 
     
     
       40. A method of forming a lactylate, said method comprising reacting a dilactide with a compound comprising an —OH group to form a lactylate, wherein the molar ratio of dilactide to the compound comprising an —OH group is from about 1:0.25 to about 1:4, wherein said reacting is carried out in the presence of a cation, and the source of said cation is selected from the group consisting of sodium stearate, potassium stearate, calcium stearate, sodium palmitate, potassium palmitate, calcium palmitate, sodium behenate, potassium behenate, calcium behenate, sodium oleate, potassium oleate, calcium oleate, sodium caprate, potassium caprate, calcium caprate, sodium isostearate, potassium isostearate, calcium isostearate, sodium caprylate, potassium caprylate, calcium caprylate, sodium laurate, potassium laurate, calcium laurate, sodium myristate, potassium myristate, calcium myristate, aluminum stearate, sodium hydroxide, calcium hydroxide, and tetramethylammonium hydroxide. 
     
     
       41. The method of claim 40, wherein said lactylate is selected from the group consisting of palmitoyl-n-lactylate, stearoyl-n-lactylate, behenoyl-n-lactylate, oleoyl-n-lactylate, caproyl-n-lactylate, capryloyl-n-lactylate, lauroyl-n-lactylate, myristoyl-n-lactylate, and mixtures thereof, and each n is individually selected from the group consisting of 1, 2, 3, 4, and 5. 
     
     
       42. The method of claim 27, wherein the source of said cation is selected from the group consisting of sodium stearate, potassium stearate, calcium stearate, sodium palmitate, potassium palmitate, calcium palmitate, sodium behenate, potassium behenate, calcium behenate, sodium oleate, potassium oleate, calcium oleate, sodium caprate, potassium caprate, calcium caprate, sodium isostearate, potassium isostearate, calcium isostearate, sodium caprylate, potassium caprylate, calcium caprylate, sodium laurate, potassium laurate, calcium laurate, sodium myristate, potassium myristate, calcium myristate, aluminum stearate, sodium hydroxide, calcium hydroxide, and tetramethylammonium hydroxide. 
     
     
       43. The method of claim 42, wherein said reactant mixture consists essentially of said dilactide and said compound comprising an —OH. 
     
     
       44. A method of forming a lactylate, said method comprising reacting a reactant mixture to form the lactylate, said reactant mixture comprising a dilactide and a compound comprising an —OH, wherein the molar ratio of dilactide to the compound comprising an —OH group is from about 1:0.25 to about 1:4, wherein said reacting is carried out in the presence of a cation, said cation is selected from the group consisting of cations of sodium, potassium, calcium, magnesium, aluminum, ammonium, and lithium, and said compound comprising an —OH is selected from the group consisting of stearic acid, palmitic acid, behenic acid, oleic acid, capric acid, caprylic acid, isostearic acid, lauric acid, myristic acid, glycerine, propylene glycol, monoglycerides, diglycerides, and propylene glycol monoester. 
     
     
       45. The method of claim 44, wherein said lactylate is selected from the group consisting of palmitoyl-n-lactylate, stearoyl-n-lactylate, behenoyl-n-lactylate, oleoyl-n-lactylate, caproyl-n-lactylate, capryloyl-n-lactylate, lauroyl-n-lactylate, myristoyl-n-lactylate, and mixtures thereof, and each n is individually selected from the group consisting of 1, 2, 3, 4, and 5. 
     
     
       46. The method of claim 27, wherein said cation is selected from the group consisting of cations of sodium, potassium, calcium, magnesium, aluminum, ammonium, and lithium, and said compound comprising an —OH is selected from the group consisting of stearic acid, palmitic acid, behenic acid, oleic acid, capric acid, caprylic acid, isostearic acid, lauric acid, myristic acid, glycerine, propylene glycol, monoglycerides, diglycerides, and propylene glycol monoester. 
     
     
       47. The method of claim 46, wherein said reactant mixture consists essentially of said dilactide and said compound comprising an —OH. 
     
     
       48. A method of forming a lactylate, said method comprising reacting a dilactide with a compound comprising an —OH group to form a lactylate, wherein the molar ratio of dilactide to the compound comprising an —OH group is from about 1:0.25 to about 1:4, wherein said reacting is carried out in the presence of a cation, said cation is selected from the group consisting of cations of Group I, II, and III metals, aluminum, and ammonium, and wherein the molar ratio of dilactide to cation is from about 1:0.25 to about 1:1. 
     
     
       49. The method of claim 27, wherein said cation is selected from the group consisting of cations of Group I, II, and III metals, aluminum, and ammonium, and wherein the molar ratio of dilactide to cation is from about 1:0.25 to about 1:1. 
     
     
       50. The method of claim 49, wherein said reactant mixture consists essentially of said dilactide and said compound comprising an —OH. 
     
     
       51. A method of forming a lactylate, said method comprising reacting, under uncatalyzed conditions, a reactant mixture to form the lactylate, said reactant mixture consisting essentially of a dilactide and a compound comprising an —OH group, and having a molar ratio of lactic acid to dilactide of less than about 0.5:1. 
     
     
       52. A method of forming a lactylate, said method comprising reacting, in the presence of a source of alkalinity, a reactant mixture to form the lactylate, said reactant mixture consisting essentially of a dilactide and a compound comprising an —OH group, and having a molar ratio of lactic acid to dilactide of less than about 0.5:1. 
     
     
       53. A method of forming a lactylate, said method comprising reacting, under uncatalyzed conditions, a reactant mixture to form the lactylate, said reactant mixture comprising a dilactide and a compound comprising an —OH group, said reactant mixture having a molar ratio of lactic acid to dilactide of less than about 0.5:1. 
     
     
       54. A method of forming a lactylate, said method comprising reacting, in the presence of a source of alkalinity, a reactant mixture to form the lactylate, said reactant mixture comprising a dilactide and a compound comprising an —OH group, said reactant mixture having a molar ratio of lactic acid to dilactide of less than about 0.5:1. 
     
     
       55. The method of claim 18, wherein said compound is selected from the group consisting of 1-monostearin, 2-monostearin, 1-monopalmitin, 1-stearic, 3-palmitic diglyceride, 1,3-distearin and, 1,2-distearin. 
     
     
       56. The method of claim 27, wherein said compound is selected from the group consisting of 1-monostearin, 2-monostearin, 1-monopalmitin, 1-stearic, 3-palmitic diglyceride, 1,3-distearin and, 1,2-distearin.