Polyglycerol fatty acid ester mixture

• US 5,466,719 A
• Filed: 08/04/1993
• Issued: 11/14/1995
• Est. Priority Date: 08/07/1992
• Status: Expired due to Term

• Current Assignee: Evonik Goldschmidt GmbH (Rag-Stiftung)
• Original Assignee: Solvay Fluor und Derivate GmbH
• Inventors: Jakobson, Gerald, Siemanowski, Werner, Uhlig, Karl-Heinz
• Primary Examiner(s): Raymond, Richard L.
• Application Number:
  US08/101,075
• Time in Patent Office: 832 Days
• Field of Search: 514/785, 514/786, 554/172, 554/173, 554/227
• US Class Current: 514/785
• CPC Class Codes: A61K 8/39 Derivatives containing from 2 to 10 oxyalkylene groups
• CPC Class Codes: A61K 8/922 of vegetable origin
• CPC Class Codes: A61Q 19/10 Washing or bathing preparations
• CPC Class Codes: C07C 69/33 esterified with hydroxy compounds having more than three hydroxy groups esters of sugars C07H
• CPC Class Codes: C10M 105/38 of polyhydroxy compounds
• CPC Class Codes: C10M 2201/02 Water
• CPC Class Codes: C10M 2207/281 of (cyclo)aliphatic monocarboxylic acids
• CPC Class Codes: C10M 2207/282 of (cyclo)aliphatic oolycarboxylic acids
• CPC Class Codes: C10M 2207/283 of polyhydroxy compounds
• CPC Class Codes: C10M 2207/286 of polymerised unsaturated acids
• CPC Class Codes: C10M 2207/289 containing free hydroxy groups
• CPC Class Codes: C11D 1/667 Neutral esters, e.g. sorbitan esters

Abstract

Polyglycerol fatty acid ester mixtures of mono- di- and polyesters of polyglycerols having a degree of polymerization of 2 to 8 and at least one saturated and/or unsaturated fatty acid, the mixtures having an HLB of greater than 8 and containing 0 to less than 5 wt-% diglycerol fatty acid esters, 20 to 65 wt-% triglycerol fatty acid esters, 20 to 50 wt-% tetraglycerol fatty acid esters and 5 to 40 wt-% higher polyglycerol fatty acid esters, in which the fatty acid component consists of one or more fatty acids selected from the saturated and/or unsaturated, branched and/or unbranched C₆ - to C₁₄ -fatty acids containing less than 10 wt-% fatty acids having more than 14 carbon atoms; bath additive preparations containing such polyglycerol fatty acid ester mixtures; methods of using such polyglycerol fatty acid ester mixtures, and a process for preparing such mixtures.

Claims

1. A polyglycerol fatty acid ester mixture of mono-, di- and polyesters of a polyglycerol having a degree of polymerization of 2 to 8 and at least one fatty acid selected from the group consisting of saturated and unsaturated, branched and unbranched C₆ - to C₁₄ -fatty acids containing less than 10 wt-% of fatty acids having more than 14 carbon atoms, wherein said polyglycerol fatty acid ester mixture has an HLB of greater than 8 and contains

0 to 5 parts by weight diglycerol fatty acid esters,

to 65 parts by weight triglycerol fatty acid esters,to 50 parts by weight tetraglycerol fatty acid esters, and

5 to 40 parts by weight higher polyglycerol fatty acid esters,

in a total of 100 parts by weight of said ester mixture.

2. A polyglycerol fatty acid ester mixture according to claim 1, having an HLB of greater than 10 and containing

0 to 3 parts by weight of diglycerol fatty acid esters,

to 32 parts by weight of triglycerol fatty acid esters,to 49 parts by weight tetraglycerol fatty acid esters, andto 34 parts by weight higher polyglycerol fatty acid esters,

in a total of 100 parts by weight of said mixture, and wherein the fatty acid consists of at least one fatty acid selected from the group consisting of saturated and unsaturated, branched and unbranched C₈ - to C₁₂ -fatty acids containing less than 5 wt-% of fatty acids having more than 14 carbon atoms.

3. A polyglycerol fatty acid ester mixture according to claim 1, containing 5 to 20 wt-% pentaglycerol fatty acid esters.

4. A polyglycerol fatty acid ester mixture according to claim 1, in which the fatty acid consists of at least one fatty acid selected from the group consisting of caprylic acid, capric acid, lauric acid, undecenoic acid, 2-ethylhexanoic acid and coconut fatty acid.

5. A polyglycerol fatty acid ester mixture according to claim 1, containing more than 50 wt-% monoesters and diesters.

6. A bath additive composition comprising:

10 to 60 wt-% of a polyglycerol fatty acid ester mixture of mono-, di- and polyesters of a polyglycerol having a degree of polymerization from 2 to 8 and at least one fatty acid selected from group consisting of saturated and unsaturated, branched and unbranched C₆ - to C₁₄ -fatty acids containing less than 10 wt-% of fatty acids having more than 14 carbon atoms;

10 to 60 wt-% of at least one oil or oil-component having cosmetic or therapeutic activity selected from the group consisting of natural and synthetic, mineral, ethereal and fatty animal and vegetable oils, and

0 to 70 wt-% water;

wherein said polyglycerol fatty acid ester mixture has an HLB of greater than 8 and contains

0 to 5 parts by weight diglycerol fatty acid esters,

20 to 65 parts by weight triglycerol fatty acid esters,

20 to 50 parts by weight tetraglycerol fatty acid esters, and

5to 40 parts by weight higher polyglycerol fatty acid esters,

in a total of 100 parts by weight of said ester mixture.

7. A composition according to claim 6, further comprising at least one solvent.

8. A composition according to claim 6, which is an oil bath composition.

9. A composition according to claim 6, comprising:

15 to 50 wt-% polyglycerol fatty acid ester mixture in which the fatty acid consists of at least one fatty acid selected from the group consisting of saturated and unsaturated, branched and unbranched C₈ - to C₁₂ -fatty acids containing less than 5 wt-% of fatty acids having more than 14 carbon atoms,

15 to 50 wt-% oil or oil component having cosmetic or therapeutic activity, and

0.5 to 60 wt-% water,

wherein said polyglycerol fatty acid ester mixture contains

0 to 3 parts by weight diglycerol fatty acid esters,

22 to 32 parts by weight triglycerol fatty acid esters,

39 to 49 parts by weight tetraglycerol fatty acid esters, and

24 to 34 parts by weight higher polyglycerol fatty acid esters,

in a total of 100 parts by weight of said ester mixture.

10. A process for preparing a polyglycerol fatty acid ester mixture of mono-, di- and polyesters of polyglycerols having a degree of polymerization of 2 to 8 and at least one saturated and/or unsaturated fatty acid, said process comprising the steps of initially heating a reaction mixture comprising

a polyglycerol containing 0 to 5 wt-% diglycerol, 20 to 65 wt-% triglycerol, 20 to 50 wt-% tetraglycerol, and 5 to 40 wt-% higher polyglycerols, and

at least one fatty acid selected from the group consisting of saturated and unsaturated, branched and unbranched C₆ - to C₁₄ -fatty acids containing less than 10 wt-% fatty acids having more than 14 carbon atoms, in a molar ratio of polyglycerol to fatty acid of 4:

1 to 1;

1 and in the presence of at least one catalyst, to a temperature of at least 140°

C. and reducing the pressure to at most 600 mbar;

subsequently heating the reaction mixture in a temperature range from 140°

to 220°

C. under control of a temperature program, and simultaneously reducing the pressure under control of a pressure program from 600 to 10 mbar;

removing resulting water of reaction by continuous distillation, and

upon attaining an acid number of less than 3, cooling the resulting polyglycerol fatty acid ester mixture.

11. A process according to claim 10, wherein said polyglycerol and said fatty acid are reacted in a molar ratio of 2.5:

1 to 1.5;

1.

12. A process according to claim 10, wherein said subsequent heating and pressure reduction are effected in steps.

13. A process according to claim 10 wherein said subsequent heating and pressure reduction are effected continuously.

14. A process according to claim 10, further comprising purifying the cooled polyglycerol fatty acid ester mixture.

15. A process according to claim 10, wherein said mixture is initially heated to 145°

C. and the pressure is initially reduced to 500 mbar, and subsequently the mixture is heated to a temperature of from 145°

to 190°

C. and the pressure is simultaneously reduced to from 500 to 20 mbar.

16. A process according to claim 10, wherein said catalyst is an acidic catalyst.

17. A process according to claim 10, wherein said polyglycerol contains:

0 to 3 wt-% diglycerol,

22 to 32 wt-% triglycerol,

39 to 49 wt-% tetraglycerol, and

24 to 34 wt-% higher polyglycerols.

18. A process according to claim 10, wherein said at least one fatty acid is selected from the group consisting of saturated and unsaturated, branched and unbranched C₈ - to C₁₂ -fatty acids containing less than 5 wt-% of fatty acids having more than 14 carbon atoms.

19. A process according to claim 10, wherein the resulting polyglycerol fatty acid ester mixture is cooled to a temperature in the range from 30°

to 110°

C.;

said process further comprising the steps of;

treating the cooled polyglycerol fatty acid ester mixture with an organic solvent or solvent mixture;

extracting the solvent-treated mixture with water in at least one extracting step to remove any unreacted polyglycerol and obtain an organic phase, and

freeing said organic phase from organic solvent and residual water by distillation;

wherein an amount of a basic compound at least equivalent to the amount of catalyst used is added to the organic solvent or to the water in a first of said at least one extracting step.

20. A process according to claim 19, wherein said resulting polyglycerol fatty acid ester mixture is cooled to a temperature in the range from 60°

to 80°

C., the extracting is carried out in a single extraction step, and the organic phase is freed of organic solvent and residual water by vacuum distillation or vacuum evaporation.

21. A process according to claim 19, wherein an amount of basic compound at least equivalent to the acid number of the polyglycerol fatty acid ester mixture is added to the water used in said first extracting step.

22. A process according to claim 20, wherein said organic solvent or solvent mixture has a water absorption capacity of less than 30 wt-%.

23. A process according to claim 22, wherein said organic solvent or solvent mixture has a water absorption capacity of less than 20 wt-%.

24. A process according to claim 20, wherein said organic solvent or solvent mixture forms an azeotropic mixture with water during the distillation.

25. A process according to claim 20, wherein said organic solvent is ethyl acetate.

26. A process according to claim 25, wherein said organic solvent is ethyl acetate saturated with water.

27. A process according to claim 19, wherein said basic compound comprises sodium hydroxide.

28. A process according to claim 27, wherein said sodium hydroxide is in the form of an aqueous sodium hydroxide solution.

29. A process according to claim 19, wherein said basic compound comprises at least one basic substance selected from the group consisting of alkali metal carbonates and basic ion exchangers.

30. A process according to claim 29, wherein said basic compound comprises sodium carbonate or potassium carbonate.

31. A process according to claim 10, further comprising allowing said cooled polyglycerol fatty acid ester mixture to stand for at least about one-half hour, and separating any precipitated polyglycerols.

32. A process according to claim 31, wherein said cooled polyglycerol fatty acid ester mixture is allowed to stand for from 1 to 10 hours.

33. A process according to claim 10, wherein the step of subsequently heating the reaction mixture in a temperature range from 140°

to 220°

C. under control of a temperature program, and simultaneously reducing the pressure under control of a pressure program from 600 to 10 mbar is carried out in a time interval of from 2 to 6 hours.

34. A process according to claim 15, wherein the step of subsequently heating the reaction mixture in a temperature range from 145°

to 190°

C. and simultaneously reducing the pressure from 500 to 20 mbar is carried out in a time interval of from 3 to 4 hours.

35. A process according to claim 10, wherein said step of subsequently heating the reaction mixture in a temperature range from 140°

to 220°

C. under control of a temperature program is carried out stepwise in from 3 to 6 steps.

36. A process according to claim 15, wherein said step of subsequently heating the reaction mixture in a temperature range from 145°

to 190°

C. is carried out stepwise in 4 or 5 steps.

37. A process according to claim 10, wherein said step of reducing the pressure from 600 to 10 mbar is carried out stepwise in from 3 to 6 steps.

38. A process according to claim 15, wherein said step of reducing the pressure from 500 to 20 mbar is carried out stepwise in 4 or 5 steps.

39. A process according to claim 16, wherein said acidic catalyst is employed in combination with an acidic reducing compound.

40. A process according to claim 39, wherein said acidic catalyst is a compound containing at least one sulfonic acid group, and said acidic reducing compound is hypophosphorous acid.

41. A process according to claim 10, wherein said reaction mixture is heated under an inert gas atmosphere.

42. A process according to claim 41, wherein said reaction mixture is heated under a nitrogen atmosphere.