Percarboxylic acid solutions

• US 6,274,542 B1
• Filed: 11/02/1999
• Issued: 08/14/2001
• Est. Priority Date: 12/21/1996
• Status: Expired due to Fees

• Current Assignee: Solvay Interox Limited
• Original Assignee: Solvay Interox Limited
• Inventors: Sankey, John P., Morton, Kelly J., Lawton, Valerie, Carr, Graham, James, Alun P.
• Primary Examiner(s): Ogden, Necholus
• Assistant Examiner(s): Petruncio, John M
• Application Number:
  US09/331,395
• Time in Patent Office: 651 Days
• Field of Search: 510/376, 510/375, 510/372
• US Class Current: 510/376
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 25/22 containing ingredients stabilising the active ingredients
• CPC Class Codes: A01N 37/04 polybasic
• CPC Class Codes: A01N 37/06 Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
• CPC Class Codes: A01N 37/16 containing the group; Thio analogues thereof
• CPC Class Codes: A01N 37/40 having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
• CPC Class Codes: A01N 41/04 Sulfonic acids; Derivatives thereof
• CPC Class Codes: A01N 57/20 containing acyclic or cycloaliphatic radicals
• CPC Class Codes: A01N 59/00 Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
• CPC Class Codes: A01N 59/02 Sulfur; Selenium; Tellurium; Compounds thereof
• CPC Class Codes: A01N 59/26 Phosphorus; Compounds thereof
• CPC Class Codes: C07C 407/00 Preparation of peroxy compounds
• CPC Class Codes: C07C 409/24 the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids

Abstract

Storage stable aqueous acidic solutions, often having a pH of up to 1 containing an ester peracid and/or an acid peracid can be obtained by reacting a diester satisfying the general formula R¹—O—CO—R²—CO—O—R³ in which R¹ and R³ each represents a alkyl group containing from 1 to 4 carbon atoms which may the same of different and R² represents an aliphatic alkylene group optionally unsaturated which may be linear or branched containing from 2 to 6 carbon atoms with aqueous hydrogen peroxide in the presence of an acid, such as sulphuric acid and permitting the compositions to progress towards equilibrium concentrations. By starting with a diester, perhydrolysis generates an ester peracid which is a particularly effective peracid. The process can be controlled to produce solutions containing a high peracid content and within a wide range of ratios of ester peracid to acid peracid.

Claims

1. A process for the production of aqueous percarboxylic acid solutions by reaction of a peroxygen compound and a precursor of the percarboxylic acid in the presence of an acid catalyst wherein the peroxygen compound comprises hydrogen peroxide and the precursor comprises an aliphatic diester satisfying the general formula R¹—

O—

CO—

R²—

CO—

O—

R³ wherein R¹ and R³ each represents an alkyl group containing from 1 to 4 carbon atoms which may be the same or different and R² represents an alkylene group which may be linear or branched containing from 2 to 6 carbon atoms and optionally unsaturated, and wherein the reaction mixture expressed in terms of its reactants comprises at least 3% diester.

2. The process according to claim 1 wherein the reaction mixture expressed in terms of its reactants comprises from 5 to 90% w/w diester.

3. The process according to claim 1 wherein the reaction mixture expressed in terms of its reactants comprises hydrogen peroxide selected in the range of up to 30% w/w.

4. The process according to claim 1 wherein the reaction mixture expressed in terms of its reactants comprises at least 4% w/w hydrogen peroxide.

5. The process according to claim 1 wherein the reaction mixture expressed in terms of its reactants comprises at least 1 mole of hydrogen peroxide per 4 moles of diester.

6. The process according to claim 5 wherein the mole ratio of hydrogen peroxide:

diester is selected in the range of from 10;

1 to 1;

4.

7. The process according to claim 6 wherein at least an equimolar amount of hydrogen peroxide is employed per mole of diester.

8. The process according to claim 1 wherein the reaction mixture expressed in terms of its reagents comprises at least 50% w/w diester.

9. The process according to claim 8 wherein the reaction mixture expressed in terms of its reagents comprises from 70 to 85% w/w diester and from 1 to 1.25 moles of hydrogen peroxide per mole of diester.

10. The process according to claim 1 wherein the reaction mixture expressed in terms of its reagents and water comprises from 50 to 90% w/w water, hydrogen peroxide selected in the range of from 4 to 25% w/w and diester selected in the range of from 5 to 45% w/w.

11. The process according to claim 10 wherein the weight ratio of diester to hydrogen peroxide is selected in the range of 4:

1 to 2;

3.

12. The process according to claim 10 wherein the reaction mixture expressed in terms of its reagents and water comprises 75 to 85% water and hydrogen peroxide selected in the range of from 4 to 12% w/w and diester selected in the range of from 5 to 15% w/w.

13. The process according to claim 1 conducted in at least two stages, in the first stage of which a reaction mixture is employed which expressed in terms of its reactants comprises at least 50% w/w diester and at least 1 mole of hydrogen peroxide per mole of diester, said mixture being stored until at least 75 molar % of the equilibrium proportion of peracid species is attained and thereafter the mixture is diluted with water and optionally at least one of the reactants to produce a composition comprising at least 50% w/w water.

14. The process according to claim 13 wherein the diluted mixture contains, expressed in terms of the reactants, a total of 5 to 15% w/w diester and 4 to 12% w/w hydrogen peroxide.

15. The process according to claim 1 wherein the solution is stored before use until its percarboxylic acid content reaches or exceeds at least 90% of the amount of percarboxylic acid present at equilibrium.

16. The process according to claim 1 wherein aqueous hydrogen peroxide is introduced into diester at a rate controlled to maintain the mixture as a single phase.

17. The process according to claim 16 wherein the aqueous hydrogen peroxide has a concentration selected in the range of from 27 to 55% w/w H₂O₂.

18. The process recording to claim 16 wherein water is introduced into the mixture of diester and hydrogen peroxide at a rate controlled to maintain the mixture as a single phase.

19. The process according to claim 16 wherein the proportion of water provided in total from the aqueous hydrogen peroxide and the water is at least 50% by weight of the final composition.

20. The process according to claim 1 wherein the solution has a pH of from −

2 to 1.

21. The process according to claim 1 wherein, in the formula, R¹ and R³ are each selected from methyl and ethyl groups.

22. The process according to claim 21 wherein R¹ and R³ are both methyl.

23. The process according to claim 1 wherein, in the formula, R² is saturated.

24. The process according to claim 1 wherein, in the formula, R² is selected from linear groups containing from 2 to 4 carbon atoms and mixtures of any two or all three of them.

25. The process according to claim 1 wherein the reaction mixture contains up to 10% w/w of an acid introduced before, during or after the reaction.

26. The process according to claim 1 wherein the reaction mixture contains from 0.1 to 2.5% w/w of an inorganic or organic acid catalyst having a pK_a of below 1.

27. The process according to claim 1 wherein the reaction mixture contains from 0.025 to 1% w/w of at least one stabiliser selected from hydroxy-substituted aromatic carboxylic acids and their ester derivatives, and organic polyphosphonic acids or mixtures of any two or more thereof.

28. The process according to claim 27 wherein the hydroxy-substituted aromatic carboxylic acid comprises p-hydroxy benzoic acid, and the organic polyphosphonic acid comprises hydroxyethylidenediphosphonic acid or ethylene or cyclohexane diaminotetramethylene phosphonic acid or diethylene triaminopentamethylene phosphonic acid.

29. The process according to claim 1 wherein the reaction mixture contains at least one surfactant introduced before, during or after the reaction.

43. The process according to claim 3 wherein the reaction mixture expressed in terms of its reactants comprises no more than 20% w/w hydrogen peroxide.

44. The process according to claim 9 wherein the reaction mixture expressed in terms of its reactants comprises from 75 to 85% w/w diester.

45. The process according to claim 13 wherein the reaction mixture comprises at least an equimolar amount of hydrogen peroxide and diester.

46. The process according to claim 13 wherein the resultant composition comprises at least 75% w/w water.

50. The process according to claim 1 conducted in at least two stages, in the first stage of which aqueous hydrogen peroxide and the diester are agitated together to form a single phase, and in the second stage of which the phase is diluted with water and again agitated until a single phase is obtained.

30. A composition comprising an ester, a peracid derivative thereof, hydrogen peroxide and water comprising at from 2 to 30% w/w hydrogen peroxide, 5 to 90% w/w water and 3 to 90% w/w of an aliphatic diester satisfying the general formula R¹—

O—

CO—

R²—

CO—

O—

R³ in which R¹ and R³ each represents an alkyl group containing from 1 to 4 carbon atoms which may be the same or different and R² represents an alkylene group which may be linear or branched containing from 2 to 6 carbon atoms and optionally unsaturated, the % w/w for the diester including the peracidic derivative thereof and any acidic derivative of the ester generated in situ, the composition including a residual concentration of the diester.

31. The composition according to claim 30 comprising at least 0.1% w/w ester peracid.

33. The composition according to claim 30 wherein the concentration of hydrogen peroxide is not more than 20% w/w.

34. The composition according to claim 33 wherein the concentration of hydrogen peroxide is from 4to 12%.

35. The composition according to claim 30 wherein the concentration of diester and its derivatives is from 3 to 15% w/w.

36. The composition according to claim 30 wherein the weight ratio of diester and derivatives thereof to hydrogen peroxide is selected in the range of from 4:

1 to 2;

3.

37. The composition according to claim 36 wherein the diester is a dimethyl.

38. The composition according to claim 30 wherein R² in the formula for the diester represents an alkylene group containing from 2 to 4 carbons or a mixture of any 2 or 3 such diesters.

39. The composition according to claim 30 comprising additionally a surfactant.

40. The composition according to claim 30 containing from 0.025 to 1% w/w of at least one stabiliser selected from hydroxy-substituted aromatic carboxylic acids and their ester derivatives, and organic polyphosphonic acids or mixtures of any two or more thereof.

41. The composition according to claim 30 comprising additionally a non halide mineral acid selected from sulphuric or phosphoric or sulphamic acid or an organic sulphonic acid at a concentration of from 0.05 to 10% w/w.

47. The composition according to claim 31 comprising from 0.3 to 3% w/w ester peracid.

48. The composition according to claim 36 wherein the weight ratio of diester and derivatives thereof to hydrogen peroxide is from 3:

2 to 2;

3.

49. The composition according to claim 39 wherein said surfactant comprises up to 20% w/w.

51. The composition wording to claim 30 wherein the diester comprises a mixture of diesters of succinic acid, glutaric acid and adipic acid.

52. The composition according to claim 51 wherein the mixture of diesters comprises 10-20% w/w of succinic acid, 40-70% w/w of glutaric acid and 20-33% w/w of adipic acid.

32. A composition containing hydrogen peroxide, a peracid and an ester and hydrolysis perhydrolysis derivatives thereof comprising at least 2% w/w hydrogen peroxide, and at least 3% w/w diester including hydrolysis and perhydrolysis derivatives thereof, of which at least 0.1 is an ester peracid, the composition including a residual concentration of the diester.

42. A composition comprising an ester, a peracid derivative thereof, hydrogen peroxide and water comprising from 2 to 30% w/w hydrogen peroxide, 5 to 90% w/w water and 3 to 90% w/w of an aliphatic diester satisfying the general formula R¹—

O—

CO—

R²—

CO—

O—

R³ in which R¹ and R³ each represents an alkyl group containing from 1 to 4 carbon atoms which may be the same or different and R² represents an alkylene group which may be linear or branched containing from 2 to 6 carbon atoms and optionally unsaturated, the % for the diester including the peracidic derivative thereof and any acidic derivative of the ester generated in situ and containing a C1 to C4 alcohol in the range of from 1 to 20% w/w and at a mole ratio to the aliphatic diester of greater than 1;

1.