Antioxidant combination for oxidation and deposit control in lubricants containing molybdenum and alkylated phenothiazine

• US 6,797,677 B2
• Filed: 05/30/2002
• Issued: 09/28/2004
• Est. Priority Date: 05/30/2002
• Status: Expired due to Term

• Current Assignee: Afton Chemical Corporation
• Original Assignee: Afton Chemical Corporation
• Inventors: Gatto, Vincent J., Esche, Carl K. Jr.
• Primary Examiner(s): McAvoy, Ellen M.
• Application Number:
  US10/158,096
• Publication Number:
  US 20030224950A1
• Time in Patent Office: 852 Days
• Field of Search: 508/251, 508/252, 508/253, 508/254, 508/167, 508/170
• US Class Current: 508/167
• CPC Class Codes: C10M 163/00 Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential

Abstract

The invention relates to a lubricating oil composition having improved antioxidant properties, and which contains a molybdenum compound and an alkylated phenothiazine. Further, it may also include a secondary diarylamine, preferably an alkylated diphenylamine. This combination of additives provides improved oxidation control and friction modifier performance to the lubricating oil. The composition is particularly suited for use as a crankcase lubricant, or a transmission lubricant, including low levels and zero levels of phosphorus.

Claims

1. A lubricating composition consisting essentially of a major amount of lubricating oil, and minor amounts of an oil soluble secondary diarylamine, an oil soluble molybdenum compound, and an oil soluble C_4-24 alkylated phenothiazine, wherein said molybdenum compound is selected from the group consisting of molybdenum trioxides, ammonium molybdates, sodium molybdates, potassium molybdates, molybdenum dithiocarbamates, compounds prepared by reacting molybdenum trioxide with a secondary amine and carbon disulfide, compounds prepared by reacting a sulfur-free molybdenum source with a secondary amine, carbon disulfide, and an additional sulfur source, compounds prepared by reacting a molybdenum halide with a secondary amine and carbon disulfide, compounds prepared by reacting a molybdenum source with a basic nitrogen compound and a sulfur source, compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound, compounds prepared by reacting an olefin, sulfur, an amine and a molybdenum source, compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound and an organic sulfur source, compounds prepared by reacting a phenolic compound, an amine and a molybdenum source with a sulfur source, compounds prepared by reacting a triglyceride, a basic nitrogen compound, a molybdenum source, and a sulfur source, compounds prepared by reacting alkali metal alkylthioxanthate salts with molybdenum halides, compounds prepared by reacting a tetralkylthiuram disulfide with molybdenum hexacarbonyl, compounds prepared by reacting an alkyl dixanthogen with molybdenum hexacarbonyl, compounds prepared by reacting alkali metal alkylxanthate salts with dimolybdenum tetra-acetate, compounds prepared by reacting (NH₄)₂Mo₃S₁₃*₂H₂O with an alkali metal dialkyldithiocarbarnate or tetraalkyl thiuram disulfide, compounds prepared by reacting an ester or acid with a diamine, a molybdenum source and carbon disulfide, compounds prepared by reacting an alkali metal dialkyldithiocarbarnate with 3-chloropropionic acid, followed by molybdenum trioxide, compounds prepared by reacting basic nitrogen compounds with a molybdenum source, compounds prepared by reacting a hydrocarbyl substituted hydroxy alkylated amine with a molybdenum source, compounds prepared by reacting a phenol aldehyde condensation product, a mono-alkylated alkylene diamine, and a molybdenum source, compounds prepared by reacting a fatty oil, diethanolanilne, and a molybdenum source, compounds prepared by reacting a fatty oil or acid with 2-(2-aminoethyl)aminoethanol, and a molybdenum source, compounds prepared by reacting a secondary amine with a molybdenum source, compounds prepared by reacting a diol, diamino, or amino-alcohol compound with a molybdenum source, compounds prepared by reacting a fatty oil, mono-alkylated alkylene diamine, and a molybdenum source, compounds prepared by reacting a fatty acid, mono-alkylated alkylene diamine, glycerides, and a molybdenum source.

2. The lubricating composition as described in claim 1, wherein the diarylamine comprises an alkylated diphenylamine.

3. The lubricating composition as described in claim 2, wherein the alkylated diphenylamine has a concentration of about 0.1 to 2.5 wt. % in the lubricating composition.

4. The lubricating composition as described in claim 3, wherein the alkylated diphenylamine has a concentration of about 0.2 to 1.5 wt. % in the lubricating composition.

5. The lubricating composition as described in claim 1, wherein the oil soluble molybdenum compound further comprises sulfur.

6. The lubricating composition as described in claim 1, wherein the oil soluble molybdenum compound has a concentration sufficient to provide about 20 to 1000 ppm of molybdenum in the lubricating composition.

7. The lubricating composition as described in claim 6, wherein the oil soluble molybdenum compound has a concentration sufficient to provide about 20 to 200 ppm of molybdenum in the lubricating composition.

8. The lubricating composition as described in claim 1, wherein the oil soluble alkylated phenothiazine has a concentration of about 0.05 to 1.5 wt. % in the lubricating composition.

9. The lubricating composition as described in claim 8, wherein the oil soluble alkylated phenothiazine has a concentration of about 0.1 to 1.0 wt. % in the lubricating composition.

10. The lubricating composition as described in claim 1, wherein the alkylated phenothiazine is disubstituted, with each substituted alkyl group comprising from four to about twenty-four carbon atoms.

11. The lubricating composition as described in claim 10, wherein each substituted alkyl group on the alkylated phenothiazine comprises four to, but including, eight carbon atoms.

12. The lubricating composition as described in claim 1, wherein the alkylated phenothiazine comprises dioctylphenothiazine.

13. The lubricating composition as described in claim 1, wherein the alkylated phenothiazine comprises monooctylphenothiazine.

14. The lubricating composition as described in claim 1, wherein the alkylated phenothiazine comprises dinonylphenothiazine.

15. The lubricating composition as described in claim 1, wherein the alkylated phenothiazine comprises monononylphenothiazine.

16. The lubricating composition as described in claim 1, wherein the alkylated phenothiazine comprises mono C₁₄ alkylphenothiazine.

17. The lubricating composition as described in claim 1, wherein the alkylated phenothiazine comprises di C₁₄ alkylphenothiazine.

18. A lubricating composition consisting essentially of a major amount of lubricating oil, an oil soluble molybdenum compound, and an oil soluble C_4-24 alkylated phenothiazine, wherein said molybdenum compound is selected from the group consisting of molybdenum trioxides, ammonium molybdates, sodium molybdates, potassium molybdates, molybdenum dithiocarbamates, compounds prepared by reacting molybdenum trioxide with a secondary amine and carbon disulfide, compounds prepared by reacting a sulfur-free molybdenum source with a secondary amine, carbon disulfide, and an additional sulfur source, compounds prepared by reacting a molybdenum halide with a secondary amine and carbon disulfide, compounds prepared by reacting a molybdenum source with a basic nitrogen compound and a sulfur source, compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound, compounds prepared by reacting an olefin, sulfur, an amine and a molybdenum source, compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound and an organic sulfur source, compounds prepared by reacting a phenolic compound, an amine and a molybdenum source with a sulfur source, compounds prepared by reacting a triglyceride, a basic nitrogen compound, a molybdenum source, and a sulfur source, compounds prepared by reacting alkali metal alkylthioxanthate salts with molybdenum halides, compounds prepared by reacting a tetralkylthiuram disulfide with molybdenum hexacarbonyl, compounds prepared by reacting an alkyl dixanthogen with molybdenum hexacarbonyl, compounds prepared by reacting alkali metal alkylxanthate salts with dimolybdenum tetra-acetate, compounds prepared by reacting(NH₄)₂Mo₃S₁₃*₂H₂O with an alkali metal dialkyldithiocarbamate or tetraalkyl thiuram disulfide, compounds prepared by reacting an ester or acid with a diamine, a molybdenum source and carbon disulfide, compounds prepared by reacting an alkali metal dialkyldithiocarbamate with 3-chloropronionic acid, followed by molybdenum trioxide, compounds prepared by reacting basic nitrogen compounds with a molybdenum source, compounds prepared by reacting a hydrocarbyl substituted hydroxy alkylated amine with a molybdenum source, compounds prepared by reacting a phenol aldehyde condensation product, a mono-alkylated alkylene diamine, and a molybdenum source, compounds prepared by reacting a fatty oil, diethanolamine, and a molybdenum source, compounds prepared by reacting a fatty oil or acid with 2-(2-aminoethyl)aminoethanol, and a molybdenum source, compounds prepared by reacting a secondary amine with a molybdenum source, compounds prepared by reacting a diol, diamino, or amino-alcohol compound with a molybdenum source, compounds prepared by reacting a fatty oil, mono-alkylated alkylene diamine, and a molybdenum source, compounds prepared by reacting a fatty acid, mono-alkylated alkylene diamine, glycerides, and a molybdenum source.

19. The lubricating composition as described in claim 18, wherein the oil soluble molybdenum compound further comprises sulfur.

20. The lubricating composition as described in claim 18, wherein the oil soluble molybdenum compound has a concentration sufficient to provide about 20 to about 1000 ppm of molybdenum in the lubricating composition.

21. The lubricating composition as described in claim 20, wherein the oil soluble molybdenum compound has a concentration sufficient to provide about 20 to about 200 ppm of molybdenum in the lubricating composition.

22. The lubricating composition as described in claim 18, wherein the oil soluble alkylated phenothiazine has a concentration of about 0.05 to 1.5 wt. % in the lubricating composition.

23. A lubricating composition as described in claim 22, wherein the oil soluble alkylated phenothiazine has a concentration of about 0.1 to 1.0 wt. % in the lubricating composition.

24. A lubricating composition as described in claim 18, wherein at least one of the alkyl groups of the alkylated phenothiazine comprises from four to about twenty-four carbon atoms.

25. The lubricating composition as described in claim 18, wherein the alkylated phenothiazine is disubstituted, with each substituted alkyl group comprising from about four to about twenty-four carbon atoms.

26. The lubricating composition as described in claim 18, wherein each substituted alkyl group has four to, but including, eight carbon atoms.

27. A lubricating composition as described in claim 18, wherein the alkylated phenothiazine comprises dioctylphenothiazine.

28. The lubricating composition as described in claim 18, wherein the alkylated phenothiazine comprises monooctylphenothiazine.

29. The lubricating composition as described in claim 18, wherein the alkylated phenothiazine comprises dinonylphenothiazine.

30. The lubricating composition as described in claim 18, wherein the alkylated phenothiazine comprises monononylphenothiazine.

31. The lubricating composition as described in claim 18, wherein the alkylated phenothiazine comprises mono C₁₄ alkylphenothiazine.

32. The lubricating composition as described in claim 18, wherein the alkylated phenothiazine comprises di C₁₄ alkylphenothiazine.

33. A lubricating composition additive consisting essentially of an oil soluble secondary diarylamine, an oil soluble molybdenum compound, and an oil soluble alkylated C_4-24 phenothiazine, wherein said molybdenum compound is selected from the group consisting of molybdenum trioxides, ammonium molybdates, sodium molybdates, potassium molybdates, molybdenum dithiocarbamates, compounds prepared by reacting molybdenum trioxide with a secondary amine and carbon disulfide, compounds prepared by reacting a sulfur-free molybdenum source with a secondary amine, carbon disulfide, and an additional sulfur source, compounds prepared by reacting a molybdenum halide with a secondary amine and carbon disulfide, compounds prepared by reacting a molybdenum source with a basic nitrogen compound and a sulfur source, compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound, compounds prepared by reacting an olefin, sulfur, an amine and a molybdenum source, compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound and an organic sulfur source, compounds prepared by reacting a phenolic compound, an amine and a molybdenum source with a sulfur source, compounds prepared by reacting a triglyceride, a basic nitrogen compound, a molybdenum source, and a sulfur source, compounds prepared by reacting alkali metal alkylthioxanthate salts with molybdenum halides, compounds prepared by reacting a tetralkylthiuram disulfide with molybdenum hexacarbonyl, compounds prepared by reacting an alkyl dixanthogen with molybdenum hexacarbonyl, compounds prepared by reacting alkali metal alkylxanthate salts with dimolybdenum tetra-acetate, compounds prepared by reacting (NH₄)₂Mo₃S₁₃*₂H₂O with an alkali metal dialkyldithiocarbamate or tetraalkyl thiuram disulfide, compounds prepared by reacting an ester or acid with a diamine, a molybdenum source and carbon disulfide, compounds prepared by reacting an alkali metal dialkyldithiocarbamate with 3-chloropropionic acid, followed by molybdenum trioxide, compounds prepared by reacting basic nitrogen compounds with a molybdenum source, compounds prepared by reacting a hydrocarbyl substituted hydroxy alkylated amine with a molybdenum source, compounds prepared by reacting a phenol aldehyde condensation product, a mono-alkylated alkylene diamine, and a molybdenum source, compounds prepared by reacting a fatty oil, diethanolamine, and a molybdenum source, compounds prepared by reacting a fatty oil or acid with 2-(2-aminoethyl) aminoethanol, and a molybdenum source, compounds prepared by reacting a secondary amine with a molybdenum source, compounds prepared by reacting a diol, diamino, or amino-alcohol compound with a molybdenum source, compounds prepared by reacting a fatty oil, mono-alkylated alkylene diamine, and a molybdenum source, compounds prepared by reacting a fatty acid, mono-alkylated alkylene diamine, glycerides, and a molybdenum source.

34. The lubricating composition additive as described in claim 33, wherein the diarylamine is an alkylated diphenylamine.

35. The lubricating composition additive as described in claim 33, wherein the oil soluble molybdenum compound further comprises sulfur.

36. A lubricating composition additive as described in claim 33, wherein the oil soluble molybdenum compound has a concentration sufficient to provide about 20 to 1000 ppm of molybdenum in the lubricating composition.

37. The lubricating composition additive as described in claim 33, wherein the oil soluble molybdenum compound has a concentration sufficient to provide about 20 to 200 ppm of molybdenum in the lubricating composition.

38. A lubricating composition additive as described in claim 33, wherein at least one of the alkyl groups of the alkylated phenothiazine comprises from four to about twenty-four carbon atoms.

39. The lubricating composition additive as described in claim 33, wherein the alkylated phenothiazine is disubstituted, with each substituted alkyl group comprising from about four to about twenty-four carbon atoms.

40. The lubricating composition additive as described in claim 39, wherein each substituted alkyl group comprises four to, but including, eight carbon atoms.

41. The lubricating composition additive as described in claim 33, wherein the alkylated phenothiazine comprises dioctylphenothiazine.

42. The lubricating composition additive as described in claim 33, wherein the alkylated phenothiazine comprises monooctylphenothiazine.

43. The lubricating composition additive as described in claim 33, wherein the alkylated phenothiazine comprises dinonylphenothiazine.

44. The lubricating composition additive as described in claim 33, wherein the alkylated phenothiazine comprises monononylphenothiazine.

45. The lubricating composition additive as described in claim 33, wherein the alkylated phenothiazine comprises mono C₁₄ alkylphenothiazine.

46. The lubricating composition additive as described in claim 33, wherein the alkylated phenothiazine comprises di C₁₄ alkylphenothiazine.

47. A lubricating composition additive consisting essentially of an oil soluble molybdenum compound and an oil soluble alkylated C_4-24 phenothiazine, wherein said molybdenum compound is selected from the group consisting of molybdenum trioxides, ammonium molybdates, sodium molybdates, potassium molybdates, molybdenum dithiocarbamates, compounds prepared by reacting molybdenum trioxide with a secondary amine and carbon disulfide, compounds prepared by reacting a sulfur-free molybdenum source with a secondary amine, carbon disulfide, and an additional sulfur source, compounds prepared by reacting a molybdenum halide with a secondary amine and carbon disulfide, compounds prepared by reacting a molybdenum source with a basic nitrogen compound and a sulfur source, compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound, compounds prepared by reacting an olefin, sulfur, an amine and a molybdenum source, compounds prepared by reacting ammonium tetrathiomolybdate with a basic nitrogen compound and an organic sulfur source, compounds prepared by reacting a phenolic compound, an amine and a molybdenum source with a sulfur source, compounds prepared by reacting a triglyceride, a basic nitrogen compound, a molybdenum source, and a sulfur source, compounds prepared by reacting alkali metal alkylthioxanthate salts with molybdenum halides, compounds prepared by reacting a tetralkylthiuram disulfide with molybdenum hexacarbonyl, compounds prepared by reacting an alkyl dixanthogen with molybdenum hexacarbonyl, compounds prepared by reacting alkali metal alkylxanthate salts with dimolybdenum tetra-acetate, compounds prepared by reacting (NH₄)₂Mo₃S₁₃*₂H₂O with an alkali metal dialkyldithiocarbamate or tetraalkyl thiuram disulfide, compounds prepared by reacting an ester or acid with a diamine, a molybdenum source and carbon disulfide, compounds prepared by reacting an alkali metal dialkyldithiocarbamate with 3-chloropropionic acid, followed by molybdenum trioxide, compounds prepared by reacting basic nitrogen compounds with a molybdenum source, compounds prepared by reacting a hydrocarbyl substituted hydroxy alkylated amine with a molybdenum source, compounds prepared by reacting a phenol aldehyde condensation product, a mono-alkylated alkylene diamine, and a molybdenum source, compounds prepared by reacting a fatty oil, diethanolamine, and a molybdenum source, compounds prepared by reacting a fatty oil or acid with 2-(2-aminoethyl)aminoethanol and a molybdenum source, compounds prepared by reacting a secondary amine with a molybdenum source, compounds prepared by reacting a diol, diamino, or amino-alcohol compound with a molybdenum source, compounds prepared by reacting a fatty oil, mono-alkylated alkylene diamine, and a molybdenum source, compounds prepared by reacting a fatty acid, mono-alkylated alkylene diamine, glycerides, and a molybdenum source.

48. The lubricating composition additive as described in claim 47, wherein the oil soluble molybdenum compound further comprises sulfur.

49. The lubricating composition additive as described in claim 47, wherein at least one of the alkyl groups of the alkylated phenothiazine comprises from four to about twenty-four carbon atoms.

50. The lubricating composition additive as described in claim 47, wherein the alkylated phenothiazine is disubstituted, with each substituted alkyl group comprising from about four to about twenty-four carbon atoms.

51. The lubricating composition additive as described in claim 50, wherein each substituted alkyl group comprises four to, but including, eight carbon atoms.

52. The lubricating composition additive as described in claim 47, wherein the alkylated phenothiazine comprises dioctylphenothiazine.

53. The lubricating composition additive as described in claim 47, wherein the alkylated phenothiazine comprises monoctylphenothiazine.

54. The lubricating composition additive as described in claim 47, wherein the alkylated phenothiazine comprises dinonylphenothiazine.

55. The lubricating composition additive as described in claim 47, wherein the alkylated phenothiazine comprises monononylphenothiazine.

56. The lubricating composition additive as described in claim 47, wherein the alkylated phenothiazine comprises mono C₁₄ alkylphenothiazine.

57. The lubricating composition additive as described in claim 47, wherein the alkylated phenothiazine comprises di C₁₄ alkylphenothiazine.

58. A method for improving the antioxidancy and/or anti-Wear properties of a lubricating composition comprising including in the lubricating composition an oil soluble molybdenum compound and an oil soluble alkylated C₄-C₂₄ phenothiazine.

59. The method as described in claim 58, further comprising including in the lubricating composition an oil soluble secondary diarylamine.

60. The method as described in claim 59, wherein the diarylamine is an alkylated diphenylamine.

61. The method as described in claim 59, wherein the secondary diarylamine has a concentration of about 0.1 to 2.5 wt. % in the lubricating composition.

62. The method as described in claim 59, wherein the secondary diarylamine has a concentration of about 0.2 to 1.5 wt. % in the lubricating composition.

63. The method as described in claim 58, wherein the oil soluble molybdenum compound further comprises sulfur.

64. The method as described in claim 58, wherein the oil soluble molybdenum compound has a concentration sufficient to provide about 20 to about 1000 ppm of molybdenum in the lubricating composition.

65. The method as described in claim 64, wherein the oil soluble molybdenum compound has a concentration sufficient to provide about 20 to 200 ppm of molybdenum in the lubricating composition.

66. The method as described in claim 58, wherein the oil soluble alkylated phenothiazine has a concentration of about 0.05 to 1.5 wt. % in the lubricating composition.

67. The method as described in claim 66, wherein the oil soluble alkylated phenothiazine has a concentration of about 0.1 to 1.0 wt. % in the lubricating composition.

68. The method as described in claim 58, wherein at least one of the alkyl groups of the alkylated phenothiazine comprises from four about twenty-four carbon atoms.

69. The method as described in claim 58, wherein the alkylated phenothiazine is disubstituted, with each substituted alkyl group comprising from about four to about twenty-four carbon atoms.

70. The method as described in claim 69, wherein each substituted alkyl group has four to but including eight carbon atoms.

71. The method as described in claim 58, wherein the alkylated phenothiazine comprises dioctylphenothiazine.

72. The method as described in claim 58, wherein the alkylated phenothiazine comprises monooctylphenothiazine.

73. The method as described in claim 58, wherein the alkylated phenothiazine comprises dinonylphenothiazine.

74. The method as described in claim 58, wherein the alkylated phenothiazine comprises monononylphenothiazine.

75. The method as described in claim 58, wherein the alkylated phenothiazine comprises mono C₁₄ alkylphenothiazine.

76. The method as described in claim 58, wherein the alkylated phenothiazine comprises di C₁₄ alkylphenothiazine.

77. The method as described in claim 58, further comprising including in the lubricating composition an oil soluble alkylated diphenylamine, an oil soluble phosphorus compound, and an oil soluble hindered phenolic derived from 2,6-di-tert-butyiphenol.

78. The method as described in claim 58, further comprising including in the lubricating composition an oil soluble alkylated diphenylamine, an oil soluble phosphorus compound, and an oil soluble calcium-containing detergent.

79. A method for lubricating an engine, comprising lubricating said engine with a lubricating composition of claim 1.

80. A method for lubricating an engine, comprising lubricating said engine with a lubricating composition of claim 18.

81. A method for lubricating an engine, comprising lubricating said engine with a lubricant containing the lubricant composition additive of claim 33.

82. A method for lubricating an engine, comprising lubricating said engine with a lubricant containing the lubricant composition additive of claim 47.

83. The composition of claim 1, wherein the composition comprises zero phosphorus.

84. The composition of claim 1, wherein the composition comprises essentially zero phosphorus.

85. The composition of claim 18, wherein the composition comprises zero phosphorus.

86. The composition of claim 18, wherein the composition comprises essentially zero phosphorus.

87. The composition of claim 33, wherein the composition comprises zero phosphorus.

88. The composition of claim 33, wherein the composition comprises essentially zero phosphorus.