ADDITIVE PACKAGE AND LUBRICATING OIL COMPOSITION

• US 20170349853A1
• Filed: 06/02/2017
• Published: 12/07/2017
• Est. Priority Date: 06/03/2016
• Status: Active Grant

• Current Assignee: Infineum International Limited (Infineum)
• Original Assignee: 1nfineum International Limited
• Inventors: Strong, Anthony J., Woodward, Philip J.
• Granted Patent: US 10,640,724 B2
• Time in Patent Office: Days
• CPC Class Codes: C10M 129/44 containing hydroxy groups
• CPC Class Codes: C10M 129/54 containing hydroxy groups
• CPC Class Codes: C10M 129/70 of monocarboxylic acids
• CPC Class Codes: C10M 137/10 Thio derivatives
• CPC Class Codes: C10M 145/28 of alkylene oxides containing 2 carbon atoms only
• CPC Class Codes: C10M 165/00 Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
• CPC Class Codes: C10M 2207/128 containing hydroxy groups; Ethers thereof
• CPC Class Codes: C10M 2207/262 derived from hydroxy substituted aromatic acids, e.g. salicylates
• CPC Class Codes: C10M 2207/281 of (cyclo)aliphatic monocarboxylic acids
• CPC Class Codes: C10M 2209/104 of alkylene oxides containing two carbon atoms only
• CPC Class Codes: C10M 2209/109 esterified
• CPC Class Codes: C10M 2209/112 having dihydric acid centres
• CPC Class Codes: C10M 2223/045 Metal containing thio derivatives
• CPC Class Codes: C10N 2020/04 Molecular weight; Molecular weight distribution
• CPC Class Codes: C10N 2030/04 Detergent property or dispersant property
• CPC Class Codes: C10N 2030/06 Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• CPC Class Codes: C10N 2030/10 Inhibition of oxidation, e.g. anti-oxidants
• CPC Class Codes: C10N 2030/12 Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• CPC Class Codes: C10N 2030/18 Anti-foaming property
• CPC Class Codes: C10N 2030/52 Base number [TBN]
• CPC Class Codes: C10N 2040/25 : Internal-combustion engines
• CPC Class Codes: F01M 9/02 : having means for introducing additives to lubricant

Abstract

An additive package is disclosed for preparing an automotive crankcase lubricating oil composition for an internal combustion engine. The additive package is made by admixing:

• • (i) 50 mass % or less of an oil of lubricating viscosity;
  • (ii) 50 mass % or less of at least one overbased metal detergent, preferably at least one overbased metal hydroxybenzoate detergent;
  • (iii) 50 mass % or less of an oil-soluble block or graft co-polymer of at to least one polymeric block A which is derived from a hydroxycarboxylic acid and at least one polyalkylene block B which is a residue of a polyalkylene glycol, and
  • (iv) optionally, at least one further additive selected from a dispersant, an antioxidant and/or an antiwear agent.

The additive package includes less than 2.00 mass % preferably less than 1.50 mass %, of a friction modifier which is a monoester of a C₅ to C₃₀ carboxylic acid and which is free of nitrogen.

Component (ii) is preferably an overbased metal hydroxybenzoate detergent.

Component (iii) acts as a friction modifier and can be used as a replacement for a friction modifier such as glycerol monooleate.

The additive package exhibits improved stability.

Claims

1. An additive package for preparing an automotive crankcase lubricating oil composition for an internal combustion engine, comprising or made by admixing:

(i) 50 mass % or less of an oil of lubricating viscosity;

(ii) 50 mass % or less of at least one overbased metal detergent;

(iii) 50 mass % or less of an oil-soluble block or graft co-polymer of at least one polymeric block A which is derived from a hydroxycarboxylic acid and at least one polyalkylene block B which is a residue of a polyalkylene glycol, and

(iv) optionally, at least one further additive selected from a dispersant, an antioxidant and/or an antiwear agent;

wherein the additive package includes less than 2.00 mass %, of a friction modifier which is a monoester of a C₅ to C₃₀ carboxylic acid and which is free of nitrogen.

3. The additive package as claimed in claim 1, wherein the hydroxycarboxylic acid is a hydroxystearic acid.

5. The additive package as claimed in claim 1, wherein the polyalkylene glycol in component (iii) is polyethylene glycol.

7. The additive package as claimed in claim 1, wherein the molecular weight of the polymeric block A in component (iii) is in the range 1000 to 2800 as measured by Gel Permeation Chromatography.

9. The additive package as claimed in claim 1, wherein the number average molecular weight of the polymeric block B in component (iii) is in the range 500 to 4600 as measured by Gel Permeation Chromatography.

11. The additive package as claimed in claim 1, wherein the number average molecular weight of the block copolymer in component (iii) is in the range 3000 to 5000, as measured by Gel Permeation Chromatography.

13. The additive package as claimed in claim 1, wherein the block copolymer in component (iii) has the structure AB or ABA, with the proviso that, where the block copolymer in component (iii) has the structure ABA, the A blocks may be the same or different.

15. The additive package as claimed in claim 1, wherein the friction modifier is glycerol monoester.

17. The additive package as claimed in claim 1, wherein component (iii) is a block or graft copolymer having a general formula (A-COO)₂-B, wherein each polymeric component A has a molecular weight of at least 500 and is the residue of an oil-soluble complex monocarboxylic acid having the general structural formula

19. The additive package as claimed in claim 17, wherein R is an alkyl group containing up to 25 carbon atoms, R is a straight-chain alkyl group containing 1 to 24 carbon atoms and R₂ is a straight-chain alkylene group containing 1 to 24 carbon atoms.

21. The additive package as claimed in claim 19, wherein R₃ is hydrogen or a C₁-C₃ alkyl group.

23. The additive package as claimed in claim 17, wherein each of the polymeric components A has a molecular weight of at least 1000 as measured by Gel Permeation Chromatography.

25. The additive package as claimed in claim 17, wherein the polymeric component B has a number average molecular weight of at least 1000 as measured by Gel Permeation Chromatography.

27. The additive package as claimed in claim 17, wherein the polymeric components A are derived from poly(12-hydroxystearic acid) chain-terminated with stearic acid and the polymeric component B is derived from polyethylene glycol.

29. The additive package or the composition as claimed in claim 15, which is water-soluble and in which the component B constitutes at least 65% by weight of the total copolymer component (iii).

31. The composition as claimed in claim 29, which is soluble in aliphatic hydrocarbons and in which the component B constitutes not more than 40% by weight of the total copolymer component (iii).

33. The composition as claimed in claim 31, in which each polymeric component A is of molecular weight of approximately 1750 as measured by Gel Permeation Chromatography and the B component is of molecular weight 1500 as measured by Gel Permeation Chromatography, the B component constituting approximately 30% by weight of the total copolymer.

38. The additive package as claimed in claim 1, further containing other additive components, different from (iii), selected from one or more ashless dispersants, corrosion inhibitors, antioxidants, zinc dihydrocarbyl dithiophosphates, pour point depressants, antiwear agents, friction modifiers other than a monoester of a C₅ to C₃₀ carboxylic acid which is nitrogen-free, demulsifiers and anti-foam agents.

40. The additive package as claimed in claim 1, wherein the overbased metal detergent is a metal hydroxybenzoate detergent.

41. The additive package as claimed in claim 40, wherein the metal hydroxybenzoate detergent is an alkaline earth alkylsalicylate detergent.

42. The additive package as claimed in claim 41, wherein the alkaline earth alkylsalicylate detergent is a calcium salicylate detergent.

43. The additive package as claimed in claim 42, wherein the calcium salicylate detergent has a TBN as defined in ASTM D2896 of 50 to 450 mg KOH/g.

44. The additive package as claimed in claim 43, wherein calcium salicylate detergent has a TBN as defined in ASTM D2896 of 200 to 300, mg KOH/g.

50. The additive package as claimed in claim 1, wherein the block copolymer (iii) has a hydrophilic/lipophilic balance (HLB) of at least 6.5.

51. The additive package as claimed in claim 50, wherein the block copolymer (iii) has a hydrophilic lipophilic balance (HLB) in the range 7 to 9.

55. A method of improving the storage stability of an additive package for preparing automotive crankcase lubricating oil composition for an internal combustion engine;

the method comprising incorporating into the additive package, in respective amounts of 50 mass % or less, one or more additives (iii) as defined in claim 1;

the additive package including at 50 mass % or less of at least one overbased metal detergent.

2. An automotive crankcase lubricating oil composition, for an internal combustion engine, comprising or made by admixing:

(i) in excess of 50 mass % of an oil of lubricating viscosity;

(ii) less than 50 mass % of at least one overbased metal detergent;

(iii) less than 50 mass % of an oil-soluble block or graft co-polymer of at least one block A which is derived from a hydroxycarboxylic acid and at least one polyalkylene block B which is a residue of a polyalkylene glycol, and

(iv) optionally, at least one further additive selected from a dispersant, an antioxidant and/or a antiwear agent;

wherein the lubricating oil composition includes less than 0.10 mass % of a friction modifier which is a monoester of a C₅ to C₃₀ carboxylic acid and which is free of nitrogen.

4. The composition as claimed in claim 2, wherein the hydroxycarboxylic acid is a hydroxystearic acid.

6. The composition as claimed in claim 2, wherein the polyalkylene glycol in component (iii) is polyethylene glycol.

8. The composition as claimed in claim 2, wherein the molecular weight of the polymeric block A in component (iii) is in the range 1000 to 2800 as measured by Gel Permeation Chromatography.

10. The composition as claimed in claim 2, wherein the number average molecular weight of the polymeric block B in component (iii) is in the range 500 to 4600 as measured by Gel Permeation Chromatography.

12. The composition as claimed in claim 2, wherein the number average molecular weight of the block copolymer in component (iii) is in the range 3000 to 5000, as measured by Gel Permeation Chromatography.

14. The composition as claimed claim 2, wherein the block copolymer in component (iii) has the structure AB or ABA, with the proviso that, where the block copolymer in component (iii) has the structure ABA, the A blocks may be the same or different.

16. The composition as claimed in claim 2, wherein the friction modifier is glycerol monoester.

18. The composition as claimed in claim 2, wherein component (iii) is a block or graft copolymer having a general formula (A-COO)₂-B, wherein each polymeric component A has a molecular weight of at least 500 and is the residue of an oil-soluble complex monocarboxylic acid having the general structural formula

20. The composition as claimed in claim 18, wherein R is an alkyl group containing up to 25 carbon atoms, R₁ is a straight-chain alkyl group containing 1 to 24 carbon atoms and R₂ is a straight-chain alkylene group containing 1 to 24 carbon atoms.

22. The composition as claimed in claim 20, wherein R₃ is hydrogen or a C₁-C₃ alkyl group.

24. The composition as claimed in claim 18, wherein each of the polymeric components A has a molecular weight of at least 1000 as measured by Gel Permeation Chromatography.

26. The composition as claimed in claim 18, wherein the polymeric component B has a number average molecular weight of at least 1000 as measured by Gel Permeation Chromatography.

28. The composition as claimed in claim 18, wherein the polymeric components A are derived from poly(12-hydroxystearic acid) chain-terminated with stearic acid and the polymeric component B is derived from polyethylene glycol.

30. The additive package as claimed in claim 28, which is soluble in aliphatic hydrocarbons and in which the component B constitutes not more than 40% by weight of the total copolymer component (iii).

32. The additive package as claimed in claim 30, in which each polymeric component A is of molecular weight of approximately 1750 as measured by Gel Permeation Chromatography and the B component is of molecular weight 1500 as measured by Gel Permeation Chromatography, the B component constituting approximately 30% by weight of the total copolymer.

34. The composition as claimed in claim 2, having not greater than 1600 ppm by mass of phosphorus, expressed as phosphorus atoms.

35. The composition as claimed in claim 34, having not greater than 800 ppm by mass of phosphorus, expressed as phosphorus atoms.

36. The composition as claimed in claim 35, having not greater than 500, ppm by mass of phosphorus, expressed as phosphorus atoms.

37. The composition as claimed in any claim 2, having a sulfated ash value of up to 1.0 and a sulfur content of up to 0.4 mass %.

39. The composition as claimed in claim 2, further containing other additive components, different from (iii), selected from one or more ashless dispersants, corrosion inhibitors, antioxidants, zinc dihydrocarbyl dithiophosphates, pour point depressants, antiwear agents, friction modifiers other than a monoester of a C₅ to C₃₀ carboxylic acid which is nitrogen-free, demulsifiers and anti-foam agents.

45. The composition as claimed in claim 2, wherein the overbased metal detergent is a metal hydroxybenzoate detergent.

46. The composition as claimed in claim 45, wherein the metal hydroxybenzoate detergent is an alkaline earth alkylsalicylate detergent.

47. The composition as claimed in claim 46, wherein the alkaline earth alkylsalicylate detergent is a calcium salicylate detergent.

48. The composition as claimed in. claim 47, wherein the calcium salicylate detergent has a TBN as defined in ASTM D2896 of 50 to 450 mg KOH/g.

49. The composition as claimed in claim 48, wherein calcium salicylate detergent has a TBN as defined in ASTM D2896 of 200 to 300, mg KOH/g.

52. The composition as claimed in claim 2, wherein the block copolymer (iii) has a hydrophilic lipophilic balance (HLB) of at least 6.5.

53. The composition as claimed in claim 52, wherein the block copolymer (iii) has a hydrophilic/lipophilic balance (HLB) in the range 7 to 9.

54. A method of improving the friction-reduction properties of an automotive crankcase lubricating oil composition for an internal combustion engine;

the method comprising incorporating into the composition, in respective amounts of 50 mass % or less, one or more additives (iii) as defined in claims 2;

the automotive crankcase lubricating oil composition or the additive package including at less than 50 mass % at least one overbased metal detergent.

56. A method of lubricating an internal combustion engine during operation of the engine comprising:

(i) providing a composition as claimed in claim 2 to the crankcase of the combustion engine;

(iii) providing a hydrocarbon fuel in the combustion engine; and

(iv) combusting the fuel in the combustion engine.