Additive package and lubricating oil composition

• US 10,640,724 B2
• Filed: 06/02/2017
• Issued: 05/05/2020
• Est. Priority Date: 06/03/2016
• Status: Active Grant

• Current Assignee: Infineum International Limited (Infineum)
• Original Assignee: Infineum International Limited (Infineum)
• Inventors: Strong, Anthony J., Woodward, Philip J.
• Primary Examiner(s): Toomer, Cephia D
• Application Number:
  US15/611,842
• Publication Number:
  US 20170349853A1
• Time in Patent Office: 1,068 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 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. A method of lubricating an automotive internal combustion engine during operation of the engine comprising:

(i) providing to a crankcase of the automotive internal combustion engine an automotive crankcase lubricating oil composition comprising or made by admixing;

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

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

(c) 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, the oil-soluble block or graft copolymer having a general formula (A-COO)_m-B, wherein m is 1 or 2, wherein each polymeric component A has a molecular weight of at least 500 and has the general structural formula

2. The method of claim 1, wherein the hydroxycarboxylic acid is a hydroxystearic acid.

3. The method of claim 1, wherein the polyalkylene glycol in component (i)(c) is polyethylene glycol.

4. The method of claim 1, wherein one or more of the following are satisfied:

the molecular weight of the polymeric block A in component (i)(c) is from 1000 to 2800 as measured by Gel Permeation Chromatography;

the number average molecular weight of the polymeric block B in component (i)(c) is from 500 to 4600 as measured by Gel Permeation Chromatography; and

the number average molecular weight of the copolymer in component (i)(c) is from 3000 to 5000, as measured by Gel Permeation Chromatography.

5. The method of claim 1, wherein the copolymer in component (i)(c) has the structure AB or ABA, with the proviso that, where the block copolymer in component (i)(c) has the structure ABA, the A blocks may be the same or different.

6. The method of claim 1, wherein the friction modifier is glycerol monoester, and wherein the automotive crankcase lubricating oil composition comprising component (c) and less than 0.10 mass % of the glycerol monoester exhibits a lower friction coefficient than an otherwise identical automotive crankcase lubricating oil composition, except comprising substantially none of component (c) and more than 0.10 mass % of the glycerol monoester, when friction coefficients are measured at HFRR testing times greater than 751 seconds.

7. The method of claim 1, 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.

8. The method of claim 7, wherein R₃ is hydrogen or a C₁-C₃ alkyl group.

9. The method of claim 1, wherein the or each of the polymeric components A has a molecular weight of at least 1000 as measured by Gel Permeation Chromatography, and/or the polymeric component B has a number average molecular weight of at least 1000 as measured by Gel Permeation Chromatography.

10. The method of claim 1, wherein the or each of 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.

11. The method of claim 1, wherein the automotive crankcase lubricating oil composition comprises not greater than 1600 ppm by mass of phosphorus, expressed as phosphorus atoms.

12. The method of claim 11, wherein the automotive crankcase lubricating oil composition comprises not greater than 800 ppm by mass of phosphorus, expressed as phosphorus atoms.

13. The method of claim 12, wherein the automotive crankcase lubricating oil composition comprises not greater than 500 ppm by mass of phosphorus, expressed as phosphorus atoms.

14. The method of claim 1, wherein the automotive crankcase lubricating oil composition has a sulfated ash content of up to 1.0 and a sulfur content of up to 0.4 mass %.

15. The method of claim 1, wherein said automotive crankcase lubricating oil composition further contains one or more other additive components, different from component (i)(c), selected from the group consisting of 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.

16. The method of claim 1, wherein the overbased metal detergent is a metal hydroxybenzoate detergent.

17. The method of claim 16, wherein the metal hydroxybenzoate detergent is an alkaline earth alkylsalicylate detergent.

18. The method of claim 17, wherein the alkaline earth alkylsalicylate detergent is a calcium salicylate detergent.

19. The method of claim 18, wherein the calcium salicylate detergent has a TBN, as defined in ASTM D2896, of 50 to 450 mg KOH/g.

20. The method of claim 19, wherein calcium salicylate detergent has a TBN, as defined in ASTM D2896, of 200 to 300 mg KOH/g.

21. The method of claim 1, wherein the copolymer (i)(c) has a hydrophilic/lipophilic balance (HLB) of at least 6.5.

22. The method of claim 21, wherein the copolymer (i)(c) has a hydrophilic/lipophilic balance (HLB) from 7 to 9.

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

(i) providing to a crankcase of the automotive internal combustion engine an automotive crankcase lubricating oil composition comprising or made by admixing;

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

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

(c) 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, the oil-soluble block or graft co-polymer exhibiting at least one of the following;

the molecular weight of the polymeric block A is from 1000 to 2800 as measured by Gel Permeation Chromatography;

the number average molecular weight of the polymeric block B is from 500 to 4600 as measured by Gel Permeation Chromatography; and

the number average molecular weight of the copolymer is from 3000 to 5000, as measured by Gel Permeation Chromatography; and

(d) optionally, at least one further additive comprising a dispersant, an antioxidant, and/or an antiwear agent,

wherein the automotive crankcase 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;

(ii) providing a hydrocarbon fuel in the automotive internal combustion engine; and

(iii) combusting the fuel in the automotive internal combustion engine,

wherein;

the or each of 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;

or

the oil-soluble block or graft copolymer in component (i)(c) has a general formula (A-COO)_m-B, wherein m is 1 or 2, wherein each polymeric component A has a molecular weight of at least 500 has the general structural formula

24. The method of claim 23, wherein the hydroxycarboxylic acid is a hydroxystearic acid.

25. The method of claim 23, wherein the polyalkylene glycol in component (i)(c) is polyethylene glycol.

26. The method of claim 23, wherein the copolymer in component (i)(c) has the structure AB or ABA, with the proviso that, where the block copolymer in component (i)(c) has the structure ABA, the A blocks may be the same or different.

27. The method of claim 23, wherein the friction modifier is glycerol monoester, and wherein the automotive crankcase lubricating oil composition comprising component (c) and less than 0.10 mass % of the glycerol monoester exhibits a lower friction coefficient than an otherwise identical automotive crankcase lubricating oil composition, except comprising substantially none of component (c) and more than 0.10 mass % of the glycerol monoester, when friction coefficients are measured at HFRR testing times greater than 751 seconds.

28. The method of claim 23, wherein the oft-soluble block or graft copolymer in component (i)(c) has a general formula (A-COO)_m-B, wherein m is 1 or 2, wherein each polymeric component A has a molecular weight of at least 500 has the general structural formula

29. The method of claim 28, 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.

30. The method of claim 29, wherein R₃ is hydrogen or a C₁-C₃ alkyl group.

31. The method of claim 23, wherein the or each of the polymeric components A has a molecular weight of at least 1000 as measured by Gel Permeation Chromatography, and/or the polymeric component B has a number average molecular weight of at least 1000 as measured by Gel Permeation Chromatography.

32. The method of claim 23, wherein the or each of 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.

33. The method of claim 23, wherein the automotive crankcase lubricating oil composition comprises not greater than 800 ppm by mass of phosphorus, expressed as phosphorus atoms.

34. The method of claim 33, wherein the automotive crankcase lubricating oil composition comprises not greater than 500 ppm by mass of phosphorus, expressed as phosphorus atoms.

35. The method of claim 23, wherein the automotive crankcase lubricating oil composition has a sulfated ash content of up to 1.0 and a sulfur content of up to 0.4 mass %.

36. The method of claim 23, further containing one or more other additive components, different from component (i)(c), selected from the group consisting of 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.

37. The method of claim 23, wherein the overbased metal detergent is a metal hydroxybenzoate detergent.

38. The method of claim 37, wherein the metal hydroxybenzoate detergent is an alkaline earth alkylsalicylate detergent.

39. The method of claim 38, wherein the alkaline earth alkylsalicylate detergent is a calcium salicylate detergent.

40. The method of claim 39, wherein the calcium salicylate detergent has a TBN, as defined in ASTM D2896, of 50 to 450 mg KOH/g.

41. The method of claim 40, wherein calcium salicylate detergent has a TBN, as defined in ASTM D2896, of 200 to 300 mg KOH/g.

42. The method of claim 23, wherein the copolymer (i)(c) has a hydrophilic/lipophilic balance (HLB) of at least 6.5.

43. The method of claim 42, wherein the copolymer (i)(c) has a hydrophiliclipophilic balance (HLB) from 7 to 9.

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

providing to a crankcase of the automotive internal combustion engine an automotive crankcase lubricating oil composition comprising or made by admixing;

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

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

(c) less than 50 mass % of an oil-soluble block or graft copolymer 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

(d) optionally, at least one further additive comprising a dispersant, an antioxidant, and/or an antiwear agent,

wherein the automotive crankcase 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;

(ii) providing a hydrocarbon fuel in the automotive internal combustion engine; and

(iii) combusting the fuel in the automotive internal combustion engine,

wherein the oil-soluble block or graft copolymer in component (i)(c) has a general formula (A-COO)_m-B, wherein m is 1 or 2, wherein each polymeric component A has a molecular weight of at least 500 has the general structural formula

45. The method of claim 44, wherein the hydroxycarboxylic acid is a hydroxystearic acid and/or the polyalkylene glycol in component (i)(c) is polyethylene glycol.

46. The method of claim 44, wherein the friction modifier is glycerol monoester, and wherein the automotive crankcase lubricating oil composition comprising component (c) and less than 0.10 mass % of the glycerol monoester exhibits a lower friction coefficient than an otherwise identical automotive crankcase lubricating oil composition, except comprising substantially none of component (c) and more than 0.10 mass % of the glycerol monoester, when friction coefficients are measured at HFRR testing times greater than 751 seconds.

47. The method of claim 44, 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, R₂ is a straight-chain alkylene group containing 1 to 24 carbon atoms, and R₃ is hydrogen or a C₁-C₃ alkyl group.

48. The method of claim 44, wherein one or more of the following are satisfied:

the molecular weight of the polymeric block A in component (i)(c) is from 1000 to 2800 as measured by Gel Permeation Chromatography;

the number average molecular weight of the polymeric block B in component (i)(c) is from 500 to 4600 as measured by Gel Permeation Chromatography; and

the number average molecular weight of the copolymer in component (i)(c) is from 3000 to 5000, as measured by Gel Permeation Chromatography.

49. The method of claim 44, wherein the automotive crankcase lubricating oil composition comprises not greater than 800 ppm by mass of phosphorus, expressed as phosphorus atoms.

50. The method of claim 49, wherein the automotive crankcase lubricating oil composition comprises not greater than 500 ppm by mass of phosphorus, expressed as phosphorus atoms.

51. The method of claim 44, wherein the automotive crankcase lubricating oil composition has a sulfated ash content of up to 1.0 and a sulfur content of up to 0.4 mass %.

52. The method of claim 44, further containing one or more other additive components, different from component (i)(c), selected from the group consisting of 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.

53. The method of claim 44, wherein the metal hydroxybenzoate detergent is a calcium salicylate detergent.

54. The method of claim 53, wherein calcium salicylate detergent has a TBN, as defined in ASTM D2896, of 200 to 300 mg KOH/g.

55. The method of claim 44, wherein the copolymer (i)(c) has a hydrophilic lipophilic balance (HLB) from 7 to 9.