Crankcase lubricant for modern heavy duty diesel and gasoline fueled engines

• US 6,004,910 A
• Filed: 03/07/1995
• Issued: 12/21/1999
• Est. Priority Date: 04/28/1994
• Status: Expired due to Term

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation), ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Ritchie, Andrew James Dalziel, Outten, Edward F., Waddoups, Malcolm, Lapinas, Arunas T., Bloch, Ricardo Alfredo
• Primary Examiner(s): MEDLEY, MARGARET B
• Application Number:
  US08/396,501
• Time in Patent Office: 1,750 Days
• Field of Search: 252/32.7 E, 252/51.5 A, 252/51.5 R, 508/294, 508/375, 508/376, 508/380, 508/435
• US Class Current: 508/294
• 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
• CPC Class Codes: C10M 2205/00 Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
• CPC Class Codes: C10M 2205/02 containing acyclic monomers
• CPC Class Codes: C10M 2205/026 Butene
• CPC Class Codes: C10M 2205/06 containing conjugated dienes
• CPC Class Codes: C10M 2207/023 having hydroxy groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C10M 2207/024 having at least two phenol groups but no condensed ring
• CPC Class Codes: C10M 2207/026 with tertiary alkyl groups
• CPC Class Codes: C10M 2207/027 Neutral salts thereof
• CPC Class Codes: C10M 2207/028 Overbased salts thereof
• CPC Class Codes: C10M 2207/121 having hydrocarbon chains of seven or less carbon atoms
• CPC Class Codes: C10M 2207/122 monocarboxylic
• CPC Class Codes: C10M 2207/125 having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
• CPC Class Codes: C10M 2207/129 having hydrocarbon chains of thirty or more carbon atoms
• CPC Class Codes: C10M 2207/16 Naphthenic acids
• CPC Class Codes: C10M 2207/26 Overbased carboxylic acid salts
• 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 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 2207/287 : Partial esters
• CPC Class Codes: C10M 2207/288 : containing free carboxyl groups
• CPC Class Codes: C10M 2207/289 : containing free hydroxy groups
• CPC Class Codes: C10M 2209/084 : Acrylate; Methacrylate
• CPC Class Codes: C10M 2209/086 : polycarboxylic, e.g. maleic acid
• CPC Class Codes: C10M 2209/104 : of alkylene oxides containing two carbon atoms only
• CPC Class Codes: C10M 2215/04 : having amino groups bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2215/042 : containing hydroxy groups; Alkoxylated derivatives thereof
• CPC Class Codes: C10M 2215/086 : Imides
• CPC Class Codes: C10M 2215/22 : Heterocyclic nitrogen compounds
• CPC Class Codes: C10M 2215/221 : Six-membered rings containing nitrogen and carbon only
• CPC Class Codes: C10M 2215/225 : the rings containing both nitrogen and oxygen
• CPC Class Codes: C10M 2215/226 : Morpholines
• CPC Class Codes: C10M 2215/24 : having hydrocarbon substituents containing thirty or more carbon atoms , e.g. nitrogen derivatives of substituted succinic acid
• CPC Class Codes: C10M 2215/26 : Amines
• CPC Class Codes: C10M 2215/28 : Amides; Imides
• CPC Class Codes: C10M 2215/30 : Heterocyclic compounds
• CPC Class Codes: C10M 2217/043 : Mannich bases
• CPC Class Codes: C10M 2217/046 : Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
• CPC Class Codes: C10M 2217/06 : Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
• CPC Class Codes: C10M 2219/046 : Overbasedsulfonic acid salts
• CPC Class Codes: C10M 2219/06 : Thio-acids; Thiocyanates; Derivatives thereof
• CPC Class Codes: C10M 2219/062 : having carbon-to-sulfur double bonds
• CPC Class Codes: C10M 2219/066 : Thiocarbamic type compounds
• CPC Class Codes: C10M 2219/068 : Thiocarbamate metal salts
• CPC Class Codes: C10M 2219/087 : containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
• CPC Class Codes: C10M 2219/088 : Neutral salts
• CPC Class Codes: C10M 2219/089 : Overbased salts
• CPC Class Codes: C10M 2219/10 : Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
• CPC Class Codes: C10M 2219/102 : containing sulfur and carbon only in the ring
• CPC Class Codes: C10M 2219/104 : containing sulfur and carbon with nitrogen or oxygen in the ring
• CPC Class Codes: C10M 2219/106 : Thiadiazoles
• CPC Class Codes: C10M 2223/045 : Metal containing thio derivatives
• CPC Class Codes: C10M 2223/065 : containing sulfur
• CPC Class Codes: C10M 2227/061 : Esters derived from boron
• CPC Class Codes: C10M 2229/041 : containing aliphatic substituents
• CPC Class Codes: C10N 2010/02 : Groups 1 or 11
• CPC Class Codes: C10N 2010/04 : Groups 2 or 12
• CPC Class Codes: C10N 2010/06 : Groups 3 or 13
• CPC Class Codes: C10N 2010/12 : Groups 6 or 16
• CPC Class Codes: C10N 2010/14 : Group 7
• CPC Class Codes: C10N 2010/16 : Groups 8, 9, or 10
• CPC Class Codes: C10N 2040/25 : Internal-combustion engines
• CPC Class Codes: C10N 2040/251 : Alcohol-fuelled engines
• CPC Class Codes: C10N 2040/255 : Gasoline engines
• CPC Class Codes: C10N 2040/28 : Rotary engines

Abstract

A lubricating oil having an ashless nitrogenous TBN source together with ash containing detergent having a TBN in excess of 100, a source of magnesium, and metal dihydrocarbyl dithiophosphate with predominantly or exclusively secondary hydrocarbyl groups is described. It comprises a major amount of an oil of lubricating viscosity having a sulfated ash content between 0.35 and 2 mass percent and A) a nitrogenous TBN source selected from the group consisting of ashless nitrogen containing dispersants, ashless nitrogen containing dispersant viscosity modifiers, oil soluble aliphatic, oxyalkyl, or arylalkyl amines and mixtures thereof; B) a metal salt of an oil soluble acid having a TBN in excess of 100; C) at least 500 ppm (mass) magnesium; and D) at least one metal dihydrocarbyl dithiophosphate. The nitrogenous TBN source provides at least about 1.5 TBN to the finished lubricant. The metal salt of an oil soluble acid provides at least about 40% of the total TBN of the composition. At least 50 mole per cent of the hydrocarbyl groups on the dithiophosphate are secondary. Overbased magnesium sulfonate may be used as the metal salt of an oil soluble sulfonic acid having a TBN in excess of 100 and the additive providing at least 500 ppm (mass) magnesium. The lubricant may be free of aromatic amines having at least two aromatic groups attached directly to the nitrogen. It may have at least 100 ppm (mass) boron and at least 1000 ppm (mass) phosphorous. The boron-to-nitrogen ratio is at least 0.1.

Claims

1. A crankcase lubricant having a sulfated ash content between 0.35 and 2 mass percent comprising a major amount of an oil of lubricating viscosity to which the following components have been added:

A) a nitrogenous TBN source selected from the group consisting of ashless nitrogen containing dispersants, ashless nitrogen containing dispersant viscosity modifiers, oil soluble aliphatic, oxyalkyl, or arylalkyl amines and mixtures thereof wherein said nitrogen containing dispersant is selected from the group consisting of oil soluble salts, amides, imides, amino-esters, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides;

long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and

Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine wherein the long chain hydrocarbon has an M_n of 300 to 20,000;

B) a metal salt of an oil soluble acid having a TBN in excess of 100;

C) a magnesium salt of an oil soluble organic acid in an amount providing at least 500 ppm (mass) magnesium, and

D) at least one metal dihydrocarbyl dithiophosphate

wherein the nitrogenous TBN source provides at least about 1.5 TBN to the lubricant;

the metal salt of an oil soluble acid provides at least about 40% of the total TBN of the lubricant; and

at least 50 mole percent of the hydrocarbyl groups on the metal dithiophosphate are secondary.

2. The lubricant of claim 1 wherein the metal salt of an oil soluble acid having a TBN in excess of 100 is a metal salt of an oil soluble sulfonic acid.

3. The lubricant of claim 2 wherein the metal salt of an oil soluble sulfonic acid is a magnesium salt that also provides the required 500 ppm (mass) magnesium.

4. The lubricant of claim 1 further characterized by having no more than 0.2 mass percent active ingredient of aromatic amines having at least two aromatic groups attached directly to the nitrogen.

5. The lubricant of claim 1 further comprising a boron containing additive in an amount that provides at least 100 ppm (mass) boron.

6. The lubricant of claim 5 wherein the boron-to-nitrogen mass ratio is larger than 0.1.

7. The lubricant of claim 1 wherein the lubricant has at least 1000 ppm mass phosphorous.

10. The crankcase lubricant of claims 1, 3, 5, 7 or 9 wherein at least 75 mole per cent of the hydrocarbyl groups on the metal dithiophosphate are secondary.

12. The lubricant of claim 1 wherein said long chain hydrocarbon has an M_n of from about 1500 to about 5,000.

13. The lubricant of claim 1 wherein said long chain hydrocarbon has an M_n of from about 1500 to about 3,000.

14. The lubricant of claim 3 wherein said long chain hydrocarbon has an M_n of from about 1500 to about 5,000.

8. A concentrate comprising:

A) A nitrogenous TBN source of selected from the group consisting of ashless nitrogen containing dispersants, oil soluble aliphatic, oxyalkyl, or arylalkyl amines and mixtures thereof wherein said nitrogen containing dispersant is selected from the group consisting of oil soluble salts, amides, imides, amino-esters, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides;

long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and

Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine wherein the long chain hydrocarbon has an M_n of 300 to 20,000;

B) a metal salt of an oil soluble acid having a TBN in excess of 100;

C) a magnesium salt in an amount that provides at least 3100 ppm (mass) magnesium, and

D) at least one metal dihydrocarbyl dithiophosphate

wherein the nitrogenous TBN source provides at least about 10 TBN to the concentrate;

the metal salt of an oil soluble acid provides at least about 40% of the total TBN of the concentrate and at least 50 mole per cent of the hydrocarbyl groups on the metal dithiophosphate are secondary.

9. A crankcase lubricant having a sulfated ash content between 0.35 and 2 mass per cent comprising a major amount of an oil of lubricating viscosity to which the following components have been added:

A) a nitrogenous TBN source selected from the group consisting of ashless nitrogen containing dispersants, ashless nitrogen containing dispersant viscosity modifiers, oil soluble aliphatic, oxyalkyl, or arylalkyl amines and mixtures thereof wherein said nitrogen containing dispersant is selected from the group consisting of oil soluble salts, amides, imides, amino-esters, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides;

long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and

Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine wherein the long chain hydrocarbon has an M_n of 300 to 20,000;

B) a metal salt of an oil soluble acid having a TBN in excess of 100;

C) a magnesium salt in an amount providing at least 500 ppm (mass) magnesium;

D) at least one metal dihydrocarbyl dithiophosphate, and

E) at least 0.0008 mole % oil soluble hindered phenol antioxidant wherein the nitrogenous TBN source provides at least about 1.5 TBN to the lubricant;

the metal salt of an oil soluble acid provides at least about 40% of the total TBN of the composition, at least 50 mole per cent of the hydrocarbyl groups on the metal dithiophosphate are secondary and the lubricant is free of aromatic amines having at least two aromatic groups attached directly to the nitrogen.

11. A crankcase lubricant having a sulfated ash content between 0.35 and 2 mass per cent comprising a major amount of an oil of lubricating viscosity to which the following components have been added:

A) a nitrogenous TBN source selected from the group consisting of ashless nitrogen containing dispersants, ashless nitrogen containing dispersant viscosity modifiers, oil soluble aliphatic, oxyalkyl, or arylalkyl amines and mixtures thereof wherein said nitrogen containing dispersant is selected from the group consisting of oil soluble salts, amides, imides, amino-esters, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides;

long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and

Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine wherein the long chain hydrocarbon has an M_n of 300 to 20,000;

B) a metal salt of an oil soluble acid having a TBN in excess of 100;

C) a magnesium salt in an amount providing at least 500 ppm (mass) magnesium;

D) at least one metal dihydrocarbyl dithiophosphate

E) at least 0.0003 mole % oil soluble hindered phenol antioxidant, and

F) a boron containing additive in an amount that provides at least 100 ppm (mass) boron

wherein the nitrogenous TBN source provides at least about 1.5 TBN to the lubricant;

the metal salt of an oil soluble acid provides at least about 40% of the total TBN of the composition, at least 75 mole per cent of the hydrocarbyl groups on the metal dithiophosphate are secondary, the lubricant is free of aromatic amines having at least two aromatic groups attached directly to the nitrogen, the lubricant contains at least 1000 ppm (mass) phosphorous, and the boron-to-nitrogen ratio is larger than 0.1.