Lubricant antioxidant compositions containing a metal compound and a hindered amine

1. A lubricant composition which comprises at least 50 wt % of a lubricating base oil and

an oil-soluble metal compound providing between about 100 and about 1680 parts per million of metal to the lubricant composition, the metal compound being chosen from the group consisting of molybdenum, tungsten, titanium and boron compounds, and

an oil-soluble first hindered amine providing between about 0.5 and about 1.5 wt % of oil-soluble hindered amine to the lubricant composition,

wherein the first hindered amine is one or more chosen from the group consisting of:

(a) a compound of the formula

where R 26 is H, O or a hydrocarbon from 1 to 25 carbon atoms, an alkoxy radical with the oxygen bound to the nitrogen with the alkyl portion containing 1 to 25 carbon atoms, or a COR group, the R being a hydrocarbon containing from 1 to 25 carbon atoms; R 27 , R 28 , R 32 , R 33 are hydrocarbons with 1 to 25 carbon atoms; R 29 , R 31 are H or hydrocarbons with 1 to 25 carbon atoms; when n=1, R 30 is OH, H, O, NH 2 , NR 2 where R is a hydrocarbon with 1 to 25 carbon atoms, an ester group O 2 CR where R is a hydrocarbon with 1 to 25 carbon atoms, or a succinimide group; when n=2, R 30 is the diacyl radical of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms;

(b) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine,

(c) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

(d) di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,

(e) bis (1-octyloxy-2,2,6,-tetramethyl-4-piperidyl) sebacate

(f) polymer-bound piperidine compound,

(g) a compound of the group consisting of 2,2,6,6-tetramethylpiperidines, 1,2,2,6,6-pentamethylpiperidines, 1-oxo-2,2,6,6-tetramethylpiperidines, and 1-alkoxy-2,2,6,6-tetramethylpiperidines, and

(h) a compound of the group consisting of di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, di(,2,2,6,6-tetramethylpiperidin-4-yl) sebacate and bis (1-octyloxy-2,2,6,-tetramethyl-4-piperidyl) sebacate.

2. The lubricant composition according to claim 1 , further comprising an oil-soluble diarylamine providing between about 0.5 and about 1.5 wt % of oil-soluble diarylamine to the lubricant composition.

3. The lubricating composition according to claim 1 , wherein the oil-soluble metal compound is an oil-soluble molybdenum compound.

4. The lubricating composition according to claim 1 , wherein the oil-soluble metal compound is an oil-soluble tungsten compound.

5. The lubricating composition according to claim 3 , wherein the oil-soluble molybdenum compound is one or more chosen from the group consisting of:

(i) a molybdenum dithiocarbamate compound of the formula:

where x=0 to 4, and where (R 1 R 2 NCS 2 ) is a dithiocarbamate (DTC) where R 1 and R 2 is a hydrocarbon containing from 1 to 25 carbon atoms or R 1 and R 2 is a hydrocarbon with an ether linkage(s) containing from 1 to 5 oxygen atoms and 1 to 25 carbon atoms, R 1 and R 2 being the same or different,

(ii) a molybdenum dithiocarbamate compound of the formulas:

Mo 3 S 7 (DTC) 4 or

Mo 3 S 4 (DTC) 4

where the DTC is a dithiocarbamate (R 3 R 4 NCS 2 ) and R 3 and R 4 is a hydrocarbon containing from 1 to 25 carbon atoms or R 3 and R 4 is a hydrocarbon with an ether linkage(s) containing from 1 to 5 oxygen atoms and 1 to 25 carbon atoms, R 3 and R 4 being the same or different,

(iii) a molybdenum dithiophosphate compound of the formula:

where x=0 to 4, and where the (R 5 O)(R 6 O)PS 2 is a dithiophosphate (DTP) and R 5 and R 6 is a hydrocarbon containing from 1 to 25 carbon atoms or R 5 and R 6 is a hydrocarbon with an ether linkage(s) containing from 1 to 5 oxygen atoms and 1 to 25 carbon atoms, R 5 and R 6 being the same or different,

(iv) a glycol molybdenum complex,

(v) an organic amide molybdenum complex,

(vi) an amine molybdenum complex,

(vii) a molybdenum complex obtained by reacting a fatty oil, diethanolamine and molybdenum source,

(viii) a reaction product of a molybdenum source with a fatty acid and a 2-(2-aminoethyl)aminoethanol,

(ix) a reaction product of a fatty oil, a mono-alkylated diamine, and a molybdenum source, and

(x) one or more of the group consisting of molybdenum naphthenate, molybdenum octoate and molybdenum 2-ethylhexanoate.

6. The lubricating composition according to claim 4 , wherein the oil-soluble tungsten compound is chosen from one or more of the group consisting of:

(i) the reaction product of an amine with a tungsten source, the tungsten source being selected from the group consisting of tungsten trioxide, tungstic acid and an alkali metal tungstate, and the amine is of the formula R 51 R 52 R 53 N wherein R 51 , R 52 , and R 53 may be identical or different, and are selected from the group consisting of hydrogen and an alkyl group containing between 1 and 30 carbon atoms,

(ii) a tungsten dithiophosphate of the formula:

where x=0 to 4, and R 7 , and R 8 are hydrocarbons containing from 1 to 30 carbon atoms, R 7 and R 8 being the same or different, and

(iii) a tungsten dithiocarbamate of the formula:

where x=0 to 4, and R 9 and R 10 are hydrocarbons containing from 1 to 30 carbon atoms, R 9 and R 10 being the same or different.

7. A lubricant composition which comprises at least 50 wt % of a lubricating base oil and

an oil-soluble molybdenum compound providing between 1 and 2,000 parts per million of molybdenum to the lubricant composition, and

an oil-soluble first hindered amine providing between about 0.001 and about 2 wt % of oil-soluble hindered amine to the lubricant composition, wherein

the oil-soluble molybdenum compound is a reaction product of a second hindered amine and a molybdenum source, and one of the following:

(a) water,

(b) the reaction product of a fatty oil with a multifunctional amine, and water, and

(c) a diol, and water; wherein

the second hindered amine is one or more chosen from the group consisting of:

(a) a compound of the formula

where R 26 is H, O or a hydrocarbon from 1 to 25 carbon atoms, an alkoxy radical with the oxygen bound to the nitrogen with the alkyl portion containing 1 to 25 carbon atoms, or a COR group, the R being a hydrocarbon containing from 1 to 25 carbon atoms; R 27 , R 28 , R 32 , R 33 are hydrocarbons with 1 to 25 carbon atoms; R 29 , R 31 are H or hydrocarbons with 1 to 25 carbon atoms; when n=1, R 30 is OH, H, O, NH 2 , NR 2 where R is a hydrocarbon with 1 to 25 carbon atoms, an ester group O 2 CR where R is a hydrocarbon with 1 to 25 carbon atoms, or a succinimide group; when n=2, R 30 is the diacyl radical of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms;

(b) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine,

(c) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

(d) di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,

(e) bis (1-octyloxy-2,2,6,-tetramethyl-4-piperidyl) sebacate

(f) polymer-bound piperidine compound,

(g) a compound of the group consisting of 2,2,6,6-tetramethylpiperidines, 1,2,2,6,6-pentamethylpiperidines, 1-oxo-2,2,6,6-tetramethylpiperidines, and 1-alkoxy-2,2,6,6-tetramethylpiperidines, and

(h) a compound of the group consisting of di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, di(,2,2,6,6-tetramethylpiperidin-4-yl) sebacate and bis (1-octyloxy-2,2,6,-tetramethyl-4-piperidyl) sebacate.

8. The lubricating composition of claim 7 , wherein the fatty oil is coconut oil.

9. The lubricating composition according to claim 7 , wherein the diol is 2-ethyl-1,3-hexanediol or 1,2-dodecanediol.

10. The lubricating composition according to claim 7 , wherein the multifunctional amine is diethanolamine.

11. The lubricating composition according to claim 2 , wherein the diarylamine is of the formula:

wherein R 43 and R 44 each independently represent an aryl group having from 6 to 30 carbon, atoms, and R 45 represents either a H atom or an alkyl group containing from 1 to 30 carbon atoms.

12. The lubricating composition according to claim 2 , wherein at least one of said aryl groups has from 7 to 20 carbon atoms.

13. The lubricating composition according to claim 2 , wherein each of the aryl groups of the amine is selected from phenyl, naphthyl, alkylphenyl and alkylnaphthyl wherein the alkyl portion has from 4 to 18 carbon atoms.

14. The lubricating composition according to claim 2 , wherein both aryl groups are alkylaryl having from 7 to 20 carbon atoms.

15. The lubricating composition according to claim 1 , comprising an amount of oil-soluble molybdenum or tungsten compound to provide about 125 to about 700 ppm metal in the lubricating composition.