Sulfurized olefins as antiwear/extreme pressure additives for lubricants and fuels and compositions thereof

• US 4,711,736 A
• Filed: 02/24/1986
• Issued: 12/08/1987
• Est. Priority Date: 02/24/1986
• Status: Expired due to Fees

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Horodysky, Andrew G., Law, Derek A.
• Primary Examiner(s): Dixon, Jr., William R.
• Assistant Examiner(s): McAvoy, Ellen M.
• Application Number:
  US06/831,967
• Time in Patent Office: 652 Days
• Field of Search: 252/47, 252/47.5
• US Class Current: 508/226
• CPC Class Codes: C10L 1/2493 compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds
• CPC Class Codes: C10L 10/08 for improving lubricity; for reducing wear
• CPC Class Codes: C10M 135/02 Sulfurised compounds
• CPC Class Codes: C10M 159/12 Reaction products
• 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 2219/02 Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
• CPC Class Codes: C10M 2219/022 of hydrocarbons, e.g. olefines polyolefins C10M2221/041
• CPC Class Codes: C10M 2227/00 Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions

Abstract

Reaction products of olefins, elemental sulfur, hydrogen sulfide, water and nitrogen-containing polymers provide multifunctional additives having antiwear/extreme pressure and thermal and oxidative stability characteristics for lubricants and fuels.

Claims

1. A multifunctional additive product having antiwear/extreme pressure, friction modifying and thermal or oxidative stability characteristics suitable for use in an oil of lubricating viscosity or grease thereof prepared in a process comprising reacting in a suitable reaction zone an olefinic-hydrocarbyl compound having at least one olefinic double bond with elemental sulfur, hydrogen sulfide, water and a polymeric succinimide having at least one free amine group.

2. The additive product of claim 1, wherein the reaction temperature varies from about 130 to about 200°

C., the olefin to sulfur ratio varies from about 2;

1 to about 1;

2, the olefin to sulfur to hydrogen sulfide ratio may vary from about 1;

0.5-2.0;

0.2-1.0 and the water-to-olefin ratio may vary from about 0.1% to about 70 wt. % or more based on the weight of the olefin at a pressure of from about 300-900 psi.

3. The additive product of claim 1 wherein the process is a one step--one pot process.

4. The additive product of claim 1 wherein said process is carried out in the presence of a rate accelerating catalyst.

5. The additive product of claim 4 wherein said rate accelerating catalyst is selected from the group consisting of n-butylamine, di-n-butylamine, n-octylamine, triethylamine, diisopropylamine, cyclohexylamine, dicyclohexylamine, quinoline and attapulgite acid clay.

6. The additive product of claim 5 wherein the rate accelerating catalyst is n-butylamine.

7. The additive product of claim 1 wherein the olefinic compound is selected from the group consisting essentially of ethylene, propylene, 1-butene, cis and trans-2-butene, isobutylene, diisobutylene, triisobutylene, pentene, cyclopentene, hexene, cyclohexene, octene, 1-decene, butadiene, isoprene, divinyl benzene, pinene, p-menthene and limonene and mixtures thereof.

8. The additive product of claim 7 wherein the olefin is a C₃ -C₈ olefin.

9. The additive product of claim 7 wherein the olefin is isobutylene.

10. The additive product of claim 1 wherein the succinimide polymer is the reaction product of a polyalkenyl succinic anhydride and tetraethylene pentamine.

11. The additive product of claim 10 wherein the succinimide polymer is the reaction product of a polyisobutenyl succinic anhydride and tetraethylene pentamine.

12. A process for making a multifunctional additive product having antiwear/extreme pressure, frictional modifying and thermal or oxidative stability characteristics suitable for use in oils of lubricating viscosity or greases prepared therefrom comprising reacting in a suitable reaction zone an olefinic hydrocarbyl compound having at least one olefinic double bond, elemental sulfur, hydrogen sulfide, water and a succinimide polymer having at least one free amine group.

13. The process in accordance with claim 12 wherein said process is a one step--one pot process.

14. The process in accordance with claim 12 wherein the pressure varies from about 300 to about 900 psi and the temperature varies from about 130°

to 200°

C. and the molar ratio of olefin to sulfur varies from about 2;

1 to about 1;

2;

the molar ratio of olefin to sulfur to hydrogen sulfide varies from 1;

05-2.0;

0.2-1.0 and the wt. ratio of water to olefin varies from about 0.1% to about 70 wt. % or more based on the weight of the olefin at a pressure of from about 300 to 900 psi.

15. The process in accordance with claim 13 wherein said process is carried out in the presence of a rate accelerating catalyst.

16. The process in accordance with claim 15 wherein said rate accelerating catalyst is selected from the group consisting essentially of n-butylamine, di-n-butylamine, n-octylamine, triethylamine, diisopropylamine, cyclohexylamine, dicyclohexylamine, quinoline and attapulgite acid clay.

17. The process in accordance with claim 16 wherein the rate accelerating catalyst is n-butylamine.

18. The process in accordance with claim 15 wherein the olefin is selected from the group consisting essentially of ethylene, propylene, 1-butene, cis and trans-2-butene, isobutylene, diisobutylene, triisobutylene, pentene, cyclopentene, hexene, cyclohexene, octene, 1-decene, butadiene, isoprene, divinyl benzene, pinene, p-menthene and limonene.

19. The process in accordance with claim 18 wherein the olefin is isobutylene.

20. The process in accordance with claim 13 wherein the succinimide polymer has a molecular weight of from about 500 to 50,000.

21. The process in accordance with claim 13 wherein the succinimide polymer is the reaction product of a polyalkenyl succinic anhydride and tetraethylene pentamine.

22. The process in accordance with claim 21 wherein the succinimide polymer is the reaction product of a polybutenyl succinic anhydride and tetraethylene pentamine.

23. A lubricant composition comprising a major amount of an oil of lubricating viscosity or grease prepared therefrom and a minor amount sufficient to impart extreme pressure, antiwear activity, friction modifying and thermal and oxidative stability characteristics thereto of an additive product prepared in a process comprising reacting in a suitable reaction zone an olefinic hydrocarbyl compound having at least one olefinic double bond with elemental sulfur, hydrogen sulfide, water and a succinimide polymer having at least one free amine group.

24. The lubricant composition of claim 23 wherein in said process the pressure varies from about 300 to 900 psi and the temperature varies from about 130°

to 200°

C. and the molar ratio of olefin to sulfur varies from about 2;

1 to about 1;

2, olefin to sulfur to hydrogen sulfide ratio of from about 1;

0.5-2.0;

0.2-1.0 and a water-to-olefin ratio of from about 1% to about 50% or more based on the weight of the olefin at a pressure of from about 300-900 psi.

25. The lubricant composition of claim 23 wherein the reaction process is carried out in the presence of a rate accelerating catalyst.

26. The lubricant composition of claim 23 wherein said rate accelerating catalyst is selected from the group consisting of n-butylamine, di-n-butylamine, n-octylamine, triethylamine, diisopropylamine, cyclohexylamine, dicyclohexylamine, quinoline and attapulgite acid clay.

27. The lubricant composition of claim 26 wherein the rate accelerating catalyst is n-butylamine.

28. The lubricant composition of claim 23 wherein the olefin is selected from ethylene, propylene, 1-butene, cis and trans-2-butene, isobutylene, diisobutylene, triisobutylene, pentene, cyclopentene, hexene, cyclohexene, octene, 1-decene, butadiene, isoprene, divinyl benzene, pinene, p-menthene and limonene.

29. The lubricant composition of claim 28 wherein the olefin is isobutylene.

30. The lubricant composition of claim 28 wherein the succinimide polymer is the reaction product of a polyalkenyl succinic anhydride and tetraethylene pentamine.

31. The lubricant composition of claim 28 wherein the succinimide polymer is the reaction product of a polybutenyl succinic anhydride and tetraethylene pentamine.

32. The lubricant composition of claim 23 wherein said lubricant comprises a major amount of an oil of lubricating viscosity.

33. The lubricant composition of claim 32 wherein said oil is selected from mineral oils, synthetic oils or mixtures thereof.

34. The lubricant composition of claim 32, wherein said oil is a mineral oil or mixtures thereof.

35. The lubricant composition of claim 32 wherein said oil is a synthetic oil or mixture thereof.

36. The lubricant composition of claim 23 wherein said lubricant comprises a major amount of a grease.

37. The lubricant composition of claim 23 wherein said additive product varies from about 0.10 to about 20 wt. % of the total composition.