Thiadiazole compounds and lubricant additives thereof

• US 5,102,568 A
• Filed: 02/05/1988
• Issued: 04/07/1992
• Est. Priority Date: 10/15/1985
• Status: Expired due to Fees

• Current Assignee: Atochem North America Inc (Arkema)
• Original Assignee: Atochem North America Inc (Arkema)
• Inventors: King, James P., Hill, Billy L.
• Primary Examiner(s): DIXON JR, WILLIAM R
• Application Number:
  US07/152,682
• Time in Patent Office: 1,523 Days
• Field of Search: 252/45, 252/47, 252/47.5, 252/48.2, 252/48.8, 252/56 D, 252/58, 252/403, 548/127, 548/130, 548/135, 548/140
• US Class Current: 508/274
• CPC Class Codes: C07D 285/04 not condensed with other rings
• CPC Class Codes: C07D 285/125 with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
• CPC Class Codes: C07D 417/12 linked by a chain containing hetero atoms as chain links
• CPC Class Codes: C10M 135/36 the ring containing sulfur and carbon with nitrogen or oxygen
• 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

Abstract

Novel thiadiazole compounds of the formula

[Z--S--Q--S].sub.x M

where: Q is a bivalent thiadiazole ring; Z is a succinate group; M is hydrogen, a metal ion selected from the Periodic Table Groups IA, IIA, IIIA, IB, IIB, IIIB, IVB, VB, and VIB, a (MoO₂)⁺² radical, or an amine salt; and X is a whole number equal to the valence of M are used as lubricant additives for providing antiwear and antioxidant properties to lubricant compositions.

Claims

1. The compound of the name bis[N,N'"'"'-dioleyl- 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinamide]-S-zinc(2+).

2. The compound of the name bis[N-2-ethylhexyl)-2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinimide]-S-molybdenum dioxide.

3. The compound of the name bis[dihexadecyl-2(2-thio-1,3,4-thiadiazol-5-yl-thio)-succinate]-S-tributylamine.

4. A composition comprising a mixture of:

(a) from 1-99 mole percent of the compound of the formula;

space="preserve" listing-type="equation">[Z--S--Q--S].sub.x M,

wherein;

Q is a bivalent thiadiazole ring moiety selected from the group consisting of 1,3,4-thiadiazole when M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB and IIIA or a (MoO₂)⁺² radical or an amine salt;

1,2,4-thiadiazole;

1,2,3-thiadiazole; and

1,2,5-thiadiazole;

Z is a succinate group of the structure ##STR3## wherein A is an oxygen, with the proviso;

when A is oxygen a is 1, b is zero, c is 1, and d is zero;

R, R'"'"', R" and R'"'"'" are less than 31 carbons each and are independently selected from the group consisting of hydrogen, alkyl, branched or straight chain alkenyl of 1 through 22 carbon atoms, arylalkyl, and heterocyclicalkenyl;

with the proviso that only one of R or R" is hydrogen and with the further proviso that the number one and four carbon atoms of the succinate group Z can be linked by a single A in which case when A is oxygen a, b, c, and d are zero;

M is hydrogen and x is 1;

M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB, and IIIA;

M is a (MoO₂)⁺² radical;

or M is an amine salt; and

x is a whole number equal to the valence of M; and

(b) from 99-1 mole percent of the compound of the formula;

space="preserve" listing-type="equation">[Z--S--Q--S].sub.x M

wherein;

Q is a bivalent thiadiazole ring moiety selected from the group consisting of 1,3,4-thiadiazole when M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB and IIIA or a (MoO₂)⁺² radical or an amine salt;

1,2,4-thiadiazole;

1,2,3-thiadiazole; and

1,2,5-thiadiazole;

Z is a succinate group of the structure ##STR4## wherein A is an oxygen atom, with the proviso;

when A is oxygen a is 1, b is zero, c is 1, and d is zero;

R and R" are less than 31 carbon atoms each and are independently selected from the group consisting of alkyl, branched or straight chained alkenyl of 1 through 22 carbon atoms, arylalkyl and heterocyclicalkenyl;

R'"'"' and R'"'"'" are less than 31 carbons each and are independently selected from the group consisting of hydrogen, alkyl, branched or straight chain alkenyl of 1 through 22 carbon atoms, arylalkyl, and heterocyclicalkenyl;

with the further proviso that the number one and four carbon atoms of the succinate group Z can be linked by a single A in which case when A is oxygen a, b, c, and d are

M is hydrogen and x is 1;

M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB, and IIIA;

M is a (MoO₂)⁺² radical;

or M is an amine salt; and

x is a whole number equal to the valence of M.

5. A lubricant composition comprising:

(a) a minor amount of the compound of the structure

space="preserve" listing-type="equation">[Z--S--Q--S].sub.x M

wherein;

Q is a bivalent thiadiazole ring moiety selected from the group consisting of 1,3,4-thiadiazole when M is a metal ion selected from the Periodic Table Groups IA, IIA, IIIA, IB, IIB, IIIB, IVB, VB, VIB, or a (MoO₂)⁺² radical or an amine salt;

1,2,4-thiadiazole;

1,2,3-thiadiazole; and

1,2,5-thiadiazole;

Z is a succinate group of the structure ##STR5## wherein A is an oxygen or nitrogen atom, with the proviso;

when a is oxygen a is 1, b is zero, c is 1, and d is zero; and

when A is nitrogen a, b, c, and d are each 1;

R, R'"'"', R", and R'"'"'" are less than 31 carbons each and are independently selected from the group consisting of hydrogen, alkyl, branched or straight chain alkenyl of 1 through 22 carbon atoms, arylalkyl, and heterocyclicalkenyl;

with the further proviso that the number one and four carbon atoms of the succinate group Z can be linked by a single A in which case when A is oxygen a, b, c, and d are zero, and when A is nitrogen a is one and b, c, and d are zero;

M is hydrogen and x is 1;

M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB, and IIIA;

or M is a (MoO₂)⁺² radical or M is an amine salt; and

x is a whole number equal to the valence of M; and

(b) a major amount of a grease or oil of lubricating viscosity.

6. The composition as defined in claim 5 wherein M is selected from the group consisting of zinc, copper with a valence state of 2, cobalt with a valence state of 2, (MoO₂)⁺² radical, aluminum, antimony with a valence state of 3, potassium, cesium, calcium, boron, tin, and molybdenum.

7. The composition as defined in claim 5 wherein R, R'"'"', R", and R'"'"'" are each independently selected from the group consisting essentially of decyl, tridecyl, oleyl, 2-ethylhexyl, and isocetyl.

8. The composition as defined in claim 5 wherein Q is the 1,3,4-thiadiazole moiety.

9. The composition as defined in claim 5 wherein the compound is bis[ditridecyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinate]-S-zinc(2+).

10. The composition as defined in claim 5 wherein the compound is bis[ditridecyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinate]-S-dibutyltin.

11. The composition as defined in claim 5 wherein the compound is bis[dioleyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinate]-S-molybdenum dioxide.

12. The compound as defined in claim 5 wherein the compound is bis[ditridecyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinate]-S-molybdenum dioxide.

13. The composition as defined in claim 5 wherein the compound is bis[ditridecyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinate]-S-cobalt(2+).

14. The composition as defined in claim 5 wherein the compound is bis[ditridecyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinate]-S-nickel(2+).

15. The composition as defined in claim 5 wherein the compound is bis[N,N'"'"'-dioleyl-2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinamide]-S-zinc(2+).

16. The composition as defined in claim 5 wherein the compound is bis[N-(2-ethylhexyl)-2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinimide]-S-molybdenum dioxide.

17. The compound as defined in claim 5 wherein the compound is bis[diisocetyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinate]-S-zinc(2+).

18. The composition as defined in claim 5 wherein the compound is bis[dihexadecyl-2(2-thio-1,3,4-thiadiazol-5-yl-thio)-succinate]-S-tributylamine.

19. The composition as defined in claim 5 wherein the compound is bis[dihexadecyl-2(2-thio-1,3,4-thiadiazol-5-yl-thio)-succinate]-S-copper(+2).

20. The composition as defined in claim 5 wherein the compound is bis[dihexadecyl-2(2-thio-1,3,4-thiadiazol-5-yl-thio)-succinate]-S-calcium(+2).

21. The composition as defined in claim 5 wherein the compound is bis[dihexadecyl-2(2-thio-1,3,4-thiadiazol-5-yl-thio)-succinate]-S-boron(+3).

22. The composition as defined in claim 5 wherein the compound is dihexadecyl-2(2-thio-1,3,4-thiadiazol-5-yl-thio)-succinate-S-potassium.

23. The composition as defined in claim 5 wherein the compound is dihexadecyl-2(thio-1,3,4-thiadiazol-5-yl-thio)-succinate-S-cesium.

24. The composition as defined in claim 5 wherein A is oxygen and only one of R or R" is hydrogen.

25. A composition comprising:

a major amount of grease or oil of lubricating viscosity; and

a minor amount of a mixture of

(a) from 1-99 mole percent of the compound of the formula;

space="preserve" listing-type="equation">[Z--S--Q--S].sub.x M

wherein;

Q is a bivalent thiadiazole ring moiety selected from the group consisting of 1,3,4-thiadiazole when M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB and IIIA or a (MoO₂)⁺² radical or an amine salt;

1,2,4-thiadiazole;

1,2,3-thiadiazole; and

1,2,5-thiadiazole;

Z is a succinate group of the structure ##STR6## wherein A is an oxygen, with the proviso;

when A is oxygen a is 1, b is zero, c is 1, and d is zero;

R, R'"'"', R" and R'"'"'" are less than 31 carbons each and are independently selected from the group consisting of hydrogen, alkyl, branched or straight chain alkenyl of 1 through 22 carbon atoms, arylalkyl, and heterocyclicalkenyl;

with the proviso that only one of R or R" is hydrogen and with the further proviso that the number one and four carbon atoms of the succinate group Z can be linked by a single A in which case when A is oxygen a, b, c, and d are zero;

M is hydrogen and x is 1;

M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB, and IIIA;

M is a (MoO₂)⁺² radical;

or M is an amine salt; and

x is a whole number equal to the valence of M and

(b) from 99-1 mole percent of the compound of the formula;

space="preserve" listing-type="equation">[Z--S--Q--S].sub.x M

wherein;

Q is a bivalent thiadiazole ring moiety selected from the group consisting of 1,3,4-thiadiazole when M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB and IIIA or a (MoO₂)⁺²) radical or an amine salt;

1,2,4-thiadiazole;

1,2,3-thiadiazole; and

1,2,5-thiadiazole;

Z is a succinate group of the structure ##STR7## wherein A is an oxygen atom, with the proviso;

when A is oxygen a is 1, b is zero, c is 1, and d is zero;

R and R" are less than 31 carbon atoms each and are indpendently selected from the group consisting of alkyl, branched or straight chained alkenyl of 1 through 22 carbon atoms, arylalkyl and heterocyclicalkenyl;

R'"'"' and R'"'"'41 are less than 31 carbons each and are independently selected from the group consisting of hydrogen, alkyl, branched or straight chain alkenyl of 1 through 22 carbon atoms, arylalkyl, and heterocyclicalkenyl;

with the further proviso that the number one and four carbon atoms of the succinate group Z can be linked by a single A in which case when A is oxygen a, b, c, and d are zero;

M is hydrogen and x is 1;

M is a metal ion selected from the Periodic Table Groups IA, IIA, IB, IIB, IIIB, IVB, VB, VIB, and IIIA;

M is a (MOO₂)⁺² radical;

or M is an amine salt; and

x is a whole number equal to the valence of M.

26. The compound ditridecyl 2-(2-mercapto-1,3,4-thiadiazol-5-ylthio)-succinate.

27. The compound N,N'"'"'-dioleyl-2-(2-mercapto-1,3,4-thiadiazol-5-ylthio)-succinamide.

28. The compound N-oleyl-2-(2-mercapto-1,3,4-thiadiazol-5-ylthio)-succinimide.

29. The compound diisocetyl 2-(2-mercapto-1,3,4-thiadiazol-5-ylthio)-succinate.