ADDITIVE FOR LUBRICANT COMPOSITIONS COMPRISING A SULFUR-CONTAINING AND A SULFUR-FREE ORGANOMOLYBDENUM COMPOUND, AND A TRIAZOLE OR A DERIVATIZED TRIAZOLE

Abstract

A lubricating composition for use in heavy duty diesel engines which is formulated to allow the use of organomolybdenum compounds but which overcomes the issue of Cu and/or Pb corrosion. The lubricant is characterized by having a synergistic additive composition comprising (A) a sulfur-free organo-molybdenum compound, (B) a sulfur-containing organo-molybdenum compound and (C) a triazole derivative prepared by reacting 1,2,4-triazole, a formaldehyde source and an amine; (A), (B) and (C) being present in an amount sufficient to allow the lubricating composition to pass the High Temperature Corrosion Bench Test ASTM D 6594 with respect to Cu and/or Pb corrosion.

Claims

1. A lubricating composition comprising a lubricant base, and an additive composition comprising (A) a sulfur-free organo-molybdenum compound, (B) a sulfur-containing organo-molybdenum compound and (C) a triazole derivative prepared by reacting 1,2,4-triazole, a formaldehyde source and an amine; (A), (B) and (C) being present in an amount sufficient to reduce copper and/or lead corrosion.

2. The lubricating composition according to claim 1, wherein the total molybdenum content is about 50 ppm to 800 ppm.

3. The lubricating composition according to claim 2, wherein the total molybdenum content is about 75 ppm to about 350 ppm.

4. The lubricating composition according to claim 1, wherein the triazole derivative is present in an amount from about 0.001-1.0% by weight of the lubricating composition.

5. The lubricating composition according to claim 4, wherein the triazole derivative is present in an amount from about 0.005-0.4% by weight of the lubricating composition.

6. The lubricating composition according to claim 2, wherein the ratio of (A):(B) based on molybdenum content is from about 0.25:1 to 4:1.

7. The lubricating composition according to claim 1, wherein the total molybdenum content is about 75 ppm to about 350 ppm, and the triazole derivative is present in an amount from about 0.005-0.4% by weight of the lubricating composition.

8. The lubricating composition according to claim 5, wherein the ratio of (A):(B) based on molybdenum content is from about 0.25:1 to 4:1.

9. The lubricating composition according to claim 8, wherein the ratio of (A):(B) based on molybdenum content is about 1:1.

10. The lubricating composition according to claim 1 wherein the triazole derivative is selected from an alkylated diphenylamine derivative of triazole and an alkylamine derivative of triazole.

11. The lubricating composition according to claim 10 wherein the alkylated diphenylamine derivative of triazole is selected from mono-butylated diphenylamine derivative of triazole, di-butylated diphenylamine derivative of triazole, mono-butylated mono-octylated diphenylamine derivative of triazole, mono-octylated diphenylamine derivative of triazole, di-octylated diphenylamine derivative of triazole and di-nonylated diphenylamine derivative of triazole.

12. The lubricating composition according to claim 10 wherein the alkylamine derivative of triazole is a bis(alkyl)aminomethyl derivative of triazole.

13. The lubricating composition according to claim 12 wherein the alkylamine derivative of triazole is 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,4-triazole.

14. The lubricating composition according to claim 1 wherein the sulfur-free organo-molybdenum source is a sulfur-free molybdenum ester/amide complex.

15. The lubricating composition according to claim 1 wherein the sulfur-containing molybdenum source is selected from molybdenum dithiophosphate, molybdenum dithiocarbamate and a trinuclear molybdenum dithiocarbamate.

16. The lubricating composition according to claim 1, wherein the reduction of copper and/or lead corrosion is according to the High Temperature Corrosion Bench Test ASTM D 6594.

17. The lubricating composition of claim 1, wherein the lubricating oil is one that is determined to be corrosive to Cu and/or Pb according to the High Temperature Corrosion Bench Test ASTM D 6594 when at least one of A, B or C are not present.

18. An additive composition for use with a lubricating oil composition, the additive composition comprising (A) a sulfur-free organo-molybdenum composition, (B) a sulfur-containing organo-molybdenum composition and (C) a triazole derivative prepared from 1,2,4-triazole, a formaldehyde source and an amine source; wherein the ratio of (A):(B) based on the amount of molybdenum provided by each is from about 0.25:1 to 4:1; and the weight ratio of [the total weight of (A)+(B)]:(C) is from about 50:1 to 1:2.

19. A composition according to claim 18 where the triazole derivative is chosen from the group consisting of one or more in combination of 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,4-triazole, or 1-(N-(4-butylphenyl)-N-(phenyl)aminomethyl)-1,2,4-triazole, or 1-(N,N-bis(4-butylphenyl)aminomethyl)-1,2,4-triazole, or 1-(N-(4-octylphenyl)-N-(phenyl)aminomethyl)-1,2,4-triazole, or 1-(N-(4-butylphenyl)-N-(4-octylphenyl)aminomethyl)-1,2,4-triazole, or 1-(N,N-bis(4-octylphenyl)aminomethyl)-1,2,4-triazole, and 1-(N,N-bis(4-nonylphenyl)aminomethyl)-1,2,4-triazole.

20. A composition according to claim 18, wherein the sulfur-free molybdenum composition is a molybdenum ester/amide complex.

21. A composition according to claim 18, wherein the sulfur-containing molybdenum composition is a molybdenum dithiophosphate, a molybdenum dithiocarbamate, a trinuclear molybdenum dithiocarbamate, or any combination of these.

22. A method of reducing high temperature corrosion in heavy duty diesel engines, comprising the steps of: (1) determining whether a heavy duty diesel engine oil is corrosive to Cu and/or Pb according to the High Temperature Corrosion Bench Test ASTM D 6594 when at least one of the following are not present in the engine oil: (A) a sulfur-free organo-molybdenum source, (B) a sulfur-containing organo-molybdenum source, and (C) a triazole derivative prepared from 1,2,4-triazole, a formaldehyde source and an amine source; and (2) if the engine oil is determined to be corrosive according to step (1), adding to the engine oil one or more of (A), (B) and (C) in an amount sufficient to allow the engine oil to reduce Cu and/or Pb corrosion according to the High Temperature Corrosion Bench Test ASTM D 6594.

23. The method according to claim 22, wherein the molybdenum content of the finished heavy duty diesel engine oil is between 50 ppm and 800 ppm.

24. The method according to claim 22, wherein the triazole derivative is present in the heavy duty diesel engine oil between 0.001% and 1.0%

25. The method according to claim 18, wherein the ratio of sulfur-free organo-molybdenum source to sulfur-containing organo-molybdenum source, based on molybdenum content, is from 0.25:1 to 4:1.

26. The method according to claim 22, wherein the sulfur-free organo-molybdenum source is a molybdenum ester/amide complex.

27. The method according to claim 22, wherein the sulfur-containing organo-molybdenum source is selected from molybdenum dithiophosphate, molybdenum dithiocarbamate and trinuclear molybdenum dithiocarbamate.

28. The method according to claim 22, wherein the triazole derivative is chosen from the group consisting of 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,4-triazole, or 1-(N-(4-butylphenyl)-N-(phenyl)aminomethyl)-1,2,4-triazole, or 1-(N,N-bis(4-butylphenyl)aminomethyl)-1,2,4-triazole, or 1-(N-(4-octylphenyl)-N-(phenyl)aminomethyl)-1,2,4-triazole, or 1-(N-(4-butylphenyl)-N-(4-octylphenyl)aminomethyl)-1,2,4-triazole, or 1-(N,N-bis(4-octylphenyl)aminomethyl)-1,2,4-triazole, and 1-(N,N-bis(4-nonylphenyl)aminomethyl)-1,2,4-triazole.

Description

EXAMPLES

Examples 1A Thru 3C

[0133] Corrosivity of lubricants towards copper and lead metals was evaluated using the high temperature corrosion bench test (HTCBT) according to the ASTM D 6594 test method. Details of the test method can be found in the annual book of ASTM standards. For the test specimen 1002 grams of lubricant was used. Four metal specimens of copper, lead, tin and phosphor bronze were immersed in a test lubricant. The test lubricant was kept at 135 C. and dry air was bubbled through the lubricant at 50.5 L/h for 1 week. API CJ-4 specifications for heavy duty diesel engine oil limits the metal concentration of copper and lead in the oxidized oil as per ASTM D 6594 test methods to 20 ppm maximum and 120 ppm maximum respectively. After the test, the lubricants were analyzed for the Cu and Pb metal content in the oil using inductive coupled plasma (ICP) analytical technique.

[0134] In Table 1, base blend is SAE 15W-40 viscosity grade fully formulated heavy duty diesel engine oil consisting of one or more base oils, dispersants, detergents, VI Improvers, antioxidants, antiwear agents, pour point depressants and any other additives such that when combined with the invention makes a fully formulated motor oil. Base blend is then further formulated as described in the examples 1A to 3C. The following components of the invention were evaluated: Molybdenum dithiocarbamate (A) is a commercial branched tridecyl amine based molybdenum dithiocarbamate containing 10% molybdenum by weight available from Vanderbilt Chemicals, LLC as MOLYVAN 3000. Molybdenum Ester/Amide is a commercial molybdate ester containing 8% molybdenum by weight available from Vanderbilt Chemicals, LLC as MOLYVAN 855. 1,2,4-Triazole (C) is 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,4-triazole. All the formulations in Table 1 have a total molybdenum content of 150 ppm. In examples 1A thru 1B, when only a single molybdenum source is used (either sulfur-containing molybdenum (A) or sulfur-free molybdenum (B)) and triazole C is not present, the passing rate in the HTCBT is very low (16.6% for Cu and 66.66% for Pb). In examples 2A thru 2G, when two of the three components are present (A+B, A+C or B+C), the passing rate in the HTCBT increases to 52.38% for Cu and 71.42% for Pb. However, the most striking results are obtained when all three components are present (A+B+C) as illustrated in examples 3A thru 3C. In this case a very high passing rate of 77.7% for Cu and 100% for Pb is obtained. This highlights the significant improvement in both Cu and Pb corrosion as measured in the HTCBT when a three component system containing A, B and C is present. Of even more significance is the extremely low treat levels of the 1,2,4-triazole (C) that are required in order to observe this effect. Table 1 clearly illustrates that 1,2,4-triazole (C) levels as low as 0.005 percent by weight are effective to reduce both Cu and Pb corrosion in the HTCBT.

TABLE-US-00002 TABLE 1A Examples 1 Additive 2 Additives A B A + B A + C A + C A + C B + C B + C B + C 1A 1B 2A 2B 2C 2D 2E 2F 2G 1 Base Blend* 99.85 99.8125 99.835 99.845 99.84 99.8 99.81 99.805 99.765 2 Molybdenum Dithiocarbamate (A) 0.15 0.075 0.15 0.15 0.15 3 Molybdenum Ester/Amide (B) 0.1875 0.09 0.185 0.185 0.185 4 1,2,4 Triazole (C) 0.005 0.01 0.05 0.005 0.01 0.05 5 Total 100 100 100 100 100 100 100 100 100 6 Molybdenum (ppm) 150 150 150 150 150 150 150 150 150 7 Cu Run 1 10 46 55 6 6 440 10 7 400 8 Cu Run 2 402 405 460 6 644 7 10 7 294 9 Cu Run 3 72 172 116 62 50 5 35 7 8 10 Avg. Cu (20 ppm max.) 161.33 207.67 210.33 24.67 233.33 150.67 18.33 7.00 234.00 11 Pb Run 1 46 144 72 44 8 16 126 130 20 12 Pb Run 2 6 11 8 42 42 28 138 138 20 13 Pb Run 3 44 140 70 36 16 30 167 118 96 14 Avg. Pb (120 ppm max.) 32.00 98.33 50.00 40.67 22.00 24.67 143.67 128.67 45.33 15 ASTM D 6594 Fail Fail Fail Fail Fail Fail Fail Fail Fail 16 Cu Run 1 P F F P P F P P F 17 Cu Run 2 F F F P F P P P F 18 Cu Run 3 F F F F F P F P P 19 Pb Run 1 P F P P P P F F P 20 Pb Run 2 P P P P P P F F P 21 Pb Run 3 P F P P P P F F P 22 Cu Pass (%) 16.66% 52.38% 23 Pb Pass (%) 66.66% 71.42% *Base Blend is fully formulated heavy duty diesel engine oil with SAE 15W40 viscosity grade

TABLE-US-00003 TABLE 1B Components (wt. %) 3 Additives A + B + C A + B + C A + B + C Examples 3A 3B 3C 1 Base Blend* 99.83 99.825 99.785 2 Molybdenum Dithiocarbamate 0.075 0.075 0.075 (A) 3 Molybdenum Ester/Amide (B) 0.09 0.09 0.09 4 1,2,4 Triazole (C) 0.005 0.01 0.05 5 Total 100 100 100 6 Molybdenum (ppm) 150 150 150 7 Cu Run 1 7 7 6 8 Cu Run 2 7 550 5 9 Cu Run 3 33 11 5 10 Avg. Cu (20 ppm max.) 15.67 189.33 5.33 11 Pb Run 1 56 63 65 12 Pb Run 2 60 12 62 13 Pb Run 3 70 65 54 14 Avg. Pb (120 ppm max.) 62.00 46.67 60.33 15 ASTM D 6594 Pass Fail Pass 16 Cu Run 1 P P P 17 Cu Run 2 P F P 18 Cu Run 3 F P P 19 Pb Run 1 P P P 20 Pb Run 2 P P P 21 Pb Run 3 P P P 22 Cu Pass (%) 77.77% 23 Pb Pass (%) 100% *Base Blend is fully formulated heavy duty diesel engine oil with SAE 15W40 viscosity grade

Examples 4 Thru 29

[0135] In Table 2-6, base blend is SAE 0W-20 viscosity grade fully formulated engine oil consisting of one or more base oils, dispersants, detergents, VI Improvers, antioxidants, antiwear agents, pour point depressants and any other additives such that when combined with the invention makes a fully formulated motor oil. Base blend is then further formulated as described in the examples shown in table 2-6.

[0136] Corrosivity of these formulations towards copper and lead metals was evaluated using high temperature corrosion bench test (HTCBT) according to the ASTM D 6594 test methods and modified HTCBT method. In the modified HTCBT method, The test lubricant was kept at 165 C. and dry air was bubbled through the lubricant at 50.5 L/h for 48 hours. After the test, the lubricants were analyzed for the Cu and Pb metal in the oil using inductive coupled plasma (ICP) analytical technique.

[0137] A, B, and C are as described previously. Molybdenum dithiocarbamate (D) is a commercial mixed tridecyl/2-ethylhexyl amine based molybdenum dithiocarbamate containing 10% molybdenum by weight available from Adeka Corporation. 1,2,4-Triazole (E) is 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,4-triazole from a different source compared to (C). Molybdenum dithiophosphate (F) is commercial molybdenum di(2-ethylhexyl)phosphorodithioate containing 8.5% molybdenum by weight available from Vanderbilt Chemicals, LLC. Molybdenum Trinuclear (G) is a trinuclear molybdenum dithiocarbamate containing 5.5% molybdenum by weight. Molybdenum dithiocarbamate (H) is a tridecyl amine based molybdenum dithiocarbamate containing 6.9% molybdenum by weight. N,N-Bis(2-ethylhexyl)-ar-methyl-1H-benzotriazole-1-methanamine (I) is an alkylamine derivative of tolutriazole corrosion inhibitor available from Vanderbilt Chemicals, LLC as CUVAN 303. 2,5-dimercapto-1,3,4-thiadiazole derivative (J) is a sulfur-based corrosion inhibitor available from Vanderbilt Chemicals LLC as CUVAN 826. In Tables 2 thru 6, the molybdenum content formulated into the lubricants is such that 160 ppm molybdenum is derived from the sulfur-free organo-molybdenum source (B) and approximately 160 ppm molybdenum is derived from a sulfur-containing molybdenum source.

[0138] Tables 2 thru 5 clearly show that the three-way combination of sulfur-free organomolybdenum (B), sulfur-containing organo-molybdenum (A, D, F, G, H) and 1,2,4-Triazole (C, E) are highly effective at reducing Cu and Pb corrosion in the HTCBT or modified HTCBT. Also, other corrosion inhibitors such as (I) and (D are ineffective at simultaneously reducing both Cu and Pb corrosion in the HTCBT and modified HTCBT.

TABLE-US-00004 TABLE 2 Examples 4 5 6 7 8 1 Base Blend* 99.64 99.44 99.44 99.44 99.44 2 Molybdenum Ester/Amide 0.2 0.2 0.2 0.2 0.2 (B) 3 Molybdenum 0.16 0.16 0.16 0.16 0.16 Dithiocarbamate (D) 4 1,2,4-Triazole (C) 0.2 5 1,2,4-Triazole (E) 0.2 6 N,N Bis(2-ethylhexyl)-ar- 0.2 methyl-1H-benzotriazole-1- methanamine (I) 7 2,5 dimercapto-1,3,4- 0.2 thiadiazole derivative (J) 8 Total 100 100 100 100 100 9 Using ASTM D6594 10 Cu (20 ppm max.) Run 1 15 4 4 14 389 11 Cu (20 ppm max.) Run 2 16 4 4 14 394 12 Pb (120 ppm max.) Run 1 53 2 3 197 20 13 Pb (120 ppm max.) Run 1 53 2 2 194 19 14 Modified HTDBT Method 15 Cu (20 ppm max.) Run 1 77 4 4 31 63 16 Cu (20 ppm max.) Run 2 75 4 4 47 42 17 Pb (120 ppm max.) Run 1 3 3 2 100 4 18 Pb (120 ppm max.) Run 1 3 3 2 20 4

TABLE-US-00005 TABLE 3 Examples 9 10 11 12 13 1 Base Blend* 99.637 99.437 99.437 99.437 99.437 2 Molybdenum Ester/Amide 0.2 0.2 0.2 0.2 0.2 (B) 3 Molybdenum 0.163 0.163 0.163 0.163 0.163 Dithiocarbamate (A) 4 1,2,4-Triazole (C) 0.2 5 1,2,4-Triazole (E) 0.2 6 N,N Bis(2-ethylhexyl)-ar- 0.2 methyl-1H-benzotriazole-1- methanamine (I) 7 2,5 dimercapto-1,3,4- 0.2 thiadiazole derivative (J) 8 Total 100 100 100 100 100 ASTM D6594 Cu (20 ppm max.) Run 1 97 4 4 4 390 Cu (20 ppm max.) Run 2 101 4 12 2 366 Pb (120 ppm max.) Run 1 41 2 <1 13 114 Pb (120 ppm max.) Run 2 52 1 224 190 102 Modified HTCBT Method Cu (20 ppm max.) Run 1 164 6 4 26 50 Cu (20 ppm max.) Run 2 164 4 3 25 214 9 Pb (120 ppm max.) Run 1 28 8 2 14 6 10 Pb (120 ppm max.) Run 2 20 22 2 165 17

TABLE-US-00006 TABLE 4 Examples 14 15 16 17 18 1 Base Blend* 99.617 99.417 99.417 99.417 99.417 2 Molybdenum Ester/Amide 0.2 0.2 0.2 0.2 0.2 (B) 3 Molybdenum 0.183 0.183 0.183 0.183 0.183 Dithiophosphate (F) 4 1,2,4-Triazole (C) 0.2 5 1,2,4-Triazole (E) 0.2 6 N,N Bis(2-ethylhexyl)-ar- 0.2 methyl-1H-benzotriazole-1- methanamine (I) 7 2,5 dimercapto-1,3,4- 0.2 thiadiazole derivative (J) 8 Total 100 100 100 100 100 ASTM D 6594 Cu (20 ppm max.) Run 1 136 4 4 23 234 Cu (20 ppm max.) Run 2 154 4 4 24 246 Pb (120 ppm max.) Run 1 12 3 2 189 73 Pb (120 ppm max.) Run 2 7 2 3 180 56 Modified HTCBT Method 9 Cu (20 ppm max.) Run 1 14 4 4 32 54 Cu (20 ppm max.) Run 2 56 5 5 30 72 10 Pb (120 ppm max.) Run 1 3 4 3 62 8 Pb (120 ppm max.) Run 2 5 5 5 61 16

TABLE-US-00007 TABLE 5 Examples 19 20 21 22 23 1 Base Blend* 99.51 99.31 99.31 99.31 99.31 2 Molybdenum Ester/Amide 0.2 0.2 0.2 0.2 0.2 (B) 3 Molybdenum Tri-nuclear (G) 0.29 0.29 0.29 0.29 0.29 4 1,2,4-Triazole (C) 0.2 5 1,2,4-Triazole (E) 0.2 6 N,N Bis(2-ethylhexyl)-ar- 0.2 methyl-1H-benzotriazole-1- methanamine (I) 7 2,5 dimercapto-1,3,4- 0.2 thiadiazole derivative (J) 8 Total 100 100 100 100 100 ASTM D 6594 Cu (20 ppm max.) Run 1 33 6 5 23 296 Cu (20 ppm max.) Run 2 23 5 5 27 288 Pb (120 ppm max.) Run 1 50 12 10 148 32 Pb (120 ppm max.) Run 2 48 11 10 134 44 Modified HTCBT Method 9 Cu (20 ppm max.) Run 1 26 8 6 28 131 Cu (20 ppm max.) Run 2 67 6 6 26 144 10 Pb (120 ppm max.) Run 1 5 1 1 22 3 Pb (120 ppm max.) Run 2 4 2 1 24 2

TABLE-US-00008 TABLE 6 Examples 24 25 26 27 28 29 1 Base Blend* 100 99.565 99.365 99.365 99.365 99.365 2 Molybdenum Ester/Amide 0.2 0.2 0.2 0.2 0.2 (B) 3 Molybdenum 0.235 0.235 0.235 0.235 0.235 Dithiocarbamate (H) 4 1,2,4-Triazole (C) 0.2 5 1,2,4-Triazole (E) 0.2 6 N,N Bis(2-ethylhexyl)-ar- 0.2 methyl-1H-benzotriazole-1- methanamine (I) 7 2,5 dimercapto-1,3,4- 0.2 thiadiazole derivative (J) 8 Total 100 100 100 100 100 100 ASTM D 6594 Cu (20 ppm max.) Run 1 5 14 4 5 22 374 Cu (20 ppm max.) Run 2 4 12 4 5 15 347 Pb (120 ppm max.) Run 1 2 66 11 10 260 4 Pb (120 ppm max.) Run 2 3 74 13 8 267 22 Modified HTCBT Method 9 Cu (20 ppm max.) Run 1 71 64 4 4 31 41 Cu (20 ppm max.) Run 2 5 44 4 4 32 33 10 Pb (120 ppm max.) Run 1 2 4 3 4 62 4 Pb (120 ppm max.) Run 2 1 14 6 4 64 4

Examples 30 Thru 33

[0139] In Table 7, base blend is SAE 15W-40 viscosity grade fully formulated heavy duty diesel engine oil consisting of one or more base oils, dispersants, detergents, VI Improvers, antioxidants, antiwear agents, pour point depressants and any other additives such that when combined with the invention makes a fully formulated motor oil. Base blend is then further formulated as described in the examples 30-33.

[0140] Corrosivity of these formulations towards copper and lead metals was evaluated using high temperature corrosion bench test (HTCBT) according to the ASTM D 6594 test methods. Details of the test method can be found in the annual book of ASTM standards. For the test specimen 1002 grams of lubricant was used. Four metal specimens of copper, lead, tin and phosphor bronze were immersed in a test lubricant. The test lubricant was kept at 135 C. and dry air was bubbled through at 50.5 L/h for 1 week. API CJ-4 specifications for heavy duty diesel engine oil limits the metal concentration of copper and lead in the oxidized oil as per ASTM D 6594 test methods to 20 ppm maximum and 120 ppm maximum respectively. After the test, lubricant were analyzed for the Cu and Pb metal in the oil using inductive coupled plasma (ICP) analytical technique.

[0141] A, B and C are as described previously. Dioctylated diphenylamine derivative of 1,2,4-triazole (P-1) was that prepared in Example P-1. Butylated/octylated diphenylamine derivative of 1,2,4-triazole (P-2) was that prepared in example P-2.

TABLE-US-00009 TABLE 7 30 31 32 33 Commercial 15W40 oil 99.64 99.44 99.24 99.24 Molybdenum dithiocarbamate (A) 0.16 0.16 0.16 0.16 Molybdenum ester/amide (B) 0.2 0.2 0.2 0.2 1,2,4-triazole (C) 0.2 Dioctylated diphenylamine 0.4 derivative of 1,2,4-triazole (50% active) (P-1) Butylated/octylated diphenylamine 0.4 derivative of 1,2,4-triazole (50% active) (P-2) Total 100 100 100 100 Mo (ppm) 320 320 320 320 ASTM D6594 Cu (20 ppm Max.) Run 1 225 7 51 8 Cu (20 ppm Max.) Run 2 265 6 48 7 Pb (120 ppm Max.) Run 1 101 47 67 40 Pb (120 ppm Max.) Run 2 116 43 99 50

[0142] The results clearly show that that 1,2,4-triazole (C), dioctylated diphenylamine derivative of 1,2,4-triazole (50% active) (P-1), and butylated/octylated diphenylamine derivative of 1,2,4-triazole (P-2) are all effective to reduce corrosion in the three-way additive system containing sulfur-free organo-molybdenum, sulfur-containing organo-molybdenum and derivatized triazole.

Example P-1

Preparation of 1-(N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)aminomethyl)-1,2,4-triazole in 50% process oil

[0143] In a 500 mL three-necked round bottom flask equipped with a temperature probe, overhead stirrer and Dean Stark set up were charged VANLUBE 81 (dioctyl diphenylamine) (62.5 g, 0.158 mole), 1,2,4-triazole (11.0 g, 0.158 mole), paraformaldehyde (5.5 g, 0.158 mole), water (3 g, 0.166 mole) and process oil (37.7 g). The mixture was heated under nitrogen to 100-105 C. with rapid mixing. Mixing was continued at 100 C. for one hour. After one hour, water aspirator vacuum was applied and the reaction temperature was raised to 120 C. The reaction mixture was held at this temperature for an hour. The expected amount of water was recovered, suggesting a complete reaction occurred. The reaction mixture was allowed to cool to 90 C., and transferred to a container. A light amber liquid (102.93 g) was isolated.

Example P-2

Preparation of Mixed Butylated/Octylated Diphenylamine Derivative of 1,2,4-Triazole in 50% Process Oil

[0144] In a 500 mL three-necked round bottom flask equipped with a temperature probe, overhead stirrer and Dean Stark set up were charged VANLUBE 961 (mixed butylated/octylated diphenylamine) (60 g, 0.201 mole), 1,2,4-triazole (13.9 g, 0.200 mole), paraformaldehyde (6.8 g, 0.207 mole), water (3.8 g, 0.208 mole) and process oil (77 g). The mixture was heated under nitrogen to 100-105 C. with rapid mixing. Mixing was continued at 100 C. for one hour. After one hour, water aspirator vacuum was applied and the reaction temperature was raised to 120 C. The reaction mixture was held at this temperature for an hour. The expected amount of water was recovered, suggesting a complete reaction occurred. The reaction mixture was allowed to cool to 90 C., and transferred to a container. A dark amber liquid (138.86 g) was isolated.