CA1284488C

CA1284488C - Ashless anti-wear additives

Info

Publication number: CA1284488C
Application number: CA000533770A
Authority: CA
Inventors: Morton Beltzer; Said Jahanmir
Original assignee: Exxon Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 1986-04-14
Filing date: 1987-04-03
Publication date: 1991-05-28
Anticipated expiration: 2008-05-28
Also published as: AU7147887A; EP0243026A2; KR870010168A; AU597640B2; BR8701761A; JPS62243692A; EP0243026A3

Abstract

ABSTRACT OF THE DISCLOSURE

An anti-wear additive for a functional fluid, such as a lube oil, is disclosed. The additive comprises selected substituted pyridines, pyrimidines, pyrazines, pyridazines and/or fused ring derivatives thereof.

Description

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BACXGROUND OF T~E lNVENTION
, The present invention is directed at an additive for a functional fluid. More specifically, the present invention is directed at an ashless anti-wear additive for lube oil.

- Several factors are combining to increase the demands on the wear protection capability of pas-senger car engine oil~. In the formulation of lube oils, an anti-wear additive frequently is added to decrease the wear associated with operation. In lube oils for internal combustion engines, the anti-wear additive often comprises a pho~phorus compound, such as zinc dialkyldithiopho~pha~e. While this additive has proven effective in reducing engine wear, the phos-phoru~ pre~ent has been determined to be a catalyst poison, when minor amounts of the lube oil are com-busted in the internal combustion engine.

In addition, the severe operating conditions of high speed engines and the use of fast burn engines with higher combustion temperatures increase the oil sump temperature. Moreover, engine manufacturers are recommending lower viscosity oi1, such as 5W30 for faster cold starting and improved fuel economy.

U.S. Patent No. 3,374,173 discloses 2,4,6 tri-amino substituted pyrimidines are effective in imparting high temperature stability to lubricants. In a preferred embodiment the tri-amino substituted py-rimidine is prepared from a 2,4,6 trichloropyrimidine.

, .. -- 2 --Japanese Patent Publication No. 58,103,594 discloses the addition of a substituted benzothiazole as an anti-wear additive for a lub~icating oil used in freon comp~essors.

In "80undary Lubricating Studies Structure-Activity Correlations in Alkylpyridines", Journal of the Institute of Petroleum, Volume 59, Number 565 (January, 1973), A. H. Miller discloses that pyridine, benzopyridine and certain alkylpyridines are effective as anti-wear agents in lube oils.

~ .S. Patent No. 4,113,725 discloses com-pounds of the general formula:

~X] - C

~n which X i3 a heterocyclic radical derived from pyridine, pyridazine, pyrimidine, pyrazine or triazine;
and A, B and C are each hydrogen, alkyl, aralkyl, alkenyl, aryl, alkaryl, hydroxyalkyl, hydroxyaryl, carboxy, alkylcarboxy, hydroxy, phosphono, phosphato, sulfonato, mercapto or a nitrogen-containing substi-tuent having from about 1 to about 500 atoms, prefer-ably from about 1 to 100 carbon atoms, provided that at least one of A, 8, or C is one of the nitrogen-con-taining substituents. The nitrogen-containing substituents include alkyl-amino, arylamino, succini-mide amino, lactam amino and the like.

Accordingly, it would be desirable to pro-vide a phosphorus-free anti-wear additive ~or a func-tional fluid, such as a lube oil.

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It also is advantageous to provide anti-wear additive for a lube oil which is soluble in the lube oil and which is effective at relatively low concent~a-tions. It also would be desirable to provide an ash-less anti-wear additive to minimize depositions on catalytic converters.

The present invention is directed at an additive for a functional fluid, such as a lube oil comprising:

A. a basestock; and B. -an anti-wear compound selected from the group consisting of substituted pyridine, pyrimidine, pyrazine, pyridazine, fused ring derivatives thereof and mixtures thereof.

The p~esent invention is directed at a functional fluid having improved anti-wear properties, ~aid functional fluid comprising:

A. a basestock; and, B. an anti-wear compound selected from the group consisting of:

~ N

fused ring derivatives thereof and mixtures thereof, where R may be a single or multiple substituent. R
preferably is selected from the group consisting of halogens, chloromethyl, dichloromethyl, trichloro-methyl, chlorobromomethyl, bromomethyl, dibromomethyl, cyano, i30cyano, methylcyano, cyanomethyl, cyanate, isocyanate, thiocyanate, isothiocyanate, nitro, nitromethyl, nitro~o, formyl, acetyl, methyl carboxyl-ate, methoxy, methylthio, thiol, disulfide.

When the anti-wear compound comprises sub-R ~
stituted pyridine, ~ the substituent preferably ha~ a bond moment of at least 1.42 Debyes if it is in the meta position and 3.9 Debyes in the ortho position.
Preferred compounds comprise meta ~ub~tltuted com-pounds. When the anti-wear compound comprises a fused ring derivative of pyridine, such as quinoline, R may have a bond or group moment of 1.25 Debyes. Where the a~t ~ elar compound comprises substituted py~rimidine ~ or substituted pyridazine ~ pre-ferr substituents also have a dipole m ent of }.4 and 0.97 Debyeq, respectfully. When the~anti-wear compound comprises substituted pyrazine, ~ ~
preferably has a dipole moment of at least .4 Debyes.
For all of the above-noted compounds, preferred sub-stituents are selected from the group consisting of -Cl, -Br, -CH2Cl, -CH2ClBr, -CHC12, -CH2Br, -CHBr2, -CN, CH2CN, -NC, -CNO, -NCO, -SCN, -NCS, -N02, -CH2N02, -NO, -CHO, -COCH3, OCH3, -COOCH3, -CC13, -S2-, -SCH3, SH, and mixtures thereof.

- s -In a preferred embodiment the functional fluid comprises a lube oil. The additive preferably comprises from about 0.25 weight percent to about 2.0 weight percent of the lube oil, preferably from about 0.5 weight percent to about 1.5 weight percent of the lube oil.

The present invention also is directed at a method for decreasing wear in an internal combustion engine having lubricant circulated therethrough, said method comprising adding to the lubricant an effective amount of an anti-wear additive having the general formula:

R ~ N ~ ~

fu~ed ring derivatives thereof and mixtures thereof, having a substituent selected from the group consist-ing of -Cl, -Br, -CH2Cl, -CH2ClBr, -CHC12, -CHBr2, -CN, CH2CN, -NC, -CNO, -NCO, -SCN, -NCS, -SCN, -NO2, -CH2NO2, -NO, -CHO, -COCH3, OCH3, -COOCH3, -CC13, -S2-, SCH3, SH, and mixtures thereof.

OETAILED DESCRIPTION OF THE INVENTION

The present invention is directed at an anti-wear additive for a functional fluid, such as a lube oil, said additive compriqing:

R ~ ~ ~ R

fused ring derivatives thereof and mixtures thereof, where ~ may be a single or multiple substitute forming a dipole moment of at least 1.42 Debyes for pyridine, 0.97 Debyes for pyridazine, and 1.42 Debyes for pyrazine and pyrimidine. R preferably is selected from the group consisting of halogens, chloromethyl, di-chloromethyl, trichloromethyl, chlorobromomethyl, bromomethyl, dibromomethyl, cyano, isocyano, methyl-cyano, cyanomethyl, cyanate, isocyanate, thiocyanate, isothiocyanate, nitro, nitromethyl, nitroso, formyl, acetyl, methyl carboxylate, methoxy, methylthio, thiol, disulfide.

Preferred halogen substituents include chlorine and bromine.

Four Ball Wear tests were conducted to determine the effectiveness of various additives in reducing wear. This test is described in detail in ASTM method D-2266. In this test three balls are fixed i~ a lubricating cup and an ùpper rotating ball is pressed against the lower three balls. The test balls utilized in the following tests were made of AISI
52100 steel with a hardness of 65 ~ockwell C (840 Vickers) and a centerline roughness of 25 nm. Prior to the tests, the test cup, steel balls and all holders were degreased with 1,1,1 trichlorethane. The steel balls subsequently were washed with a laboratory detergent to remove any solvent residue, rinsed with water, and dried under nitrogen.

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The base lubricant utilized in all of the foregoing tests was 150 Neutral, a solvent extracted, dewaxed hydrofined neutral basestock having a viscosity of 32 centistokes (150 SSU) at 40C. In the following tables, results are shown for Four Ball Wear tests conducted at room temperature, at 60 kg load, 1200 rpm for 45 minutes duration utilizing 1 weight percent of each additive.

After the wear tests, the balls were de-greased and the wear scar diameter on the lower balls measured using an optical microscope. The average of at least two measurements was used in calculating the wear volume per ball. The calculated wear volume was based on the assumption that the worn volume is a cir-cular sector.

The Four Ball Wear test results are pre-sented in terms of wear volume and on the relative basis of percent wear reduction. The latter is based on the minimum wear volume of 0.054 mm3 observed using 150 neutral basestock without any anti-wear additive, although wear volumes in replicate tests in base lubricant varied widely and often exceed this value.

As shown in ~ables I to X hereinafter, it has been found that substituted pyridines, pyrimidines, pyrazines, pyridazines, quinolines, and mixtures thereof were effective anti-wear additives. ~he above-noted classes of compounds preferably include electro-negative substituents. As used herein, the term electronegative substituent is defined to mean one which attracts electrons. Where the anti-wear additive comprises pyridine, the electronegative substituent preferably has a dipole moment greater than about 1.42 Debyes. ~or compounds having more than one nitrogen in the ring, such as pyridazine and pyrimidine weaker electronegative substituent groups may be utilized, ç~

such as substituent groups having dipole moments greater than about 1.25 Debyes. For pyridazines still weaker electronegative substituents having a dipole moment of greater than 0.97 Debyes may be used. Among the preferred substituent groups are the halogens, methyl substituted halogens, cyano-substituents, alkoxy substituents, nitroso and dithio substituents. Among the preferred halogens are chlorine and bromine. Amonq the preferred methyl substituted halogens are chloro-methyl, dichloromethyl, trichloromethyl, bromomethyl, chlorobromomethyl, dibromomethyl and mixtures thereof.
Among the preferred cyano-substituents are cyano, isocyano, isocyanato, thiocyanato. ~mong the preferred nitrogen containing substituents are nitro, nitro-methyl, nitroso, and mixtures thereof. ~mong the pre-ferred alkoxy compounds are formyl-, acetyl-, methoxy and methylcarboxylate~ Other preferred substituents include methyl thio, methyl thiol, disulfide and mix-tures thereof.
A. Substituted PYridines When the pyridine substituted compounds, ~ , are utilized the substituent compound prefer-ably has a bond or group dipole moment of at least 3.9Debyes if it is in the ortho position and 1.42 Debyes if it is in the meta position. R preferably is selected from the group consisting of -Cl, -Br, CH2Cl, -CHC12, -CC12, -CC13, -CH2Br, -CHBr2, -CN, -CH2CN, -NC, -CNO, -NCO, -SCN, -NCS, -NO2, -CH2NO2, -CHO, -COCH3, -OCH3, -COOCH3, -S2, -SCH3, -SH and mixtures thereof.

In Table I the additives noted were added to 150 Neutral basestock without any additional components normally found in a fully formulated lube oil.

_ 9 _, Also shown in Table I for comparative pur-poses is the wear volume obtained with zinc dialkyl-dithiophosphate, which reduces wear by about 98.9%. For a heterocyclic additive to be seriously considered as an effective anti-wear agent, it is believed that the test results should show wear reductions of at least 95~ as compared to the basestock with no anti-wear additive.

In Table II Four Ball Wear Test data con-ducted at 100C, ambient air, 60 kg load, 1200 rpm for 45 minutes duration is shown for partially formulated lube oils. The lube oil contained all conventional additives except for ZDDP and a conventional friction reducing additive which also serves as an anti-wear agent. The other additives present in a conventional lube oil also may impart some anti-wear properties.
This may be seen from the base case in Table II where the wear volume was 0.029 mm3 with no anti-wear addi-tive, 46% less than the 0.054 mm3 wear volume reported in Table I for the basestock alone.

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Teqts similar to those conducted with the pyridine additives were conducted utilizing certain pyrimidine compounds. The test results presented in Tables III and IV utilized the same additive concentra-tions and test conditions as those presented in Tables I and II, respectively. Here also it may be seen that the pyrimidine compounds listed were effective in re-ducing wear, and that the combination of ZDDP and the pyrimidine additive generally reduced the wear below that achieved usi~g only ZODP. As shown in Table III, substituted pyrimidine compounds exhibited superior wear reduction capabilities than pyrimidine.

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Four Ball Wear Tests also were conducted utilizing pyrazine additives. The test results, pre-sented in Tables V and VI also utilized the same addi-tive concentrations and test conditions as those con-ducted for the results presented in Tables I and II, respectively. Here also, substituted pyrazine com-pounds exhibited superior wear reducing and friction réducing propertie~ to pyrazine.

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D. Substituted Pyridazines When pyridazine substituted compounds are utilized, ~ N , the substituent compound preferably has a bond or group moment of at least 0.97 Debyes. R
preferably is selected from the group consisting of chlorine, bromine, chloromethyl, dichloromethyl, tri-chloromethyl, bromomethyl, dibromomethyl, cyano, iso-cyano, cyanato, isocyanato, isothiocyanato, thio-cyanato, nitro, nitromethyl, nitroso, formyl, acetyl, methylcarboxylate, methoxy, methyl thio, thiol, disul-fide and mixtures thereof.

The utility of pyridazine compounds as anti-wear agents may be ~2en from the data presented in Tables ~II and VIII below. The test results presented in Tables VII and VIII utilized the same additive con-centrations and test conditions as those previously described for the results presented in Tables I and II, respectively. It was not possible to obtain wear reduction results for unsubstituted pyridazine, since this compound was insoluble in the basestock.

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F. Fused Ring Substituted Pyridines Fused ring derivatives of pyridines, such as qluinoline ~ substituted compounds, may be useful as anti-wear a~ent3. The substituent preferably ha~ a dipole moment of 1.25 Debyes or greater and pref-erably is ~elected from the group consisting of chlorine, bromine, chloromethyl, dichloromethyl, tri-ch}oromethyl, bromomethyl, dibromomethyl, cycano, cyanomethyl, isocyano, isocyanato, cyanato, isocyan-ato, thiocyanato, isothiocyanato, nitro, nitromethyl, nitroso, formyl, acetyl, methyl carboxylate, methoxy, acetyl, disulfide, methyl thio, thiol and mixtures thereof. The utility of quinoline compounds as anti-wear agents may be seen from the data presented below in Tables IX and X. The te~t results presented iQ these table~ were obtained usiQg the same additive concen-trations and test condltions as tho~e previously described with respect to Tables I and II, respectively c o c~ o r~
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Claims

1. A functional fluid having improved anti-wear properties, said functional fluid comprising:

A. a basestock; and, B. an anti-wear compound selected from the group consisting of substituted pyridine and sub-stituted diazine and fused ring derivatives thereof where the substituent is selected from the group con-sisting of halogens, chloromethyl, dichloromethyl, trichloromethyl, chlorobromomethyl, bromomethyl, cyano, isocyano, methylcyano, cyanomethyl, cyanate, iso-cyanate, thiocyanate, isothiocyanate, nitro, nitro-methyl, nitroso, formyl, acetyl, methyl carboxylate, methoxy, methylthio, thiol, disulfide.

2. The composition of claim 1 wherein the functional fluid comprises a lube oil and wherein the basestock comprises a lube oil basestock.

3. The lube oil of claim 2 wherein the anti-wear compound comprises from about 0.25 to about 2.0 wt.% of the lube oil.

4. The lube oil of claim 3 wherein the anti-wear compound comprises a substituted pyridine.

5. The lube oil of claim 3 wherein the anti-wear compound comprises a substituted pyrimidine.

6. The lube oil of claim 3 wherein the anti-wear compound comprises a substituted pyridazine.

7. The lube oil of claim 3 wherein the anti-wear compound comprises a substituted pyrazine.

8. The lube oil of claim 3 wherein the anti-wear compound is a substituted quinoline.

9. A method for producing a lube oil having improved anti-wear properties, said method comprising admixing with a lube oil basestock an effective amount of a compound selected from the group consisting of:

, , , fused ring derivatives thereof and mixtures thereof, where R is selected from the group consisting of halogens, methyl cyano, cyano, isocyano, cyanato, isocyanato, thiocyanato, isothiocyanato, nitro, nitro-methyl, nitroso, formyl, acetyl, methoxy, methyl thio, thiol, disulfide, chloromethyl, dichloromethyl, tri-chloromethyl, chlorobromomethyl, nitromethyl, cyano-methyl and mixtures thereof.

10. A lube oil having improved anti-wear properties comprising:

A. a basestock; and, B. a substituted pyridine or fused ring derivative thereof wherein the substituent has a dipole moment of at least 1.42 Debyes in the ortho position and 3.9 Debyes in the meta position.

11. The lube oil of claim 10 wherein the substituent is selected from the group consisting of chlorine, bromine, chloromethyl, dichloromethyl, tri-chloromethyl, bromomethyl, dibromomethyl, cyano, isocyano, cyanomethyl, cyanato, isocyanato, thiocyanato, nitro, nitromethyl, formyl, acetyl, methoxy, methylcarboxylate and mixtures thereof.

12. A lube oil having improved anti-wear properties comprising:

A. a basestock; and, B. a substituted pyrimidine wherein the substituent has a dipole moment of at least 1.25 Debyes.

13. The lube oil of claim 12 wherein the substituent is selected from the group consisting of chlorine, bromine, chloromethyl, dichloromethyl and mixtures thereof.

14. A lube oil having improved anti-wear properties comprising pyrazine suhstituted compounds wherein the substituent has a dipole moment of at least 1.42 Debyes.

15. The lube oil of claim 14 wherein the substituent is selected from the group consisting of chlorine, bromine and mixtures thereof.

16. A lube oil having improved anti-wear properties comprising:

A. a basestock; and, B. a substituted pyridazine wherein the substituent has a dipole moment of at least 1.4 Debyes.

17. The lube oil of claim 16 wherein the substituent is selected from the group consisting of chlorine, bromine, chloromethyl, dichloromethyl, tri-chloromethyl, bromomethyl, dibromomethyl, cyano, iso-cyano, cyanato, isocyanato, thiocyanato, isothio-cyanato, nitro, nitromethyl, disulfide, and mixtures thereof.