AU597640B2 - Ashless anti-wear additives - Google Patents

Description

Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE

SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: 7 '7 F/9 I Complete Specification Lodged: Accepted: Published: l Priority: t" o e e 0 "Fjlated Art: 0 a C i i .4 1~ 4. .4 I q o cNamne of Applicant: EXXON 6 RESEARCH AND ENGINEERING COMPANY 4 o Address of Applicant: b Ac'tual Inventor: 0o Address for Service: P.O. BOX 390, FLORHAM PARK, NEW JERSEY, 07932, UNITED STATES OF AMERICA.

MORTON BELTZER and SAID JAHANMIR EDWD, WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: "ASHLESS ANTI-WEAR ADDITIVES" The following statement Is a full description of this Invention, Including the best method of performing It known to 1, la BACKGROUND OF THE INVENTION The present invention is directed at an additive for a functional fluid. More specifically, the present invention is directed at an ashless antiwear additive for lube oil.

Several factors are combining to increase the demands on the wear protection capability of passenger car engine oils. In the formulation of lube oils, an anti-wear additive frequently is added to o decrease the wear associated with operation. In lube o oils for internal combustion engines, the anti-wear additive often comprises a phosphorus compound, such as zinc dialkyldithiophosphate. While this additive has proven effective in reducing engine wear, the phosphorus present has been determined to be a catalyst poison, when minor amounts of the lube oil are combusted in the internal combustion engine.

o 0. In addition, the severe operating conditions of high speed engines and the use of fast burn engines with hinher combustion temperatures increase the oil sump temperature. Moreover, engine manufacturers are recommending lower viscosity oil, such as 5W30 for faster cold starting and improved fuel economy.

o U.S. Patent No. 3,374,173 discloses 2,4,6 tri-amino substituted pyrimidinas are effective in .imparting high temperature stability to lubricants. In a' preferred embodiment the tri-amino substituted pyrimidine 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 lubricating oil used in freon compressors.

In "Boundary 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.

U.S. Patent No. 4,113,725 discloses compounds of the general formula: o A x] c

B

ooe in which X is a heterocyclic radical derived from 0 pyridine, pyridazine, pyrimidine, pyrazine or triazine; and A, B and C are each hydrogen, alkyl, aralkyl, P, alkenyl, aryl, alkaryl, hydroxyalkyl, hydroxyaryl, carboxy, alkylcarboxy, hydroxy, phosphono, phosphato, sulfonato, mercapto or a nitrogen-containing substituent having from about 1 to about 500 atoms, preferably from about 1 to 100 carbon atoms, provided that at least one of A, B, or C is one of the nitrogen-containing substituents. The nitrogen-containing S0 substituents include alkyl-amino, arylamino, succinimide amino, lactam amino and the like.

Accordingly, it would be desirable to provide a phosphorus-free anti-wear additive for a functional fluid, such as a lube oil.

S- 3 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 1 w concentrations. It also would be desirable to pro -ide an ashless 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: I A. a basestock; and B. an anti-wear compound selected from the group consisting of substituted pyridine, pyrimidine, pyrazine, pyridazine, fused ring derivatives thereof a and mixtures thereof.

t SUMMARY OF THE INVENTION a The present invention is directed at a functional fluid having improved anti-wear properties, said functional fluid comprising: a basestock; and, B an anti-wear compound selected from the group consisting of: 9 0 R R N N N n -4fused ring derivatives thereof and mixtures thereof, where R may be a single or multiple substituent. R P-fr2311 is selected froin the group consisting of halogens, chloromethyl, dichloromethyl, trichloromethyl, chlorobromomethyl, bromomethyl, dibromomethyl, cyano, isocyano, methylcyano, cyanomethyl, cyanate, isocyanate, thiocyanate, isothiocyanate, nitro, nitromethyl, nitroso, formyl, acetyl, methyl carboxylate, methoxy, methylthio, thiol, disulfide.

When the anti-wear compound comprises substituted pyridine, the substituent preferably has 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 substituted comnpounds. 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 ar,1-ea compound comprises substituted pyrimidine ferdsbor substitute Id pyridazine prefer~sustituents also have a dipole m6 tent of 1.4 and 0.97 Debyes, respectfully. When. the anti-wear compound comprises substituted pyrazine,

I,

preferably has a dipole moment of at least t.4 Debyes.

For all of the above-noted qompounds, pref.~orc.... substituents are selected from the group consisting of -Cl, -Br, -CH 2 CI, -CH 2 ClBr, -CHCl 2

-CFH

2 Br, -CHBr 2 -CN, CH 2 CN, -NC, -CNO,,-NCO, -SCN, -NCS, -N4O21 -CHI 2

NO

2 'NO, -CHO0, -COd-I 3

OCH

3 1 -'COOCH 3 P -CC).

3

-S

2

-SCH

3 SH, and mixtures thereof.

5 5 In a preferred embodiment the functional fluid comprises a lube oil. The additive preferably comprises from about 0.25 weight percent to about 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 addina to the lubricant an effective amount of an anti-wear additive having the general formula: 0 a Sv *R R N 0 a. fused ring derivatives thereof and mixtures thereof, 0 a :0 Dhaving a substituent selected from the group consista a ing of -Cl, -Br, -CH 2 Cl, -CH 2 ClBr, -CHC1 2 -CHBr 2 2, 5 -CN, CH 2 CN, -NC, -CNO, -NCO, -SCN, -NCS, -SCN, -NO 2

-CH

2

NO

2 -NO, -CHO, -COCH 3

OCH

3

-COOCH

3 -CC1 3 -S2-,

SCH

3 SH, and mixtures thereof.

S0 DETAILED DESCRIPTION OF THE :INVENTION 0 The present invention is directed at an anti-wear additive for a functional fluid, such as a lube oil, said additive comprising:

^A

R R N N fused ring derivatives thereof and mixtures thereof, where R 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, dichloromethyl, trichloromethyl, chlorobromomethyl, bromomethyl, dibromomethyl, cyano, isocyano, methylcyano, cyanomethyl, cyanate, isocyanate, thiocyanate, a isothiocyanate, nitro, nitromethyl, nitroso, formyl, acr.tyl, methyl carboxylate, methoxy, methylthio, thiol, disulfide.

o oo0 SPreferred halogen substituents include oS chlorine and bromine.

Four Ball Wear tests were conducted to determine the effectiveness of various additives in Sareducing wear. This test is described in detail in oZQ ASTM method D-2266, the disclosure of which is incorporated herein by reference. In this test three balls are fixed in a lubricating cup and an upper rotating 1 ball is pressed against the lower thriee balls. The test balls utilized in the following tests were made of AISI 52100 steel with a hardness of 65 Rockwell C (840 Vickezs) 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.

t_ -7- 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 40 0 C. 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 degreased 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 circular sector.

The Four Ball Wear test results are presented 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 mm 3 observed using 150 neutral l7asestock without any anti-wear additive, although wear volumes in replicate tests in base lubricaint varied widely and often exceed this value.

S23 As shown in Tables I to X hereinafter, it has been found that substituted pyridines, pyrimidines, pyrazines, pyridazines, quinolines, and mixtures thereof were effective anti-wear additives. The abovenoted classes of compounds preferably include electronegative substituents. As used herein, the term 0 4 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. For compounds having more than one nitrogen in the ring, such as pyridazine and pyrimidine weaker electronegative substit:uenE. groups may be utilized, -8such as substituent groups having dipole moments greater than about 1.25 Debyes. For pyridazines still weaker electronegative sub stituents 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. Ano ng the preferred methyl substituted halogens are chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, chorobromomethyl, dibromomethyl and mixtures thereof.

Among the preferrGd cyano-substituents are cyano, isocyano, isocyanato, thiocyanato. Among the preferred nitrogen containing substituents are nitro, nitromethyl, nitroso, and mixtures thereof. Among the preferred alkoxy compounds are formyl-, acetyl-, methoxy and methylcarboxylate. Other preferred substituents include methyl thio, methyl thiol, disulfide and mix- 4 4c sItures thereof.

S' A. Substituted Pyridines When the pyridine substituted compounds, are utilized the substituent compound prefer- 4. N ably has a bond or group dipole moment of at least 3.9 Debyes if it is in the ortho position and 1.42 Debyes 4 if it is in the meta position. R preferably is a selected from the group consisting of -Cl, -Br, CH 2 Cl, 4304 -CHC12, -CC1 2 -CC13, -CH 2 Br, -CHBr 2 -CN, -CH 2 CN, -NC, -CNO, -NCO, -SCN, -NCS, -NO 2

-CH

2

NO

2 -CHO, -COCH3r -0CH 3

-COOCH

3

-S

2

-SCM

3 -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.

r.

-iiLi__ ili-- ~LiYi

F

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

In Table II Four Ball Wear Test data conducted at 100 0 C, ambient air, 60 kg load, 1200 rpm for 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.

0 00e 0 This may be seen from the base case in Table II where o 0 the wear volume was 0.029 mm 3 with no anti-wear addi- 0 060 t ive, 46% less than the 0.054 mm 3 wear volume reported in Table I for the basestock alone.

0 00 o 00a 000° 0 ag 000 0 .0 00 0 00 *J 0 0 0 f 0 0

A-

*c *c a coo 0 o o ft o0 0c o a a9 a 4 c o 0 0 TABLE I PYRIDINE AND PYRIDINE DERIVATIVES AS ANTI-WEAR AGENTS IN BASESTOCK Wear Wear Additive Volume mmr 3 Reduction None 0.054 0.0 ZDDP 0.0004 99.2 Pyridine 0.054 2-(Aminomethyl) Pyridine 0.0004 99.2 ,2-(p-nitrobenzyl) pyridine 0.0044 91.4 2,4 '-Dipyridyl 0.0061 88.0 2-(2,-Aminoethyl Pyridine) 0.0008 98.4 2-Chloro-3,5-Dinitropyridine 0.0057 88.8 3-Chloropyridi-e 0.0008 98.4 2, 6-Diacetylpyridine 0.0040 92.2 Di-2-Pyridyl Ketone 0.0021 95.9 2, 3-Cyc1loheptenopyr idine 0.0025 95.1 2,2' -Dithiodipyridine 0.0007 98.6 4 ,41-Dithiodipyridine 0.0010 98.0 3-Bromopyridine 0.0013 97.5 2-(3-Thienyl) Pyridine 0.0038 92.5 2,3'-Dipyridyl 0.0038 92.5 3-Pyridine Carboxyaldehyde 0.0052 89.8 r--ui~-uiciz~- (I-1I rT~ 11 As shon in Table I, the substituted pyridines exhibited substantially superior wear reduction than unsubstituted pyridine. The utility of the present invention also may seen from Table II in which certain of the additives from Table I also were utilized in a partially formulated lubricating oil. In one series of tests, the anti-wear additives, zinc dialkyldithiophosphate and another conventional friction reducing additive both were eliminated from the otherwise complete formulated lube oil. In their place the indicated pyridine additives were added at the weight percent level. It can be seen that the pyridine compounds effectively reduced wear in Four Ball Wear Tests conducted at 100 0 C, 60 kg load, 1200 rpm for minutes test duration. Additional Four Ball Wear Tests S, were conducted in oil formulations si, ilar to that o t previously noted in which the pyridine compound and S0o. ZDDP both were added, but in which the other conventional friction additive was not utilized. These test results indicate that use of ZDDP and the pyridine "o compound generally produced better wear reduction than a. either ZDDP or the pyridine additive individually.

S00 0 "0 oo 0 a I 00 0 00 av U 0 LI. I L i i i- i..ii; m i ,i it d l~ l~ IB--CII IIIII)- -~-YII~L~ 0 *C 9* o 0 0*- 0a a tO 0 .00 A 0r 0 0 0 00 4 0J 0 004o 4 *0 0 0 0 4 0 t o 40 0 C o0 0O 0 L 4 C, *I 0 000 4 S TABLE I ~WEAR REDUCTION UTILIZING PYRIDINE-C0:TAINING COMPOUNDS Partially Formulated Lube Oil W/O ZDDP or Conventional Friction Reducing Additive With ZDDP, But W/O Conventional Friction Friction Reducing Additive Additive in Partlay Formulated Lube Oil Wear Volume mm 3 Wear Reduction Wear Volume mm 3 Wear Reduction None 2-3-Cycloheptenopyridine 2-Ainnomethylpyrilin e 2-Chloro-3,5 finitropyridine 4,4 '-Di thiodipyria zc 2,2' Dithiiaciyrwidine 3-Bromopyridine *Incompatible with ZDDP 0.0293 0.0019 0.0020 0.0013 0.0015 0.0018 0.0021 0.00 93.5 93.7 95.6 94'.9 93.9 92.8 0.0019 0.0016 0.001 0.0012 0.0021 0.0016 93,5 94.5 96.6 95.9 .92.8 94.5 ~II t L 13- B. Substituted Pyrimidines When pyrimidine substituted compounds are utilized N, the substituent preferably has a

N

bond or group moment of at least 1.4 Debyes. R preferably is selected from the group consisting of chlorine, bromine, chloromethyl, dichloromethyl and mixtures thereof.

'Tests 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 concentrations and test conditions as those presented in Tables *o I and II, respectively. Here also it may be seen that the pyrimidine compounds listed were affective in re- 0 ducing wear, and that the combination of ZDDP and the oa. pyrimidine additive generally reduced the wear below that achieved usihg only ZDDP. As shown in Table III, substituted pyrimidine compounds exhibited superior wear reduction capabilities than pyrimidine.

0a a 0 0

A

0 0 000 0 a 0 e a C 0'~0 0 0 C 0 .0 .0 .0 .0 0 0 .0 0 .0.0 00 0 000 0 .0 TABLE III PYRIMIDINE COMPOUNDS AS ANTI-WEAR AGENTS IN BASESTOCK Additive Pyrimidine* (3 wt.%) 4, 6-Dichloro-2-Methyl Thiopyrimidine tert-Butyl 5- 6-Dimethyl Pyrimidinyl-2) Thiol Carbonate 2,4 ,6-Trichloropyrimidine

ZDDP

wea r Volume mm 3 0.0013 0.0002 0.0003 0.0027 0.0008 0.0004 Wear Reduction 97.6 99.6 99.4 94.7 98.4 99. 2 Not effective at 1 wt.% 060 0 0 0 0 0 0 00 0 0 0 0g.) S 00 0 ~0 000 6 0 0 0 0~ 6 0 0 640 0 -o *#t2 0 6 60 0 0 0 0 0 00 0 0~0 0 0 0 0 0 0 S 0 000 0 0

A;

TABLE IV WEAR REDUCTION UTILIZING PYRIMIDINIE-CONTAINING COMPOUNDS Partially Formulated Lube Oil W/O ZDDP W/O With ZDDF, But W/O Conventional Friction Conventional Friction Reducing Additive Reducing Additive Wear Wear Wear Wear Volume mm 3 Reduction Volume mm 3 Reduction Additive in Partially Formulated Lube Oil None 4,6-Dichloro-2 Methyl Thio Pyrimidine 2,4, 6-Trichioropyrimidine 0.0293 0,0014 0.0023 0-00 0.0019 0.0004 95 .2 92.2 93.5 98.6 -99.0 ii r~r -16 C. Substituted Pyrazines When pyrazine substituted compounds, are utilized the substituent preferably forms a

N

dipole moment of at least 1.42 Debyes. R preferably is selected from the group consisting of chlorine, bromine and mixtures thereof.

Four Ball Wear Tests also were conducted utilizing pyrazine additives. The test results, presented in Tables V and VI also utilized the same additive concentrations and test'conditions as those conducted for the results presented in Tables I and II, respectively. Here also, substituted pyrazine compounds exhibited superior wear reducing and friction reducing properties to pyrazine.

so Ba D 9* 99 O OII B Ct s baDo i,

VS

i) CI o u:,t

IP

I

AI A 9910

I

0 O 40)1

A.

ii 000 00 0 0 *0 -b 0 0 000 0 0 0 00 0 0 *04 0 0 0 0* 1 000 0 -000 0 0 0$ 0 0 4 0 0 0 09 0 0 o 0 000 0 0 0 4 4 0 00* 9 TABLE V PYRAZINE COMPOUNDS AS ANTI-WEAR AGENTS IN BASESTOCK Additive Pyrazi ne 2-Methyl-6-Propoxypyrazine 2-Sec-Butyl-3-Me thoxypyraz ine 3-Chloro-2 ,5-Dimethylpyrazine Wear3 Volume mm 3 0.035 0. 002Fo 0.0036 0.0004 Reduction 35.1 94.5 92.9 99.2

Y;

OP C P A "C Cs Co C CO C 0 C Co C C P C~ C P CCC c C CCC C C CA C C C P C P C 0 -o C A 0~ CC 0 C 4 0 CO S C1 4 0*4 P P TABLE VI WEAR REDUCTION UTILIZING PYRAZINE-CONTAINING COMPOUNDS Partially Formulated Lube Oil W/O ZDDP or With ZDDP, But W/O Conventional Friction Conventional Friction Reducing Additive Reducing Additive Wear Wear Wear Wear Volume mm 3 Reduction Volume mm 3 Reduction Additive in Partially Formulated Lube Oil None 2-Sec-Butyl-3-Methoxy Pyrazine 3-Chloro-2,5-Dimethyl Pyrazine 0.0029 0.0021 0.0031 0.00 92.8 0.0019 0.0015 0.0034 93.5 94.9 88.4 89.4 19 19 0. 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, trichloromethyl, bromomethyl, dibromomethyl, cyano, isocyano, cyanato, isocyanato, isothiocyanato, thiocyanato, nitro, nitromethyl, nitroso, formyl, acetyl, methylcarboxylate, methoxy, methyl thio, thiol, disulfide and mixtures thereof.

6* 00 The utility of pyridazine compounds as anti- C wear agents may be seen from the data presented in Tables VII and VIII below. The test results presented in Tables VII and VIII utilized the same additive concentrations and test conditions as those previously described for the results presented in Tables I and II, respectively. It was not possible to obtain wear Soo. reduction results for unsubstituted pyridazine, since 00 this compound was insoluble in the basestock.

0a 0 0 0* 1 6 t _I 4- 8 0 900 00 9 0 0 0 0 9 90 tAo 0 co v0 0 99 09* 9 000 0 0 0-0 0 0 0 0 0 0 0 0 0 0 0 0 900 0 0 0 O 0 0 0 0- 9 O 000 0 0 0 TABL.E VII PYRIDAZINE COMPOUNDS AS ANTI-WEAR AGENTS AdditLive None Pyridazin* 3,4,g5-trichloropyridazine 3, 6-Dichlloropyridazinfe wear Volume mm 3 0.051 0.0005 0.0008 Wear Reduction 0.0 99.0 98.5 Insoluble

I

0 400 p4 4 4 p a 4 0 0 0 1b 004 4 0 444 0 0 04 4 0 0 0 p p p p 0 P 4 OpO p p 4 0 4 4 9 0*S TABLE VIII WEAR REDUCTION UTILIZING PYRIDAZINE-CONTAINING COMPOUNDS~ Partially Formulated Lube 011 W/O ZDDP and W/o With ZDDP, But W/O Conventional Friction Conventional Friction Redu6ing Additive Reducing Additive Wear Wear Wear Wear Volume mum 3 Reduction Volume mm 3 Reduction Additive in Partially leormulatedLub-e- -ail 3,4,5 Ttichloropyridazine 3 5 6-Dichloropyridazine 0.0034 0.0034 88.4 88.4 0.0012 0.0026 22 F. Fused Ring Substituted Pyridines Fused ring derivatives of pyridines, such as quinoline substituted compounds, may be useful as anti-wear agents. The substituent preferably has a dipole moment of 1.25 Debyea or greater and preferably is selected from the group consisting of chlorine, bromine, chloromethyl, dichloromethyl, trichloromethyl, b.romomethyl dibromomethyl, cycano, cyanomethyl, isocyano, isocyanato, cyanato, isocyanato, thiocyanato, isothiocyanato, nitro, nitromethyl, nitroso, formyl, acetyl, methyl carboxylate, methoxy, acetyl, disulfide, methyl thio, thiol and mixtures thereof. The utility of quifoline compounds as antiwear agents may be seen from the data presented below 4 4 in Tables IX and X. The test results presented 4n these S* tables were obtained using the same additive concentrations and test conditions as those previously described with respect to Tables I and II, respectively.

00 0 ,a 0 t9 a o-o ii 1~ on 0* a ft 0 -c 0 4 no p a 0 #00 ft a C ft. 0 C' tag 0 ft ft a a ft a ft a ft aeC ft ft 000 ft ft a. ft ft 0 0 ft C ft ft 0 ft aca ft ft a ft a a 0 Oft a gao 0 ft a TABLE IX QIJINOLINE COMPOUNDS AS ANTI-WEAR AGENTS IN BASESTOCK Additive Quinoline (3 wt.%) 4-Bromoisoquinoline 6-Me thoxyqu inoline 4-Chloro-7 (trifluaromethyl) quinoline Wear Volume mm 3 0.0028 0.0011 0.0007 0.0018 0.0033 Wear Reduction 94.8 98.0 98.7 96.7 93.9 t 4 -rn a Z 0 Coc C C C'.

6 0 00 C 6 000 0 4.0 0 000 a C 0 0 0 c Coo o 0 0 00 o a O 060 0 0 0 TABLE X WEAR REDUCTION UTILIZING QUINOLINE-CONTAINING COMPOUNDS Partially Formulated Luj.'e Oil W/O ZDDP and W/G Ester Additive WiLl ZDDP, But W/O Conventional Friction Reducing Additive Additive in Partially Formulated Lube Oil Quinoline 4-Bromoisoqu inolime 6-Methoxyquinolime 4-Chloro-7 [Trifluoromethlyll quinoline, Wear Volume mm 3 0.022 0.0018 0.0017 0.0045 Reduction 24.9 93.9 94.2 84.6 Wear Volume mm 3 0.0009 0.0012 0.0012 0014 Reduction 96.9 95.9 95.9 95.2 0.0015 94-9 0.0015 94*.90.0019 9.

96.9

Claims (17)

1. A functional fluid composition having improved anti-wear properties, which composition comprises: A, a basestock; and I fB, at least one anti-wear compound selected from substituted pyridine and substituted diazine and fused ring derivatives thereof, where the substituent is selacted from halogens, chloromethyl, dichloromethyl, chlorobromomethylt bromome4-hyl, dibromomethyl, cyavo, icocyano, methylcycano, JIsocyanomethyl, cyanate, isocyanate, thiocyanate, isothio- cyanate, nitro, nitromethyl, nitroso, formyl, acetyl, methyl carboxylate, methoxy, methyithia, thiol, disialfide.

The composition as claiwed in claim 1, wherein the basestock comprises a lubricating oil basestock.

3. The composition as claimed in claim 1 or claim 2, wherein the anti-wear compound qomprise3 from 0,25 to wt.% of the basestock.

4. The composit~ion as claimed in any preceding claim, wherein the anti-wear compound comprises a substituted pyridine.

The composition as claimed in any one of claims 1 to 3, wherein, the anti-wear compo.-nd comprises a substituted 6 pyrimidine.

6. The composition as claimed in any one of claims 1 to 3, wherein the anti-wear compound comprises a substituted pyridazine. 44 26

7. The composition as claimed in any one of claims 1 to 3, wherein the anti-wear compound comprises a substituted pyrazine.

8. The composition as claimed in any of claims 1 to 3, wherein the anti-wear compound comprises a substituted quinoline.

9. The composition as claimed in claim 1, wherein the anti-wear compound is 2,2'-dithiodipyridine.

The composition as claimed in claim 1, wherein the anti-wear compound is 4,4'-dithiopyridine. t

11. A method for producing a lubricating oil having il,. improved anti-wear properties, said method comprising admixing with a lube oil basestock an effective amount of a compound selected from: 0a fused ring derivatives thereof and mixtures thereof, where R is selected from halogens, methyl cyano, cyano, isocyano, cyanate, isocyanate, thiocyanate, isothiocyanate, nitr-. 9 4 thio disulfide, chloomethyl, dchoromethy, mixtures thereof. athiol, disulfide, chioromethyl, dichloromethyl, Th \E 27

12. A lubricating 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 at least 3.9 Debyes in the meta position, and is selected from one or more of chlorine, bromine, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, cyano, isocyano, cyanomethyl, cyanate, isocyanate, thiocyanate, thiocyanate, nitro, nitromethyl, formyl, acetyl, methoxy and methylcarboxylate, methylthio, thiol and disulfide.

13. The lubricating oil of claim 12, wherein compound B is 2,2'-dithiodipyridine. V

14. The lubricating oil of claim 12, wherein compound B is 4,4'-dithiodipyridine.

A lubricating oil having improved anti-wear properties comprising: A, a basestock; and So B, a substituted pyrimidine, wherein the substituent has a dipole moment of at least 1.25 Debyes, and is selected from one or more of chlorine, bromine, a 0 a chloromethyl and dichloromethyl.

16. A lubricating oil having improved anti-wear .I properties comprising a basestock and a pyrazine substituted compound, wherein the substituant has a dipole moment of at least 1.42 Debyes, and is selected from one or more of chlorine and bromine. i i i -rrm 28 Q oo )01 0000 0O 0I L 000 000 01 D 0 0L 0 44 4 0 0 00

17. 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 0.97 Debyes, and is selected from one or more of chlorine, bromine, chloro- methyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, cyano, isocyano, cyanate, isocyanate, thiocyanate, isothiocyanate, nitrol, nitromethyl and disulfide. DATED this 9th day of March, 1990. EXXON RESEARCH AND ENGINEERING COMPANY WATERMARK, PATENT TRADEMARK ATTORNEYS, 290 BURWOOD ROAD, HAWTHORN, VIC. 3122. AUSTRALIA. DBM:LPS:JZ (10.18) A