Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 3~
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.
_L~
- 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 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.
5UMMARY OP THE INVENTION
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:
-- 6 --
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.
" ~
~ 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 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.
- -- 10 --
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As shown in Table I, the substituted
pyridines exhibited substantially superior ~ wear
reduction than unsubstituted pyridine. The utility of
the present invention also may be seen from Table I1 in
which certain of the additives from Table I also were
utilized in a partially formulated lubricating oil. In
one series of te~ts, the anti-wear additives, zinc
dialkyldithiophosphate and another conventional fric-
tion reducing additive both were eliminated from the
otherwise complete formulated lube oil.~ In their place
the indicated pyridine additives were added at the 1.0
weight percent level. It can be seen that the pyridine
compounds effectively reduced wear in Four Ball Wear
Tests conducted at 100C, 60 kg load, 1200 rpm for 45
minutes test duration. Additional Four 3all Wear Tests
were conducted in oil formulations similar to that
previously noted in which the pyridine compound and
ZDDP both were added, but in which the other conven-
tional friction additive was not utilized. These test
results indicate that use of ZDDP and the pyridine
compound generally produced better wear reduction than
either ZDDP or the pyridine additive individually.
-- 12 --
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- 13 -
B. Substituted Pyrimidines
When pyrimidine substituted compounds are
utilized ~ ~N, the substituent preferably has a
bond or group moment of at least 1.4 Debyes. R pref-
erably is selected from the group consisting of
chlorine, bromine, chloromethy`l, dichloromethyl and
mixtures thereof.
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.
L~ ~$~
-- 14 --
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-- 16 --
C. Substituted Pyrazines
When pyrazine substituted compounds, are
N~
utilized ~ J 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, 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.
-- 17 --
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- 19 -
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.
-- 20 --
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-- 21 --
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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
-- 23 --
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