Note: Descriptions are shown in the official language in which they were submitted.
1327~0
FIEL~ OF THE INYENTION
This invention relates to lubricating oil
compositions which exhibit marked reduction in engine
carbon deposits. More particularly, this invention is
directed to ashless lubricating oil compositions which are
adapted for use in diesel engines and which contain ashless
dispersants, sul~urized alkyl phenols and organo-sul~ur
. anti-corrosion agents.
':
~ BACKGROUND OF TH~_~NVEN~ION
` It is an objective of the industry to provide
lubricating oil compositions which exhibi~ improvements in
minimized engine deposits and low rates of lubricating oil
consu~ption, particularly in diesel engine vehicles.
Among the conventionally used lubri ating oil
additives, zinc dihydrocarbyl dithiophosphates perform
multiple functions in the motor oil, namely, oxidation
, inhibition, bearing corro~ion inhibition, and extreme
pressure/antiwear protection for the valve train.
Early patents illustrated compositions using
polyisobutenylsuccinimide dispersants in combination with
zinc dialkyldithiophosphates which were employed in
lubricating oil compositions with other conventional
i additives such as detergents, viscosity index improvers,
rust inhibitors and the like. Typical of thes~ early
;. di~closures are U.S. Patents 3,018,247, 3,018,250 and
~` 3,018,291.
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Since phosphorus i~ a catalyst poison for
catalytic converters, and since the zinc itself offers a
source for sulfated ash, the art has sought to reduce or
eliminate such zinc-phosphorus-containing motor oil
components. Exemplary of prior art references directed to
the reduction in phosphorus-containing lubricant additives
are U.S. Patents 4,147,640; 4,330,420: and 4,639,324.
U.S. Patent 4,147,640 relates to lubricating oils
having improved antioxidant and antiwear properties which
are obtained by reacting an olefinic hydrocarbon having
from 6 to 8 carbon atoms and about 1 to 3 olefinic double
bond~ concurrently with sulfur and hydro~en sulfide and
thereafter reacting the resulting reaction intermediate
with additional olefin hydrocarbon. These additives are
disclosed to be generally used in conjunction with other
conventional oil additives such as overbased metal
detergents, polyisobutenylsuccinimide dispersants, and
phenolic antioxidants. While it is disclosed that the
amount of the zinc additive can be greatly reduc~d, giving
a "low ash" or "no ash" lubricant formulation, it is
apparent the patentee was referring to Zn-derived ash, and
not total SASH levels.
U.S. Patent 4,330,420 relates to low ash, low
phosphorus motor oils having improved oxidation stability
a-~ a result the inclusion of synergistic amounts of
dialkyldiphenylamine antioxidant and sulfurized
pslyolefin. It is disclosed that the synergism between
th~sQ two additives compensates for the decreased amounts
of pho phoru~ in the form of zinc dithiophosphate. The
fully formulated motor oils are said to comprise 2 to 10
wt.% of ashless disp2rsant, 0.5 to 5 wt.% of recited
magnesium or calcium deterg~nt salt-~ (to provide at least
O. 1% 9f magnesium or calcium), from 0.5 to 2.0 wt.~ of zinc
dialkyldithiophosphate; from 0.2 to 2.0 wt.~ of a
dialkyldiphenola~ine antioxidant: from 0.2 to 4 wt.% of a
sul~urlzQd polyolefin antioxidant: from 2 to 10 wt.% of a
" 13~73~0
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first, ethylene propylene VI i~prover; from 2 to lO wt.% of
a second VI improver consisting of methacrylate terpolymer,
and the balance baseoil.
U.S. Patent 4,639,324 discloses that metal
dithiophcsphate salts, while useful as antioxidants, are a
source of a~h, and discloses an ashless antioxidant
comprising a reaction product made by reacting at least one
aliphatic olefinically unsaturated hydrocarbon having from
~ to 36 carbons concurrently with sulfur and at least one
fatty acid e~ter to obtain a rea tion intermediate which is
then reacted with additional sulfur and a dimer of
cyclopentadiene or lower Cl to C4 alkyl sub~tituted
cyclopentadiene dimers. It is disclosed that these
additives in lubricating compositions are generally used in
conjunction with other conventional oil additives such a
neutral and overbased calcium or magne3ium alkaryl
sulfonates, dispersants and phenolic antioxidants. It is
disclo~ed that when using the additives of this invention,
the a~ount of the zinc additive can be greatly reduced
giving a "low ash" or "no ash" lubricant formulation.
Again, it is apparent that the patentee was referring to
Zn-derived ash, and not to total SASH.
Metal detergents have been heretofore employed in
motor oils to assist in controlling varnish formation and
corrosion, and to thereby minimize the adverse împact which
varnish and corrosion have upon the efficiency of an
int~rnal co~bustion engine by minimizing the clogging of
re~tricted openings and the reduction in the clearance of
~oving parts.
U.S. Patent 4,089,791 relates to low ash mineral
lubricating oil compositions comprising a mineral oil base
in ~inor a~ounts of an overbased alkaline ear~h metal
compound, a zinc dihydrocarbyl dithiphosphate (ZDDP) and a
substituted trialkanolamin~ compound, wherein at l~ast 50~
of the ZDDP co~pound~ consi~ts of zinc dialkaryl
dithiophosphat-s, in order eo pro~ld- a for~ulatod ~otor
.
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13273~
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oil which will pass the M5 IIC Rust Test and the L-38
Bearing Weight Loss Test. The patent illustrates three oil
formulations, containing overbased calcium detergent, ZDDP,
trialkanolamine and unspecified conventional lubricating
oil additives to provide visco~ity index i~provement,
antioxidant, dispersant and anti-foaming properties. The
illu^~trated formulations each had about o. 66 wt. 9c SASH
levels, based on the reported Ca and Zn concentrations. No
diesel motor oil formulations are illustrated.
U. S . Patent 4 ,153, 562 relate~ to an~ioxi~ants,
which are disclosed to be particularly useful for
compounded lubricating oil~ that are intended for heavy
duty use in automotive crankcase formulations of relatively
low ash content, wherein the antioxidants are prepared by
the condensation of phosphorodithioates of alkylphenol
sulfides with unsaturated compounds such as styrene. The
antioxidants are exe~plified at levels of from 0.3 to 1.25
wt.% in lube oil compositions (Example 3) which also
contain about 2.65 wt.% (a.i.) borated polyisobutenyl-
succinimide dispersant, about 0.0~ wt.% Mg as overbased
magnesium sul~onate detergent inhibitor, and about 0.10
wt.% Zn as zinc dialkyldîthiophosphate antiwear agent
(containing mixed C4/C5 alkyl groups).
U.S. Patent 4,157,972 indicates that the trend to
unleaded ~uels and ashless lubricating compositions has
neces~itated the search for non-metallic (ashless)
substitutes for m~tallo-organo detergents, and relates to
tetrahydropyri~idyl-substituted compounds which are
disclo~ed to be useful as ashless bases and rust
inhibitors. The Example~ of the Patent compare the
performance of various lubricating oil formulations in a
Ford V8 varnish test (Table I) and additional for~ulations,
which are na~ed as either "low-ash" or '~ashles~", in a
Hu~idity Cabinet Ru~t Test (Table II). The SASH levels of
th- ~low ~h~ rormulation~ ar- not report-d and c~nnot be
13273~
determined from the information given for the metal
detergent and ZDDP- components.
U.S. Patent 4,165,292 discloses that overbased
metal compounds provide effective rust inhibition in
automotive crankca~e lubricants and that in th~ absence of
overbased additives, a~ in ashle~s oils, or when such
additive~ are present in reduced amounts, as in ~'low ash"
oil~, ru~ting becomes a ~eriou~ problem. Such rust
require~ents are evaluated by AST~ Sequence IIC
engine-tests. The Patent discloses a non-ash forming
corrosion or rust inhibitor comprising a ~ombination of an
oil-soluble basic organic nitrogen compound (having a
recited basicity value) and an alkenyl or alkyl substituted
succinic acid having from 12 to 50 carbon atoms. The ba~ic
organic nitrogen compound and the carboxylic acid compound
are required to be used together to achieve the desired
rust-inhibiting properties. It is disclosed that best
results are achieved by use of an excess of amine over that
required to form the neutral salts of the substituted
succinic acid present.
U.S. Patent 4,~02,970 relates to improved
crankcase lubricating oil compositions containiny
lubricating oil dispersant, overbased metal detergent, zinc
dialkyldithiophosphate antiwear additive and
polyi~o~utenylsuccinic anhydride, in recited amounts.
Exemplary lubricating oil formulations are disclosed
containing 3 wt.% polyisobutenyl~uccinimide dispersant,
polyisobutenylcuccinic anhydride, overbased mQtal sulfonate
or overb~sed sulfuriæed phenate detergents and zinc
dialkyldithiophosphato antiwear agents, in base oil, in
amount~ of 3.0, 3.0, 2.0, 1.0 and 91.0 wt.%, respectively.
European Patent 24,146 relates to lubricating oil
co~po~itions containing copper antioxidants, and
~xemplifies copper antioxidant~ in lubricating oil
co~position~ al~o containing 1.0 wt. % of a 400 TBN
~agn~ium sulphonate (containing 9.2 wt. % magnesium), 0.3
',
.,.
.
:
~.
.~327~
-- 6 --
Wt. % of a 25û TBN calcium phenate (containing 9. 3 wt. 96 of
calcium) and a zinc dialkyldithiophosphate in which the
alkyl groups or a mixture of such groups having between 4
and 5 carbon atoms and made by reacting phosphorous
P2S5 with a mixture of about 65% isobutyl alcohol and
35% of amyl alcohol, to give a phosphorous level of 1.0 wt.
~ in lubricating oil composition.
Published British Patent Application ~, 062, 672
relates to additive compositions comprising sulfurized
alkyl phenol and an oil soluble carboxylic dispersant
containing a hydrocarbon base radical having a number
average molecular weight of at least 1300, which i5
disclosed in combination with ash-producing detergents.
However, it is extre~ely difficult to translate
lube oil development~ intend~d for passenger car and light
truck service, whether gasoline or light duty diesel
engines, into lubricating oils intended for use in heavy
duty diesel service.
R. D. Hercamp, SAE Technical Paper Series, Paper
No. 831720 (1983) reports development work on engine tes~
proc2dures to measure the rel~tive ability of various
lubricant formulations to control oil consumption in heavy
duty diesel engines. The author indicates that lab
analysis of crown land deposits on the diesel engine
pistons show an organic binder to be present which contains
high molecular w~ight esters, ~r.d the author speculates
that oxidation products in the oil may be precursors for
the binder found in the deposits. It is indicated that
i~proved antioxidants could be the key to prevent premature
1088 0~ oil consumption.
A. A. Schetelich, SAE Technical Paper Series,
Paper No. 831722 (1983) reports sn the eff ct of
lubricating oil parame~er~ on PC-l type heavy duty diesel
lubricating oil perormance. It is noted that over the
pa~t 30 year~, the trend in heavy duty diesel oil industry
has baen to decreas~ th0 sul~ated ash levels fro~ 2.5 wt.%
.
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sulfated ash (SASH) in 1960 to the typical North American
SASH lavel of 0.8 to l wt.%, and to correspondingly
decrease the HD oils total base number ~TBN) D28s6 values
from over 20 to the present typical North American TBN
values of from 7 to 10. Such reductions in SASH and TBN
levels are attributed by the author to bs3 due to
improve~ent in performance of ashless components, including
ashless diesel detergents and ashless dispersants. In
diesel engine tests, no significant correlation was seen
between the level of either piston deposits or oil
consumption and the SASH or TBN levels, for about 1~ to 2%
SASH levels and about 8 to 17% TBN levels. In contrast, a
significant correlation was seen between the level of
ashless component treat and the amount of piston deposits
(at the ~2% confidence level) and oil consumption (at the
98% confidence level). It is noted by the author~ that
this correlation is drawn with respect to diesel fuels
having average sulfur levels of less than about 0.5%. It
is indicated that the level of buildup of ash is
accelerated in the hotter engine areas. The author
concludes that at the 97% confidence level there should be
a correlation between oil consumption and piston deposits,
especially top land deposits, which are believed to
contribute to increased oil consumption due to two
phenomena: (1) these deposits decrease the amount of
blow-by flowing downwardly past the top land, which results
in a dQcreased gas loading behind the top ring of the
p~ston, which in turn leads to higher oil consu~ption; and
(2) increa~ed bore polishing of the piston cylinder liner
by the top land deposits which in turn contributes to
higher oil consumption by migration o~ the oil into the
firing chamber of the cylinder along the polished bore
pathq. Therefore, the Paper concluded that reduced ash in
the oil should be sought to reduce top land deposits, and
hence oil consumpt~on.
This 1983 Schetelich paper reports formulation of
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2 test oils, each containing about 1% SASH and having TBN
levels of lo and 9, respectively, whPrein each formulated
oil contained overbased metal detergent together with a
zinc-source.
J. A. McGeehan, SAE Paper No. 831721, pp.
4.848-4.869 (1984) summarized the results of a series of
heavy duty diesel engine tests to investigate the effect of
top land deposits, fuel sulfur and lubricant viscosity on
diesel engine oil consumption and cylinder bore polishing.
These authors also indicated that excessive top land
deposits cause high oil consumption and cylinder bore
polishing, although they added that cylinder bore
polishing is also caused in high sulfur fuels by corrosion
in oils of low alkalinity value. Therefore, they concluded
that oil should provide sufficient alkalinity to minimize
the corrosive aspect of bore polishing. The authors
reported that an experimental 0.01% sulfated ash oil, which
was tested in a AVL-Mack~WTZ675 ~turbocharged) 120-hour test
in combination with a O .2% fuel sulur, provided minimum
top land deposits and very low oil consumption, which was
said to be clue to the "very effective ashless inhibitor".
This latter component was not further defined. Further,
from the data presented by the author in Figure 4 of this
Paper, there do not appeax to be oil consumption credits to
reducing the ash level below 1~, since the oil consumption
in the engine actually rose upon reducing the SASH from l
to 0.01%. This reinforces the author's vi~w that a low,
but significant SASH level is required for sufficient
alkalinity to avoid oil consumption as a result of bore
polishing derived from corrosive aspects of the oil.
McGeehan concluded that the deposits on the top
land correlate with oil consumption but are not directly
related to the lubricant sulfated ash, and commented that
these deposits can be controlled by the crankcase oil
formulation.
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1327~0
,. g
SU~Ma~OF THE INVENTION
In accordanc~ with the present invention, there
are provided ashles3 heavy duty diesel lubricating oil
csmpositions which comprise an oil of lubricating viscosity
~ as the major component and as the ~inor component (A) at
lea~t 3 wt.% o~ a~ least one ashless dispersant, (B) at
least 2 wt.% of at least one ~ulfurized alkyl phenol, and
s ~C) at least O.l wt.% o~ at least one organo-sulfur
compound of the formula
~- R4 - (S)w ~ C ~ (S)z R
': \S/
wherein R4 and R5 are straight or branched chain alkyl,
cyclic, alicyclic, aryl, alkylaryl or arylalkyl radicals
having from 2 to about 30 carbon ato~s, and w and z ar~
number3 from 1 to about 8, wherein the lubricating oil is
; characterized by a total sulfated ash (SASH) level of less
than O.Ol wt.%.
. The improved oil~ of the pre~ent invention are
particularly useful in diesel engines powered by low sulfur
fuels. ThQrefore, the present invention also provides a
.method for i~proving the performance of a heavy duty diesel
!,lubricating oil adapted for use in a diesel engine provided
'with a~ least one tight top land piston, and preferably
furth~r adapt,ed ~or being powered by a normally liquid fuel
,:haYing a 3ul ~ur cont~nt of less than 1 wt.%, which
f~comprises controlling the metal content of the oil to
proYid~ a total sulfated ash (SASH) level in said oil of
than O.Ol wt.%, and provlding in ~aid oil (A) at least
about 3 wt.~ ashl~ss disper~ant, (B) at l~ast about 2 w~.%
;.~sulfurized alkyl phonol oxidation inhibitor, and (C) a
copper corrosion inhibiting amount of at lea~t one
organo-~ulfur compound of the formula
R4 - ts~ - C /~ - (S)z - R5
S
wh-r-in R~ and R5 ar- utra1ghe or branched ch~in alkyl,
;
1327~50
-- 10 --
cycli~, alicyclic, aryl, alkaryl or aralkyl radicals having
from 2 to 30 carbon atoms, and w and z are numbers from 1
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to about 8.
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1327~0
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11 --
DE~AIh~L DES~RIPTION OF THE INVENTIoN
Co~ponent A
Ashless, nitrogen or ester containing dispersants
useful in this invention comprise boron-free members
selected from the group consisting of (i) oil soluble
salt~, amides, imides, oxazolines and e.ters, or mix~ures
thereof, of long chain hydrocarbon ~ubstituted mono and
dicarboxylic acids or their anhydrides: (ii) long chain
aliphatic hydrocarbon having a polyamine attached directly
thereto; and (iii) Mannich condensation products formed by
condensing about a molar proportion of long chain
hydrocarbon substituted phenol with about 1 to 2 . 5 moles of
formaldehyde and about 0.5 to 2 moles of polyalkylene
polyamine; wherein said long chain hydrocarbon group in
(i), (ii) and (iii) is a polymer of a C2 to C10, e.g.,
C2 to C5 monoolefin, said polymer having a number
average molecular weight of about 300 to about 5000.
A(i) Nitrogen- or ester- containing ashless
dispersants comprise members selected from the group
consisting of oil soluble salt3, amides, imides, oxazolines
and esters, or mixture~ thereof, of long chain hydrocarbon
substituted mono and dicarboxylic acids or their anhydrides
wherein said long chain hydrocarbon group is a polymer of a
C2 to C10, e.g., C2 to C5, monoole~in, said polymer
having a number average molecular weight of from about 700
to 5000.
The long chain hydrocarbyl substituted mono or
dicarboxylic acid material, i.e. acid, anhydride, or ester,
used in the dispersant includes long chain hydrocarbon,
generally a polyolefin, substituted with an average of from
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13273~
- 12 ~
about O . 8 to 2 . o, preferably from about 1. o to 1. 6, ~ . g.,
1.1 to 1.3 moles, per mole o~ polyolefin, of an alpha or
beta- unsaturated C4 to C10 dicarboxylic acid, or
anhydride or ester thereof. Exemplary of such
dicarboxylic acids, anhydrides and esters thereof are
fumaric acid, itaconic acid, maleic acid, maleic anhydride,
chloromaleic acid, dimethyl fumarate, chloromaleic
anhydride, acrylic acid, methacrylic acid, crotonic acid,
cinnamic acid, etc.
Preferred olefin polymers for reaction with the
unsaturated dicarboxylic acidæ to form the dispersants are
polymers comprising a major molar amount of C2 to C10,
e.g. C2 to C5 monoole~in. Such olefins include
ethylene, propylene, butylene, isobutylene, pentene,
octene-1, styrene, etc. The polymers can be homopolymers
such as polyisobutylene, aC well as copolymers of two or
more of such olefins suoh as copolymers of: ethylene and
propylene; butylene and isobutylene; propylene and
isobutylene; etc. Other copolymers includ~ those in which
a minor molar amount of the copolymer monomers, e.g., 1 to
10 mole ~, is a C4 to C18 non-conjugated diolefin,
e.g., a copolymer of isobutylene and butadiene: or a
copolymer of ethylene, propylene and 1,4-hexadiene; etc.
In so~e cases, the olefin polymer may be
completely saturated, for example an ethylene-propylene
copolymer made by a Ziegler-Natta synthesis using hydrogen
as a moderator to control molecular weight.
The olefin polymers used in the dispersants will
u~ually have number average molecular weights within the
range of about 700 and about 5,000, more usually between
about 800 and about 3000. Particularly useful olefin
poly~ers have number average molecular weights within the
range o~ about 900 and about 2500 with approximately one
terminal double bond per polymer chain. An especially
useful starting material for highly po~ent dispersant
1~273~
- 13 -
additives i~ polyisobutylene. The number average molecular
weight for such polymers can be determined ~y several known
techniques. A convenient method for such determination is
by gel permeation chromatography (GPC) which additionally
provides molecular weight distribution information, see W.
W. Yau, J.J. Kirkland and D~D. Bly, "Modern Size
Exclusion Liquid Chromatography", John Wiley and Sons, New
York, 1979.
Processes for reacting the ole~in polymer with the
C4_10 unsaturated dicarboxylic acid, anhydride or ester
are known in the art. For example, the olefin polymer and
the dicarboxylic acid material may be simply heated
together as disclosed in U.S. Patents 3,361,673 and
3,401,118 to cause a thermal "ene" reaction to take place.
Or, the 018fin polymer can be first halogenated, for
example, chlorinated or brominated to about 1 to 8 wt. %,
preferably 3 to 7 wt. % chlorine, or bromine, based on the
weight of polymer, by passin~ the chlorine or bromine
through the polyolefin at a temperature of 60 to 250~C,
e.g. 120 to 160'C, for about 0.5 to 10, preferably 1 to 7
hours. The halogenated polymer may then be reacted with
sufficient unsaturated acid or anhydride at 100 to 250C,
u ually about 180~ to 235-r, for about 0.5 to 10, e.g. 3 to
8 hours, so the product ob~ai~ed will contain the desired
number of moles of the unsaturated acid per mole of the
halogenæted polymer. Processes of this general type are
taught in U.S. Patents 3,087,436; 3,172,892; 3,272,7g6 and
others.
Alternatively, the olefin polymer, and the
unsaturated acid material are mixed and heated while adding
chlorine to the hot material. Processes of this type are
disclosQd in U.S. Patent~ 3,215,707; 3,231,587: 3,912,764:
4,110,349; 4,234,435: and in U.K. 1,440,219.
By the use of halogen, about 65 to 95 wt. % of the
polyolefin, ~.g. polyisobutylene will normally react with
the d1carboxylic acid r,aterlal. Upon carrying out a
.~
13273~
- 14
thærmal raaction without the us~ of halogen or a catalys~ D
the~ usually only about S0 to 75 wt. % of the poly-
i obutyl~ne will react. Chlorination helps increase the
r~activity. For convenience, th~ aforesaid functionality
ratio~ of dicarboxylic acid producing units to polyolefin,
e.g., 0.8 to 2.0 , etc. are basad upon the total amount o~
polyolafin, that i8, the total of both the reacted and
unreacted polyolefin, used to mak~ the product.
Ths dicarboxylic acid pro~ucing material can also
be further reacted with amines, alcohols, including
polyol~, amino-alcohols, etc., to for~ other useful
dispersant additives. Thus, if the acid producing material
i8 to b~ further reacted~ e.g., neutralized, then gener~lly
a ~a~or proportion of at lea3t 50 percent of the acid unit~
up to all the acid units will he reacted.
Amine compounds useful as nucleophilic reactants
for neutxalization of the hydrocarbyl substituted
dicarboxylic acid materials include mono- and (praferably)
polyamine~, most preferably polyalXylene polyamin~s, of
about 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total
car~on atom~ and about 1 to 12, preferably 3 to 12, and
most pra~erably 3 to 9 nitrogen atoms in the molecul~.
These amines may b~ hydrocarbyl amines or may be
hydrccarbyl amines $ncluding other groups, e.g, hydroxy
groups, alkoxy groups, amide group~, nitriles, i~idazoline
groups, and the like. ~ydroxy amines with 1 to 6 hydroxy
group~, pr~erably 1 to 3 hydroxy groups are particularly
u~ful. PrQferred amines ar~ aliphatic saturated a~in~s,
including those o~ the g~neral formulas:
R-N-R', and R-~ ~ CH2)8 - N-(CH2)s ~ N-R
~" R'~ ~''' J~ R'
(I~ (II)
wherein R, R', R'' and Rf ~ ~ ar~ independently selacted from
the group con~isting of hydrog~n; Cl to C25 straight or
branched chain alkyl radicals; Cl to C12 alkoxy C~ to
.
. l327~a
- 15 -
C6 alXylene radical~; C2 to C12 hydroxy amino
alkylene radicals; and Cl to C12 alkylamino C2 to
C6 alkylene radicals; and wherein R~ can additionally
comprise a moiety of the formula:
(CH2)S~- N ~ H (III)
~t'
R'
wherein R' is as defined above, and wherein s and s~ can be
the sa~e or a dif~erent number o~ from 2 to 6, preferably 2
to 4; and t and t' can be the same or different and are
number-~ of fro~ O to 10, preferably 2 to 7/ and most
preferably about 3 to 7, with the proviso that the sum of t
and t' is not greater than 15. To assure a ~acile
reaction, it is preferred that R, R~, R~, R~, s, s', t
and t' be selected in a manner sufficient to provide the
compounds of Formulas I and II with typically at least one
primary or secondary amine group, preferably at least two
primary or secondary amine group~. This can be achieved by
selecting at least one of said R, R', R" or R''' groups to
be hydrogen or by letting t in Formula IY be at least one
when R"' i~ H or when the III moiety pos~esses a secondary
amino ~roup. The ~ost preferred amine o~ the above
for~ulas are represented by Formula II and contain at least
two pri~ary amine groups and at lea~t one, and preferably
at least thr~e, secondary amine groups.
Non-limiting examples o~ suitable amine compounds
includ~: 1,2-diaminoethane; 1,3-diaminopropane;
1,4-diaminobutane: 1,6-diaminohexane; polyethylene amines
~uch as diethylene triamine; triethylene tetramine;
tetraethylene pentamine; polypropylene amines such as
1,2-propylene dia~ine; di-(1,2-propylene)triamine:
di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diamino~
propane; N,N-di-(2-aminoethyl) ethylene diamine;
N,N-di(2-hydroxyethyl)-1,~-pxopylene dia~ine; 3-dodecyloxy-
propyla~ine; N-dodecyl 1,3-propane diamine; tris hydroxy-
.
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methylaminomethane (THAM); diisopropanol amine; diethanol
amine; triethanol amine; mono-, di-, and tri tallow amines;
amino morpholines such as N-(3-aminopropyl)morpholine; and
mixtures thereof.
Other useful amine compounds include: alicyclic
diamines such as l~4-di(aminomethyl~ cyclohexane, and
heterocyclic nitrogen compounds such as imidazolines, and
N-aminoalkyl piperazines of the general formula (IV):
H{NH-(CH2)p ~ / ~ (cH2) _ NH }
nl CH2-CH2 n2 P2 n3
wherein Pl and P2 are the same or different and are
each integers of from l to 4, and nl, n2 and n3 are
the same or different and are each integers of from l to
3. Non-limiting examples of such amines include
2-pentadecyl imidazoline; N-(2-aminoethyl) pipera2ine; etc.
Commercial mixtures of amine compounds may
advantageously be used. For example, one process for
preparing alkylene amines involves the reaction of an
alkylene dihalide (such as ethylene dichloride or propylene
dichloride) with ammonia, which results in a complex
mixture of alkylene amines wherein pairs of nitrogens are
joined by alkylene groups, forming such ~ompounds as
diethylene triamine, triethylenetetramine, tetraethylene
pentamine and isomeric piperazines. Low cost
poly(ethylenea~ines~ compounds averaging about 5 to 7
nitrogen atoms per molecule are available commercially
under trade marks such as "Polyamine H", "Polyamine 400",
"Dow Polyamine E-lOO", etc.
Useful amines also include polyoxyalkylene
polyamines such as those of the formulae:
.,
,, NH2 alkylene t O-alkylene ~ NH2 ~V)
m
,,
.~
.
,~ ~
--`` 13273~0
- 17 -
where m has a value of about 3 to 70 and preferably 10 to
3s; and
R ~ alkylene ~ O-alkylene ~ NH2 )
n a (VI)
where "n" has a value of about 1 to 40 with the proYision
that the sum of all the n's is from about 3 to about 70 and
preferably from about 6 to about 35, and R is a polyvalent
saturated hydrocarbon radical of up to ten carbon atoms
wherein the number of substituents on the R group is
represented by the value of "a", which is a number of from
3 to 6. The alkylene groups in either formula (V) or (VI~
may be straight or branched chains containing about 2 to 7,
and preferably about 2 to 4 carbon atoms.
The polyoxyalkylene polyamines of formulas (V) or
(VI) above, preferably polyoxyalkylene diamines and
polyoxyalkylene triamines, may have average molecular
weights ranging from about 200 to about 4000 and preferably
from about 400 to about 2000. The preferred polyoxyal-
kylene polyoxyalkylene polyamines include the
polyoxyethylene and polyoxypropylene diamines and the
polyoxypropylene triamines having average molecular weights
ranging from about 200 to 2000. The polyoxyalkylene
polyamines are commercially available and may be obtained,
for example, from the Jefferson Chemical Company, Inc.
under the trade marks "Jeffamines D-230, D-400, D-1000,
D-2000, T-403", etc.
The amine i5 readily reacted with the selected
dicarboxylic acid material, e.g. alkenyl succinic
anhydride, by heating an oil solution containing 5 to 95
wt. % of dicarboxylic acid material to about 100 to
250 C., preferably 125 to 175-C., generally for 1 to 10,
e.g. 2 to 6 hours until the desired amount of water is
removed. The heating is preferably carried out to favor
formatlon of imides or mixtures of imides and amides,
. ~
.~
. .
~` ~
~ .
1 327~
- 18 -
rather than amides and salts. Reaction ratios of
dicarboxylic material to equivalents of amine as well as
the other nucleophilic reactants described herein can vary
considerably, depending on the reactants and type of bonds
; formed. Generally from 0.1 to 1.0, preferably from about
0.2 to 0.6, e.g., 0.4 to 0.6, moles of dicarboxylic acid
moiety content (e.g., grafted maleic anhydride content~ is
used per equivalent of nucleophilic reactant, e.g., amine~
For example, about 0.8 mole of a pentaamine (having two
' primary amino groups and five equivalents of nitrogen per
; molecule) is preferably used to convert into a mixture of
''.J', amides and imides, the product formed by reacting one mole
of olefin with sufficient maleic anhydride to add 1.6 moles
of succinic anhydride groups per mole of olefin, i.e.,
preferably the pentaamine is used in an amount sufficient
to provide about 0.4 mole (that is, 1.6 divided by (0.8 x
5) mole) of succinic anhydride moiety per nitrogen
equivalent of the amine.
The nitrogen containing dispersants can be further
treated by boration as generally taught in U.S. Patent Nos.
, 3,087,936 and 3,254,025. This is readily accomplished by
; treating the selected acyl nitrogen dispersant with a boron
compound selected from the class consisting of boron oxide,
boron halides, boron acids and esters of boron acids in an
;~ amount to provide from about 0.1 atomic proportion of boron
for each mole of said acylated nitrogen composition to
about 20 atomic proportions of boron for each atomic
` proportion of nitrogen of said acylated nitrogen
composition. Usefully the dispersants of the inventive
combination contain from about 0.05 to 2.0 wt. %, e.g. 0.05
to 0.7 wt. % boron based on the total weight of said
borated acyl nitrogen compound. The boron, which appears
~' to be in the product as dehydrated boric acid polymers
(primarily (H~02)3), is believed to attach to the
)
327~n
~ 19 -
di~persant imides and dii~ides as amine salts, e.g., the
m~taborate salt of aid diimide.
Treating is readily carried out by adding from
about O.05 to 4, e.g. 1 to 3 wt. % (based on the weight of
said acyl nitrogen co~pound) of said boron compound,
preferably boric acid which i~ ~o~t usually added as a
slurry to said acyl nitrogen compound and heating with
stirring at fro~ about 135C. to 190, e.g. 140-170~C., for
from 1 to 5 hours follo~ed by nitrogen stripping at said
temperature ranges. or, the boron tr~atment can be carried
out by adding boric acid to the hot reaction mixture of the
dicarboxylic acid ~aterial and amine while re~oving water.
The tris (hydroxymethyl3 amino methane (THAN) can
be reacted with the aforesaid acid material to form amides,
imides or ester type additives as taught by U.K. 984,409,
or to form oxazoline compounds and borated oxazoline
compounds as described, for example, in U.S. 4,102,798;
4,116,876 and 4,113,639.
The ashles~ dispersants may also be esters derived
from the aforesaid long chain hydrocarbon substituted
dicarboxylic acid material and from hydroxy compound~ such
as monohydric and polyhydric alcohols or aromatic co~pounds
such as phenols and naphthols, etcO The polyhydric
alcohols are the most prsferred hydroxy compound and
preferably contain ~rom 2 to about 10 hydroxy radicals, for
exa~pls, ~thylene glycol, diethylene glycol, triethylene
glycol, tetr~ethylene glycol, dipropylene glycol, and other
alkylene glycols in which the alkylene radical contains
~ro~ 2 to about 8 carbon ato~s. Other useful polyhydric
alcohc~ls include glycerol, mono-oleate of glycerol,
monostearate of glycerol, monomethyl ether of glycerol,
pentaerythritol, dipentaerythritol, and mixtures thersof.
The ester disper~ant ~ay also be derived fro~
unsaturated alcohols such a~ allyl alcohol, cinnamyl
alcohol, propargyl alcohol, l-cyclohexane-3-ol, and oleyl
alcohol. Still other cla~e~ of the alcohols capable of
~L~273~
- 20 -
yielding the esters of this invention comprise the
ether-alcohols and amino-alcohols including, for example,
the oxy-alkylene, oxy-arylene-, amino-alkylene-, and
amino~arylene-substituted alcohols having one or more
oxy-alkylene, amino-alkylene or amino-arylene oxy-arylene
radicals~ They are exemplified by Cellosolve, Carbitol,
N,N,N',N'-tetrahydroxy-trimethylene di-amine, and
ether-alcohols having up to about 150 oxy~alkylene radicals
in which the alkylene radical contains from 1 to about 8
carbon atoms.
The ester dispersant may be di-esters of succinic
acids or acidic esters, i.e., partially esterified succinic
acids; as well as partially esterified polyhydric alcohols
or phenols, i.e., esters having free alcohols or phenolic
hydroxyl radicals. Mixtures of the above illustrated
esters likewise are contemplated within the scope of this
invention.
The ester dispersant may be prepared by one of
several known methods as illustrated for example in U.S.
Patent 3,381,022. The ester dispersants may also be
borated, similar to the nitrogen containing dispersants, as
described above.
Hydroxyamines which can be reacted wi~h the
aforesaid long chain hydrocarbon substituted dicarboxylic
acid materials to form dispersants include 2-amino-1-bu-
tanol, 2 amino-2-methyl-1-propanol, p-(beta-hydroxy-
ethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol,
2-a~ino-2-~ethyl-1, 3-propane-diol, 2-amino-2-ethyl-1,
3-propanediol, N-(beta-hydroxy-propyl)-N'-(beta-amino-
ethyl)-piperazine, tris(hydroxymethyl) amino-methane (also
known as trismethylolaminomethane), 2-amino-1-butanol,
ethanolamine, beta-(beta-hydroxyethoxy)ethylamine, and the
like. Mixtures of these or similar amines can also be
employed. The above description of nucleophilic reactants
suitable for reaction with the hydrocarbyl substituted
dicarboxylic acid or anhydride includes amines, alcohols,
:`~
`t~
.
'
~,
13273~0
_ 21 -
and compounds of mixed amine and hydroxy containing
reactive functional groups , i . e ., amino-alcohols.
A preferred group of ashless dispersants are those
derived from polyisobutylene substituted with succinic
anhydride groups and reacted with polyethylene amines,
e.g. tetraethylene penta~ine, pentaethylene hexamine,
polyoxyethylene and polyoxypropyl~ne amines, e.g.
polyoxypropylene diamine, trismethylolaminomethane and
pentaerythritol, and combinations thereof. one
particularly preferred dispersant combination involves a
combination of (i) polyisobutene substituted with succinic
anhydride groups and reacted with (ii) a hydroxy compound,
e.g. pentaerythritol, ~iii) a polyoxyalkylene polyamine,
e.g. polyoxypropylene diamine, and (iv) a polyalkylene
polyawine, e.g. polyethylene diamine and tetraethylene
pentamine using about 3.3 to about 2 moles each of (ii) and
(iv) and about 0.3 to about 2 moles of (iii) per mole of
(i) as described in U.S. Patent 3,804,763. Another
preferred dispersant combination involves the combination
o~ (i) polyisobutenyl succinic anhydride with (ii) a
polyalkylene polyamine, e.g. tetraethylene pentamine, and
(iii) a polyhydric alcohol or polyhydroxy-substituted
aliphatic primary amine, e.g. pentaerythritol or
trismethylola~inomethane as described in U.S. Patent
~,632,511.
iiL Also useful as ashless nitrogen-containing
disp~rsant in this invention are dispersants wherein a
nitrog~n containing polyamine is attached directly to the
long chain aliphatic hydrocarbon a3 shown in U.S. Patents
3,275,554 and 3,565,804 where the halogen group on the
halogenated hydrocarbon is displaced with various alkylene
polyamines.
Al~ Another class of nitrogen containing
dispersants which way ba used are those containing Mannich
base or ~annich conden~ation products as thay are known in
the art. Such ~nnich condens~tlon producte gen-rally are
13~73~0
- 22 -
prepared by condensing about 1 mole of a high molecular
weight hydrocarbyl substituted mono-or polyhydroxy benzene
(e.g., having a number average molecular weight of 1,000 or
greater) with about 1 to 2.5 moles of formaldehyde or
paraformaldehyde and about 0.5 to 2 moles polyalkylene
polyamine as disclosed, e.g., in U.S. Patents 3,442,808;
3,649,229 and 3,798,165. Such Mannich condensation
products may include a long chain, high molecular weight
hydrocarbon on the phenol group or may be reacted with a
compound containing such a hydrocarbon, e.g., polyalkenyl
succinic anhydride as shown in said aforementioned U.S.
Patent 3,442,808.
Component B
Component B of the compositions of this invention
is at least one sulfurized alkyl phenol as oxidation
inhibitor. Sulfurized alkyl phenols and the methods of
preparing them are known in the art and are disclosed, for
example, in the following U.S. Patents: 2,139,766;
2,198,828; 2,230,542; 2,836,565; 3,285,854; 3,538,166;
3,844,956; and 3,951,830.
:
!, In general, the sulfurized alkyl phenol may ~e
prepared by reacting an alkyl phenol with a sulfurizing
agent such as elemental sulfur, a sulfur halide (e.g.,
sulfur monochloride or sulfur dichloride), a mixture of
hydrogen sulfide and sulfur dioxide, or the like. The
r, preferred sulfurizing agents are sulfur and the sulfur
halide3, and especially the sulfur chlorides, with sulfur
dichloride (SC12) being especially preferred.
,~ The alkyl phenols which are sulfurized to produce
'~ component A are generally compounds containing at least one
s~ hydroxy group and at least one alkyl radical attched to the
same aromatic ring. The alkyl radical ordinarily contains
about 3-100 and preferably about 6-20 carbon atoms. The
, alkyl phenol may contain more than one hydroxy group as
.~
x
,~. .:,
,.~
1327~.5~
- 23 _
exemplified by alkyl resorcinols, hydroquinones and
catechols , or it may contain more than one alkyl radical;
but normally it contains only one of each. Compounds in
which the alkyl and hydroxy groups are ortho, meta and para
to each other, and mixtures of such compounds, are within
the scope of the invention. Illustrative alkyl phenols are
n-propylphenol, isopropylphenol, ~a-butylphenol,
t-butylphenol, hexylphenol, heptylphenol, octylphenol,
nonylphenol, n-dodecylphenol, (propene
tetramer)-sub-~tituted phenol, octadecylphenol,
elcosylphenol, polybutene (molecular weight about
1000)-substituted phenol, n-dodecylresorcinol and
2,4-di-t-butylphenol. Also included are methylene-bridged
alkyl phenols of the type which may be prepared by the
reaction of an alkyl phenol with formaldehyde or a
formaldehyde-yielding reagent such as trioxane or
paraformaldehyde .
The sulfurized alkyl phenol is typically prepared
by reacting the alkyl phenol with the sulfurizing agent at
a temperature within the range of about 100-250C. The
reaction may take placs in a substantially inert diluent
such as toluene, xylene, petroleum naphtha, mineral oil,
Callosolve or th~ like. If the ~ulfurizing agent is a
sulfur halide, and especially if no diluent is used, it is
frequently pre~erred to remove acidic materials such as
hydrogen halides by vacuum stripping the reaction mixture
or blowing it with an inert gas such as nitrogen. If the
sulfur~zing agent is sulfur, it is frequently advantageous
to blow tha ~ul~urized product with an inert gas such as
nitrogen or air 80 as to remove sulfur oxides and the like.
~ omlps7~ent ~
Component C of the present inventiQn is a copper
corrosion inhibitor and comprises at least one hydrocarbon
polysulfide derivative of 2, 5-dimercapto-1, 3, 4-thiadiazole
having tho for~ula:
13273~
- 24 -
N - N
S
wherein R4 and R5 are straight or branched chain alkyl,
cyclic, alicyclic, aryl, alkylaryl or arylalkyl radicals
having fro~ 2 to about 30 carbon atoms, and w and z are
numbers from l to about 8. Preferably R4 and R5 each
have from 4 to about 16 carbon atom~, and most preferably
from about 8 to about 14 carbon atoms, and preferably the
values of "w" and "z" are nu~bers of from 1 to 4.
.~ The herein-described polysulfide derivatives of
2,5-dimercapto-1,3,4-thiadia~ole can be suitably prepared
by several methods. For example, they can be prepared by
~-~ reacting 2,5-dimercapto-1,3,4-thiadiazole with a suitable
. sulfenyl chloride, or by reacting the dimercaptan with
~ chlorine and reacting the resultant disulfenyl chloride
;~ below
; N - N
. Cl - S - C C - S - Cl
.'' \S/
with a primary or tertiary mercaptan. Bis-trisulfide
derivative~ are obtained by reacting the dimereaptan with a
mercaptan ancl a sulfur chloride in molar ratios of from
1:2:2 to 1:2:4 at a temperature of from about 120 to
212-F. Higher poly ulfides may be prepared by reacting the
thiadiazole di- or trisulfides with sulfur at temperatures
of about 200-F to 400-F. Another method of preparing the
poly~ulfide~ of the present invention involves reacting
2,5-dimercapto-1,3,4- thiadiazole with a mercaptan and
sulfur in the molar ratio of from 1:1:1 to 1:4:16 at
temp~ratures of from about 160^F to about 300-F.
Compounds produced in accordance with the above
p ro c e d u r2 p re fe r~ bl y a re p ol y s u l f i d e s o f
1,3,4-thiadiazole-2,5-bis(alXyl, di-tri or tetra sulfide)
containing rro~ 2 to about 30 carbon ato~s. Desirable
;
`` ~3~73~0
- 25 -
polysulfides include 1,3,4-thiadiazole-2,5-bis
(octyldisulfide); 1,3,4-thiadiazole-2,5-bis(octyl-
trisulfide); 1,3,4-thiadiazole-2,5-bis toctyltetrasulfide),
1,3,4-thiadiazole-2,5-(nonyldisulfide); 1,3,4-thia-
diazole-2,5-(nonyltrisulfide); 1,3,4-thiadiazole-2,5-~nonyl-
tetrasulfide); 1,3,4-thiadiazole-2,5-bis(dodecyldisulfide);
1,3,4-thiadiazole-2,5-bis(dodecyltrisulfide); ~,3,4-thiadia-
zole-2,5-bis(dodecyltetrasulfide: 2-lauryldithia-5-thiaal-
phamethylstyryl-1,3,4-thiadiazole and 2-lauryl-
trithia-5-thiaalphamethylstyryl-1,3,4-thiadiazole and
mixtures thereof. Preferred materials are the derivatives
of 1,3,4-thiadiazoles such as those described in U.5.
Patents 2,?19,125; 2,?19,126; and 3,087,932; especially
preferred is the compound 2,5-bis (t-octadithio)-1,3,4
thiadiazole commercially available as Amoco 150, and
2,5-bis(nonyldithio)-1,3,4-thiadiazole, commercially
available as Amoco 158.
Preparation of Component C is further described in
U.S. Patents 2,719,125; 2,719,126; 3,087,932; and
4,410,436.
!~
'.~.
~.~
: ';
::`
,
, .
'.
`~ ,
- 13273~G
- 26 -
LUBRICATING CO~PQ~TIONS
Lubricating oil compositisns, e.g. automatic
transmi~sion fluids, heavy duty oils suitable for diesel
engine~ (that is, compression ignition engines)~ etc., can
: be prepared with the additives of the invention. Universal
type crankcase oils wherein the sa~e lubricating oil
co~positions can be u ed for both gasoline and diesel
engine can also be prepared. TheQe lubricating oil
for~ulations conventionally contain several different types
of additives that will supply the characteriatics that are
required in the formulations. A~ong these types of
additives are included viscosity index improvers, ashless
antioxidants, ashless corrosion inhibitors, pour point
depressant~, ashless antiwear agents, etc., provided the
~ully formulated oil satisfies the ashleæs SASH
: reguirements of this invention.
In the preparation of heavy duty diesel
lubricating oil formulations it is common practice to
introduce the additives in th2 form of 10 to 80 wt. %, e.g.
20 to 80 wt. % active ingredient concentrates in
hydrocarbon oil, e.g. mineral lubricating oil, or other
. suitable solvent. Usually these concentrates may be diluted
with 3 to 100, e.g. 5 to 40 parts by weight of lubricatin~
oil, per ~art by weight of the additive package, in for~ing
finished lubricants, e.g. crankcase motor oils. The
purpose of concentrates, of course, is to make the handling
o~ the various materials less difficult and awkward as well
a~ to facilitate solution or dispersion in the final
blond. Thus, a Component A ashless dispersan~ would be
usually e~ploy~d in the form oP a 40 to 50 wt. %
concentratQ, for example, in a lubricating oil fraction.
{ Components A, ~ and C of the present invention
will b~ g~nerally used in admixture with a lube oil
ba~estoc~, co~pri ing an oil of lubricating viscosity,
including natural and synthatic lubricating oils and
ixtur s th-r~o~.
.
.,
1327350
_ 27 -
Components A, B and C can be incorporated into a
lubricating oil in any convenient way. Thus, these
mixtures can be added directly to the oil by dispersing or
dissolving the same in the oil at the desired level of
concentrations of the detergent inhibitor and antiwear
agent, respectively. Such blending into the additional
lube oil can occur at room temperature or elevated
temperatures. Alternatively, the Components A, B and C can
be blended with a suitable oil-soluble solvent and base oil
to form a concentrate, and then blending the concentrate
with a lubricating oil basestock to obtain the final
formulation. Such concentrates will typically contain (on
an active ingredient (A.I.) basis) from about 10 to about
70 wt. %, and preferably from about 30 to about 60 wt. %,
Component A ashless dispersant additive, typically from
about 10 to 40 wt. %, preferably from about 10 to 30 wt. ~
Component B antioxidant additive, typically from about 0.5
to 5 wt.~, and prefsrably fro~ about 0.6 to 3 wt.~,
Component C copper corrosion inhibitor, and typically from
about 30 to 80 wt. %, preferably from about 40 to 60 wt. %,
base oil, based on the concentrate weight.
The composition~ of this invention are also
characterized a3 being ashless, that is, by a total sulfate
ash value (SASH) concentration of less than 0.01 wt.% SASH,
preferably ~ub~tantially zero. By l'total sulfated ash"
herein is mean~ the total weight % of ash which is
determined for a given oil (based on the oil's metallic
co~ponents) by ASTM D874.
The lubricating oil basestock for Components A, B
and C typically i8 adapted to perform a selected f~nction
by the incorporation o~ additional additives therein to
form lubricating oil co~po~itions (i.e., formulations~.
Natural oils include animal oils and vegetable
oils (e.g., castor, lard oil) liquid petroleu~ oils and
hydrorefined, solvent-treated or acid-treated mineral
lubricating oil~ of the paraffinic, naph~henic and mixed
.t32~3~
-- 28 --
paraffinic naphthenic types. Oils of lubricating viscosity
derived froD coal or shale are also u~eful base oils.
A13cylene oxide polymers and interpolymers and
darivatives thereof where the terminal hydroxyl groups have
been ~odified by esterification, etherification, etc.,
constitute another clas~ of known synthetic lubricating
oils. These are exemplified by polyoxyalkylene polymers
prepared by polymerization of ethylene oxide or propylene
oxide, the alkyl and aryl eth~rs of these polyoxyalkylene
polymers (e.g., ~ethyl-poly isopropylene glycol ether
having an average molecular weiqht of 1000, diphenyl ether
of poly-ethylene glycol having a Molecular weight of
500-1000, diethyl ether of polypropylene glycol having a
~olecular weight of 1000-1500); and mono- and
polycarboxylic esters thereof, for example, the acetic acid
esters, mixed C3-C8 fatty acid estQrs and C13 Oxo
acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating
oils comprises the esters of dicarboxylic acids (e.g.,
phthalic acid, succinic acid, alkyl succinic acids and
alkenyl succinic acids, maleic acid, azelaic acid, suberic
acid, sebasic acid, fumaric acid, adipic acid, linoleic
acid dim~r, malonic acid, alkylmalonic acids, lkenyl
~alonic acids) with a variety of alcohols (e.g., butyl
alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol, ~thyl~n~ glycol, diethylene glycol monoether,
propylene glycol). Specific example of these esters
includ~ dibutyl adipate, di(2-ethylh~xyl)sebacate,
di-n-h~xyl fumarat~, dioctyl sebacate, diisooctyl azelate,
dii~od~cyl azelate, dioctyl phthalate, didecyl phthalate,
dieicosyl sebacate, the 2-ethylhexyl diester of linoleic
acid dimer, and the complex ester formed by reacting one
mole of sebacic acid with two moles of tetraethylene glycol
and two mçle~ of 2-ethylhQxanoic acid.
Esters useful as synthetic oils also include those
~ade from C5 to C12 monocarboxylic acid~ and polyols
.
;
13273~ ~
-- 29 --
and polyol ethers such a~ neopentyl glycol, triDIethylol-
propane, pentaerythritol, dipsntaerythritol and
tripentaerythritol.
Silicon-ba~ed oil9 such as the polyalkyl-t
polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and
silicate oils compri e another u~eful class of ~ynthetic
lubricants: they include tetraethyl silicate,
tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate,
tetra-(4-~ethyl-2-ethylhexyl) silicate, tetra-(p-tert-
butylphenyl) ~ilicate, hexa-(4-methyl-2-pentoxy)
disiloxane, poly(methyl) siloxanes and poly(methylphenyl)
siloxanes. Other synthetic lubricating oil~ include liquid
esters of phosphorus-containing acids (e.g., tricresyl
pho~phate, trioctyl phosphate, diethyl e~ter o~
decylphosphonic acid) and polymeric ~etrahydrofuran~.
Unrefined, refined and rerefined oils can be used
in the lubricant3 of the present invention. Unrefined oils
are those obtained directly from a natural or synthetic
source without further purification treatment. For
example, a ~hale oll obtainad directly from retorting
operations, a petroleu~ oil obtained directly from
distillation or e~ter oil obtained directly ~rom an
esterification process and used without ~urther treatment
would be an unrefined oil. Refined oils are similar to the
unrefined oils except they have been further treated in one
or more purif~cation ~taps to improve one or more
propertias. ~any such pu~ification ~echniques, such as
di~till~tion, solvent extraction, acid or base extraction,
filtration and percolation are known to those skilled in
the art. Rere~ined oils are obtained by processes ~imilar
to thoso used to obtain re~inQd oil~ applied to refined
oils which have bQen alr~ady used in service. Such
rerafined oil~ are al~o known as reclaimed or reprocessed
oils and often are additionally processed by tech~iques for
r~moval of ~pent additiYes and oil breakdown products.
~h~ nov-l corpoo1eion~ Or th- pr~-nt lnv~ntion
;.
13273~0
- 30 -
can b~ used with V.I improvers to form multi grade diesel
enqinQ lubri~ating oils. vi~c08ity modifiers impart high
and low t~mperature operability to the lubricating oil and
permit it to remain relatively viscous at elevated
te~perature~ and al~o exhibit acceptable viscosity or
fluidity at low temperatures. Viscosity modiiers are
generally high molecular weight hydrocarbon polymers
including polyesters. The viscosity modifiers may also be
darivatized to include other propertie~ or functions, such
as the addition of dispersancy properties~ These oil
soluble viscosity modifying poly~ers will generally have
numb~r average molecular weights of from 103 to 106,
prererably 104 to 106, e.g., 20,000 ~o 250,000, as
determined by gPl permeation chromatography or osmometry.
Exampl~ of suitable hydrocarbon polymers include
homopolymers and copolymers o~ two or more monomers of C2
to C30, e.g. C2 to C8 olefins, including both alpha
ole~ins and internal olefin~, which may be straight or
branched, aliphatic, aromatic, alkyl-aromatic,
cycloaliphatic, etc. Frequently they will be of ethylene
with C3 to C30 ol~fins, particularly preferred being
th~ copoly~ers of ethylene and propylene. Other polymers
can be used such a~ polyisobutylenes, homcpolymers and
copolymer~ o~ C6 and higher alpha olsfins, atactic
polypropylen~, hydrogenated polymers and copolymers and
terpolymer~ o~ styrene, e.g. with isoprene and/or butadiene
and hydroqenated d~rivatives thereof. The pol~mer may be
dqgrad~d i~ molecular weight, for ~xample by mastication,
~xtrusion, oxidation or thermal degradation, and it may be
oxidiz~d and contain oxygen. Also included are d~rivatized
poly~ers such as post-gra~ted interpolymarc of
ethylen~-propylene with an active monomer ~uch as maleic
anhydride which ~ay b~ further reacted with an alcohol, or
amine, e.g. an alkylene pclyamine or hydroxy amina, e.g.
sQe U.S. Patent No~. 4,0~9,794; 4,160,739; 4,137,185; or
.
.
f
.~
: 13273~
: - - 31 -
copolymers of ethyl~ne and propylene reacted or grafted
with nitrogen compounds such as shown in U.S. Patent Nos.
4,068,056: 4,068,058; 4,146,489 and 4,149 t 984O
~;; Th2 preferred hydrocarbon pol~ners are ethylene
copolyners containing from 15 to so wt. ~ ethylene,
prsferably 30 to 80 wt. % of ethylene and 10 to 85 wt. %,
preferably 20 to 70 wt. % of one or more C3 to c28,
preferably C3 to C18, ~ore preferably C3 to c8,
alpha-olefins. While not e~sential, such copolymers
preferably have a degree of crystallinity of less than 25
wt. %, as determined by X-ray and differential scanning
calorimetry. Copolymers of ethylene and propylene are most
preferred. Other alpha-ole~ins suitable in place of
propylene to form the copolymer, or to be used in combin-
ation with ethylene and propylene, to for~ a terpolymer,
tetrapoly~er, etc. , include l-butene, l-pentene, l-hexene,
l-heptene, l-octene, l-nonene, 1-decene, etc.: also
branched chain alpha-ol~fins, such as ~-methyl-l-pentene,
4-methyl-1-hexene, 5-methylpentene-1, 4,4-di-
methyl-l-pentene, and 6-methylheptene-1, etc., and mixtures
` thereof.
- Terpoly~ers, tetrapolymer~, etc., of ethylen~,
said C3-C28 alpha-olefin, and a non-conjugated diolefin
or mixtures og such diolefins ~ay al50 be used. The amount
of the non-conjugated diolefin generally ranges from about
0.5 to 20 ~ol~ percent, preferably fro~ about 1 to about 7
mole percent, based on the total amount of ethylene and
alpha-ol~in pre~ent.
The polyester V.I. improvers are genarally
polym~rs of esters of ethylenically unsaturated C3 to
C8 ~ono- and dic~rboxylic acid~ such as methacrylic and
acrylic acids, mal~ic acid, maleic anhydride, fum~ric acid,
etc.
Example~ of unsaturat~d esters that may be used
include those of aliphatic saturated ~ono alcohols of at
l~ast 1 carbon ato~ and pr~exably of from 12 to 2G car~o~
- 13273~
-- 32 --
atom~, such as decyl acrylate, lauryl acrylate, stearyl
acrylate, eicesanyl acrylate, docosanyl aGrylate, decyl
methacrylate, dia~yl fumarate, lauryl methacrylate, cetyl
methacrylate, stearyl methacrylate, and the like and
mixtures thereo~.
:~:
Other esters include the vinyl alcohol esters of
C2 to c22 fatty or mono carboxylic acids, preferably
saturated such as vinyl acetate, vinyl laurate, vinyl
palmitate, vinyl stearate, vinyl oleate, and the li~e and
~ixturQs thereof. Copolymers of vinyl alcohol esters with
unsaturated acid esters ~uch as the copolymer of vinyl
acetate with dialkyl fumarates, can also be used.
The ester may be copolymerized with still other
unsaturated monomers such as olefins, e.g. 0.2 to 5 moles
f C2 ~ C20 aliphatic or aromatic olefin per mole of
un~aturated ester, or per mole of unsaturated acid or
anhydride followed by e-~terification. For example,
copslymers of styrene with maleic anhydride esterified with
alcohol~ and amines are known, e.g., see U.5. Patent
3,702,30~.
Such ester polymers may be grafted with, or the
ester copolymerized with, polymerizable unsaturated
nitrogen-containing monomers to impart dispersancy to the
V.I. improvers. Examples of suitable unsaturated
nitrogen-containing monomers include those containing 4 to
20 carbon atoms ~uch as amino substituted olefins as
p-(beta-diethyl~minoethyl)styrene: basic nitrogen-con-
taining heterocycles carrying a poly~erizable ethylenically
un~aturated ~ubstituent, e.g. the vinyl pyridine~ and the
vinyl alkyl pyridineR such as 2-vinyl-5-ethyl pyridine,
2-methyl-5-vinyl pyridine, 2-vinyl-pyridine, 4-vinyl-
pyridine, 3-vinyl-pyridine, 3-methyl-5-vinyl-pyridine,
4-methyl-2-vinyl-pyridine, 4-ethyl-2-vinyl-pyridine and
2-butyl-1-5-vinyl-pyridine and the liken
N-vinyl lactams are also suitable, e.g. N-vinyl
pyrrolidono~ or N-vinyl piporidon~s.
1~27~
_ 33 -
The vinyl pyrrolidones are preferred and are
ex~mpliried by N-vinyl pyrrolidone~ N-(1-methylvinyl)
pyrrolidone, N-vinyl-5 methyl pyrrolidone, N-vinyl-3,
3-di~ethylpyrrolidone, N-vinyl-5-ethyl pyrrolidone, etc.
Other antioxidants useful in thi~ invention
include oil soluble copper compounds. The copper may be
blended into the oil as any suitable oil soluble copper
compound. By oil soluble W2 mean the compound is oil
soluble under normal blending conditions in the oil or
additive package. The copper coDIpound may be in the
cuprous or cupric form. The copper may be in the form of
the copper dihydrocarbyl thio- or dithio-phosphates wherein
copper may be substituted for zinc in the coDIpounds and
reactions described above although one mole of cuprous or
cupric oxide may be reacted with one or two moles of the
dithiophosphoric acid, respectively. Alternatively the
copper may be added as the copper salt of a synthetio or
natural carboxylic acid. Examples include C10 to C18
fatty acids such as stearic or palmitic, but unsaturated
acids such as oleic or branched carboxyl ic acids such as
naphthenic acids Or molecular weight froDI 200 to 500 or
synthetic carboxylic acids are preferred because of the
improved handling and solubility properties of the
re~ulting copper carboxylates. Also useful are oil soluble
copper dithiocarbamates of the general formula
(RR'NCSS)nCu, where n is 1 or 2 and R and R' are ths same
or different hydrocarbyl radicals containing from 1 to 18
and preferably 2 to 12 carbon atoms and including radicals
such as alkyl, al~nyl, aryl, aralkyl, alkaryl and
cycloaliphatic radicals. Particularly preferred as R and R'
groups are alkyl groups of 2 to 8 carbon atoms. Thus, the
radical~ may, for example, be ethyl, n-propyl, i-propyl,
n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl,
n heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl,
phenyl, butylph~nyl, cyclohexyl, methylcyclopentyl,
propenyl, butenyl, ~tc. In order to obtain oil solubility,
,:
~'
~327~5~
- 34 -
th~ total number of carbon atom~ (i.e, R and R') will
genorally be about 5 or greater. Copper sulphonates;
phenates, and acetylacetonates may also be used.
Exemplary of useful copper co~pounds are copper
CuI and/or CuII) salts of alkenyl succinic acids or
anhydrides. The salts themselvas may be basic, neutral or
acidic. They may be ormed by reacting (a) any of the
material~ di~cussed above in the Ashless Dispersant
section, which have at least one free carboxylic acid (or
anhydride) group with (b) a reactive metal compound.
Suitable acid (or anhydride) reactive metal compounds
include those such as cupric or cuprous hydroxides, oxides,
acetates, borates, and carbonates or ba ic copper
carbonate.
Examples of the metal salts of this invention are
Cu salts of polyisobutenyl succinic anhydride (hereinafter
referred to as Cu-PIBSA), and Cu salts of polyisobutenyl
succinic acid. Preferably, the selected metal employed is
it~ divalent ~orm, e.g., Cu+2. The pre~erred substrates
are polyalkenyl succinic acids in which the alkenyl group
has a number average molecular weight (Mn) greater than
about 700. The alkenyl group desirably has a Mn from
about 900 to 1400, and up to 2500, with a Mn f about 950
being most preferred. Especially preferred, of those
l$stad abov6 in the section on Dispersants, is
polyisobutylene succinic acid (PIBSA). These materials may
d~irably b~ dissolved in a solvent, such as a mineral oil,
and hoat~d in ~he presence of a water solution (or slurry)
o~ tho m~tal bearing material. Heating may take place
b~tws~n 70- and about 200-C. Temperatures of 110~ to 140-C
ar~ entirely ad~quate. It ~ay bs necessary, depending upon
the salt produced, not to allow th~ reaction to remain at a
temperature above about 140-C for an extended period of
ti~e, e.g., longer than 5 hours, or decompoRition of tha
salt may occur.
The copper antioxidants (e.g.t Cu-PIBSA,
;
13273~
- 35 -
Cu-oleate, or mixtures thereof) will be generally employed
in an amount of from about 50-500 ppm by weight of the
metal, in the final lubricating or fuel co~position.
The copper antioxidant~ used in this invention are
inexpensive and are effective at low concentrations and
therefore do not add cubstantially to the cost of the
product. The re~ults obtained are frequently better than
those obtained with previously used antioxidants, which are
expensive and used in higher concentrations. In the
amounts e~ployed, the copper compounds do not interfere
with the performance of other components of th~ lubricating
composition.
While any effective amount of the copper
antioxidant can be ncorporated into the lubricating oil
composition, it is contemplated that such effeztive amounts
be sufficient to provide said lube oil co~position with an
amount of the copper antioxidant of from about 5 to 500
(more preferably 10 to 200, still more pre~erably 10 to
180, and ~ost preferably 20 to 130 (e.g., 90 to 120)) part
per million of added copper based on the weight of the
lubricating oil composition. Of course, the preferred
amount may depend amongst other factors on the ~uality of
the basestock lubricating oil.
Corro~ion inhibitors, also known as anti-corrosive
agent~, reduce the degradation of the non-ferrous metallic
parts contacted by the lubricating oil composition.
Illustrativ~ of corrosion inhibitors are phosphosulfurized
hydrocarbon~ and the products obtained by reaction of a
pho~phosulfurized hydrocarbon with an alkaline earth metal
oxidc sr hydroxide, preferably in the presence of an
alkylated phenol or of an alkylphenol thioester, and also
pr~ferably in the presence of carbon dioxide.
Phosphosulfurized hydrocarbons are prepared by reacting a
suitablQ hydrocarbon such as a terp~ne, a heavy petroleum
fraction o~ a C2 to C6 ol~fin polymer such as
polyisobutylene, with ~rom S to 30 weight percent of a
l3~73~a
- 36 ~
sulfid~ of pho~phoruY for 1/2 to 15 hours, at a te~perature
in th~ range of 65- to 320'C. Neutralization of the
phospho~ul~urized hydrocarbon may be efected in the manner
taught in U.S. Patent No. 1,969,324.
Othsr oxidation inhibitors can also be employed in
addition to Component B, to assist, where desired, in
further reducing the tendency of the ~ineral oils to
deteriorate in service and to th~reby reduce the formation
of product~ of oxidation such as sludge and varnish-like
deposits on the metal surfaces and to reduce viscosity
growth. Such other oxidation inhibitors include alkaline
earth metal ~alts of alkylph~nolthioesters having
preferably C5 to C12 alkyl side chains(such as calcium
nonylphenol sulfide, barium t-octylphenyl ~ulfide, etc.),
diphenyl amine, alkyl diphenyl amine~, dioctylphenylamine,
phenyl alpha-naphthyla~ine (and its alkylated derivatives),
pho~phosulfurized hydrocarbons, other sulfurized
hydrocarbons (such as sulfurized phenols, sulfurized alkyl
catechols, and the like), phenols, hindered-phenols,
bis-phenols, catechol, alkylated catechols, etc.
Friction modifiers serve to impart the proper
friction characteristics to lubricating oil compo~itions
such as auto~atic transmission fluids.
R~pr~entative examples of suitable friction
modifiers are found in U.S. Patent No. 3,933~659 which
disclo~es fatty acid esters and amides; U.S. Patent No.
4,176,074 which de~cribes molybdenum complexe~ of polyiso-
buSsnyl ~uccinic anhydride-amino alkanols: U.S. Patent No.
4,105,571 which discloses glycerol esters of dim~rized
fatty acids; U.S. Patent No. 3,779,928 which discloses
alkane phosphonic acid salts: U.S. Patent No. 3,778,375
which di~closes reaction products of a phosphonat~ with an
olea~ide; U.S. Patent No. 3,852,205 which discloses
S-carboxy-alXyl~n~ hydrocarbyl succinimide, S-carboxy-
alkylene hydrocarbyl succina~ic acid and mixture~ ther~of;
U.S. Pat-ne No. 3,879,306 which d1sclD~3e~ N-(hydroxy-
-` 13273~
- 37 -
alkyl) alkenyl-succinamiC acids or succinimides; U.s.
Patent No. 3,932,290 which discloses reaction products of
di-(lower alkyl) phosphites and epoxides; and U.s. Patent
No. 4,028,258 which discloses the alkylene oxide adduct of
phosphosulfurized N-(hydroxyalkyl) alkenyl succinimides.
The most preferred friction modifiers are glycerol mono and
dioleates, and succinate esters, or metal salts thereof, of
hydrocarbyl substituted succinic acids or anhydrides and
thiobis alkanols such as described in U.S. Patent No.
4,344,853.
Pour point depressants lower the temperature at
which the fluid will flow or can be poured. Such
depressants are well known. Typical of those additives
which usefully optimize the low temperature fluidity of the
fluid are C8-C18 dialkylfumarate vinyl acetate
copolymers, polymethacrylates, and wax naphthalene.
Foam control can be provided by an antifoamant of
th~ polysiloxane type, e.g. silicone oil and polydimethyl
siloxane.
organic, oil-soluble compounds useful as rust
inhibitors in this invention comprise nonionic surfactants
such as polyoxyalkylene polyols and esters thereof, and
anionic surfactants such as salts of alkyl sulfonic acids.
Such anti-rust compounds are known and can be made by
conventional means. Nonionic surfactants, useful as
anti-rust additives in the oleaginous compositions of this
invention, usually owe their surfactant properties to a
nu~ber of weak stabilizing groups such as ether linkages.
Nonionic anti-rust agents containing ether linkages can be
made by alkoxylating organic substrates containing active
hydrogens with an excess of the lower alkylene oxides (such
as ethylene and propylene oxides) until the desired number
of alkoxy groups have been placed in the molecule.
The preferred rust inhibitors are polyoxyalXylene
polyols and derivatives thereof. This class of aaterials
;
.` .
- 38 - 13~3~
are commercially available from various sources: Pluronic
PolyolsT~from Wyandotte Chemicals Corporation; Polyglycol
112-2T~ a liquid triol derived from ethylene oxide and
propylene oxide available from Dsw Chemical co.; and
r~l
Tergitol, dodecylphenyl or monophenyl polyethylene glycol
ethers, and Ucon, polyalkylene glycols and derivatives,
both available from Union Carbide corp. These are but a few
of the commercial products suitable as rust inhibitors in
the improved composition of the present invention.
In addition to the polyols per se, the esters
thereof obtained by reacting the polyols with various
carboylic acids are also suitable. Acids useful in
preparing these esters are lauric acid, stParic acid,
succinic acid, and alkyl- or alkenyl-substituted succinic
acids wherein the alkyl-or alkenyl group contains up to
about twenty carbon atoms.
The preferred polyols are prepared as block
polymers. Thus, a hydroxy-substituted compound, R-(OH)n
(wherein n is 1 to 6, and R is the residue of a mono- ox
polyhydric alcohol, phenol, naphthol, etc.) is reacted with
propylene oxide to form a hydrophobic base. This base is
then reacted with ethylene oxide to provide a hydrophylic
portion resulting in a molecule having both hydrophobic and
hydrophylic portions. The relative sizes of these portions
can be adjusted by regulating the ratio of reactants, time
of reaction, etc., as is obviou~ to those skilled in the
art. Thus it i5 within the skill of the art to prepare
polyol~ whose molecules are characterized by hydrophobic
and hydrophylic moieties which are present in a ratio
rendering rust inhibitors suitable for use in any lubricant
composition regardless of differences in the base oils and
the presence of other additives.
If more oil-solubility is needed in a given
lubricating composition, the hydrophobic portion can be
increased andjor the hydrophylic portion decreased. If
greater oil-in-water emulsion breaking ability is required,
, ,~
,
., ~
~ 32~3~
~ 39 - .
the hydrophylic and/or hydrophobic portions can be adjusted
to accompl ish this .
Co~pounds illustrative of R- (OH) n include
alkylene polyols such a~ the alkylene glycol , alkylene
triols, alkylene tetrols, etc., such a~ ethylene glycol,
propylene glycol, glycerol, pentaerythritol, sorbitol,
mannitol, and the like. Aromatic hydroxy compounds such as
alkylated mono- and polyhydric phenols and naphthols can
also be used, e.g., h~ptylphenol, dodecylphenol, etc.
Oth~r suitable demulsifi~rs in~lude the esters
disclosed in U.S. Patents 3,098,827 and 2,674,619.
The liguid polyols available fro~ Wyandotte
Chemical Co. under the name Pluronic Polyols and other
similar polyol~ are particularly well suited as rust
inhibitors. Thes2 Pluronic Polyols correspond to the
formula:
H0 (CH2cH2o)x(cHc~2o)y(cH2cH2o)zH (VIII
CN3
wherein x,y, and z are întegers greater than 1 such that
the --CH2CH20--groups comprise from about 10% to
about 40% by weight of the total molecular weight of the
glycol, the av~rage molecule weight of said glycol being
from about 1000 to about 5000. These products are prepared
by first condensing propylene oxide with propylene glycol
to produce the hydrophobic base
Ho(-cH-cR2-o)y-H (IX)
Thi~ cond2nsation product is then treated with ethylene
oxid~ to add hydrophylic portions to both ends o~ th~
molecule. For best results, the ethylene oxide unit~
should compri~e ~rom about 10 to about 40% by weight of the
mol~cul~. Thos~ products whQrein the molecular weight of
the polyol is from about 2500 to 4S00 and th~ ethylene
oxide unit~ compris~ ~rom about 10% to about 15% by weight
o~ th~ mol~cul~ are particularly suitabla. Th6 polyols
ha~ing a molecular weight of about 4000 with about 10~
13273~Q
- 40 -
attributahle to (CH2CH2O) units are particularly good.
Also useful are alkoxylated fatty amines, amides, alcohols
and the like, including such alkoxylated fatty acid
derivatives treated with Cg to C~6 alkyl-substituted
phenols (such as the mono- and di-heptyl, octyl, nonyl,
decyl, undecyl, dodecyl and tridecyl phenols~, as described
in U~S. Patent 3,849,501.
These compositions of our invention may also
contain other additives such as those previously described,
and other metal containing additives, for exa~ple, those
containing barium and sodium.
Other suitable additives are the thio and polythio
sulphenamides of thiadiazoles such as those described in
U.X. Patent Specification 1,560,830. When these compounds
are included in the lubricating co~position, we prefer that
they be present in an amount from 0.01 to 10, preferably
0.1 to 5.0 weight percent based on the weight of the
composition.
Some of these numerous additives can provide a
multiplicity of effects, e.g., a dispersant-oxidation
inhibitor. 'rhis approach is well known and need not be
further elaborated herein.
Co~positions when containing these conventional
additives are typically blended into the base oil in
amounts ef~ective to provide their normal attendant
function. Representative effective amounts of such
additives (as the respective active ingredients) in the
fully formulated oil are illustrated as follows:
:,,
;,~
~,.
.'''
.~
~"
,
'` ~
. .
"
.,
~ ~3273~
- 41 -
Wt.% A~Io Wt~% A.I.
_ Compositions . ~Prefer~ed) (Broad
Component A 4-7 3-10
Component B 2.2 4 2-6
Component C 0.2-0.4 0.1-0.6
Viscosity Modifiers 0 4 0-12
Other Corrosion Inhibitors 0.01-0.5 0-1.5
OthQr Oxidation Inh~bitors 0-1.5 0-5
Pour Point Depressants 0.01-0.5 .01-1.0
Anti-Foaming Agent~ 0.001-0.01 .001-0.1
Non-Metallic Anti-Wear Agents 0.001-1.5 0-5
Friction Nodifier~ 0.01-1.5 0-5
Lubricating 8as~ Oil Balance Balance
When other additive~ are employed, it may be
: .
desirable, although not nPcessary, to prepare additive
concentrates comprising concentrated solutions or
di~persions of the novel detergent inhibitor/antiwear agent
mixtures of this invention (in concentrate amounts
hereinabove described~, together with one or more of said
other additives (said concentrate when constituting an
additive mixture being referred to herein as an
additive-package) whereby several additives can be added
simultaneously to the base oil to form the lubricating oil
composition. Dissolution of the additive concentrate into
the lubricatinq oil may be facilitated by solvents and by
~ixing accompanied with mild heating, but this is not
e~sential. Th~ concentrate or additive-package will
typi~lly be ~ormulated to contain the additives in proper
ounts to provide the desired concentration in the final
formulation when the additive-package is combined with a
predetermined amount of ba~e lubricant. Thus, the detergent
inhibitor/antiwear agent mixturec of the presen~ invention
can be added to sm~ll amounts of ~ase oil or other
compatible ~olv~nts along with other desirable a~ditives to
form additive-packages containing active ingredients in
"
i
.
13273~0
. ~ 42 -
collective amount of typically from about 2.5 to about
90%, and preferably from about 15 to about 75%, and most
pre~erably ~rom about 25 to about 60% by weight additives
in tAe appropriate proportions with the remainder being
~ basa oil.
:.` The final formulations ~ay amploy typically about
:~ 10 wt. % of the additive-package with the remainder being
base oil.
~`s All of ~aid weight percent~ expre-~sed herein
~' (unless otherwis~ indicated~ are ba~ed on ac~ive ingredient
~.~ (A.I.) conten~ of the additive, and/or upon the total
- weight o~ any additiv~-package, or formulation which will
be the su~ of the A.I. weight of each additive plus the
waight of total oil or diluent.
This invention will be further understood by
reference to the following examples, wherein all parts are
. part~ by weight, unle s otherwi~e noted and which include
`~. preferr~d embodlment~ of the invention.
,
.,
, .
.
.
,~
.
`` 1327~
,
-- ~, 3
E~PL~S
A series of fully formulated SAE 15W4C lubric:ating
oils are prepared having the components identified in Table
I.
.
. .
,~ .~t
~r
~',''
,~S
'J~
'~
!,
.~
~ !
`~
t
't
` 1~273~0
' -- 44 --
.
~ o c~
,. E'l
~i U~ O
X ~ O e~ o
,`.~ Z
O ~
.~ h ~ ~ O t
,.~ ~ U~
~ ~a
.:
.
~, J~ ~ a~
J'~
~ ~ O O O O
~ ~ X~ ~u~ 3 ~ 3
~ o~ ~ ~
~ C ~ ~ ~ --I
~ h oC~ O ~ o o ~ O a~ --
13273~
- 45 -
O ~~ 3 a ~
O ~ ~ O
Z ,~ o ~ O ~ h
O 'I C ,~ C~ X--
o ~ 3 ~ U
,, ~ o ~ u ~, ~ J~
U 0- ~
Z 4~ I o ~ ~ o U
2 ~ ~o 2 U U ~ o O I ~ ~ C ` 5 3
-~ U ~ 3 ~ O ~ ~
oO 3 ~ " ~ ~ ~ X .c o ~ ~ o ~ o
o V U. C'~ 4 ,5 d' .~ ,~ C C ,~
~O C~. o .C
Ho C ~ C ~ 5 ~ ~ I .. C ~ ~;
h ~ ~ ~ ~ U ~ ~ ~ ~ U ~ " ~ ~ ~ C
0 ~3 o ~ ~g N J~ ) h ia
3~ U 5 f3~ ~ ~ o '2 ~ 3 0 ,C J o
:
- 1~273~
- 46 -
The formulations are subjected to a Cummins
NTC-400 field test (loads = refrigerated trailers; 80,000
lbs. gross vehicle weight), approx. 80% load factor;
continental United States service (ex-Alaska), with
majority of hauling from Dallas to Pacific Northwest,
wherein diesel fuels <0.3 wt% sulfur were employed.
Also included in the above tests are the following
commercial SAE 15~40 lubricating oils. These formulations
include ashless dispersant, overbased alkaline earth metal
detergent inhibitors and zinc dihydrocarbyl dithiophosphate
antiwear agents.
:,
Comparative
: Test Oils Wt% SASHTBN (D2896)
. .
Oil C 1.0 10
Oil D 1.1 12
Oil E 0.72 6.9
Oil F 1.0 10
Oil G 1.0 8
Oil H 1.0 8
Oil I 1.0 8
Oil J 0-9 7
Oil K 1.95 14
The data thereby obtained are set forth in Table
. s:
~ .~
,:~
:,j
:~,
. ..
,
,,,
".
F
,,.,~
1~273~0
-- 47 --
N ~ ~ 8 8 ~ ~o ~ ~ ~ ~ o
3 o ~ ~ ~ a ~ 3 ~ ~ s O ~ O ~ ~
æ U~ O ~ 8 8 0 0 ~0 æ ~ ~ ~ O O
¦ ~ ~ 8 ~, . oo ~ ~ ~ ~ . $ . ~ . ~ o
Ui ~s3 0 ~ 8 ~ o o
.~ t- ¦ N ~ a; ~ '.0 0 ~r ~ O N ~ . . X 1~ O O
~ S ¦ I~ ~ a~ Ul 0 N ~ ~ ~ v O ~ $ 8 ~ a~ 1~ æ O O ~ O O
I ~ O O ~g o, o q o o o o
,~ ~ ~ ~ o u~ ~ 8 O~ o O O
O g~--U7 o ~ 8 o o o o O O
¦~ ~ o ~ O ~ In O ~ ~, 0 ~ _ . . . r N O O O oN
.' ¦~ C~l ~ ;S O ON ~ O N ~i ~ tO ~ 01 N ~ O O
.. l3~ O 5~ ~ In ~ O 1'~ 0 N U- _ ~ ~ 8 8 ~ ~ o @ o 8 o
1 0 10 N 1~ O O
13~3~
48 Y
FroDI the data in Table III, it can b~ ~een that
thQ oils oP Example~ 1 and 2 provide uperior crownland
cleanline~s without sacrificing any of tAe remaining
p~r~ormance properites.
Th~ a~hl2~8 oil8 of thi~ inv~ntion are
particularly useful in heavy duty diesel engine~ employing
roller ca~ ~ollower~. The ashles oil~ o~ this invention
are pr2ferably employed in heavy duty di esel engine~ which
2mploy normally liquid ~u~l~ having a sulfur content of
less than 1 wt~%, more preferably less than 0.5 wt.t, still
more preferably less than 0.3 wt.% (e.g., fro~ about o.1 to
about 0 . 3 wt. %3, and most preferably less than o . ~
(e.g., from 100 to 500 ppm sulfur). Such nor~ally liquid
fuels include hydrocarbonaceous petrol~u~ distillate fuels
such a~ die~el fuels or fuel oils a~ defined by ASTM
Specification D396. Compre~sion ignit2d 2nyines can also
employ normally liquid fuel compositions compri~ing
non-hydrocarbonaceous materials such a~ alcohols, ethers,
organonitro compound~ and the like (e.g., methanol~
ethanol, diathyl ether, methyl ethyl e~her, nitromathane )
are also within t~e scope of this invention a~ are liquid
~uels derived from vegetable or mineral sources such as
"
corn, alfalf;~, shale and coal. Normally liquid fuels which
are mixtures of on~ or more hydrocarbonaceous uel~ and one
or more non~hydrocarbonaceous materials are also
cont~platedO Examples o~ such mixtures are combinations
o~ die3el fu~l and ether. Particularly pref~rred is No. 2
di~s~l ~u~l.
The lubricating oils of thi~ invention are
p~rticularly us~ful in the crankcase of die~el engines
having cylinders (g~n~r~lly from 1 to cylinder3 or more
por ~ngin~) wher~in there i~ housQd for vertical cyclic
r~ciprocation therein a pi~ton provided with a ~ight top
land, ~hat is, cylinder~ wh~rein the distanc~ botw*en the
piston'~ top land and th2 cylinder wall liner i~ reduced to
~ini~iz~ the a~ount Or particulat~s g~nerated in the
1~2~3~
- 49 ~
cylinder's ~iring chamber (wherein the fuel i~ co~busted to
gon~rat~ power). Such tight top lands can also provide
i~proved fuel economy and an increase in the effective
compression ratio in the cylinder. The top land comprises
the region of the generally cylindrical pi~ton above the
top pi8ton ring groove, and the top land, therefore, is
generally characterized by a circular cross-section (taken
along the longitudinal axis of the piston). The outer
periphery of the top land can co~pri~e a substantially
vertical ~urface which i8 de~igned to be substantially
parallel to the vertical walls of the cylinder liner.
(Such top lands are herein referred to as "cylindrical top
landsn.) Or, as i~ preferred, th~ top land can bs tapered
inwardly toward the center of the pi~ton fro~ the point at
which the top land ad;oin~ the top piston ring groove and
the upp~r~ost surface of the pi~ton, i.e., the 'crown".
Th~ di~tance between ~he top land and the cylinder wall
liner, herein called the "top land clearance", will
~,
prefarably range from about 0.010 to 0.030 inch for
cylindrical op lands . For tapered top lands, the lower
top land clearance (that is, the top land clearance at the
point at which the top land is adjoined to the top piston
ring groove) is prQferably from about 0.005 to 0.030 inch,
and more preferably from about 0.010 to 0.020 inch, and the
upper top land clearance, that is, the top land clearance
at th~ pi~ton crown, is preferably fro~ about 0.010 to
0.045 inch, and more preferably from about 0.015 to 0.030
inch. While the top land clearance can be le~s than the
di~ensions qiven above (e.g., less than 0.005 inch), if
such l~s~r dictance~ do not result in und~sired contact of
thQ top land portion of th~ piston with the cylinder wall
liner during operation of the engine, which is undesirable
du~ to th~ r~sultan~ ~amage to ~he liner. Gen~rally, the
h~i~ht of the top land (that i3, the vertical dlstance, as
m~a~ured along th~ cylinder wall liner, ~rom tha bottom of
th top land to th- top of tho top land) is rrO~ Dbout C.l
~327~
~ 50 =
to ~bout 1.2 inch, which is generally from about O.8 to 1.2
inch for 4-cycle d$e3el engines and fro~ about 0.1 to 0.5
inch for 2-c~cl~ diesel engine~. ~he design o~ diesel
engine~ and ~uc~ pi~tons having such tight top lands is
within the skil l of th~ skillad arti~an and need not be
fur~her dsscribed herein.
T~e principles, preferr~d embodimants, and modes
o~ operation of the present invention have been described
in the foregoing speci~ication. Th~ invention which is
intended to ~e protected herein, however, i8 not to be
construed as limitQd to the particular Porms disclosed,
~inc~ thes~ ara to be regarding a~ illustrative rather than
re~trictive. variations and changas may be made by those
~killed in the art without departing from the spirit of the
invention.
~.
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