FIELD OF THE INVENTION
[0001] This invention relates to lubricating oil compositions which exhibit marked improvements
in low temperature cylinder wear. More particularly, this invention relates to lubricating
oil compositions which contain minor proportions of mixtures of calcium and magnesium
sulfonates with primary and secondary zinc antiwear agents, in addition to dispersant
additives.
DESCRIPTION OF THE PRIOR ART
[0002] It is an objective of the industry to provide lubricating oil compositions which
exhibit improvements in low temperature cylinder wear and ring wear, and the obtainment
of concomitant improved engine life in gasoline and diesel engine vehicles. In engines
which operate at low temperatures, e.g. for gasoline engines which operate without
thermostats and are cooled by water in the absence of conventional antifreeze/coolant
additives (such as ethylene glycol), the problem of cylinder wear is especially important.
Lubrication oils which are formulated to be employed in high temperature, ethylene-glycol/water
cooled gasoline engines are generally not completely satisfactory.
[0003] U.S. Patent 2,911,367 relates to mineral oil compositions adapted to preventing rusting
and corrosion of metal surfaces which are exposed to moisture and comprise a major
proportion of a mineral lubricating oil and a minor proportion of each of an alkali
metal salt, an oil soluble sulfonic acid, a metal alkylthiophosphate, a partial ester
of a fatty acid containing at least 8 carbon atoms and a polyol containing from 3
to 6 carbon atoms and from 3 to 6 hydroxyl radicals per molecule and an ethylene glycol
C₆ branched-chain alkyl ether. The metal alkylthiophosphates are said to include magnesium,
calcium, zinc, strontium, cadmium and barium thiophosphates, of which zinc dioctyl
and zinc octyl hexyl dithiophosphates are exemplary. The sulfonate is employed in
an amount of from about 1 to about 5 weight percent based on the total composition
and the metal alkylthiophosphate, including the above-mentioned zinc octyl hexyl and
zinc dioctyl dithiophosphate, are said to be used preferably in an amount of between
about 0.1 and about 1.5 weight percent of the total composition.
[0004] U.S. Patent 3,562,159 relates to synthetic lubricants containing a carboxylic acid
ester of lubricating viscosity as the basic liquid and, as additives, an akylated
alkylene polyamine (about 5 to 30 parts by weight), a basic alkaline earth metal sulfonate
(about 5 to 15 parts by weight), a metal phosphorodithioate (about 5 to 70 parts by
weight), a basic alkaline earth metal salt of a phosphosulfurized hydrocarbon, esters
of a hydrocarbon-substituted succinic acid, and a basic alkaline earth metal salt
of an alkylphenol sulfide.
[0005] U.S. Patent 3,714,042 relates to treated overbased complexes, which are disclosed
as being useful as additives in lubricating oils, gasolines and other organic materials,
wherein basic metal complexes selected from the class consisting of sulfonate, sulfonate-carboxylate
and carboxylic complexes with up to an amount equivalent to the total basicity thereof
with high molecular weight aliphatic carboxylic acid or anhydrides containing at least
about 25 aliphatic carbon atoms per carboxy group under recited temperature conditions.
The metal of the basic metal salt complex may be magnesium or calcium (among other
recited metals). Additional additives may be used in combination with the recited
compositions, including Group II metal phosphorodithioates such as zinc dicyclohexyl
phosphorodithioate, and zinc dioctyl phosphorodithioate.
[0006] U.S. Patent 3,933,659 relates to lubricating oil compositions which comprise a major
amount of an oil of lubricating viscosity and an effective amount of an alkenyl succinimide,
a Group II metal salt of a dihydrocarbyl dithiophosohoric acid, a basic sulfurized
alkaline earth metal alkylphenate, and a compound selected from the group consisting
of certain fatty acid esters and fatty acid amides and amines. The Group II metal
salt of the dihydroycarbyl dithiophosphoric acids are indicated to be present in an
amount of from 0.5 to 1.5 weight percent of the functional fluid and the basic sulfurized
alkaline earth metal alkylphenates are indicated to be present in the functional fluid
in an amount of from about 0.4 to about 4 weight percent.
[0007] U.S. Patent 4,308,154 relates to mixed metal salts (especially zinc salts) of dialkylphosphorodithioic
acids and carboxylic acids, which are said to be useful in lubricants and functional
fluids (such as hydraulic fluids) as antioxidants and extreme pressure agents having
improved thermal stability. The mixed metal salts of this invention are said to also
include those of the Group I and Group II metals.
[0008] U.S. Patent 4,417,990 relates to mixed metal salts/sulfurized phenate compositions,
useful in lubricants and functional fluids as antioxidants and extreme pressure agents
having improved thermal stability and contains a disclosure related that of U.S. Patent
4,308,154, discussed above.
[0009] Various suggestions have been made in the prior art regarding the nature, type, and
carbon content of the alkyl or aryl groups present in dialkylphosphorodithioic acids
used to prepare desired metal salts. For example, U.S. Patent No. 2,344,393 taught
that it was previously recognized that metal dithiophosphates should have one or more
long chain alkyl groups to render them sufficiently soluble in lubricating oils to
be of practical value. The patentees found, however that the zinc salt of diamyl phosphorodithioic
acid was oil-soluble. U.S. Patent No. 3,318,808 discloses that the higher carbon containing
alkyl groups (above 4 carbon atoms) enhance oil solubility. Thus, the patent teaches
combinations of C₄ and lower primary and/or secondary alcohols with C₅ and above alcohols,
and the ratio of the alcohols is selected to suit the balance between economics and
solubility.
[0010] U.S. Patent No. 3,190,833 describes oil-soluble metal phosphorodithioates which are
the salts of metals in Group II of the periodic table and comprise preferably the
salts of calcium, barium, strontium, zinc and cadmium with phosphorodithioic acids
which contain a total of at least about 7.6 aliphatic carbon atoms per atom of phosphorus.
To improve the oil solubility of the metal salts, they are reacted with up to about
0.75 mole of an epoxide.
[0011] Another patent which relates to the preparation of phosphorodithioic acid salts as
useful additives in lubricants is U.S. Patent No. 3,000,822. This patent describes
zinc salts of a mixture of dialkyl phosphorodithioic acids wherein the alkyl groups
comprise a mixture of lower molecular weight primarily aliphatic hydrocarbon radicals
having less than 5 carbon atoms and higher molecular weight primary aliphatic hydrocarbon
radicals having at least 5 carbon atoms. The mole ratios of lower molecular weight
radicals to higher molecular weight radicals in the zinc salt is within the range
of 1:1 to 3:1.
[0012] Various suggestions have been made in the prior art for improving the utility of
lower alkyl phosphorodithioic acid salts which have a tendency to be oil insoluble.
U.S. Patent No. 4,306,984 describes a procedure for rendering oil insoluble metal
C₂-C₃ dialkyldithiophosphates oil-soluble by forming a complex between the dithiophosphate
and an alkenyl or alkyl mono- or bis-succinimide. This combination of additives is
used in lubricating oils which can be employed for crankcase lubrication of internal
combustion engines. Another method which has been suggested for preparing non-crystalline
mixtures of basic or mixed basic and neutral zinc salts of dialkyldithiophosphates
containing from 1 to 13 carbon atoms in the alkyl groups has been suggested in U.S.
Patent No. 3,843,530. The mixtures of basic or mixed basic and neutral zinc salts
described in this patent contain from 4 to 13 different alkyl groups, have an average
carbon content of 3.5 to 4.5, and contain at least 12% by weight of zinc.
[0013] U.S. Patent 4,466,895 relates to lubricating oil compositions containing metal salt
of one or more dialkylphosphorodithioic acids wherein the alkyl groups each contain
from 2 to 4 carbon atoms and at least one alkyl group is a butyl group, the total
number of carbon atoms per phosphorus atoms is less than 8, from about 30 to 90 mole
percent of the alkyl groups are primary alkyl groups, from about 10 to 70 mole percent
of the alkyl groups are secondary alkyl groups, and wherein the metal salt as zinc,
copper or iron salt, mixtures thereof, or a mixture of calcium salt and one or more
of said metal salts, provided that when only 2 alkyl groups are present, from about
30 to 80 mole percent of the alkyl groups are n-butyl groups, and from about 20 to
70 mole percent of said alkyl groups are isopropyl groups. The patentees disclose
that these metal salts are useful in lubricating oil compositions as anti-wear agents
and antioxidants. The patentees metal salts of lower dialkylphosphorodithioic acids
are illustrated in combination with a conventional higher alkyl ZDDP in suficient
formulations also containing mixtures of basic calcium petroleum sulfonate and basic
magnesium petroleum sulfonate.
[0014] Zinc dialkyl dithiophosphates, prepared from mixed dialkyldithiophosphoric acids,
have been heretofore prepared. U.S. Patent 3,293,181 relates to mixed salts prepared
from a mixture of at least two different branched chain primary alcohols, one of said
alcohols being isobutyl alcohol and the other said alcohols containing at least 6
carbon atoms.
[0015] U.S. Patent 3,397,145 discloses that the alkyl groups of the alkylthiophosphoric
acids can be straight or branched chain and that the alkyl groups may be primary,
secondary and/or tertiary substituents (e.g., same or different alkyl groups).
[0016] U.S. Patent 3,442,804 relates to zinc phosphorodithioates, useful in lubricating
compositions, in which the hydrocarbon radicals are primary alkyl radicals and consist
of a mixture of lower molecular weight radicals and higher molecular weight radicals.
[0017] U.S. Patent 4,328,111 relates to modified overbased sulfonates and phenates wherein
the basic compound is reacted with acidic compound comprising an organic carboxylic
acid, organic carboxylic acid anhydride, phosphoric acid, phosphoric acid ester, thiophosphoric
acid ester, or mixtures thereof.
[0018] U.S. Patent 4,614,602 relates to lubricant compositions containing an overbased detergent-dispersant
lubricant additive comprising a reaction product of an alkaline earth metal phenate
and an ammonium alkylbenzene sulfonate, which the patentees indicate can be used in
combination with other conventional lubricant additives, including anti-wear agents
such as ZDDP. The alkyl benzene sulfonate can comprise sulfonic acid salts derived
from alkaline earth metals, such as Ca, Mg, Ba oxides or hydroxides, alone or in admixture.
Exemplified as a modifying agent for reaction with overbased magnesium sulfonate is
2-ethylhexyl dithiophosphoric acid.
[0019] U.S. Patent 4,362,633 relates to lubricting oil additives containing molybdenum-containing
aminated sulphurized additives. The Patentee illustrates the use of such additives
in combination with mixtures containing overbased calcium phenate, overbased magnesium
sulphonate and zinc dialkyldiphiophosphates.
[0020] European Patent 24,146 relates to lubricating oil compositions containing copper
antioxidants, and exemplifies copper antioxidants in lubricating oil compositions
also containing 1.0 wt. % of a 400 TBN magnesium sulphonate (containing 9.2 wt. %
magnesium), 0.3 wt. % of a 250 TBN calcium phenate (containing 9.3 wt. % 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.
[0021] European Patent Application 92,946 relates to lubricating oil compositions having
improved fuel economy which contain glycerol partial esters, oil-soluble organic copper
compounds and oil-soluble organic copper compounds. The Patent illustrates compositions
containing such combinations in admixture with basic metal detergents and anti-wear
additives. The Patent discloses that the preferred detergent materials are the normal
or overbased calcium or magnesium phenates, sulphurized phenates, and/or sulphontes,
and further discloses that the anti-wear additives generally are the oil soluble zinc
dihydrocarbyl dithiophosphates having a total of at least 5 carbon atoms.
[0022] U.S. Patent 4,104,180 relates to a process for producing overbased carbonates. Example
11 of this Patent illustrates lubricating oils containing 1.2 wt. % neutral calcium
phenate, 1.2 wt. % zinc dialkyl dithiophosphate and 1.2 wt. % magnesium sulphonate.
[0023] N. E. Gallopoulos et al.,
ASLE Transactions, Vol. 14, pp. 1-7, (1971) investigated the interactions between a zinc dialkyl phosphoro
dithioate and lubricating oil dispersants including the effect of alkaline calcium
petroleum sulphonate on aging of mixtures of the sulphonate with zinc dialkyl phosphoro
dithioate, and concluded that chemical reactions are likely to occur. No investigation
was reported for mixtures of alkaline earth metal sulphonates.
[0024] J. A. McGeehan et al., SAE Paper 852133, 1983, pps. 879-892 investigated the effects
of zinc dithiophosphates and detergents on controlling engine wear. Zinc diaryl dithiophosphates
were concluded to be less effective in controlling valve wear in gasoline engines
than zinc dialkyl dithiophosphates. The authors concluded that the control of engine
wear requires a critical balance of zinc dithiphosphate and detergent types in order
to control gasoline engine valve train wear, diesel cylinder poor polishing wear and
diesel roller follower bronze pin wear, based on the authors' studies conducted with
various zinc dialkyl dithiophosphates and either calcium or magnesium detergents.
However, the alkyl type of these zinc dithiophosphates was not identified and mixtures
of calcium and magnesium detergents were not assessed.
[0025] However, none of the above references discloses advantages to be achieved in controlling
the relative amounts of mixed calcium/magnesium detergents and mixed primary/secondary
zinc dithiophosphate antiwear agents.
SUMMARY OF THE INVENTION
[0026] In accordance with the present invention, there are provided cylinder and ring wear
corrosion inhibiting lubricating oil compositions which comprise an oil of lubricating
viscosity as the major component and as the minor component (A) a mixture of (1) at
least one calcium overbased sulfonate or phenate detergent inhibitor, and (2) at least
one magnesium overbased sulfonate or phenate detergent inhibitor, and (B) a mixture
of (1) at least one zinc di-(primary hydrocarbyl) dithiophosphate and (2) at least
one zinc di-(secondary hydrocarbyl) dithiophosphate, wherein component (A) comprises
from about 0.7 to 0.9 weight percent of the lubricating oil composition, component
(B) comprises from about 0.7 to 1.2 weight percent of the lubricting oil composition,
and wherein the mixed calcium and magnesium detergent inhibitors are present in a
weight:weight ratio of components A(1):A(2) of from about 0.3:1.0 to about 1.3:1.0,
and the mixed zinc di(primary hydrocarbyl) dithiophosohate and the zinc di(secondary
hydrocarbyl) dithiophosphate atiwear agents are present in a weight:weight ratio of
B(1):B(2) of from about 0.7:1.0 to about 3.1:1.0.
[0027] The present invention is based on the discovery that there is a surprisingly pronounced
relationship between decreased cylinder and ring wear and the proportions of mixed
calcium/magnesium detergent inhibitors and mixed primary/secondary zinc antiwear agent
in crank case lubricating oil composition, and that such mixtures impart a degree
of decreased cylinder and ring wear per unit weight of additive not heretofore recognized
by the art. Of equal significance is the fact that other desirable affects and properties
of lubricating oils, e.g., compatibility, detergency and dispersancy, are not diminished.
DETAILED DESCRIPTION OF THE INVENTION
Component A
[0028] Component A is a mixture of basic (viz, overbased) Ca and Mg salt of one or more
organic sulfonic acid (generally a petroleum sulfonic acid or a synthetically prepared
alkaryl sulfonic acid), petroleum naphthenic acids, alkyl benzene sulfonic acids,
alkyl phenols, alkylene-bis-phenols, oil soluble fatty acids and the like, such as
are described in U.S. Patent Nos. 2,501,731; 2,616,904; 2,616,905; 2,616,906; 2,616,911;
2,616,924; 2,616,925; 2,617,049; 2,777,874; 3.027,325; 3,256,186; 3,282,835; 3,384,585;
3,373,108; 3,365,396; 3,342,733; 3,320,162; 3,312,618; 3,318,809; and 3,562,159. For
purposes of illustration, the disclosures of the above patents are hereby incorporated
in the present specification insofar as the complexes useful in this invention are
described. Among the petroleum sulfonates, the most useful products are those prepared
by the sulfonation of suitable petroleum fractions with subsequent removal of acid
sludge and purification. Synthetic alkaryl sulfonic acids are usually prepared from
alkylated benzenes such as the Friedel-Crafts reaction product of benzene and a polymer
such as tetrapropylene. Suitable acids may also be obtained by sulfonation of alkylated
derivatives of such compounds as diphenylene oxide thianthrene, phenolthioxine, diphenylene
sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane,
decahydro naphthalene and the like.
[0029] Highly basic Ca and Mg sulfonates are frequently used as detergents. They are usually
produced by heating a mixture comprising an oil-soluble sulfonate or alkaryl sulfonic
acid, with an excess of alkaline earth metal compound above that required for complete
neutralization of any sulfonic acid present and thereafter forming a dispersed carbonate
complex by reacting the excess metal with carbon dioxide to provide the desired overbasing.
The sulfonic acids are typically obtained by the sulfonation of alkyl substituted
aromatic hydrocarbons such as those obtained from the fractionation of petroleum by
distillation and/or extraction or by the alkylation of aromatic hydrocarbons as for
example those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl
and the halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
The alkylation may be carried out in the presence of a catalyst with alkylating agents
having from about 3 to more than 30 carbon atoms. For example haloparaffins, olefins
obtained by dehydrogenation of paraffins, polyolefins produced from ethylene, propylene,
etc. are all suitable. The alkaryl sulfonates usually contain from about 9 to about
70 or more carbon atoms, preferably from about 16 to about 50 carbon atoms per alkyl
substituted aromatic moiety.
[0030] The alkaline earth metal compounds which may be used in neutralizing these alkaryl
sulfonic acids to provide the sulfonates includes the oxides and hydroxides, alkoxides,
carbonates, carboxylate, sulfide, hydrosulfide, nitrate, borates and ethers of magnesium,
calcium, and barium. Examples are calcium oxide, calcium hydroxide, magnesium acetate
and magnesium borate. As noted, the alkaline earth metal compound is used in excess
of that required to complete neutralization of the alkaryl sulfonic acids. Generally,
the amount ranges from about 100 to 220%, although it is preferred to use at least
125%, of the stoichiometric amount of metal required for complete neutralization.
[0031] Various other preparations of basic alkaline earth metal alkaryl sulfonates are known,
such as U.S. Patents 3,150,088 and 3,150, 089 wherein overbasing is accomplished by
hydrolysis or an alkoxide-carbonate complex with the alkaryl sulfonate in a hydrocarbon
solvent-diluent oil.
[0032] A preferred Mg sulfonate additive is magnesium alkyl aromatic sulfonate having a
total base number ranging from about 300 to about 400 with the magnesium sulfonate
content ranging from about 25 to about 32 wt. %, based upon the total weight of this
additive system dispersed in mineral lubricating oil. A preferred Ca sulfonate additive
is calcium alkyl aromatic sulfonate having a total base number ranging from about
300 to about 400 with the calcium sulfonate content ranging from about 25 to about
32 wt. %, based upon the total weight of this additive system dispersed in mineral
lubricating oil.
[0033] As an example of a particularly convenient process for the preparation of the complexes
used, an oil-soluble sulfonic acid, such as a synthetically prepared didodecylbenzene
sulfonic acid, is mixed with an excess of lime (e.g., 10 equivalents per equivalent
of the acid) and a promoter such as methanol, heptylphenol, or mixture thereof, and
a solvent such as mineral oil, at 50°C-150°C and the process mass is then carbonated
until a homogenous mass is obtained. Complexes of sulfonic acids, carboxylic acids,
and mixtures thereof are obtainable by processes such as are described in U.S. Patent
No. 3,312,618. Another example is the preparation of a magnesium sulfonate normal
magnesium salt thereof, an excess of magnesium oxide, water, and preferably also an
alcohol such as methanol.
[0034] The carboxylic acids useful for preparing sulfonate carboxylate complexes, and carboxylate
complexes, i.e., those obtainable from processes such as the above wherein a mixture
of sulfonic acid and carboxylic acid or a carboxylic acid alone is used in lieu of
the sulfonic acid, are oil-soluble acids and include primarily fatty acids which have
at least about 12 aliphatic carbon atoms and not more than about 24 aliphatic carbon
atoms. Examples of these acids include: palmitic, stearic, myristic, oleic, linoleic,
dodecanoic, behenic, etc. Cyclic carboxylic acids may also be employed. These include
aromatic and cyclo-aliphatic acids. The aromatic acids are those containing a benzenoid
structure (i.e., benzene, naphthalene, etc.) and an oil-solubilizing radical or radicals
having a total of at least about 15 to 18 carbon atoms, preferably from about 15 to
about 200 carbon atoms. Examples of the aromatic acids include: stearyl-benzoic acid,
phenyl stearic acid, mono- or polywax-substituted benzoic or naphthoic acids wherein
the wax group consists of at least about 18 carbon atoms, cetyl hydroxybenzoic acids,
etc. The cycloaliphatic acids contemplated have at least about 12, usually up to about
30 carbon atoms. Examples of such acids are petroleum naphthenic acids, cetyl cyclohexane
carboxylic acids, di-lauryl decahydronaphthalene carboxylic acids, di-octyl cyclopentane
carboxylic acids, etc. The thiocarboxylic acid analogs of the above acids, wherein
one or both of the oxygen atoms of the carboxyl group are replaced by sulfur, are
also contemplated.
[0035] The ratio of the sulfonic acid to the carboxylic acid in mixtures is at least 1:1
(on a chemical equivalent basis) and is usually less than 5:1, preferably from 1:1
to 2:1.
[0036] The terms "basic salt" and "overbased salt" are used to designate metal salts wherein
the metal is present in stoichiometrically larger amounts than the sulfonic acid radical.
[0037] As used in the present specification and claims, the term "complex" refers to basic
metal salts which contain metal in an amount in excess of that present in a neutral
or normal metal salt. The "base number" of a complex is the number of milligrams of
KOH to which one gram of the complex is equivalent as measured by titration. The commonly
employed methods for preparing the basic salts involve heating a mineral oil solution
of the normal metal salt of the acid with a metal neutralizing agent such as the oxide,
hydroxide, carbonate, bicarbonate or sulfide at a temperature above 5°C and filtering
the resulting mass. The use of a "promoter" in the neutralization step to aid the
incorporation of a large excess of metal is known and is preferred for the preparation
of such compositions. Examples of compounds useful as the promoter include phenolic
substances such as phenol, naphthol, alkyl phenols, thiophenol, sulfurized alkyl phenols,
and condensation products of formaldehyde with a phenolic substance; alcohols such
as methanol, 2-propanol, octanol, cellosolve, carbitol, ethylene glycol, stearyl alcohol
and cyclohexanol; and amines such as aniline, phenylene diamine, phenothiazine, phenol
beta-naphthylamine and dodecylamine.
[0038] Usually, the basic composition obtained according to the above-described method is
treated with carbon dioxide until its base number is less than about 50, as determined
by ASTM procedure D2896 (TBN). In many instances, it is advantageous to form the basic
product by adding the Ca or Mg base portionwise and carbonating after the addition
of each portion. Products with very high metal ratios (10 or above) can be obtained
by this method. As used herein, the term "metal ratio" refers to the ratio of total
equivalents of alkaline earth metal in the sulfonate complex to equivalents of sulfonic
acid anion therein. For example, a normal sulfonate has a metal ratio of 1.0 and a
calcium sulfonate complex containing twice as much calcium as the normal salt has
a metal ratio of 2.0. The compositions suitable for use as Component A have metal
ratios of at least about 1.1, for example, from about 1.1 to about 30, with metal
ratios of from about 2 to 20 being preferred.
[0039] It is frequently advantageous to react the basic sulfonate with anthranilic acid,
by heating the two at about 140-200°C. The amount of anthranilic acid used is generally
less than about 1 part (by weight) per 10 parts of sulfonate, preferably 1 part per
40-200 parts of sulfonate. The presence of anthranilic acid improves the oxidation-
and corrosion-inhibiting effectiveness of the sulfonate.
[0040] Basic alkaline earth metal sulfonates are known in the art and methods for their
preparation are described in a number of patents, such as U.S. Patent Nos. 3,027,325;
3,312,618; and 3,350,308. Any of the sulfonates described in these and numerous other
patents are suitable for use in the present invention.
[0041] The basic Ca and Mg salts are preferably separately prepared and then admixed in
the controlled amounts as provided herein. It will be generally convenient to admix
such separately prepared detergent inhibitors in the presence of the diluent or solvent
used in their preparation.
[0042] Preferably, the basic Ca detergent inhibitor and basic Mg detergent inhibitor are
employed in an amount of from about 0.3 to 1.3 parts, and more preferably from about
0.8 to 1.2 parts, of the Ca detergent inhibitor per part of the Mg detergent inhibitor.
[0043] The Component A (that is, the sum of A(1) and (2)) will generally be employed in
the fully formulated lubricating oil in a concentration of from about 0.7 to 0.9 wt.%.
[0044] The Component A can also contain other alkaline earth and/or alkali metal detergent
inhibitors, (e.g. basic or neutral Na, K and Li sulfonates, and salicylates, and basic
or neutral Ba sulfonates, phenates and salicylates). Examples of each mixtures as
Component A are mixtures of overbased Ca sulfonte, overbased Mg sulfonate and overbased
Na sulfonate detergent inhibitors.
Component B
[0045] This component is a mixture of (1) a metal salt of a di(primary hydrocarbyl) dithiophosphoric
acid and (2) a metal salt or a di(secondary hydrocarbyl) dithiophosphoric acid. The
acids from which B-1 metal salts can be derived can be illustrated by acids of the
formula (I)

wherein R′ and R² are the same or different and are alkyl, cycloalkyl, aralkyl, alkaryl
or substantially hydrocarbon radical of a similar structure. The acids from which
B-2 metal salts can be derived can be illustrated by acids of the formula (II):

wherein R³, R⁴, R⁵ and R⁶ are the same or different and are alkyl, cycloalkyl, alkaryl,
aralkyl, or a substantially hydrocarbon radical of a similar structure.
[0046] By "substantially hydrocarbon" is meant radicals containing substituent groups such
as ether, ester, nitro or halogen which do not materially affect the hydrocarbon character
of the radical.
[0047] Therefore, the acids of formula I can be seen to comprise di-primary-hydrocarbyl
substituents wherein each oxygen-bonded carbon is primary, that is, -CH₂-O. Correspondingly,
the acids of formula II can be seen to comprise di-secondary hydrocarbyl substituents
wherein each oxygen bonded carbon is secondary, that is, >CH-O.
[0048] Specific examples of suitable R¹ through R⁶ radicals include isopropyl, isobutyl,
n-butyl, sec-butyl, n=hexyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, decyl, dodecyl,
tetradecyl, hexadecyl, octadecyl, butylphenyl, o,p-depentylphenyl, octylphenyl, polyisobutene-(molecular
weight 350)-substituted phenyl, tetrapropylene-substituted phenyl, beta-octylbutylnaphthyl,
cyclopentyl, cyclohexyl, phenyl, chlorophenyl, o-dichlorophenyl, bromophenyl, naphthenyl,
2-methylcyclohexyl, benzyl, chlorobenzyl, chloropentyl, dichlorophenyl, nitrophenyl,
dichlorodecyl and xenyl radicals. Alkyl radicals having about 3-30 carbon atoms, and
aryl radicals having about 6-30 carbon atoms, are preferred. Particularly preferred
R¹ through R⁶ radicals are alkyl of 3 to 18 carbons.
[0049] The phosphorodithioic acids are readily obtainable by the reaction of phosphorus
pentasulfide and an alcohol or phenol. The reaction involves mixing, at a temperature
of about 20-200°C, 4 moles of the alcohol or phenol with one mole of phosphorus pentasulfide.
Hydrogen sulfide is liberated as the reaction takes place.
[0050] The metal salts which are useful in this invention include those salts containing
Group I metals, Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt
and nickel. Zinc is the preferred metal. Examples of metal compounds which may be
reacted with the acid include lithium oxide, lithium hydroxide, lithium carbonate,
lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate,
sodium propylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium
carbonate, potassium methylate, silver oxide, silver carbonate, magnesium oxide, magnesium
hydroxide, magnesium carbonate, magnesium ethylate, magnesium propylate, magnesium
phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate,
calcium propylate, calcium pentylate, zinc oxide, zinc hydroxide, zinc carbonate,
zinc propylate, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide,
cadmium carbonate, cadmium ethylate, barium oxide, barium hydroxide, barium hydrate,
barium carbonate, barium ethylate, barium pentylate, aluminum oxide, aluminum propylate,
lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butylate, cobalt oxide,
cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide
and nickel carbonate.
[0051] In some instances, the incorporation of certain ingredients such as small amounts
of the metal acetate or acetic acid used in conjunction with the metal reactant will
facilitate the reaction and result in an improved product. For example, the use of
up to about 5% of zinc acetate in combination with the required amount of zinc oxide
facilitates the formation of a zinc phosphorodithioate.
[0052] The preparation of metal phosphorodithioates is well known in the art and is described
in a large number of issued patents, including U.S. Patents 3,293,181; 3,397,145;
3,396,109; and 3,442,804, the disclosures of which are hereby incorporated by reference
insofar as the preparation of metal salts of organic phosphorodithioic acids useful
in this invention are described.
[0053] The relative amounts of metal salts B-1 and B-2 which are employed are critical to
the present invention. Metal salt B-1 (that is, the metal salts of the di-(primary
hydrocarbyl) dithiophosphoric acids of formula I) should be used in an amount of from
about 0.7 to 3.1, and preferably from about 0.8 to 1.55 parts by weight per part by
weight of the metal salt B-2 (that is the metal salts of the di-(secondary hydrocarbyl)
dithiophosphoric acids of formula II). The Component B (that is, the sum of B(1) and
B(22) will be generally used in the fully formulated lubricating oil in a concentration
of from about 0.7 to 1.2 wt.%, and preferably from about 0.8 to 1.1 wt.%.
[0054] The B-1 and B-2 metal salts are preferably made separately and then admixed to form
the mixed antiwear component B. Alternatively, a mixture of primary and secondary
acids I and II can be charged in the formation of mixed B-1 and B-2 metal salts
in situ, to form the Component B having the desired ratio of metal salt B-1 equivalents to
metal salt B-2 equivalents.
LUBRICATING COMPOSITIONS
[0055] Lubricating oil compositions, e.g., heavy duty oils suitable for gasoline and diesel
engines, etc., can be prepared with the additives of the invention. Universal type
crankcase oils wherein the same lubricating oil compositions can be used for both
gasoline and diesel engine can also be prepared. These lubricating oil formulations
conventionally contain several different types of additives that will supply the characteristics
that are required in the formulations. Among these types of additives are included
viscosity index improvers, antioxidants, corrosion inhibitors, other detergents, ashless
dispersants, pour point depressants, other antiwear agents, etc.
[0056] In the preparation of lubricating oil formulations it is common practice to introduce
the additives in the 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 lubricating oil, per part by weight of the additive package, in forming finished
lubricants, e.g. crankcase motor oils. the purpose of concentrates, of course, is
to make the handling of the various materials less difficult and awkward as well as
to facilitate solution or dispersion in the final blend. Thus, a Component A Ca/Mg
hydrocarbyl sulfonate mixture or a Ca/Mg alkyl phenate would be usually employed in
the form of a 40 to 50 wt. % concentrate, for example, in a lubricating oil fraction.
[0057] Components A and B of the present invention will be generally used in admixture with
a lube oil basestock, comprising an oil of lubricating viscosity, including natural
and synthetic lubricating oils and mixtures thereof.
[0058] Components A and B 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 and
B 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 9 to about 18 wt. %, Component A detergent inhibitor additive, typically
from about 10 to 25 wt. %, Component B antiwear agent additive, and typically from
about 30 to 90 wt. %, preferably from about 40 to 60 wt. %, base oil, based on the
concentrate weight.
[0059] The lubricating oil basestock for Components A and B typically is adapted to perform
a selected function by the incorporation of additional additives therein to form lubricating
oil compositions (i.e., formulations).
[0060] Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid
petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating
oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of
lubricating viscosity derived from coal or shale are also useful base oils.
[0061] Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal
hydroxyl groups have been modified by esterification, etherification, etc., constitute
another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene
polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl
and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-poly isopropylene
glycol ether having an average molecular weight of 1000, diphenyl ether of poly-ethylene
glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol
having a molecular weight of 1000-1500) ; and mono- and polycarboxylic esters thereof,
for example, the acetic acid esters, mixed C₃-C₈ fatty acid esters and C₁₃ Oxo acid
diester of tetraethylene glycol.
[0062] 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 dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids)
with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific
examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl
fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl 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 moles of 2-ethylhexanoic acid.
[0063] Esters useful as synthetic oils also include those made from C₅ to C₁₂ monocarboxylic
acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol and tripentaerythritol.
[0064] Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane
oils and silicate oils comprise another useful class of synthetic lubricants; they
include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate,
tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)
disiloxane, poly(methyl) siloxanes and poly(methylphenyl) siloxanes. Other synthetic
lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl
phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric
tetrahydrofurans.
[0065] Unrefined, refined and rerefined oils can be used in the lubricants of the present
invention. Unrefined oils are those obtained directly from a natural or synthetic
source without further purification treatment. For example, a shale oil obtained directly
from retorting operations, a petroleum oil obtained directly from distillation or
ester oil obtained directly from an esterification process and used without further
treatment would be an unrefined oil. Refined oils are similar to the unrefined oils
except they have been further treated in one or more purification steps to improve
one or more properties. Many such purification techniques, such as distillation, solvent
extraction, acid or base extraction, filtration and percolation are known to those
skilled in the art. Rerefined oils are obtained by processes similar to those used
to obtain refined oils applied to refined oils which have been already used in service.
Such rerefined oils are also known as reclaimed or reprocessed oils and often are
additionally processed by techniques for removal of spent additives and oil breakdown
products.
[0066] The novel detergent inhibitor/antiwear agent mixtures of the present invention can
be used with V.I improvers to form multi-grade automobile engine lubricating oils.
Viscosity modifiers impart high and low temperature operability to the lubricating
oil and permit it to remain relatively viscous at elevated temperatures and also exhibit
acceptable viscosity or fluidity at low temperatures. Viscosity modifiers are generally
high molecular weight hydrocarbon polymers including polyesters. The viscosity modifiers
may also be derivatized to include other properties or functions, such as the addition
of dispersancy properties. These oil soluble viscosity modifying polymers will generally
have number average molecular weights of from 10³ to 10⁶, preferably 10⁴ to 10⁶, e.g.,
20,000 to 250,000, as determined by gel permeation chromatography or osmometry.
[0067] Examples of suitable hydrocarbon polymers include homopolymers and copolymers of
two or more monomers of C₂ to C₃₀, e.g. C₂ to C₈ olefins, including both alpha olefins
and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic,
cycloaliphatic, etc. Frequently they will be of ethylene with C₃ to C₃₀ olefins, particularly
preferred being the copolymers of ethylene and propylene. Other polymers can be used
such as polyisobutylenes, homopolymers and copolymers of C₆ and higher alpha olefins,
atactic polypropylene, hydrogenated polymers and copolymers and terpolymers of styrene,
e.g. with isoprene and/or butadiene and hydrogenated derivatives thereof. The polymer
may be degraded in molecular weight, for example by mastication, extrusion, oxidation
or thermal degradation, and it may be oxidized and contain oxygen. Also included are
derivatized polymers such as post-grafted interpolymers of ethylene-propylene with
an active monomer such as maleic anhydride which may be further reacted with an alcohol,
or amine, e.g. an alkylene polyamine or hydroxy amine, e.g. see U.S. Patent Nos. 4,089,794;
4,160,739; 4,137,185; or copolymers of ethylene 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 4,149,984.
[0068] The preferred hydrocarbon polymers are ethylene copolymers containing from 15 to
90 wt. % ethylene, preferably 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, more preferably C₃
to C₈, alpha-olefins. While not essential, 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-olefins
suitable in place of propylene to form the copolymer, or to be used in combination
with ethylene and propylene, to form a terpolymer, tetrapolymer, etc. , include 1-butene,
1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc.; also branched
chain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene, 4-methylpentene-1,
4,4-dimethyl-1-pentene, and 6-methylheptene-1, etc., and mixtures thereof.
[0069] Terpolymers, tetrapolymers, etc., of ethylene, said C₃-C₂₈ alpha-olefin, and a non-conjugated
diolefin or mixtures of such diolefins may also be used. The amount of the non-conjugated
diolefin generally ranges from about 0.5 to 20 mole percent, preferably from about
1 to about 7 mole percent, based on the total amount of ethylene and alpha-olefin
present.
[0070] The polyester V.I. improvers are generally polymers of esters of ethylenically unsaturated
C₃ to C₈ mono- and dicarboxylic acids such as methacrylic and acrylic acids, maleic
acid, maleic anhydride, fumaric acid, etc.
[0071] Examples of unsaturated esters that may be used include those of aliphatic saturated
mono alcohols of at least 1 carbon atom and preferably of from 12 to 20 carbon atoms,
such as decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl
acrylate, decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetyl methacrylate,
stearyl methacrylate, and the like and mixtures thereof.
[0072] 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 like and mixtures thereof. Copolymers of vinyl
alcohol esters with unsaturated acid esters such as the copolymer of vinyl acetate
with dialkyl fumarates, can also be used.
[0073] The esters may be copolymerized with still other unsaturated monomers such as olefins,
e.g. 0.2 to 5 moles of C₂ - C₂₀ aliphatic or aromatic olefin per mole of unsaturated
ester, or per mole of unsaturated acid or anhydride followed by esterification. For
example, copolymers of styrene with maleic anhydride esterified with alcohols and
amines are known, e.g., see U.S. Patent 3,702,300.
[0074] 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 such as amino substituted olefins as p-(beta-diethylaminoethyl)styrene;
basic nitrogen-containing heterocycles carrying a polymerizable ethylenically unsaturated
substituent, e.g. the vinyl pyridines and the vinyl alkyl pyridines 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 like.
[0075] N-vinyl lactams are also suitable, e.g. N-vinyl pyrrolidones or N-vinyl piperidones.
[0076] The vinyl pyrrolidones are preferred and are exemplified by N-vinyl pyrrolidone,
N-(1-methylvinyl) pyrrolidone, N-vinyl-5-methyl pyrrolidone, N-vinyl-3, 3-dimethylpyrrolidone,
N-vinyl-5-ethyl pyrrolidone, etc.
[0077] Ashless dispersants useful in this invention comprise nitrogen or ester containing
dispersants selected from the group consisting of oil soluble salts, amides, imides,
oxazolines and esters, or mixtures 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, monoolefin, said polymer having
a number average molecular weight of from about 700 to 5000.
[0078] 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 about 0.8 to 2.0, preferably from
about 1.0 to 1.6, e.g., 1.1 to 1.3 moles, per mole of polyolefin, of an alpha or beta-
unsaturated C₄ to C₁₀ dicarboxylic acid, or anhydride or ester thereof. Exemplary
of such mono- and 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.
[0079] Preferred olefin polymers for reaction with the unsaturated dicarboxylic acids to
form the dispersants are polymers comprising a major molar amount of C₂ to C₁₀, e.g.
C₂ to C₅ monoolefin. Such olefins include ethylene, propylene, butylene, isobutylene,
pentene, octene-1, styrene, etc. The polymers can be homopolymers such as polyisobutylene,
as well as copolymers of two or more of such olefins such as copolymers of: ethylene
and propylene; butylene and isobutylene; propylene and isobutylene; etc. Other copolymers
include 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.
[0080] In some 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.
[0081] The olefin polymers used in the dispersants will usually 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 polymers have number average molecular
weights within the range of about 900 and about 2500 with approximately one terminal
double bond per polymer chain. An especially useful starting material for highly potent
dispersant additives is polyisobutylene. The number average molecular weight for such
polymers can be determined by 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.
[0082] Processes for reacting the olefin 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 olefin 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 passing 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 250°C, usually about 180° to 235°C, for about 0.5 to 10, e.g.
3 to 8 hours, so the product obtained will contain the desired number of moles of
the unsaturated acid per mole of the halogenated polymer. Processes of this general
type are taught in U.S. Patents 3,087,436; 3,172,892; 3,272,746 and others.
[0083] 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 disclosed
in U.S. Patents 3,215,707; 3,231,587; 3,912,764; 4,110,349; 4,234,435; and in U.K.
1,440,219.
[0084] By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g. polyisobutylene
will normally react with the dicarboxylic acid material. Upon carrying out a thermal
reaction without the use of halogen or a catalyst, then usually only about 50 to 75
wt. % of the polyisobutylene will react. Chlorination helps increase the reactivity.
For convenience, the aforesaid functionality ratios of dicarboxylic acid producing
units to polyolefin, e.g., 0.8 to 2.0 , etc. are based upon the total amount of polyolefin,
that is, the total of both the reacted and unreacted polyolefin, used to make the
product.
[0085] The dicarboxylic acid producing materials can also be further reacted with amines,
alcohols, including polyols, amino-alcohols, etc., to form other useful dispersant
additives. Thus, if the acid producing material is to be further reacted, e.g., neutralized,
then generally a major proportion of at least 50 percent of the acid units up to all
the acid units will be reacted.
[0086] Amine compounds useful as nucleophilic reactants for neutralization of the hydrocarbyl
substituted dicarboxylic acid materials include mono- and (preferably) polyamines,
most preferably polyalkylene polyamines, of about 2 to 60, preferably 2 to 40 (e.g.
3 to 20), total carbon atoms and about 1 to 12, preferably 3 to 12, and most preferably
3 to 9 nitrogen atoms in the molecule. These amines may be hydrocarbyl amines or may
be hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy groups,
amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to
6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful. Preferred
amines are aliphatic saturated amines, including those of the general formulas:

wherein R, R′, R˝ and R‴ are independently selected from the group consisting of
hydrogen; C₁ to C₂₅ straight or branched chain alkyl radicals; C₁ to C₁₂ alkoxy C₂
to C₆ alkylene radicals; C₂ to C₁₂ hydroxy amino alkylene radicals; and C₁ to C₁₂
alkylamino C₂ to C₆ alkylene radicals; and wherein R‴ can additionally comprise a
moiety of the formula:

wherein R′ is as defined above, and wherein s and s′ can be the same or a different
number of from 2 to 6, preferably 2 to 4; and t and t′ can be the same or different
and are numbers of from 0 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 facile
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 III and IV with typically at least
one primary or secondary amine group, preferably at least two primary or secondary
amine groups. 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 IV be at least one when R‴ is
H or when the V moiety possesses a secondary amino group. The most preferred amine
of the above formulas are represented by Formula IV and contain at least two primary
amine groups and at least one, and preferably at least three, secondary amine groups.
[0087] Non-limiting examples of suitable amine compounds include: 1,2-diaminoethane; 1,3-diaminopropane;
1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene triamine;
triethylene tetramine; tetraethylene pentamine; polypropylene amines such as 1,2-propylene
diamine; di-(1,2-propylene)triamine; di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diaminopropane;
N,N-di-(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine;
3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane
(THAM); diisopropanol amine: diethanol amine; triethanol amine; mono-, di-, and tri-tallow
amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.
[0088] Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl)
cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl
piperazines of the general formula (Va):

wherein p₁ and p₂ are the same or different and are each integers of from 1 to 4,
and n₁, n₂ and n₃ are the same or different and are each integers of from 1 to 3.
Non-limiting examples of such amines include 2-pentadecyl imidazoline: N-(2-aminoethyl)
piperazine; etc.
[0089] 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 compounds as diethylene triamine, triethylenetetramine, tetraethylene
pentamine and isomeric piperazines. Low cost poly(ethyleneamines) compounds averaging
about 5 to 7 nitrogen atoms per molecule are available commercially under trade names
such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.
[0090] Useful amines also include polyoxyalkylene polyamines such as those of the formulae:
NH₂―alkylene O-alkylene NH₂ (VI)
where m has a value of about 3 to 70 and preferably 10 to 35; and

where "n" has a value of about 1 to 40 with the provision 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 (VI) or (VII) may be straight
or branched chains containing about 2 to 7, and preferably about 2 to 4 carbon atoms.
[0091] The polyoxyalkylene polyamines of formulas (VI) or (VII) 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
polyoxyalkylene 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 name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.
[0092] The amine is 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. 1 to 6 hours until the desired amount of water is removed. The heating is
preferably carried out to favor formation of imides or mixtures of imides and amides,
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 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.
[0093] 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 (incorporated herein by reference
thereto). 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 (HBO₂)₃), is believed to attach to the
dispersant imides and diimides as amine salts e.g. the metaborate salt of said diimide.
[0094] Treating is readily carried out by adding from about 0.05 to 4, e.g. 1 to 3 wt. %
(based on the weight of said acyl nitrogen compound) of said boron compound, preferably
boric acid which is most usually added as a slurry to said acyl nitrogen compound
and heating with stirring at from about 135°C. to 190, e.g. 140-170°C., for from 1
to 5 hours followed by nitrogen stripping at said temperature ranges. Or, the boron
treatment can be carried out by adding boric acid to the hot reaction mixture of the
dicarboxylic acid material and amine while removing water.
[0095] The tris(hydroxymethyl) amino methane (THAM) 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.
[0096] The ashless dispersants may also be esters derived from the aforesaid long chain
hydrocarbon substituted dicarboxylic acid material and from hydroxy compounds such
as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols,
etc. The polyhydric alcohols are the most preferred hydroxy compound and preferably
contain from 2 to about 10 hydroxy radicals, for example, ethylene glycol, diethylene
glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and other alkylene
glycols in which the alkylene radical contains from 2 to about 8 carbon atoms. Other
useful polyhydric alcohols include glycerol, mono-oleate of glycerol, monostearate
of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, and
mixtures thereof.
[0097] The ester dispersant may also be derived from unsaturated alcohols such as allyl
alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexane-3-ol, and oleyl alcohol.
Still other classes of the alcohols capable of 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.
[0098] 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.
[0099] 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.
[0100] Hydroxyamines which can be reacted with the aforesaid long chain hydrocarbon substituted
dicarboxylic acid materials to form dispersants include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol,
p-(beta-hydroxy-ethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-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, and compounds of mixed amine and hydroxy containing reactive
functional groups, i.e., amino-alcohols.
[0101] A preferred group of ashless dispersants are those derived from polyisobutylene substituted
with succinic anhydride groups and reacted with polyethylene amines, e.g. tetraethylene
pentamine, pentaethylene hexamine, polyoxyethylene and polyoxypropylene 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 polyamine, e.g. polyethylene diamine
and tetraethylene pentamine using about 0.3 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 of (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 trismethylolaminomethane as described in U.S. Patent
3,632,511.
[0102] The antioxidants useful in this invention include oil soluble copper compounds. The
copper may be blended into the oil as any suitable oil soluble copper compound. By
oil soluble we mean the compound is oil soluble under normal blending conditions in
the oil or additive package. The copper compound 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 compounds 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 synthetic or natural carboxylic acid. Examples include
C₁₀ to C₁₈ fatty acids such as stearic or palmitic, but unsaturated acids such as
oleic or branched carboxylic acids such as napthenic acids of molecular weight from
200 to 500 or synthetic carboxylic acids are preferred because of the improved handling
and solubility properties of the resulting 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 the same or different hydrocarbyl radicals
containing from 1 to 18 and preferably 2 to 12 carbon atoms and including radicals
such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly
preferred as R and R′ groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals
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,
butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc. In order to obtain
oil solubility, the total number of carbon atoms (i.e, R and R′) will generally be
about 5 or greater. Copper sulphonates, phenates, and acetylacetonates may also be
used.
[0103] Exemplary of useful copper compounds are copper (Cu
I and/or Cu
II) salts of alkenyl succinic acids or anhydrides. The salts themselves may be basic,
neutral or acidic. They may be formed by reacting (a) any of the materials discussed
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 basic copper carbonate.
[0104] 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 its divalent form, e.g., Cu⁺². The
preferred substrates are polyalkenyl succinic acids in which the alkenyl group has
a number average molecular weight (M
n) greater than about 700. The alkenyl group desirably has a M
n from about 900 to 1400, and up to 2500, with a M
n of about 950 being most preferred. Especially preferred, of those listed above in
the section on Dispersants, is polyisobutylene succinic acid (PIBSA). These materials
may desirably be dissolved in a solvent, such as a mineral oil, and heated in the
presence of a water solution (or slurry) of the metal bearing material. Heating may
take place between 70° and about 200°C. Temperatures of 110° to 140°C are entirely
adequate. It may be necessary, depending upon the salt produced, not to allow the
reaction to remain at a temperature above about 140°C for an extended period of time,
e.g., longer than 5 hours, or decomposition of the salt may occur.
[0105] The copper antioxidants (e.g., Cu-PIBSA, 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 composition.
[0106] The copper antioxidants used in this invention are inexpensive and are effective
at low concentrations and therefore do not add substantially to the cost of the product.
The results obtained are frequently better than those obtained with previously used
antioxidants, which are expensive and used in higher concentrations. In the amounts
employed, the copper compounds do not interfere with the performance of other components
of the lubricating composition, in many instances, completely satisfactory results
are obtained when the copper compound is the sole antioxidant in addition to the ZDDP.
The copper compounds can be utilized to replace part or all of the need for supplementary
antioxidants. Thus, for particularly severe conditions it may be desirable to include
a supplementary, conventional antioxidant. However, the amounts of supplementary antioxidant
required are small, far less than the amount required in the absence of the copper
compound.
[0107] While any effective amount of the copper antioxidant can be incorporated into the
lubricating oil composition, it is contemplated that such effective amounts be sufficient
to provide said lube oil composition with an amount of the copper antioxidant of from
about 5 to 500 (more preferably 10 to 200, still more preferably 10 to 180, and most
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 quality of the basestock lubricating oil.
[0108] Corrosion inhibitors, also known as anti-corrosive agents, reduce the degradation
of the metallic parts contacted by the lubricating oil composition. Illustrative of
corrosion inhibitors are phosphosulfurized hydrocarbons and the products obtained
by reaction of a phosphosulfurized hydrocarbon with an alkaline earth metal oxide
or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol
thioester, and also preferably in the presence of carbon dioxide. Phosphosulfurized
hydrocarbons are prepared by reacting a suitable hydrocarbon such as a terpene, a
heavy petroleum fraction of a C₂ to C₆ olefin polymer such as polyisobutylene, with
from 5 to 30 weight percent of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature
in the range of 150° to 600°F. Neutralization of the phosphosulfurized hydrocarbon
may be effected in the manner taught in U.S. Patent No. 1,969,324.
[0109] Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service
which deterioration can be evidenced by the products of oxidation such as sludge and
varnish-like deposits on the metal surfaces and by viscosity growth. Such oxidation
inhibitors include alkaline earth metal salts of alkylphenolthioesters having preferably
C₅ to C₁₂ alkyl side chains, calcium nonylphenol sulfide, barium t-octylphenyl sulfide,
dioctylphenylamine, phenylalphanaphthylamine, phosphosulfurized or sulfurized hydrocarbons,
etc.
[0110] Friction modifiers serve to impart the proper friction characteristics to lubricating
oil compositions such as automatic transmission fluids.
[0111] Representative examples of suitable friction modifiers are found in U.S. Patent No.
3,933,659 which discloses fatty acid esters and amides; U.S. Patent No. 4,176,074
which describes molybdenum complexes of polyisobutenyl succinic anhydride-amino alkanols;
U.S. Patent No. 4,105,571 which discloses glycerol esters of dimerized fatty acids;
U.S. Patent No. 3,779,928 which discloses alkane phosphonic acid salts; U.S. Patent
No. 3,778,375 which discloses reaction products of a phosphonate with an oleamide;
U.S. Patent No. 3,852,205 which discloses S-carboxy-alkylene hydrocarbyl succinimide,
S-carboxy-alkylene hydrocarbyl succinamic acid and mixtures thereof; U.S. Patent
No. 3,879,306 which discloses N-(hydroxy-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 disclosures of the
above references are herein incorporated by reference. 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.
[0112] 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.
[0113] Foam control can be provided by an antifoamant of the polysiloxane type, e.g. silicone
oil and polydimethyl siloxane.
[0114] 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 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 number 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.
[0115] The preferred rust inhibitors are polyoxyalkylene polyols and derivatives thereof.
This class of materials are commercially available from various sources: Pluronic
Polyols from Wyandotte Chemicals Corporation; Polyglycol 112-2, a liquid triol derived
from ethylene oxide and propylene oxide available from Dow Chemical Co.; and 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.
[0116] 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, stearic
acid, succinic acid, and alkyl- or alkenyl-substituted succinic acids wherein the
alkyl- or alkenyl group contains up to about twenty carbon atoms.
[0117] 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- or 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 obvious to those skilled in the art. Thus it is within the
skill of the art to prepare polyols 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.
[0118] If more oil-solubility is needed in a given lubricating composition, the hydrophobic
portion can be increased and/or the hydrophylic portion decreased. If greater oil-in-water
emulsion breaking ability is required, the hydrophylic and/or hydrophobic portions
can be adjusted to accomplish this.
[0119] Compounds illustrative of R-(OH)n include alkylene polyols such as the alkylene glycols,
alkylene triols, alkylene tetrols, etc., such as 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.,
heptylphenol, dodecylphenol, etc.
[0120] Other suitable demulsifiers include the esters disclosed in U.S. Patents 3,098,827
and 2,674,619.
[0121] The liquid polyols available from Wyandotte Chemical Co. under the name Pluronic
Polyols and other similar polyols are particularly well suited as rust inhibitors.
These Pluronic Polyols correspond to the formula:

wherein x,y, and z are integers greater than 1 such that the -CH₂CH₂O- groups comprise
from about 10% to about 40% by weight of the total molecular weight of the glycol,
the average 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

This condensation product is then treated with ethylene oxide to add hydrophylic
portions to both ends of the molecule. For best results, the ethylene oxide units
should comprise from about 10 to about 40% by weight of the molecule. Those products
wherein the molecular weight of the polyol is from about 2500 to 4500 and the ethylene
oxide units comprise from about 10% to about 15% by weight of the molecule are particularly
suitable. The polyols having a molecular weight of about 4000 with about 10% attributable
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 C₉ to C₁₆ 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, which is also hereby incorporated by reference in its entirety.
[0122] These compositions of our invention may also contain other additives such as those
previously described, and other metal containing additives, for example, those containing
barium and sodium.
[0123] The lubricating composition of the present invention may also include copper lead
bearing corrosion inhibitors. Typically such compounds are the thiadiazole polysulphides
containing from 5 to 50 carbon atoms, their derivatives and polymers thereof. Preferred
materials are the derivatives of 1,3,4 thiadiazoles such as those described in U.S.
Patents 2,719,125; 2,719,126; and 3,087,932; especially preferred is the compound
2,5 bis (t-octadithio)-1,3,4 thiadiazole commercially available as Amoco 150. Other
similar materials also suitable are described in U.S. Patents 3,821,;236; 3,904,537;
4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882.
[0124] Other suitable additives are the thio and polythio sulphenamides of thiadiazoles
such as those described in U.K. Patent Specification 1,560,830. When these compounds
are included in the lubricating composition, 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.
[0125] Some of these numerous additives can provide a multiplicity of effects, e.g., a dispersant-oxidation
inhibitor. This approach is well known and need not be further elaborated herein.
[0126] Compositions when containing these conventional additives are typically blended into
the base oil in amounts effective 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:
Compositions |
Wt.% A.I. (Preferred) |
Wt.% A.I. (Broad) |
Total Component A(1) + A(2) Detergents |
0.7-0.9 |
0.7-0.9 |
Component B Antiwear Agents |
0.8-1.1 |
0.7-1.2 |
Viscosity Modifier |
0.01-4 |
0.01-12 |
Corrosion Inhibitor |
0.01-1.5 |
.01-5 |
Oxidation Inhibitor |
0.01-1.5 |
.01-5 |
Dispersant |
0.1-8 |
.1-20 |
Pour Point Depressant |
0.01-1.5 |
.01-5 |
Anti-Foaming Agents |
0.001-0.15 |
.001-3 |
Friction Modifiers |
0.01-1.5 |
.01-5 |
Mineral Oil Base |
Balance |
Balance |
[0127] When other additives are employed, it may be desirable, although not necessary, to
prepare additive concentrates comprising concentrated solutions or dispersions 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 lubricating oil may be facilitated by solvents and by mixing accompanied
with mild heating, but this is not essential. The concentrate or additive-package
will typically be formulated to contain the additives in proper amounts to provide
the desired concentration in the final formulation when the additive-package is combined
with a predetermined amount of base lubricant. Thus, the detergent inhibitor/antiwear
agent mixtures of the present invention can be added to small amounts of base oil
or other compatible solvents along with other desirable additives to form additive-packages
containing active ingredients in collective amounts of typically from about 2.5 to
about 90%, and preferably from about 15 to about 75%, and most preferably from about
25 to about 60% by weight additives in the appropriate proportions with the remainder
being base oil.
[0128] The final formulations may employ typically about 10 wt. % of the additive-package
with the remainder being base oil.
[0129] All of said weight percents expressed herein (unless otherwise indicated) are based
on active ingredient (A.I.) content of the additive, and/or upon the total weight
of any additive-package, or formulation which will be the sum of the A.I. weight of
each additive plus the weight of total oil or diluent.
[0130] This invention will be further understood by reference to the following examples,
wherein all parts are parts by weight, unless otherwise noted and which include preferred
embodiments of the invention.
EXAMPLES
[0131] A series of fully formulated lubricating oils were prepared containing the selected
detergent inhibitors, zinc dialkyl dithiophosphate anti-wear agents, ashless dispersants,
anti-oxidants and fuel economy additives. The data thereby obtained are summarized
in Table I below.

[0132] The data in Table I show that the improved lubricating formulation of this invention
provide decreased cam wear without reduction in camnose merits as compared to the
control, and that superior rocker pad demerits results can also be achieved.
EXAMPLE 7; COMPARATIVE B
[0133] An additional series of formulations were prepared and employed as lubricating oils
in water-cooled, gasoline-fueled test automobiles having engines without thermostats.
The data thereby obtained are summarized in Table II below.
[0134] It was surprisingly found that the oil of Example 7 provided much lower cylinder
wear and lower lifter wear than the oil of Comparative B, even though the oil drain
intervals and the test length for the oil of Example 7 was much longer.

[0135] The principles, preferred embodiments, and modes of operation of the present invention
have been described in the foregoing specification. The invention which is intended
to be protected herein, however, is not to be construed as limited to the particular
forms disclosed, since these are to be regarding as illustrative rather than restrictive.
Variations and changes made be made by those skilled in the art without departing
from the spirit of the invention.