Note: Descriptions are shown in the official language in which they were submitted.
~ 2~8~7~8
2579B
.~
TITLE: IMPROVED LUBRICATING COMPOSITIONS AND
ADDITIVES USEFUL THEREIN
; FIELD OF THE INVENTION
This invention relates to compositions useful as
additives for lubricants and functional fluids, and to
additive concentrates, lubricants and functional fluids
containing said additives. More particularly, this
invention relates to compositions comprising a major
amount of an oil of lubricating viscosity, (A) a metal
salt selected from the group consisting of sulfonates,
phenates, carboxylates and mixtures thereof, (B) an
~ aliphatic carboxylic acid or anhydride, or carboxylic
i acid containing derivative thereof, wherein the aliphatic
group contains at least about 20 carbon atoms and
optionally (C) a metal salt of (C)(I) at least one
organic phosphorus acid or a mixture of (C)(I) at least
, one organic phosphorus acid and (C)(II) at least one
carboxylic acid. Also disclosed are lubricants and
functional fluids containing these additives and methods
; for improving the wet filterability of lubricants and
functional fluids. This invention also relates to the
retention of zinc when compositions containing
, zinc-containing additives are exposed to water.
BACKGROUND OF THE INVENTION
Depending upon their intended use, lubricants are
required to meet a variety of performance requirements.
It is known in the art to add various chemical additives
,
,- ~
- 2 - 2 08 ~768
to a lubricating oil basestock in order to provide or
reinforce needed properties.
For very mild applications, the lubricant may
contain nothing more than the lubricating base stock,
although even in this case, additives such as oxidation
and corrosion inhibitors and antifoam agents are often
included.
More often, especially when lubricating machinery
such as engines, gears, transmissions, hydraulic systems
and the like, it is necessary that the lubricant provides
some degree of antiwear and extreme pressure performance.
Chemical additives to provide extreme pressure and
antiwear performance are known. These include, but are
not limited to, phosphorus-containing additives,
sulfur-containing additives and others. Phosphorus
:"~
;,additives include metal-free and metal-containing
,i
-~derivatives of phosphorus acids.
Adams et al, U.S. 4,938,884, describes
phosphorus-containing coupled amides as lubricating oil
' additives.
!Hoke (U.S. Patents 4,032,461; 4,208,357; and
`~4,282,171, refers to various phosphorus and
,sulfur-containing amides and thioamides.
iMetal salts of phosphorodithioic acids are known
lubricant additives. See, for example, Le Suer et al,
U.S. 3,390,082 and Chamberlin, U.S. 4,326,974.
Metals salts of mixtures of carboxylic and
3phosphorus acids are also known, as are post-treated
metal salts of phosphorus acids. See, for example,
Clason et al, U.S. 4,308,154, Schroeck, U.S. 4,289,635,
Schroeck, U.S. 4,507,215 and Schroeck, U.S. 4,263,150.
?Metals salts of organic acids, and particularly
-~overbased metal salts of organic acids are also
well-known lubricating oil additives.
Grover, in U.S. 4,466,894, describes lubricants
having, inter alia, improved hydrolytic stability.
','
,
. . -~
"
,.
`:
;- _ 3 _ 2Q~768
For many applications, lubricating oils described in
the aforementioned patents provide exemplary performance.
However, in several applications, it has been found to be
desirable, and sometimes necessary, that the lubricant
possess even further enhanced performance
characteristics.
Many lubricating oil compositions such as functional
fluids, and especially hydraulic fluids, are used in
equipment designed to very close tolerances. For
example, a hydraulic fluid which is employed as the
lubricant and power transmitting fluid in hydraulic pumps
must provide extreme pressure, antiwear and oxidation
performance. Because of the close operating tolerances,
~ it is usually necessary that hydraulic fluids be kept
; meticulously clean. To accomplish this end, very fine
filters are employed to remove solid contaminants from
the circulating hydraulic fluid. The filter must remove
abrasive contaminants, but still must allow free fluid
' flow through the system.
; It has been recently observed that lubricating oil
compositions, including hydraulic fluids, containing
metal salts of organic acids, and particularly those
containing overbased metal salts, when exposed to mois-
ture, may clog filters. Such moisture may arise from,
for example, environmental contamination or condensation
of atmospheric moisture. When the filters become
clogged, fluid flow is reduced, or in extreme cases,
essentially stops. Filterability of moisture (water)
containing lubricating compositions is referred to herein
~ as wet filterability.
j The nature of the moisture-contaminated lubricating
oil is not understood, that is, it is not known with
` certainty whether, for example, the moisture (water) is
; simply dispersed within the oil composition, whether a
chemical reaction has taken place or if the moisture is
s incorporated in some other fashion. What is known is
that when the oil composition is contaminated with
',`~ . :
,-............... . . . ......................... ...
. ,~ ~ . .
; ~ _ 4 _ 208~768
:;:
moisture, filterability, especially filterability through
fine filters, is impaired.
In general, moisture contamination contributing to
filterability difficulties is present in the oil composi-
tion in amounts ranging up to about 1% by weight of the
oil composition, although more than 1% by weight of water
may be present as a contaminant and may contribute to
filterability difficulties.
It has also been observed with zinc-containing
-,lubricating oil compositions that, when the oil composi-
tion is exposed to water, loss of zinc from the lubri-
'cating oil composition may take place. In some cases as
much as 50~ or even more of the zinc originally present
may be lost. since zinc compounds are frequently used to
provide enhanced antiwear and/or antioxidancy, loss of
zinc may result in reduced performance.
lAccordingly, it would be beneficial to provide a
;'lubricant or functional fluid that does not tend to
-generate materials that clog filters when the fluid is
~iexposed to moisture. Likewise, it would be beneficial if
a zinc-containing lubricating oil composition resisted
,loss of zinc when the oil is exposed to water.
SUMMARY OF THE INVENTION
The present invention provides compositions useful
as additives for lubricants and additive concentrates and
lubricants containing these additives. Lubricants and
,functional fluids containing these additives have a
reduced tendency to clog filters when the lubricants are
`exposed to moisture and resist depletion of zinc when
exposed to water.
` The present invention provides a composition com-
prising a major amount of an oil of lubricating viscos-
ity, and minor amounts of (A) a metal salt selected from
the group consisting of sulfonates, phenates, carbox-
ylates and mixtures thereof, (B) an aliphatic carboxylic
acid or anhydride, or carboxylic-acid group containing
'.
`
,.~
.~,, . . ~ , .
,. ~
~.
. ~
:, :
.
f 5 20~7S~
derivative thereof, wherein the aliphatic group contains
at least about 20 carbon atoms and optionally (C) a metal
salt of (C)(I) at least one organic phosphorus acid or
mixture of (C)(I) at least one organic phosphorus acid
and (C)(II) at least one carboxylic acid. Component (B)
is present in an effective amount to improve wet filter-
ability of the composition. In another embodiment, the
composition may comprise a phosphite. These compositions
are useful as lubricating compositions, and functional
fluids, such as hydraulic fluids.
Further, the present invention provides a method for
improving the wet filterability of lubricants and func-
tional fluid compositions. Also provided is a method for
imparting to lubricating oil compositions the ability to
resist depletion of zinc when the compositions are
exposed to water.
.:,
,~
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The term "hydrocarbon based group" is used
throughout this specification and in the appended claims
to denote a group having a carbon atom directly attached
to the remainder of the molecule and having a
predominantly hydrocarbon character within the context of
this invention. Thus, the term "hydrocarbon based group"
includes hydrocarbon, as well as substantially
hydrocarbon, groups. Substantially hydrocarbon describes
groups may contain non-hydrocarbon substituents, or
non-carbon atoms in a ring or chain, which do not alter
the predominantly hydrocarbon nature of the group.
Hydrocarbon based groups can contain up to three,
preferably up to one, non-hydrocarbon substituent, or
non-carbon heteroatom in a ring or chain, for every ten
carbon atoms, provided this non-hydrocarbon substituent
or non-carbon heteroatom does not significantly alter the
predominantly hydrocarbon character of the group.
Preferably, hydrocarbon-based groups are purely
hydrocarbon, that is, they are substantially free of
.~ .
. .
, ... ... , , , , ~
." .~ .
.
.
- .: ,
. . .
i ~ - 6 - 2088768
non-hydrocarbon substituents or heteroatoms. Those
.
skilled in the art will be aware of such heteroatoms,
such as oxygen, sulfur and nitrogen, or substituents,
which include, for examplej hydroxyl, halo (especially
chloro and fluoro), alkoxyl, alkyl mercapto, alkyl
sulfoxy, etc.
Examples of hydrocarbon based groups include, but
are not necessarily limited to, the following:
(1) hydrocarbon groups, that is, aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl,
cycloalkenyl) groups, aromatic-, aliphatic- and
alicyclic-substituted aromatic groups and the like as
well as cyclic groups wherein the ring is completed
through another portion of the molecule (that is, for
example, any two indicated substituents may together form
an alicyclic radical);
(2) substituted hydrocarbon groups, that is, those
groups containing non-hydrocarbon groups or atoms which,
in the context of this invention, do not alter the
predominantly hydrocarbon character of the group; those
skilled in the art will be aware of such groups (e.g.,
halo (especially chloro and fluoro), hydroxy, alkoxy,
mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.);
(3) hetero groups, that is, groups which will,
while havi~g a predominantly hydrocarbon character within
the context of this invention, contain atoms other than
carbon present in a ring or chain otherwise composed of
carbon atoms. Suitable heteroatoms will be apparent to
those of ordinary skill in the art and include, for
example, sulfur, oxygen, nitrogen and such substituents
as, e.g., pyridyl, furyl, thienyl, imidazolyl, etc. In
general, no more than about 2, preferably no more than
one, non-hydrocarbon substituent or non-carbon atom in a
ring moiety, will be present for every ten carbon atoms
in the hydrocarbyl group. More preferred, however, the
hydrocarbyl groups are purely hydrocarbon and contain
!'
::
~. '
'`'~, . .
,
., ~
.
7 203 87 ~g
substantially no such non-hydrocarbon groups or
substituents.
(A) The Metal Sulfonate. Phenate or Carboxylate
Component (A) is a metal salt selected from the
group consisting of sulfonates, phenates or carboxylates.
These salts may be normal salts or they may be overbased
salts. Overbased salts are preferred.
The metals may be alkali or alkaline earth metals,
copper or zinc. In a preferred embodiment the metals are
alkali or alkaline earth metals, more preferably, sodium,
potassium, calcium or magnesium.
The Normal Metal Salt
Component (A) may be a normal metal salt, that is, a
salt wherein the metal content is substantially that
which is present according to the stoichiometry of the
metal and the particular organic compound reacted with
the metal. These salts are sometimes referred to as
"neutral" salts despite the fact that, depending upon the
nature of the anion and cation, the salt may display
basic properties, i.e., may display basic character as
opposed to neutral or acidic character, especially in
aqueous media. For the purposes of this invention, metal
salts of sulfonic acids, phenols and carboxylic acids are
preferred. Preferred metals are alkali or alkaline earth
metals, copper or zinc. Normal metal salts are readily
prepared by the reaction of an acid with a metal compound
such as a hydroxide or carbonate, double displacement
reactions, such as the reaction of a sodium salt with
calcium chloride, etc. The skilled worker is aware of
numerous means for preparing normal metal salts, and
further elaboration here is unnecessary.
The Overbased Metal Salt
The terms "overbased," "superbased," and
"hyperbased," are terms of art which are generic to
well-known classes of metal-containing materials which
have generally been employed as detergents and/or
dispersants in lubricating oil compositions. Overbased
.
"
, ~ , . . .
i~ ' ,
.'', . ~ , ~ ~ -
~ 8 20~768
; -.
materials are characterized by a metal content in excess
of that which would be present according to the
....
stoichiometry of the metal and the particular organic
compound reacted with the metal, e.g., a carboxylic or
.-,
~ sulfonic acid or phenol. Thus, if a monocarboxylic acid,
,,
~ ~ O
:, ~
~ R C OH
.,~ . .
s iS neutrallzed with a baslc metal compound, e.g., calcium
. hydroxide, the "normal" metal salt produced will contain
one equivalent of calcium for each equivalent of acid,
i.e.,
. "
.,
,~, O O
.,~ 11 11
i; R -- C - O - Ca - O -_ C- _ R
.
However, as is well known in the art, various processes
are are available which result in an inert organic liquid
solution of a product containing more than the
stoichiometric amount of metal. The solutions of these
products are referred to herein as overbased materials.
Following these procedures, the carboxylic acid or an
alkali or alkaline earth metal salt thereof can be
. ~
reacted with a metal base and the product will contain an
amount of metal in excess of that necessary to neutralize
the acid, for example, 4~5 times as much metal as present
in the normal salt or a metal excess of 3.5 equivalents.
The actual stoichiometric excess of metal can vary
: considerably, for example, from about O.1 equivalent to
'J about 50 or more equivalents depending on the reactions,
- the process conditions, and the like. The overbased
i materials useful in accordance with the present invention
contain from about 1.1 to about 40 or more equivalents of
metal, more preferably from about 1.5 to about 30 and
most preferably from about 2 to about 25 equivalents of
metal for each equivalent of m-terial which is overbased.
, :~
:;.,
:................ .
..;.
:, .
.s~
. :
.
:` - 9 - 208~7~8
.,
In the present specification and claims the term
"overbased" is used to designate materials containing a
stoichiometric excess of metal and is, therefore,
inclusive of those materials which have been referred to
in the art as overbased, superbased, hyperbased, etc., as
discussed supra, and hereinbelow.
It is recognized herein that in many chemical
reactions, slightly more or sl,gh~ly iess of a component
may be incorporated into the resulting product. In the
present case, it is recognized that very small amounts of
excess metal may be incorporated into what is otherwise a
substantially neutral product. For the purposes of this
invention, such products are not considered "overbased".
The terminology "metal ratio" is used in the prior
art and herein to designate the ratio of the total
chemical equivalents of the metal in the overbased
material (e.g., a metal sulfonate or carboxylate) to the
chemical equivalents of the metal in the product which
would be expected to result in the reaction between the
organic material to be overbased (e.g., sulfonic or
carboxylic acid) and the metal-containing reactant (e.g.,
calcium hydroxide, barium oxide, etc.) according to the
known chemical reactivity and stoichiometry of the two
reactants.
The equivalent weight of the acidic organic compound
iæ its molecular weight divided by the number of acidic
groups (i.e., sulfonic acid, carboxy or acidic hydroxy
groups) present per molecule. In many cases the acidic
organic compound contains a diluent such as oil or
unreacted alkylate. Often the acidic organic compound is
not a pure single species. In these and in other
situations as appropriate, the eguivalent weight of the
acidic organic compound can be determined by a suitable
analytical technique such as acid number (e.g. ASTM
procedures D-664 and/or D-974). Thus, in the normal
calcium carboxylate discussed above, the metal ratio is
one, and in the overbased carboxylate, the metal ratio
.,
~ .
~' .
? : . : : . : -
~': ~ ' . ~ ' ,'. ',
`' "-.' ' ' ~ .'
' ~ '
.
O- 208~7~
may be 4.5. Obviously, if there is present in the
material to be overbased more than one compound capable
of reacting with the metal, the "metal ratio" of the
product will depend upon whether the number of
equivalents of metal in the overbased product is compared
to the number of equivalents expected to be present for a
given single component or a combination of all such
components.
The metal ratio may be expressed in terms of
percentages. For a normal metal salt, the percentage is
100%; for overbased materials, the percentage is greater
than 100. For the overbased calcium carboxylate example
above, the percentage is 450.
Generally, overbased materials are prepared by
treating a reaction mixture comprising the organic
material to be overbased, a reaction medium consisting
essentially of at least one inert, organic solvent for
said organic material, a stoichiometric excess of a metal
base, and a promoter with an acidic material. Methods
for preparing the overbased materials for use in the
present invention, as well as an extremely diverse group
of overbased materials, are well known in the art and are
disclosed for example in the following U.S. Patent Nos.
2,616,904: 2,616,905; 2,616,906, 2,616,911; 2,616,924;
2,616,925; 2,617,049; 2,695,910: 2,723,234; 2,723,235;
2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874;
2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361;
2,861,951; 2,883,340; 2,915,517; 2,959,551; 2,968,642;
2,971,014; 2,989,463; 3,001,981; 3,027,325; 3,070,581;
3,108,960; 3,147,232; 3,133,019; 3,146,201; 3,152,991;
3,155,616; 3,170,880; 3,170,881; 3,172,855; 3,194,823;
3,223,630; 3,232,883; 3,242,079; 3,242,080; 3,250,710;
3,256,186; 3,274,135; 3,492,231; 4,230,586 and 4,466,894.
These patents disclose processes, materials which can be
overbased, suitable metal bases, promoters, and acidic
materials, as well as a variety of specific overbased
,
S
~' ' ' :
20~7~8
products useful in this invention and are, accordingly,
incorporated herein by reference.
An important characteristic of the organic materials
which are overbased is their solubility in the particular
réaction medium utilized in the overbasing process. As
the reaction medium used frequently comprises petroleum
fractions, particularly mineral oils, these organic
materials have generally been oil-soluble. However, if
another reaction medium is employed (e.g., aromatic
hydrocarbons, aliphatic hydrocarbons, kerosene, etc.) it
is not essential that the organic material be soluble in
mineral oil as long as it is soluble in the given
reaction medium. Obviously, many organic materials which
are soluble in mineral oils will be soluble in many of
the other indicated suitable reaction media.
Materials which can be overbased are generally
oil-soluble organic acids including sulfonic acids,
phosphorus acids, thiophosphorus acids, sulfur acids,
alkylphenols, coupled alkylphenols, carboxylic acids,
thiocarboxylic acids, and the like, as well as the
corresponding alkali and alkaline earth metal salts
thereof. Representative examples of each of these
classes of organic acids, as well as other organic acids,
e.g., nitrogen acids, arsenic acids, etc., are disclosed
along with methods of preparing overbased products
therefrom in the above-cited patents and are,
accordingly, incorporated herein by reference. U.S.
Patent No. 2,777,874 identifies organic acids suitable
for preparing overbased materials. Similarly, U.S. Patent
Nos. 2,616,904; 2,695,910; 2,767,164; 2,767,209;
3,147,232; 3,274,135; etc., disclose a variety of organic
acids suitable for preparing overbased materials as well
as representative examples of overbased products prepared
from such acids. Overbased acids wherein the acid is a
phosphorus acid, a thiophosphorus acid, phosphorus
acid-sulfur acid combination, and sulfur acid prepared
from polyolefins are disclosed in U.S. Patent Nos.
~, . . .
" ' , , '
.. . . . ' - .
,; ' ' : '
.~ ~ ' ' .
, .
, . . .
`
- 12 - 2Q~7~8
2,883,340; 2,915,517; 3,001,981; 3,108,960 and 3,232,883.
Overbased phenates are disclosed in U~S. Patent No.
2,959,551, while overbased ketones are found in U.S.
Patent No. 2,798,852. A variety of overbased materials
derived from oil-soluble metal-free, non-tautomeric
neutral and basic organic polar compounds such as ester,
amines, amides, alcohols, ethers, sulfides, sulfoxides,
and the like are disclosed in U.S. Patent Nos. 2,968,642;
2,971,014 and 2,989,463. Another class of materials
which can be overbased are the oil-soluble,
nitro-substituted aliphatic hydrocarbons, particularly
nitro-substituted polyolefins such as polyethylene,
polypropylene, polyisobutylene, etc. Materials of this
type are illustrated in U.S. Patent No. 2,959,551.
Likewise, mixtures of alkylated phenols and the
oil-soluble reaction product of alkylene polyamines such
as propylene diamine or N-alkylated propylene diamine
with formaldehyde or formaldehyde producing compound
(e.g., paraformaldehyde) can be overbased. The process
and products obtained thereby are disclosed in U.S.
3,372,118. Other compounds suitable for overbasing are
disclosed in the above-cited patents or are otherwise
well-known in the art. For the purposes of this
invention, overbased sulfonic acids, phenols and
carboxylic acids are preferred.
The metal compounds used in preparing the overbased
materials are normally the basic salts, oxides and
hydroxides of alkali and alkaline earth metals, although
corresponding metal compounds such as lead, zinc,
manganese, copper, etc., can be used in the preparation
of overbased materials. Mixtures of different metal
compounds can be used to prepare mixed metal overbased
products. The anionic portion of the metal compound can
be hydroxyl, oxide, carbonate, hydrogen carbonate,
acetate, hydrogen sulfite, halide, amide, borate, etc.,
as disclosed in the above-cited patents. For purposes of
this invention the preferred overbased materials are
i, ,
.
., .
.. . .
' : :
' ' ' :
~ 13 - 20~7b8
prepared from alkali and alkaline earth metal oxides,
hydroxides, and alcoholates such as the alkaline earth
metal lower alkoxides. The more preferred metals are
calcium, magnesium, sodium, lithium, and/or barium. The
most preferred alkali metal is sodium, and calcium is the
most preferred alkaline earth metal. As mentioned
hereinabove, mixed metal overbased products are also
useful.
The promoters, that is, the materials which permit
the incorporation of the excess metal into the overbased
material, are also quite diverse and well known in the
art as evidenced by the cited patents. A particularly
comprehensive discussion of suitable promoters is found
in U.S. Patent Nos. 2,777,874; 2,695,910 and 2,616,904.
These include the alcoholic and phenolic promoters which
are preferred. The alcoholic promoters include the
alkanols of one to about eighteen carbon atoms,
preferably one to about twelve carbon atoms, and more
preferably one to about five carbon atoms, such as
methanol, ethanol, n-butanol, amyl alcohol, octanol,
isopropanol, isobutanol, and mixtures of these and the
like. Polyols are also useful promoters. A particularly
preferred polyol is ethylene glycol. Phenolic promoters
include a variety of hydroxy- substituted benzenes and
naphthalenes. A particularly useful class of phenols are
the alkylated phenols of the type listed in U.S. Patent
No. 2,777,874, e.g., heptylphenols, octylphenols, and
nonylphenols. Mixtures of various promoters are
sometimes used.
Suitable acidic materials are also disclosed in the
above-cited patents, for example, U.S. Patent No.
2,616,904. Included within the known group of useful
acidic materials are liquid acids such as formic acid,
acetic acid, nitric acid, sulfuric acid, hydrochloric
acid, hydrobromic acid, carbamic acid, substituted
carbamic acids, etc. Acetic acid is a very useful acidic
material, although inorganic acidic materials such as
,~ ~
. . ,
.
, . .
- 14 - 20~7~
boric acid, HCl, SO2, S03, CO2, H2 ' 2 3'
ordinarily employed as the acidic materials. The most
preferred acidic materials are carbon dioxide and acetic
acid, with carbon dioxide being especially preferred.
When the metal reactant used in the overbasing
process is an oxide or alkoxide, H2O can be used as the
acidic material. Examples include overbasing with MgO or
aluminum isopropoxide.
In preparing overbased materials, the material to be
overbased, an inert, non-polar, organic solvent therefor,
the metal base, the promoter and the acidic material are
brought together and a chemical reaction ensues. The
exact nature of the resulting overbased product is not
known. However, it can be adequately described for
purposes of the present specification as a single phase
homogeneous mixture of the solvent and (1) either a metal
complex formed from the metal base, the acidic material,
and the material being overbased and/or (2) an amorphous
metal salt formed from the reaction of the acidic
material with the metal base and the material which is
said to be overbased. Thus, if mineral oil is used as
the reaction medium, carboxylic acid as the material
which is overbased, Ca(OH)2 as the metal base, and carbon
dioxide as the acidic material, the resulting overbased
material can be described for purposes of this invention
as an oil solution of either a metal-containing complex
of the acidic material, the metal base, and the
carboxylic acid or as an oil solution of amorphous
calcium carbonate and calcium carboxylate.
The temperature at which the acidic material is
contacted with the remainder of the reaction mass depends
to a large measure upon the promoting agent used. With a
phenolic promoter, the temperature usually ranges from
about 80-C to 300-C, and preferably from about 100-C to
about 200-C. When an alcohol or mercaptan is used as the
promoting agent, the temperature usually will not exceed
,
; . -
.:~
., ,
.. . .
" ~:
- 15 - 208~7~
the reflux temperature of the reaction mixture and
preferably will not exceed about 100C.
In view of the foregoing, it should be apparent that
the overbased material~ may retain all or a portion of
the promoter. That is, if the promoter is not volatile
(e.g., an alkyl phenol) or otherwise readily removable
from the overbased material, at least some promoter
remains in the overbased product. The presence or
absence of the promoter in the overbased material does
not represent a critical aspect of the invention.
Obviously, it is within the skill of the art to select a
volatile promoter such as a lower alkanol, e.g.,
methanol, ethanol, etc., so that the promoter can be
readily removed prior to incorporation within the
compositions of the present invention.
One preferred class of overbased materials is the
metal-overbased water-insoluble organic acids, preferably
those containing at least eight aliphatic carbons,
although the acids may contain as few as six aliphatic
carbon atoms if the acid molecule includes an aromatic
ring such as phenyl, naphthyl, etc. Representative
organic acids suitable for preparing these overbased
materials are discussed and identified in detail in the
above-cited patents. In particular, U.S. Patent Nos.
2,616,904 and 2,777,874 disclose a variety of very
suitable organic acids. Overbased carboxylic and
sulfonic acids and phenols are particularly suitable.
Suitable carboxylic acids include aliphatic,
~ .
cycloaliphatic and aromatic mono- and polybasic
carboxylic acids free from acetylenic unsaturation,
including naphthenic acids, alkyl- or alkenyl-substituted
cyclopentanoic acids, alkyl- or alkenyl-substituted
cyclohexanoic acids, and alkyl- or alkenyl-substituted
aromatic carboxylic acids. The aliphatic acids generally
contain from about 8 to about 50, and preferably from
; about 12 to about 25, carbon atoms. The cycloaliphatic
and aliphatic carboxylic acids can be saturated or
' ' .:
: . . '
,
~. - 16 -
2~7~
unsaturated. Specific examples include 2-ethylhexanoic
acid, linolenic acid, propylene tetramer-substituted
maleic acid, behenic acid, isostearic acid, pelargonic
acid, capric acid, palmitoleic acid, linoleic acid,
lauric acid, oleic acid, ricinoleic acid, undecylic acid,
dioctylcyclopentanecarboxylic acid, myristic acid,
dilauryldecahydronaphthalene-carboxylic acid,
stearyl-octahydroindenecarboxylic acid, palmitic acid,
alkyl- and alkenylsuccinic acids, acids formed by
. oxidation of petrolatum or of hydrocarbon waxes, and
commercially available mixtures of two or more carboxylic
.: acids, such as tall oil acids, rosin acids, and the like.
. Other carboxylic acids include propenyl-
substituted glutaric acid, polybutenyl-substituted
succinic acids derived from a polybutene (Mn equals about
i 200-1500, preferably about 300-1500),
propenyl-substituted succinic acids derived from
polypropylenes (Mn equals 200-1000), acids, acids formed
by oxidation of petrolatum or of hydrocarbon waxes,
available mixtures of two or more carboxylic acids and
? mixtures of these acids, their metal salts, and/or their
1 anhydrides.
In one embodiment, the carboxylic acids are aromatic
. carboxylic acids. A group of useful aromatic carboxylic
,~ acids are those of the formula
,
., ~
~ (~-XH)b
(Rl)a -Ar ~
(XH) C
wherein Rl is an aliphatic hydrocarbon based group
preferably derived from polyalkenes, a is a number in the
range of l to about 4, usually l or 2, Ar is an aromatic
group, each X is independently sulfur or oxygen,
preferably oxygen, b is a number in the range of from 1
to about 4, usually l or 2, c is a number in the range of
. , .
.~
,~
:, ' . ~ ' '
.: :
- 17 - 20~7~
zero to about 4, usually 1 to 2, with the proviso that
the sum of a, b and c does not exceed the number of
valences of Ar. Examples of aromatic carboxylic acids
include substituted benzoic, phthalic and salicylic
acids.
The Rl group is a hydrocarbon based group that is
directly bonded to the aromatic group Ar. Examples of Rl
groups include substituents derived from polymerized
; olefins such as polyethylenes, polypropylenes,
polybutylenes, ethylene-propylene copolymers, chlorinated
olefin polymers and oxidized ethylene-propylene
copolymers.
: The aromatic group Ar may have the same structure as
any of the aromatic groups Ar discussed below. Examples
of the aromatic groups that are useful herein include the
polyvalent aromatic groups derived from benzene,
~ naphthalene, anthracene, etc., preferably benzene.
j Specific examples of Ar groups include phenylenes and
naphthylene, e.g., methylphenylenes, ethoxyphenylenes,
isopropylphenylenes, hydroxyphenylenes,
dipropoxynaphthylenes, etc.
Within this group of aromatic acids, a useful class
of carboxylic acids are those of the formula
'
; ~ (COOH)b
(R~
(OH)C
wherein Rl is defined above, a is a number in the range
of from 1 to about 4, preferably 1 to about 3; b is a
number in the range of 1 to about 4, preferably 1 to
about 2, c is a number in the range of zero to about 4,
preferably 1 to about 2, and more preferably 1; with the
proviso that the sum of a, b and c does not exceed 6.
~, . .. .
:
. .
:
' ' ': .
~ . . . .
- 18 - 2 ~3 g7
Preferably, b and c are each one and the carboxylic acid
is a salicylic acid.
Overbased salts prepared from salicylic acids
wherein the aliphatic hydrocarbon based substituents (Rl)
are derived from polyalkenes, particularly polymerized
lower 1-mono-olefins such as polyethylene, polypropylene,
po~yisobutylene, ethylene/propylene copolymers and the
like and having average carbon contents of about 50 to
about 400 carbon atoms are particularly useful.
The above aromatic carboxylic acids are well known
or can be prepared according to procedures known in the
art. Carboxylic acids of the type illustrated by these
formulae and processes for preparing their neutral and
basic metal salts are well known and disclosed, for
example, in U.S. Patents 2,197,832; 2,197,835; 2,252,662;
2,252,664; 2,714,092; 3,410,798; and 3,595,791. These
patents are incorporated by reference for disclosure of
carboxylic acids, their basic salts and processes of
making the same.
Zinc, calcium and magnesium salts of the aromatic
carboxylic acids, and especially the salicylic acids, are
preferred.
The sulfonic acids for use in the preparation of
component (A) include those represented by the formulas
Ra(SO3H)r and (Rb)XT(SO3H)y. In these formulas, Ra is an
aliphatic or aliphatic-substituted cycloaliphatic
hydrocarbon or essentially hydrocarbon radical free from
acetylenic unsaturation and containing up to about 60
carbon atoms. When Ra is aliphatic, it usually contains
at least about 15 carbon atoms; when it is an
aliphatic-substituted cycloaliphatic radical, the
aliphatic substituents usually contain a total of at
least about 12 carbon atoms. Examples of Ra are alkyl,
alkenyl and alkoxyalkyl radicals, and
aliphatic-substituted cycloaliphatic radicals wherein the
aliphatic substituents are alkyl, alkenyl, alkoxy,
alkoxyalkyl, carboxyalkyl and the like. Generally, the
.
.
. . ,
.~ '
.
19 20~768
cycloaliphatic nucleus is derived from a cycloalkane or a
cycloalkene such as cyclopentane, cyclohexane,
cyclohexene or cyclopentene. Specific examples of Ra are
cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl,
-octadecenyl, and radicals derived from petroleum,
saturated and unsaturated paraffin wax, and olefin
polymers including polymerized monoolefins and diolefins
containing about 2-8 carbon atoms per olefinic monomer
unit. Ra can also contain other substituents such as
phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro,
amino, nitroso, lower alkoxy, lower alkylmercapto,
carboxy, carbalkoxy, oxo or thio, or interrupting groups
such as -NH-, -O- or -S-, as long as the essentially
hydrocarbon character thereof is not destroyed.
; Rb is generally a hydrocarbon or substantially
hydrocarbon radical free from acetylenic unsaturation and
containing from about 4 to about 60 aliphatic carbon
atoms, preferably an aliphatic hydrocarbon radical such
as alkyl or alkenyl. It may also, however, contain
substituents or interrupting groups such as those
enumerated above provided the essentially hydrocarbon
character thereof is retained. In general, any
non-hydrocarbon atoms present in Ra or Rb do not account
ifor more than 10% of the total weight thereof.
'Preferably, Ra and Rb are substantially free of
non-hydrocarbon atoms.
The radical T is a cyclic nucleus which may be
derived from an aromatic hydrocarbon such as benzene,
naphthalene, anthracene or biphenyl, or from a
heterocyclic compound such as pyridine, indole or
isoindole. Ordinarily, T is an aromatic hydrocarbon
nucleus, especially a benzene or naphthalene nucleus.
The subscript x is at least 1 and is generally 1-3.
The subscripts r and y have an average value of about 1-4
per molecule, more often about 1.
Illustrative sulfonic acids useful in the
preparation of component A are mahogany sulfonic acids,
., .
:~ .
. ,
,............... :
f
`. . ' . . . . . ...
;,.............. .
208~76g
`~ - 20 -
petrolatum sulfonic acids, mono- and polywax-substituted
naphthalene sulfonic acids, cetylchlorobenzene sulfonic
acids, cetylphenol sulfonic acids, cetylphenol disulfide
sulfonic acids, cetoxycapryl benzene sulfonic acids,
dicetyl thianthrene sulfonic acids, dilauryl
beta-naphthol sulfonic acids, dicapryl nitronaphthalene
sulfonic acids, saturated paraffin wax sulfonic acids,
; unsaturated paraffin wax sulfonic acids,
hydroxy~substituted paraffin wax sulfonic acids,
tetraisobutylene sulfonic acids, tetra-amylene sulfonic
acids, chloro-substituted paraffin wax sulfonic acids,
petroleum naphthene sulfonic acids, cetylcyclopentyl
fulsonic acids, lauryl cyclohexyl sulfonic acids, mono-
and polywax-substituted cyclohexyl sulfonic acids,
postdedecylbenzene sulfonic acids, "dimer alkylate"
sulfonic acids, and the like. These sulfonic acids are
well-known in the art and require no further discussion
herein.
It is desirable that the overbased materials, have a
metal ratio of at least about 1.1, preferably at least
about 1.5, and more preferably at least 2 to about 4. An
especially suitable group of the preferred sulfonic acid
and carboxylic acid overbased materials has a metal ratio
of at least about 7Ø While overbased materials having
a metal ratio of 75 have been prepared, normally the
maximum metal ratio will not exceed about 50 and, in most
cases, not more than about 40. Especially preferred are
`'those having a metal ratio from about 7 to about 20,
except for overbased phenols, wherein the metal ratio
generally ranges up to about 10, more often up to about
5.
The overbased materials utilized in the compositions
of the invention usually contain from about 10% to about
70% by weight of metal-containing components. The exact
nature of these metal-containing components is not known.
The remainder of the overbased materials comprise the
inert organic reaction medium and any promoter which is
''' '' . . ' -' ' . :
. ' . ' : .
... , . , . ' .'
- : . ' . `: . '
.
.
, . . . . . .
., -~
21 2~8~7~8
,
not removed from the overbased product. For purposes of
this application, the organic material which is subjected
; to overbasing is considered a part of the
metal-containing components. Normally, the liquid
i reaction medium constitutes at least about 30% by weight
of the reaction mixture utilized to prepare the overbased
materials.
In one particularly preferred embodiment, component
A is prepared from phenols: that is, compounds containing
a hydroxy radical bound directly to an aromatic ring.
The term "phenol" as used herein includes compounds
having more than one hydroxy group bound to an aromatic
ring, such as catechol, resorcinol and hydroquinone. It
also includes alkylphenols such as the cresols and
ethylphenols, and alkenylphenols. Preferred are phenols
containing at least one alkyl or alkenyl substituent
containing about 3-100 and especially about 6-50 carbon
. .
atoms, such as heptylphenol, octylphenol, dodecylphenol,
tetrapropenealkylated phenol, octadecylphenol and
polybutenylphenols. Phenols containing more than one
i substituent may also be used, but the monoalkylphenols
are preferred because of their availability and ease of
production.
Also useful are condensation products of the
above-described phenols with at least one lower aldehyde,
j the term "lower" denoting aldehydes containing not more
than 7 carbon atoms. Suitable aldehydes include
formaldehyde, acetaldehyde, propionaldehyde, the
butyraldehydes, the valeraldehydes and benzaldehyde.
Also suitable are aldehyde-yielding reagents such as
paraformaldehyde, trioxane, methylol, Methyl Formcel and
, paraldehyde. Formaldehyde and the formaldehyde-yielding
reagents are especially preferred.
; In a particularly preferred embodiment, the metal
phenates are overbased metal phenates, more preferably
overbased sulfurized metal phenates, preferably alkaline
earth metal phenates, and especially calcium phenates.
:
's ~ ~ - - .
; ~.. . .
,, - . ~:
;.
.j ,
- 22 - 2 ~ ~ ~ 7 ~ 8
The phenol group of the phenates includes an
aromatic moiety with at least one hydrocarbon-based
radical and an oxygen atom attached to such aromatic
moiety, as indicated in Formula I, below. The phenol
group may be sulfurized and reacted with a metal, as
discussed below, to form component (A). As used herein,
the term "normal" metal phenates is used to refer to
those phenates wherein the ratio of equivalents of metal
to the phenolic 0 group is about 1:1, in accordance with
Formula I
(Ra ~ Ar - 0 -)xM
wherein (~a ~ Ar - 0-) is the phenol group; M is a metal:
x is the valence of M. Ar is an aromatic moiety which is
preferably benzene; R is a hydrocarbon-based radical; and
a is an integer of from 1 up to the number of unsatisfied
valences in Ar, preferably 1 or 2. As used herein, the
term overbased metal phenates refers to metal phenates
wherein the ratio of metal to the phenol group is greater
than that of normal metal phenates. Such phenates are
sometimes referred to interchangeably as "basic" or
"overbased". Component (A) generally contains up to
about 1000%, preferably up to about 500%, of the metal
present in the corresponding normal metal phenate.
Advantageously, component (A) contains from about 250% to
about 450%, preferably up to about 350%, of the metal
present in the corresponding normal metal phenate.
Any of alkali or alkaline earth metals, copper or
zinc may be used in the phenate of component (A);
however, alkaline earth metal compounds are preferred,
and calcium is especially preferred.
As mentioned hereinabove, component (A) preferably
comprises a sulfurized metal phenate and the metal
contents referred to hereinabove apply equally to this
preferred embodiment. When component (A) is a sulfurized
phenate it has a phenol to sulfur group molar ratio of
from about 2:1 to about 1:2, preferably about 2:1 to
about 1:1, and advantageously about 4:3.
,.
, ., . . . - .
... . . . . . . .
,, .
.. , -
:;
: . .
20~7~8
-- 23 --
,~.
The term "basic" is used herein the same way in which
it was used in the definition of other components above,
that is, it refers to salts having a metal ratio in
excess of 1. The neutral and basic salts of phenol
sulfides provide antioxidant and detergent properties to
the oil compositions of the invention.
In a particularly preferred embodiment, component
(A) includes, for example, basic sulfurized tetrapropenyl
phenate with, for example, about 230% or 380% of the
calcium present in the corresponding normal calcium
phenate, and a phenol to sulfur group molar ratio of
about 4:3.
The alkylphenols from which the neutral and
overbased salts are prepared generally comprise phenols
containing hydrocarbon substituents with at least about 6
carbon atoms; the substituents may contain up to about
700 aliphatic carbon atoms. Also included are
substantially hydrocarbon substituents, as defined
hereinabove. The preferred hydrocarbon substituents are
derived from the polymerization of olefins such as
ethylene, propene, etc.
The term "al~ylphenol sulfides" is meant to include
di-(alkylphenol)monosulfides, disulfides, polysulfides,
and other products obtained by the reaction of the
alkylphenol with sulfur monochloride, sulfur dichloride
or elemental sulfur. The molar ratio of the phenol to
the sulfur compound can be, depending on the sulfur
compound, from about 1:0.5 to about l:l.S, or higher.
For example, phenol sulfides are readily obtained by
mixing, at a temperature above about 60-C, one mole of an
alkylphenol and about 0.5-1 mole of sulfur dichloride.
The reaction mixture is usually maintained at about
lOO-C for about 2-5 hours, after which time the resulting
sulfide is stripped of volatiles and filtered. When
elemental sulfur is used, temperatures of about 200-C or
higher are sometimes desirable. It is also desirable
:`
''''
....... .
.. ,~ . . -
, .~ . .
~. .
. ~,. .
~'r: ~ :
. ,., '
~ .
;- - 24 - 20~76~
that the drying operation be conducted under nitrogen or
a similar inert gas.
A commonly employed method for preparing the basic
~or overbased) salts of these phenols comprises heating
the phenol with a stoichiometric excess of a metal
neutralizing agent such as a metal oxide, hydroxide,
carbonate, bicarbonate, sulfide, etc., at temperatures
above about 50OC. Yarious promoters may be used in the
overbasing process to aid in the incorporation of the
excess metal. Promoters include such compounds as
phenolic substances including phenol; alcohols such as
methanol, 2-propanol, octyl alcohol, etc.; amines such as
aniline and dodecyl amine, etc. Preferably, the basic
salt is treated with carbon dioxide after it has been
formed. The techniques of overbasing various phenols are
described in the prior art and can be utilized as
processes for preparing the basic or overbased phenols
used in the present invention.
The preparation of sulfurized metal phenates is also
well known to those skilled in the art. Neutral salts
are prepared by mixing and heating a basic metal compound
with the desired phenol compound.
The preparation of basic (overbased) phenates can be
accomplished by any of the standard techniques known to
those skilled in the art for producing basic sulfurized
metal phenates. These technigues include, for example,
one-step processes wherein sulfurization and basing (or
overbasing) with the metal are effected simultaneously,
and two-step processes wherein the phenol is first
sulfurized, forming an alkylphenol sulfide, then based.
Each of these techniques is well known to those skilled
in the art and, accordingly, need not be further
discussed herein. ~he source of sulfur is generally
elemental sulfur, or sulfur halide, for example, SC12 or
S2C12 Patents disclosing suitable procedures for
preparing component (B) include U.S. Pat. Nos. 2,680,096;
.; : :
... .
~,, .
.
. .
2~7~8
- 25 -
3,036,971; 3,178,368; 3,437,595; and Re 29,661, these
patents being incorporated herein by reference.
Suitable basic alkyl phenol sulfides are disclosed,
for example, in U.S. Pat. Nos. 3,372,116, 3,410,798 and
3,562,159, 4,021,419 and 4,740,321 which are hereby
incorporated by reference.
The metal salts, component (A), are generally
employed in the compositions of this invention in amoun.s
ranging from about 0.1 to about 10% by weight of the
total lubricating oil composition. More often, they are
used in amounts ranging from about 0.02 to about 5%,
frequently up to about 2~ and preferably from about 0.04%
to about 1% by weight of the lubricating compositions.
The following examples illustrate the preparation of
metal salts useful as component (A). All temperatures
are in degrees Celsius, all parts are parts by weight
unless indicated otherwise. These examples are intended
to be illustrative only, and are not intended to be
construed as limiting the scope of this invention.
Examples A-l through A-10 are non-limiting examples
of the preparation of metal carboxylates, sulfonates and
mixtures thereof.
Example A-l
To 790 parts of an oil solution containing
equivalent based on neutralization number of an alkylated
benzenesulfonic acid and 71 parts of polybutenyl succinic
anhydride (equivalent weight about 560) containing
predominantly isobutene units in 176 parts of mineral oil
is added 320 parts (8 eguivalents) of sodium hydroxide
and 640 parts (20 equivalents) of methanol. The
temperature of the mixture increases to 89-C (reflux)
over 10 minutes due to exotherming. During this period,
the mixture is blown with carbon dioxide at 4 cfh (cubic
feet per hour). Carbonation is continued for about 30
minutes as the temperature gradually decreases to 74-C.
The methanol and other volatile materials are stripped
:.
~,
,
. ', ' ~
.
~ - 26 - 2 ~ ~ ~ 7 ~ 8
from the carbonated mixture by blowing nitrogen through
it at 2 cfh while the temperature is slowly increased to
150-C over 90 minutes. After stripping is completed, the
remaining mixture is held at 155C-165C for about 30
minutes and filtered to yield an oil solution of the
desired basic sodium sulfonate having a metal ratio of
about 7.75.
Example A-2
Following the procedure of Example A-l, a solution
of 780 parts (1 equivalent) of an alkylated
benzenesulfonic acid (57% by weight 100 neutral mineral
oil and unreacted alkylated benzene) and 119 parts of the
polybutenyl succinic anhydride in 442 parts of mineral
oil is mixed with 800 parts (20 equivalents) of sodium
hydroxide and 704 parts (22 equivalents) of methanol.
The mixture is blown with carbon dioxide at 7 cfh for 11
minutes as the temperature slowly increases to 97OC. The
rate of carbon dioxide flow is reduced to 6 cfh and the
temperature decreases slowly to 88-C over about 40
minutes. The rate of carbon dioxide flow is reduced to 5
cfh for about 35 minutes and the temperature slowly
decreases to 73'C. The volatile materials are stripped
by blowing nitrogen through the carbonated mixture at 2
cfh for 105 minutes as the temperature is slowly
increased to 160-C. After stripping is completed, the
mixture is held at 160-C for an additional 45 minutes and
then filtered to yield an oil solution of the desired
basic sodium sulfonate having a metal ratio of about
19.75.
Exam~le A-3
A mixture of 906 parts of an oil solution of an
alkyl phenyl sulfonic acid (having a molecular weight of
450), 564 parts mineral oil, 600 parts toluene, 98.7
parts magnesium oxide and 120 parts water is blown with
carbon dioxide at a temperature of 78--85-C for 7 hours
at a rate of about 3 cubic feet of carbon dioxide per
:
:,
. .
,, :
.
~,', ' ~ ,
, . . .
.~ :
~ . ~
~27 - 20~7~8
hour. The reaction mixture is constantly agitated
throughout the carbonation. After carbonation, the
reaction mixture is stripped to 165C/20 torr and the
residue filtered. The filtrate is an oil solution (34%
oil) of the desired overbased magnesium sulfonate having
a metal ratio of about 3.
Example A-4
A polybutenyl succinic anhydride is prepared by
reacting a chlorinated polybutene (having an average
chlorine content of 4.3% and derived from a polybutene
consisting predominantly of isobutene units having a
number average molecular weight of about 1150) with
maleic anhydride at about 200C. To a mixture of 1246
parts of this succinic anhydride and 1000 parts of
toluene there is added at 25 C, 76.6 parts of barium
oxide. The mixture is heated to 115-C and 125 parts of
water is added drop-wise over a period of one hour. The
mixture is then allowed to reflux at 150-C until all the
barium oxide is reacted. Stripping and filtration
provides a filtrate containing the desired product.
Exam~le A-5
A basic calcium sulfonate having a metal ratio of
about 15 is prepared by carbonation, in increments, of a
mixture of calcium hydroxide, a neutral sodium petroleum
sulfonate, calcium chloride, methanol and an alkyl
phenol, followed by removal of volatile materials and
filtration of the residue.
., .
¢; Example A-6
, A mixture of 323 parts of mineral oil, 4.8 parts of
water, 0.74 parts of calcium chloride, 79 parts of lime,
; and 128 parts of methyl alcohol is prepared, and warmed
to a temperature of about 50-C. To this mixture there is
' added 1000 parts of an alkyl phenyl sulfonic acid having
l a molecular weight of 500 with mixing. The mixture then
:i
.
~ ,
,.~ . , : ,
g: -
"
~ 28 - 208~7~
is blown with carbon dioxide at a temperature of about
SOoC at a rate of about 5.4 pounds per hour for about 2.5
hours. After carbonation, 102 additional parts of oil
are added and the mixture is stripped of volatile
materials at a temperature of about 150-155C at 55 mm.
pressure. The residue is filtered and the filtrate is
the desired oil solution of the overbased calcium
sulfona~e having calcium content of about 3.7% and a
metal ratio of about 1.7.
Example A-7
A mixture of 490 parts (by weight) of a mineral oil,
110 parts of water, 61 parts of heptylphenol, 340 parts
of barium mahogany sulfonate, and 227 parts of barium
oxide is heated at 100C for 0.5 hour and then to 150-C.
Carbon dioxide is then bubbled into the mixture until the
mixture is substantially neutral. The mixture is
filtered and the filtrate found to have a sulfate ash
content of 25%.
Example A-8
Add to a flask about 512 parts by weight of a
mineral oil solution containing about 0.5 equivalent of a
substantially neutral magnesium salt of an alkylated
salicylic acid wherein the alkyl group has an average of
about 18 aliphatic carbon atoms, about 30 parts by weight
of an oil mixture containing about 0.037 equivalent of an
alkylated benzenesulfonic acid together with about 15
parts by weight (0.65 equivalents) of magnesium oxide and
about 250 parts by weight of xylene. Heat to a
temperature of about 60-C to 70-C. Increase the heat to
about 85-C and add approximately 60 parts by weight of
water. Hold the reaction mass at a reflux temperature of
about 95-C to lOO-C for about 1 l/2 hours and
subsequently strip at a temperature of 155-160-C, under a
vacuum, and filter. The filtrate will comprise the basic
,
,;~
~ .
. , .
.~ , . ' :
29~7~S~
- 29 -
carboxylic magnesium salt containing 200~ of the
stoichiometrically equivalent amount of magnesium.
Example A-9
Prepare a substantially neutral magnesium salt of an
alkylated salicylic acid wherein the alkyl groups have
; from 16 to 24 aliphatic carbon atoms by reacting
approximately stoichiometric amounts of magnesium
chloride with a substantially neutral potassium salt of
the alkylated salicylic acid. Charge a flask with a
reaction mass comprising approximately 6580 parts by
weight of a mineral oil solution containing about 6.50
equivalents of the substantially neutral magnesium salt
of the alkylated salicylic acid and about 388 parts by
weight of an oil mixture containing about 0.48 equivalent
; of an alkylated benzenesulfonic acid together with
approximately 285 parts by weight (14 equivalents) of
magnesium oxide and approximately 3252 parts by weight of
xylene. Heat to a temperature of about 55-C to 75C.
Increase the temperature to about 82-C and add
approximately 780 parts by weight of water to the
reaction and then heat to the reflux temperature. Hold
; the reaction mass at the reflux temperature of about
95-lOO-C for about one hour and subsequently strip at a
temperature of about 170-C, under S0 torr and filter.
The filtrate will comprise the basic carboxylic magnesium
¦ salts and have a sulfated ash content of 15.7% (sulfated
;~ ash) corresponding to 276% of the stoichiometrically
; equivalent amount.
:.
~ Example A-lO
i A reaction mixture comprising 2900 grams (3
equivalents) of an oil solution of the magnesium salt of
polyisobutylene (average molecular weight--480)-
substituted salicyclic acids, 624 grams of mineral oil,
I 277 grams (l equivalent) of a commercial mixture of tall
oil acids, 1800 geams of xylene, 195 grams (9
'~-
. .
.. . .
; ,
'~ ' ' ''
.,. ~
, ~
~~ 30 _ 2~876~
.
equivalents) of magnesium oxide, and 480 grams of water
are carbonated at the reflux temperature (about 95C) for
one hour. The carbonated mixture is then stripped by
first heating to 160-C with nitrogen blowing (3 cubic
feet per hour) and thereafter heating to 165-C at a
pressure of 30 mm. (Hg). This stripped carbonated
product is filtered, the filtrate being an oil solution
of the desired basic magnesium salt. The salt is
characterized by a metal ratio of 2.7.
The following ~xamples A-11 through A-15 illustrate
the preparation of phenol salts.
Example A-ll
A phenol sulfide is prepared by reacting sulfur
dichloride with a polyisobutenyl phenol in which the
polyisobutenyl substituent has an average of 23.8 carbon
atoms, in the presence of sodium acetate tan acid
acceptor used to avoid discoloration of the product). A
mixture of 1755 parts of this phenol sulfide, 500 parts
of mineral oil, 335 parts of calcium hydroxide and 407
parts of methanol is heated to about 43-50-C and carbon
dioxide is bubbled through the mixture for about 7.5
hours. The mixture is then heated to drive off volatile
matter, an additional 422.5 parts of oil are added to
provide a 60% solution in oil. This solution contains
5.6% calcium and 1.59% sulfur.
,
;~ Exam~le A-12
;~' To 6072 parts (22 moles OH) of a tetrapropenyl-
~ substituted phenol (prepared by mixing, at 138-C and in
P the presence of a sulfuric acid treated clay, phenol and
tetrapropylene), there are added at 9O--95-C, 1134 parts
(11 moles) of sulfur dichloride. The addition is made
over a 4-hour period whereupon the mixture is bubbled
with nitrogen for 2 hours, heated to 150-C and filtered.
To 861 parts (3 equivalents) of the above product, 1068
parts of mineral oil, and 90 parts of water, there are
:, ~ ,........................... .
. ` .
;,............................... : ~ : .
,: :
:,.
. "~ .
~ - 31 - 2Q~76~
added at 70C, 122 parts (3.3 equivalents) of calcium
hydroxide. The mixture is maintained at 110C for 2
hours, heated to 165-C and maintained at this temperature
until it is dry. Thereupon, the mixture is cooled to
25-C and 180 parts of methanol are added. The mixture is
heated to 50-C and 366 parts (9.9 equivalents) of calcium
hydroxide and 50 parts (0.633 equivalent) of calcium
acetate are added. The mixture is agitated for 45
minutes and is then treated at 50-70-C with carbon
dioxide at a rate of 2-5 cubic feet per hour for 3 hours.
The mixture is dried at 165-C and the residue is
filtered. The filtrate has a calcium content of 3.3%, a
neutralization number of 39 (basic) and a metal ratio of
4.4.
Example A-13
To 5880 parts (12 moles OH) of a polyisobutene-
substituted phenol (prepared by mixing, at 54-C and in
the presence of boron trifluoride, equimolar amounts of
phenol and a polyisobutene having a number average
molecular weight of about 350) and 2186 parts of mineral
oil, there are added over 2.5 hours and at 90-110-C, 618
parts (6 moles) of sulfur dichloride. The mixture is
heated to 150-C and bubbled with nitrogen. To 3449 parts
(5.25 equivalents) of the above product, 1200 parts of
mineral oil, and 130 parts of water, there are added at
70-C, 147 parts (5.25 equivalents) of calcium oxide. The
mixture is maintained at 95-110-C for 2 hours, heated to
and maintained at 160-C for one hour and then cooled to
60-C whereupon 920 parts of l-propanol, 307 parts (10.95
equivalents) of calcium oxide, and 46.3 parts (0.78
equivalent) of acetic acid are added. The mixture is
then contacted with carbon dioxide at a rate of 2 cubic
feet per hour for 2.5 hours. The mixture is dried at
190-C and the residue is filtered to give the desired
product.
~ .
:''
.'' , ~ .
, .,
.~
- 32 - 20 3 ~ 76
Example A-14
A mixture of 48s parts (1 moles OH) of a
polyisobutene-substituted phenol wherein the substituent
has a number average molecular weight of about 400, 32
parts (1 equivalent) of sulfur, 111 parts (3 equivalents)
of calcium hydroxide, 16 parts (0.2 equivalent) of
calcium acetate, 485 parts of diethylene glycol
monomethyl ether and 414 parts of mineral oil is heated
at 120-205-C under nitrogen for 4 hours. Hydrogen
sulfide evolution begins as the temperature rises above
125C. The material is allowed to distill and hydrogen
sulfide is absorbed in a sodium hydroxide solution.
Heating is discontinued when no further hydrogen sulfide
absorption is noted: the remaining volatile material is
removed by distillation at 95C/10 mm pressure. The
distillation residue is filtered. The product thus
obtained is a 60% solution of the desired product in
mineral oil.
/
Example A-15
To a mixture of 3192 parts (12 equivalents) of
tetrapropenyl-substituted phenol, 2400 parts of mineral
oil and 465 parts (6 equivalents) of 40% aqueous
formaldehyde at 82 C, is added, over 45 minutes, 960
parts (12 equivalents) of 50% aqueous sodium hydroxide.
, Volatile materials are removed by stripping at 160-C
under nitrogen and subsequently under vacuum, and to the
residue is added 618 parts (12 equivalents) of sulfur
dichloride over 3 hours. Toluene, 1000 parts, and 1000
parts of water are added and the mixture is heated under
reflux for 2 hours. Volatile materials are then removed
at 180-C by blowing with nitrogen and the intermediate is
filtered.
To 1950 parts (4 equivalents) of the intermediate
thus obtained i8 added 135 parts of the polybutenyl
succinic anhydride wherein the polybutenyl group has a
molecular weight of about 1000 and consists primarily of
, .
i;,......... .
~ .
: . :
- 33 -
2~768
isobutene units. The mixture is heated to Sl~C, and 78
parts of acetic acid and 431 parts of methanol are added,
; followed by 325 parts (8.8 equivalents) of calcium
~-~ hydroxide. The mixture is blown with carbon dioxide and
is finally stripped with nitrogen blowing at 158~C and
; filtered while hot, using a filter aid. The filtrate is
a 68% solution in mineral oil of the desired product and
contains 2.63~ sulfur and 22.99% calcium sulfate ash.
The Carboxylic Acid or Anhvdride
Component (B) is an aliphatic carboxylic acid or an
~ anhydride thereof, wherein the aliphatic group contains
; at least about 20 carbon atoms and up to about 500 carbon
atoms, preferably from about 30 to about 300 carbon atoms
and often from about 30 to about 150 carbon atoms. In
. "
,, another embodiment, component (B) is an aliphatic
substituted succinic anhydride or acid containing from
:~ about 20 to about 500 carbon atoms in the aliphatic
substituent, preferably from about 30 to about 400 carbon
atoms, and often from about 50 to about 200 carbon atoms.
~ Patents describing useful aliphatic carboxylic acids or
;i anhydrides and methods for preparing them include, among
numerous others, U.S. Pat. Nos. 3,215,707 (Rense):
3,219,666 (Norman et al), 3,231,587 (Rense); 3,912,764
(Palmer); 4,110,349 (Cohen); and 4,234,435 (Meinhardt et
al); and U.K. 1,440,219.
As indicated in the above-mentioned patents, which
~ are hereby incorporated by reference for their disclosure
-I of compounds useful as component (B) of this invention,
the carboxylic acids (or various derivatives thereof) are
; usually derived by the reaction of a carboxylic acid
:
containing compound with a polyalkene or halogenated
derivative thereof or a suitable olefin.
The polyalkenes from which the carboxylic acids (B)
are derived are homopolymers and interpolymers of
polymerizable olefin monomers of 2 to about 16 carbon
atoms; usually 2 to about 6 carbon atoms. The
.: ~
., .
:
; ~ 34 ~ 2~ ~ ~7~8
interpolymers are those in which two or more olefin
monomers are interpolymerized according to well-known
conventional procedures to form polyalkenes having units
within their structure derived from each of said two or
more olefin monomers. Thus, "interpolymer(s)" as used
herein is inclusive of copolymers, terpolymers,
tetrapolymers, and the like. As will be apparent to
those of ordinary skill in the art, the polyalkenes from
which the substituent groups are derived are often
conventionally referred to as "polyolefin(s)".
The olefin monomers from which the polyalkenes are
derived are polymerizable olefin monomers characterized
by the presence of one or more ethylenically unsaturated
groups (i.e., >C=C<); that is, they are monolefinic
monomers such as ethylene, propylene, butene-l,
isobutene, and octene-l or polyolefinic monomers (usually
diolefinic monomers) such as butadiene-1,3 and isoprene.
These olefin monomers are usually polymerizable
terminal olefins: that is, olefins characterize by the
presence in their structure of the group >C=CH2.
However, polymerizable internal olefin monomers
(sometimes referred to in the literature as medial
olefins) characterized by the presence within their
structure of the group
--C--C=C--C--
can also be used to form the polyalkenes. When internal
olefin monomers are employed, they normally will be
employed with terminal olefins to produce polyalkenes
which are interpolymers. For purposes of this invention,
when a particular polymerized olefin monomer can be
classified as both a terminal olefin and an internal
olefin, it will be deemed to be a terminal olefin. Thus,
1,3-pentadiene ~i.e., piperylene) is deemed to be a
terminal olefin for purposes of this invention.
Preferred carboxylic ac.ids include polyolefin
substituted succinic acids, succinic anhydrides, ester
acids or lactone acids.
.
'',. :
~ ,. . .
... . . . .
,
; ,. : : .~, -, ... . .
',' ` ': ~ " '
:~ 2~3'~7~
Component (B) is generally used in the lubricating
oil compositions of this invention in amounts ranging
from about 0.01% to about 10% by weight of the
lubricating oil composition, preferably from about 0.0196
to about 5% by weight and often up to about 1% by weight.
Most preferably, component (B) is present in amounts
~ ranging from about 0.02% to about 1% by weight.
j~ Non-limiting examples of compounds useful as
....
` component (B) include those in the following examples:
.,
Example B-l
A mixture of 6400 parts (4 moles) of a polybutene
comprising predominantly isobutene units and having a
molecular weight of about 1600 and 408 parts (4.16 moles)
of maleic anhydride is heated at 225-240C for 4 hours.
It is then cooled to 170~C and an additional 102 parts
~i(1.04 moles) of maleic anhydride is added, followed by 70
jparts (0.99 mole) of chlorine; the latter is added over 3
hours at 170-215-C. The mixture is heated for an
;~additional 3 hours at 215-C and is then vacuum stripped
at 220 C and filtered through diatomaceous earth. The
product is the desired polybutenyl-substituted succinic
anhydride having a saponification number of 61.8.
Example B-2
~A monocarboxylic acid is prepared by chlorinating a
;~polyisobutene having a molecular weight of 750 to a
product having a chlorine content of 3.6~ by weight,
converting the product to the corresponding nitrile by
reaction with an equivalent amount of potassium cyanide
in the presence of a catalytic amount of cuprous cyanide
and hydrolyzing the resulting nitrile by treatment with
50% excess of a dilute aqueous sulfuric acid at the
reflux temperature.
,, ,
Example El-3
:'
..... .
~ ~ .
".. ~ ~ .
. .
..... .
-
- 36 - 20~7~8
A high molecular weight mono-carboxylic acid is
prepared by telomerizing ethylene with carbon
tetrachloride to a telomer having an average of 35
ethylene radicals per molecule and hydrolyzing the
telomer to the corresponding acid in according with the
procedure described in British Patent No. 581,899.
~ Exam~le B-4
; A polybutenyl succinic anhydride is prepared by the
reaction of a chlorinated polybutylene with maleic
, anhydride at 200~C. The polybutenyl radical has an
, average molecular weight of 805 and contains primarily
; isobutene units. ~he resulting alkenyl succinic
, anhydride is found to have an acid number of 113
(corresponding to an equivalent weight of 500).
`'
, Exam~le B-5
A lactone acid is prepared by reacting 2 equivalents
of a polyolefin (Mn about soo) substituted succinic
anhydride with 1.02 equivalents of water at a temperature
of about 90-C in the presence of a catalytic amount of
( concentrated sulfuric acid. Following completion of the
reaction, the sulfuric acid catalyst is neutralized with
sodium carbonate and the reaction mixture is filtered.
''
,1 Exam~le B-6
An ester acid is prepared by reacting 2 equivalents
J of an alkyl substituted succinic anhydride having an
;' average of about 35 carbon atoms in the alkyl group with
1 mole of ethanol.
''
Example B-7
~ A reactor is charged with 1000 parts of polybutene
;~ having a molecular weight determined by vapor phase
isometry of about 950 and which consists primarily of
, isobutene units, followed by the addition of 108 parts of
;~' moleic anhydride. The mixture is heated to llO-C
. .
.. . .. . .
,, ~ . : -
'`,'
... .
., -
,.
- 37 - 20~`Q7~g
followed by the sub-surface addition of 100 parts C12
over 6.5 hours at a temperature ranging from 110 to
188C. The exothermic reaction is controlled as not to
;' exceed 188C. The batch is blown with nitrogen then
stored.
Example 8-8
i
i The procedure of Example B-7 is repeated employing
1000 parts of polybutene having a molecular weight
~; determined by vapor phase isometry of about 1650 and
consisting primarily of isobutene units and 106 parts
moleic anhydride. C12 is added beginning at 13 0 C and
' added a near continuous rate such that the maximum
:~ temperature of 188C is reached near the end of
chlorination. The residue is blown with nitrogen and
~; collected.
(C) The Metal Salts of an Oraanic Phos~horus Acid or
Mixture of Organic Phosphorus Acid and Carboxylic Acid
The compositions of the present invention may also
~j contain (C) a metal salt of (C)(I) at least one organic
, phosphorus acid or mixture of (C)(I) at least one organic
phosphorus acid and (C)(II) at least one carboxylic acid.
The phosphorus acid (8)(I) is preferably at least
' one acid of the general formula
,, RlX ~
~ 1 / P ( X ) X~I
"., R2X
, .
; wherein Rl and R2 is the same or different and each of Rl
and R2 is independently H or a hydrocarbon-based group
with the proviso that at least one of Rl and R2 is a
hydrocarbon-based group and each X is independently S or
. O.
In a preferred embodiment, the phosphorus acid
(C)(I) has the general formula
.~ . . .
.:
.
:..
.
. ,:,
.,.
~ 38 - 2~3~7~
R10
\ P(S)SH,
R20~
.
wherein R1 and R2 are as defined hereinabove. These are
referred to as phosphorodithioic acids.
The hydrocarbon-based groups Rl and R2 may be alkyl,
cycloalkyl, aralkyl or alkaryl groups. Illustrative
alkyl groups include isopropyl, isobutyl, n-butyl,
sec-butyl, the various amyl groups, n-hexyl,
ethylisobutyl carbinyl, heptyl, 2-ethylhexyl, diisobutyl,
isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc.
Illustrative alkaryl groups include lower alkylphenyl
groups such as butylphenyl, amylphenyl, heptylphenyl,
etc. Cycloalkyl groups likewise are useful and these
include chiefly cyclohexyl and the lower alkyl-cyclohexyl
radicals. Lower alkyl groups contain from one to about
seven carbon atoms. Many substituted hydrocarbon groups
may also be used, e.g., chloropentyl, dichlorophenyl, and
dichlorodecyl.
The preparation of these acids is well known in the
art and i8 described in the patent literature and
numerous other texts and publications. See for example
the books, "Lubricant Additives," by C. V. Smalheer and
R. K. Smith, published by Lezius-Hiles Co., Cleveland,
Ohio (1967) and "Lubricant Additives," by M. W. Ranney,
published by Noyes Data Corp., Parkrid~e, New Jersey
(1973), and the following U.S. Patents:
2,261,047 3,211,648 3,4~2,188
2,540,084 3,211,649 3,413,327
2,838,555 3,213,020 3,446,735
2,861,907 3,213,021 3,502,677
2,862,947 3,213,022 3,573,292
2,952,699 3,305,598 3,859,300
2,987,410 3,328,298 4,002,686
., .
:.
-
.
.~ . ~ , .
.
.. .
39 - 2 ~ ~ g 76
3,004,996 3,335,158 4,089,793
3,089,867 3,376,221 4,123~370
3,151,075 3,390,082 4,308,154
, 3,190,833 3,401,185 4,466,895
4,507,215
These books and patents are hereby incorporated by
, reference for relevant disclosures contained therein.
Preferred acids of the general formula
' ~ R10~
; P(S)(S)H
~' R20/'
are readily obtainable from the reaction of phosphorus
pentasulfide (P2S5) with an alcohol or mixtures of
alcohols. The reaction involves mixing at a temperature
of about 20-C to about 200-C, 4 moles of the alcohol with
one mole of phosphorus pentasulfide. Hydrogen sulfide is
liberated in this reaction. The oxygen-containing
analogs of these acids are conveniently prepared by
treating the dithioic acid with water or steam which, in
effect, replaces one or both of the sulfur atoms.
The mixed phosphates (R0)xP(OH)y are readily
prepared by reacting 3 moles of an alcohol wi~h 1 mole of
phosphorus pentoxide (P2O5).
The expression "hydrocarbon-based group" as used
herein with respect to Rl and R2 is used to define a
monovalent radical derived from a hydrocarbon-based
material by removal of a hydrogen from a carbon atom of
the hydrocarbon-based material. This carbon atom is
directly bonded to the remainder of the molecule. The
hydrocarbon-based groups may be straight chains, e.g.,
isopropyl-, n-pentyl, sec-butyl-, etc. or branched, e.g.,
2-methyl-4-pentyl-, isooctyl-, etc.
,
~' .
.,. ~. .
.
.... .
.. : ..
- 40 -
20337~8
Preferably the groups Rl and R2 are substantially
saturated. The terminology ~'substantially saturated" as
used herein is intended to define radicals free from
acetylenic unsaturation (-C C-) in which there is not
more than one ethylenic linkage (-C=C-) for every 10
carbon-to carbon (preferably 20) covalent bonds. The
so-called "double bonds" in aromatic rings (e.g.,
benzene) are not to be considered as contributing to
unsaturation with respect to the terminology
-"substantially saturated". Usually there will be no more
than an average of one ethylenic linkage per
substantially saturated monovalent radical as described
hereinbefore. Preferably, (with the exception of
aromatic rings) all the carbon-to-carbon bonds in a
substantially saturated radical will be saturated
linkages: that is, the radical will be free from
acetylenic and ethylenic linkages. For the purposes of
this disclosure, aromatic unsaturation is not to be
considered ethylenic unsaturation.
In general, the hydrocarbon-based radical may
contain at least 3 carbon atoms and up to about 100
carbon atoms with a preferred range from 3 to about 50
carbon atoms, more preferably from about 3 to about 16
carbon atoms. Other preferred ranges are from about 6 to
about 18 carbons, more preferably from about 6 to about 8
carbons. Mixtures wherein Rl and R2 are different are
useful. Typical examples of R and R1 include isopropyl-,
n-butyl-, n-pentyl-, 4-methyl-2-pentyl-, isooctyl-,
n-dodecyl-, etc. Mixtures, such as isopropyl- and
isooctyl, sec-butyl and n-decyl-, isopropyl- and
4-methyl-2-pentyl- and the like are useful. Mixtures are
often statistical mixtures which comprise a mixture
wherein some of the molecules have both Rl and R2 alike
and additional molecules wherein Rl and R2 are different.
The term "lower" when used herein to denote radicals
such as lower alkyl is intended to describe a radical
containing up to about 7 carbon atoms.
.,
.,; , . :, ,
: ~ : , ... ~ . : . :
.' ' ' ~
~ ^ - 41 - 20~37~8
Methods for preparing the metal salts (C) are well
known and are described in detail in the patent
literature. Most frequently, the salts are prepared by
reacting one or more of the phosphorus-containing acids
~ described hereinabove with a metal base. Suitable metal
i bases include the free metals previously enumerated and
their oxides, hydroxides, alkoxides and basic salts.
Examples include sodium hydroxide, calcium hydroxide,
; zinc oxide, copper oxide, calcium acetate and the like.
Other methods include "double-displacement" reactions
wherein one metal salt of a phosphorus acid is reacted
with a salt, such as a halide, of another metal. Metal
exchange may take place. For example, a sodium
dithiophosphate can be reacted with calcium chloride to
form a calcium dithiophosphate and sodium chloride.
Sodium chloride is then removed by means commonly used in
i the art, such as filtration, water washing, etc. These
and other methods are described in the books and U.S.
Patents listed hereinabove which describe the method of
preparation of the various phosphorus acids. Each of the
above-listed books and patents is hereby incorporated by
reference for disclosures relating to the preparation of
the metal salts.
Also contemplated for use in the lubricating
compositions of this invention are metal salts of
phosphorus-containing acids as described hereinabove-,
which have been post-treated with other reagents to
' improve various properties. Examples include
post-treatments with phosphites, epoxides, amines and the
like. Such post-treatments and products so obtained are
describ-d in the Lollowing U.S. Patents:
.
.,. ~ .
.. - :
.
- 42 - 2~7~
3,004,996 3,213,022
3,1Sl,075 3,213,023
3,211,648 4,263,150
3,211,649 4,289,635
3,213,020 4,507,215
3,213,021
. ~
As noted hereinabove, the metal salts (C) useful in
the lubricating compositions of this invention may be
metal salts of a mixture of (C)(I) at least one organic
phosphorus acid and (C)(II) at least one carboxylic acid
wherein the various elements of the formula are as
described hereinabove.
These metal salts are salts of at least two acidic
- components. The phosphorus-containing acids (C)(I) have
been described hereinabove.
, The carboxylic acid reactant (C)(II) may be a
monocarboxylic or polycarboxylic acid, usually containing
from 1 to about 3 carboxy groups and preferably only 1.
It may contain from about 2 to about 40, preferably from
about 2 to about 20 carbon atoms. The preferred
carboxylic acids are those having the formula R3CoOH~
wherein R is an aliphatic or alicyclic hydrocarbon-based
group preferably free from acetylenic unsaturation.
Suitable acids include acetic, propionic, butanoic,
hexanoic, decanoic, dodecanoic, octadecanoic and
eicosanoic acids, as well as olefinic acids such as
acrylic, oleic, linoleic, and linoleic acid dimer. For
the most part, R3 is a saturated aliphatic radical and
especially a branched alkyl radical such as the isopropyl
or 3-heptyl radical. Illustrative polycarboxylic acids
J are oxalic, malonic, succinic, alkyl- and
' alkenylsuccinic, glutaric, adipic, pimelic, sebacic,
maleic, fumaric and citric acids.
The salt of a mixture of ~C)(I) and (C)(II) may be
prepared by merely blending a metal salt of compoment
.
.
. - .
- .
.. . .
... .
~:~` "' ' ' ' ' '
,
` _ 43 _ 2~76~
.,
`' (C)(I) with a metal salt of component (C)(II) in the
desired ratio. This ratio is between about 0.5:1 and
about 500:1 on an equivalent basis. Preferably, the
ratio is between about 0.5:1 and about 200:1.
Advantageously, the ratio can be from about 0.5:1 to
about 100:1, preferably from about 0.5:1 to about 50:1,
and more preferably from about 0.5:1 to about 20:1.
Further, the ratio can be from about 0.5:1 to about
4.5:1, preferably about 2.5:1 to about 4.25:1. For this
purpose, the equivalent weight of a phosphorus containing
acid (C)(I) is its molecular weight divided by the number
of acidic groups, and that of a carboxylic acid is its
molecular weight divided by the number of carboxy groups
therein. The information required to determine
equivalents can usually be determined from the structural
formula of components (C)(I) and (C)(II) or empirically
through well-known titration procedures.
A second and preferred method for preparing the
metal salts of mixtures of acids (C)(I) and (C)(II) is to
prepare a mixture of the acids in the desired ratio and
to react the acid mixture with a suitable metal base.
When this method of preparation is used, it is frequently
possible to prepare a neutral salt or a salt containing
an excess of metal with respect to the number of
equivalents of acid present: thus, mixed metal salts
containing as many as 2 equivalents and especially up to
about 1.5 eguivalents of metal per equivalent of acid may
' be prepared. The equivalent of a metal for this purpose
1 is its atomic weight divided by its valence.
The term "neutral salt" refers to salts
characterized by metal content equal to that which would
be present according to the stoichiometry of the metal
and the particular organic compound reacted with the
metal. Thus, if a phosphorodithioic acid, (R0)2PSSH, is
neutralized with a basic metal compound, e.g., zinc
oxide, the neutral metal salt produced would contain one
i
:;
, :.
- .
~'. , .
.. : - .
~; ,
~ 20~87fi~
,
equivalent of zinc for each equivalent of acid, i.e.,
[(R0)2PSS]2Zn.
However, component (C) can contain more or less than
the stoichiometric amount of metal. The products
containing less than the stoichiometric amount of metal
are acidic materials. The products containing more than
the stoichiometric amount of metal are overbased
materials. Component (C) may have about 80% to about
200~, preferably about 100~ to about 150%, more
preferably about 100~ to about 135%, and advantageously
about 103% to about 110% of the metal present in the
corresponding neutral salt.
Variants of the above-described methods may also be
used to prepare the mixed metal salts of this invention.
~; For example, a metal salt, component (C) may be blended
with the free acid as component (C)(II), and the
resulting blend reacted with additional metal base.
Suitable metal bases for the preparations of the
metal salts (C) of this invention include the free metals
previously enumerated and their oxides, hydroxides,
alkoxides and basic salts. Examples are sodium
hydroxide, sodium methoxide, sodium carbonate, potassium
hydroxide, potassium carbonate, magnesium oxide,
magnesium hydroxide, calcium hydroxide, calcium acetate,
zinc oxide, zinc acetate, lead oxide, nickel oxide,
copper oxide, antimony trioxide and the like.
The temperature at which the metal salts used in
this invention are prepared is generally between about
30-C and about 150-C, preferably up to about 125-C. If
~1 component (C) is prepared by neutralization of a mixture
of acids with a metal base, it is preferred to employ
i temperatures above about 50-C and especially above about
75-C. It is frequently advantageous to conduct the
reaction in the presence of a substantially inert,
normally liquid organic diluent such as naphtha, benzene,
xylene, mineral oil or the like. If the diluent is
mineral oil or is physically and chemically similar to
... .
, .
: ~:~ . . - , .
. . . - .
,
,
:' , . .:, ,: . .
,. : ,
2~8~S7fi~
,,
mineral oil, it frequently need not be removed before
using component (C) in the compositions of the invention.
Component (C), when present, is generally used in
the lubricating oil compositions of this invention in
amounts ranging up to about lO~ of the total weight of
the lubricating oil composition. More often, component
(C), when used, is present in amounts ranging from about
0.05% to about 5%, preferably from about 0.1 to about 2~
and more preferably from about O.l to about 1% by weight
of the lubricating oil composition.
As mentioned hereinabove, and as illustrated by the
numerous references incorporated herein which describe
the metal salts of phosphorus-containing acids, the metal
salts and derivatives thereof are well known in the art.
The following examples are provided to illustrate several
of the metal salts useful as component (C) in this
invention. It is emphasized that these examples are
provided for illustrative purposes and are not to serve
as a limitation on the scope of the invention.
, ..
Example (C-l)
One mole of an O,O-di(alkyl)phosphorodithioic acid
containing 40 mole % isopropyl and 60 mole %
4-methyl-2-pentyl group is reacted with an oil slurry of
1.08 equivalents (0.54 moles) of zinc oxide at about
l90-F (88-C). H2O is evolved. The reaction mixture is
steam stripped followed by vacuum stripping. Oil is
added if necessary to adjust the phosphorus content of
the residue to about 9.5%. The oil solution is filtered.
Example (C-2)
The procedure of Example B-l is repeated employing l
mole of di(4-methyl-2-pentyl)dithiophosphoric acid and
1.1 equivalents (0.55 moles) of an oil slurry of zinc
oxide. The filtered product contains 8.5% phosphorus.
~ . , . - , . . .
: . :
- 46 - 2Q ~ 1~ 7~ ~
Example ~C-3)
The procedure of Example B-2 is repeated except no
oil diluent is employed. The filtered product contains
i 9.25% phosphorus.
Example (C-4)
A mixture of 67 parts (1.63 equivalents) of zinc
oxide and 48 parts of mineral oil is prepared at room
temperature. A mixture of 303 parts (1 equivalent) of
the O,O-di(alkyl)phosphorodithioic acid described in
; Example 2 and 36 parts (0.25 equivalents) of
~, 2-ethylhexanoic acid is added over 10 minutes and a
slight exotherm is observed. When addition is complete,
the temperature is increased to 80-C for 3 hours. The
mixture is vacuum stripped at lOO-C and filtered.
~, Exam~le C-5
Following the procedure of Example C-4, a product is
prepared from 383 parts (1.2 equivalents) of a dialkyl
phosphorodithioic acid containing 65% isobutyl and 35 %
amyl groups, 43 parts (0.3 equivalent) of 2-ethylhexanoic
acid, 71 parts (1.73 equivalents) of zinc oxide and 47
parts of mineral oil. The resulting metal salt, obtained
as a 90% solution in mineral oil, contains 11.07% zinc.
/
Example C-6
Following the procedure of Example C-4, a product is
prepared from 474 parts (1.2 equivalents) of a
dialkylphosphorodithioic acid containing 80% 2-ethylhexyl
groups and 20% isobutyl groups, 43 parts (0.3 equivalent)
of 2-ethylhexanoic acid, 80 parts (1.95 equivalents) of
zinc oxide and 57 parts of mineral oil. The resulting
m-tal salt is obtained ao a 91~ solution in mineral oil.
. ,
. .
.
.. . .
.~ i .
, . .
, ~ . - .
... .
2 ~ ~ ~o 7 ~ 8
,
~,
Example C-7
A mixture of 118 parts (2.8 equivalents) of zinc
oxide, 25 parts (0.25 equivalent) of sebacic acid and 72
parts of mineral oil is stirred at room temperature and a
mixture of 584 parts (2 equivalents) of the
dialkylphosphorodithioic acid of Example 2 and 36 parts
(0.25 equivalent) of 2-ethyl-hexanoic acid is added over
30 minutes. The temperature increases to 65~C during the
addition. The solution is heated to 80 C for 3 hours and
vacuum stripped at 180-C. The residue is filtered to
yield the desired metal salt (90% solution in mineral
oil) containing 11.7% zinc.
Exam~le C-8
A product is prepared by the procedure of Example
C-4 except that an equivalent amount of oleic acid is
substituted for the 2-ethylhexanoic acid.
... .
Examples C-9 to C-ll
Triphenyl phosphite is heated with a zinc salt of a
mixture of a dialkylphosphorodithioic acid and a
carboxylic acid. The dialkylphosphorodithioic acid used
, in the preparation of the zinc salt is itself prepared by
j the reaction of at least one alcohol with phosphorus
-l pentasulfide which contains a stoichiometric excess of
j sulfur. The reaction conditions and results are given in
Table I. The salts are prepared by reacting zinc oxide
,;.~
with 4 equivalents of the dialkylphosphorodithioic acid
and 1 equivalent of the carboxylic acid, a total of 1.3
equivalents of zinc oxide being used per equivalent of
acid. The reactions are carried out in a small amount of
mineral oil as diluent.
. .
.
.,
.~
. . .
:.
.,
.. : , ., : ,
< , - :
- 48 - 20~7~
, . .
,
,
,~ I ~
. o o o
, ~ i ~ .
,, , ,i ,,
.,
",
.;
u~ _o ~n
In~ In ~ ~ ~
r
D~
.,
H U~ ~ ~ <'
~"~
."'' ~
~' O
O - ~ ~1, ~
,, r~ ~ r~ '
U~ X X X
~1 .C S S
"' /\ `.~ ~C ~
,.~ ~0 ~ W
'',~'
,;~
~I
,' ~
O ~-
1 ~ ~ ~-
X
'
- ,
, .
:, , , : . ' ' ~
,. ' : ' ' ' ~
':
:. :
'
,
208876~
Example C-12
A reaction mixture is prepared by the addition of
3120 parts (24.0 moles) of 2-ethylhexanol and 444 parts
(6.0 moles) of isobutyl alcohol. With nitrogen blowing
at 1.0 cubic feet per hour, 1540 parts (6.9 moles) of
P2S5 is added to the mixture over a two-hour period while
maintaining the temperature at 60-78OC. The mixture is
held at 75C for one hour and is stirred an additional
two hours while cooling. The mixture is filtered through
diatomaceous earth. At 25C, 4745 parts (12.5 moles) of
this filtered mixture is added to a mixture of 590 parts
(14.4 moles) of ZnO, 114 parts of a commercially
available mixture of C15 18 alpha-olefins and 457 parts
of diluent oil over a thirty minute period. The exotherm
increases the temperature to 70 C. The mixture is heated
to 85 C and maintained at that temperature for three
hours. The mixture is stripped to 110-C at 25 mm. Hg.
The mixture is filtered twice through diatomaceous earth.
... .
~xample C-13
A slurry is prepared by the addition of 486.6 parts
(11.86 equivalents) of ZnO and 243.1 parts diluent oil.
With medium speed stirring 1204 parts (3.6 equivalents)
of O,O-di(4-methyl-2-pentyl)phosphorodithioic acid are
added to the slurry and the temperature of the resulting
mixture is increased from 56-C to 87-C over a period of
minutes. 2407 parts (7.2 equivalents) of
O,O-di-(4-methyl-2-pentyl)phosphorodithioic acid are
added to the mixture. The temperature of the mixture is
maintained at 86-C for 4 hours. 500 parts of the mixture
are poured off. The remaining 3831 parts of mixture are
mixed with 156.04 parts of a commercially available
mixture of C15_18 alpha-olefins. The mixture is stripped
to 105-C at 15 mm. Hg. The temperature of the mixture is
increased from 22-C to 105-C over a 3 1/2 hour period.
The mixture is held at 105-C under a nitrogen flow of 0.5
cubic feet per hour for an additional two hours before
~'
,: . - , ~
'''' ' '. , ~'. ~ , '
.,: .
'
. .
: .
~ 50 - 2~7 6~
; being allowed to cool. The mixture is cooled and
filtered through diatomaceous earth. The filtrate is the
' product.
:
Example C-14
The process of Example C-l is repeated replacing the
zinc oxide with about 1.15 equivalents of cuprous oxide.
Example C-15
The process of Example C-l is repeated employing
0,0-di(2-ethylhexyl)phosphorodithioic acid.
, ~,
Example C-16
The process of Example C-15 is repeated employing 1
; equivalent of copper (I) oxide for each equivalent of
,~ zinc oxide.
Examples C-17-20
The process of Example C-15 is repeated employing 1
-'b, equivalent of:
~;~xample No. Metal Com~ound
17 Manganese (IV) oxide
18 Nickel ~II) oxide
~, 19 Molybdenum (VI) oxide
,~j 20 Tin (II) oxide
;,.
, Additional representative examples of metal salts
i useful as component (C) in the compositions of this
invention appear in the patents and publications herein
incorporated by reference. Other examples will occur to
one skilled in the art.
~D) The Triazole
The triazole which may be used in this invention may
be benzotriazole and alkyl-substituted benzotriazole.
The alkyl substituent generally contains up to 15 carbon
atoms, preferably up to 8 carbon atoms. In addition to
the alkyl substituent, the triazoles may contain other
,
.
.....
:
.
'
, ~ :. ' ~ ' ' . "
- 51 - 2~ 68
substituents on the aromatic ring such as halogens and
nitro groups. Examples of suitable compounds are
benzotiazole and the tolyltriazoles, ethylbenzotriazoles,
hexylbenzotriazoles, octylbenzotriazoles, chlorobenzo-
triazoles and nitrobenzotriazoles. Benzotriazole and
tolyltriazole are particularly preferred.
The amount of triazole included in the composition
generally is less than 5%, more orten less than 1~ by
weight. When the composition of the invention is to be
used in a lubricating oil such as a hydraulic fluid, only
small amounts of the triazole compound are required to
obtain improved hydrolytic stability. Generally the
composition of the invention will contain an amount of
triazole compound which will provide an additive
concentrate for lubricants and functional fluid which
contains as little as loO ppm of the triazole and
preferably less than 50 ppm of the triazole. When
formulated into finished lubricants and functional
fluids, the compositions of the invention are prepared to
provide the lubricant or functional fluid with a
stabilizing amount of the triazole which generally is
less than 20 ppm, and may be less than 3 ppm of finished
lubricant or functional fluid.
It is sometimes useful to incorporate, on an
optional, as-needed basis other known additives which
include, but are not limited to, dispersants, detergents,
antioxidants, anti-wear agents, extreme pressure agents,
emulsifiers, demulsifiers, foam inhibitors, friction
modifiers, anti-rust agents, corrosion inhibitors,
viscosity improvers, pour point depressants, dyes, and
solvents to improve handleability which may include alkyl
and/or aryl hydrocarbons. These optional additives may
be present in various amounts depending on the intended
application for the final product or may be excluded
therefrom.
. .
, .
, . ,: , , ~ :
- . : : . -'
. . .
.
.
.
. . . , - . . .
-
- 52 - 2~ ~ ~7 6 8
~Dispersants include, but are not limited to,
- hydrocarbon substituted succinimides, succinamides,
carboxylic esters, Mannich dispersants and mixtures
thereof as well as materials functioning both as
dispersants and viscosity improvers. The dispersants
include nitrogen-containing carboxylic dispersants, ester
dispersants, Mannich dispersants or mixtures thereof.
Nitrogen-containina carboxylic dispersants are prepared
by reacting a hydrocarbyl carboxylic acylating agent
(usually a hydrocarbyl substituted succinic anhydride)
with an amine (usually a polyamine). Ester dispersants
are prepared by reacting a polyhydroxy compound with a
hydrocarbyl carboxylic acylating agent. The ester
dispersànt may be further treated with an amine. Mannich
dispersants are prepared by reacting a hydroxy aromatic
compound with an amine and aldehyde. The dispersants
listed above may be post-treated with reagents such as
;urea, thiourea, carbon disulfide, aldehydes, ketones,
carboxylic acids, hydrocarbon substituted succinic
anhydride, nitriles, epoxides, boron compounds,
phosphorus compounds and the like. These dispersants are
generally referred to as ashless dispersants even though
they may contain elements such as boron or phosphorus
which, on decomposition, will leave a non-metallic
residue.
Extreme pressure agents and corrosion- and
oxidation-inhibiting agents include chlorinated
compounds, sulfurized compounds, phosphorus containing
compounds including, but not limited to,
phosphosulfurized hydrocarbons and phosphorus esters,
metal containing compounds and boron containing
compounds.
Chlorinated compounds are exemplified by chlorinated
aliphatic hydrocarbons such as chlorinated wax.
Examples of sulfurized compounds are organic
sulfides and polysulfides such as benzyl disulfide,
bis(chlorobenzyl)disulfide, dibutyl tetrasulfide,
:
, .. . . . .
.," ' '' '' ' ~ .
. . .
~: .
:''`''. ' ' ~ ' .
:, - .
,., ~, ,.
- 2 ~ 8
sulfurized methyl ester of oleic acid, sulfurized
alkylphenol, sulfurized dipentene, and sulfurized
terpene.
Phosphosulfurized hydrocarbons include the reaction
product of a phosphorus sulfide with turpentine or methyl
oleate.
Phosphorus esters include dihydrocarbon and
trihydrocarbon phosphites, phosphates and metal and amine
salts thereof.
Phosphites may be represented by the following
formulae:
.
., O
,,, 11
R50 P OR5
H
or
(R50)3P
wherein each R5 is independently hydrogen or a
hydrocarbon based group, provided at least one R5 is a
hydrocarbon based group.
Preferably each R5 is independently a hydrogen or
hydrocarbon based group having from 1 to about 24, more
preferably from 1 to about 18, and more preferably from
about 2 to about 8 carbon atoms, provided that at least
one R5 is a hydrocarbon based group, Each R5 may be
independently alkyl, alkenyl or aryl. When R5 is aryl it
contains at least 6 carbon atoms; preferably 6 to about
18 carbon atoms. Examples of alkyl or alkenyl groups are
propyl, butyl, hexyl, heptyl, octyl, oleyl, linoleyl,
stearyl, etc. Examples of aryl groups are phenyl,
naphthyl, heptylphenyl, etc. Preferably each R5 is
independently propyl, butyl, pentyl, hexyl, heptyl, oleyl
or phenyl, more preferably butyl, oleyl or phenyl and
more preferably butyl or oleyl.
,:.- , . . . : .
. -. - : -,
,
. . .
,'
~ ~ 54 ~ 2~76~
The R5 groups may also comprise a mixture of
hydrocarbyl groups derived from commercial alcohols.
Examples of preferred monohydric alcohols and alcohol
mixtures include commercially available "Alfol" alcohols
marketed by Continental Oil Corporation. Alfol 810 is a
mixture containing alcohols consisting essentially of
straight-chain, primary alcohols having 8 to 10 carbon
atoms. Alfol 812 is a mixture comprising mostly C12
fatty alcohols. Alfol 1218 is a mixture of synthetic,
primary, straight-chain alcohols having from 12 to 18
carbon atoms. Alfol 20+ alcohols are mixtures of 18-28
primary alcohols having mostly, on an alcohol basis, C20
alcohols as determined by GLC (gas-liquid-
chromatography).
Another group of commercially available alcohol
mixtures includes the "Neodol" products available from
Shell Chemical Company. For example, Neodol 23 is a
mixture of C12 and C13 alcohols; Neodol 25 is a mixture
of C12 and C15 alcohols; and Neodol 45 is a mixture of
C14 and C15 linear alcohols. Neodol 91 is a mixture of
Cg, C10 and Cll alcohols.
Phosphites and their preparation are known and many
phosphites are available commercially. Particularly
useful phosphites are dibutylhydrogen phosphite, trioleyl
phosphite and triphenyl phosphite. Preferred phosphite
esters are generally dialkyl hydrogen phosphites.
A number of dialkyl hydrogen phosphites are
commercially available, such as lower dialkyl hydrogen
phosphites, which are preferred. Lower dialkyl hydrogen
phosphites include dimethyl, diethyl, dipropyl, dibutyl,
dipenyl and dihexyl hydrogen phosphites.
Phosphate esters include mono-, di- and
trihydrocarbon-based phosphates of the general formula
(R50)3PO
.,,
. ~ . ....
. . .
.
. ~ , . . .
,, ,
': ' '
.i .
- 55 - 20~7t3
'~
wherein R5 is as defined for the phosphites described
hereinabove. Examples include mono-, di- and trialkyl ;
mono-, di and triaryl and mixed alkyl and aryl.
Specific, non-limiting examples include, tri lower alkyl
phosphate, dialkyl phosphates, and the like.
Particularly preferred are the reaction products of
phosphorus pentoxide (P205) with alcohols in a ratio of 3
hydroxyl groups to one P205 yielding a mixture of mono-
and dialkyl phosphates. Also available or readily
prepared by known techniques are diheptyl, dicyclohexyl,
pentylphenyl, dipentylphenyl, tridecyl, distearyl,
dimethyl naphthyl, oleyl 4-pentylphenyl, polypropylene
(molecular weight 500)-substituted phenyl, and
diisobutyl-substituted phenyl phosphites. Also mixed
alkyl hydrogen phosphites are useful in the present
invention. Examples of mixed alkyl hydrogen phosphites
include ethyl, butyl: propyl, pentyl: and methyl, pentyl
hydrogen phosphites.
Metal containing compounds include metal
thiocarbamates, such as zinc dioctyldithiocarbamate, and
~arium heptylphenyl dithiocarbamate and molybdenum
compounds.
Boron containing compounds include borate esters and
boron-nitrogen containing compounds prepared, for
example, by the reaction of boric acid with a primary or
secondary alkyl amine.
Viscosity improvers include, but are not limited to,
polyisobutenes, polymethacrylate acid esters,
polyacrylate acid esters, diene polymers, polyalkyl
styrenes, alkenyl aryl conjugated diene copolymers,
polyolefins and multifunctional viscosity improvers.
Pour point depressants are a particularly useful
type of additive often included in the lubricating oils
described herein. See for example, page 8 of "Lubricant
Additives" by C. V. Smalheer and R. Kennedy Smith
(Lesius-Hiles Company Publishers, Cleveland, Ohio, 1967).
:
.
:, ~: .
~;, . ,.,
. .
-
...
- 56 - ~ 7~
Anti-foam agents used to reduce or prevent the
formation of stable foam include silicones or organic
polymers. Examples of these and additional anti-foam
compositions are described in "Foam Control Agents", by
Henry T. Kerner (Noyes Data Corporation, 1976), pages
125-162.
These and other additives are described in greater
detail in U.S. Patent 4,582,618 ~column 14, line 52
through column 17, line 16, inclusive), herein
incorporated by reference for its disclosure of other
additives that may be used in combination with the
present invention.
The components may be blended together in any
suitable manner and then admixed, for example with a
diluent to form a concentrate as discussed below, or with
a lubricating oil, as discussed below. Alternatively,
components can be admixed separately with such diluent or
lubricating oil. In preparing concentrates, it is
preferred that the triazole, if used, be dissolved first
in the diluent by heating to a temperature of about
80-90C followed by cooling before the remaining
components are blended into the diluent. The blending
technique for mixing the components is not critical and
can be effected using any standard technique, depending
upon the specific nature of the materials employed. In
general, blending can be accomplished at room
temperature; however, blending can be facilitated by
heating the components.
As previously indicated, the compositions of the
present invention are useful as additives for lubricants
and functional fluids. They can be employed in a variety
of lubricants based on diverse oils of lubricating
viscosity, including natural and synthetic lubricating
oils and mixtures thereof. The lubricants include
crankcase lubricating oils for spark-ignited and
compression-ignited internal combustion engines,
including automobile and truck engines, two-cycle
,;,
,, .
. I .
~.j
,
.. .
;
: :
,, .
' ,
: 2~7~
- 57 -
.~
engines, aviation piston engines, marine and railroad
diesel engines, and the like. Also contemplated are
lubricants for gas engines, stationary power engines and
turbines and the like. Transaxle lubricants, gear
lubricants, metal-working lubricants and other
lubricating oil and grease compositions, as well as
functional fluids such as hydraulic fluids and automatic
transmissions fluids, benefit from the incorporation
therein of the compositions of the present invention. As
discussed hereinabove, this invention provides special
benefits when the composition is exposed to water.
The lubricating compositions and methods of this
invention employ an oil of lubricating viscosity,
including natural or synthetic lubricating oils and
mixtures thereof. Natural oils include animal oils,
vegetable oils, mineral lubricating oils, solvent or acid
treated mineral oils, and oils derived from coal or
shale. Synthetic lubricating oils include hydrocarbon
oils, halo-substituted hydrocarbon oils, alkylene oxide
polymers, esters of carboxylic acids and polyols, esters
of polycarboxylic acids and alcohols, esters of
phosphorus-containing acids, polymeric tetrahydrofurans,
silicon-based oils and mixtures thereof.
Specific examples of the oils of lubricating
viscosity are described in U.S. Patent 4,326,972 and
European Patent Publication 107,282, both herein
incorporated by reference for their disclosures relating
to lubricating oils. A basic, brief description of
lubricant base oils appears in an article by D. V. Broc~,
"Lubricant Base Oils", Lubrication Engineerina, volume
43, pages 184-185, March, 1987. This article is herein
incorporated by reference for its disclosures relating to
lubricating oils. A description of oils of lubricating
viscosity occurs in U.S. Patent 4,582,618 (column 2, line
37 through column 3, line 63, inclusive), herein
incorporated by reference for its disclosure to oils of
lubricating viscosity.
.
,
..
.:,
~ ,
~58 - 2 ~ 8 ~ 7 6 8
;
; Component (A) and component (B) are generally used
in relative amounts of A:B ranging from about 5:1 to
about 1:5, more often from about 2:1 to about l:Z, by
weight.
- When component (C) is present, it is generally used
-~in amounts relative to component (A) ranging from about
A:C = 1:40 to 2:1, preferably from about 1:20 to about
1:1, more preferably from about 1:10 to about 1:1.
~'Component (A) is used in the lubricating oil com-
positions of this invention in amounts ranging from about
0.01 to about 5% by weight, often up to about 2% by
',weight. A preferred range is from about 0.01 to about 1%
by weight of the total weight of the composition.
Components (B) and (C) are utilized in amounts
within the above-specified amounts relative to component
(A).
The following examples illustrate compositions of
the present invention. The amount of each component in
the Examples also reflects the amount of oil present in
,the indicated components.
.
,
,,
i
"'
.
":~
;, ,:
,~4
.,`3
.;
~.3
:,
, ~
~ ~ .
:,~
,
. .
,: :r~.
,
. .
.~ , , .
J`~
. , ~ ,
7 ~ 8
-- 59 --
. ... . ...
a) o ~ 0 o ~o o ~ 1
~r
o~ ,~ o ~ o
~ .,1
I ~ a~ . . . .
~ o~ ,~ o ~ o
o
:Z
0 a~
_~ CO
. ~ li3
H
~ ~ I` CO ~ 00 1~ OD cr~ I
m ,~ o
.¢ ~1
E~ ~ o ~ ,~ o ~D O
. ~D ~
~r
~" ~
~ O
,' , ,a ~
m m m
o
N ~ ~/ a o
~x X ~ ,0~ ~ ~ O X ~ ~ ~ a
O O J~ S~ ~ O
N N O ~ N ~ ~ ~ ~ ~ ~1 (~ ~1 (1-1
O O O 11) (d N Cl 1~ 0 0 0 0 0 0 _I O O O
~ UUU~ UUUU~UUUU
o ~ o ~ o a~
, ~ 'O 'O ~ N :~ ~1 ~ N
~ O O O _I C X ~:) C ~ Q. OO O O ~ ~1 0 0 0
O ~ ~ ~ O ~ ~ O -1 ~ O ~ 1 0
U ~ m ~ m u
.
;~
:
.
.
-. .
.
~ .
.: . "
.
20~7~
- 60 -
As indicated hereinabove, the compositions of this
-Iinvention are useful as additives for a wide variety of
lubricating compositions. Preferred lubricating
compositions are functional fluids, with hydraulic fluids
being particularly preferred. The following are
non-limiting examples of lubricating compositions of this
invention.
Example 6
~To a 100 neutral mineral oil basestock is added,
- with mixing and gentle heating, 1~ by weight of the
product of Example A-l, 0.3~ by weight of the product of
Example B-4, and 0.01 percent by weight of a silicone
antifoam.
;'
' Exam~le 7
To a mineral oil basestock (250 neutral) is added
0.85 percent by weight of the additive concentrate of
Example 1.
,';'
Example 8
Example 7 is repeated except additive concentrate of
Example 1 is replaced with that of Example 4.
Exam~le 9
~~To the lubricating oil composition of Example 6 is
,',added 0.05% by weight of the product of Example C-l.
;l Example 10
`To Sun Tulsa IS0 46 base oil is added 0.81 percent
i;~by weight of the additive concentrate of Example 3.
,~ ,
'~ Example 11
To Sun Tulsa IS0 46 base oil is added 0.1 percent by
~,weight of the additive concentrate of Example 2.
,
:,
,, .
:~ .
~i
:,
: :
; .:
. ~........................................................ .
., .
2~887~
- 61 -
Example 12
Example 7 is repeated except the additive
concentrate of Example 4 replaces that of Example 1.
Example 13
- To a hydraulic fluid basestock (ISO 46) is added o.i
parts of dibutyl hydrogen phosphite, 0.01 parts of
tolyltriazole, 0.1 parts of a magnesium salicylate, 0.05
parts of the reaction product of propylene oxide with
tetrapropenyl succinic anhydride, 0.2 parts of tricresyl
phosphate, 0.25 parts of hindered phenol, 0.25 parts of
di(nonylphenyl) amine and 0.05 parts of the product of
Example B-7.
Example 14
A hydraulic fluid is prepared according to the
procedure of Example 13 replacing 0.05 parts of the
product of Example B-7 with 0.03 parts of the product of
Example B-6.
Example 15
A composition comprising an oil of lubricating
viscosity, 0.85 percent by weight of the product of
Example A-4, 0.15 parts of the product of Example B-6,
0.2 parts of hindered phenol, 0.002 percent by weight of
' tolyltriazole and 0.01 percent by weight of an organic
~ polymer antifoam.
:',
Example 16
The composition of Example 7 replacing the product
of Example C-11 with that of Example C-16.
;~ The filterability of hydraulic fluids can be
determined employing the AFNOR E48-690/l test published
by l'Association Francaise DeNormalisation, Tour Europe
Cedex 7 92 080 Paris-La Defense, France. Thls test
. .
,
~ - 62 - 2~7fi~
consists of filtering, under constant pressure, at
constant temperature, through a membrane with a
determined absolute stopping power, a specified volume of
fluid contained in a container of defined dimensions.
This test employs an essentially uncontaminated fluid.
Filterability indices of the fluid (IFl, and IF2)
are defined for a given fluid by the ratios:
T300 T200 T - T
IFl = and IF2 =
2 T50 2 (Tloo T50)
in which
T~oo is the passage time, through the membrane, of
300 cm of fluid,
T~oo is the passage time, through the membrane, of
200 cm of fluid,
T100 is the passage time, through the membrane, of
100 cm of fluid,
; T50 is the passage time, through the membrane, of 50
cm of fluid.
This ratio therefore consists of comparing the filtration
~r' speeds of the fluid in the course of the test. These
ratios as well as the filtration speeds of the various
, segments for each sample are indicative of the ease of
filtration of the fluids.
A modification of this test entails the use of a
~, water-treated fluid. To the fluid is added a fixed
;' amount of water, the mixture is agitated, then stored.
After the aging period, the water-treated fluid is
evaluated as above.
The results of the filtration of the water-free and
the water-containing fluids are compared. It has been
observed that when the fluids are contaminated with
water, filtration of fluids of the present invention is
significantly improved compared to similar fluids that do
not contain the acidic material, component (B).
,
., .
.
'~' .
~ .~
~ ! - 63 - 208~76~
It has also been observed that when a fluid contains
zinc, usually as a zinc salt, depletion of zinc may occur
when the fluid is exposed to ASTM D-943 test conditions,
which are oxidation conditions including the presence of
water. The compositions of this invention resist
depletion of zinc under those test conditions.
While this invention has been explained in relation
to its preferred embodiments, it is to be understood that
various modifications thereof will become apparent to
those skilled in the art upon reading the disclosure.
Therefore, it is to be understood that the invention
disclosed herein is intended to cover such modifications
as fall within the scope of the appended claims.
,,
?
.~
,,
. ~', '
.
:.,.
