Note: Descriptions are shown in the official language in which they were submitted.
. L-2152R ~.~ 7 6 00 4
ADDITIVES FOR LUBRICANTS AND FU~CTIONAL
FLUIDS WHICH EXHIBIT IMPROVED
PERFORMANCE AND METHOD FOR P PARING SAME
BACKGROUND OF THE INVENTION
1. Field of the Invention
- :-
Thi~ invention relate~ t3 a sulfur-ba~ed addi~ive
exhibiting improved performance for u6e in lubr~cants and
~unctional fluid More specifically, labile-sulfur free
additive6 for lubricants and functional Pluids are
ob~ai~ed by treatment with copper, or copper and another
material reactive with labile-6ulfur or with alpha-ole~ins
in order to substantially eliminate the detrimental metal
corro~ivity and the d~trimental degradation of ela~tome~
materials which are exhibited by labile-sulfur containing
additives.
2. De~cription of the Prior Art
Sulfur-based additive6 have been widely used in
various lubricants, e.g., crankca6e lubricating oil~, gear
lubricants, metal-working lubricants and the like, and in
variou~ functional fluids, e.g., hydraulic fluid~,
automatic transmis6ion fluid6, heat transfer fluids and
the like. The mo~t common o such ~ulfur-based additive~
are phenolsulfides, disulfide6, polysulfides, salts
thereof, overba6ed 6alts thereof, and mixture~ thereof.
These additives ~unction a~ oxidation inhibitor~, antiwear
~,
-- 2
additives and load carrying additives for these different
cate~ories of fluids.
While theRe sulfur-based additives have been found to
be quite effective for ~he above-men~ioned functions, t~ey
have generally been found to be corrosive to metal6 such
as copper and copper alloys which are widely used as
bearings and bearin~ liners and have been found to cause
the degradation of elastomer materials which are used as
seal6 or sealant devices.
To overcome this problem, various co-additives such
as aryltria~ole6 and various thiadiazoles have been
included with the6e sulfur-based additive6 in lubricants
and functional fluids. However, a~ide from their expense,
these co-additives create further complications in
lubricant formula~ion, e.g., additional solubilizers may
be required as well a~ additional blending steps are
neces ary.
In U.S. Patent 4,309,2g3, it is disclosed ~hat
phenolsulfides, disulfiaes or polysulfides, oligomers
thereof or mixtures of same when ~reated with alkylvinyl
ethers reduce metal corrosivity when incorporated into
lubricants and like fluids. The alkylvinyl ethers of this
patent are reactive with the phenolic hydroxyl groups
which are generally treated in succes6ive steps where the
reaction produ~t is not removed from the additive. This
particular treatment or process has the problem, aside
from the expense of alkylvinyl e~hers, of not eIiminating
corro~ive labile-sulfur contained in these types o~
additivas and, in addition, they reguire special handling
~ecause of their high volatility.
While a number of approaches have been attempted to
solve the corrosion problem associated with sulfur-based
additives for lubricants and functional fluids, the prior
art has not disclosed any which are entirely successful or
are not without other problems, e.g., creating formulation
problems, inhihiting the desired effects of ~hese
additives, ~nd the like.
.
o~
- 3 -
SUMMARY OF THE INVENTION
-
In accordance with the present invention, a highly
effective and a relatively economic method for eliminating
the metal corrosion and elastomer degradation problem
associated with sulfur-based additives for lubricants ancl
functional fluids has been discovered.
~ In accordance with a first aspect of the present
; invention, it has been found that treating sulfur-based
additives, particularly phenolsulfides, disulfides, poly-
sulfides, salts thereof, overbased salts thereof, and
mixtures thereof with copper metal, copper salts or copper
metal or salts and an optional additional reactive
material, an essentially labile-sulfur free additive is
obtained which will not corrode metals, particularly
copper or copper-alloys, and will not degrade elastomer
sealant materials.
In accordance with a second aspect of the present
invention, it has been found that treating sulfur-based
additives with olefins, particularly alpha-olefins, an
essentially labile~sulfur free additive for lubricants and
functional fluids may be obtained which will not corrode
metals, particularly copper and copper-alloys, and will
not degrade elastomer sealant materials.
Still further in accordance with the present
invention, labile-sulfur free additives exhibiting
improved performance, labile-sulfur free additive
concentrates, lubricant and functional fluid compositions
containing such additives and a method for lubricating
copper and copper-alloy bearings by applying lubricant and
functional fluid compositions containing such additives
thereto are contemplated and within the scope of the
present invention.
These and other aspects of the invention will become
clear to thosa skilled in the art upon the reading and
understanding of the specification.
'
.
2~
DESCRIPTION OF THE PREFERXED EMBODIMENTS
It has surprisingly been discovered that an
additive, free of labile-sulfur useful in lubricants and
functional fluids may be obtained by a highly effective
; 5 and relatively economic method. This method gives a
labile-sulfur free additive for lubricants and functional
fluids which does not corrode metals, or only to a minor,
insigniicant extent and will not degrade elastomer
materials or only to a minor, insignificant extent.
The method of the present invention in a first
aspect involves contacting sulfur-based additives for
lubricants and functional fluids with copper or copper and
another material reactive with labile-sulfur at an
elevated temperature followed by filtering off copper
sulfide and other particulate from the thus treated
; additive to give an essentially labile-sulfur free
additive. In another aspect of the present invention, a
sulfur-based additive is contacted with an olefin,
preferably an alpha-olefin, at an elevated temperature to
produce an essentially labile-sulfur free additive for
lubricants and functional fluids. By this method, to be
further described in detail, essentially all labile-sulfur
is removed from these additives where the resulting
treated additive contains at most about 0.4~ by weight of
; 25 labile-sulfur. Employing thus treated additives in
lubricants and functional fluids substantially eliminates
the problem of metal corrosion and elastomer degradation
previously exhibited by sulfur-based additives. Moreover,
the method of the present invention does not have some of
the other inherent problems associated with previous
approaches to overcome the metal corrosion and elastomer
degradation problem such as various formulating problems,
inhibition of the properties of these additives and the
like.
It was found in accordance with a first aspect of
the present invention that sulfur-based additives may be
treated with copper or copper and another labile-sulfur
reactive material. As
,
~.~27~
-- 5
used herein, copper includes metallic copper as well as
copper salts. The physical form of metallic copper used
in the method of the invention is not particularly
critical and may include turnings, granules and powder.
For the purposes of the present invention, copper powder
has been found to be particularly useful. Copper salts
that may be useful within tha scope o* the present
invention there may be mentioned oxides, oleates and
halides, preferably chlorides. The amount of copper used
to treat various sulfur-based additives should be suffic-
ient. to essentially remove all labile-sulfur contained by
the additive. The amount of copper utilized in the method
of the present invention preferably ranges from about 5~
by weight based on the additive to about 0.01% by weight
and more preferably in the range of about 1.0~ to about
0.1~ by weight of the additive.
As other reactive materials that may be used in
combination with copper to treat various sulfur-based
additives there may be mentioned unsaturated natural oils
including vegetable and animal oils such as soybean oil,
lard and the like; various olefins, particularly alpha-
olefins which preferably have 4 to 30 carbon atoms and
most preferably 10 to 20 carbon atoms; the Diels-Alder
reaction products of butadiene and esters of acrylic acid,
preferably butylacrylate; organic phosphites such as tri-
phenol phosphite; basic metal salts such as sodium hydrox-
ide, potassium hydroxide, sodium carbonate and the like;
and various amines, including primary and secondary
amines. The amount of these other reactive materials used
with ~opper in the method of the present in~ention is not
particularly critical wherein the amount of labile-sulfur
present in the partiaular additive to be treated and
economics will be determinative of the actual amount used.
The amount used within the practice of the present inven~
t.ion preferably ranges from about 1 part of other reactive
~76~
-- 6 --
material to about 10 parts copper to 10 parts other
reactive material to about l part copper.
As previously mentioned, a second aspect of the
present invention involves contacting sulfur-based
additives with an olefin, preferably alpha-olefins having
4 to about 30 carbon atoms and most preferably 10 to about
20 carbon atoms. The amount of olefin used to treat
various sulfur-based additives is not particularly
critical to the invention and should be sufficient to
remove essentially all labile-sulfur from the particular
sulfur-based additive. It has been found that this amount
is preferably in the range of about 10% to about 0.1% by
weight of the additive and most preferably in the range of
about 5% to about 1% by weight based on the additive.
The method of the present invention is generally
conducted at atmospheric pressure, however, higher
~ pressures may be utilized, particularly if the treating
; agent is an olefin. The contacting of the sulfur-based
additives with the treating agents of the present
invention is conducted at temperatures sufficient to react
essentially all the labile-sulfur present in the
particular additive which is usually at an elevated
temperature, preferably in the temperature range of from
about 100C to about 250C and most preferably from about
25 130C to about 160C. However, it is pointed out that the
temperature range may vary widely depending upon the
particular treating agent and/or the presence of a
catalyst.
The additives that may be treated according to the
method of the present invention include any sulfur-based
additive which is used in lubricants and functional
fluids. The most common of such additives are
phenolsulfides, disulfides, polysulfides, salts thereof
and overbased salts thereof. These "sulfurized" phenols
includes alkyl and dialkyl phenols wherein the alkyl group
may range from about 6 to about 100 carbon atoms. Many of
;, ,.
, ~ "..~;
~7~
- 7 -
these sul~urized phenols are commercially available or may
be prepared by initially reacting a phenol or alkylphenol
with a sulfur monohalide (e.g. sulfurmonochloride). This
reaction may be conducted in the presence of excess base
to result in the salts of the mixture of sulfides,
disulfides or polysulfides that may be pxoduced depending
upon the reaction conditions. It is the resulting product
of this reaction which is then treated in accordance with
the method o~ the present invention. However, the
overbased salts may be prepared after the txeatment in
accordance with the present invention. U.SO Patents
2,971,940 and 4,309,293 disclose various sulfurized phenols
which are illustrative of sulfur based additives that may
be treated according to the method of the present
invention.
One particular class o~ phenates for use in this
invention are the basic (i.e., overbased, etc.) Group IIA
metal sul~urized phenates made by sulfurizing a phenol as
described hereinabove with a sulfurizing agent such as
~20 sulfur, a sulfur halide, or sulfide or hydrosulfide salt.
A'Techniques for making these sulfurized phenates are
described in U.S. Patents 2,680,096, 3,036,971 and
3,775,321.
~ As previously indicated, the additives of fhe
present invention, which are essentially labile-sulfur
free, ~ind use in a wide range of lubricants and functional
fluids. Such additives may be employed in a variety of
lubricants based on diverse oils of lubricating viscosity,
including natural and synthetic lubricating oils and
mi~tures thereof. The lubricants include crankcase
lubricating oils ~or spark ignited and compression ignited
internal combustion engines, including automobile and
truck engines, 2-cycle 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 ..~..
7~
-- 8
lubrican~, qear lubricants, metal-working lubricants and
other lubricating oil and grease compositions are ~it~in
the cope of the pre6ent invention~ Various functional
fluid~ to which the additives of the present invention may
be added include hydraulic fluid~, heat transfer ~luid~5
automatic tran~mission fluîd~ and the like.
Na~ural oils include animal oils and vegetable oils
(e.g., castor, lard oil) liquid petroleum oil6 and
hydrorefined, solvent-treated or acid-treated mineral
lubricating oils of the parafEinic, naphthenic and mixed
paraffinic-naphthenic types. Oils of lubricating
viscosity derived from coal or shale are also useful ba~e
oils.
Synthetic lubricating oils include hydrocarbon oils
and halo-su~stituted hydrocarbon oils 6uch as polymerized
and in~erpoly~erized olefins ~e.g., polybutylenes,
polypropylenes, propylene-isobutylene copolymer~,
chlorinated polybutylenes, poly~l-hexene6),
poly(l-octenes), poly(l-decenes)~: alkylbenzenes (e.g.,
dodecylbenzene~, te~radecylbenzenes, dinonylbenzenes,
di~2-ethylhexyl)benzenes]; polyphenyls (e.g., b}phenyls,
terphenyls, alkylated polyphenols) and alkylated diphenyl
ethers and alkylated diphenyl sulfides and ~he
deri~ati~e~, analogs a~d homologs thereof.
Alkylene oxide polymers and interpolymers and
derivatives thereof where the terminal hydroxyl groups
have been modified by esteri~ication, etherification,
etc., constitute anGther cla6~ of known ~ynthetic
lubricating oils. These are exemplified by
polyoxyalkylene polymers prepared by polymerization o
ethylene oxide or propylene oxide, ~he alkyl and aryl
ether6 of the6e polyoxyalkylene polymer~ (e.g.,
methyl-polyisopropylene glycol ether having an average
molecular weight of 1000, diphenyl ether of poly-ethylene
glycol having a molecular weight of 500-1000, diethyl
ether o~ polypropylene glycol havinq a molecular weight of
1000-1500) and mono- and polycarboxylic ester~ thereo~,
.
- 9
for example, the ace~ic acid e6ters, mixed C3-C8 fa~ty
acid esters and C13 Oxo acid diester of tetraethylene
glycol.
Another sui~able class of synthetic lubricating oils
comprises the esters of dicarboxylic acids (e.g., phthalic
acid, succinic acid, alkyl suc~inic acids and alke~yl
succinic acids, maleic acid, azelaic acid, suberic acid,
sebacic acid, fumaric acid, adipic acid, linoleic acid
dimer, malonic acid, alkylmalonic acids, alkenyl malonic
acids) with a variety of alcohols (e.g., butyl alcohol,
hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol,
ethylene glycol, diethylene glycol monoether, propylene
glycol). Specific examplee of these esters include
dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl
fumarate, dioctyl sebacate, dii600ctyl azelate, diisodecyl
azelate, dioctyl phthalate, didecyl phthalate, dieico~yl
sebacate, the 2-ethylhexyl die ter of linoleic acid dimer,
and the complex ester formed by reacting one mole of
sebacic acid with two moles of ~etraethylene glycol and
two moleæ of 2-e~hylhexa~oic acid.
~ sters useful as syn~hetic oils also include those
made from C5 to ~12 monocarboxylic acids and pQlyols
and polyol e~her such as neopentyl glycol,
trimethylolpropane, pentaerythritol, dipentaerythritol and
tripentaerythritol.
Silicon-based oils such as the polyalkyl-, polyaryl-,
polyalkoxy-, or polyaryloxysiloxane oils and silica~e oils
compri~e another useful clas6 of synthetic lubricants;
they include tetraethyl silicate, tetraisopropyl silicate,
tetra-(2-ethylhexyl) silicate,
tetra-(4-methyl-Z-ethylhexyl) silicate,
tetra-(p-tert-butylphenyl) silicate,
hexa-(4-methyl-2-pentoxy)di6iloxane, poly(methyl)siloxanes
and poly(methylphenyl) siloxanes. Other synthetic
lubricatin~ oils include liquid esters o~
phosphoru~-containing acids (e.g., tricresyl phosphate,
-- 10 --
trioctyl pho~phate, die~hyl e6ter of decylphosphonic acid)
a~d polymeric tetrahydrofurans.
Unrefined, refined and rerefined oils can be used in
the lu~ricants of the present invention. Unrefined oils
are those obtained directly from a natural or synthetic
~ource without further purification treatment~ For
example, a hale oil obtained directly from retorting
operation6, a petroleum oil obtained directly from
di~tillation or ester oil obtained directly from an
es~erification process and used without further treatment
would be an unrefined oil. Refined oils ar~ similar to
the unrefined oils except they have been further treated
in one or more purification steps to improve one or more
propertie~. Many such purification techniques, such as
distillation, solvent extraction, acid or base extraction,
filtration and percolation are known to ~hose skilled in
the art. Rerefined oils are obtained by proce6se6 similar
to those u6ed to ob~ain refined oils applied to refined
oils which have been already used in service. Such
rerefined oil~ are also known as reclaimed or reprocessed
oils and often are additionally processed by techniques
for removal of ~pent additives and oil breakdown products.
Generally the lubricants of the present invention
contain a performance and lubricating improving amount of
one or more of the treated sulfur-based additives of this
in~ention which do not corrode metals or only to a minor,
insignificaQ~ extent and do not degrade elastomel
material~ or only to a minor, insignificant extent.
Normally the amount employed will be about 0.05% to a~out
20%, preferably about 0.1~ to about 10% of the tatal
weight of the lubricating compo6ition. This amount is
exclusive of solvent~diluent medium. In lubricating
compositions operated under ext~emely adverse condition6,
such as lubricating compositions for marine diesel
engines, the metal salt6 of this invention may be present
in amounts of up to about 30% by weight, or more, of the
total weight of the lubricating composition.
~" 3;~7~
-- 11 --
The inventio~ also contempla~es the use o~ other
addi~ives in combination with the treated additives of
this invention. Such additives include, for exa~ele,
deteLgents and dispersants of the ash-producing or ashless
type, and other oxidation-inhibiting agents, pour point
depressing agent~, extreme pressure agents, antiwear
agents, color stabilizers and anti-foam agents.
The ash-producing detergents are exempli~ied by
oil-soluble neutral and basic salts of alkali or alkaline
earth metals with sulfonic acids, carboxylic acids, or
organic phosphorus acids characterized by at lea~t one
direct carbon-to-phosphorus linkage such as tho6e prepared
by the treatment of an olefin polymer (e.g., polyisobutene
having a molecular weight of 1000) with a phosphorizing
,
agent such as phosphorus trichloriae, phosphorus
heptasulfide, phosphorus pentasulfide, phosphorus
trichloride and sulfur, white phospharus and a sulfur
halide, or pho6phorothioic chloride. The most commonly
u~ed salts of ~uch acids are those of sodium, potassiu~,
lithium, calcium, magne~ium, strontium and barium.
The term "basic salt" is used to designate metal
salts wherein the metal is present in stoichiometrically
l~rger amounts than the organic acid radical. The
commonly em210yed methods for preparinq the basic salts
involve heating a mineral oil solution of an acid with a
stoichiomet~ic excess of a metal neutrali~ing agent such
a~ the metal oxide, hydroxide, carbonate, bicarbonate, or
sulfide at a temperature of about 50C. and fi1tering the
resulting mass. The use of a "promoter" in the
neutraliziation step to aid the incorporation of a large
excess of metal likewi6e is known. Examples of compound
u~eful as the promoter include phenolic substances such as
phenol, naphthol, alkylphenol, thiophenol, ~ulfurized
alkylphenol, and condensation products o~ formaldehyde
with a phenolic substance: alcohols ~uch as methanol,
2-propanol, octyl alcohol, cellosolve, carbitol, ethylene
glycol, stearyl alcohol, and cyclohexyl alcohol: and
- 12 -
amines such as aniline, phenylenediamine, phenothiazine,
phenyl-B-naphthylamine, and dodecyla~ine. A particularly
effective method for prep~ring the ba~ic salts compr~es
~ixing an acid with an excess of a ~asic alkaline earth
metal neutralizing agent and at lea~t one alcohol
promoter, and carbo~ating the mixture at a~ elevated
temperature ~uch a~ 60-200C.
A6hles~ detergents and dispersants ~re so c~lled
de~pite the fact that, depending on it~ constitution, the
dispersant ~ay upon combu~ion yield a non-volatile
material ~uch a boric oxide or phosphorus pentoxide;
howe~er, it does not ordinarily contain metal and
therefore doe~ not yield a metal-contai~ing a~h on
combustion. Many typ~6 are known in the art, and any of
~hem are ~ui~able for use in the lubricant compositions of
thi~ invention. The following are illus~rative:
(1) Reac~ion produc~s of carboxylic acids (or
derivative6 thereof) containing at least about 3~ and
preferably at least a~out 54 carbon ~toms with nitrogen
containing compound6 ~uch as amine, organic hydroxy
compound~ such as phenols and alcohols, and/or basic
inorganic ma~erials. Examples of ~hese "carboxylic
di~persants~ are de~cribed in British Pa~ent 1,306,52g and
in many U.S. patent~ including the following:
3,163,603 3,351,55Z 3,541,012
3,184,474 3,381,0Z2 3,543,678
3,215,707 3,39~,141 3,542,68~
3,219,666 3,415,750 ~,557,637
3,271,310 3,433,744 3,574,101
3,272,746 3,444,170 3,576,743
3,~81,357 3,44~,0~8 3,630,904
3,306,908 3,448,049 3,63Z,510
3,311,558 3,451,933 3,632,511
3,316,177 3,45~,607 3,~97,4Z8
3,340,281 3,467,668 3,7Z5,441
3,341,54~ 3,501,405 4,234,g35
3,346,493 3,522,179 Re 26,433
. .
.2'760~D~
- 13 -
(2) Rea~tion products of rela~ively high molecular
weight aliphatic or alicyclic halide~ with amines,
preferably polyalkylene polyamines. The6e may be
characterized as "amine di~persants~ and example6 thereof
are de6cribed for example, in the following U.S. patent~:
3, 275, 554 3, 454, 555
3, 438, 757 3, 5S5, 804
(3) ~eaction products of alkyl phenols in which the
alkyl group contains at lea6t about 30 carbon ~toms with
aldehydes tespecially formaldehyde) and a~ines ~especially
polyalkylene polyamines), which may be characteri~ed as
"Mannich dispersants~. The materials described in the
following U.S. patents are illu6trative:
2,459,112 3,442,808 3,591,598
2,962,442 3,448,047 3,600,372
~,9~4,550 3,454,~97 3,634,515
3,036,003 3,459,661 3,649,z29
3,166,516 3,461,172 3,6~9~,57
3,~36,770 3,4g3,520 3,725,~77
3,355,270 3,539,6~3 3,725,g80
3,368,972 3,558,743 3,726,882
3,~13,347 3,586,629 3,980,569
(4) Product~ obtained by post-treating the
carboxylic, amine or Mannich dispersant~ with such
reagents as urea, thiourea, carbon disulfide, aldehydes,
ketones, carboxylic acids, hydrocarbon-substituted
succinic anhydrîde~, nitriles, epoxides, boron compounds,
phosphoru~ compoundæ or the like. Exemplary ma~erialæ of
thi~ kind are described in the following U.S. patentB:
3,036,003 3,28Z,955 3,493,520 3,639,242
3,087,936 3,312,619 3,502,677 3,649,229
3,Z00,107 3,366,569 3,513,093 3,649,659
3,216,g36 3,367,943 3,533,945 3,65~,836
.3,2.54,025 3,373,111 3,539,633 3,697,574
3~z~6~la5 3,403,10Z 3,573,010 3,70Z,757
3,278,550 3,442,808 3,579,450 3,703,536
~27~
- 14 -
3,280,234 3,455,831 3,591,598 3,704,308
3,281,~28 3,455,832 3,600,372 3,708,422
(5) Interpol~mers o~ oil solubilizing monomers
such as decyl methacrylate, vinyl decyl ether and high
molecular weight olefins with monomers containing polar
substituents, e.g., aminoalkyl acrylates or acrylamides
and poly-(oxyethylene)-substituted acrylates. ~hese may
~e. characterized as "polymeric dispersants" and examples
thereof are disclosed in the following U.S. patents:
3,32~,658 3,666,730
3,449,250 3,687,849
3,519,565 3,702,300
Extreme pressure agents and corrosion- and
: oxidation inhibiting agents are exemplified by chlorinated
aliphatic hydrocarbons such as chlorinated wax;
phosphosulfurized hydrocarbons such as the reaction product
of a phosphorus sulfide with turpentine or methyl oleate,
phosphorus esters including principally dihydrocarbon and
trihydrocarbon phosphites such as dibutyl phosphite,
:~ 20 diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl
phosphite, dipentylphenyl phosphite, tridecyl phosphite,
distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-
pentylphenyl phosphite, polypropylene (molecular weight
500)-substituted phenyl phosphite, diisobutyl-substituted
phenyl phosphite; metal thiocarbamates, such as zinc
dioctyldithiocarbamate, and barium heptylphenyl
dithiocarbamate; Group II metal phosphorodithioates such
as zinc dicyclohexylphosphorodithioate, zinc
dioctylphosphorodithioate, barium di(heptylphenyl)-
phosphorodithioate, cadmium dinonylphosphorodithioate, andthe zinc salt of a pho~phorodithioic acid produced by the
reaction of phosphorus pentasulfide with an equimolar
mixture of isopropyl alcohol and n-hexyl alcohol.
Many of the above-mentioned extreme pressure
agents and corrosion oxidation inhibitors also serve as
: antiwear agents. Zinc dialkylphosphorodithioates are a
~ well known example.
:1
~27~
Pour point depressants are a particularly useful
type of additive often included in the lubricating oils
described herein. The use of such pour point depressants
in oil based compositions to improve low temperature
properties of oil-based compositions is well known in the
art. See, for example, page 8 of "Lubricant Additives" by
C.V. Smalheer and R. Kennedy Smith (Lezius-~iles Co.,
publishers, Cleveland, Ohio, 1967~.
Examples o~ useful pour point depressants are
polymethacrylates, polyacrylates; polyacrylamides;
condensation products of haloparaffin waxes and aromatic
compounds: vinyl carboxylate polymers; and terpolymers
of dialkylfumarates, vinylesters of fatty acids and
alkylvi.nylethers. Pour point depressants useful for the
purposes of this invention, techniques for their
~ preparation and their uses are described in U. S. Patents
; 2,387,501; 2,015,748: 2,655,479: 1,815,022; 2,191,498;
2,666,746; 2,721~877; 2,721,878; and ~,250,715.
Anti-foam agents are used to reduce or prevent
`:~ 20 the formation of stable foam. Typical anti-foam agents
:` include silicones or organic polymers. Additional anti-
~oam c~mpositions are described in "Foam Control Agents",
~: by Henry T. Kerner (Noyes Data Corporation, 1976~, pages
:: 125-162.
T~e labile-sulfur free additive compositions of
this invention can be added directly to the lubricant.
Prefe.rably, however, they are diluted with a substantially
: inert, normally liquid organic diluent such as mineral
. oil, naphtha, benzene, toluene or xylene, to form an
additive concentrate. These concentrates u~ually contain
~rom about 5% to 90% by weight of the additive of this ....
:,
- 16 -
invention and may contain, in addition, one or more other
additives kno~n in ~he art or described hereinabove. The
remainder of the concantrate i6 the sub~tantially iner~
normally liquid diluent.
The following non-limiting examples ~re afforded in
order that those skilled in the art may more readily
understand the present invention and specified preferred
embodiments ~hereof with respect to the method of the
present invention in accordance with the foregoing
description.
EXAMPLE 1
While maintaining a temperature of 55 1000 parts
phenol and 68 par~6 sulfonated polystyrene cataly~t
(marketed as Amberlyst-15 by Rohm and Haas Company) are
charged to a reac~or equipped with a stirrer, condenser,
thermometer and su~surface gas iDlet tube. The reactor
content~ are then heated to 120 while nitrogen blowing
for Z hours. 12~2 ear~s propylene tetramer is charged,
and the reaction mixture i6 stirred at 120 ~or 4 hours.
Agitation is ~topped, and the batch is allowed to settle
or 0.5 hour. Tbe crude supernatant reaction mixture is
filtered and vacuum stripped until a maximum of O.S
percent re6idual propylene tetramer remains.
Y~A~PLY Z
Benzene (217 parts) i6 added to phenol (324 parts,
3.45 moles) at 38C and the mixture is heated to 47C.
Boron trifluoride (8.8 parts, 0.13 mole) is blown into the
mixture over a one-half hour period at 38-52C.
Polyisobutene (1000 parts, 1.0 mole) derived from the
polymeri~ation o~ C4 monomer~ predominating in
isobutylene is added to the mixture at 52-58C over a ~.5
hour period. The mixture i~ held at 52C for one
additional hour. A 26% solution of aqueous ammonia (15
parts) is added and the mixture heated to 70C over a
two-hour period. The mixtura is then filtered and the
~1 :27~
- 17 -
filtrate i6 the aesired crude polyisobutene-~ub~tituted
phenol. This intermediate is stripped by heatinq 1465
parts to 167C and the pressure is reduced to lOmm as the
material i5 he~ted ~o 21~C in a 6-hour period. A 64%
yield of stripped ~olyisobutene-sub~tituted phenol
(Mn=885) is obtained as the re6idue.
XAMPLE 3
~ commercial mixture o~ ethylene polyamines (41
parts, l.o equivalent) corresponding in empirical formul~
to penta(ethylene)hexamine is added to a mixture of the
substituted phenol (400 parts, 0.38 equivalent) described
in Example 2 and diluent oil (181 parts) at 65C. The
mixture i~ heated to 93C and paraformaldehyde (12 parts,
0.4 equivale~t) added. The mixture is heated from
93-140C over a ~-hour period and then held at 1~0C for 4
hours under nitrogen. The mix~ure is cooled to 93C and
additional paraformaldehyde ~12 parts~ 0.4 equivalent) is
added. The mixture is heated from 93-160C for a total of
12 hour~. The total amount of di~illate collected is
13.2 parts. An additional amount of diluent oil (119
parts~ is added ~o the mixture which i~ then filtered.
The filtrate i8 a 40% oil solution of the desired Mannich
condensation product containing 1.87% nitrogen.
EXAMPLE 4
To 1850 parts (1.0 equivalent) of the Mannich
condensate described in Example 3 is added sulfur flower~
(6~ parts, 2.0 equivalents) at 80C. The mi~ture i8
heated to 160C over a 10-hour period removing the
hydrogen sulfide evolved (35 gram6). The mixture is then
iltered. The filtrate i8 a 40% oil solution of the
desirea sulfurized product containing 1.79% nitrogen and
1.4~% sulfur.
,, .
- 18 -
EXAMPLE 5
A reactor equipped with a stirrer, condenser,
~hermometer and subsurfa~e addition tube is charged with
1000 parts of the reaction product of Example 1. The
temperature i~ ad justed to 4~-49 and 319 parts sulfur
dichloride i6 added while the temperature is ~ep~ below
60~n The ba~ch is then hea~ed to 88 93 while nitrogen
blowing until the 3cid number ~using bro~phenol blue
indicator) is less than 4Ø 400 parts diluent oil is
then added, and the mixture i6 mixad thoroughly.
~AMPL~ 6
Following the procedure of Example 5, 1000 parts of
the reaction product of Example 1 i6 reacted with 175
parts of sulfur dîchloride. The reaction prodsc~ is
diluted with 400 parts dilue~t oil.
EXAMPL~ 7
Following ~he procedure of Example 5, 1000 parts of
the reaction produc~ of Example 1 is reacted with 319
parts of sulfur dichloride. 788 parts diluent oil is
added to the reaction product, and the materials are mixed
thoroughly.
Ex~MprE 8
Following the procedure of Example 6, 1000 parts of
the reaction product of Example 2 are reacted with 44
parts of sulfur dichloride to produce the sulfurized
phenol.
EXAMPLE 9
Following the procedure of Example 7, 1000 parts o~
the reaction product of Example 2 are reacted with 80
part6 of sulfur dichloride.
_ ~76~
-- 19 --
E~MPLE 10
A reactor equipped with a stirrer, condenser,
thermometer and subsurface gas inlet tube is charged with
1000 parts phenol, ~8.4 parts SuperFiltrol* (a sulfuric
acid treated clay supplied by Filtrol Corporation) and 845
parts of a mixture o~ isomeric heptenes. The reactants
are heated to 120 while nitrogen blowing. The reaction
is then continued at 120 for 4 hours. The reaction
mixture is filtered, and vacuum stripped to remove water,
unreacted heptenes, and excess phenol The residue after
stripping is the product.
EXAMPL~ 11
Following the procedure of Example 10, 1000
parts of C24_28 alpha-olefin, 903 parts phenol and 46
parts SuperFiltrol are reacted to prepare an alkylated
phenol.
EXA~PL~ 12
Following the procedure of Example 10, 1090
parts phenol, 585 parts isomeric nonenes, and 200 parts of
a slurry of 10 parts Amberlyst* 15 in 190 parts nonenes
are reacted to form the substituted phenol.
EXAMPLæ 13
A 5-litre, 4~necked flask, equipped with a
stirrer, thermowell, re~lux condenser and subsurface tube
is charged with 3493 parts of the reaction product of
Example 7. 57 part~ C15_18 alpha-ole~in is added while
stirring and the reaction mixture is then heated to 150C
with nitrogen blowing. Heating and nitrogen blowing is
continued at 150. The reaction mixture is filtered using
a diatomaceous earth filter aid.
* Trade Mark
- l9a -
EXAMPLE 14
To a reactor as described in Example 13, is
charged 3000 parts of the reaction product o~ Example 7 and
49 parts of C15_l~ alpha-olefin. The reflux condenser is
,
~.~7~
- 20 -
then removed and the apparatus is arranged for
distillation. The mixture is heated to 150 with nitro~en
blowin~ over 2 hours. The reaction product i~ then
filtered using a diatomaceous earth filter aid.
EX~MPLE 15
Following the procedure of Example 14, 3000 parts of
the reaction product of Example 8 are reacted with 40
part8 of C15 18alpha~olefin.
EXAMPLE 16
To a reactor as described in Example 13, i~ charged
3000 parts of the reaction ~roduct of Exam~le 4 and 12
parts of C15 18alpha-olefin. The materials are heated
to 150 over 1 hour while subsurface nitrogen blowing.
The ~ixture is then filtered using a diatomaceotls earth
filter aid.
EXAMPrlE 17
To a l-liter, 4-necked flask equipped with a ~tirrer,
nitrogen inlet, subsurface tube, thermowell and Dean-Stark
trap Z conden~er was charged with 500 part~ of the
reaction mix~ure o~ Example 7. With fa t ~tirring, 7.5
parts cuprou~ oxide is charged followed by heating ~o 180
with nitrogen blowing. Heating was conti~ued at 180 for
3 hours, while a small amount of yellow-colored distillate
was remo~ed in the Dean-Stark trap. The mixture wa6 then
cooled to 150 and held at 150 for an additional 3
hours. The reaction mixture was then filtered using a
di~tomaceous earth ~ilter aid. The reaction product
contained o.ofi percent copper.
EXAMPLE 18
To a reactor equipped as described in Example 17, is
charged 406 parts of the reaction product of Example 4.
With fast stirring, 2.4 parts cupric oxide and 1.2 parts
copper metal powder is charged, followed by heating ~o
.
~ ~.27~34
- 21 -
155 with a slight nitrogen purge. The mix~ure was heated
at 155 for 5 hours. The materials were then filtered
using a diatomaceous earth filter aid.
EXAMPLE 1 9
~ l-literO 4-necked flask equipped with a Etirrer,
thermowell, and reflux condenser is charged with 600 p~rts
o~ the reaction produc~ of Example 7. With fast stirring,
3 parts copper metal powder is added, the mix~ure is
heated to 120 and i~ held at 120 for 5 hours. ~he
reaction mixture is ~iltered using a diatomaceous earth
filter aid.
EXAMPLE 20
Following the procedure of Example 19, 2400 parts of
the reac~ion product of Example 8 ars treated with 3 parts
of copper metal powder.
EXAMPLF. 21
Following the procedure of Example 1~, ~000 parts of
the reaction product of Example 7 i6 heated at 150 with 5
parts copper me~al powder. The filtered product contains
0.005 percent copper.
EXAMPLE 22
A l-liter, 4-necked flaæk equipped with a stirrer,
thermometer, below sur~ace gas inlet and a Dean-Stark trap
is charged with 475 parts of the reaction product of
Example 7. The material is heated to 80C, Z5 parts
copper metal powder is added and the reaction mixture is
heated to 155 over 0.5 hour followed by heating at
155-160 for 5 hour~. The material is filtered at 140
using a diatomaceous earth ~ilter aid. The product
contains 0.0~32 percent copper.
- ~ 2~ 4
-- 22 --
EXAMPLE ? 3
To a l--liter, 4-necked flask equipped with a stirrer,
thermowell, condenser, subsurface tube, nitrogen inlet and
Dean-Stark trap was charged with 200 parts of the reaction
product o~ Example 7 and 1~5 parts of diluent oil. The
materi~ls ~re hea~ed to 80~ followed by the addition of
1.7 parts copper metal powder. The mixture is heated to
155 and held at 155 for 5 hours while maintaining a
light nitrogen purge. The materials are filtered using a
diatomaceous earth filter aid.
EXA~PLE 24
The procedure of Example 23 is followed except 885
parts of the reaction product of Example 7, 641 parts
diluent oil and 76 parts copper metal powder are used.
EXAMPLE 25
A reactor equipped with a s~irrer, thermowell,
subsurface nitrogen inlet and Dean-Star~ trap is ~harged
with 400 part~ of the reaction product o~ Example ~. The
ma~erial is heated to 150 and held a~ 150 for 5 hour~
while nitrogen blowing. 107 part6 diluent oil is added
and the material i~ filtered at 100 using a diatomaceous
earth filter aid.
EXAMPLE 2 6
A reactor equipped with a stirrer, condenser,
thermowell, and subsurface tube i6 charged with 469 parts
of the reaction product of E~ample 5 and 60 parts
C15 18alpha-olefin. The materials are heated to 150
and held at S hour~ at 150 under a nitrogen purge. 65
parts diluent oil is added. The materials are stirred and
the mixture is filtered using a diatomaceous earth filter
aid.
7~
-- 23 --
E~AMPLE 27
The procedure of Example 26 is followed except 1000
parts of the reaction product of Example 5, 158 parts
diluent oil and 110 part~ C15 18alpha-olefin are
employed.
EXAMPLE 28
The procedure of Example Z6 is followed except 7so
parts of the reaction product of Example 5, 40 parts
C15 18alpha-olefin and 171 parts diluent oil are
-
employed.
EXAMPLE 29
The procedure of Exam~le 26 is followed except 7~0
parts of the reaction product of Example 5, 16 parts o~
C15 18alpha-olefin and 195 parts diluent oil are
employed.
EXAMPLE ~O
The procedure of Example 29 is followed except ~he
heating is conducted at 93 for 8 hours.
EXAUPLE 31
The procedure of Example 29 is followed except 50
~ p ~ o~ C15_1~alpha-olefin replaces the
f propylenetetramer.
EXAMPLE 32
A l-liter, 4-necked flask equipped with a stirrer,
nitrogen inlet, ~ubsurface tube, thermowell Dean~Stark
trap and condenser is charged with 386 parts of the
reaction product of Example 5. The material is heated to
150 and 5.8 parts cupric hydroxide is added. The
materials are heated to 180 while water is removed. A
total of approximately 1 gram water was obtained in the
Dean-Stark trap. The total heating time wa~ 2 hours. The
.
. .
7~
- 24 _
product was filtered using a diatomaceous earth ~ilter
aid. The filtered product contains 0.3~ percent copper.
EXAMPLE 33
A reactor as described in Example 6 is charged with
351 parts of the reaction product of E~ample 5. The
material is heated to 50 and 4.5 parts cupric oxide and
1.1 parts copper me~al powder i6 added. The mixtura is
he~ed to 150~ and held at 150 for 2 hours. The
materials were then heated to 180 over 1 hour and heating
at 180 is continued for 4 additional hours. The
materials are filtered using a diatomaceous earth Eilter
aid. The filtered product contains 0.43 percent oop~er.
~XAMPLE 34
To a rea~tor a~ described in Example 32 is charged
351 parts o~ the reaction product of Exam~le 5. The
materials i~ heated to 50~ and 5.3 parts cuprous oxide ig
charged. The mixture i~ stirred a~ fast speed for 0.5
hour followed by the addition of 2.2 parts acetic acid.
The mix~ure is heated to 10~ o~er 0.5 hour, heated to
150 over 0.5 hour and held at 150 for ~.5 hours. The
temperature is increased to 180 and held at ~80 for 3
additional hours. The reaction mixture i6 filtered using
a diatomaceous earth filter aid. The filtered product
contain~ 0.113 percent copper.
EXAa~qPLE 3 5
A 2-liter reactor equipped with a stirrer,
thermometer, below surEace nitrogen inlet and Dean-Stark
trap is charged with 990 parts of the reaction produc~ of
Example 5. The material is heated to 90 at which time 10
parts of copper metal powder i6 added. The materials are
heated with nitrogen blowing to 150 over 0,.35 hour and
held at 150-154~ for 5.5 hours. 285 parts diluent oil is
added, the materials are mixed thoroughly and filtered at
105 using a diatomaceous earth filter aid.
~ 27~
- 25 -
EXAMPLE 3~
A reactor as described in Example ~5 is charged with
980 part~ of the reaction product of Example 5 and ZO
parts of a C15 l~alpha-olefin. The materials are mixed
and heated to ssoc followed by addition of 10 parts of a
50 percent aqueous NaOH solution. The ma~erials are
hea~ed to 150 with nitrogen blowing over 0.3 hour, and
held at 150 for 5.5 hours. The mixture is cooled to ~0
and 2~4 part~ diluent oil is added. The materials are
then filtered at 100 using a diatomaceous earth ~ er
aid.
EXAMPLE 37
Cupric chloride aihydrate (51 parts) and 125 par~s
toluene are charged to a 250 milliliter flask equipped
with a sub~urface nitrogen inlet and a Dean-Stark trap.
The materials are azeotroped for Z hours to dry. A
2~ er reactor equipped with a stirrer, thermowell, and
Dean-Stark trap is charged with 710 parts of ~he reaction
produc~ of Example 5 and llo parts xylene. 48 parts of a
50 percent aqueous NaOH solution i~ added at 80, and the
reaction mixture is refluxed at 105-}80 for 4.75 hours.
The mixture is cooled and 150 parts isopropynol i8 added.
Uost of the toluene is decanted from the dried cu~ric
chloride and ~he ~olid is added to the solution in the
2-liter flask. Remaining cupric chloride was washed from
the 250 milliliter flask using 17~ parts methanol. The
materials in the 2-liter flask are then held at 55-600 for
0.5 hour then refluxed at 68-70 for 2 L 5 hours, and
stripped to 165 at 8 torr. The residue is filtered at
115~ using a diatomaceous earth filter aid. The filtered
product contained no sodium and 1.72 percent copper.
EXAMPLE 38
The procedure of Example ~ i6 repeated that 312
par~s of the reaction product of Example 6, 32 parts of 50
percent aqueous sodium hydroxide, ~4 parts of cupric
-- ~2~ 4
- 26 -
chloride dihydrate, 125 parts toluene, loo parts xylene,
130 part~ methanol, loO parts of the isobu~anol/primary
amyl alcohol mix~ure, and 75 par~s isopropanol are
employed.
EXA~PLE 39
A 2-liter, 4-necked reactor eguipped with a stirrer,
addition funnel, ~ubsurface ~ube, thermowell, and
condenser is charged with 800 partæ oP the reaction
product of Example 12. The materials are heated to 50
with a light nitrogen purge. Sulfur dichloride is added
dropwise over 5 hours. The materials are heated to 150
and nitrogen blown for Z hours at 150. 646 parts diluent
oil are added and the materials are stirred at 100 Por 1
hour. 1537 parts of the reaction product are transf erred
to a ~-liter flask and 7.7 parts copper powder is added.
The materials are heated to 150 with ~ast stirring. The
materials are then held for S hours at 150, ~hen filtered
using a diatomaceous earth filter aid. The filtered
product contains 13 parts per million copper.
EXAMPLE 40
A 3-liter, 4-necked fla~k e~uipped with a stirrer,
subsurface tube, addition funnel, thermowell and reflux
condenser is charged with 787 parts of the reaction
product o~ Example 10. The material is heated to soo and
ulfurdichloride is added dropwise over ~.25 hours. The
materials are heated to 150 with nitrogen blowing and
held at 150 with nitrogen blowing for 1.5 hours. 638
parts of diluent oil is added and the materials are
stirred for O.Z5 hour. The mixture is reheated to 150
and 7.6 parts of copper metal powder is added. The
materials are mixed for 5 hours at 150 with a slight
nitrogen purge. The material~ are filtered u~ing a
diatomaceous earth filter aid. The filtered material
contains 20 parts per million copper.
-- 27 --
EXAMPLE 4 1
A 3-liter reactor equipped with a stirrer,
thermowell, subsurface gas inlet and reflux condenser is
charged with lOoO parts of the product of Example 6 and S3
parts of C16_18alpha-olefin. The mixture is heated to
goo with a ni~rogen purge and held at soo with continuing
~he nitrogen purge for 2 hours. The temperature of the
reaction mixture is reduced to 50 at which time 320 parts
methanol, 26 parts glacial acetic acid and 221 parts
calcium hydroxide are charged. The materials are heated
to reflux (68) and held at reflux for 0~5 hour. The
mixture i~ cooled to 45 and 200 parts toluene is added.
The materials are heated to reflux and blown with Co~
for 1.75 hours at 45-50C. The reaction mixture is
stripped to 160 while nitrogen blowing at 2 cubic fee~
per hour. To the stripped material i6 added 273 parts
diluent oil and 83 parts of polyi~obutenol ~uccinic
anhydride ~herein the polyiso~utenol group has a molecular
wei~ht of abou~ 1000. The mixture is stirred at 160 for
2 hours~ The reaction mixture is filtered u~ing a
diatomaceou~ earth filter aid.
EXAMPLE 42
A 3-liter reactor equipped as described in ~xample 4].
i6 charged with 700 parts of the reaction product as
described in Example 21 and 204 parts of diluent oil. The
mixture is heated to 55 and 85 parts methanol, 11 par~s
acetic acid, 58 parts calcium hydroxide and 57 parts
toluene are added. The mixture iB blown with Coz for
0.5 hour at 0.5 cubic feet per hour at a temperature of
6s-70C. The reaction mixture is ~tripped to 150 at 1.5
cu~ic feet nitrogen purge. The residue is fi}tered using
a diatomaceou earth filter aid~
EXAMPLE 43
A 3-liter reactor as described in Example 42 is
charged with 1250 parts of the reaction product of Example
~ %7G0~4
- 2~ -
~ which has been post-~rea~ed with a C15 18alpha-olefin
and 330 parts diluent oil. The material6 are heated to
40 and 151 part~ methanol, 103 parts calcium hydroxide,
and 30 parts acetic acid is charged. C02 blowing at 1
cubic foot per hour is begun and continued for
approximately 0.5 hour. The reaction mixture is stripped
to 160 with nitrogen blowing at 1 cubic foot per hour.
The residue is filtered usin~ a diatomaceous earth filter
aid.
EX~MPLE 44
A 5-liter reactor equipped with a stirrerc
thermowell, subsurface gas inlet tube and reflux condenser
i~ charged wi~h 1975 parts of the reaction product of
Example 5 and Z~7 parts of C16 18alpha~olef in- The
material~ are heated ~o 100 and held at Z hours at 150
with nitrogen blowing. The mixture i6 cooled to goo and
500 parts diluent oil is added. The materials are cooled
to sso and ~oo parts methanol, 40 parts acetic acid and
204 parts calcium hydroxide are charged. The materials
are blown with C0z at 1 cubic foot per hour for 1.1
hours at 65-70. The reaction mixture i~ stripped to 160
under a nitrogen purge at 1.5 cubic feet per hour for 1
hour. ~68 part6 diluent oil i~ added and the material i8
then thoroughly mixed and filtered using a diatoma~eous
earth filter aid.
EXAMPLE 45
The procedure of Example 44 is followed except 104
parts of C16 18alpha-olefin are employed.
E~AMPLE 46
A 2-liter reactor is charged with 790 parts of the
reaction product of 2xample 5 and 41 parts o
C15 18alpha-olefin. The ~ixture i6 heated to 90 with a
nitrogen purge, cooled to 80, 429 parts diluent oil are
added, and the mixture i6 stirred while cooling to 60.
- 29 -
Methanol, 177 parts, 16 parts acetic acid and 81 parts
calcium hydroxide are charged and the materials are heated
to reflux ~70C) and held at reflux for 0.5 hour. The
materials are cooled to 45 and blown with C02 at 1
cubic foo~ per hour for 0.75 hour at 45-50~. The
materials are ~tripped to 160 while nitrogen blowing at 1
ubic foot per hour for 2 hours. The residue is filtered
with a diatomaceous ear~h filter aid.
EX~MPLE 47
To a reactor as described in Example 13, is ~harged
3000 parts of the reaction product of Example 7 and 49
parts of C15 18alpha-olefin. With rapid stirring, 15
parts copper metal powder is added and the mixture is
heated at 150~ for 4 hours while nitrogen blowing. The
mixture is then fiItered using a diatomacaous earth filter
aid.
EXAMPLE 48
~ ollowing the procedure of ~xample 47, 3000 parts of
the reaction product of Example 9 are reacted with 40
parts of C15 18alpha-olefin and 10 parts of copper metal
powder.
To further illustrate the efficacy of the treatment
method of the present invention, several of the thus
reacted sulfur-based additives were tested for
labile-sulfur according to the test procedure of ASTM-D
166Z. Results from this tes~ are set out in Table I.
:, .. .. ~.
~7~
- 30 -
TABLE I
; Ex. No. Amount of Labile-Sulfur
~ 13 0.35
: 1~ 0.37
5 17 0.06
18 0.18
19 0.63
21 0.43
22 0.07
10 25 1.14 (control)
27 0.27
41 0.06
44 Nil
Nil
:
1 - Represents weight percent of labile-sulfur based on
~: weight of additive.
:
The additives treated according to the method of the
present invention, which showed very little or no
labile-sulfur, demonstrated greatly improved performance
: 20 in that the detrimental metal corrosivity and elastomer
degradation originally exhibited by these additives before
treatment had essentially been eliminated.
The following examples illustrate an additive
concentrate and a lubricant formulated with a sulfur-based
additive treated according to the method of the present
invention.
B
~'' ~æ7~004
-
- 31 -
EXAMPLE TO ADDITIVE CONCENTRATE
A sulfur-based concentrate was formulated from the
following components:
Product of Ex. Z3 12.07
Copper deactivator 0.33
~AmocQ 1~0)
Diphenylamine based l.Bs
antioxidant
Zinc dial~ylphosphoro 9.23
dithioate
Reaction product oP 13.34
pentaerythritol and
ethylene polyamine
with polyisobutenyl
succinic anhydride
Reaction produc~ of 12.0Z
ethylene polyamine
with eolyi B obutenyl
succinic anhydride
Basic magnesium 2.65
petroleum sulfonate
Basic calcium petroleum 4.6Z
sulfonate
Silicone antifoam 0.012
Nonylphenoxypoly- 0.98
(ethyleneoxy)ethanol
HLB=8.9 (Surfonic
N-go)
~ineral oi.l . As needed ~o bring to 100
parts total
Other additive concentrates employing compo~itions o
the invention in combination with varying amount~ of the
above additives were also prepared.
A lubrication oil composition i~ prepared by blending
11.6~% by weight of the above-described additive
concentrate in a 15W-40 oil which contains polymeric
viscosity improvers.
760~L
While the invention has been described and
illustrated with respect to certain preferred embodiments
thereof, those skilled in the art will appreciate that
various changes, modifications and substitu~ions can be
made therein without departure from the ~pirit of the
invention. For example, different temperature ranges,
reaction times and reactan~ ratios other than the
preferred ranges set forth hereinabove may be applicable
as a consequence of the nature of the various reactants
and components thus employed in the proce6s of the
invention. Qther expected variations or differences in
results are contemplated in accordance with the conditions
and practices of the present invention. It is intended,
therefore, that the invention be limited only by the scope
of the claims which follow.
