Note: Descriptions are shown in the official language in which they were submitted.
~LZ~'~320~
~UI.1~URIZ~D' ~L~F'IN`-CONT~'INING' t~MPO'~ NS
-- . . .
B'ACgG~ND' ~F' i~ 'INVENq~It)N
This in~ention relates to compositions useful as
additives for lubricants, and, more particularly, for addi-
tives useful in multipurpose industrial oils for use ingear, hydraulic and other specialt~ applications. In its
broadest sense, the ~nvention relates to sulfuriæed olefin-
containing compositions and lubricants and concentrates
containing such composit~ons.
It is well known that the high pressure which
occurs in certain types of gears and bearings may cause
rupture of lubricant films with consequent damage to the
machinery~ Because of the se~ere conditions under which
they are used, industrial and gear lubricants ordinarily
15 must contain additives whtch maximi2e their capability of
func~ioning under extreme pressure conditions. It has been
suggested that certain compounds of metal-reactive elements,
such as compounds of chlorine, sulfur, phosphorus and lead
impart extreme pressure properties to various lubricants.
20 Among the various compositions kno~n to ser~e this purpose
are various phosphorus- and sulfur-containing compositions,
chiefly salts and esters of dialkylphosphoxodithioic acids,
and sulfurization products of various aliphatic olefinic
compounds. These two type~ of compositlons ha~e been used
25 in combination in lubr~cants of this type, and they serve to
increase the e~ecti~eness of the lubricant under conditi~
of extreme pressure. 'r~'
~2~1208
- 2 -
Many of the known sulfurization products of
olefinic compounds contain substantial amounts of active
sulfur. The presence of active sulfur in a lubricant often
has deleterious side effects such as staining of copper
parts, increased wear on the metal components being lu-
bricated, and a decrease in extreme pressure properties
with the passage of time.
Various compositions prepared by the sulfuriza-
tion of olefins have been described in the prior art as
10 being useful in lubricant compositions. For example, U.S.
Patent 4,191,659 describes the preparation of sulfurized
olefinic compositions by the catalytic reaction of sulfur
and hydrogen sulfide with olefinic compounds containing from
3 to 30 carbon atomæ. Such compounds are reported ~o be
15 useful in lubricating compositions, particularly those
prepared for use as industrial gear lubriaants.
~UMM~ F TEE INVEN~ION
~ composition is described which comprises (A? at
least one aliphatic ole~inie compound and (B) the sulfur~-
zation product of at least one aliphatic, arylaliphatic or
alicyclic olefinic hydrocaxbon containing from about 3-3a
carbon atoms wherein the weight ratio of A to B is no
25 greater than 1:1. Such compositions are useful as lubricant
additive comFositions, and more particularly, as additive
compositions in industrial and gear lubricants. The com-
positions when added to lubricants pxo~ide longer lasting
extreme pressure properties and anti-wear capability and
30 ~educe staining o~ copper part~.
Component A in the compositions of the invention
is at least one aliphatic olefinic compound which ~enerally
will contain at least about 8 carbon atoms and preferably
between about 8 and 3a carbon atoms. The aliphatic olefinic
35 compound useful as componen~ ~ in the compositions of the
invention ma~ be an ole~n~c ~ydroca~bon such as l-octene,
1-decene, l-tetradecene, l-octadecene, 1-eicosene, etc.
Aliphatic olefinic compounds containing internal double
~L2~ !3208
bonds also are useful as component ~, and examples of such
olefins include 2-decene t 5-decene, 9-octadecene, etc. The
a-olefins are preferred, especially those containing from 12
to 20 carbon atoms. Mixtures of these olefins are available
commercially, and such mixtures are contemplated for use in
this invention.
Component A also may be a fatty acid, a fatty acid
ester, or mixtures thereof. The term "fatty acid" as used
herein refers to acids which may be obtained by hydrolysis
10 of naturally occurring vegetable or animal fats or oils.
These fatty acids usually contain from 16 to 20 carbon atoms
and are mixtures of saturated and unsaturated fatty acids.
The unsaturated fatty acids generally contained in ~he
naturally occurring vegetable or animal fats and oils ma~
15 contain one or more double bonds and such acids include palmi-
toleic acid, oleic acid, linoleic acid, linolenic acid,
petroselenic acid, erucic acid, gadoleic acid, vaccenic
acid, ricinoleic acid and minor amounts of compounds con-
taining more than 20 carbon atoms such as behenic acid~
The unsaturated fatty acids useful as component A
may compri~e mixtures of acids such as those ob~ained from
tall oil or by the hydrolysis of peanut oll, soybean oil,
cottonseed oil, sunflower seed oil, or wheat germ oi~. Tall
oil is a mixture of rosin acids, mainly abietic acid, and
25 unsaturated fatty acids, mainly oleic and linoleic acids.
Tall oil is a by-product of the sulfate process for the
manufacture of wood pulp.
The most preferred aliphattc olefinic compounds
useful as component A in the compositions ~f the invention
30 are fatty acid esters which contain olefinic unsaturation in
the fatty acid moiety. Of these types, the most particu-
larl~ preferred are the ~a~ty Qils, that i~, naturally
occurring esters of gl~cerol with the fatty acids described
above, and synthetic esters of similar structure. Examples
35 o~ naturall~ occurrl~g fats and o~s containlng unsaturation
include animal fats such as neat's-foot oil, lard oil, depot
fat, bee~ tallo~, etc. Examples of naturally occurrin~
vegetable oils use~ul as component A ~nclude cottonseed oil,
~2(~8Z08
-- 4 --
corn oil, poppy-seed oil, safflower oil, sesame oil, soybean
oil, sunflower seed oil and wheat germ oil.
The fatty acid esters which are useful as com-
ponent A in the invention also may be prepared from alipha-
tic olefinic acids of the type described above such as oleicacid, linoleic acid, linolenic acid, and behenic acid by
reaction with alcohols and polyols. Examples of aliphatic
alcohols which may be reacted with the above-identified
acids include monohydric alcohols such as methanol, ethanol,
10 n-propanol, isopropanol, the butanols, etc.; and polyhydric
alcohols including e~hylene glycol, propylene glycol,
trimethylene glycol, neopentyl glycol, glycerol, etc~
Component B in the compositions of this lnvention
is a sulfurization product of at least one alipha~ic, aryl-
15 aliphatic, or alicyclic olefinic compound containing about3-30 carbon atoms. The olefinic compounds which ma~ be
sulfurized to form component B are diverse in nature. They
contain at least one olefinic double bond, which is defined
aæ a non-aromatic dauble bond; that is, one connecting two
20 aliphatic carbon atoms. In its broadest sense, the olefin
may be defined b~ the ~ormula RlR2C=CR3R4, wherein each of
Rl, R2, R3 and R4 is hydrogen or an organic radical. In
general, the R values in the above formula which are not
hydrogen may be sa~isfied by such groups as -R5j -C(R5)3,
25 -COOR5, -CON(R5) 2 ~ -COON(Rs~ 4
NR5
-COOM, -CN, -C-Rs, -X or -YRs, whereîn:
Ea~h Rs is independently hydrogen, alkyl, alkenyl,
aryl, alkylaryl, substituted alkyl or substituted alkenyl,
with the pro~iso that any two R 5 groups can be alkylene or
30 substituted alkylene whereby a ring of up to about 12 carbon
atoms is formed;
M is one equivalent of a metal cation tpre~erably
Group I or II, e.g., sodium~ potassium, barium, calcium~; -
X is halogen (e.g., chloxo, bromo, or iodo);
~ is ox~gen ox divalent sulfur.
)!3Z08
- 5 -
Any two of Rl, R2, R3, and R4 may also together
form an alkylene or substituted alkylene group; i.e., the
olefinic compound may be alicyclic.
The nature of the substituents in the substituted
moieties described above is not normally a critical aspect
of the invention and any such substituent is useful so long
as it is or can be made compatible with lubricating environ-
ments and does not interfere under the contemplated reaction
conditions. Thus, substituted compounds which are so un-
stable as to deleteriously decompose under the reactionconditions employed are not contemplated. However, certain
substituents such as keto or aldehydo can desirably undergo
sulfurization. The selection of suitable substituents is
within the skill of the art or may be established through
routine testing Typical of such substituents include any
of the above-listed moieties as well as hydroxy, carboxy,
carbalkoxy, amidine, amino, sulfonyl, sulfinyl, sulfonate,
nitro, phosphate, phosphite, alkali metal mercapto and the
like.
The olefinic compound i5 usually one in which each
R group which is not hydrogen is independently alkyl or
alkenyl, or (less often~ a corresponding substituted radi-
cal. Monoolefinic and diolefinic compounds, particularly
the former, are preferred~ and especially terminal mono-
25 olefinic hydrocarbons; that is, those compounds in which R3
and R4 are hydrogen and R~ and R2 are alkyl (that is, the
olefin is aliphatic~. Olefinic compounds having about 3-30
and especially about 3-20 carbon atoms are particularly
desirable.
The ole~inic compound also can be an arylaliphatic
compound, particularly wherein the aryl group is a phenyl or
substituted phenyl group. Specific examples include sty-
rene, ~-methyl styrene, vinyl toluene, 4-ethyl vinyl benzene,
e~c~
Propylene, isobutene and thetr dimers, trimers and
tetramers, and mixtures thereof are especially pre~erred
olefinic compounds. Of these compounds, isobutene and
~2~ZO~
-- 6 --
diisobutene are particularly desirable because of their
availability and the particularly high sulfur-containing
compositions which can be prepared therefrom.
The sulfurizing reagent used for the preparation
5 of component B may be, for example, sulfur, a sulfur halide
such as sulfur monochloride or sulfur dichloride, a mixture
of hydrogen sulfide and sulfur or sulfur dioxida, or the
like. Sulfur-hydrogen sulfide mixtures are often preferred
and are frequently referred to hereinafter; however, it will
10 be understo~d that other sulfurization agents may/ when
appropriate, be substituted therefor.
The amounts of sulfur and hydrogen sulfide per
mole of olefinic compound are, respectively, usually about
0.3-3.0 gram-atoms and about 0.1-1.5 moles. The preferred
15 ranges are about 0.5-2.0 gram-atoms and about 0.4-1.25 moles
respectively, and the most desirable ranges are about 0.8-
1.8 gram-atoms and about 0.4-0.8 mole respecti~ely.
The temperature ra~ge in which the sul~urization
reaction is carried out is generally about 50-350C, The
20 pre~erred range is about 100-2aOC., with about 125-180C.
being especially suitable. The reaction is often preferably
conductad under superatmospheric pressure; this may be and
usually is autogenous pressure (i.e., the pressure which
naturally develops during the course o~ the reactlon~ but
25 may also be externally applied pressure. The exact pressure
deveioped durin~ the reaction i~ dependent upon such factors
as the design and operation of the system, the reaction
temperature, and the vapar pressure of the reactants and
products and it may vary dur~ng the course of the reaction.
It is frequently advantageous to incorporate
materials useful as sulfurization catalysts in the reaction
mixture. These materials may be acidic, bas~c or neutral,
but are preferably basic materials, especially nitrogen
bases including ammonia and amines The amount of catalyst
35 used is generally about 0 05 2.0~ o~ the weight of the
Glefinic compound. In the case of the preferred ammonia and
amine catalysts, about Q.0005-0.5 mole per mole of olefin is
~208208
-- 7
preferred, and about 0.001-0.1 mole is especially desirable.
Following the preparation of the sulfurized
mixture, it is preferred to remove substantially all low
boiling materials, typically by ventiny the reaction vessel
or by distillation at atmospheric pressure, vacuum dis-
tillation or stripping, or passage of an inert gas such as
nitrogen through the mlxture at a suitable temperature and
pressure.
A further optional step in the preparation of
component B is the treatment of the sulfurized product,
obtained as described hereinabove, to reduce active sulfur.
An illustrative method is treatment with an alkali metal
sulfide as described in U.S. Patent 3,498,915. Other
optional treatments may be employed to remove insoluble by-
products and improve such qualities as the odor, color andstaining characteristics of the sulfurized compositions.
U.S. Patent 4,119,549 discloses suitable sulfuriza-
tion products useful as component B. Several specific
sulfurized compositions are described in the working examples
thereof. The following example illustrates the preparation
of one such composition.
Example A
Sulfur (629 parts, 19.6 moles) is charged to a
jacketed high-pressure reactor which is fitted with an
agitator and internal cooling coils. Refrigerated brine is
circulated through the coils to cool the reactor prior to
the introduction of the gaseous reactants. After sealing
the reactor, evacuating to about 6 torr and cooling, 1100
parts (19.6 moles) of isobutene, 334 parts (9.8 moles) of
hydrogen sulfide and 7 parts of n-butylamine are charged to
the reactor. The reactor is heated using steam in the
external jacket, to a temperature of about 171C. over about
1.5 hours. A maximum pressure oE 720 psig. is reached at
about 138C. during this heat-up. Prior to reaching the
peak reaction temperature, the pressure starts to decrease
and continues to decrease steadily as the gaseous reactants
B%08
- 8 -
are consumed. ~fter about 4.75 hours at about 171C., theunreacted hydrogen sulfide and isobutene are vented to a
recovery system. Ater the pressure in the reactor has
decreased to atmospheric, the sulfurized mixture is re-
covered as a liquid.
As mentioned above, the sulfurizing agent may besulfur, and the reaction is effected by heating the olefinic
compound with sulfur at a temperature of from 100-250C.,
usually about 150 210C~ with efficient agitation and in an
lO inert atmosphere (e.g., nitrogen). The weight ratio of
olefin to sulfur may be as high as 15:1 and is generally
between about 5:1 and 10:1.
It is frequently advantageous to add the sulfur
portionwise to the olefin. While it is usually preferred
15 that the reaction mixture consist entirely of the olefin and
sulfur, the reaction may be effected in the presence of an
inert solvent such as alcohol, ether, ester, aliphatic
hydrocarbon or halogenated aromatic hydrocarbon which is a
liquid at the xeaction temperatures employed.
Following the reacti~n, insoluble by-products may
be removed by filtrati~n, usually at an elevated te~perature
~about 80-120C.). The f~ltrate is the desired sulfurized
product
The compositionS of this invention typically con-
25 tain components ~ and B in a ~eight ratio no grea~er thanl:l. Generall~, the weight ratio of component A to com-
ponent B is from about 0.2:1 to about l:l, and more pre-
ferably, from about 0 2:1 to about 0.5:1. The compositions
of the invention may be prepared merely by blending the
30 ingredients, either undiluted or in substantially inert
diluentsO The diluent, if any, may be the oil used as a
lubricant base and may include other additives such a~ those
described hereinafter.
The follo~ing examples are illustrative of the
35 compositions of thls ~nventi~n:
o~
ul ~
: ~ ~9
~o ~ ~
c~ ~
~ ~ u~ co
~D
~d U~ L ~
'; O O
..,
,
a
CO
:~ .
~, . o o
. ~ er
~ .
~. o
:~
. ~ : ~ .
. ~ . ~ , 4
'~ '. ' ~ U~
,~ 'O O
,. .,
._~
4r ~
O ta
rl ~ X
O~1 ~ O ~1
~ ~ -~ ~ 0
: ~C~ O ~ O
.~a~
1 ~ ~ 1 ~ o . c~
O U r~ ~ O
a) ~ ~u o ~ ~ o ~
: haJ .4 ~_1 ~ c) ~ o
:,~,d o~ ~o ~ g a) E~
Hr~
~z~zo~
- 10 -
As previously indicated, the compositions of this
invention are useful as additi~es for lubricants, in which
they function primarily as extreme pressure and anti-wear
agents; the addition of the compositions of the invention
also results in a reduction in staining of copper parts.
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. These
lubricants include crankcase lubricating oils for spark-
10 ignited and compression-ignitsd internal combustion engines,
including automobile and truck engines, two-cycle engines,
aviation piston engines, marine and railroad diesel engines,
and the like. They can also be used in gas engines, sta-
tionary power engines and turbines and the like. Automatic
15 transmission fluids, transaxle lubricants, metal-working
lubricants, hydraulic fluids and other lubricating oil and
grease compositions can al~o benefit from the incorporation
therein of the compositions of the present invention.
However, the compositions are particularly useful in gear
20 lubricants and eQpecially industrial gear lubricants~
Natural oils in~lude liquid petroleum oils and
solvent-treated or acid-treated mineral lubri~ating oils of
the paraffinic, naphthenic and mixed paraffinic-naphtheni~
types. Oils of lubricating viscosity derived from coal or
25 shale are also useful base oil~. Synthetic lubricating oils
include hydrocarbon oils and halo-substituted hydrocarbon
oils such as polymerized and interpolymerized olefins le.g.,
polybutylenes, polypropylenes, propylene-isobutylene co-
polymers, chIorinated polybutylenes, poly(l-hexenes), poly-
30 (l-octenes), poly(l-decenes), etc. and mixtures thereof];
alkylbenzenes le.g., dodecylbenzenes, tetxadecylbenzenes,
dinonylbenzenes, di(2-ethylhexyl)benzenes, etc.]; poly-
phenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls,
etc.), alkylated diphenyl ethers and alkylated diphenyl
35 sulfides and the derivatives, analogs and homologs thereof
and the like.
~L2~3208
Alkylene oxide polymers and interpolymers and
derivatives thereof where the terminal hydroxyl groups have
been modified by esterification, etherification, etc.
constitute another class of known synthetic lubricating
oils. These are exemplified by the oils prepared through
polymerization of ethylene oxide or propylene oxide t the
alkyl and aryl ethers of these polyoxyalkylene polymers
(e.g., methyl-polyisopropylene glycol ether having an
average molecular weight of 1000, diphenyl ether of poly-
10 ethylene glycol having a molecular weight of 500-1000,
diethyl ether of polypropylene glycol having a molecular
weight of 1000-1500, e~c.) or mono- and polycarboxylic
esters thereof, for example, the acetic acid esters, mixed
C3-C8 fatty acid esters, or the Cl 3 OXO acid diester of
15 tetraethylene glycol.
Another suitable class of synthetic lubricatîng
oils comprises the esters of dicarboxylic acids (e.gc,
phthalic acid, succinic acid, alkyl suc¢inic acids and
alkenyl succinic acids, maleic acid, azelaic acid, su-
20 beric acid, sebacic acid, fumaric acid, adipic acid, lin-
oleic acid dimer, malonic acid, alkyl malonic acids, al
kenyl malonic acids, etc.) with a vaxiety of alcohols (e.g.,
butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethyl-
hexyl alcohol, ethylene glycol, diethylene glycol monoether,
25 propylene glycol, etc.). Specific examples of these esters
include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-
hexyl fumarate, dioctyl sebacate, diisooctyl azelate, di-
isodecyl azelate, dioctyl phthalate, didecyl phthalate,
dieicosyl sebacate, the 2-ethylhexyl diester of linoleic
30 acid dLmer, the complex ester formed by reacting one mole of
sebacic acid with two moles of tetraethylene glycol and two
moles of 2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those
made from Cs to Cl 2 monocarboxylic acids and polyols and
35 polyol ethers such neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol, tripentaexythritol~ etc.
3~
- 12 -
Silicon~based oils such as the polyalkyl-, poly-
aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and si-
licate oils comprise another useful class of synthetic
lubricants [e.g., tetraethyl silicate, tetraisopropyl
silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-
ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate,
hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-silox-
anes~ poly(methylphenyl)siloxanes, etc.]. Other synthetic
lubricating oils include liquid esters of phosphorus-con-
10 taining acids (e.g., tricresyl phosphate, trioctyl phos-
phate, diethyl ester of decylpho~phonic acid, etc.), poly-
meric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils (and mix-
tures of each with each other) of the type disclosed here-
15 inabove can be used in the lubricant compositions of thepresent invention. Unrefined oils are those obtained di
rectly from a natural or synthetic source without further
purification treatment. For example, a shale oil obtained
directly from retorting operations, a petroleum oil obtained
20 directly from distillation or ester oil obtained directly
from an esterification process and used without further
trea~ment would be an unrefined oil. Refined oils are
similar to the unrefined oils except they have been further
treated in one or more purification steps to improve one or
25 more properties. Many such purification techniques are known
to those of skill in the art such as solvent extraction,
acid or base extraction~ fil~ration, percolation, etc.
Rerefined oils are obtained by processes similar to those
used to obtain refined oils applied to refined oils which
30 have been already used in service. Such rerefined oils are
also known as reclaimed or reprocessed oils and often are
additionally processed by techniques directed to removal of
spent additives and oil breakdown products.
Generally, the lubricants of the present invention
35 contain an amount of the composition of this invention
sufficient to provide it with extreme pressure and anti~wear
properties. Normally this amount will be about 0.01 to
~Z~82~8
- 13 -
about 10~, preferably about 0 01 to about 5% of the total
weight of the lubricant. In lubricating oils operated under
extremely adverse conditions, the reaction products of this
invention may be present in amounts of up to about 20% by
weight.
The invention also contemplates the use of other
additives in combination with the compositions o this
invention. Such additivex include, for example, detergents
and dispersants of the ash-producing or ashless type, cor-
10 rosion- and oxidation-inhibiting agents, pour point de-
pressing agents, auxiliary extreme pressure agents, color
stabilizers and anti-foam agents.
The ash-producing detergents are exemplified by
oil-soluble neutral and basic salts of alkali or alkaline
15 earth metals ~ith sulfonic acids, carboxylic acids, or
organic phosphorus acids characterized by at least one
direct carbon-to-phosphorus linkage such as those prepared
by the treatment of an olefin polymer (e.g., polyisobutene
having a molecular weight of 1000) with a phosphorizing
20 agent such as phosphoru~ trichloride, phosphorus hepta-
sulfide, phosphorus pen~asulfide, phosphorus ~richloride and
sulfur, white phosphorus and a sulfur halide, or phosphoro-
thioic chloride. The most commonly used salts of such acids
are those of sodium, potassium, lithium, calcium, magnesium,
25 strontium and barium.
The term "basic salt" is used to designate metal
salts wherein the metal is present in stoichiometrically
larger amounts than the organic acid radical. The commonly
employed methods for preparing the basic salts involva heat-
30 ing a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal
oxide, hydroxide, carbonate, bicarbonate, or sulfide at a
temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid
35 the incorporation of a large excess of metal likewise is
known. Examples of compounds useful as the promoter include
phenolic substances such as phenol, naphthol, alkylphenol,
~LZ~Z. ~
- 14 -
thiophenol, sulfurized alkylphenol, and condensation pro-
ducts of formaldehyde with a phenolic substance; alcohols
such as methanol, 2-propanol, octyl alcohol, cellosolve,
car~itol, ethylene glycol, stearyl alcohol, and cyclohexyl
alcohol; and amines such as aniline, phenylenediamine,
phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A
particularly effective method for preparing the basic salts
comprises mixing an acid with an excess of a basic alkaline
earth metal neutralizing agent and at least one alcohol
10 promoter, and carbonating the mixture at an elevated tem~
perature such as 60-200C.
Ashless detergents and dispersant~ are so called
despite the ~act that, depending on its constitution t the
dispersant may upon combustion yield a non-volatile material
15 such as boric oxide or phosphorus pentoxide; howe~er, it
does not ordinarily contain metal and therefore does not
yield a metal-contaîning ash on combustion. Many types are
known in the art, and any o them are suitable for u~e in
the lubricants o~ this invention. The following are illus-
20 trative:
(1) Reaction produc~s of carboxylic acids (orderivatives thereof) containing at least about 34 and pre-
ferably at least about 54 carbon atoms with nikrogen-con-
taining compounds ~uch as amine, organic hydroxy compounds
25 such as phenols and alcohols, and~or basic inorganic ma-
terials. Examples of these "carhoxylic disper~ants" are
described in British Patent 1, 306 ~ 529 and in many U.S.
patents including the following:
3 ~ 163 ~ 603 3 ~ 351 ~ 552 3 ~ 541,012
3~184~474 3~381~Q22 3~542t678
3~215~707 3~399~141 3~542~680
3~219~666 3~415~750 3~567~637
3l271,310 3~433~744 3~574~101
3~272~746 3~444~170 3~576~743
3~281~357 3~448~048 3~30~904
3~306~908 3~448 jO49 3,632r510
3~311~558 3~451~933 3~632~511
r
~21)~3:208
- 15 -
3,316rl77 3,454,607 3,697,428
3,340,281 3,467,66~ 3,725,441
3,341,542 3,501,405 Re 26,433
3,346,493 3,522,179
(2) Reaction products of relatively high molecu-
lar weight aliphatic or alicyclic halides with amines, pre-
ferably polyalkylene polyamines. These may be characteri~ed
as "amine dispersants" and examples thereof are described
for example, in the following U.S. patents:
3,275,554 3,454,555
3,438,757 3,565,804
(3) Reaction products of alkyl phenols in which
the alkyl group contains a~ least about 30 carbon atoms with
aldehydes (especially formaldehyde) and amines (especially
15 polyalkylene polyamines), which may be characterized as
"Mannich dispersants". The materials described in the
following U.S. patents are illustrative:
2,459,1123,44~,808 3,591,598
2,962,4423,448,047 3,600,372
2~ 2,984,5503,454,497 3,634~515
3,036,0033,459,661 3,649,229
3,166,5163,461,172 3,697,574
3,236,7703,493,520 3,725,277
3,355,2703,539,633 3,725,4
3,368,9723,558,743 3~726,88
3,413,3473,586,6~9 3,980,569
(4) Products obtained by post-treating the car-
boxylic, amine or Mannich dispersants with such reagents as
urea, thiourea, carbon disulfide, aldehydes, ketones, car-
30 boxylic acids, hydrocarbon-substituted succinic anhydrides,
nitriles, epoxides, boron compounds, phosphorus compounds or
the like. Exemplary materials of this kind are described in
the following U.S. patents:
8208
- 16 -
3,036,003 3,282,955 3,493,520 3,639,242
3,087,936 3,312,619 3,502,677 3,649,229
3,200,107 3,366,569 3,513,093 3,649,659
3,216,936 3,367,943 3,533,945 3,658,836
3,254,025 3,373,111 3,539,633 3,697,574
3,256,185 3,403,102 3,573,010 3,702,757
3,278,550 3,442,808 3,579,450 3,703,536
3,280,234 3,455,831 3,591,598 3,704,308
3,281,428 3,455,832 3,600,372 3,708,522
(5) ~nterpolymers of 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. These may be
characterized as "polymeric dispersants" and examples thereof
are disclosed in the following U.S. patents:
3,329,658 3,666,730
3,449,250 3,687,849
3,519,565 3,702,300
The above-noted patents disclose ashless dispersants.
Auxiliary extreme pressure agents and corrosion-
and oxidation-inhibiting agents are exemplified by chlo-
rinated aliphatic hydrocarbons such as chlorinated wax;
aromatic sulfides and polysulfides such as benzyl disulfide,
bis(chlorobenzyl) disulfide, and sulfurized alkylphenol;
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, di-
heptyl phosphite, dicyclohexyl phosphite, pentylphenylphosphite, dipentylphenyl phosphite, tridecyl phosphite,
distearyl phosphite, dimethyl naphthyl phospite, oleyl 4-
pentylphenyl phosphite, polypropylene (molecular weight
500)~substituted phenyl phosphite, diisobutyl-substituted
8Z~8
- 17 -
phenyl phosphite; metal thiocarbamates, such as zinc di-
octyldithiocarbamate, and barium heptylphenyl dithiocar-
bamate; Group II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithioate, zinc dioctylphosphorodi-
thioate, barium di(heptylphenyl)phosphorodithioate,cadmium dinonylphosphorodithioate, and the zinc salt of a
phosphorodithioic acid produced by the reaction of phos-
phorus pentasulfide with an equimolar mixture of isopropyl
alcohol and n-hexyl alcohol.
Tha compositions of this invention can be added
directly to the lubricant. Preferably, 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 concen-
15 trates usually contain about 20-90~ by weight of the com-
position of this invention such as the compositions of
Examples 1-6 and may contain, in addition, one or more other
additives known in the art or described hereinabove.
Illustrative lubricants of this invention comprise
20 principally mineral oil (e.g., SAE lOW-40 for an internal
combustion engine lubricant and SAE 75W-90 for a gear
lubricant~ in combination with about 0.5-5.0~ by weight or
more of the composition of the invention such as Examples 1-
6 and with other known lubricant additives. The following
25 specific examples in Table II illustrate lubricating com-
positions according to the invention. Unless otherwise
indicated, all amounts listed, except those for mineral oil,
are exclusive of oil present as diluent.
1;~ 320~
-- 18 --
o I o ~ 3
tl 1-- ~ O O 1~
O r~ ~ X X Q-1- I n P
o o
p~ N 1-- ~ O ~ '~
I-h (D lDl't I p' N ` ~3
O r~ ~ ~ O ~D ~
O ~D
O 1~
J- ~ ~ t'~ O
h ID ~ O ~C
O P )~C
~ S 1
n o
r~
,~..
o
n
. ' ~ H
~ '~ ~ O ~ 'O O CO
f:~ 'o a b o '~ o~ u~ .,
Ln o ~ ~a ~ co ,,
Ln Ul . .
~ ~ :p,
c) o 'o ~ ~ ~ oo :
'o o o o ~ ~ ~n ': U~
~ ~n o o~ o ~I co ':
Ln Ln .
S~ ,0 '~ '.0 0 o ~D ,~
~ o ~ 1 1 t ' IL~
p o o o ~P co o~ ': ~D
~ ~-- Ul ~ O ~ ~ .
~n Ul ''~S~
u~ ' : r~
O ~ ~ ~ O O CO ~:
~ 1 1 ' 1 ~ I ~ O '
o ~ p 1~ ~ U~ Ul ':
~ ~n p 5: ~ ~1 .
L~l Ln .
~O
O ,0 0 ~ O 1-- CO 1_
C~ ~ 'O O Ul ~ 1-- .
m ul .,
