Note: Descriptions are shown in the official language in which they were submitted.
w092/l8588 PCT/US~/~lS~4
-1- 2085~1 ~
Title: LUBRICATING COMPOSITIONS
FIELD OF THE INVEN~ION
This invention relates to lubricating oil compo-
sitions containing overbased alkali metal salts of at least
one acidic organic compound, at least one dispersant, at
least one metal dithiophosphate, at least one antioxidant,
and at least one magnesium overbased metal salt of an
acidic organic compound.
INTRODUCTION TO THE INVENTION
As engines, specifically spark-ignited and diesel
engines, preferably spark-ignited engines, have increased
in power output and complexity, the performance require-
ments of lubricating oils have been increased to provide
lubricating oils that exhibit a reduced tendency to deteri-
orate under conditions of use and thereby to reduce wear
and the formation of such undesirable deposits as varnish,
sludge, carbonaceous materials and resinous materials which
tend to adhere to various engine parts and reduce efficien-
cy of engines.
Alkaline earth metal detergents are used to
suspend degradation products in a motor oil and to neutral-
ize acid products within the oil of engines. Usually, thealkaline earth metal is a calcium detergent and particular-
ly a calcium overbased sulfonate or a calcium phenate.
Canadian Patent 1,055,700 relates to basic alkali
sulfonate dispersions and processes. U.S. Patent 4,326,972
relates to concentrates, lubricant compositions and methods
for improving fuel economy of internal combustion engines.
These compositions have as an essential ingredient a
specific sulfurized composition and a basic alkali metal
sulfonate. U.S. Patent 4,904,401 relates to lubricating
oil co~positions. These compositions may contain a basic
W092/l8588 PCT/US~/015~4
2085615
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alkali metal salt of at least one sul~onic or carboxylic
acid. U.S. Patent 4,938,881 relates to lubricating oil
compositions and concentrates. These compositions and
concentrates include at least one basic alkali metal salt
of sulfonic or carboxylic acid. U.S. Patent 4,952,328
relates to lubricating oil compositions. These composi-
tions co~tain from about 0.01% to about 2% by weight of at
least one basic alkali metal salt of sulfonic or carboxylic
acid.
SUMMARY OF THE INVENTION
The invention relates to a lubricating oil
composition, comprising:
a major amount of an oil of lubricating viscosi-
ty; and
(A) an amount of at least one alkali metal
overbased salt of an acidic organic compound to provide at
least about 0.0019 equivalents of alkali metal per 100
grams of the lubricating composition;
(8) at least about 1.60% by weight of at least
one dispersant;
(C) at least one metal dihydrocarbyl dithiopho-
sphate;
(D) at least one antioxidant; and
(E) at least one magnesium overbased metal salt
of an acidic organic compound provided that the lubricating
oil composition is free of calcium overbased sulfonate and
calcium overbased phenate; provided that the composition
contains less than about 0.08% by weight calcium; and
provided that (C) and (D) are not the same.
DET~II,ED D~SCRIP~ON OF THE INVENTION
~he term "hydrocarbyl" includes hydrocarbon, as
well as substantially hydrocarbon, groups. Substantially
hydrocarbon describes groups which contain non-hydrocarbon
substituents which do not alter the predominately hydrocar-
bon nature of the group.
W092/18s88 PCT/US~/01S74
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-3-
Examples of hydrocarbyl groups include the
following:
(1) hydrocarbon substituents, that i8, aliphatic
(e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl,
cycloalkenyl) substituents, aromatic-, aliphatic- and
alicyclic-substituted aromatic substituents and the like as
well as cyclic substituents 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 substituents, that
is, those substituents containing non-hydrocarbon groups
which, in the context of this invention, do not alter the
predominantly hydrocarbon substituent; those skilled in the
art will be aware of such groups (e.g., halo (especially
chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmer-
capto, nitro, nitroso, sulfoxy, etc.);
(3) hetero substituents, that is, substituents
which will, while having a predominantly hydrocarbon
character within the context of this invention, contain
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, ~uryl, thienyl, imidazolyl, etc. In
general, no more than about 2, preferably no more than one,
non-hydrocarbon substituent will be present for every ten
carbon atoms in the hydrocarbyl group. Often, there will
be no such non-hydrocarbon substituents in the hydrocarbyl
group and the hydrocarbyl group is purely hydrocarbon.
Throughout this specification and claims, refer-
ences to percentages by weight of the various components
are on a chemical basis unless otherwise indicated. An
equivalent weight of an amine or a polyamine is the molecu-
lar weight of the amine or polyamine divided by the total
WO92/18588 PCT/US~/01S~4
208~61~
number of nitrogens present in the molecule ~he number ofequivalents of the acylating agent depends on the total
number of carboxylic functions present. The equivalent
weight of a hydroxyamine used to form carboxylic ester
S derivatives is its molecular weight divided by the number
of hydroxyl groups present, and the nitrogen atoms present
are igno~ed. An equivalent weight of a hydroxy-substituted
amine to be reacted with the acylating agents to form
carboxylic amine derivatives is its molecular weight
divided by the total number of nitrogen groups present in
the molecule. An equivalent weight of polyhydric alcohol
is its molecular weight divided by the total number of
hydroxyl groups present in the molecule.
The terms "substituent" and "acylating agent" or
"substituted succinic acylating agent" are to be given
their normal meanings. For example, a substituent is an
atom or group of atoms that has replaced another atom or
group in a molecule as a result of a reaction. The term
acylating agent or substituted succinic acylating agent
refers to the compound per se and does not include unre-
acted reactants used to form the acylating agent or substi-
tuted succinic acylating agent.
A)_,alkali Metal Overbased Salts:
The present lubricating compositions contain A)
an alkali metal overbased salt of an acidic organic com-
pound. The overbased salts are single phase, homogeneous,
Newtonian systems 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. The amount of excess
metal is commonly expressed in terms of metal ratio. ~he
term "metal ratio" is the ratio of the total equivalents of
the metal to the equivalents of the acidic organic com-
pound. A salt having 4.5 times as much metal as present in
3S a normal salt will have metal excess of 3.5 equivalents, or
WO92/18588 PCT/US92/~lS74
2085~1~
--5--
a ratio of 4.5. In the present invention, these salts
preferably have a metal ratio from about 1.5 to about 40,
preferably about 3 to about 30, more preferably about 3 to
about 25.
5The overbased materials are prepared by reacting
an acidic material, typically carbon dioxide, with a
mixture comprising an acidic organic compound, a reaction
medium comprising at least one inert, organic solvent for
said organic material, a stoichiometric excess of the metal-
10compound, typically a metal hydroxide or oxide, and a
promoter. In another embodiment, the basic alkali metal
salts are prepared by reacting water with a mixture com-
prising an acidic organic compound, a reaction medium and
a promoter. These metal salts and methods of making the
15same are described in U.S. Patent 4,627,928. This disclo-
sure is hereby incorporated by reference.
The acidic organic compounds are selected from
the group consisting of: carboxylic acids, sulfonic acids,
phosphorus acids, phenols and derivatives thereof. Prefer-
20ably, the overbased materials are prepared from carboxylic
acids or sulfonic acids. The carboxylic and sulfonic acids
may have substituent groups derived from polyalkenes. The
polyalkene is characterized as containing from at least
about 8 carbon atoms, preferably at least about 30, more
25preferably at least about 35 up to about 300 carbon atoms,
preferably 200, more preferably up to about 100. In one
embodiment, the polyalkene is characterized by an Mn
(number average molecular weight) value of at least about
400, preferably about 500. Generally, the polyalkene is
30characterized by an Mn value of about 500, preferably about
700, more preferably about 800, still more preferably about
900 up to about 5000, preferably up to about 2500, more
preferably up to about 2000, still more preferably up to
about 1500. In another embodiment Mn varies between about
W0~2/1858X PCT/US~/OIS74
208~61a
--6--
500, preferably about 700, more preferably about 800 up to
about 1200 or 1300.
The abbreviation Mn is the conventional symbol
representing number average molecular weight. Gel perme-
ation chromatography (GPC) is a method which provides both
weight average and number average molecular weights as well
as the entire molecular weight distribution of the poly-
mers. For purpose of this invention a series of fraction-
ated polymers of isobutene, polyisobutene, is used as thé
calibration standard in the GPC.
The polyalkenes include homopolymers and inter-
polymers of polymerizable olefin monomers of 2 to about 16
carbon atoms; usually 2 to about 6, preferably 2 to about
4, more preferably 4. The olefins may be monoolefins such
as ethylene, propylene, 1-butene, isobutene, and 1-octene;
or a polyolefinic monomer, preferably diolefinic monomer,
su_h 1,3-butadiene and isoprene. Preferably, the inter-
polymer is a homopolymer. An example of a preferred
homopolymer is a polybutene, preferably a polybutene in
which about 50% of the polymer is derived from isobutylene.
The polyalkenes are prepared by conventional procedures.
Suitable carboxylic acids from which useful
alkali metal salts can be prepared include aliphatic,
cycloaliphatic and aromatic mono- and polybasic carboxylic
acids free from acetylenic unsaturation, including naph-
thenic acids, alkyl- or alkenyl-substituted cyclopentanoic
acids, and alkyl- or alkenyl-substituted cyclohexanoic
acids, preferably alkenyl-substituted succinic acids or
anhydrides. 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 carbox-
ylic acids are preferred, and they can be saturated or
unsaturated.
Illustrative carboxylic acids include 2-ethyl-
3S hexanoic acid, palmitic acid, stearic acid, myristic acid,
wos2/l8s88 PCT/US92/01S74
2 ~
-7-
oleic acid, linoleic acid, behenic acid, hexatriacon~anoic
acid, tetrapropylenesubstituted glutaric acid, polybutenyl
substituted succinic acid derived from polybutene (Mn
equals about 200-1500, preferably about 300-1500, more
preferably about 800-1200), polypropylene substituted
succinic acid derived from polypropene (Mn equal 200-2000,
preferably about 300-1500, more preferably about 800-1200),
acids formed by oxidation of petrolatum or of hydrocarbon
waxes, commercially available mixtures of two or more
carboxylic acids such as tall oil acids, and rosin acids,
octadecyl-substituted adipic acid, chlorostearic acid,
9-methylstearic acid, dichlorostearic acid, stearyl-benzoic
acid, eicosane-substituted naphthoic acid, dilauryl-deca-
hydro-naphthalene carboxylic acid, and mixtures of these
acids, their metal salts, and/or their anhydrides.
In another embodiment, the carboxylic acid is an
alkyloxyalkylene-acetic acid or alkylphenoxy-acetic acid,
more preferably alkylpolyoxyalkylene-acetic acid or salts
thereof. Some specific examples of these compounds in-
clude: iso-stearylpentaethyleneglycolacetic acid; iso-
stearyl-0-( CH2CH20 ) 5CH2CO2Na; lauryl-O-~ CH2CH20 ) 2 5CH2C02H;
lauryl-0-(CH2CH20) 3 3CH2C02H; oleyl-0-(CH2CH20)4CH2C02H; lauryl-0-
(CH2CH20)45CH2CO2H; lauryl-O-(CH2CH20)~0CH2CO2H; lauryl-O-(CH2-
CH20)~6CH2C02H; octyl-phenyl-0-(CH2CH20)8CH2C02H; octyl-phenyl-
0-(CH2CH20)~9CH2C02H; 2-octyldecanyl-0-(CH2CH20)6CH2C02H. These
acids are available commercially from Sandoz Chemical under
the tradename Sandopan acids.
In one preferred embodiment, the carboxylic acids
are aromatic carboxylic acids. A group of useful aromatic
carboxylic acids are those of the formula
WO92/~8588 PCT/USn/01S74
208~ ~ 15 -8-
( C XH ) b
(R~)~ Ar \ (XIII)
(XH) c
wherein R~ is an aliphatic hydrocarbyl group prefe~rably
derived from the above-described polyalkenes, a is a number
in the range of 0 to about 4, usually 1 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 from 1 to 2, c is a number in the range of
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 acids include substituted and
non-substituted benzoic, phthalic and salicylic acids.
The Rl group is a hydrocarbyl group that is
directly bonded to the aromatic group Ar. Examples of R~
groups include substituents derived from polymerized
olefins such as polyethylenes, polypropylenes, polyiso-
butylenes, 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, naph-
thalene, anthracene, etc., preferably benzene. Specific
examples of Ar groups include phenylenes and naphthylene,
e.g., methylphenylenes, ethoxyphenylenes, isopropylphenyl-
enes, hydroxyphenylenes, dipropoxynaphthylenes, etc.
Within this group of aromatic acids, a useful
class of carboxylic acids are those of the formula
WO92/18S88 PCT/US~/OIS74
_9_ 2 08 5 S1 5
~ (COOH) b
(R~) ~
(OH)c
wherein RI is defined above, a is a number in the range of
from zero 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, prefera-
bly 1 to about 2, and more preferably 1; with the proviso
that the sum of a, b and c does not exceed 6. Preferably,
b and c are each one and the carboxylic acid is a salicylic
acid.
The salicylic acids preferably are aliphatic
hydrocarbon-substituted salicyclic acids. Overbased salts
prepared from such salicyclic acids wherein the aliphatic
hydrocarbon substituents are derived from the above-de-
scribed polyalkenes, particularly polymerized lower 1-mono-
olefins such as polyethylene, polypropylene, polyisobutyl-
ene, ethylene/propylene copolymers and the like and having
average carbon contents of about 50 to about 400 carbon
atoms, based on number average molecular weight, 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 exam-
ple, 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.
The sulfonic acids are preferably mono-, di-, and
tri-aliphatic hydrocarbon-substituted aromatic sulfonic
acids. The hydrocarbon-substituent may be derived form any
of the above-described polyalkenes. Such sulfonic acids
W092/18S88 PCTtUS92~01S~4
2~85615
--10--
include mahogany sul~onic acids, bright stock ~ul~onic
acids, petroleum sulfonic acids, mono- and polywax-substi-
tuted 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
10 wax sulfonic acids, tetraisobutylene sulfonic acids, tetra-
amylene sulfonic acids, chloro-substituted paraffin wax
sul~onic acids, nitros`o-substituted paraffin wax sulfonic
acids, cetylcyclopentyl sulfonic acids, lauryl cyclohexyl
sulfonic acids, mono- and polywax-substituted cyclohexyl
15 sulfonic acids, dodecylbenzene sulfonic acids, didodecyl-
benzene sulfonic acids, dinonylbenzene sulfonic acids,
cetylchlorobenzene sulfonic acids, dilauryl beta-naphthal-
ene sulfonic acids, the sulfonic acid derived by the treat-
ment of at least one of the above-described polyalkenes
20 (preferably polybutene) with chlorosulfonic acid, nitro-
naphthalene sulfonic acid, paraffin wax sulfonic acid,
cetyl-cyclopentane, sulfonic acid, lauryl-cyclohexane
sulfonic acids, polyethylenyl substituted sulfonic acids
derived form polyethylene (Mn=300-1500, preferably about
25 600 to about 1500, more preferably about 800 to about 1200,
preferably 750), etc., "dimer alkylate" sulfonic acids, and
the like.
Alkyl-substituted benzene sulfonic acids wherein
the alkyl group contains at least 8 carbon atoms, including
30 dodecyl benzene "bottoms" sulfonic acids, are particularly
useful. The latter are acids derived from benzene which
has been alkylated with propylene tetramers or isobutene
trimers to introduce 1, 2, 3, or more branched-chain C~2
substituents on the benzene ring. Dodecyl benzene bottoms,
35 principally mixtures of mono- and di-dodecyl benzenes, are
-
W092/l~8 PCT/US~/01574
208~
--11--
available as by-products from the manufacture of household
detergents. Similar products obtained from alkylation
bottoms formed during manufacture o~ linear alkyl sulfon-
ates (LAS) are also useful in making the sulfonates used in
this invention.
A preferred group of sulfonic acids are mono-,
di-, and tri-alkylated benzene and naphthalene (including
hydrogenated forms thereof) sulfonic acids. Illustrative
of the synthetically produced alkylated benzene and naph-
thalene sulfonic acids are those containing alkyl substitu-
ents having from about 8 to about 30 carbon atoms, prefera-
bly about 12 to about 30 carbon atoms, and advantageously
about 24 carbon atoms. Such acids include di-isododecyl-
benzene sulfonic acid, wax-substituted phenol sulfonic
acid, wax-substituted benzene sulfonic acids, polybutenyl-
substituted sulfonic acid, polypropylenyl-substituted
sulfonic acids derived from polypropylene having a number
average molecular weights (Mn) of about 300-1000, more
preferably 500-700, cetyl-chlorobenzene sulfonic acid,
di-cetylnaphthalene sulfonic acid, di-lauryldiphenylether
sulfonic acid, diisononylbenzene sulfonic acid, di-isoocta-
decylbenzene sulfonic acid, stearylnaphthalene sulfonic
acid, and the like.
The production of sulfonic acids from detergent
manufacture by-products by reaction with, e.g., S03, iS well
known to those skilled in the art. See, for example, the
article "Sulfonates" in Kirk-Othmer "Encyclopedia of
Chemical Technology", Second Edition, Vol. 19, pp. 291 et
seq. published by John Wiley & Sons, N.Y. (1969).
The phosphorus-containing acids useful in making
the salts of the present invention include any phosphorus
acids such as phosphoric acid or esters; and thiophosphorus
acids or esters, including mono and dithiophosphorus acids
or e8ters.
W0~2/18588 PCT/~IS~/01S74
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-12-
In a preferred embodiment, the phosphorus-
containing acid is the reaction product of the above
polyalkene and phosphorus sulfide. Useful phosphorus
sulfide-containing sources include phosphorus pentasulfide,
phosphorus sesquisulfide, phosphorus heptasulfide and the
like.
The reaction of the polyal~ene and the phosphorus
sulfide generally may occur by simply mixing the two at a
temperature above 80C, preferably between 100C and 300C.
Generall~, the products have a phosphorus content from
about o.os% to about lO~, preferably from about 0.1% to
about 5%. The relative proportions of the phosphorizing
agent to the olefin polymer is generally from 0.1 part to
50 parts of the phosphorizing agent per lO0 parts of the
olefin polymer.
The phosphorus-containing acids useful in the
present invention are described in U.S. Patent 3,232,883
issued to Le Suer. This reference is herein incorporated
by reference for its disclosure to the phosphorus-contain-
ing acids and methods for preparing the same.
The phenols useful in making the overbased saltsof the invention can be represented by the formula (Rl)~-Ar-
(OH)b, wherein Rl is defined above; Ar is an aromatic group;
a and b are independently numbers of at least one, the sum
of a and b being in the range of two up to the number of
displaceable hydrogens on the aromatic nucleus or nuclei of
Ar. Preferably, a and b are independently numbers in the
range of 1 to about 4, more preferably 1 to about 2. Rl and
a are preferably such that there is an average of at least
about 8 aliphatic carbon atoms provided by the R~ groups for
each phenol compound.
- While the term "phenol" is used herein, it is to
be understood that this term is not intended to limit the
aromatic group of the phenol to benzene. Accordingly, it
is to be understood that the aromatic group as represented
W092/185X8 PCT/US~/01574
2B35~
-13-
by "Ar", as well as elsewhere in other ~ormulae in thi~
specification and in the appended claims, can be mononucle-
ar such as a phenyl, a pyridyl, or a thienyl, or polynucle-
ar. The polynuclear groups can be of the fu~ed type
wherein an aromatic nucleus is fused at two point~ to
another nucleus such as found in naphthyl, anthranyl, etc.
The polynuclear group can also be of the linked type
wherein at least two nuclei (either mononuclear or polynu-
clear) are linked through bridging linkages to each other.
These bridging linkages can be chosen from the group
consisting of alkylene linkages, ether linkages, keto
linkages, sulfide linkages, polysulfide linkages of 2 to
about 6 sulfur atoms, etc.
The number of aromatic nuclei, fused, linked or
both, in Ar can play a role in determining the integer
values of a and b. For example, when Ar contains a single
aromatic nucleus, the sum of a and b is from 2 to 6. When
Ar contains two aromatic nuclei, the sum of a and b is from
2 to 10. With a tri-nuclear Ar moiety, the sum of a and b
is from 2 to 15. The value for the sum of a and b is
limited by the fact that it cannot exceed the total number
of displaceable hydrogens on the aromatic nucleus or nuclei
of Ar.
The promoters, that is, the materials which
facilitate the incorporation of the excess metal into the
overbased material, are also quite diverse and well known
in the art. A particularly comprehensive discussion of
suitable promoters is found in U.S. Patents 2,777,874;
2,695,910; 2,616,904; 3,384,586; and 3,492,231. These
patents are incorporated by reference for their disclosure
of promoters. In one embodiment, promoters include the
alcoholic and phenolic promoters. The alcoholic promoters
include the alkanols of one to about 12 carbon atoms such
as methanol, ethanol, amyl alcohol, octanol, isopropanol,
and mixtures of these and the like. Phenolic promoters
w092/18s8x PCT/US~/OIS74
208~61~
include a variety of hydroxy-substituted benzenes and
naphthalenes. A particularly useful class o~ phenols are
the alkylated phenols of the type listed in U.S. Patent
2,777,874, e.g., heptylphenols, octylphenols, and nonyl-
phenols. Mixtures of various promoters are sometimes used.
Acidic materials, which are reacted with the
mixture of acidic organic compound, promoter, metal com-
pound and reactive medium, are also disclosed in the above
cited patents, for example, U.S. Patent 2,616,904. Includ-
ed within the known group of useful acidic materials areliquid acids such as formic acid, acetic acid, nitric acid,
boric acid, sulfuric acid, hydrochloric acid, hydrobromic
acid, carbamic acid, substituted carbamic acids, etc.
Acetic acid is a very useful acidic material although
inorganic acidic compounds such as HCl, S2~ S3~ C02, ~S,
N203, etc., are ordinarily employed as the acidic materials.
Preferred acidic materials are carbon dioxide and acetic
acid, more preferably carbon dioxide.
The alkali metals present in the overbased alkali
metal salts include principally lithium, sodium and potas-
sium, with sodium and potassium being preferred and with
sodium most preferred. The overbased metal salts are
prepared using a basic alkali metal compound. Illustrative
of basic alkali metal compounds are hydroxides, oxides,
alkoxides (typically those in which the alkoxy group
contains up to 10 and preferably up to 7 carbon atoms),
hydrides and amides of alkali metals. Thus, useful basic
alkali metal compounds include sodium hydroxide, potassium
hydroxide, lithium hydroxide, sodium propoxide, lithium
methoxide, potassium ethoxide, sodium butoxide, lithium
hydride, sodium hydride, potassium hydride, lithium amide,
sodium amide and potassium amide. Especially preferred are
sodium hydroxide and the sodium lower alkoxides (i.e.,
those containing up to 7 carbon atoms).
W09t/l8588 P~/USn/01S74
20~615
-15-
The methods for preparing the overbased materials
as well as an extremely diverse group of overbased materi-
als are well known in the prior art and are disclosed, for
example, in the following U.S. Patent Nos.: 2,616,904;
2,616,905; 2,616,906; 3,242,080; 3,250,710; 3,256,186;
3,274,135; 3,492,231; and 4,230,586. These patents dis-
close processes, materials which can be overbased, suitable
metal bases, promoters, and acidic materials and these
disclosures are incorporated herein by reference for these
disclosures.
Other descriptions of basic sulfonate salts which
can be incorporated into the lubricating oil compositions
of this invention and techniques for making them can be
found in the following U.S. Patents: 2,174,110; 2,202,781;
lS 2,239,974; 2,319,121; 2,337,552; 3,488,284; 3,595,790; and
3,798,012. These are hereby incorporated by reference for
their disclosures in this regard.
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 80C to about 300C, and preferably from about 100C
to about 200C. When an alcohol or mercaptan is used as
the promoting agent, the temperature usually will not
exceed the reflux temperature of the reaction mixture.
In another embodiment, the alkali metal overbased
salts are borated alkali metal overbased salts. Borated
overbased metal salts are prepared by reacting a boron
compound with a detergent or by using boric acid to over-
base the organic acid. Boron compounds include boron
oxide, boron oxide hydrate, boron trioxide, boron trifluor-
ide, boron tribromide, boron trichloride, boron acid such
as boronic acid, boric acid, tetraboric acid and metaboric
acid, boron hydrides, boron amides and various esters of
boron acids. The boron esters are preferably lower alkyl
W092/l8588 PCT/US~/015~4
20~5~15 -16-
(1-7 carbon atoms) esters of boric acid. Preferably, the
boron compounds are boric acid. Generally, the overbased
metal salt is reacted with a boron compound at about 50C
to about 250c, preferably 100C to about 200C. The
reaction may be accomplished in the presence of a solvent
such as mineral oil, naphtha, kerosene, toluene or xylene.
The overbased metal salt is reacted with a boron compound
in amounts to provide at least about 0.5 to about 5 percent
by weight boron to the composition, preferably about 1 to
about 4 percent by weight, more preferably about 3.
Borated overbased compositions, lubricating
compositions containing the same and methods of preparing
borated overbased compositions are found in U.S. Patent
4,744,922 issued to Fischer et al; U.S. Patent 4,792,410
issued to Schwind et al and PCT Publication WO88/03144.
The disclosures relating to the above are hereby incorpo-
rated by reference.
The overbased alkali metal salts of this inven-
tion and their preparations are illustrated in the follow-
ing examples.
Example A-l
A solution of 780 parts (1 equivalent) of an
al~ylated benzenesulfonic acid (57% by weight 100 neutral
mineral oil and unreacted alkylated benzene) and 119 parts
(0.2 equivalent) 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 equiva-
lents) of methanol. The mixture is blown with carbon
dioxide at 7 cfh. (cubic feet per hour) for 11 minutes as
the temperature slowly increases to 97C. The rate of
carbon dioxide flow is reduced to 6 cfh. ~nd the tempera-
ture decreases slowly to 88C 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 73C.
The volatile materials are stripped by ~lowing nitrogen
WO ~18S88 PCTtUS~/OlS~4
2~85~1~
-17-
through the carbonated mixture at 2 cfh. ~or 105 minutes as
the temperature is slowly increa~ed to 160C. A~ter
stripping is completed, the mixture is held at 160C 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.
Example A-2
Following the procedure of Example A-1, 836 parts
(l equivalent) of a 48% 100 neutral mineral oil solution of
a sodium petroleum sulfonate and 63 parts (0.11 equivalent)
of the polybutenyl succinic anhydride is heated to 600C and
treated with 280 parts (7 equivalents) of sodium hydroxide
and 320 parts (10 equivalents) of methanol. The reaction
mixture is blown with carbon dioxide at 4 cfh. for about 45
minutes. During this time, the temperature increases to
85C and then slowly decreases to 74C. The volatile
material is stripped by blowing with nitrogen at 2 cfh.
while the temperature is gradually increased to 160C.
After stripping is completed, the mixture is heated an
additional 30 minutes at 160C and then is filtered to
yield the sodium salt in solution. ~he product has a metal
ratio of 8Ø
Example A-3
A sodium carbonate overbased (20:1 equivalent)
sodium sulfonate (lOOO parts, 7.84 equivalents) is mixed
with 130 parts of lOO neutral mineral oil in a reaction
vessel. The mixture of the sodium carbonate overbased
sodium sulfonate and the mineral oil is heated to 75C.
Boric acid (486 parts, 7.84 moles) is then added slowly
without substantially changing the temperature of the
mixture.
The reaction mixture is then slowly heated to
100C over a period of about l hour while removing sub-
stantially all of the distillate. About one-half of the
carbon dioxide is removed, without substantial foaming.
WO ~/l8.~ PCTJUS~/015~4
2~ 61~
-18-
The product is then further heated to 150C for about 3
hours while removing all of the distillate. It is observed
that at the latter temperature, substantially all of the
water is removed and very little additional carbon dioxide
is evolved from the product. The product is then held for
another hour at 150C until the water content of the
product is less than about 0.3%.
The product is recovered by allowing it to cool
to 100C-120C followed by filtration. The filtrate has
6.12% boron, 14.4% Na, and 35% 100 neutral mineral oil.
Example A-4
A reaction vessel is charged with 1122 parts (2
equivalents) of a polybutenyl substituted succinic anhy-
dride, 105 parts (0.4 equivalents) of tetrapropenyl phenol,
1122 parts of xylene and lO00 grams of 100 neutral mineral
oil. The reaction mixture is stirred and heated to 80C
under nitrogen, where 580 parts of a 50% aqueous solution
of sodium hydroxide is added to the vessel over 10 minutes.
The reaction mixture is heated from 80C to 120C over 1.3
hours. Water is removed by azeotropic reflux and the
temperature rises to 150C over 6 hours while 300 parts of
water is collected. (1) The reaction is cooled to 80C
where 540 parts of a 50% aqueous solution of sodium hydrox-
ide is added to the vessel. (2) The reaction mixture is
heated to 140C over 1.7 hours and water is removed at
reflux conditions. (3) The reaction mixture is carbonated
at 1 scfh (standard cubic feet per hour) while removing
water for 5 hours. Steps (1)-(3) above are repeated using
560 parts of an aqueous sodium hydroxide solution. Steps
(1)-(3) are repeated using 640 parts of an aqueous sodium
hydroxide solution. Steps (1)-(3) are then repeated with
another 640 parts of a 50% aqueous sodium hydroxide solu-
tion. The reaction mixture is cooled and 1000 parts of 100
neutral mineral oil are added to the reaction mixture. The
reaction mixture is vacuum stripped to 115-C, 30 millime-
WO92/18588 PCT/US~/01574
~a3s~
-19-
ters of mercury. The reaction is f$1tered through diatoma-
ceous earth. The ~iltrate has a total ba~e number o~ 361
(theoretical 398), 43.4~ sulfated ash (theoretical 50,3)
and a specific gravity of 1.11.
Example A-5
A reaction vessel is charged with 1561 parts
(1.11 equivalents) of an oil solution of a bright stock
sulfonic acid derived from Mobil 150 bright stock (molecu-
lar weight 600 and 72% bright stock diluent), 107 parts
(0.27 equivalent) of sulfur coupled tetrapropylene substi-
tuted phenol (27% 100 neutral mineral oil), 178 parts (0.31
equivalent) of a polybutenyl substituted succinic anhydride
derived from a polybutene (Mn equals 960), 118 parts 100
neutral mineral oil and 1000 parts toluene. The mixture i5
heated to 100C whereupon 591 parts (7.4 equivalents) of a
50~ agueous solution of sodium hydroxide is added to the
reaction mixture. The reaction mixture is blown with
carbon dioxide for 1.75 hours at 1 scfh while 275 parts of
water are removed. The reaction is cooled at 90C and the
275 parts of water are readded to the reaction mixture.
The reaction is heated to 100C and the temperature is
maintained for two hours, whereupon 31 parts (0.05 equiva-
lent) of the above polybutenyl succinic anhydride and 36
parts (0.09 equivalent) of the sulfur coupled tetrapropenyl
phenol are added in 100 parts of toluene. The reaction
mixture is blown with carbon dioxide for four hours at
117C while 350 parts of water are removed. The reaction
is cooled to 80C where 434 parts (5.4 equivalents) of the
aqueous sodium hydroxide are added to the reaction mixture.
The mixture is blown with carbon dioxide for 3.5 hours
while 550 parts of water are removed. The reaction is
cooled to 90C where 600 parts (7.5 equivalents) of the
aqueous sodium hydroxide are added to the reaction mixture.
The mixture is blown with carbon dioxide for eight hours at
a temperature o~ 105-112C while 870 parts of water are
wo 92/18588 PCr/USg2~OlS74
208~61~
-20-
removed. The reaction mixture is cooled to 40C where 601
parts (7.5 equivalents) of the aqueous sodium hydroxide are
added to the reaction mixture. The reaction mixture i5
heated to 110-112C and blown with carbon dioxide for
seven hours while 1150 parts of water are removed. The
reaction is cooled to 60C where 164 parts (2.1 equiva-
lents) of aqueous sodium hydroxide are added to the reac-
tion mixture. The reaction mixture is heated to 110C-
120C and blown with carbon dioxide for 7 hours, while a
total of 1410 parts of water are removed.
The mixture is blown with nitrogen at 2 scfh for
six hours at 140C. The product is filtered through
diatomacous earth and the filtrate is the desired product.
The filtrate has a total base number of 446.
B~ Dispersants
The lubricating compositions contain at least one
dispersant. The dispersants are selected from the group
consisting of: (a) nitrogen-containing carboxylic dispers-
ants, (b) amine dispersants, (c) ester dispersants, (d)
Mannich dispersants, (e) dispersant viscosity improvers and
(f) mixtures thereof. In one embodiment, the dispersants
may be post-treated with such reagents as urea, thiourea,
carbon disulfide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, nitriles,
epoxides, boron compounds, phosphorus compounds, etc.
The nitrogen-containing carboxylic dispersants
include reaction products of hydrocarbyl-substituted
carboxylic acylating agents such as substituted carboxylic
acids or derivatives thereof with an amine.
The hydrocarbyl-substituted carboxylic acylating
agent may be derived from a monocarboxylic acid or a
polycarboxylic acid. Polycarboxylic acids generally are
preferred. ~he acylating agents may be a carboxylic acid
or derivatives of the carboxylic acid such as the halides,
esters, anhydrides, etc., preferably acid, esters or
WO92/18588 PCT/US~/01S74
20~.561~
-21-
anhydrides, more preferably anhydrides. Preferably the
carboxylic acylating agent is a succinic acylating agent.
The hydrocarbyl-substituted carboxylic acylating agent
includes agents which have a hydrocarbyl group derived ~rom
the above-described polyalkene.
In one embodiment, the hydrocarbyl groups are
derived from polyalkenes having an Mn value of at least
about 1300 up to about 5000, and the Mw/Mn value is from
about 1.5 to about 4, preferably from about 1.8 to about
103.6, more preferably about 2.5 to about 3.2. The prepara-
tion and use of substituted succinic acylating agents
wherein the substituent is derived from such polyalkenes
are described in U.S. Patent 4,234,435, the disclosure of
which is hereby incorporated by reference.
15The hydrocarbyl-substituted carboxylic acylating
agents are prepared by a reaction of one or more polyal-
kenes with one or more unsaturated carboxylic reagent. ~he
unsaturated carboxylic reagent generally contains an
alpha-beta olefinic unsaturation. The carboxylic reagents
may be carboxylic acids per se and functional derivatives
thereof, such as anhydrides, esters, amides, imides, salts,
acyl halides, and nitriles. These carboxylic acid reagents
may be either monobasic or polybasic in nature. When they
are polybasic they are preferably dicarboxylic acids,
although tri- and tetracarboxylic acids can be used.
Specific examples of useful monobasic unsaturated carboxyl-
ic acids are acrylic acid, methacrylic acid, cinnamic acid,
crotonic acid, 2-phenylpropenoic acid, etc. Exemplary
polybasic acids include maleic acid, fumaric acid, mesa-
conic acid, itaconic acid and citraconic acid. Generally,the unsaturated carboxylic acid or deri~ative is maleic
anhydride or maleic or fumaric acid or ester, preferably,
~aleic acid or anhydride, more preferably maleic anhydride.
The polyalkene may be reacted with the carboxylic
reagent such that there is at least one mole of reagent for
W092/1X588 PCT/US~/015~4
2~8~
-22-
each mole of polyalkene that reacts. Pre~erably, an exce~s
of reagent is used. This excess is generally between about
5~ to about 25%.
In another embodiment, the acylating agents are
s prepared by reacting the above described polyalkene with an
excess of maleic anhydride to provide substituted succinic
acylating agents wherein the number of succinic groups for
each equivalent weight of substituent group is at least
1.3. The maximum number will not exceed 4.5. A suitable
range is from about 1.4 to 3.5 and more specifically from
about 1.4 to about~2.5 succinic groups per equivalent
weight of substituent groups. In this embodiment, the
polyalkene preferably has an Mn from about 1300 to about
5000 and a Mw/Mn of at least 1.5, as described above, the
value of Mn is preferably between about 1300 and 5000. A
more preferred range for Mn is from about 1500 to about
2800, and a most preferred range of Mn values is from about
1500 to about 2400.
For purposes of this invention, the number of
eguivalent weights of substituent groups is deemed to be
the number obtained by dividing the Mn value of the poly-
alkene from which the substituent is derived into the total
weight of the substituent groups present in the substituted
succinic acylating agents. Thus, if a substituted succinic
acylating agent is characterized by a total weight of sub-
stituent group of 40,000, and the Mn value for the poly-
alkene from which the substituent groups are derived is
2000, then that substituted succinic acylating agent is
characterized by a total of 20 (40,000/2000=20) equivalent
weights of substituent groups. Therefore, that particular
succinic acylating agent or acylating agent mixture must
also be characterized by the presence within its structure
of at least 26 succinic groups to meet one of the require-
ments of the succinic acylating agents used in this inven-
tion.
wo92/l8s8~ PCT/US~/01574
20~61~
-23-
The ratio of succinic groups to the equivalent
weight of substituent group present in the acylating sgent
can be determined from the saponification number of the
reacted mixture corrected to account for unreacted poly-
alkene present in the reaction mixture at the end of thereaction (generally referred to as filtrate or residue in
the following examples). Saponification number is deter-
mined using the ASTM D-94 procedure. The formula for
calculatlng the ratio from the saponification number is as
follows:
Ratio - LMn~(Sap No.. corrected)
112,200 - 98(Sap No., corrected)
The corrected saponification number is obtained
by dividing the saponification number by the percent of the
polyalkene that has reacted. For example, if 10~ of the
20polyalkene did not react and the saponification number of
the filtrate or residue is 95, the corrected saponification
number is 95 divided by 0.90 or 105.5.
The conditions, i.e., temperature, agitation,
solvents, and the like, for reacting an acid reactant with
25a polyalkene, are known to those in the art. Examples of
patents describing various procedures for preparing useful
acylating agents include U.S. Patents 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
30al); and U.X. 1,440,219. The disclosures of these patents
are hereby incorporated by reference.
The following examples illustrate the carboxylic
acylating agents and methods for preparing them. The
desired acylating agents are sometimes referred to in the
35examples as "residue" without specific ~etermination or
mention of other materials present or the ~mounts thereof.
Example I
A mixture of 510 parts (0.28 mol4e) of polybutene
(Mn-1845; Mw=5325) and 59 parts (0.59 ~mole) of maleic
WO~2/l8SX8 PC~/US~/01S74
2 08~ 24-
anhydride is heated to 110C. This mixture is heated to
190C in 7 hours during which 43 parts (0.6 ~ole) o~
gaseous chlorine is added beneath the surface. At lgO-
192C an additional 11 parts (0.16 mole) of chlorine is
added over 3.5 hours. The reaction mixture is stripped by
heating at 190-193C with nitrogen blowing for 10 hours.
The residue is the desired polybutene-substituted succinic
acylating agent having a saponification equivalent number
of 87 as determined by ASTM~procedure D-94.
Example II
A mixture of 1000 parts (0.495 mole) of poly-
butene (Mn=2020; Mw=6049) and 115 parts (1.17 moles) of
maleic anhydride is heated to 110C. This mixture is
heated to 184C in 6 hours during which 85 parts (1.2
moles) of gaseous chlorine is added beneath the surface.
At 184-189C an additional 59 parts (0.83 mole) of chlorine
is added over 4 hours. The reaction mixture is stripped by
heating at 186-190C with nitrogen blowing for 26 hours.
The residue is the desired polybutene-substituted succinic
acylating agent having a saponification equivalent number
of 87 as determined by ASTM procedure D-94.
Th~ above-described carboxylic acylating agents
are reacted with amines to form the nitrogen-containing
carboxylic dispersants of the present invention. The amine
may be a monoamine or polyamine, typically a polyamine,
preferably ethylene amines, amine bottoms or amine conden-
sates. The amines can be aliphatic, cycloaliphatic,
aromatic, or heterocyclic, including aliphatic-substituted
cycloaliphatic, aliphatic-substituted aromatic, aliphatic-
substituted heterocyclic, cycloaliphatic-substituted
aliphatic, cycloaliphatic-substituted heterocyclic, aromat-
ic-substituted aliphatic, aromatic-substituted cycloali-
phatic, aromatic-substituted heterocyclic, heterocyclic-
substituted aliphatic, heterocyclic-substituted alicyclic,
WO92/185~ PCT/US~/01574
2as~
-25-
and heterocyclic-substituted aromatic amines and may be
saturated or unsaturated.
The monoamines generally contain from 1 to about
24 carbon atoms, preferably 1 to about 12, and more prefer-
ably 1 to about 6. Examples of monoamines useful in the
present invention include methylamine, ethylamine, propyl-
amine, butylamine, cyclopentylamine, cyclohexylamine,
octylamine, dodecylamine, allylamine, cocoamine, stearyl-
amine, and laurylamine. Examples of secondary amines
include dimethylamine, diethylamine, dipropylamine, dibu-
tylamine, dicyclopentylamine, dicyclohexylamine, methyl-
butylamine, ethylhexylamine, etc. Tertiary amines include
trimethylamine, tributylamine, methyldiethylamine, ethyl-
dibutylamine, etc.
In another embodiment, the amine may be a hy-
droxyamine. Typically, the hydroxyamines are primary,
secondary or tertiary alkanol amines or mixtures thereof.
Such amines can be represented by the formulae:
~N - R' OH,
/ N R' -OH,
R5
and
_ " N R' OH
R~
wherein each R'l is independently a hydrocarbyl group of one
to about eight carbon atoms or hydroxyhydrocarbyl group of
two to about eight carbon atoms, preferably one to about
WO92/18S88 PCT/US~2/01574
2085~ 26-
four, and R' is a divalent hydrocarbyl group o~ about two
to about 18 carbon atoms, preferably two to about ~our.
The group -R'-OH in such formulae represents the hydroxy-
hydrocarbyl group. R' can be an acyclic, alicyclic or
aromatic group. Typically, R' is an acyclic straight or
branched alkylene group such as an ethylene, 1,2-propylene,
1,2-butylene, 1,2-octadecylene, etc. group. Where two R'~
groups are present in the same molecule they can be joined
by a direct carbon-to-carbon bond or through a heteroatom
(e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or
8-membered ring structure. Examples of such heterocyclic
amines include N-(hydroxyl lower alkyl)-morpholines,
-thiomorpholines, -piperidines, -oxazolidines, -thiazoli-
dines and the like. Typically, however, each R', is inde-
pendently a methyl, ethyl, propyl, butyl, pentyl or hexyl
group.
Examples of these alkanolamines include mono-,
di-, and triethanol amine, diethylethanolamine, ethyleth-
anolamine, butyldiethanolamine, etc.
The hydroxyamines can also be an ether N-(hy-
droxyhydrocarbyl)amine. These are hydroxypoly(hydrocarbyl-
oxy) analogs of the above-described hydroxy amines (these
analogs also include hydroxyl-substituted oxyalkylene
analogs). Such N-(hydroxyhydrocarbyl) amines can be
conveniently prepared by reaction of epoxides with afore-
described amines and can be represented by the formulae:
H2N - (R'O)~ H,
H
~ N -(R'O)~-- H,
R J
and
WO92/18S88 PCT~US92/01S~4
-27- 2 08~ ~l S
R ~
/ N - (R~O)~ --H
R',
wherein x is a number from about 2 to about 15 and R, and R'
are as described above. R'1 may also be a hydroxypoly-
(hydrocarbyloxy) group.
Suitable amines also include polyoxyalkylene
polyamines, e.g., polyoxyalkylene diamines and polyoxyal-
kylene triamines, having average molecular weights ranging
from about 200 to 4000 and preferably from about 400 to
2000. Illustrative examples of these polyoxyalkylene
polyamines may be characterized by the formulae: NH2-
Alkylene (O-Alkylene)QNH2, wherein m has a value of about 3
lS to 70 and preferably about lO to 35; and R(Alkylene(O-
Alkylene)~NH2) ~, wherein n is such that the total value is
from about l to 40 with the proviso that the sum of all of
the n's is from about 3 to about 70 and generally from
about 6 to about 35 and R is a polyvalent saturated hydro-
carbon radical of up to lO carbon atoms having a valence of
3 to 6. The alkylene groups may be straight or branched
chains and contain from l to 7 carbon atoms and usually
from l to 4 carbon atoms. The various alkylene groups
present may be the same or different.
The preferred polyoxyalkylene polyamines include
the polyoxyethylene and polyoxypropylene diamines and the
polyoxypropylene triamines having average molecular weights
ranging from about 200 to 2000. The polyoxyalkylene
polyamines are co~mercially available an may be obtained,
Sor example, from the Jefferson Chemical Company, Inc.
under the trade name "Jeffamines D-230, D-400, D-lO00, D-
2000, T-403, etc.".
U.S. Patents 3,804,763 and 3,948,800 are express-
ly incorporated herein by reference for their disclosUre of
such polyoxyalkylene polyamines and process for acylating
W092/1~5~8 PCT/US~/OIS74
20~5~
-28-
them with carboxylic acid acylating agents which processes
can be applied to their reaction with the acylating re-
agents used in this invention.
The nitrogen-containing carboxylic dispersant may
be derived from a polyamine. The polyamine may be aliphat-
ic, cycloaliphatic, heterocyclic or aromatic. Examples of
the polyamines include alkylene polyamines, hydroxy con-
taining polyamines, arylpolyamines, and heterocyclic
polyamines.
Alkylene polyamines are represented by the
formula
HN-(Alkylene-lN)~R2
R2 R2
wherein n has an average value from 1 to about 10, prefera-
bly about 2 to about 7, more preferably about 2 to about 5,
and the "Alkylene" group has from 1 to about 10 carbon
atoms, preferably about 2 to about 6, more preferably about
2 to about 4. R2 is independently preferably hydrogen; or
an aliphatic or hydroxy-substituted aliphatic group of up
to about 30 carbon atoms. Preferably R2 is defined the same
as R'~.
Such alkylene polyamines include methylene
polyamines, ethylene polyamines, butylene polyamines,
propylene polyamines, pentylene polyamines, etc. The
higher homologs and related heterocyclic amines such as
piperazines and N-amino alkyl-substituted piperazines are
also included. Specific examples of such polyamines are
ethylene diamine, triethylene tetramine, tris-(2amino-
ethyl)amine, propylene diamine, trimethylene diamine,tripropylene tetramine, tetraethylene pentamine, hexa-
ethylene heptamine, pentaethylenehexamine, etc.
Higher homologs obtained by condensing two or
more of the above-noted alkylene amines are similarly
W092/l858X PC~/USn/0lS74
2~85~1~
-29-
uaeful as are mixtures of two or more o~ the aforedescribed
polyamines.
Ethylene polyamines, such as those mentioned
above, are use~ul. Such polyamines are described in detail
under the heading Ethylene Amines in Kirk Othmer's ~Ency-
clopedia of Chemical Technology", 2d Edition, Vol. 7, pages
22-37, Interscience Publishers, New York (1965). Such
polyamines are most conveniently prepared by the reaction
of ethylene dichloride with ammonia or by reaction of an
ethylene imine with a ring opening reagent such as water,
ammonia, etc. These reactions result in the production of
a complex mixture of polyalkylene polyamines including
cyclic condensation products such as the aforedescribed
piperazines. Ethylene polyamine mixtures are useful.
Other useful types of polyamine mixtures are
those resulting from stripping of the above-described
polyamine mixtures to leave as residue what is often termed
"polyamine bottoms". In general, alkylene polyamine
bottoms can be characterized as having less than two,
usually less than 1% (by weight) material boiling below
about 200C. A typical sample of such ethylene polyamine
bottoms obtained from the Dow Chemical Company o~ Freeport,
Texas designated "E-100" has a specific gravity at 15.6C
of 1.0168, a percent nitrogen by weight of 33.15 and a
viscosity at 40C of 121 centistokes. Gas chromatography
analysis of such a sample contains about 0.93% "Light Ends"
(most probably DETA), 0.72% TETA, 21.74% tetraethylene
pentaamine and 76.61% pentaethylene hexamine and higher (by
weight). These alkylene polyamine bottoms include cyclic
condensation products such as piperazine and higher analogs
of diethylenetriamine, triethylenetetramine and the like.
These alkylene polyamine bottoms can be reacted
solely with the acylating agent or they can be used with
other amines, polyamines, or mixtures thereof.
WO92/18588 PCT/US~/015~4
2~ S -30-
Another useful polyamine i5 a condensation reac-
tion between at least one hydroxy compound with at least
one polyamine reactant containing at least one primary or
secondary amino group. The hydroxy compounds are pref era-
bly polyhydric alcohols and amines. The polyhydric alco-
hols are described below. (See carboxylic ester disper-
sants.) Preferably the hydroxy compounds are polyhydric
amines. Polyhydric amines include any of the above-de-
scribed monoamines reacted with an alkylene oxide (e.g.,
ethylene oxide, propylene oxide, butylene oxide, etc.)
having two to about 20 carbon atoms, preferably two to
about four. Examples of polyhydric amines include tri-(hy-
droxypropyl)amine, tris-(hydroxymethyl)amino methane, 2-
amino-2-methyl-1,3-propanediol, N,N,N',N'-tetrakis(2-
hydroxypropyl)ethylenediamine, and N,N,N',N'-tetrakis(2-
hydroxyethyl)ethylenediamine, preferably tris(hydroxy-
methyl)aminomethane (THAM).
Polyamine reactants, which react with the poly-
hydric alcohol or amine to form the condensation products
or condensed amines, are described above. Preferred poly-
amine reactants include triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), pentaethylenehexamine
(PEHA), and mixtures of polyamines such as the above-
described "amine bottoms".
The condensation reaction of the polyamine
reactant with the hydroxy compound is conducted at an
elevated temperature, usually about 60C to about 26SC,
(preferably about 220C to about 250C) in the presence of
an acid catalyst.
The amine condensates and methods of making the
same are described in PCT publication W086/05501 which is
incorporated by reference for its disclosure to the conden-
sates and methods of making. The preparation of such
polyamine condensates may occur as follows: A 4-necked
3-liter round-bottomed flask equipped with glass stirrer,
WO92/18588 PC~/US92/01574
2~g~
-31-
thermowell, subsur~ace N2 inlet, Dean-Stark trap, and
Friedrich condenser is charged with: 129g grams o~ HPA
Taft Amines (amine bottoms available commercially from
Union Carbide Co. with typically 34.1% by weight nitrogen
and a nitrogen distribution of 12.3% by weight primary
amine, 14.4% by weight secondary amine and 7.4% by weight
tertiary amine), and 727 grams of 40% aqueous tris(hydroxy-
methyl)aminomethane (THA~). This mixture is heated to 60C
and 23 grams of 85% H3PO4 is added. The mixture is then
heated to 120C over 0.6 hour. With N2 sweeping, the
mixture is then heated to 150C over 1.25 hour, then to
235C over 1 hour more, then held at 230-235C for 5 hours,
then heated to 240C over 0.75 hour, and then held at
240-245OC for 5 hours. The product is cooled to 150C and
filtered with a diatomaceous earth filter aid. Yield: 84
(1221 grams).
In another embodiment, the polyamines are hy-
droxy-containing polyamines. Hydroxy-containing polyamine
analogs of hydroxy monoamines, particularly alkoxylated
alkylenepolyamines (e.g., N,N(diethanol)ethylene diamine)
can also be used. Such polyamines can be made by reacting
the above-described alkylene amines with one or more of the
above-described alkylene oxides. Similar alkylene oxide-
alkanol amine reaction products can also be used such as
the products made by reacting the aforedescribed primary,
secondary or tertiary alkanol amines with ethylene, propyl-
ene or higher epoxides in a 1.1 to 1.2 molar ratio.
Reactant ratios and temperatures for carrying out such
reactions are known to those skilled in the art.
Specific examples of alkoxylated alkylenepoly-
amines include N-(2-hydroxyethyl) ethy~lenediamine, N,N-
bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl)-
piperazine, mono(hydroxypropyl)-substituted tetraethylene-
pentamine, N-(3-hydroxybutyl)-tetramethy~ene diamine, etc.
Higher homologs obtained by condensation of the above-
W092/l8~ PCT/US~/01S74
208~6~
-32-
illustrated hydroxy-containing polyamines through amino
groups or through hydroxy groups are likewise useful.
Condensation through amino groups results in a higher amine
accompanied by removal of ammonia while condensation
through the hydroxy groups results in products containing
ether linkages accompanied by removal of water. Mixtures
of two or more of any of the aforesaid polyamines are also
useful.
In another embodiment, the amine is a heterocy-
clic polyamine. The heterocyclic polyamines include
aziridines, azetidines, azolidines, tetra- and dihydrc-
pyridines, pyrroles, indoles, piperidines, imidazoles, di-
and tetrahydroimidazoles, piperazines, isoindoles, purines,
morpholines, thiomorpholines, N-aminoalkylmorpholines,
N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,
N,N'-diaminoalkylpiperazines, azepines, azocines, azonines,
azecines and tetra-, di- and perhydro derivatives of each
of the above and mixtures of two or more of these heterocy-
clic amines. Preferred heterocyclic amines are the satu-
rated 5- and 6-membered heterocyclic amines containing only
nitrogen, oxygen and/or sulfur in the hetero ring, espe-
cially the piperidines, piperazines, thiomorpholines,
morpholines, pyrrolidines, and the like. Piperidine,
aminoalkylsubstituted piperidines, piperazine, aminoalkyl-
substituted piperazines, morpholine, aminoalkylsubstitutedmorpholines, pyrrolidine, and aminoalkyl-substituted
pyrrolidines, are especially preferred. Usually the
aminoalkyl substituents are substituted on a nitrogen atom
forming part of the hetero ring. Specific examples of such
heterocyclic amines include N-aminopropylmorpholine,
N-aminoethylpiperazine, and N,N'-diaminoethylpiperazine.
Hydroxy heterocyclic polyamines are also useful. Examples
include N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclo-
pentylamine, parahydroxyaniline, N-hydroxyethylpiperazine,
and the like.
W092/18S88 PCT/US~/~1~74
2 0 ~ 5
-33-
Hydrazine and substituted-hydrazine can also be
used to form nitrogen-containing carboxylic dispersants.
At least one of the nitrogens in the hydrazine must contain
a hydrogen directly bonded thereto. Preferably there are
at least two hydrogens bonded directly to hydrazine nitro-
gen and, more preferably, both hydrogens are on the same
nitrogen. The substituents which may be present on the
hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl,
and the like. Usually, the substituents are alkyl, espe-
cially lower alkyl, phenyl, and substituted phenyl such as
lower alkoxy substituted phenyl or lower alkyl substituted
phenyl. Specific examples of substituted hydrazines are
methylhydrazine, N,N-dimethyl-hydrazine, N,N'-dimethylhy-
drazine, phenylhydrazine, N-phenyl-N~-ethylhydrazine, N-
(para-tolyl)-N'-(n-butyl)-hydrazine, N-(para-nitrophenyl)-
hydrazine, N-(para-nitrophenyl)-N-methyl-hydrazine, N,N'-
di(para-chlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhy-
drazine, and the like.
Nitrogen-containing carboxylic dispersants and
methods for preparing the same are described in U.S.
Patents 4,234,435; 4,952,328; 4,938,881; 4,957,649; and
4,904,401. The disclosures of nitrogen-containing car-
boxylic dispersants and other dispersants contained in
those patents is hereby incorporated by reference.
The following examples illustrate the nitrogen-
containing carboxylic dispersants and methods for preparing
them.
Example B-1
A mixture is prepared by the addition of 8.16
parts (0.20 equivalent) of a commercial mixture of ethylene
polyamines having from about 3 to about lO nitrogen atoms
per molecule to 113 parts of mineral oil and 161 parts
(0.24 equivalent) of the substituted succinic acylating
agent prepared in Example I at 138C. The reaction mixture
is heated to 150C in 2 hours and stripped by blowing with
W092/l8588 PC'r/US~/015~4
2~S~S
-34-
nitrogen. The reaction mixture i8 filtered to yield the
filtrate as an oil solution of the desired ~roduct,
Example B-2
A mixture is prepared by the addition o~ 18,2
parts (0,433 equivalent) of a commercial mixture of ethyl-
ene polyamines having from about 3 to 10 nitrogen atoms per
molecule to 392 parts of mineral oil and 348 parts (0,52
equivalent) of the substituted succinic acylating agent
prepared in Example II at 140C, The reaction mixture is
heated to 150C in 1,8 hours and stripped by blowing with
nitrogen. The reaction mixture is filtered to yield the
filtrate as an oil solution (55% oil) of the desired
product.
Examples B-3 through B-8 are prepared by fol-
15 lowing the general procedure set forth in Example B-l.
Equivalent
Ratio of
Acylating
Example Amine Agent (Ex. I) Percent
Number Reactant(s~ To Reactants Diluent
B-3 Pentaethylene 4:3 40%
hexamine~
B-4 Tris(2-aminoethyl) 5:4 S0%
amine
B-5 Imino-bis-propyl- 8:7 40%
amine
B-6 Hexamethylene 4:3 40%
diamine
B-7 1-(2-Aminoethyl)- 5:4 40%
2-methyl-2-
imidazoline
B-8 N-Aminopropyl- 8:7 40%
pyrrolidone
a ~ A co~mercial mixture of eth~lene polyamines
corresponding in empirical formula to penta-
ethylene hexamine.
W092/l8S8X PCTJUS~/01S74
2 0 ~
Example B-s
A mixture of 3660 parts (6 equivalents) of a sub-
stituted succinic acylating agent prepared as in Example I
in 4664 parts of diluent oil is prepared and heated at
about 110C whereupon nitrogen is blown through the mix-
ture. To this mixture there are then added 210 parts (5.25
equivalents) of an alkylene polyamine mixture, comprising
80% of ethylene polyamine bottoms from Union Carbide and
20~ of a commercial mixture of ethylene polyamines corre-
sponding in empirical formula to diethylene triamine, over
a period of one hour and the mixture is maintained at 110C
for an additional 0.5 hour. The polyamine mixture is
characterized as having an equivalent weight of about
43.3.After heating for 6 hours at 155C while removing
water, a filtrate is added and the reaction mixture is
filtered at about 150C. The filtrate is the oil solution
of the desired product.
The dispersant may also be an amine dispersant.
Amine dispersants are hydrocarbyl-substituted amines.
These hydrocarbyl-substituted amines are well known to
those skilled in the art. These amines are disclosed in
U.S. patents 3,275,554; 3,438,757; 3,454,555; 3,565,804;
3,755,433; and 3,822,289. These patents are hereby incor-
porated by reference for their disclosure of hydrocarbylamines and methods of making the same.
Typically, amine dispersants are prepared by
reacting olefins and olefin polymers (polyalkenes) with
amines ~mono- or polyamines). The polyalkene may be any of
the polyalkenes described above. The amines may be any of
the amines described above. Examples of amine dispersants
include poly(propylene)amine; N,N-dimethyl-N-poly(ethyl-
ene/propylene)amine, (50:50 mole ratio of monomers); poly-
butene amine; N,N-di(hydroxyethyl)-N-polybutene amine; N-
(2-hydroxypropyl)-N-polybuteneamine;N-polybutene-aniline;
W092/1~S888~ 61~ pcT/usn/o1s74
-36-
N-polybutenemorpholine; N-poly(butene)ethylenediamine; N-
poly(propylene)trimethylenediamine; N-poly(butene)diethyl-
enetriamine;N',N'-poly(butene)tetraethylenepentamine;N,N-
dimethyl-N'-poly(propylene)-1,3-propylenediamine and the
like.
In another embodiment, the dispersant may also be
an ester dispersant. The ester dispersant is prepared by
reacting at least one of the above hydrocarbyl-substituted
carboxylic acylating agents with at least one organic
hydroxy compound and optionally an amine. In another
embodiment, the ester dispersant is prepared by reacting
the acylating agent with at least one of the above-de-
scribed hydroxy amine.
The organic hydroxy compound includes compounds
of the general formula R"(OH)m wherein R~ is a monovalent
or polyvalent organic group joined to the -OH groups
through a carbon bond, and m is an integer of from l to
about 10 wherein the hydrocarbyl group contains at least
about 8 aliphatic carbon atoms. The hydroxy compounds may
be aliphatic compounds such as monohydric and polyhydric
alcohols, or aromatic compounds such as phenols and naph-
thols. The aromatic hydroxy compounds from which the
esters may be derived are illustrated by the following
specific examples: phenol, beta-naphthol, alpha-naphthol,
cresol, resorcinol, catechol, p,p'-dihydroxybiphenyl,
2-chlorophenol, 2,4-dibutylphenol, etc.
The alcohols from which the esters may be derived
preferably contain up to about 40 aliphatic carbon atoms,
preferably from 2 to about 30, more preferably 2 to about
10. They may be monohydric alcohols such as methanol,
ethanol, isooctanol, dodecanol, cyclohexanol, etc. In one
embodiment, the hydroxy compounds are polyhydric alcohols,
such as alkylene polyols. Preferably, the polyhydric
alcohols contain from 2 to about 40 carbon atoms, more
preferably 2 to about 20; and preferably from 2 to about 10
w~s2/l8s8x PC~/US~/OIS74
~ n ~
-37-
hydroxyl groups, more preferably 2 to about 6. Polyhydric
alcohols include ethylene glycols, including di-, tri- and
tetraethylene glycols; propylene glycols, including di-,
tri- and tetrapropylene glycols; glycerol; butane diol;
hexane diol; sorbitol; arabitol; mannitol; sucrose; fruc-
tose; glucose; cyclohexane diol; erythritol; and penta-
erythritpls, including di- and tripentaerythritol; prefera-
bly, diethylene glycol, triethylene glycol, glycerol,
sorbitol, pentaerythritol and dipentaerythritol.
The polyhydric alcohols may be esterified with
monocarboxylic acids having from 2 to about 30 carbon
atoms, preferably about 8 to about 18, provided that at
least one hydroxyl group remains unesterified. Examples of
monocarboxylic acids include acetic, propionic, butyric and
fatty carboxylic acids. The fatty monocarboxylic acids
have from about 8 to about 30 carbon atoms and include
octanoic, oleic, stearic, linoleic, dodecanoic and tall oil
acids. Specific examples of these esterified polyhydric
alcohols include sorbitol oleate, including mono- and
dioleate, sorbitol stearate, including mono- and distear-
ate, glycerol oleate, including glycerol mono-, di- and
trioleate and erythritol octanoa~e.
The carboxylic ester dispersants may be prepared
- by any of several known methods. The method which is
preferred because of convenience and the superior proper-
ties of the esters it produces, involves the reaction of a
the carboxylic acylating agents described above with one or
more alcohols or phenols in ratios of from about 0.5
equivalent to about 4 equivalents of hydroxy compound per
equivalent of acylating agent. The esterification is
usually carried out at a temperature above about 100C,
preferably between 150C and 300C. The water formed as a
by-product is removed by distillation as the esterification
proceeds. The preparation of useful carboxylic ester
W092/18588 PCT/US~/01574
2 08~ 38-
dispersant is described in U.S. Patents 3,522,179 and
4,234,435.
The carboxylic ester dispersants may be further
reacted with at least one o~ the above described amines and
preferably at least one of the above described polyamines.
The amine is added in an amount sufficient to neutralize
any nonesterifed carboxyl groups. In one preferred embodi-
ment, the nitrogen-containing carboxylic ester dispersants
are prepared by reacting about 1.0 to 2.0 equivalents,
preferably about 1.0 to 1.8 equivalents of hydroxy com-
pounds, and up to about 0.3 equivalent, preferably about
0.02 to about 0.25 equivalent of polyamine per equivalent
of acylating agent.
In another embodiment, the carboxylic acid
acylating agent may be reacted simultaneously with both the
alcohol and the amine. There is generally at least about
0.01 equivalent of the alcohol and at least 0.01 equivalent
of the amine although the total amount of equivalents of
the combination should be at least about 0.5 equivalent per
equivalent of acylating agent. These nitrogen-containing
carboxylic ester dispersant compositions are known in the
art, and the preparation of a number of these derivatives
is described in, for example, U.S. Patents 3,957,854 and
4,234,435 which have been incorporated by reference previ-
ously.
The carboxylic ester dispersants and methods ofmaking the same are known in the art and are disclosed in
U.S. Patents 3,219,666; 3,381,022; 3,522,179; and 4,234,435
which are hereby incorporated by reference for their
disclosures of the preparation of carboxylic ester dispers-
ants.
The following examples illustrate the ester
dispersants and the processes for preparing such esters.
WO92/18588 PCT/US~/01S74
20~5~1~
-39-
Example B-10
A substantially hydrocarbon-substituted succinic
anhydride is prepared by chlorinating a polybutene having
a number average molecular weight of 1000 to a chlorine
content of 4.5~ and then heating the chlorinated polybutene
with 1.2 molar proportions of maleic anhydride at a temper-
ature of 150-220C. A mixture of 874 grams (1 mole) of the
succinic anhydride and 104 grams (1 mole) of neopentyl
glycol is maintained at 240-250C/30 mm for 12 hours. ~he
residue is a mixture of the esters resulting from the
esterification of one and both hydroxy groups of the
glycol.
Example B-ll
A mixture of 3225 parts (5.0 equivalents) of the
polybutene-substituted succinic acylating agent prepared in
Example II, 289 parts (8.5 equivalents) of pentaerythritol
and 5204 parts of mineral oil is heated at 224-235C for
5.5 hours. The reaction mixture is filtered at 130C to
yield an oil solution of the desired product.
The carboxylic ester derivatives which are des-
cribed above resulting from the reaction of an acylating
agent with a hydroxy-containing compound such as an alcohol
or a phenol may be further reacted with any of the above-
described amines, and particularly polyamines in the manner
described previously for the nitrogen-containing dispers-
ants.
In another embodiment, the carboxylic acid
acylating agent may be reacted simultaneously with both the
alcohol and the amine. There is generally at least about
0.01 equivalent of the alcohol and at least 0.01 equivalent
of the amine although the total amount of equivalents of
the combination should be at least about 0.5 equivalent per
equivalent of acylating agent. These carboxylic ester
derivative compositions are known in the art, and the
preparation of a number of these derivatives is described
W092/l8588 PCT/US~/n1S74
2 08~ 6~5 _40_
in, for example, U.S. Patents 3,957,854 and 4,234,435 which
are hereby incorporated by reference. The following
specific examples illustrate the preparation of the esters
wherein both alcohols and amines are reacted with the
acylating agent.
Example B-12
A mixture of 1000 parts of polybutene having a
number average molecular weight of about lOoO and 108 parts
(l.l moles) of maleic anhydride is heated to about 190C
and lO0 parts (1.43 moles) of chlorine are added beneath
the surface over a period of about 4 hours while maintain-
ing the tempe~ature at about 185-190C. The mixture then
is blown with nitrogen at this temperature for several
hours, and the residue is the desired polybutenyl-substi-
tuted succinic acylating agent.
A solution of 1000 parts of the above-prepared
acylating agent in 857 parts of mineral oil is heated to
about 150C with stirring, and 109 parts (3.2 equivalents)
of pentaerythritol are added with stirring. The mixture is
blown with nitrogen and heated to about 200OC over a period
of about 14 hours to form an oil solution of the desired
carboxylic ester intermediate. To the intermediate, there
are added 19.25 parts (.46 equivalent) of a commercial
mixture of ethylene polyamines having an average of about
3 to about lO nitrogen atoms per molecule. The reaction
mixture is stripped by heating at 205C with n-trogen
blowing for 3 hours and filtered. The filtrate is an oil
solution (45% lO0 neutral mineral oil) of the desired
amine-modified carboxylic ester which contains 0.35%
nitrogen.
The dispersant may also be a Mannich dispersant.
Mannich dispersants are generally formed by the reaction of
at least one aldehyde, at least one of the above described
amine and at least one alkyl substituted hydroxyaromatic
compound. The reaction may occur from room temperature to
W O 92/18588 PC~r~U~92/01574
208~
-41-
2250C, usually from 50 to about 200c ~75C-150C mo~t
preferred), with the amounts of the reagents being such
that the molar ratio of hydroxyaromatic compound to ~ormal-
dehyde to amine is in the range from about ~1:1:1) to about
(1:3:3)-
The first reagent is an alkyl substituted hy-
droxyaromatic compound. This term includes phenols (which
are preferred), carbon-, oxygen-, sulSur- and nitrogen-
bridged phenols and the like as well as phenols direct~y
linked through covalent bonds (e.g. 4,4'-bis(hydroxy)bi-
phenyl), hydroxy compounds derived from fused-ring hydro-
carbon (e.g., naphthols and the like); and polyhydroxy
compounds such as catechol, resorcinol and hydroquinone.
Mixtures of one or more hydroxyaromatic compounds can be
used as the first reagent.
The hydroxyaromatic compounds are those sub-
stituted with at least one, and preferably not more than
two, aliphatic or alicyclic groups having at least about 6
(usually at least about 30, more preferably at least 50)
carbon atoms and up to about 400 carbon atoms, preferably
300, more preferably 200. These groups may be derived from
the above described polyalkenes. In one e~bodiment, the
hydroxy aromatic compound is a phenol substituted with an
aliphatic or alicyclic hydrocarbon-based group having an Mn
of about 420 to about 10,000.
The second reagent is a hydrocarbon-based alde-
hyde, preferably a lower aliphatic aldehyde. Suitable
aldehydes include formaldehyde, benzaldehyde, acetaldehyde,
the butyraldehydes, hydroxybutyraldehydes and heptanals, as
well as aldehyde precursors which react as aldehydes under
the conditions of the reaction such as paraformaldehyde,
paraldehyde, formalin and methal. Formaldehyde and its
precursors (e.g., paraformaldehyde, trioxane) are pre-
- ferred. Mixtures of aldehydes may be used as the second
reagent.
WO 92/18~88 PC'r/US92/û1S~4
2o~56~
-42-
The third reagent is any amine described above.
Preferably the amine i5 a polyamine as descr~bed above.
Mannnich disper~ants are described in the follow-
ing patents: U.s. Patent 3,980,569; u.s. Patent 3,877,~g9;
and U.S. Patent 4,454,059 (herein incorporated by reference
for their disclosure to Mannich dispersants).
The dispersant may also be a dispersant-viscosity
improver. The dispersant-viscosity improvers include
polymer backbones which are functionalized by reacting with
an amine source. A true or normal block copolymer or a
random block copolymer, or combinations of both are uti-
lized. They are hydrogenated before use in this invention
to remove virtually all of their olefinic double bonds.
Techniques for accomplishing this hydrogenation are well
known to those of skill in the art. Briefly, hydrogenation
is accomplished by contacting the copolymers with hydrogen
at superatmospheric pressures in the presence of a metal
catalyst such as colloidal nickel, palladium supported on
charcoal, etc.
In general, it is preferred that these block
copolymers, for reasons of oxidative stability, contain no
more than about 5 percent and preferably no more than about
0.5 percent residual olefinic unsaturation on the basis of
the total number of carbon-to-carbon covalent linkages
within the average molecule. Such unsaturation can be
measured by a number of means well known to those of skill
in the art, such as infrared, NMR, etc. Most preferably,
these copolymer~ contain no discernible unsaturation, as
determined by the aforementioned analytical techniques.
The block copolymers typically have number
average molecular weights (Mn) in the range of about 10,000
to absut 500,000 preferably about 30,000 to about 200,000.
The weight average molecular weight (Mw) for these copoly-
mers is generally in the range of about 50,000 to about
500,000, preferably about 30,000 to about 300,000
wo92/l8s88 PCT/US~/0l5~4
208551~
-43-
The amine source may be an unsaturated amine
compound or an unsaturated carboxylic reagent which is
capable of reacting with an amine. The unsaturated carbox-
ylic reagents and amines are described above.
Examples of saturated amine compounds include
N-(3,6-dioxaheptyl)maleimide, N-(3-dimethylaminopropyl)-
maleimidq, and N-(2-methoxyethoxyethyl)maleimide. Pre-
ferred amines are ammonia and primary amine containing
compounds. Exemplary of such primary amine-containing
compounds include ammonia, N,N-dimethylhydrazine, methyl-
amine, ethylamine, butylamine, 2-methoxyethylamine, N,N-di-
methyll,3-propanediamine, N-ethyl-N-methyl-1,3-propanedi-
amine, N-methyl-1,3-propanediamine, N-(3-aminopropyl)-
morpholine, 3-methoxypropylamine, 3-isobutyoxypropylamine
and 4,7-dioxyoctylamine, N-(3-aminopropyl)-N-1-methyl-
piperazine, N-(2-aminoethyl)piperazine, (2-aminoethyl)pyr-
idines, aminopyridines, 2-aminoethylpyridines, 2-amino-
methylfuran, 3-amino-2-oxotetrahydrofuran, N-(2-amino-
ethyl)pyrolidine, 2-aminomethylpyrrolidine, 1-methyl-2-
aminomethylpyrrolidine, l-amino-pyrrolidine, 1-(3-amino-
propyl)-2-methylpiperidine~ 4-aminomethylpiperidine,
N-(2-aminoethyl)morpholine, 1-ethyl-3-aminopiperidine,
1-aminopiperidine, N-aminomorpholine, and the like. Of
these compounds, N-(3-aminopropyl)morpholine and N-ethyl-
N-methyl-1,3-propanediamine are preferred with N,N-di-
methyl-1,3-propanediamine being highly preferred.
Another group of primary amine-containing com-
pounds are the various amine terminated polyethers. The
amine terminated polyethers are available commercially from
Texaco Chemical Company under the general trade designation
~Jeffamine0". Specific examples of these materials include
Jeffamine~ M-600; M-1000; M-2005; and M-2070 amines.
Examples of dispersant-viscosity improvers are
given in the following references:
WO92/185X8 PCT/US~/01S74
2~ 44-
EP 171,167 3,6a7,90
3,687,849 4,670,173
3,756,954 4,320,012
4,320,019
(herein incorporated by reference for their disclosure to
dispersant-viscosity improvers).
The above dispersants may be post-treated with
one or more post-treating reagents selected from the group
consisting of boron compounds (discussed above~, carbon
disulfide, hydrogen sulfide, sulfur, sulfur chlorides,
alkenyl cyanides, carboxylic acid acylating agents, alde-
hydes, ketones, urea, thiourea, guanidine, dicyanodiamide,
hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl
thiophosphates, hydrocarbyl thiophosphites, phosphorus
sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl
thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothio-
cyanates, epoxides, episulfides, formaldehyde or formalde-
hyde-producing compounds with phenols, and sulfur with
phenols.
The following U.S. Patents are expressly incor-
porated herein by reference for their disclosure of post-
treating processes and post-treating reagents applicable to
the carboxylic derivative compositions of this invention:
U.S. Patent Nos. 3,087,936; 3,254,025; 3,256,185;
3,278,550; 3,282,955; 3,284,410; 3,338,832; 3,533,945;
3,639,242; 3,708,522; 3,859,318; 3,865,813; 4,234,435; etc.
U.K. Patent Nos. 1,085,903 and 1,162,436 also describe such
processes.
In one embodiment, the disper$ants are post-
treated with at least one boron compound. The reaction of
the dispersant with the boron compounds can be effected
simply by mixing the reactants at the desired temperature.
Ordinarily it is preferably between about 50C and about
250C. In some instances it may be 25C or even lower.
The upper limit of the temperature is the decomposition
point of the particular reaction mixture and/or product.
W092/18588 PCT/US~/01S74
2 0 ~
-45-
The amount o~ boron compound reacted with the
dispersant generally is sufficient to provlde from a~out
0.1 to about lO atomic proportions of boron for each mole
of dispersant, i.e., the atomic proportion of nitrogen or
hydroxyl group contained in the dispersant. The preferred
amounts of reactants are such as to provide from about 0.5
to about 2 atomic proportions of boron for each mole of
dispersant. To illustrate, the amount of a boron compound
having one boron atom per molecule to be used with one mole
of an amine dispersant having five nitrogen atoms per
molecule is within the range from about 0.1 mole to about
50 moles, preferably from about 0.5 mole to about 10 moles.
C) Metal Dihyd~ocarby~ Dithiophoshate
The oil compositions of the present invention
also contain (C) at least one metal dihydrocarbyl dithio-
phosphate characterized by the formula
(R30 \ PSS ) M
Z
wherein R3 and R4 are each independently hydrocarbyl groups
containing from 3 to about 13 carbon atoms, preferably from
3 to about 8, M is a metal, and z is an integer equal to
the valence of M.
The hydrocarbyl groups R3 and R4 in the dithio-
phosphate may be alkyl, cycloalkyl, aralkyl or alkaryl
groups. Illustrative alkyl groups include isopropyl,
isobutyl, n-butyl, sec-butyl, the various amyl groups,
n-hexyl, methylisobutyl carbinyl, heptyl, 2-ethylhexyl,
diisobutyl, isooctyl, nonyl, behenyl, decyl, dodecyl,
tridecyl, etc. Illustrative lower alkylphenyl groups
include butylphenyl, amylphenyl, heptylphenyl, etc. Cyclo-
alkyl groups likewise are useful and these include chiefly
cyclohexyl and the lower alkyl-cyclohexyl radicals. Many
W092/1858K PCT/US~/01S74
208~ ~5 -46-
substituted hydrocarbon groups may also be used, e.g ,
chloropentyl, dichlorophenyl, and dichlorodecyl.
The phosphorodithioic acids from which the metal
salts useful ln this invention are prepared are well known.
Examples of dihydrocarby~ phosphorodithioic acids and metal
salts, and processes for preparing such acids and salts are
found in, for example, U.S. Patents 4,263,150; 4,289,635;
4,308,154; and 4,417,990. These patents are hereby incor-
porated by reference for such disclosures.
The phosphorodithioic acids are prepared by the
reaction of phosphorus pentasulfide with an alcohol or
phenol or mixtures of alcohols. The reaction involves four
moles of the alcohol or phenol per mole of phosphorus
pentasulfide, and may be carried out within the temperature
range from about 50C to about 200C. Thus the preparation
of 0,0-di-n-hexyl phosphorodithioic acid involves the
reaction of phosphorus pentasulfide with four moles of
n-hexyl alcohol at about 100C for about two hours.
Hydrogen sulfide is liberated and the residue is the
defined acid. The preparation of the metal salt of this
acid may be effected by reaction with metal oxide. Simply
mixing and heating these two reactants is sufficient to
cause the reaction to take place and the resulting product
is sufficiently pure for the purposes of this invention.
The metal salts of dihydrocarbyl dithiophosphates
which are useful in this invention include those salts
containing Group I metals, Group II metals, aluminum, lead,
tin, molybdenum, manganese, cobalt, and nickel. Group I
and Group II (including Ia, Ib, IIa and IIb) are defined in
the Periodic Table of the Elements in the Merck Index, 9th
Edition (1976). The Group II metals, aluminum, tin, iron,
cobalt, lead, molybdenum, manganese, nickel and copper are
among the preferred metals. 2inc and copper are especially
use~ul metals. In one embodiment, the lubricating composi-
t~ons contain a zinc dihydrocarbyl dithiophosphate and a
wos2/l8s88 PCT/US~/015~4
2o~5~l~
-47-
copper dihydrocarbyl dithiophosphate. Examples of metal
compounds which may be reacted with the acid include
lithium oxide, lithium hydroxide, sodium hydroxide, sodium
carbonate, potassium hydroxide, potassium carbonate, silver
oxide, magnesium oxide, magnesium hydroxide, calcium oxide,
zinc hydroxide, strontium hydroxide, cadmium oxide, cadmium
hydroxide, barium oxide, aluminum oxide, iron carbonate,
copper hydroxide, copper oxide, lead hydroxide, tin butyl-
ate, cobalt hydroxide, nickel hydroxide, nickel carbonate,
zinc oxide, etc.
In some instances, the incorporation of certain
ingredients such as small amounts of the metal acetate or
acetic acid in conjunction with the metal reactant will
facilitate the reaction and result in an improved product.
For example, the use of up to about 5% of zinc acetate in
combination with the required amount of zinc oxide facili-
tates the formation of a zinc phosphorodithioate.
In one preferred embodiment, the alkyl groups R3
and RP are derived from secondary alcohols such as isopropyl
alcohol, secondary butyl alcohol, 2-pentanol, 2-methyl-4-
pentanol, 2-hexanol, 3-hexanol, etc.
Especially useful metal phosphorodithioates can
be prepared from phosphorodithioic acids which in turn are
prepared by the reaction of phosphorus pentasulfide with
mixtures of alcohols. In addition, the use of such mix-
tures enables the utilization of cheaper alcohols which in
themselves may not yield oil-soluble phosphorodithioic
acids or salts thereof. Thus a mixture of isopropyl and
hexyl alcohols can be used to produce a very effective,
oil-soluble metal phosphorodithioate. For the same reason
mixtures of phosphorodithioic acids can be reacted with the
metal compounds to form less expensive, oil-soluble salts.
The mixtures of alcohols may be mixtures of dif-
ferent primary alcohols, mixtures of different secondary
alcohols or mixtures of primary and secondary alcohols.
WO92/l8~88 PCT~US~/01S~4
~ 6 1 ~ ~
-48-
Examples of useful mixtures include: n-butanol and n-oc-
tanol; n-pentanol and 2-ethyl-1-hexanol; isobutanol and
n-hexanol; isobutanol and isoamyl alcohol; isopropanol and
2-methyl-4-pentanol; isopropanol and sec-butyl alcohol;
isopropanol and isooctyl alcohol; etc. Particularly useful
alcohol mixtures are mixtures of secondary alcohols con-
taining at least about 20 mole percent of isopropyl alco-
hol, and in a preferred embodiment, at least 40 mole
percent of isopropyl alcohol.
Generally, the oil compositions of the present
invention will contain varying amounts of one or more of
the above-identified metal dithiophosphates such as from
about 0.01 to about 2% by weight, and more generally from
about 0.01 to about 1% by weight based on the weiaht of the
total oil composition. The metal dithiophosphates are
added to the lubricating oil compositions of the invention
to improve the anti-wear and antioxidant properties of the
oil compositions.
The following examples illustrate the preparation
of metal phosphorodithioates.
Example C-l
A phosphorodithioic acid is prepared by reacting
a mixture of alcohols comprising 6 moles of g-methyl-2-
pentanol and 4 moles of isopropyl alcohol with phosphorus
pentasulfide. The phosphorodithioic acid then is reacted
with an oil slurry of zinc oxide. The amount of zinc oxide
in the slurry is about 1.08 times the theoretical amount
required to completely neutralize the phosphorodithioic
acid. The oil solution of the zinc phosphorodithioate
~0 obtained in this manner (10% oil) contains 9.5% phosphorus,
20.0% sulfur and 10.5% zinc.
Additional specific examples of metal phosphoro-
dithioates useful in the lubricating oils of the present
invention are listed in the following table. These metal
W092/~8s88 PCT/US~tO15~4
2~35~
-49-
dithiophosphates are prepared by the general procedure o~
Example C-1.
~ABLE
Component C: Metal Phosphorodithioates
~R30
/ PSS 1 M
R40 J z
Example R3 R4 M z -
C-2 (isopropyl + isooctyl) (60:40)~ Zn 2
C-3 n-nonyl n-nonyl Ba 2
C-4 cyclohexyl cyclohexyl Zn 2
C-5 isobutyl isobutyl Zn 2
C-6 hexyl hexyl Ca 2
C-7 n-decyl n-decyl Zn 2
C-8 4-methyl-?-pentyl 4-methyl-2-pentyl Cu 2
C-g (n-butyl + dodecyl) (l:l)w Zn 2
C-10 (isopropyl + isooctyl) (l:l)w Ba 2
C-11 (isopropyl+4-methyl-2 pentyl)+(40:60)m Cu 2
C-12 (isobutyl + isoamyl) (65:35)m Zn 2
C-13 (isopropyl+sec-butyl) (40:60)m Zn 2
Another class of the phosphorodithioate additives
contemplated for use in the lubricating composition of this
invention comprises the adducts of the metal phosphorodi-
thioates described above with an epoxide. The metal
phosphorodithioates useful in preparing such adducts are
~or the most part the zinc phosphorodithioates. The epox-
ides may be alkylene oxides or arylalkylene oxides. The
arylalkylene oxides are exemplified by styrene oxide,
p-ethylstyrene oxide, alpha-methylstyrene oxide, 3-beta-
naphthyl-1,1,3-butylene oxide, m-dodecylstyrene oxide, and
p-chlorostyrene oxide. The alkylene oxides include princi-
pally the lower alkylene oxides in which the alkylene
rad~cal contains 8 or less carbon atoms. Examples of such
W092/18S8~ PCr/US~tO1574
~o~5f)~i
-50-
lower alkylene oxides are ethylene oxide, propylene oxide,
1,2-butene oxide, trimethylene oxide, tetramethylene oxide,
butadiene monoepoxide, 1,2-hexene oxide, and epichlorohy-
drin. Other epoxides useful herein include, for example,
S butyl 9,10-epoxy-stearate, epoxidized soya bean oil,
epoxidized tung oil, and epoxidized copolymer of styrene
with butadiene.
The adduct may be obtained by simply mixing the
metal phosphorodithioate and the epoxide. The reaction is
usually exothermic and may be carried out within wide
temperature limits from about 0C to about 3000C. Because
the reaction is exothermic, it is best carried out by
adding one reactant, usually the epoxide, in small incre-
ments to the other reactant in order to obtain convenient
control of the temperature of the reaction. The reaction
may be carried out in a solvent such as benzene, toluene,
xylene, mineral oil, naphtha, or n-hexene.
The chemical structure of the adduct is not
known. For the purpose of this invention adducts obtained
by the reaction of one mole of the phosphorodithioate with
from about 0.25 mole to 5 moles, usually up to about 0.75
mole or about 0.5 mole of a lower alkylene oxide, particu-
larly ethylene oxide and propylene oxide, have been found
to be especially useful and therefore are preferred.
The preparation of such adducts is more speci-
fically illustrated by the following examples.
Example C-14
A reactor is charged with 2365 parts (3.33 moles)
of the zinc isopropyl-isooctyl phosphorodithioate (wherein
the molar ratio of isopropyl to isooctyl is (1:0.7)), and
while stirring at room temperature, 38.6 parts (0.67 mole)
of propylene oxide are added with an exotherm of from
24-31C. The mixture is maintained at 80-9ooc for 3 hours
and then ~acuum stripped to 101C at 7 mm.Hg. The residue
is ~iltered using a filter aid, and the filtrate is an oil
wos2/l8s88 PCT/USn/0l~74
2 ~
-51-
solution (11.8~ oil) o~ the desired ~alt containing 17 1%
sulfur, 8.17% zinc and 7.44% phosphorus.
Another class of the phosphorodithioate additives
contemplated as useful in the lubricating compositions o~
the invention comprises mixed metal salts of (a) at least
one phosphorodithioic acid as defined above and (b~ at
least one aliphatic or alicyclic carboxylic acid. The
carboxylic acid may be a monocarboxylic or polycarboxylic
acid, usually containing from 1 to about 3 carboxy group~,
preferably one. It may contain from about 2 to about 40,
preferably from about 2 to about 20 carbon atoms, and
advantageously about 5 to about 20 carbon atoms. The
carboxylic acid may be any of the above-described carbox-
ylic acids. The preferred carboxylic acids are those
having the formula R5CoOH~ wherein R5 is an aliphatic or
alicyclic hydrocarbon-based radical preferably free from
acetylenic unsaturation. Suitable acids include the
butanoic, pentanoic, hexanoic, octanoic, nonanoic, deca-
noic, dodecanoic, octadecanoic and eicosanoic acids, as
well as olefinic acids such as oleic, linoleic, and lino-
lenic acids and linoleic acid dimer. For the most part, R5
is a saturated aliphatic group and especially a branched
alkyl group such as the isopropyl or 3-heptyl group.
Illustrative polycarboxylic acids are succinic, alkyl- and
alkenylsuccinic, adipic, sebacic and citric acids.
The mixed metal salts may be prepared by merely
blending a metal salt of a phosphorodithioic acid with a
metal salt of a carboxylic acid in the desired ratio. The
ratio of equivalents of phosphorodithioic to carboxylic
acid salts is between about 0.5:1 to about 400:1. Prefera-
bly, 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
pre~erably ~rom about 0.5:1 to about 20:1. Further, the
ratio can be ~rom about 0.5:1 to about 4.5:1, preferably
W092/l8588 PCT/US~/~IS74
2~ 8 about 2.5:1 to about 4.25:1. For this purpose, the equiva-
lent weight of a phosphorodithioic acid is its molecular
weight divided by the number of -PSSH groups therein, and
that of a carboxylic acid is its molecular weight divided
by the number of carboxy groups therein.
A second and preferred method for preparing ~he
mixed metal salts useful in this invention is to prepare a
mixture of the acids in the desired ratio and to react the
acid mixture with one of the above described metal com-
pounds. When this method of preparation is used, it is
frequently possible to prepare 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 equivalents of
metal per equivalent of acid may be prepared. The equiv-
alent of a metal for this pur~ose is its atomic weight
divided by its valence.
Variants of the above-described methods may also
be used to prepare the mixed metal salts useful in this
invention. For example, a metal salt of either acid may be
blended with an acid of the other, and the resulting blend
reacted with additional metal bas-e.
The temperature at which the mixed metal salts
are prepared is generally between about 30C and about
150C, preferably up to about 125C. If the mixed salts
are prepared by neutralization of a mixture of acids with
a metal base, it is preferred to employ temperatures above
about 50C and especially above about 75C. It is fre-
quently advantageous to conduct the reaction in the pres-
ence 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 mineral oil, it frequently need
not be removed before using the mixed metal salt as an
additive for lubricants or functional fluids.
W092/18588 PCT/US~/OIS~4
2 0 ~
-53~
U.S. Patents 4,308,lS4 and 4,417,990 describe
procedures for preparing these mixed metal salts and
disclose a number of examples of such mixed salts. Such
disclosures of these patents are hereby incorporated ~y
reference.
The preparation of the mixed salts is illustrated
by the following example.
Example C-15
A mixture of 67 parts (1.63 equivalents) of zinc-
oxide and 48 parts of mineral oil is stirred at room
temperature and a mixture of 401 parts (1 equivalent) of
di-(2-ethylhexyl) phosphorodithioic acid and 36 parts (0.25
equivalent) of 2-ethylhexanoic acid is added over 10
minutes. The temperature increases to 40C during the
addition. When addition is complete, the temperature is
increased to 80C for 3 hours. The mixture is then vacuum
stripped at 100C to yield the desired mixed metal salt as
a 91% solution in mineral oil.
D~ An Antioxidant
The compositions of the present invention also
include an antioxidant (D), with the proviso that (D) the
antioxidant and (C) the metal dithiophosphate are not the
same. For instance, (C) and (D) may both be metal dithio-
phosphates provided that the metal of (C) is not the same
as the metal of (D). The antioxidants are selected from
the group consisting of: sulfur-containing compositions,
alkylated aromatic amines, phenols, and oil-soluble transi-
tion metal containing compounds.
- The antioxidant also may be one or more sulfur-
containing compositions. Materials which may be sulfurized
to form the sulfurized organic compositions of the present
invention include oils, fatty acids or esters, olefins or
polyolefins made thereof or Diels-Alder adducts.
Oils which may be sulfurized are natural or
synthetic oils including mineral oils, lard oil, carboxylic
W092/18S88 PCT/US~/01~74
20 8~ 6~ _54-
acid esters derived from aliphatic alcohols and ~a~ty acidg
or aliphatic carboxylic acids (e.g., myristyl oleate and
oleyl oleate) sperm whale oil, synthetic sperm whale oil
substitutes and synthetic unsaturated esters or glycerides.
5Fatty acids generally contain from about 8 to
about 30 carbon atoms. The unsaturated fatty acids gener-
ally contained in the naturally occurring vegetable or
animal fats and such acids include palmitoleic acid, oleic
acid, linoleic acid, linolenic acid, and erucic acid. The
lOfatty acids may comprise mixtures of acids, such as those
obtained from naturally occurring animal and vegetable
oils, including beef tallow, depot fat, lard oil, tall oil,
peanut oil, corn oil, safflower oil, sesame oil, poppy-seed
oil, soybean oil, cottonseed oil, sunflower seed oil, or
15wheat germ oil. Tall oil is a mixture of rosin acids,
mainly abietic acid, and 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 fatty acid esters also may be prepared from
20aliphatic olefinic acids of the type described above by
reaction with any of the above-described alcohols and poly-
-018. Examples of aliphatic alcohols include monohydric
alcohols such as methanol, ethanol; n- or isopropanol; n-,
iso-, sec-, or tertbutanol, etc.; and polyhydric alcohols
25including ethylene glycol, propylene glycol, trimethylene
glycol, neopentyl glycol, glycerol, etc.
The olefinic compounds which may be sulfurized
are diverse in nature. They contain at least one olefinic
double bond, which is defined as a non-aromatic double
30bond; that is, one connecting two aliphatic carbon atoms.
In its broadest sense, the olefin may be defined ~y the
formula R-1R~C=CR~R-4, wherein each of R-1, R~, R~ and R-4 is
hydrogen or an organic group. In general, the R- groups in
the above formula which are not hydrogen may be satisfied
W092/18588 PCT/US~/015~4
20~5~1~
-55-
by such groups as -C(R 5 ) 3, -COOR5, -CoN(R5)2~ -COON(R~
-COOM, -CN, -X, -YR5 or -Ar, wherein:
each R 5 iS independently hydrogen, alkyl, alke-
nyl, aryl, substituted alkyl, substituted alkenyl or
substituted aryl, with the proviso that any two R5 groups
can be alkylene or substituted alkylene whereby a ring of
up to about 12 carbon atoms is formed;
M is one equivalent of a metal cation (preferably
Group I or II, e.g., sodium, potassium, barium, calcium);
X is halogen (e.g., chloro, bromo, or iodo);
Y is oxygen or divalent sulfur;
Ar is an aryl or substituted aryl group of up to
about 12 carbon atoms.
Any two of Rl, R~, R~ and R-4 may also together
form an alkylene or substituted alkylene group; i.e., the
olefinic compound may be alicyclic.
The olefinic compound is usually one in which
each R group which is not hydrogen is independently alkyl,
alkenyl or aryl group. Monoolefinic and diolefinic com-
pounds, particularly the former, are preferred, and espe-
cially terminal monoolefinic hydrocarbons; that is, those
compounds in which R~ and R-4 are hydrogen and R-l and R~ are
alkyl or aryl, especially alkyl (that is, the olefin is
aliphatic) having 1 to about 30, preferably 1 to about 16,
more preferably 1 to about 8, and more preferably 1 to
about 4 carbon atoms. Olefinic compounds having about 3 to
30 and especially about 3 to 16 (most often less than 9)
carbon atoms are particularly desirable.
Isobutene, propylene and their dimers, trimers
and tetramers, and mixtures thereof are especially pre-
ferred olefinic compounds. Of these compounds, isobutylene
and diisobutylene are particularly desirable because of
their availability and the particularly high sulfur con-
taining compositions which can be prepared therefrom.
w092/18s88 PCT/US~/01574
2 o 8~
-56-
In another embodiment, the sulfurized organic
compound i~ a sulfurized terpene compound. The term
"terpene Gompound" as used in the specification and claims
is intended to include the various isomeric terpene hydro-
carbons having the empirical formula C,~H,6, such as con-
tained in turpentine, pine oil and dipentenes, and the
various synthetic and naturally occuring oxygen-containing
derivatives. Mixtures of these various compounds generally
will be utilized, especially when natural products such as
pine oil and turpentine are used. Pine oil, for example,
comprises a mixture of alpha-terpineol, beta-terpineol,
alpha-fenchol, camphor, borneol/isoborneol, fenchone,
estragole, dihydro alpha-terpineol, anethole, and other
mono-terpene hydrocarbons. The specific ratios and amounts
of the various components in a given pine oil will depend
upon the particular source and the degree of purification.
A group of pine oil-derived products are available commer-
cially from Hercules Incorporated. It has been found that
the pine oil products generally known as terpene alcohols
available from Hercules Incorporated are particularly
useful in the preparation of the sulfurized products of the
invention. Pine oil products are available from Hercules
under such designations as alpha-Terpineol, Terpineol 318
Prime, Yarmor 302, Herco pine oil, Yarmor 302W, Yarmor F
and Yarmor 60.
In another embodiment, the sulfurized organic
composition is at least one sulfur-containing material
which comprises the reaction product of a sulfur source and
at least one Diels-Alder adduct. Generally, the molar
ratio of sulfur source to Diels-Alder adduct is in a range
of from about 0.75 to about 4.0, preferably about 1 to
about 2.0, more preferably about 1 to about 1.8. In one
embodiment the molar ratio of sulfur to adduct is from
about 0.8:1 to 1.2:1.
WO 92/18S88 PCr/US92/OlS74
2 0 8.~
-57-
The Diels-Alder adducts are a well-known, art-
recognized class of compounds prepared by the diene synthe-
sis or Diels-Alder reaction. A summary oS the prior art
relating to this class of compounds is found in the Russian
monograph, Dienovyi Sintes, Izdatelstwo Akademii Nauk SSSR,
1963 by A.S. Onischenko. (Translated into the English
language by L. Mandel as A.S. OnischenXo, Diene Synthesis,
N.Y., Daniel Davey and Co., Inc., 1964.) This monograph
and references cited therein are incorporated by reference
into the present specification.
Basically, the diene synthesis (Diels-Alder
reaction) involves the reaction of at least one conjugated
diene with at least one ethylenically or acetylenically
unsaturated compound, these latter compounds being known as
dienophiles. Piperylene, isoprene, methylisoprene, chloro-
prene, and 1,3-butadiene are among the preferred dienes for
use in preparing the Diels-Alder adducts. Examples of
cyclic dienes are the cyclopentadienes, fulvenes, 1,3-cy-
clohexadienes, 1,3-cycloheptadienes, 1,3,5-cycloeptatri-
enes, cyclooctatetraene, and 1,3,5-cyclononatrienes.
A preferred class of dienophiles are those having
at least one electron-accepting groups selected from groups
such as formyl, cyano, nitro, carboxy, carbohydrocarbyloxy,
etc. Usually the hydrocarbyl and substituted hydrocarbyl
groups, if not present, will not contain more than 10
carbon atoms each.
One preferred class of dienophiles are those
wherein at least one carboxylic ester group represented by
~C(O) O-Ro where Ro is the residue of a saturated aliphatic
alcohol of up to about 40 carbon atoms, the aliphatic
alcohol from which -Ro is derived can be any of the above-
described mono or polyhydric alcohols. Preferably the
alcohol is a lower aliphatic alcohol, more preferably
methanol, ethanol, propanol, or butanol.
WO92/18588 PCT/US'~/01S~4
2~6~
-~8-
In addition to the ethylenically unsaturated
dienophiles, there are many useful acetylenically unsatu-
rated dienophiles such as propiolaldehyde, methyl-ethynyl-
ketone, propylethynylketone, propenylethynylketone, propio-
S lic acid, propiolic acid nitrile, ethyl-propiolate, tetro-
lic acid, propargylaldehyde, acetylene-dicarboxylic acid,
the dimethyl ester of acetylenedicarboxylic acid, diben-
zoylacetylene, and the like.
Normally, the adducts involve the reaction of
equimolar amounts of diene and dienophile. However, if the
dienophile has more than one ethylenic linkage, it is
possible for additional diene to react if present in the
reaction mixture.
It is freguently advantageous to incorporate
materials useful as sulfurization promoters in the reaction
mixture. These materials may be acidic, basic or neutral.
Useful neutral and acidic materials include acidified clays
such as "Super Filtrol" (sulfuric acid treated diatomaceous
earth), p-toluenesulfonic acid, phosphorus-containing re-
agents such as phosphorus acids (e.g., dialkyl-phosphorodi-
thioic acids, phosphorus acid esters (e.g., triphenyl phos-
phate), phosphorus sulfides such as phosphorus pentasulfide
and surface active agents such as lecithin.
The preferred promoters are basic materials.
These may be inorganic oxides and salts such as sodium
hydroxide, calcium oxide and sodium sulfide. The most
desirable basic promoters, however, are nitrogen bases
including ammonia and amines.
~he amount of promoter material used is generally
about 0.0005-2.0% of the combined weight of the terpene and
olefinic compounds. In the case of the preferred ammonia
and amine catalysts, about 0.0005-0.5 mole per mole of the
c~mbined weight is preferred, and about 0.001-0.1 is espe-
cially desirable.
W092/18588 PC~/US92/01574
208~
-59-
Water is also present in the reaction mixture
either as a promoter or as a diluent for one or more of the
promoters recited hereinabove. The amount of water, when
present, is usually about 1-25~ by weight of the olefinic
compound. The presence of water is, however, not essential
and when certain types of reaction equipment are used it
may be advantageous to conduct the reaction under substan-
tially anhydrous conditions.
When promoters are incorporated into the reaction
mixture as described hereinabove, it is generally observed
that the reaction can be conducted at lower temperatures,
and the product generally is lighter in color.
The sulfur source or reagent used for preparing
any of the sulfur-containing materials of this invention
may be, for example, sulfur, a sulfur halide such as sulfur
monochloride or sulfur dichloride, a mixture of hydrogen
sulfide and sulfur or sulfur dioxide, or the like. Sulfur,
or mixtures of sulfur and hydrogen sulfide often are
preferred. ~owever, it will be understood that other
sulfurization reagents may, when appropriate, be substitut-
ed therefor. Commercial sources of all the sulfurizing
reagents are normally used for the purpose of this inven-
tion, and impurities normally associated with these commer-
cial products may be present without adverse results.
When the sulfurization reaction is effected by
the use of sulfur alone, the reaction is effected by merely
heating the reagents with the sulfur at temperatures of
from about 50 to 250C, usually, from about 150 to about
210C. The weight ratio of the materials to be sulfurized
to sul~ur is between about 5:1 and about 15:1, generally
between about 5:1 and about 10:1. The sulfurization
reaction is conducted with efficient agitation and general-
ly in an inert atmosphere (e.g., nitrogen). If any of the
components or reagents are appreciably volatile at the
reaction temperature, the reaction vessel may be sealed and
WO92/18588 PCT/US~/~1574
z~S6~
-60-
maintained under pressure. It is frequently advantageous
to add the sulfur portionwise to the mixture o~ the other
components.
When mixtures of sulfur and hydrogen sulfide are
utilized in the process of the invention, the amounts of
sulfur and hydrogen sulfide per mole of component(s) to be
sulfurized are, respectively, usually about 0.3 to about 3
gram-atoms and about 0.1 to about 1.5 moles. A preferred
range is from about 0.5 to about 2.0 gram-atoms and about
0.4 to about 1.25 moles, respectively, and the most desir-
able ranges are about 0.8 to about 1.8 gram-atoms, and
about 0.4 to about 0.8 mole, respectively. In reaction
mixture operations, the components are introduced at levels
to provide these ranges. In semi-continuous operations,
they may be admixed at any ratio, but on a mass balance
basis, they are present so as to be consumed in amounts
within these ratios. Thus, for example, if the reaction
vessel is initially charged with sulfur alone, the terpene
and/or olefinic compound and hydrogen sulfide are added
incrementally at a rate such that the desired ratio is
obtained.
When mixtures of sulfur and hydrogen sulfide are
utilized in the sulfurization reaction, the temperature
range of the sulfurization reaction is generally from about
50 to about 350C. The preferred range is about 100 to
about 200C with about 120 to about 180C being especially
suitable. The reaction often is conducted under super
atmospheric pressure which may be and usually is autogenous
pressure (i.e., pressure which naturally developed during
the course of the reaction), but may also be externally
applied pressure. The exact pressure developed during the
reaction is dependent upon such factors as design and
operation of the system, the reaction temperature, and the
vapor pressure of the reactants and products, and it may
vary during the course of the reaction.
,
W~92/18588 P~/~g~5
-61-
While it is preferred generally that the reaction
mixture consists entirely of the components and reagents
described above, the reaction also may be effected in the
presence of an inert solvent (e.g., an alcohol, ether,
ester, aliphatic hydrocarbon, halogenated aromatic hydro-
carbon, etc.) which is liquid within the temperature ra~ge
employed. When the reaction temperature is relatively
high, for example, at about 200C, there may be some evolu-
tion of sulfur from the product which is avoided i8 a lower
reaction temperature such as from about 150-170C is used.
In some instances, it may be desirable to treat
the sulfurized product obtained in accordance with the
procedures described herein to reduce active sulfur. The
term "active sulfur" includes sulfur in a form which can
cause staining of copper and similar materials, and stan-
dard tests are available to determine sulfur activity. As
an alternative to the treatment to reduce active sulfur,
metal deactivators can be used with the lubricants contain-
ing sulfurized compositions.
The following examples relate to sulfurized
compositions of the present invention.
Example D-l
A reaction vessel is charged with 780 parts
isopropyl alcohol, 752 parts water, 35 parts of a 50% by
weight aqueous solution of sodium hydroxide, 60 parts of
sulfuric acid treated diatomaceous earth ~Super Filtrol
available from Engelhard Corporation, Menlo Park, New
Jersey) and 239 parts of sodium sulfide. The mixture is
stirred and heated to 77-80C. The reaction temperature is
maintained for two hours. The mixture is cooled to 71C
where 1000 parts of the sulfurized olefin prepared by
reacting 337 parts of sulfur monochloride with 1000 parts
of a mixture of 733 parts of l-dodecene and 1000 parts of
Neodene 1618, a C~l8 olefin mixture available from Shell
Chemical, is added to the mixture. The reaction mixture is
W092/l8588 PCT/US~/01574
~,o~6~ '
-62-
heated to 77-80C and the temperature is maintained until
the chlorine content i~ a maximum o~ 0.5. The reac~ion
~ixture is vacuum stripped to 80C and 20 millimeters of
mercury. The residue is filtered through diatomaceous
earth. The filtrate has 19.0~ sulfur and a specific
gravity of 0.95.
Example D-2
A mixture of 100 parts of soybean oil and 50
parts of commercial Cl6 ~-olefins is heated to 175C. under
nitrogen and 17.4 parts of sulfur is added gradually,
whereupon an exothermic reaction causes the temperature to
rise to 205C. The mixture is heated at 188-200C. for 5
hours, allowed to cool gradually to 90C. and filtered to
yield the desired product containing 10.13~ sulfur.
Example D-3
A mixture of 100 parts of soybean oil, 3.7 parts
of tall oil acid and 46.3 parts of commercial CI~J8 ~-olefins
is heated to 165C. under nitrogen and 17.4 parts of sulfur
is added. The temperature of the mixture rises to 191C.
It is maintained at 165-200C. for 7 hours and is then
cooled to 90C. and filtered. The product contains 10.13%
sulfur.
Example D-4
A mixture of 93 parts (0.5 equivalent) of pine
oil and 48 parts (1.5 equivalents) of sulfur is charged to
a reaction vessel equipped with condenser, thermometer and
stirrer. The mixture is heated to about 140C with nitro-
gen blowing and maintained at this temperature for about 28
hours. After cooling, 111 parts of a Cl6 alpha-olefin
(available from Gulf Oil Chemicals Company ~under the
general trade name Gulftene 16) are added through an
addition funnel, and after addition is complete, the
addition funnel is replaced with a nitrogen tube. The
reaction mixture is heated to 170C with nitrogen blowing
3S and maintained at the temperature for about 5 hours. The
W092/l8S88 PCT/US~/01574
2~85~15
-63-
mixture is cooled and filtered through a filter aid The
filtrate is the desired product having a sulfur content of
19.01% (theory 19.04%).
Example D-5
(a) A mixture comprising 400 grams of toluene
and 66.7 grams of aluminum chloride is charged to a two-
liter flask fitted with a stirrer, nitrogen inlet tube, and
a solid carbon dioxide-cooled reflux condenser. A second
mixture comprising 640 grams (5 moles) of butylacrylate and-
240.8 grams of toluene is added to the AlC13 slurry over a
0.25-hour period while maintaining the temperature within
the range of 37-58C. Thereafter, 313 grams (5.8 moles) of
butadiene are added to the slurry over a 2.75-hour period
while maintaining the temperature of the reaction mass at
60-61C by means of external cooling. The reaction mass is
blown with nitrogen for about 0.33-hour and then trans-
ferred to a four-liter separatory funnel and washed with a
solution of 150 grams of concentrated hydrochloric acid in
1100 grams of water. Thereafter, the product is subjected
to two additional water washings using 1000 ml of water for
each wash. The washed reaction product is subsequently
distilled to remove unreacted butylacrylate and toluene.
The residue of this first distillation step is subjected to
further distillation at a pressure of 9-10 millimeters of
mercury whereupon 785 grams of the desired adduct are
collected over the temperature of 105-115C.
(b) A butadiene-butylacrylate Diels-Alder adduct
(4550 grams, 25 moles) and 1600 grams (50 moles) of sulfur
flowers are charged to a 12 liter flas~, fitted with
stirrer, reflux condenser, and nitrogen inlet tube. The
reaction mixture is heated at a tempera~ure within the
range of- 150-155C for 7 hours while tassing nitrogen
therethrough at a rate of about 0.5 cubic feet per hour.
After heating, the mass is permitted bo cool to room
W092/l85~ PCT/US~/01S74
2 0 ~
temperature and filtered, the sulfur-containing product
being the filtrate.
component (D) may also be an alkylated aromatic
amine. Alkylated aromatic amines include compounds repre-
sented by the formula
Ar3 N Ar4
wherein Ar3 and Ar' are independently mononuclear or polynu-
clear, substituted or unsubstituted aromatic groups; and R6
is hydrogen, halogen, OH, NH2, SH, NO2 or a hydrocarbyl
group of from 1 to about 50 carbon atoms. A~3 and Al~ may
be any of the above-described aromatic groups. When AU3
and/or Ar4 are substituted aromatic groups, the number of
substituents on Ar3 and/or Ar4 range independently up to the
number of positions available on Ar3 and/or Ar4 for substi-
tution. These substituents are independently selected from
the group consisting of halogen (e.g., chlorine, bromine,
etc.), OH, N~, SH, NO~ or hydrocarbyl groups of from 1 to
about 50 carbon atoms.
In a preferred embodiment, component (D) is
represented by the formula
~\
~/
R7~_N
wherein R7 and R8 are independently hydrogen or hydrocarbyl
groups of from 1 to about 50 carbon atoms, preferably
hydrocarbyl groups of from about 4 to about 20 carbon
atoms. Examples of aromatic amines include P,P'-dioctyldi-
phenylamine; octylphenyl-beta-naphthylamine; octylphenyl-
~lpha-naphthylamine, phenyl-alpha-naphthylamine; phenyl-
W092/l8~ PCT/US~/01~74
2 0 ~
-65-
beta-naphthylamine; p-octylphenyl-alpha-naphthylamine and
4-octylphenyl-1-octyl-beta-naphthylamine and di~nonyl-
phenyl)amine, with di(nonylphenyl)amine preferred.
U.S. Patents 2,558,285; 3,601,632; 3,368,975; and
3,505,225 disclose diarylamines within the scope of compo-
nent (D). These patents are incorporated herein by refer-
ence.
The antioxidants (D) of the present invention may
contain one or more of several types of phenolic compounds
which may be metal-free phenolic compounds.
In one embodiment, the antioxidant of the present
invention includes at least one metal-free hindered phenol.
Alkylene coupled derivatives of said hindered phenols also
can be used. Hindered phenols are defined (in the specifi-
cation and claims) as those containing a sterically hinder-
ed hydroxyl group, and these include those derivatives of
dihydroxy aryl compounds wherein the hydroxyl groups are in
the o- or p-position to each other.
The metal-free hindered phenols may be represent-
ed by the following Formulae I, II and III.
OH
~ (I)
R~
OH OH
Rs ~ R9 (II)
Rl
W092/l8588 PCT/US92/01574
2~6~ -
-66-
p~ OH
Rs ~ C(R~2)~ ~ R9 (III)
Rl RJo
wherein each R9 is independently an alkyl group containing
from 3 to about 9 carbon atoms, each Rl is hydrogen or an
alkyl group, Rll is hydrogen or an alkyl group containing
from 1 to about 9 carbon atoms, and each Rl2 is independent-
ly hydrogen or a-methyl group. In the preferred embodi-
ment, Rl is an alkyl group containing from about 3 to about
50 carbo~ atoms, preferably about 6 to about 20, more
preferably from about 6 to about 12. Examples of such
groups include hexyl, heptyl, octyl, decyl, dodecyl,
lS tripropenyl, tetrapropenyl, etc. Examples of R9, Rl and R"
groups include propyl, isopropyl, butyl, secondary butyl,
tertiary butyl, heptyl, octyl, and nonyl. Preferably, each
R9 and Rll are tertiary groups such as tertiary butyl,
tertiary amyl, etc. The phenolic compounds of the type
represented by Formula I may be prepared by various tech-
niques, and in one embodiment, such phenols are prepared in
stepwise manner by first preparing the para-substituted
alkyl phenol, and thereafter alkylating the para-substi-
tuted phenol in the 2- and/or 6-position as desired. ~hen
it is desired to prepare coupled phenols of the type
represented by Formulae II and III, the second step alkyla-
tion is conducted under conditions which result in the
alkylation of only one of the positions ortho to the
hydroxyl group. Examples of useful phenolic materials of
the type represented by Formula I include: 2-t-butyl-
4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-
dodecyl phenol; 2,6-di-t-butyl-4-butylphenol; 2,6-di-
t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol;
2-methyl-6-di-t-butyl-4-heptyl phenol; 2,4-dimethyl-6-t-
butyl phenol; 2,6-t-butyl-4-ethyl phenol; 4-t-butyl cate-
WO 92/1858% PCr/USg2/OlS74
2~,5&1,j'
-67-
chol; 2,4-di-t-butyl-p-cresol; 2,6-di-t-butyl-4-methyl
phenol; and 2-methyl-6-di-t-butyl-4-dodecyl phenol
Examples of the ortho coupled phenols of the type
represented by Formula II include: 2,2'-bis(6-t- butyl-4-
heptyl phenol); 2,2'-bis(6-t-butyl-4-octyl phenol); 2,6-
bis-(1'-methylcyclohexyl)-4-methyl phenol; and 2,2'-bis(6-
t-butyl-4-dodecyl phenol).
Alkylene-coupled phenolic compounds of the type
represented by Formula III can be prepared from the phenols
represented by Formula I wherein Rll is hydrogen by reaction
of the phenolic compound with an aldehyde such as formalde-
hyde, acetaldehyde, etc. or a ketone such as acetone.
Procedures for coupling of phenolic compounds with alde-
hydes and ketones are well known in the art, and the
procedures do not need to be described in detail herein.
To illustrate the process, the phenolic compound of the
type represented by Formula I wherein Rll is hydrogen is
heated with a base in a diluent such as toluene or xylene,
and this mixture is then contacted with the aldehyde or
ketone while heating the mixture to reflux and removing
water as the reaction progresses. Examples of phenolic
compounds of the type represented by Formula III include
2,2'-methylene-bis(6-t-butyl-4-heptylphenol);2,2'-methyl-
ene-bis(6-t-butyl-4-octyl phenol); 2,2'-methylene-bis-(4-
dodecyl-6-t-butyl phenol); 2,2'-methylene-bis-(4-octyl-6-
t-butyl phenol); 2,2'-methylene-bis-(4-octyl phenol);
2,2'-methylene-bis-(4-dodecyl phenol); 2,2'-methylene-bis-
(4-heptyl phenol); 2,2'-methylene-bis(6-t-butyl-4-dodecyl
phenol); 2,2'-methylene-bis(6-t-butyl-4-tetrapropenyl
phenol); and 2,2'methylene-bis(6-t-butyl-4-butyl phenol).
The alkylene-coupled phenols may be obtained by
reacting a phenol (2 equivalents) with 1 equivalent of an
aldehyde or ketone. Lower molecular weight aldehydes are
preferred and particularly preferred examples of useful
aldehydes include formaldehyde, a reversible polymer
W092/185XX PCT/US~/~1~74
20 8~ 6~ ~ -68-
thereof such as paraformaldehyde, trioxane, acetaldehyde,
etc. As used in this specification and claims, the word
"formaldehyde" shall be deemed to include such reversible
polymers. The alkylene-coupled phenols can be derived from
phenol or substituted alkyl phenols, and substitued alkyl
phenols are preferred. The phenol must have an ortho or
para position available for reaction with the aldehyde.
In one embodiment, the phenol will contain one or
more alkyl groups which may or may not result in a steri-
cally hindered hydroxyl group. Examples of hinderedphenols which can be used in the formation of the alkylene-
coupled phenols include: 2,4-dimethylphenol; 2,4-di-t-
butyl phenol, 2,6-di-t-butyl phenol; 4-octyl-6-t-butyl
phenol; etc.
In one preferred embodiment, the phenol from
which the alkylene-coupled phenols are prepared are phenols
substituted in the para position with aliphatic groups
containing at least 6 carbon atoms as described above.
Generally, the alkyl groups contain from 6 to 12 carbon
atoms. Preferred alkyl groups are derived from polymers of
ethylene, propylene, l-butene and isobutene, preferably
propylene tetramer or trimer.
The reaction between the phenol and the aldehyde,
polymer thereof or ketone is usually carried out between
room temperature and about 150C, preferably about
50-125C. The reaction preferably is carried out in the
presence of an acidic or basic material such as hydrochlo-
ric acid, acetic acid, ammonium hydroxide, sodium hydroxide
or potassium hydroxide. The relative amounts of the
reagents used are not critical, but it is generally conve-
nient to use about 0.3 to about 2.0 moles of phenol per
equivalent of formaldehyde or other aldehyde.
The following examples illustrate the preparation
of phenolic compounds of the type represented by Formulae
1 and III.
w092/18588 PCTtUS92/01~74
2~615
-69-
Example D-6
A reaction vessel is charged with 3192 parts (12
moles) of a 4-tetrapropenyl phenol. The phenol i5 heated
to 80C in 30 minutes and 21 parts (0.2 mole) of a 93%
sulfuric acid solution is added to the vessel. The mixture
is heated to 85C and 1344 parts (24 moles) of iaobutylene
is added over 6 hours. The temperature is maintained
between 85-91C. After introduction of isobutylene, the
reaction is blown with nitrogen at 2 standard cubic feet
per hour for 30 minutes at 85C. Calcium hydroxide (6
parts, 0.2 mole) along with 12 parts of water is added to
the reaction vessel. The mixture is heated to 130C under
nitrogen for 1.5 hours. The reaction is vacuum stripped at
130C and 20 millimeters of mercury for 30 minutes. The
residue is cooled to 90C and the residue is filtered
through diatomaceous earth to give the desired product.
The desired product has a specific gravity of 0.901 and a
percent hydroxyl (Grignard) equals 4.25 (theoretical 4.49).
Example D-7
A reaction vessel is charged with 798 parts (3
moles) of 4-tetrapropenyl phenol. The phenol is heated to
95-100C where 5 parts of a 93% solution of sulfuric acid
is added ~o the vessel. 168 parts (3 moles) of isobutylene
is added to the vessel over 1.7 hours at 100C. After
introduction of the isobutylene the reaction is blown with
nitrogen at 2 standard cubic feet per hour for one-half
hour at 100C. 890 parts of the above-described phenol
(2.98 moles) is added to a reaction vessel and heated to
- 34-40C. A 37% aqueous formaldehyde solution (137 grams,
1.7 moles) is added to the vessel. The mixture is heated
to 135C with removal of water. Nitrogen blowing at 1.5
scfh begins at 105-110C. The reaction is held at 120C
for 3 hours under nitrogen. The reaction is cooled to 83C
where 4 parts (0.05 mole) of a 50% aqueous sodium hydroxide~
solution is added to the vessel. The reaction is heated to
W0~2/l8588 PCT~US92/01574
2~85~
-70-
135C under nitrogen. ~he reaction is vacuum stripped to
135C and 20 millimeters of mercury for 10 minute~. The
reaction is cooled to 95C and the residue is filtered
through diatomaceous earth. The product has a percent
hydroxyl (Grignard) of 5.47 (theoretical 5.5) and a molecu-
lar weight (vapor phase osmometry) of 682 (theoretical
667).
Example D-8
The general procedure of Example D-6 is repeated
except that the 4-heptyl phenol is replaced by an equiva-
lent amount of tri-propylene phenol. The substituted phenol
obtained in this manner contains 5.94% hydroxyl.
Example D-9
The general procedure of Example D-7 is repeated
except that the phenol of Example D-6 is replaced by the
phenol of Example D-8. The methylene coupled phenol
prepared in this manner contains 5.74% hydroxyl.
In another embodiment, the lubricant compositions
of the present invention may contain a metal-free (or ash-
less) alkyl phenol sulfide.
The alkyl phenols from which the sulfides areprepared also may comprise phenols of the type discussed
above and represented by Formula I wherein RIJ is hydrogen.
For example, the alkyl phenols which can be converted to
alkyl phenol sulfides include: 2-t-butyl- 4-heptyl phenol;
2-t-butyl-4-octyl phenol; and 2-t- butyl-4-dodecyl phenol.
The term "aIkylphenol sulfides" is meant to
include di-(alkylphenol)monosulfides, disulfides, poly-
sulfides, and other products obtained by the reaction of
the alkylphenol with s~lfur monochloride, sulfur dichloride
or elemental sulfur. One mole of phenol is reacted with
about 0.5-1.5 moles, or higher, or sulfur compound. For
example, the alkyl phenol sulfides are readily obtained by
mixing, one mole of an alkylphenol and 0.5-2.0 moles of
~ulfur dichloride. The reaction mixture is usually main-
WO92/1~8 PCT/US~/01574
2~8~
-71-
tained at about lOO9C ~or about 2-5 hours, a~ter which time
the resulting sulfide is dried a~d filtered. When elemen-
tal sulfur is used, temperatures of about 150-250C or
higher are typically used. It is also desirable that the
S drying operation be conducted under nitrogen or a similar
inert gas.
Suitable basic alkyl phenol sulfides are dis-
closed, for example, in U.S. Patents 3,372,116; 3,410,798;
and 4,021,419, which are hereby incorporated by reference.
These sulfur-containing phenolic compositions
described in U.S. Patent 4,021,419 are obtained by sulfu-
rizing a substituted phenol with sulfur or a sulfur halide
and thereafter reacting the sulfurized phenol with formal-
dehyde or a reversible polymer thereof. Alternatively the
substituted phenol can be first reacted with formaldehyde
and thereafter reacted with sulfur or a sulfur halide to
produce the desired alkyl phenol sulfide. The disclosure
of U.S. Patent 4,021,419 is hereby incorporated by refer-
ence for its disclosure of such compounds, and methods for
preparing such compounds. A synthetic oil of the type
described below is used in place of any mineral or natural
oils used in the preparation of the salts for use in this
invention.
In another embodiment, the antioxidant (D) may be
phenothiazine, substituted phenothiazines, or derivatives
such as represented by Formula IV
IRl3s(o) Rl4
(Rl5) ~ S ~ (R~5)(IV)
wherein Rl4 is selected from the group consisting of higher
alkyl groups, or an alkenyl, aryl, alkaryl or aralkyl group
- and mixtures thereof; Rl3 is an alkylene, alkenylene or an
W092/l8588 PCT/US~/01S74
20~ ~ 6 ~ -72-
aralkylene group, or mixtures thereof; each Rl5 i~ indepen-
dently alkyl, alkenyl, aryl, alkaryl, arylalkyl, halogen,
hydroxyl, alkoxy, alkylthio, arylthio, or fused aromatic
rings, or mixtures thereof; a and b are each independently
0 or greater.
In another embodiment, the phenothiazine deriva-
tives may be represented by Formula V
(R ~ } (R
1 (O), (V)
R'3
(Rls) ~ S ~ (Rl5) b
wherein Rl3, Rl4, Rl5, a and b are as defined with respect to
Formula IV.
The above-described phenothiazine derivatives,
and methods for their preparation are described in U.S.
Patent 4,785,095, and the disclosure of this patent is
hereby incorporated by reference for its teachings of such
methods and compounds. In one embodiment, a dialkyldi-
phenylamine is treated with sulfur at an elevated tempera-
ture such as in the range of 145C to 205C for a suffi-
cient time to complete the reaction. A catalyst such as
iodine may be utilized to establish the sulfur bridge.
Phenothiazine and its various derivatives can be
converted to compounds of Formula IV by contacting the
phenothiazine compound containing the free NH group with a
thio alcohol of the formula Rl4SRl3OH where Rl4 and Rl3 are
defined with respect to Formula IV. The thio alcohol may
WO 92J18S88 PCI/US92/OlS74
2~8~
be obtained by the reaction of a mercaptan RI~SH with an
alkylene oxide under basic conditions. Alternatively, the
thio alcohol may be obtained by reacting a terminal olefin
with mercaptoethanol under free radical conditions. The
reaction between the thio alcohol and the phenothiazine
compound generally is conducted in the presence of an inert
solvent such as toluene, benzene, etc. A strong acid
catalyst such as sulfuric acid or para-toluene sulfonic
acid at about 1 part to about 50 parts of catalyst per 1000
parts of phenothiazine is preferred. The reaction is
conducted generally at reflux temperature with removal of
water as it is formed. Conveniently, the reaction tempera-
ture may be maintained between 80C and 170C.
When it is desired to prepare compounds of the
type represented by Formulae IV and V wherein x is 1 or 2,
i.e., sulfones or sulfoxides, the derivatives prepared by
the reaction with the thio alcohols described above are
oxidized with an oxidizing agent such as hydrogen peroxide
in a solvent such as glacial acetic acid or ethanol under
an inert gas blanket. The partial oxidation takes place
conveniently at from about 20C to about 150C. The
~ollowing examples illustrate the preparation of phenothi-
azines which may be utilized as the non-phenolic antioxi-
dant (D) in the functional fluids of the present invention.
Example D-10
One mole of phenothiazine is placed in a one-
liter, round bottom flask with 300 ml. of toluene. A
nitrogen blanket is maintained in the reactor. To the
mixture of phenothiazine and toluene is added 0.05 mole of
sulfuric acid catalyst. The mixture is then heated to
reflux temperature and 1.1 moles of n-dodecylthioethanol is
added dropwise oYer a period of approximately 90 minutes.
Water is continuously removed as it is f ormed in the
reaction process.
W092/1858% ~ PCT/US~/01~74
2 0 ~ J
-74-
The reaction mixture is continuously stirred
under reflux until substantially no further water is
evolved. The reaction mixture is then allowed to cool to
90C. The sulfuric acid catalyst is neutralized with
sodium hydroxide. The solvent is then removed under a
vacuum of 2 KPa at 110C. The residue is filtered giving
a 95% yield of the desired product.
In another embodiment, the antioxidant (D) is a
transition metal-containing composition. The transition-
metal-containing antioxidant is oil-soluble. The composi-
tions generally contain at least one transition metal
selected from titanium, manganese, cobalt, nickel, copper,
and zinc, preferably manganese, copper, and zinc, more
preferably copper. The metals may be in the form of
nitrates, nitrites, halides, oxyhalides, carboxylates,
borates, phosphates, phosphites, sulfates, sulfites,
carbonates and oxides. The transition metal-containing
composition is generally in the form of a metal-organic
compound complex. The organic compounds include carboxylic
acids and esters, mono- and dithiophosphoric acids, dithio-
carbamic acids and dispersants. Generally, the transition
metal-containing compositions contain at least about 5
carbon atoms to render the compositions oil-soluble.
In one embodiment, the organic compound is a
carboxylic acid. The carboxylic acid may be a mono- or
polycarboxylic acid containing from 1 to about 10 carboxyl-
ic groups and 2 to about 75 carbon atoms, preferably 2 to
about 30, more preferably 2 to about 24. Examples of
monocarboxylic acids include 2-ethylhexanoic acid, octanoic
acid, decanoic acid, oleic acid, linoleic acid, stearic
acid and gluconic acid. Examples of polycarboxylic acids
include succinic, malonic, citraconic acids as well as
substituted versions of these acids. The carboxylic acid
may be one of the above-described hydrocarbyl-substituted
carboxylic acylating agents.
W092/l8588 PCT/US~/OlS74
203~fil S
-75-
In another embodiment, the organic compound is a
mono- or dithiophosphoric acid. The dithiophosphoric acids
may be any of the above-described phosphoric acids (see
dihydrocarbyl dithiophosphate). A monothiophosphoric acid
is prepared by treating a dithiophosphoric acid with steam
or water.
In another embodiment, the organic compound is a
mono- or dithiocarbamic acid. Mono- or dithiocarbamic acid
is prepared by reacting carbon disulfide or carbon oxy-
sulfide with a primary or secondary amine. The amines may
be any of the amines described above.
In another embodiment, the organic compound may
be any of the phenols, aromatic amines, or dispersants
described above. In a preferred embodiment, the transition
metal-containing composition is a lower carboxylic acid-
transition metal-dispersant complex. The lower alkyl
carboxylic acids contain from 1 to about 7 carbon atoms and
include formic acid, acetic, propionic, butanoic, 2-ethyl-
hexanoic, benzoic acid, adn salicylic acid. The dispersant
may be any of the dispersants described above, preferably
the dispersant is a nitrogen-containing carboxylic disper-
sant. The transition metal complex is prepared by blending
a lower carboxylic acid salt of a transition metal with a
dispersant at a temperature from about 25C up to the
decomposition temperature of the reaction mixture, usually
from about 25C up to about 100C. A solvent such a
xylene, toluene, naphtha or mineral oil may be used.
Example D-11
The metal complex is obtained by heating at 160C
for 32 hours 50 parts of copper diacetate monohydrate, 283
parts of 100 neutral mineral oil, 250 milliliters of xylene
and 507 parts of an acylated nitrogen intermediate prepared
by reacting 4,392 parts of a polybutene-substituted succin-
ic anhydride (prepared by the reaction of a chlorinated
polybutene ha~ing a number average molecular weight of 1000
W092/18S88 ~CT/US~/01574
208~ 76-
and a chlorine content of 4.3% and 20~ molar excess of
maleic anhydride) with 540 parts of an alkylene amine
polyamine mixture of 3 parts by weight of triethylene
tetramine and 1 part by weight of diethylene triamine, and
3240 parts of 100 neutral mineral oil at 130C-240C for
3.5 hours. The reaction is vacuum stripped to 110C and 5
millimeters of mercury. The reaction is filtered through
diatomaceous earth to yield a filtrate which has 59% by
weight oil, 0.3% by weight copper and 1.2% by weight
nitrogen.
Example D-12
(a) A mixture of 420 parts (7 moles) of isopro-
pyl alcohol and 518 parts (7 moles) of n-butyl alcohol is
prepared and heated to 60OC under a nitrogen atmosphere.
Phosphorus pentasulfide (647 parts, 2.91 moles) is added
over a period of one hour while maintaining the temperature
at 65-77C. The mixture is stirred an additional hour
while cooling. The material is filtered thorugh a filter
aid, and the filtrate is the desired phosphorodithioic
acid.
(b) A mixture of 69 parts (0.97 equivalent) of
cuprous oxide and 38 parts of mineral oil is prepared and
239 parts (0.88 eguivalent) of the phosphorordithioic acid
prepared in Example D-13(a) are added over a period of
about 2 hours. The reaction is slightly exothermic during
the addition, the mixture is thereafter stirred for an
additional 3 hours while maintaining the temperature at
about 70C. The mixture is stripped to 105C/10 mm.Hg. and
filtered. The filtrate is a dark-green liquid containing
17.3% copper.
E~ gDesiu Overbased Sa~ts
The lubricating compositions of the present
invention also contain at least one magnesium overbased
~ulfonic, carboxylic, or phosphorus acid or derivative
thereo~, preferably sulfonic acid. The acids have been
w092/18~ PCT/US~/01~4
2 ~ ; 6l ~
-77-
described above. Generally, the magnesium salts have the
same metal ratios as described for alkali metal sal~
The magnesium salts are prepared by a manner
similar to the alkali metal salt~ except basic magnesium
compounds, preferably magnesium oxide or magnesium hydrox-
ide, are used instead of basic alkali metal compounds.
Magnesium overbased salts and methods of prepar-
ing them are described in U.S. Patents 3,629,109;
4,129,508; 4,627,928; and 4,775,490. These references are
incorporated by reference for these disclosures.
The following examples describe magnesium salts
useful in the present invention.
Example E-1
A reaction mixture comprising 906 grams (1.5
- 15 equivalents) of an oil solution of alkylphenylsulfonic acid
having (average molecular weight 450), 564 grams of mineral
oil, 600 grams of toluene, 95.7 grams of magnesium oxide
(4.4 equivalents), and 120 grams of water are carbonated at
a temperature of about 78-85C for about seven hours at a
rate of about three cubic feet of carbon dioxide per hour
during which time the reaction mixture is constantly
agitated. ~he carbonation is stopped and the reaction
product stripped by heating to 165C at a pressure of 20
mm. (Hg.). The stripped product is filtered. The fil-
trate is an oil-solution of the desired basic magnesium
sulfonate having a metal ratio of about 3.
Example E-2
A reaction mixture comprising 135 parts mineral
oil (all "parts" are parts by weight unless otherwise
indicated), 330 parts xylene, 200 parts (0.235 equivalent)
- o~ a mineral oil solution of an alkylphenylsulfonic acid
(average molecular weight 425), 19 parts (0.068 equivalent)
o~ tall oil acids, 60 parts (about 2.75 equivalents) of
magnesium oxide, 83 parts methanol, and 62 parts water are
car~onated at a rate of 15 parts of carbon dioxide per hour
WO9~/18588 PCT/US92/01S74
2 0 ~ a
-78-
for about two hours at the methanol reflux temperature.
The carbon dioxide inlet rate is then reduced to about 7
parts per hour and the methanol is removed by raising the
temperature to about 98C over a three hour period. The 47
parts of water are added and carbonation is continued for
an additional 3.5 hours at a temperature of about 95C.
The carbonated mixture is then stripped by heating to a
temperature of 140-145C over a 2.5 hour period. This
results in an oil solution of a basic magnesium salt
characterized by a metal ratio of about 10.
Then, the carbonated mixture is cooled to about
600-6soc and 208 parts xylene, 60 parts magnesium oxide, 83
parts methanol and 62 parts water are added thereto.
Carbonation is resumed at a rate of 15 parts per hour for
two hours at the methanol reflux temperature. The carbon
dioxide addition rate is reduced to 7 parts per hour and
the methanol is removed by raising the temperature to about
95C over a three hour period. An additional 41.5 parts of
water are added and carbonation is continued at 7 parts per
hour at a temperature of about 90-95C for 3.5 hours. The
carbonated mass is then heated to about 150-160C over a
3.5 hour period and then further stripped by reducing the
pressure to 20 mm. (Hg.) at this temperature. The carbon-
ated reaction product is then filtered. The filtrate is an
oil-solution of the desired basic magnesium salt character-
ized by a metal ratio of 20.
Lu~iLcating_~me_sitions
Lubricating compositions of the present invention
are effective in lubricating compression and spark-ignited
e~gines, preferably spark-ignited. The compositions of the
present invention provide effective protection to engines
under operating conditions. As described above, the
lubricating compositions comprise a major amount of an oil
o~ lubricating viscosity and (A) at least one alkali metal
overbased salt of a sulfonic, carboxylic or phosphorus acid
WO92/~8sX8 PCT/US~/01~4
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or derivatives thereof, (B) at least one disperæant, (C) at
least one metal dihydrocarbyl dithiophosphate, (D) at least
one antioxidant and (E) at least one magnesium overbased
metal salt of a sulfonic, carboxylic or phosphorus acid or
derivative thereof.
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 dicarboxylic acids
and polyols, esters of phosphorus-containing acids, poly-
meric tetrahydrofurans and silcon-based oils.
Specific examples of the oils of lubricating
viscosity are described in U.S. Patent 4,326,972 and
~uropean Patent Publication 107,282, both herein incorpo-
rated by reference for their disclosures relating to
lubricating oils. A basic, brief description of lubricant
base oils appears in an article by D. V. B~Qç~, "Lubricant
Oils", Lubricant En~ineerina, 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 throuqh column 3,
line 63, inclusive), herein incorporated by reference for
its disclosure to oils of lubricating viscosity.
The above components are generally present in
amounts to provide effective protection to the engines.
The alkal metal salt (A) is present in an amount to provide
at least about 0.0019 equivalent of alkali metal per 100
grams of lubricating composition, preferably about 0.0025,
re preferably about 0.0031, and still more preferably
about 0.0037. Generally, the alkali metal salt (A) is
W0~2/l8588 PCT/US~/01S~4
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present in an amount to provide up to about 0.0075 equiva-
lent of alkali metal per loO grams of lubricating composi-
tion, preferably up to about 0.0050. In another embodi-
ment, the alkali metal salt ~A) i8 present in an amount
from about 0.15% by weight of the composition, preferably
about 0.20%, more preferably about 0.25%, still more
preferab~y about 0.30%. Generally, the alkali metal salt
(A) is present in an amount up to about 0.60~ by weight of
the composition, preferably up to about 0.40%. The disper-
sant (B) is generally present in an amount of at leastabout 1.60%, preferably about 1.8%, more preferably about
2.25% by weight of the composition. The dispersant (B) is
generally present in an amount up to about 5.0%, preferably
- about 4.0%, more preferably 3.5% by weight of the composi-
tion. The metal hydrocarbyl dithiophosphate (C) is gener-
ally present in an amount from about 0.1%, preferably from
about 0.5%, more preferably from about 0.7~ up to about
2.0%, preferably up to about 1.75%, more preferably up to
about 1.5% by weight of the composition. The antioxidant
(D) is generally present in an amount from about 0.01$,
preferably from about 0.03% up to about 2.0%, preferably up
to about 1.0% by weight of the composition. In another
embodiment, the antioxidant is present in an amount to
provide from about 50, preferably from about 100, more
preferably from about 125 up to about 2000, generally up to
about 1000, preferably up to about 500, preferably up to
about 200, more preferably up to about 150 ppm transition
metal to the lubricating composition. The magnesium
overbased sulfonate (E) is present in an amount from at
least about 0.15%, preferably from about 0.20%, more
preferably from about 0.25~ by weight of the composition.
The magnesium sulfonate ~E) is generally present in an
a unt up to about 2.0%, preferably up to about 1.5%, more
preferably up to about 1.0% by weight of the composition.
W092/185~ PCT/US92/01574
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The lubricating compositions of the pre~ent
invention are free o~ calcium overbased sulfonate. The use
of the term "~ree of" refers to compositions which are
substantially free of calcium overbased sulronate. The
metal ratio of calcium overbased sulfonates is typically
1.5 to 40. In another embodiment, the compositions are
free of calcium overbased phenates, including calcium
overbzsed alkylene-coupled phenates and calcium overbased
sulfur-coupled phenates. The lubricating compositions of
the present invention generally contain less than about
0.08% by weight calcium, preferably less than about 0.07~,
more preferably less than about o.o5~ by weight calcium
metal. Some calcium may be present in some of the addi-
tives of the present invention as a contaminant. These
small quantities of calcium are acceptable provided they do
not adversely affect the compositions of the present
invention.
The lubricating compositions o~ the present
invention may be used, by themselves or in combination with
any other known additive which includes, but is not limited
to anti-wear agents, extreme pressure agents, emulsifiers,
demulsifiers, friction modifiers, anti-rust agents, corro-
sion inhibitors, viscosity improvers, pour point depres-
sants, dyes, and foam inhibitors. These additives may be
present in various amounts depending on the needs of the
final product.
Corrosion inhibitors, extreme pressure and anti-
wear agents include but are not limited to metal salts of
- a phosphorus acid, chlorinated aliphatic hydrocarbons;
phosphorus esters including dihydrocarbyl and trihydrocar-
byl phosphites; boron-containing compounds including borate
esters; dimercaptothiadiazole derivatives; benzotriazole
derivatives; amino-mercaptothiadiazole derivatives; and
molybdenum compounds.
W092/l8588 PCT/US~/~1574
~o~5~ a -82-
Viscosity improvers include but are not limited
to polyisobutenes, polymethyacrylate acid esters, poly-
acrylate acid esters, diene polymers, polyalkyl styrenes,
alkenyl aryl conjugated diene copolymers (preferably
styrene-maleic anyhydride copolymer esters), 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).
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 ~.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 lubricating compositions of the present
invention are prepared by blending components (A)-(D) above
with or without additional optional additives in an oil of
lubricating viscosity. Blending is accomplished by mixing
(usually by stirring) the ingredients from room temperature
up to the decomposition temperature of the mixture or
individual components. Generally, the ~ngredients are
blended at a temperature from about 25C up to about 250C,
preferably up to about 200C, more preferably up to about
150C, still more preferably up to about ~00C.
~he following tables contain examples which
illustrate lubricants of the present invention. "Bal." in
the table represents that the balance of bhe composition is
W092/18s88 PCT/US~/01S74
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oil. The amount of each compound in Examples 1-g ia ~ea-
sured in percent by volume and reflects the amount of oil
containing products of the indicated additives.
Product of Lubricants (~ by volume)
Example:_ 1 2 3 4 5
A-l 0.35 0.26 --- 0.35 0.35
A-4 --- --- 0.30 ~~~ ~~~
B-l 5.5 --- 5.5 5.5 5.5
B-12 --- 6.3 --- ___ ___
C-l 0.75 0.75 0.38 0.75 0.75
D-l --- 0.53 --- --- ---
D-3 --- --- 0.5 --- --~
D-6 --- --- --- 0.31 ---
Basic magnesium
alkylated benzene
sul~onate (42% oil,
metal ratio=15) 0.5 0.5 0.5 0.5 0.5
Copper O,O'-iso-
propyl methyl-amyl
dithiophosphate 0.08 --- 0.15 0.08 0.08
Sulfur-coupled-tetra-
propenyl phenol --- --- --- --- 0.5
Glycerol monooleate
or oleyl amide --- 0.1 0.1 --- 0.1
8% Hydrogenated
styrene-butadiene
in 100 neutral
mineral oil 6.5 6.5 6.0 8.5 8.5
Silicon antifoam
agent 80ppm 80ppm 80ppm 80ppm 80ppm
Oil Bal. 8al. Bal. Bal. Bal.
WO92/l8588 PCT/US~/01574
2o85~l~
-84-
Product of Lubricants (% by volume)
E~ample:_ 6 7 _8 9
A-1 0.35 0.25 0.25 0.32
B-1 6.0 5.0 6.3 5.5
C-1 0.81 0.84 0.77 l.o
D-6 --- 0.35 0.75 ---
Basic magnesium alkyl-
ated benzene sulfon-
ate (42~ oil, metal
ratio=15) 0.5 0.5 0.70 0.40
Basic magnesium alkyl-
ated benzene sulfonate
(42~ oil, metal ratio=3) 1.5 0.3 0.5 0.20
Copper 0,0'-isopropyl
methyl-amyl dithio-
phosphate 0.12 0.08 0.17 ---
Di(nonylphenyl) amine --- --- --- 0.50
Glycerol monooleate
or oleyl amide 0.2 0.1 0.1 0.1
8% hydrogenated
styrene-butadiene
copolymer in 100
neutral mineral oil 7.5 12.8 8.0 8.5
Silicon antifoam agents 80ppm 80ppm 80ppm 80ppm
Oil Bal. Bal. Bal. Bal.
The lubricating oil compositions of the present
invention exhibit a reduced tendency to deteriorate under
conditions of use and thereby reduce wear and the formation
of such undesirable deposits as varnish, sludge, carbona-
ceous materials and resinous materials which tend to adhere
to the various engine parts and reduce the efficiency of
the engines. ~ubricating oils also can be formulated in
accordance with this invention which result in improved
W092/18588 PCT/US~/01~74
2 ~
-85-
fuel economy when used in the crankcase of a passenger
automobile.
While the invention has been explained in rela-
tion 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 specification.
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.
