Note: Descriptions are shown in the official language in which they were submitted.
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Title: LUBRICANTS CONTAINING A BIlVIETALLIC DETERGENT SYSTEM
AND A METHOD OF REDUCING NOX EMISSIONS EMPLOYING
SAME
Field of the Invention
This invention relates generally to lubricating oil compositions and methods
of reducing exhaust emissions, reducing fuel consumption and cleaning
combustion
chambers of internal combustion engines.
Background of the Invention
The International Lubricant Standardization and Approval Cornmittee
(ILSAC) GF-2 specification requires passenger car motor oils to provide
enhanced
fuel economy in a modem low friction engine (ASTM Sequence VI-A). Previous
investigations have indicated that the choice of detergent system and friction
modifier used in a motor oil has a large impact on the fuel economy of the
lubricant.
Further studies indicate that detergent systems can affect tailpipe emissions.
Emissions from internal combustion engines are the primary cause of air
pollution in many cities and metropolitan areas. Such emissions include
uncombusted hydrocarbons, hydrocarbons formed in the combustion process,
sulfur
oxides, nitrogen oxides, and particulate matter. To attempt to reduce the
quantities
of these emissions, the federal and state governments have imposed emission
standards. These standards typically apply to new engines but have also been
... -,~~.
applied on a fleet-average basis to include previously manufactured engines in
the
emission reduction strategy. Over time, the standards have required lower and
lower
levels of emissions. New standards have been proposed that will further
significantly reduce the level of emissions that will be permitted. There
have,
accordingly, been many and diverse attempts to reduce the levels of emissions,
both
of newly manufactured engines and of previously manufactured engines, through
modification and add-on equipment programs.
A fundamentally sound way to reduce the level of vehicle emissions is by
reducing the amount of fuel consumed during operation.
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Hydrocarbon emissions are undesirable because of the role they play in air
pollution and also because they represent an energy loss from that available
in the
hydrocarbon fuel. Sulfur oxides not only contribute to local air pollution,
but also
are the principal cause of acid rain. Urban smog is caused primarily by
nitrogen
oxides (NOX). The black smoke of engine exhaust is typically caused by
particulate
emissions which add to the local air pollution and may cause health problems,
including cancer, known to be caused by the polycyclic aromatic compounds in
the
solvent organic fraction of the particulates.
The levels of emissions of an engine are interrelated by complex and poorly
understood mechanisms. It is known, for example, that adding anhydrous alcohol
to
gasoline reduces the hydrocarbon content of the fuel, and also tends to reduce
the
levels of emitted particulates and carbon monoxide. Increasing the temperature
of
the in-cylinder combustion usually results in more complete combustion of the
fuel,
reducing hydrocarbon emissions, but also results in increased nitrogen oxides
and
affects the polycyclic aromatic hydrocarbon constituents of the particulates.
Sulfur
oxide emissions can be reduced by using low sulfur fuels, but it is known that
reducing sulfur in the fuel normally changes the aromatics and boiling range
of the
fuel, both of which affect the amount of particulates emitted.
As noted above, at the same time, improved fuel economy is required.
U.S. Patent No. 4,326,972 (Chamberlin, III, April 27, 1982) relates to fuel
economy of internal combustion engines, especially gasoline engines, which is
improved by lubricating such engines with specific lubricant compositions in
which
the essential ingredients are a specific sulfurized composition and a basic
alkali
metal sulfonate. Additional ingredients may include at least one oil-
dispersible
detergent or dispersant, a viscosity improving agent, and a specific salt of a
phosphorus acid.
U.S. Patent No. 4,952,328 (Davis et al., August 28, 1990) describes a
lubricating oil formulation which is useful in internal combustion engines.
More
particularly, lubricating oil compositions for internal combustion engines are
described which comprise (A) at least about 60% by weight of oil of
lubricating
viscosity, (B) at least about 2.0% by weight of at least one carboxylic
derivative
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composition produced by reacting (B-1) at least one substituted succinic
acylating
agent with (B-2) from about 0.70 equivalent up to less than one equivalent,
per
equivalent of acylating. agent, of at least one amine compound characterized
by the
presence within its structure of at lest one HN< group, and wherein said
substituted
succinic acylating agent consists of substituent groups and succinic groups
wherein
the substituent groups are derived from a polyalkene, said polyalkene being
characterized by an M n value of about 1300 to about 5000 and an M w / M n
value
of about 1.5 to about 4.5, said acylating agents being characterized by the
presence
within their structure of an average of at least 1.3 succinic groups for each
equivalent
weight of substituent groups, and (C) from about 0.01 to about 2% by weight of
at
least one basic alkali metal salt of sulfonic or carboxylic acid. The oil
compositions
of the invention also may contain (D) at least one metal dihydrocarbyl
dithiophosphate and/or. (E) at least one carboxylic ester derivative
composition,
and/or (F) at least one partial fatty acid ester of a polyhydric alcohol,
and/or (G) at
least one neutral or basic alkaline earth metal salt of at least one acidic
organic
compound. In one embodiment, the oil compositions of the present invention
contain the above additives and other additives described in this
specification in
amounts sufficient to enable the oil to meet all the performance requirements
of API
Service Classification SG.
U.S. Patent No. 5,256,322 (Cohu, October 26, 1993) relates to a lubricating
oil for use in methanol fueled internal combustion engines, the lubricating
oil having
a total base number from 9.0 to about 14.0 and comprising:
a) a suitable base oil;
b) overbased sodium - sulfonate in an amount sufficient to provide a
base number from about 1.0 to about 2.0 in said lubricating oil; and
c) at least one metal sulfonate selected from the group consisting of
overbased calcium sulfonate, overbased magnesium sulfonate and mixtures
thereof
in an amount sufficient to provide a base number from about 8.0 to about 12.0
in
said lubricating oil.
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U.S. Patent No. 5,562,864 (Salomon et al., October 8, 1996) describes a
lubricating oil composition which comprises a major amount of an oil of
lubricating
viscosity and
(A) at least about 1% by weight of at least one carboxylic derivative
composition produced by reacting
(A-1) at least one substituted succinic acylating agent containing at
least about 50 carbon atoms in the substituent with
(A-2) from about 0.5 equivalent up to about 2 moles, per equivalent
of acylating agent (A-1), of at least one amine compound characterized by the
presence within its structure of at least one HN< group; and
(B) an amount of at least one alkali metal overbased salt of a carboxylic
acid or a mixture of a carboxylic acid and an organic sulfonic acid sufficient
to
provide at least about 0.002 equivalent of alkali metal per 100 grams of the
lubricating oil composition provided that when the alkali metal salt comprises
a
mixture of overbased al.kali metal salts of a hydrocarbyl-substituted
carboxylic acid
and a hydrocarbyl-substituted sulfonic acid, then the carboxylic acid
comprises more
than 50% of the acid equivalents of the mixture; and either
(C-1) at least one magnesium overbased salt of an acidic organic
compound provided that the lubricating composition is free of calcium
overbased
salts of acidic organic compounds; or
(C-2) at least one calcium overbased salt of an acidic organic
compound provided that the lubricating composition is free of magnesium
overbased
salts of acidic organic compounds.
U.S. Patent No. 5,726,133 (Blahey et al., March 10, 1998) is directed to a
low, ash natural gas engine oil which contains an additive package including a
particular combination of detergents and also containing other standard
additives
such as dispersants, antioxidants, antiwear agents, metal deactivators,
antifoamants
and pour point depressants and viscosity index improvers. The low ash natural
gas
engine oil exhibits reduced deposit formation and enhanced resistance to oil
oxidation and nitration.
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U.S. Patent No. 5,804,537 (Boffa et al., September 8, 1998) relates to a low
phosphorus passenger car motor oil containing an oil of lubricating viscosity
as the
major component and a tri-metal detergent mixture as a minor component,
wherein
the tri-metal detergent mixture comprises at least one calcium overbased metal
detergent, at least one magnesium overbased metal detergent and at least one
sodium
overbased metal detergent, wherein the .tri-metal detergent mixture is present
in the
oil composition in an amount such that the total TBN contributed to the oil
composition by the tri-metal detergent mixture is from about 2 to about 12,
and
wherein the calcium overbased detergent contributes from about 8 to about 42%
of
the total TBN contributed by the tri-metal detergent mixture, the magnesium
overbased detergent contributes from about 29 to about 60% of the total TBN
contributed by the tri-metal detergent mixture, and the sodium overbased
detergent
contributes from about 15 to about 64% of the total TBN contributed by the tri-
metal
detergent mixture.
Summary of the Invention
This invention is directed to a lubricating oil composition comprising a major
amount of an oil of lubricating viscosity and an additive system comprising
(A) from about 0.1 to about 5% by weight of a detergent composition
comprising at least two metal overbased compositions wherein said detergent
composition consists essentially of
(A-1) at least one alkali metal overbased detergent and
(A-2) at least one calcium overbased detergent,
wherein the ratio of total base number on a per 100 TBN and diluent-free basis
contributed by the alkali metal detergent to the total base number contributed
by the
calcium detergent ranges from about (99.5-20) to about (0.5-80);
(B) from about 1 to about 10% by weight of a succinimide dispersant;
and
(C) from about 0.1 to about 5% by weight of a metal dihydrocarbyl
dithiophosphate of the formula
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R1O
PSS M
R20 /
n
wherein R' and R 2 are each, independently, hydrocarbyl groups containing from
3 to
13 carbon atoms, M is a metal and n is an integer equal to the valence of M.
Also included are methods for reducing fuel consumption and exhaust
emissions of internal combustion engines and methods for cleaning the
combustion
chamber thereof.
Detailed Descriytion of the Invention
In the method of this invention, the combustion chamber of an internal
combustion engine is cleaned utilizing a NOX emission-reducing amount of a
lubricating oil composition comprising components (A), (B), and (C). Within
this
invention, the words "cleaned", "clean" or "cleaning" signify removal. of
particulate
solids from the combustion chamber in the case of a combustion chamber that
contains deposits and/or the prevention or reduction of particulate solids
build-up in
the combustion chamber. The lubricating compositions of this invention also
provide
a fuel-economy improving benefit.
As used herein, the terms hydrocarbyl substituent, hydrocarbyl group,
hydrocarbon group, and the like, are used to refer to a group having one or
more
carbon atoms directly attached to the remainder of a molecule and having a
hydrocarbon or predominantly hydrocarbon character. Examples include:
(1) purely hydrocarbon groups, that is, aliphatic (e.g., alkyl, alkenyl or
alkylene), alicyclic (e.g., cycloalkyl, cycloalkenyl) groups, aromatic
=groups, and
aromatic-, aliphatic-, and alicyclic-substituted aromatic groups, as well as
cyclic
groups wherein the ring is completed through another portion of the molecule;
(2) substituted hydrocarbon groups, that is, hydrocarbon groups containing non-
hydrocarbon groups which, in the context of this invention, do not alter the
predominantly hydrocarbon nature of the group (e.g., halo, hydroxy, alkoxy,
mercapto,
alkylmercapto, nitro, nitroso, and sulfoxy);
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(3) hetero substituted hydrocarbon groups, that is, hydrocarbon groups
containing substituents which, while having a predominantly hydrocarbon
character, in
the context of this invention, contain other than carbon in a ring or chain
otherwise
composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen. In
general,
no more than two, and in one embodiment no more than one, non-hydrocarbon
substituent is present for every ten carbon atoms in the hydrocarbon group.
In general, no more than about three nonhydrocarbon groups or heteroatoms
and preferably no more than one, will be present for each ten carbon atoms in
a
hydrocarbyl group. Typically, there will be no such groups or heteroatoms in a
hydrocarbyl group and it will, therefore, be purely hydrocarbyl.
The hydrocarbyl groups are preferably free from acetylenic unsaturation.
Ethylenic unsaturation, when present will generally be such that there is no
more than
one ethylenic linkage present for every ten carbon-to-carbon bonds. The
hydrocarbyl
groups are often completely saturated and therefore contain no ethylenic
unsaturation.
The term "lower" as used herein in conjunction with terms such as hydrocarbyl,
alkyl, alkenyl, alkoxy, and the like, is intended to describe such groups
which contain a
total of up to 7 carbon atoms.
As used herein, the expression "consisting essentially of' permits the
inclusion
of substances which do not materially affect the basic and novel
characteristics of the
composition under consideration. Accordingly, the expressions "consists
essentially
of' or "consisting essentially of' mean that the recited embodiment, feature,
component, etc. must be present and that other embodiments, features,
components,
etc., may be present provided the presence thereof does not materially affect
the
performance, character or effect of the recited embodiment, feature,
component, etc.
The presence of impurities or a small amount of a material that has no
material effect
on a composition is permitted. Also, the intentional inclusion of small
amounts of one
or more non-recited components that otherwise have no material effect on the
character or performance of a composition is still included within the
definition of
"consisting essentially of.
The expression "total base number" (TBN) refers to a measure of the amount
of acid (perchloric or hydrochloric) needed to neutralize the basicity of a
product or a
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composition, expressed as milligrams KOH/gram of sample. It is measured using
Test
Method ASTM D-2896.
Oil of Lubricating Viscosity
The lubricating compositions of this invention employ an oil of lubricating
viscosity, including natural or synthetic lubricating oils and mixtures
thereof. Mixtures
of mineral oil and synthetic oils, particularly polyalphaolefin oils and
polyester oils, are
often used.
Natural oils include animal oils and vegetable oils (e.g. castor oil, lard oil
and
other vegetable acid esters) as well as mineral lubricating oils such as
liquid petroleum
oils. and solvent-treated or acid treated mineral lubricating oils of the
paraffinic,
naphthenic or mixed paraffinic-naphthenic types. Hydrotreated or hydrocracked
oils
are included within the scope of useful oils of lubricating viscosity.
Oils of lubricating viscosity derived from coal or shale are also useful.
Synthetic lubricating oils include hydrocarbon oils and halosubstituted
hydrocarbon
oils such as polymerized and interpolymerized olefins, etc. and mixtures
thereof,
alkylbenzenes, polyphenyl, (e.g., biphenyls, terphenyls, alkylated
polyphenyls, etc.),
alkylated diphenyl ethers and alkylated diphenyl sulfides and their
derivatives, analogs
and homologues thereof and the like.
Alkylene oxide polymers and interpolymers and derivatives thereof, and those
where terminal hydroxyl groups have been modified by esterification,
etherification,
etc., constitute other classes of known synthetic lubricating oils that can be
used.
Another suitable class of synthetic lubricating oils that can be used
comprises
the esters of dicarboxylic acids and those made from C5 to C12 monocarboxylic
acids
and polyols or polyether polyols.
Other synthetic lubricating oils include liquid esters of phosphorus-
containing
acids, polymeric tetrahydrofurans, alkylated diphenyloxides and the like.
Unrefined, refined and rerefined oils, either natural or synthetic (as well as
mixtures of two or more of any of these) of the type disclosed hereinabove can
used in
the compositions of the present invention. Unrefined oils are those obtained
directly
from a natural or synthetic source without further purification treatment.
Refined oils
are similar to the unrefined oils except they have been further treated in one
or more
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purification steps to improve one or more properties. Rerefined oils are
obtained by
processes similar to those used to obtain refined oils applied to refined oils
which have
been already used in service. Such rerefined oils often are additionally
processed by
techniques directed to removal of spent additives and oil breakdown products.
Specific examples of the above-described oils of lubricating viscosity are
given
in Chamberlin III, U.S. 4,326,972 and European Patent Publication 107,282,
A basic, brief description of lubricant base oils appears in an article by
D.V.
Brock, "Lubrication Engineering", Volume 43, pages 184-5, March, 1987,
(A) The Detergent
At least two metal overbased detergent compositions are present as (A-1) and
(A-2). Component (A-1) is at least one alkali metal overbased detergent and (A-
2) is
at least one calcium overbased detergent. Overbased detergents used in this
invention are prepared by reacting a metal oxide or metal hydroxide with a
substrate
and carbon dioxide gas. The substrate is usually an acid, usually an acid
selected
from the group consisting of aliphatic substituted sulfonic acids, aliphatic
substituted
carboxylic acids and aliphatic substituted phenols. The alkali metals comprise
at
least one of lithium and sodium with sodium being preferred.
While an alkali metal overbased detergent and a calcium metal overbased
detergent are both present, they are usually present as separately overbased
compositions. That is, an alkali metal overbased composition and a calcium
overbased composition are separately prepared then incorporated into the
lubricating
oil composition. Two separate metal overbased compositions are used. However,
an acid simultaneously overbased with both sodium and calcium containing
reagents
is also useful in the instant invention.
The terminology "overbased", relates to metal salts (sulfonates, carboxylates
and phenates) wherein the amount of metal present exceeds the stoichiometric
amount. Such salts are said to have conversion levels in excess of 100% (i.e.,
they
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comprise more than 100% of the theoretical amount of metal needed.to convert
the
acid to its "normal", "neutral" salt). The expression "metal ratio", often
abbreviated
as MR, is used in the prior art and herein to designate the ratio of total
chemical
equivalents of metal in the overbased salt to chemical equivalents of the
metal in a
neutral salt according to known chemical reactivity and stoichiometry. Thus,
in a
normal or neutral salt, the metal ratio is one and in an overbased salt MR is
greater
than one. They are commonly referred to as overbased, hyperbased or superbased
salts and are usually salts of organic sulfur acids, carboxylic acids, or
phenols.
The alkali metal overbased detergent typically has a metal ratio of at least
10:1, preferably at least 13:1 and most preferably at least 16:1. The calcium
overbased detergent typically has a metal ratio of at least 10:1, preferably
at least
12:1 and more preferably at least 20:1.
Sulfonic acids include the mono- or poly-nuclear aromatic or cycloaliphatic
compounds which, when overbased, are called sulfonates. The oil-soluble
sulfonates
can be represented for the most part by the following formulae:
[R3)x -T - (SO3)y]zMf M
[R4(S03)g]hMi (II)
In the above formulae, M is a metal cation as described hereinabove; T is a
cyclic
nucleus such as, for example, benzene, naphthalene, anthracene, phenanthrene,
diphenylene oxide, thianthrene, phenothioxine, diphenylene sulfide,
phenothiazine,
diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, petroleum
naphthenes, decahydro-naphthalene, cyclopentane, etc.; R3 in Formula I is an
aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl,
etc.; x
is at least 1, and (R3)X + T contains a total of at least 15 carbon atoms, R4
in Formula
II is an aliphatic group containing at least about 9, preferably at least
about 12 and
often at least about 15 carbon atoms and M is a metal cation. Examples of type
of
the R4 radical are alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc.
Specific
examples of R4 are groups derived from petrolatum, saturated and unsaturated
paraffin wax, and polyolefins, including polymerized C2, C3, C4, C5, C6, etc.,
olefins
containing up to about 7000 carbon atoms in the polymer. The groups T, R3, and
R4
in the above formulae can also contain other inorganic or organic substituents
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addition to those enumerated above such as, for example, hydroxy, mercapto,
halogen, nitro, amino, nitroso, sulfide, disulfide, etc. In the above Formulae
I and II,
each of x, y, z and f and. g, i, and h is at least 1.
Specific examples of sulfonic acids useful in this invention are mahogany
sulfonic acids; bright stock sulfonic acids; sulfonic acids derived from
lubricating oil
fractions having a Saybolt viscosity from about 100 seconds at 100 F to about
200
seconds at 210 F; petrolatum sulfonic acids; mono- and poly-wax -substituted
sulfonic and polysulfonic acids of, e.g., benzene, naphthalene, phenol,
diphenyl
ether, naphthalene disulfide, diphenylamine, thiophene, alpha-
chloronaphthalene,
etc.; other substituted sulfonic acids such as alkyl benzene sulfonic acids
(where the
alkyl group has at least 8 carbons), cetylphenol mono-sulfide sulfonic acids,
dicetyl
thianthrene disulfonic acids, dilauryl beta naphthyl sulfonic acid, dicapryl
nitronaphthalene sulfonic acids, and alkaryl sulfonic acids such as dodecyl
benzene
"bottoms" sulfonic acids.
The bottoms acids are derived from benzene which has been alkylated with
propylene tetramers or isobutene trimers to introduce 1,2,3, or more branched-
chain
C12 substituents on the benzene ring. Dodecyl benzene bottoms, principally
mixtures of mono- and di-dodecyl benzenes, are available as by-products from
the
manufacture of household detergents. Similar products obtained from alkylation
bottoms formed during manufacture of linear alkyl sulfonates (LAS) are also
useful
in making the sulfonates used in this invention.
The production of sulfonates from detergent manufacture-by-products by
reaction with, e.g., SO3, is well known to those skilled in the art. See, for
example,
the articles "Sulfonation and Sulfation", Vol. .23, pp. 146 at seq. and
"Sulfonic
Acids", Vol. 23, pp. 194 et seq, both in Kirk-Othmer "Encyclopedia of Chemical
Technology", Fourth Edition, published by John Wiley & Sons, N.Y. (1997).
Also included are aliphatic sulfonic acids containing at least about 7 carbon
atoms, often at least about 12 carbon atoms in the aliphatic group, such as
paraffin
wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-
substituted
paraffin wax sulfonic acids, hexapropylene sulfonic acids, tetra-amylene
sulfonic
acids, polyisobutene sulfonic acids wherein the polyisobutene contains from 20
to
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7000 or more carbon atoms, chloro-substituted paraffin wax sulfonic acids,
nitroparaffin wax sulfonic acids, etc.; cycloaliphatic sulfonic acids such as
petroleum
naphthene sulfonic acids, cetyl cyclopentyl sulfonic acids, lauryl cyclohexyl
sulfonic
acids, bis-(di-isobutyl) cyclohexyl sulfonic acids, etc.
With respect to the sulfonic acids or salts thereof described herein and in
the
appended claims, it is intended that the term "petroleum sulfonic acids" or
"petroleum sulfonates" includes all sulfonic acids or the salts thereof
derived from
petroleum products. A particularly valuable group of petroleum sulfonic acids
are
the mahogany sulfonic acids (so called because of their reddish-brown color)
obtained as a by-product from the manufacture of petroleum white oils by a
sulfonic
acid process.
Other descriptions of overbased sulfonate salts and techniques for making
them can be found in the following U.S. Pat. Nos. 2,174,110; 2,174,506;
2,174,508;
2,193,824; 2,197,800; 2,202,781; 2,212,786; 2,213,360; 2,228,598; 2,223,676;
2,239,974; 2,263,312; 2,276,090; 2,276,297; 2,315,514; 2,319,121; 2,321,022;
2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027; 2,374,193;
2,383,319;'3,312,618; 3,471,403; 3,488,284; 3,595,790; and 3,798,012.
Carboxylic acids from which suitable alkali and calcium overbased
detergents for use in this invention can be made include aliphatic mono- and
polybasic carboxylic acids. The aliphatic carboxylic acids generally contain
at least
9 carbon atoms, often at least 15 carbon atoms and preferably at least 18
carbon
atoms. Usually, they have no more than 400 carbon atoms. Generally, if the
aliphatic carbon chain is branched, the acids are more oiI-soluble for any
given
carbon atoms content. The aliphatic carboxylic acids can be saturated or
unsaturated. Specific examples include linolenic acid, linoleic acid, behenic
acid,
isostearic acid, stearic acid, palmitoleic acid, lauric acid, oleic acid,
ricinoleic acid,
commercially available mixtures of two or more carboxylic acids, such as tall
oil
acids, rosin acids, and the like.
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Preferred aliphatic carboxylic acids are of the formula
RS - CHCOOH
CHZCOOH
wherein R5 is an aliphatic hydrocarbon-based group of at least 7 carbon atoms,
often
at least 12 carbon atoms and preferably, at least 15 carbon atoms, and not
more than
about 400 carbon atoms, and reactive equivalents thereof.
In another embodiment, the carboxylic acid is a hydrocarbyl-substituted
carboxyalkylene-linked phenol; dihydrocarbyl ester of alkylene dicarboxylic
acids,
the alkylene group being substituted with a hydroxy group and an additional
carboxylic acid group; alkylene-linked polyaromatic molecules, the aromatic
moieties whereof comprise at least one hydrocarbyl-substituted phenol and at
least
one carboxy phenol; and hydrocarbyl-substituted carboxyalkylene-linked
phenols.
These carboxylic compounds are prepared by reacting a phenolic reagent
with a carboxylic reagent of the general formula
R1CO(CR2R3)xCOOR6
wherein R1, R2 and R3 are independently H or a hydrocarbyl group, R6 is H or
an
alkyl group, and x is an integer ranging from 0 to about and reactive
equivalents
thereof. Compounds of this type are described in several U.S. Patents
including
numbers 5,281,346; 5,336,278 AND 5,356,546.
Unsaturated hydroxycarboxylic compounds prepared by reacting olefinic
compounds with this carboxylic compound are also useful. Compounds of this
type
are described in several U.S. Patents including US Patents 5,696,060;
5,696,067;
5,777,142 and 6,020,500.
Aromatic carboxylic acids are useful for preparing metal salts useful in the
compositions of this invention. These include aromatic carboxylic acids such
as
hydrocarbyl substituted benzoic, phthalic and salicylic acids.
Salicylic acids and other aromatic carboxylic acids are well known or can be
prepared according to procedures known in the art. Carboxylic acids of this
type and
processes for preparing their neutral and basic metal salts are well known and
disclosed, for example, in U.S. Patents 2,197,832; 2,197,835; 2,252,662;
2,252,664;
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2,714,092; 3,410,798; and 3,595,791.
In the context of this invention, phenols are considered organic acids. Thus,
overbased salts of phenols (generally known as phenates) are also useful in
making
(A) of this invention and are well known to those skilled in the art.
A commonly available class of phenates are those made from phenols of the
general fonnula
(OH)b
(R 5 (R 6
)a ~ )c
wherein R5 is as described hereinabove, R6 is a lower aliphatic of from 1 to 6
carbon
atoms, a is an integer of from 1 to 3, b is 1 or 2 and c is 0 or 1.
One particular class of phenates for use in this invention are the overbased
phenates made by sulfurizing a phenol as described hereinabove with a
sulfurizing
agent such as sulfur, a sulfur halide or sulfide or hydrosulfide salt.
Techniques for
making sulfurized phenates are described in U.S. Pat. Nos. 2,680,096;
3,036,971;
and 3,775,321-
Other phenates that are useful are those that are made from phenols that have
been linked through alkylene (e.g., methylene) bridges. These are made by
reacting
single or multi-ring phenols with aldehydes or ketones, typically in the
presence of
an acid or basic catalyst. Such linked phenates, as well as sulfurized
phenates, are
described in detail in U.S. Pat. No. 3,350,038,
Salicylic acids may be considered to be carboxylic acids or phenols.
Hydrocarbyl substituted salicylic acids are useful for preparing metal salts
useful in
the compositions of this invention.
Preferred overbased metal salts are the hydrocarbyl substituted sulfonic acid
salts.
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The alkali metal and calcium overbased salts are present in the compositions
used in this invention in relative amounts on a per 100 TBN and diluent free
basis
ranging from about (99.5 - 20) to about (0.5 - 80), preferably from about
(99.5-40)
to about (0.5-60), more preferably from about (99-45) to about (1-55) and most
preferably from about (98-50) to about (2-50).
The following specific illustrative examples describe how to make alkali
metal overbased detergents (A-1) and calcium overbased detergents (A-2). In
these
examples and in subsequent sets of example, as well as in this specification
and the
appended claims, all percentages, parts and ratios are by weight and
temperatures are
in degrees Celsius ( C) unless expressly stated otherwise.-Filtrations are
conducted
using a diatomaceous earth filter aid.
Example (A)-1
A flask is charged with 835 parts oil, 118 parts of polyisobutenyl (molecular
weight of 1000) substituted succinic anhydride having a saponification number
of
100, a solution of 5.9 parts calcium chloride dissolved in 37 parts water, and
118
parts of a mixture of alcohols comprising 61% isobutyl alcohol, 25.5% 2-methyl-
l-
butanol and 25.5% primary amyl alcohol. To the stirred contents are stirred
are
added 93 parts calcium hydroxide. An alkyl benzene sulfonic acid (1000 parts,
1.8
equivalents) is added at a rate which maintains the temperature below 80 C
while
stirring is continued. Volatiles are removed at 150 C. and the contents are
cooled to
about 50 C. At this temperature are added 127 parts of the aforedescribed
mixed
alcohols, 277 parts methyl alcohol and 88 parts of a 31% in oil solution of a
methylene coupled alkylated calcium phenate. The first of three calcium
hydroxide
additions, 171 parts per addition, is added and the contents are carbonated to
a direct
base number of 50-60. The fourth addition of 171 parts calcium hydroxide is
added
and the contents are carbonated to a direct base number of 45-55. Volatiles
are
removed at 150 C and the contents are filtered to give a product containing
41% oil,
300 total base number, metal ratio of 11.0, 40.7% calcium sulfate ash and 1.8%
sulfur.
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Example (A)-2
A sodium overbased sulfonic acid is prepared by adding 121 parts of the
polyisobutenyl succinic anhydride of Example (A)-1, 583 parts diluent oil, 84
parts
of a tetrapropene-substituted phenol and 417 parts (0.83 equivalents) of an
alkyl
benzene sulfonic acid to a reaction vessel. The contents are heated and
stirred to
49 C. and 102 parts of a 50% aqueous solution of sodium hydroxide are added,
allowing the temperature to rise to 82 C. The temperature is then increased to
86 C.
and held at this temperature for one hour. Four increments of 184 parts (4.61
equivalents) of sodium hydroxide beads are added and each increment is
followed
with carbon dioxide blowing at 150 C. until 103 parts carbon dioxide is
absorbed.
Diluent, oil, 35 parts, is added and the contents are filtered to give a
product
containing 31% oil, 448 total base number, metal ratio of 23.0, 19.45% sodium
and
1.2% sulfur.
Example (A)-3
A reactor is charged with 470 parts diluent oil, 92 parts of the
polyisobutenyl
succinic anhydride of Example (A)-1, 23 parts acetic acid, 24 parts water and
92
parts (2.5 equivalents) of calcium hydroxide. After stirring for 0.1 hour, 109
parts of
the mixture of alcohols of Example (A)-1 are added followed by 1000 parts (1.4
equivalents) of an alkyl benzene sulfonic acid. The sulfonic acid is added at
a rate to
maintain the temperature at 75 C. The contents are stripped of volatiles by
heating
to 150 C. At 49 C., then an additional 109 parts of the mixture of alcohols,
69 parts
of the alkylated calcium phenate of Example (A)-1 and 216 parts of methyl
alcohol.
Four increments of 137 parts each (3.7 equivalents) of calcium hydroxide are
added
and each increment is followed with carbon dioxide blowing at about 62 C. The
contents are stripped of volatiles at 146 C., 292 parts oil is added and the
contents
are filtered to give a product having 42% oil, 300 total base number, 12%
calcium,
metal ratio of 11.0 and 1.78% sulfur.
Example (A)-4
Add to a flask about 512 parts by weight of a mineral oil solution containing
about 0.5 equivalent of a substantially neutral magnesium salt of an alkylated
salicylic
acid wherein the alkyl group has an average of about 18 aliphatic carbon
atoms, about
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30 parts by weight of an oil mixture containing about 0.037 equivalent of an
alkylated
benzenesulfonic acid together with about 15 parts by weight (0.65 equivalents)
of
magnesium oxide and about 250 parts by weight of xylene. Heat to a temperature
of
about 60 C to 70 C. Increase the heat to about, 85 C and add approximately 60
parts
by weight of water. Hold the reaction mass at a reflux temperature of about 95
C to
100 C for about 1 1/2 hours and subsequently strip at a temperature of 155-160
C;
under a vacuum, and filter. The filtrate will comprise the basic carboxylic
magnesium
salt containing 200% of the stoichiometrically equivalent amount of magnesium.
Exampl.e (A)-5
Prepare a substantially neutral magnesium salt of an alkylated salicylic acid
wherein the alkyl groups have from 16 to 24 aliphatic carbon atoms by reacting
approximately stoichiometric amounts of magnesium chloride with a
substantially
neutral potassium salt of the alkylated salicylic acid. Charge a flask with a
reaction
mass comprising approximately 6580 parts by weight of a mineral oil solution
containing about 6.50 equivalents of the substantially neutral magnesium salt
of the
alkylated salicylic acid and about 388 parts by weight of an oil mixture
containing
about 0.48 equivalent of an alkylated benzenesulfonic acid together with
approximately 285 parts by weight (14 equivalents) of magnesium oxide and
approximately 3252 parts by weight of xylene. Heat to a temperature of about
55 C to
75 C. Increase the temperature to about 82 C and add approximately 780 parts
by
weight of water to the reaction and then heat to the reflux temperature. Hold
the
reaction mass at the reflux temperature of about 95-100 C for about one hour
and
subsequently strip at a temperature of about 170 C, under 50 torr and filter.
The
filtrate will comprise the basic carboxylic magnesium salts and have a
sulfated ash
content of 15.7% (sulfated ash) corresponding to 276% of the
stoichiometrically
equivalent amount.
Example (A)-6
A reaction mixture comprising 2900 grams (3 equivalents) of an oil solution of
the magnesium salt of polyisobutylene (average molecular weight--480)-
substituted
salicylic acids, 624 grams of mineral oil, 277 grams (1 equivalent) of a
commercial
mixture of tall oil acids, 1800 grams of xylene, 195 grams (9 equivalents) of
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magnesium oxide, and 480 grams of water are carbonated at the reflux
temperature
(about 95 C) for one hour. The carbonated mixture is then stripped by first
heating to
160 C with nitrogen blowing (3 cubic feet per hour) and thereafter heating to
165 C at
a pressure of 30 mm. (Hg). This stripped carbonated product is filtered, the
filtrate
being an oil solution of the desired basic magnesium salt. The salt is
characterized by
a metal ratio of 2.7.
The following example A-7 illustrates the preparation of phenol salts.
Example (A)-7
A phenol sulfiae is prepared by reacting sulfur dichloride with a
polyisobutenyl
phenol in which the polyisobutenyl substituent has an average of 23.8 carbon
atoms, in
the presence of sodium acetate (an acid acceptor used to avoid discoloration
of the
product). A mixture of 1755 parts of this phenol sulfide, 500 parts of mineral
oil, 335
parts of calcium hydroxide and 407 parts of methanol is heated to about 43-50
C and
carbon dioxide is bubbled through the mixture for about 7.5 hours. The mixture
is
then heated to drive off volatile matter, an additional 422.5 parts of oil are
added to
provide a 60% solution in oil. This solution contains 5.6% calcium and 1.59%
sulfur.
(B) The Succinimide Dispersant
Succinimide dispersants are the reaction product of a hydrocarbyl substituted
succinic acylating agent and an amine. The succinimide dispersants formed
depend
upon the type of the hydrocarbyl substituted succinic acylating agent
employed.
Two types of hydrocarbyl substituted succinic acylating agents are envisioned
as
Type I and Type II. Type I succinic acylating agent is of the formula
O O
LH R7 - I CH and R7 - CH - C
CH2- COH CH2 C~ O
~O 2 0
wherein R7 is a hydrocarbyl based substituent having from about 30, often from
about 40 up to about 500 carbon atoms and preferably from about 50 to about
300,
often to about 200 and frequently to about 100 carbon atoms. Type I
hydrocarbyl-
substituted succinic acylating agents are prepared by reacting one mole of an
olefin
18
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polymer or chlorinated analog thereof with one mole of an unsaturated
carboxylic
acid or derivative thereof such as fumaric aeid; maleic,acid. or maleic
anhydride.
Typically, the succinic acylating agents are derived from maleic acid, its
isomers,
anhydride and chloro and bromo derivatives. .
R7 is preferably an olefin, preferably alpha-olefin, polymer-derived group
formed by polymeiization of monomers such as ethylene, propylene, 1-butene,
isobutene, 1-pentene, 2-pentene, 1-hexene and 3-hexene. Such groups usually
contain
from about 30, frequently from about 40, up to about 500, often from about 50
up to
about 300, often up to about 200, more often up to about 100 carbon atoms. R7
may
also be derived from a high molecular weight substantially saturated petroleum
fraction. The hydrocarbon-substituted succinic acids and their derivatives
constitute
the most preferred class of carboxylic acids:
Included among the useful carboxylic reactants are aliphatic hydrocarbon
substituted cyclohexene dicarboxylic acids and anhydrides which may be
obtained
from the reaction of e.g., maleic anhydride with an olefin while the reaction
mass is
being treated with chlorine.
Patents describing useful aliphatic succinic acids, anhydrides, and reactive
equivalents thereof and methods for preparing them include, among numerous
others,
U.S. Pat. Nos. 3,163,603 (LeSuer), 3,215,707 (Rense); 3,219,666 (Norman et
al),
3,231,587 (Rense); 3,306,908 (LeSuer); 3,912,764 (Palmer); 4,110,349 (Cohen);
and
4,234,435 (Meinhardt et al); and U-K. 1,440,219 -
lt should be understood
that these patents also disclose derivatives, such as succinimides, etc. which
are not
reactive equivalents of succinic acids and anhydrides. These are 'not
contemplated as
being reactive equivalents of succinic acids or anhydrides.
As indicated in the above-mentioned patents, which are hereby incorporated by
reference for their disclosure of compounds useful as reactants for preparing
the
dispersants used in this invention, the succinic acids (or reactive
equivalents thereof)
include those derived by the reaction of a maleic or fumaric carboxylic acid
or reactive
equivalent thereof with a polyalkene or halogenated derivative thereof or a
suitable
olefin.
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The hydrocarbyl group is referred to hereinafter, for convenience, as the
"substituent" and is often an aliphatic group derived from a polyalkene. The
polyalkene is characterized by M n(number average molecular weight) of at
least
about 300, preferably at least about 500, more preferably at least about 1000,
up to
about 7,000. Advantageously, the polyalkene has M n in the range of about 400
to
about 7,000, more preferably about 800 to about 3000, more preferably about
800 to
about 2000. The polyalkene typically has an M W/ M n value of at least about
1.2, often
from about 1.5 up to about 5. M W is the conventional symbol representing the
weight
average molecular weight. The aliphatic hydrocarbyl group may also be derived
from
higher molecular weight olefins, cracked wax, and other sources readily
available in
the art.
There is a general preference for aliphatic, hydrocarbon polyalkenes free
from aromatic and cycloaliphatic groups. Within this general preference, there
is a
further preference for polyalkenes which are derived from the group consisting
of
homopolymers and interpolymers of terminal hydrocarbon olefins of 2 to about
16
carbon atoms, preferably from about 2 to about 6 carbon atoms, more preferably
2 to
4 carbon atoms. Interpolymers optionally containing up to about 40% of polymer
units derived from internal olefins of up to about 16 carbon atoms are also
within a
preferred group. Another preferred class of polyalkenes are the latter more
preferred
polyalkenes optionally containing up to about 25% of polymer units derived
from
internal olefins of up to about 6 carbon atoms.
Interpolymers are those in which two or more olefin monomers are
interpolymerized according to well-known conventional procedures to form
polyalkenes having units within their structure derived from each of said two
or more
olefin monomers. Thus, "interpolymer(s)", or "copolymers" as used herein is
inclusive
ofpolymers derived from two different monomers, terpolymers, tetrapolymers,
and the
like. As will be apparent to those of ordinary skill in the art, the
polyalkenes from
which the substituent groups are derived are often conventionally referred to
as
"polyolefin(s)".
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The olefin monomers. from which the polyalkenes are derived are
polymerizable olefin monomers characterized by the presence of one or more
ethylenically unsaturated groups (i.e., >C=C<); that is, they are monolefinic
monomers
such as ethylene, propylene, 1-butene, isobutene, and 1-octene or polyolefinic
monomers (usually diolefinic monomers) such as 1,3-butadiene and isoprene. For
purposes of this invention, when a particular polymerized olefin monomer can
be
classified as both a terminal olefin and an internal olefin, it will be deemed
to be a
terminal olefin. Thus, 1,3-pentadiene (i.e., piperylene) is deemed to be a
terminal
olefin for purposes of this invention.
In one preferred embodiment, the substituent is derived from polybutene,
that is, polymers of C4 olefins, including 1-butene, 2-butene and isobutylene.
Those
derived from isobutylene, i.e., polyisobutylenes, are especially preferred. In
another
preferred embodiment, the substituent is derived from polypropylene. In
another
preferred embodiment, it is derived from ethylene-alpha olefin polymers,
particularly
ethylene-propylene polymers and ethylene-alpha olefin-diene, preferably
ethylene-
propylene -diene polymers. In one embodiment the olefin is an ethylene-
propylene-
diene copolymer having M a ranging from about 900 to about 2500. An example of
such materials are the TRILENE polymers marketed by the Uniroyal Company,
Middlebury, CT, USA.
Polypropylene and polybutylene, particularly polyisobutylene, are preferred.
These typically have number average molecular weight ranging from about 300 to
about 7000, often to about 5,000, more often from about 700 to about 2,000.
One preferred source of substituent groups are polybutenes obtained by
polymerization of a C4 refinery stream having a butene content of 35 to 75
weight
percent and isobutylene content of 15 to 60 weight percent in the presence of
a
Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These
polybutenes contain predominantly (greater than 80% of total repeating units)
isobutylene repeating units of the configuration
CH3
-CHZ
CH3
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These polybutenes are typically monoolefinic, that is they contain but one
olefinic
bond per molecule.
The polybutene may be a polyolefin comprising a mixture of isomers
wherein from about 50 percent to about 65 percent are tri-substituted olefins
wherein
one substituent contains from 18 to about 500 aliphatic carbon atoms, often
from
about 30 to about 200 carbon atoms, more often from about 50 to about 100
carbon
atoms, and the other two substituents are lower alkyl.
When the polybutene is a tri-substituted olefin, it frequently comprises a
mixture of cis- and trans- 1-lower alkyl, 1-(aliphatic hydrocarbyl containing
from 30
to about 100 carbon atoms), 2-lower alkyl ethene and 1,1-di-lower alkyl,
2-(aliphatic hydrocarbyl containing from 30 to about 100 carbon atoms) ethene.
In one embodiment, the monoolefinic groups of the polybutenes are
predominantly vinylidene groups, i.e., groups of the formula
CH2 = (t
especially those of the formula
-CH2 -C= CH2
I
CH3
although the polybutenes may also comprise other olefinic configurations.
In one embodiment the polybutene is substantially monoolefinic, comprising
at least about 30 mole %, preferably at least about 50 mole % vinylidene
groups,
more often at least about 70 mole % vinylidene groups. Such materials and
methods
for preparing them are described in U.S. Patents 5,071,919; 5,137,978;
5,137,980;
5,286,823 and 5,408,018, and in published European patent application EP
646103-
Al. They are
commercially available, for example under the tradenames ULTRAVIS (BP
Chemicals) and GLISSOPAL" (BASF).
Specific characterization of polyolefin reactants used in this invention can
be
accomplished using techniques known to those skilled in the art. These include
general qualitative analysis by infrared and determinations of average
molecular
weight, e.g., M n and M W, etc. employing vapor phase osmometry (VPO) and gel
22
CA 02394289 2008-07-31
permeation chromatography (GPC). Structural details can be elucidated
employing
proton and carbon 13 (C13) nuclear magnetic resonance (NMR) techniques. NMR is
useful for determining substitution characteristics about olefinic bonds, and
provides
some details regarding the nature of the substituents. More specific details
regarding
substituents about olefinic bonds can be obtained by cleaving the substituents
from
the olefin by, for example, ozonolysis, then analyzing the cleaved products,
also by
NMR, GPC, VPO, and by infra-red analysis and other techniques known to the
skilled person.
Gel permeation chromatography (GPC) is a method which provides both
weight average and numberaverage molecular weights as well as the entire
molecular
weight distribution of the polymers. For purpose of this invention a series of
fractionated polymers of isobutene, polyisobutene, is used as the calibration
standard
in the GPC. The techniques for determining M n and M W values of polymers are
well
known and are described in numerous books and articles. For example, methods
for
the determination of M,, and molecular weight distribution of polymers is
described in
W.W. Yau, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid
Chromatography", J. Wiley & Sons, Inc., 1979.
The preparation of polyalkenes as described above which meet the various
criteria for M Il and M W/ M n is within the skill of the art and does not
comprise part of
the present invention. Techniques readily apparent to those skilled in the art
include
controlling polymerization temperatures, regulating the amount. and type of
polymerization initiator and/or catalyst, employing chain terminating groups
in the
polymerization procedure, and the like. Other conventional techniques such as
stripping (including vacuum stripping) a very light end and/or oxidatively or
mechanically degrading high molecular weight polyalkene to produce lower
molecular
weight polyalkenes can also be used.
Polyalkenes having the M r, and M W values discussed above are known in
the art and can be prepared according to conventional procedures. For example,
some of these polyalkenes are described and exemplified in U.S. Patent
4,234,435.
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Several such polyalkenes, especially polybutenes, are commercially
available.
The Type II hydrocarbyl substituted succinic acylating agent is characterized
as a polysuccinated hydrocarbyl substituted succinic acylating agent such that
more
than one mole of an unsaturated carboxylic acid or derivative is reacted with
one
mole of an olefin polymer or chlorinated analog thereof. U.S. Pat. No.
4,234,435
discloses procedures for the
preparation of polysuccinated hydrocarbyl-substituted succinie acylating
agents and
dispersants prepared therefrom.
In another embodiment, the Type II succinic acylating agent consists of
substituent groups and succinic groups wherein the substituent groups are
derived
from polyalkenes characterized by an M n value of at least about 1200 and an
M.W/Mn ratio of at least about 1.5, and wherein said acylating agents are
characterized by the presence within their structure of an average of at least
about
1.3 succinic groups for each equivalent weight of substituent groups.
This Type II succinic acylating agent can be characterized by the presence
within its structure of two groups or moieties. The first group or moiety is
referred
to hereinafter, for convenience, as the "substituent group(s)" and is derived
from a
polyalkene. The polyalkene from which the substituted groups are derived is
characterized by an M n(number average molecular weight) value of at least
1200
and more generally from about 1500 to about 5000, and an M W/ M n~value of at
least
about 1.5 and more generally from about 1.5 to about 6. The second group or
moiety
is referred to herein as the "succinic group(s)". The succinic groups are
those groups
characterized by the structure
0 0
X--C-C--C-C -x (VIII)
1 1
wherein X and X' are the same or different provided at least one of X and X'
is such
that the second substituted succinic acylating agent can function as
carboxylic
acylating agents. That is; at least one of X and X' must be such that the
substituted
acylating agent can form amides or amine salts with, and otherwise function as
a
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conventional carboxylic acid acylating agents. Transesterification and
transamidation reactions are considered, for purposed of this invention, as
conventional acylating reactions.
Thus, X and/or X' is usually -OH, -0-hydrocarbyl, -O- M+ where. M+
represents one equivalent of a metal, ammonium or amine cation, -NH2, -Cl, -
Br,
and together, X and X' can be -0- so as to form the anhydride. The specific
identity
of any X or X' group which is not one of the above is not critical so long as
its
presence does not prevent the remaining group from entering into acylation
reactions. Preferably, however, X and X' are each such that both carboxyl
functions
of the succinic group (i.e., both -C-(O)X and -C(O)X' can enter into acylation
reactions.
One of the unsatisfied valences in the grouping
-C-C -
of Formula VIII forms a carbon-to-carbon bond with a carbon atom in the
substituent
group. While other such unsatisfied valence may be satisfied by a similar bond
with
the same or different substituent group, all but the said one such valence are
usually
satisfied by hydrogen; i.e., -H.
The Type II succinic acylating agents are characterized by the presence
within their structure of an average of at least about 1.3 succinic groups
(that is,
groups corresponding to Formula VIII) for each equivalent weight of
substituent
groups. For purposes of this invention, the number of equivalent weight of
substituent groups is deemed to be the number corresponding to the quotient
obtained by dividing the M n value of the polyalkene from which the
substituent is
derived into the total weight of the substituent groups present in the
substituted
succinic acylating agents. Thus, if the Type II succinic acylating agent is
characterized by a total weight of substituent group of 40,000 and the M n
value for
the polyalkene from which the substituent groups are derived is 2000, then
that
second substituted succinic acylating agent is characterized by a total of 20
(40,000/2000=20) equivalent weights of substituent groups. Therefore, that
CA 02394289 2002-06-13
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particular second succinic acylating agent must also be characterized by the
presence
within its structure of at least 26 succinic groups to meet one of the
requirements of
the novel succinic acylating agents of this invention.
Polyalkenes having the M n and M, values discussed above are known in
the art and can be prepared according to conventional procedures. Several such
polyalkenes, especially polybutenes, are commercially available.
In one preferred erribodiment, the succinic groups will normally correspond
to the formula
- CH - C(O)R10
I (IX)
CH2 - C(O)R"
wherein R10 and R11 are each independently selected from the group consisting
of
-OH, -Cl, -0-lower alkyl, and when taken together, R10 and R" are -0-. In the
latter case, the succinic group is a succinic anhydride group. All the
succinic groups
in a particular Type II succinic acylating agent need not be the same, but
they can be
the same. Preferably, the succinic groups will correspond to
O
-CH-C/ OH - CH-C~ '__1 (X)
~ 1 O
CH2 C - OH CH2 ~
O \O
(A) (B)
and mixtures of (X(A)) and (X(B)). Providing Type II succinic acylating agents
wherein the succinic groups are the same or different is within the ordinary
skill of
the art and can be accomplished through conventional procedures such as
treating
the substituted succinic acylating agents themselves (for example, hydrolyzing
the
anhydride to the free acid or converting the free acid to an acid chloride
with thionyl
chloride) and/or selecting the appropriate maleic or fumaric reactants.
As previously mentioned, the minimum number of succinic groups for each
equivalent weight of substituent group is 1.3. The maximum number generally
will
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not exceed 6. Preferably the minimum will be 1.4; usually 1.4 to about 6
succinic
groups for each equivalent weight of substituent group. A range based on this
minimum is at least 1.5 to about 3.5, and more generally about 1.5 to about
2.5
succinic groups per equivalent weight of substituent groups.
From the foregoing, it is clear that the Type II succinic acylating agents can
be represented by the symbol R8(R9)d wherein R8 represents one equivalent
weight
of substituent group, R9 represents one succinic group corresponding to
Formula
(VIII), Formula (IX), or Formula (X), as discussed above, and d is a number
equal to
or greater than 1.3. The more preferred embodiments of the invention could be
similarly represented by, for example, letting R8 and R9 represent more
preferred
substituent groups and succinic groups, respectively, as discussed elsewhere
herein
and by letting the value of d vary as discussed above.
In addition to preferred substituted succinic groups where the preference
depends on the number and identity of succinic groups for each equivalent
weight of
substituent groups, still further prefererices are based on the identity and
characterization of the polyalkenes from which the substituent groups are
derived.
With respect to the value of M n for example, a minimum of about 1200,
often at least about 1300 or about 1500 and a maximum of about 5000 are
preferred,
more preferably from about 1500 to about 2800, and most preferably from about
1500 to about 2400. With polybutenes, an especially preferred minimum value
for
M n is about 1700 and an especially preferred range of M n values is from
about
1700 to about 2400.
A minimum M,,/ M n value of about 1.8 is preferred with a range of about
1.8 up to about 5.0 also being preferred. More preferred is about 2.0 to about
4.5,
and especially preferred is about 2.5 with a range of from about 2.5 to about
4.0 also
being especially preferred.
These preferred characteristics of succinic acylating agents are both
independent and dependent. They are independent in the sense that, for
example, a
preference for a minimum of 1.4 or 1.5 succinic groups per equivalent weight
of
substituent groups is not tied to a more preferred value of M n or M W/ M n.
They are
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dependent in the sense that, for example, when a preference for a minimum of
1.4 to
1.5 succinic groups is combined with more preferred values of M n and/or M W/
M n,
the combination of preferences does, in fact, describe still further more
preferred
embodiments of this component. Thus, the various parameters are intended to
stand
alone with respect to the particular parameter being discussed but can also be
combined with other parameters to identify further preferences. This same
concept
is intended to apply throughout the specification with respect to the
description of
preferred values, ranges, ratios, reactants, and the like unless a contrary
intent is
clearly demonstrated or apparent.
The polyalkenes from which the substituent groups of the Type II acylating
agents are derived are homopolymers and interpolymers of polymerizable olefin
monomers. These are essentially the same as those described hereinabove with
the
further limitation of M H, and M W/ M n particular to Type II succinic
acylating
agents.
In preparing the Type II succinic acylating agent, one or more of the above-
described polyalkenes is reacted with one or more acidic reactants selected
from the
group consisting of maleic or fumaric reactants of the general formula
X(O)C-CH=CH-C(O)X' (XI)
wherein X and X' are as defined hereinbefore. Preferably the maleic and
fumaric
reactants will be one or more compounds corresponding to the formula
R10 C(O)-CH=CH-C(O)R11 (XII)
wherein R10 and R11 are as previously defined herein. Ordinarily, the maleic
or
fumaric reactants will be maleic acid, fumaric acid, maleic anhydride, or a
mixture
of two or more of these. Especially preferred reactants are the maleic
reactants with
maleic anhydride preferred.
The one or more polyalkenes and one or more maleic or fumaric reactants
can be reacted according to any of several known procedures in order to
produce the
Type I or Type II acylating agents of the present invention.
In preparing the succinimide dispersant, the hydrocarbyl substituted succinic
acylating agent is reacted with (a) ammonia or (b) an amine having at least
one -NH2
group.
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Ordinarily substituted succinic anhydride is reacted directly with ammonia or
the amine although in some circumstances it may be desirable first to convert
the
anhydride to the acid.
Amine Reactants
Suitable amine reactants, as defined herein, include monoamines and
polyamines. The amine reactants must contain at least one -NH2 group. Thus,
only
amines having at least one primary amino group are used in preparing the
succinimide
dispersants of this invention. Polyamines may be used and are preferred,
provided
that they contain at least one primary amine group. The monoamines generally
contain
from 1 to about 24 carbon atoms, preferably 1 to about 12, and more preferably
1 to
about 6. Examples of monoamines useful in the present invention include
primary
amines, for example methylamine, ethylamine, propylamine, butylamine,
octylamine,
and dodecylamine.
In another embodiment, the monoamine may be a hydroxyhydrocarbylamine,
usually hydroxyalkylamines. Typically, hydroxyalkylamines are primary
alkanolamines. Alkanol amines that can react to form amide can be represented,
for
example, by the formula:
HzN-R'-OH
wherein R' is a divalent hydrocarbyl group of about two to about 18 carbon
atoms,
preferably two to about four. The group -R'-OH in such formulae represents the
hydroxyhydrocarbyl 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.
Examples of these alkanolamines include monoethanolamine, propanolamine,
etc.
The hydroxyhydrocarbylamines can also be ether N-(hydroxyhydrocarbyl)
amines. These are hydroxy poly(hydrocarbyloxy) analogs of the above-described
hydroxy amines (these analogs also include hydroxyl-substituted oxyalkylene
analogs).
Such N-(hydroxyhydrocarbyl) amines can be conveniently prepared, for example,
by
reaction of epoxides with aforedescribed amines and can be represented by the
formula:
H2N-(R'O)X-H
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wherein x is a number from about 2 to about 15 and R' is as described above.
Other useful amines include ether amines of the general formula
R6OR'NH2
wherein R6 is a hydrocarbyl group, preferably an aliphatic group, more
preferably an
alkyl group, containing from 1 to about 24 carbon atoms and Rl is a divalent
hydrocarbyl group, preferably an alkylene group, containing from two to about
18
carbon atoms, more preferably two to about 4 carbon atoms. Especially
preferred ether
amines are those available under the name SURFAM, produced and marketed by Sea
Land Chemical Co., Westlake, Ohio.
The amine is preferably a polyamine. The polyamine may be aliphatic,
cycloaliphatic, heterocyclic or aromatic. Examples of the polyamines include
alkylene
polyamines, hydroxy containing polyamines, arylpolyamines, and heterocyclic
polyamines.
Alkylene polyamines are represented by the formula
HN4Alkylene-N+,,RS
R5 R5
wherein n has an average value between about 1 and about 10, preferably 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. R5 is independently hydrogen or an aliphatic or hydroxy-substituted
aliphatic group
of up to about 30 carbon atoms, preferably H or lower alkyl, most preferably
H. At
least one amino group must be a primary amino group.
Alkylene polyamines include methylene polyamines, ethylene polyamines,
butylene polyamines, propylene polyamines, pentylene polyamines, etc. Higher
homologs and related heterocyclic amines such as N-amino alkyl-substituted
piperazines are also included. Specific examples of such polyamines are
ethylene
diamine, diethylene triamine, triethylene tetramine, tris-(2-aminoethyl)amine,
propylene diamine, trimethylene diamine, tripropylene tetramine, tetraethylene
pentamine, hexaethylene heptamine, pentaethylenehexamine, aminoethyl
piperazine,
dimethyl aminopropylamine, etc.
CA 02394289 2008-07-31
Higher homologs obtained by condensing two or more of the above-noted
alkylene amines are similarly useful as are mixtures of two or more of the
aforedescribed polyamines.
Ethylene polyamines, such as some of those mentioned above, are preferred.
They.are described in detail under the heading "Diamines and Higher Amines" in
Kirk
Othmer's "Encyclopedia of Chemical Technology", 4th Edition, Vol. 8, pages 74-
108,
John Wiley and Sons, New York (1993) and in Meinhardt, et al, U.S. 4,234,435.
Such polyamines are 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 polyanune bottoms can be
characterized as
having less than two, usually less than 1% (by weight) material boiling below
about
200 C. A typical sample of such ethylene polyarnine bottoms obtained from the
Dow
Chemical Company of Freeport, Texas, designated "E-100" has a specific gravity
at
15.6 C of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40
C of 121
centistokes. Gas chromatography analysis of such a sample contains about 0.93%
"Light Ends" (most probably diethylenetriamine), 0.72% triethylenetetramine,
21.74%
tetraethylenepentamine and 76.61% pentaethylene hexamine and higher (by
weight).
These alkylene polyarnine bottoms include cyclic condensation products such as
piperazine and higher analogs of diethylenetriamine, triethylenetetramine and
the like.
Another useful polyamine is a condensation product obtained by reaction of at
least one hydroxy compound with at least one polyamine reactant containing at
least
one primary or secondary amino group. The hydroxy compounds are preferably
polyhydric alcohols and amines. Preferably the hydroxy compounds are
polyhydric
amines. Polyhydric amines include any of the above-described monoamines
reacted
with an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide,
etc.)
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-having two to about 20 carbon atoms, preferably two to about four. Examples
of
polyhydric amines include tris-(hydroxymethyl)amino methane and 2-amino-2-
methyl-
1,3-propanediol.
Polyamine reactants, which react with the polyhydric alcohol or amine to form
the condensation products or condensed amines, are described above. Preferred
polyamine reactants include triethylenetetramine (TETA), tetraethylenepentan-
iine
(TEPA), pentaethylenehexarnine (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 60 C to about
265 C
in the presence of an acid catalyst.
The anZine condensates and methods of making the same are described in
Steckel (US Patent 5,053,152) which discloses
the condensates and methods of making amine condensates.
In another embodiment, the polyamines are hydroxy-containing polyamines.
Hydroxy-containing polyamine analogs of hydroxy monoamines, particularly
alkoxylated alkylenepolyamines 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-alkanolamine reaction products can
also be
used such as the products made by reacting the aforedescribed primary,
secondary or
tertiary alkanolamines with ethylene, propylene 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. As noted hereinabove, such hydroxy-
containing
polyamines must have at least one -NH2 group.
Specific examples of alkoxylated alkylenepolyamines include N-(2-
hydroxyethyl) ethylenediamine, N,N-di-(2-hydroxyethyl)-ethylenediarnine, mono-
(hydroxypropyl)-substituted tetraethylenepentarnine, N-(3-hydroxybutyl)-
tetramethylene diamine, etc. Higher homologs obtained by condensation of the
above
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
32
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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 usetul.
In another embodiment, the polydmine may be a heterocyclic polyamine. The
heterocyclic polyamines include aminoalkyl substituted heterocycles, including
aminoalkyl substituted aziridines, azetidines, azolidines, azepines, azocines,
azonines,
azecines, tetra- and dihydropyridines, pyrroles, indoles, piperidines,
imidazoles, di- and
tetrahydroimidazoles, piperazines, isoindoles, purines; N-
aminoalkylthiomorpholines,
N-aminoalkylrnorpholines, N-aminoal.kylpiperazines, N,N'-bisaminoalkyl
piperazines,
and tetra-, di- and perhydro derivatives of each of the above and mixtures of
two or
more of these heterocyclic amines. Preferred heterocyclic amines are the
aminoalkyl
substituted saturated 5- and 6-membered heterocyclic amines containing only
nitrogen,
or nitrogen with oxygen andlor sulfur in the hetero ring, especially the
piperidines,
piperazines, thiomorpholines, morpholines, pyrrolidines, and the like.
Aminoalkylsubstituted piperidines, aminoalkylsubstituted piperazines,
aminoalkylsubstituted morpholines, . and aminoallcyl-substituted pyrrolidines,
are
especially preferred. Usually the aminoall.yl substituents are substituted on
a nitrogen
atom forming part of the hetero ring. Specific examples of such heterocyclic
amines
include N-aminopropylmorpholine, N-amino-ethylpiperazine, and N,N'
diaminoethyl-
piperazine. Hydroxy alkyl substituted heterocyclic polyamines are also useful.
In another embodiment, the amine is a polyalkene-substituted amine. These
polyalkene-substituted amines are well known to those skilled in the art. They
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.
Typically, polyalkene-substituted amines are prepared by reacting halogenated-
, preferably chlorinated-, olefins and olefin polymers (polyalkenes) with
amines
(mono- or polyamines). The amines may be any of the amines described above.
Examples of these compounds include poly(propylene)amine; polybutene amine;
N-poly(butene) ethylenediamine; N-poly(propylene)trimethylenediamine;
N-poly(butene)diethylenetriamine; N',N'-poly(butene)tetraethylenepentamine;
and the
like.
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The polyalkene substituted amine is characterized as containing from at least
about 8 carbon atoms, preferably at least abotit 30, more preferably at least
about 35 up
to about 300 carbon atoms, preferably 200, more preferably 100. In one
embodiment,
the polyalkene substituted amine is characterized by an n (number average
molecular
weight) yalue of at least about 500. Generally, the polyalkene substituted
amine is
characterized by an n value of about 500 -to about 5000, preferably about 800
to about
2500. In another embodiment n varies between about 500 to about 1200 or 1300.
The polyalkenes from which the polyalkene substituted amines are derived
include homopolymers and interpolymers, preferably homopolymers, 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, such 1,3-butadiene and isoprene. 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.
The number of equivalents of acylating agent depends on the total number of
carboxylic functions present. In the determination of the number of
equivalents of
acylating agent, carboxyl functions which are not capable of reacting as a
carboxylic
acid acylating agent are excluded. In general, there is one equivalent of
acylating agent
for each carboxy group in the acylating agents. Conventional methods for
determining
the number of carboxyl functions (e.g., acid number, saponification number,
etc.) are
available and are well known to those skilled in the art.
An equivalent weight of monoamine is the molecular weight of the amine. The
equivalent weight of mixtures of monoamines can be determined by dividing the
atomic weight of nitrogen (14) by the %N contained in the mixture and
multiplying by
100. Equivalent weight of polyamines can be determined similarly.
Amounts of polyamines are often referred to in equivalents. One equivalent of
a polyamino compound or derivative thereof is its formula weight divided by
the
average number of nitrogen atoms therein which contain a basic -NH2 group.
Thus
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ethylene diamine contains 2 equivalents; N,N-dimethyl-propanediamine contains
one
equivalent.
In another embodiment, the polyamine may be a hydroxyamine provided that
the polyamine contains at least, one condensable -NH2 group. Typically, the
hydroxyamines are primary alkanol amines. Such amines can be represented by
mono-
and poly-N-hydroxyalkyl substituted alkylene polyamines wherein the alkylene
polyamines are as described hereinabove; especially those that contain two to
three
carbon atoms in the alkylene radicals and the alkylene polyamine contains up
to seven
amino groups.
The succinimide dispersants are frequently basic, that, is they display a base
number. The base number is usually expressed as total base number as described
hereinabove. The base number of the succinimide dispersant arises from the
presence of the amine reactant, usually the amount of unreacted amino moiety
present in the dispersant. These base numbers can vary over a wide range, but
values ranging from about 5 to about 200, on a diluent-free basis, often from
about
15 to about 100, frequently from about 30 to about 60. In one preferred
embodiment, the dispersant has TBN of at least about 40.
Specific examples of the process by which the succinic dispersants may be
prepared follow:
Example (B)-1
A polyisobutenyl succinic anhydride is prepared by the reaction of a
chlorinated polyisobutylene with maleic anhydride at 200 C. The polyisobutenyl
radical has average molecular weight of 850 and the resulting alkenyl succinic
anhydride is found to have an acid number of 113 (corresponding to an
equivalent
weight of 500). To a mixture of 500 grams (1 equivalent) of this
polyisobutenyl
succinic anhydride and 160 grams of toluene are added at room temperature 35
grams (1 equivalent) of diethylene triamine. The addition is made portionwise
over
0.25 hour with an initial exothermic reaction causing the temperature to rise
to 50 C.
The mixture is heated and a water-toluene azeotrope distilled from the
mixture.
When water formation essentially ceases, the mixture is heated to 150 C. at
reduced
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pressure to remove the toluene. The residue is diluted with 350 grams of
mineral
oil. The solution has %N = 1.6.
Example (B)-2
The procedures of Example (B)-1 is repeated using 31 grams (1 equivalent) of
ethylene diamine as the amine reactant. The product has %N = 1.4.
Example (B)-3
The procedure of Example (B)-1 s repeated using 55.5 grams (1.5
equivalents) of an ethylene amine mixture having a composition corresponding
to
that of triethylene tetramine. The resulting product has %N = 1.9.
10. Example (B)-4
The procedure of Example (B)-1 is repeated using 55.0 grams (1.5
equivalents) of triethylene tetramine as the amine.reactant. The resulting
product
. has %N = 2.2.
Example (B)-5
To a mixture of 140 grams of toluene and 400 grams (0.78 equivalent) of a
polyisobutenyl succinic anhydride (having an acid number of 109 and prepared
from
maleic anhydride and the chlorinated polyisobutylene of Example (B)-1) there
is
added at room temperature 63.6 grams (1.55 equivalents) of an ethylene amine
mixture having an average composition corresponding to that of tetraethylene
pentamine (Polyamine H, Union Carbide). The mixture is heated to distill water-
toluene azeotrope and then to 150 C. at reduced pressure to remove the
remaining
toluene. The residual polyamide has %N = 4.7%.
Example (B)-6
The procedure of Example (B)-1 was repeated using 46 grams (1.5
equivalents) of ethylene diamine as the amine reactant. The product has %N =
1.5.
Example (B)-7
A polyisobutenyl succinic anhydride having an acid number of 105 and an
equivalent weight of 540 is prepared by the reaction of a chlorinated
polyisobutylene
(having an average molecular weight of 1,050 and a chlorine content of 4.3%)
and
maleic anhydride. To a mixture of 300 parts by weight of the polyisobutenyl
succinic anhydride and 160 parts of weight of mineral oil there are added at
65-
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95 C. an equivalent amount (25 parts of weight) of Polyamine H. This mixture
is
heated to 150 C. to remove water formed in the reaction then is N2 blown at
this
temperature to remove remaining water. The residue is diluted with 79 parts
mineral
oil. The oil has %N = 1.6%.
Example (B)-8
A mixture of 2,112 grams (3.9 equivalent) of the polyisobutenyl succinic
anhydride of Example (B)-7, 136 grams (3.9 equivalents) of diethylene
triamine, and
1,060 grams of mineral oil s heated at 140-150 C. for one hour. Nitrogen is
bubbled
through the mixture at this temperature for four more hours to aid in the
removal of
water. The residue is diluted with 420 grams of mineral oil. The oil solution
has
%N = 1:3.
Example (B)-9
To a solution of 1,000 grams (1.87 equivalents) of the polyisobutenyl
succinic anhydride of Example (B)-7, in 500 grams of mineral oil is added, at
85-
95 C. 70 grams (1.87 equivalents) of tetraethylene pentamine. The mixture is
heated
at 150-165 C. for four hours, blowing with nitrogen to aid in the removal of
water.
The residue is diluted with 200 grams of mineral oil. The oil solution has %N
= 1.4.
Example (B)-10
A mixture of 510 parts (0.28 mole) of polyisobutene ( M n= 1845; M, _
5325) and 59 parts (0.59 mole) of maleic anhydride is heated to 110 C. This
mixture is heated to 190 C. for seven hours during which 43 parts (0.6 mole)
of
gaseous chlorine are added beneath the surface. At 190 -192 C. an additional
11
parts (0.16 mole) of chlorine are added over 3.5 hours. The reaction mixture
is
stripped by heating at 190 -193 C. with nitrogen blowing for 10 hours. The
residue
is a polyisobutene-substituted Type II succinic acylating agent having a
saponification number of 87 (ASTM D-94).
A mixture is prepared by the addition, at 138 C, of 10.2 parts (0.25
equivalent)of a commercial mixture of ethylene polyamines having about 3 to
about
10 nitrogen atoms per -molecule to 113 parts of mineral oil and 161 parts
(0.25
equivalent) of the substituted succinic acylating agent prepared above. The
reaction
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mixture is heated to 150 C. in 2 hours and stripped by blowing with nitrogen.
The
reaction mixture is filtered..
Example (B)-11
A mixture of 1000 parts (0.495 mole) of polyisobutene ( M 2020; M W=
6049) and 115 parts (1.17 moles) of maleic anhydride is heated to 110 C. This
mixture is heated to 184 C. in 6 hours during which 85 parts (1.2 moles) of
gaseous
chlorine is added beneath the surface. At 184 -189 C. an additional 59 parts
(0.83
mole) of chlorine is added over 4 hours. The reaction mixture is stripped by
heating
at 186 -190 C. with nitrogen blowing for 26 hours. The residue is a
polyisobutene-
substituted Type II succinic acylating agent having a saponification
equivalent
number of 87.
A mixture is prepared by the addition, at 140 -145 C, of 57 parts (1.38
equivalents) of a commercial mixture of ethylene polyamines having from about
3 to
10 nitrogen atoms per molecule to 1067 parts of mineral oil and 893 parts
(1.38
equivalents) of the above-prepared succinic acylating agent. The reaction
mixture is
heated to 155 C. in 3 hours and stripped by blowing with nitrogen. The
reaction
mixture is filtered.
Example (B)-12
A reactor is charged with 1000 parts (0.5 mole) of polyisobutene ( M n=
2000, M, = 7000). At 135 C. 106 parts (1.08 moles) of maleic anhydride are
added, the temperature is increased to 165 C. and gaseous chlorine, 90 parts
(1.27
moles) is added over. a six hour period. During the chlorine addition, the
temperature increases to 190 C. This is a Type II succinic anhydride
having'acid
number = 95.
To 1000 parts of the above product are added 1050 parts diluent oil. The
materials are heated to 110 C. at which time 69.4 parts (1.83 equivalents) of
polyamines are added while the temperature increases to 132 C. The temperature
is
increased to 150 C. while blowing with N2. Oil, 145 parts, is added and the
contents
are filtered. The filtrate contains 53% oil, %N = 1.1 and has TBN =21.
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Example (B)-13
A solution is prepared from 1000 parts of the succinic anhydride of Example
(B)-12 and 1181 parts mineral oil. The solution is heated to 110 C and 59.7
parts of
an ethylene amine mixture (25% diethylene triamine and the balance
polyethylene
amine bottoms, Union Carbide) are added over 2 hours while the temperature is
allowed to rise exothermically to 127 C. The temperature is increased to 152 C
and
is maintained for 1 hour with N2 blowing then the materials are filtered. The
filtrate
is adjusted with additional mineral oil to 55% oil, base no =15 and %N =0.9.
Example (B)-14
A reactor is charged with 1000 parts of polybutene having a number average
molecular weight determined by vapor phase osmometry of about 950 and which
consists primarily of isobutene units, followed by the addition of 108 parts
of maleic
anhydride. The mixture is heated to 110 C followed by the sub-surface addition
of
100 parts Cl2 over 6.5 hours at a temperature ranging from 110 to 188 C. The
exothermic reaction is controlled as not to exceed 188 C. The batch is blown
with
nitrogen then stored.
A succinimide dispersant is prepared by reacting 1000 parts of the substituted
succinic anhydride of this example with 85 parts of a commercial ethylene
polyamine
mixture having an average nitrogen content of about 34.5% in 820 parts mineral
oil
diluent under conditions described in LeSuer, U.S. 3,172,892. The product
contains
1.5% N and has TBN = 30.
For environmental reasons, it has now become desirable to eliminate or
reduce the level of chlorine in lubricating oil compositions. One method of
eliminating chlorine contained in lubricant and fuel additives is avoid
chlorine in the
manufacturing process. Another approach is to treat compositions to remove
chlorine. One procedure for treating chlorine-containing compositions to
reduce the
level of chlorine therein is described in European patent publication EP
665,242.
The procedure described therein comprises introducing a source of iodine or
bromine into the composition, contacting the components of the resulting
mixture
for a sufficient amount of time to reduce the chlorine content without
substantially
incorporating iodine or bromine. This procedure successfully reduces chlorine
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content, but, in some instances, it is desirable to further reduce the amount
of
chlorine in compositions which are to be utilized in lubricants and fuels.
One method for reducing the amount of chlorine in additive compositions
based on polyalkenyl-substituted dicarboxylic acids is to prepare such
hydrocarbon-
substituted dicarboxylic acids in the absence of chlorine, and procedures have
been
described for preparing such compounds by the "ene" process in which the
polyolefin and the unsaturated dicarboxylic acid are heated together,
optionally in
the presence of a catalyst. Using this procedure, it is often more difficult
to
incorporate an excess of the succinic groups into the polyalkenyl-substituted
succinic
acylating agents.
In yet another method, the amount of chlorine employed during reaction to
prepare the polyalkenyl substituted acylating agent is reduced. In particular,
this
method is employed when the polyolefin reactant has M n ranging from about 300
to
about 10,000, more often from about 500 to about 2,500, and has a high level
of tri-
and tetra- substituted unsaturated end groups, especially in amounts up to
about 90
mole %. Chlorine is used on a molar basis up to an amount equal to the number
of
moles of tetra- and tri- substituted end groups. Preferably, the halogen to
polyolefin
molar ratio is about 0.9:1 or less.
The reaction is conducted under conditions of time and temperature, typically
wherein said temperature ranges between about 20 C. - 175 C, to effect the
reaction
of the end groups and the chlorine to produce a polyolefin having labile
chlorine
substituents.
In one embodiment, the chlorination is conducted in the presence of a
substantially chlorine inert liquid, for example hexane, as a solvent, and
wherein said
mixture is heated at a temperature of less than about 70 C. In another
embodiment, the
reaction is camed out using a dilution gas. Preferred dilution gases are N20,
CO2 or
N2.
The polyalkenyl substituted acylating agent is,prepared by reacting the labile
chlorine containing polyolefin with an a-(3-unsaturated compound, said
compound
comprising a-0-unsaturated acids, anhydrides, derivatives or mixtures thereof
and
reacting the mixture under time and temperature parameters selected to effect
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reaction of the polyolefin with the a-o-unsaturated compound to produce a
polyolefin substituted reaction product having low chlorine content.
Typically, the
chlorine content of said substituted reaction product is 1000 parts per
million or less
on an oil-free basis.
Preferably, the polyolefin substituted reaction product is a polybutene
substituted succinic acid, anhydride or mixture thereof or derivative thereof.
The following examples illustrate several methods for reducing chlorine
content.
Example (B)-15
A polyisobutenyl (molecular weight of 1000) succinic anhydride is prepared
according to Example (B)-7. After obtaining the anhydride, 1000 parts of it is
treated with 4 parts of iodine which lowers the chlorine content to 0.1
percent. This
anhydride is diluted with 667 parts of diluent oil and 1000 parts of the oil
diluted
anhydride is reacted with 103 parts of a commercial mixture of polyamines. A
succinimide dispersant is obtained having a 40% oil content, 45 total base
number
and 2.0% nitrogen.
Example (B)-16
Following essentially the same procedure of Example (B)-12, 1000 grams of
the polyisobiitene is reacted with a total of 106 grams maleic anhydride and a
total of
90 grams chlorine. After obtaining the anhydride, 1000 parts of it is treated
with 4
parts of iodine which lowers the chlorine content to 0.1 percent. To 1000
grams of
this anhydride are added 207 grams of diluent oil. The contents are heated to
110 C.
and 39 grams of a commercial mixture of polyamines are added over a two-hour
period while allowing the contents to exotherm to 127 C. The contents are
heated to
152 C. and held for one hour with nitrogen blowing to remove water of
reaction.
Additional oil is added, 23 grams, and the contents are filtered to give a
product
containing 50% oil, 1.05% nitrogen, 250 ppm halogen and 18 total base number.
(C) The Metal Dihydrocarbyl Dithiophosphate
The metal dihydrocarbyl dithiophosphate is characterized by the formula
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CA 02394289 2008-07-31
R I O (Xlif)
PSS M
R20-
n
wherein R' and R2 are each independently hydrocarbyl groups containing from 3
to
about 13 carbon atoms, M is a metal, and n is an integer equal to the valence
of M.
The hydrocarbyl groups R' and R2 in the dithiophosphate may be alkyl,
cycloalkyl, aralkyl or alkaryl groups, or a substantially hydrocarbon group of
similar
structure. By "substantially hydrocarbon" is meant hydrocarbons which contain
substituent groups such as ether, ester, nitro, or halogen which do not
materially
affect the hydrocarbon character of the group.
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.
IIlustrative lower
alkylphenyl groups include butylphenyl, amylphenyl, heptylphenyl, etc.
Cycloalkyl
groups likewise are useful and these include chiefly cyclohexyl and the lower
alkyl-
cyclohexyl radicals. Many substituted hydrocarbon groups may also be used,
e.g.,
chlorophentyl, dichlorophenyl, and dichlorodecyl.
In another embodiment, at least one of R' and R2 in Formula XIII is an
isopropyl or secondary butyl group. In yet another embodiment, both R' and R2
are
secondary alkyl groups.
The phosphorodithioic acids from which the metal salts useful in this
invention are prepared are well known. Examples of dihydrocarbyl
phosphorodithioic acids and metal salts, and processes for preparing such
acids and
salts are found in, for example, U.S. Pat. Nos. 4,263,150; 4,289,635;
4,308,154; and
4,417,990.
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
200 C. Thus, the preparation of O,O-di-n-hexyl phosphorodithioic acid involves
the
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reaction of phosphorus pentasulfide with four moles of n-hexyl alcohol at
about
100 C. 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, nickel or mixtures thereof. The
Group II
metals, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel and
copper are among the preferred metals. Zinc and copper either alone or in
combination are especially useful metals. In one embodiment, the lubricant
compositions of the invention contain 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, lead hydroxide, tin butyrate, cobalt
hydroxide,
nickel hydroxide, nickel carbonate, 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 facilitates the formation of a zinc phosphorodithioate.
In one preferred embodiment, the alkyl groups R' and R2 are derived from
secondary alcohols such as isopropyl alcohol, secondary butyl alcohol, 2-
pentanol, 4-
methyl-2-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 mixtures
enables
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the utilization of cheaper alcohols which in themselves may not yield oil-
soluble
phosphorodithioic acids.
Useful mixtures of metal salts of dihydrocarbyl dithiophosphoric acid are
obtained by reacting phosphorus pentasulfide with a mixture of (a) isopropyl
or
secondary butyl alcohol, and (b) an alcohol containing at least 5 carbon atoms
wherein at least 10 mole percent, preferably 20 or 25 mole percent, of the
alcohol in
the mixture isopropyl alcohol, secondary butyl alcohol or a mixture 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 different primary alcohols,
mixtures of different secondary alcohols or mixtures of primary and secondary
alcohols. Examples of useful mixtures include: n-butanol and n-octanol; n-
pentanol
and 2-ethyl-l-hexanol; isobutanol and n-hexanol; isobutanol and isoamyl
alcohol;
isopropanol and 4-methyl-2-pentanol; isopropanol and sec-butyl alcohol;
isopropanol and isooctyl alcohol; etc. Particularly useful alcohol mixtures
are
mixtures of secondary alcohols containing at least about 20 mole percent of
isopropyl alcohol, and in a preferred embodiment, at least 40 mole percent of
isopropyl alcohol.
The following examples illustrate the preparation of metal
phosphorodithioates prepared from mixtures of alcohols.
Example (C)-1
A phosphorodithioic acid is prepared by reacting a mixture of alcohols
comprising 6 moles of 4-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 and
theoretical amount required to completely neutralize the phosphorodithioic
acid.
The oil solution of the zinc phosphorodithioate obtained in this manner (10%
oil)
contains 9.5% phosphorous, 20.0% sulfur and 10.5% zinc.
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Example (C)-2
A phosphorodithioic acid is prepared by reacting finely powdered
phosphorus pentasulfide with an alcohol mixture containing 11.53 moles (692
parts
by weight) of isopropyl alcohol and 7.69 moles (1000 parts by weight) of
isooctanol.
The phosphorodithioic acid obtained in this manner has an acid number of about
178-186 and contains 10.0% phosphorus and 21.0% sulfur. This phosphorodithioic
acid is then reacted with an oil slurry of zinc oxide. The quantity of zinc
oxide
included in the oil slurry is 1.10 times the theoretical equivalent of the
acid number
of the phosphorodithioic acid. The oil solution of the zinc salt prepared in
this
manner contains 12% oil, 8.6% phosphorus, 18.5% sulfur and 9.5% zinc.
Example (C)-3
A phosphorodithioic acid is prepared by reacting a mixture of 1560 parts (12
moles) of isooctyl alcohol and 180 parts (3 moles) of isopropyl alcohol with
756
parts (3.4 moles) of phosphorus pentasulfide. The reaction is conducted by
heating
the alcohol mixture to about 55 C. and thereafter adding the phosphorus
pentasulfide
over a period of 1.5 hours while maintaining the reaction temperature at about
60 -
75 C. After all of the phosphorus pentasulfide is added, the mixture is heated
and
stirred for an additional hour at 70 -75 C., and thereafter filtered through a
filter aid.
Zinc oxide (282 parts, 6.87 moles) is charged to a reactor with 278 parts of
mineral oil. The above-prepared phosphorodithioic acid (2305 parts, 6.28
moles) is
charged to the zinc oxide slurry over a period of 30 minutes with an exotherm
to
60 C. The mixture then is heated to 80C. and maintained at this temperature
for 3
hours. After stripping to 100 C. and 6 mm. Hg., the mixture is filtered twice
through a filter aid, and the filtrate is the desired oil solution of the zinc
salt
containing 10% oil, 7.97% zinc (theory 7.40); 7.21% phosphorus (theory 7.06);
and
15.64% sulfur (theory 14.57).
Example (C)-4
Isopropyl alcohol (396 parts, 6.6 moles) and 1287 parts (9.9 moles) of
isooctyl alcohol are charged to a reactor and.heated with stirring to 59C.
Phosphorus
pentasulfide (833 parts, 3.75 moles) is then added under a nitrogen sweep. The
addition of the phosphorus pentasulfide is completed in about 2 hours at a
reaction
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temperature between 59 -63 C. The mixture then is stirred at 45 -63 C. for
about
1.45 hours and filtered. The filtrate is the desired phosphorodithioic acid.
A reactor is charged with 312 parts (7.7 equivalents) of zinc oxide and 580
parts of mineral oil. While stirring at room temperature, the above-above-
prepared
phosphorodithioic acid (2287 parts, 6.97 equivalents) is added over a period
of about
1.26 hours with an exotherm to 54 C. The mixture is heated to 78 C. and
maintained at 75 -85 C. for 3 hours. The reaction mixture is vacuum stripped
to
100 C. at 19 mm. Hg. The residue is filtered through a filter aid, and the
filtrate is
an oil solution (19.2% oil) of the desired zinc salt containing 7.86% zinc,
7.76%
phosphorus and 14.8% sulfur.
Example (C)-5
The general procedure of Example (C)-4 is repeated except that the mole
ratio of isopropyl alcohol to isooctyl alcohol is 1:1. The product obtained in
this
manner is an oil solution (10% oil) of the zinc phosphorodithioate containing
8.96%
zinc, 8.49% phosphorus and 18.05% sulfur.
Example (C)-6
A phosphorodithioic acid is prepared in accordance with the general
procedure of Example (C)-4 utilizing an alcohol mixture containing 520 parts
(4
moles) of isooctyl alcohol and 360 parts (6 moles) of isopropyl alcohol with
504
parts (2.27 moles) of phosphorus pentasulfide. The zinc salt is prepared by
reacting
an oil slurry of 116.3 parts of mineral oil and 141.5 parts (3.44 moles of
zinc oxide
with 950.8 parts (3.20 moles) of the above-prepared phosphorodithioic acid.
The
product prepared in this manner is an oil solution (10% mineral oil) of the
desired
zinc salt, and the oil solution counting 9.36% zinc, 8.81% phosphorus and
18.65%
sulfur.
Example (C)-7
A mixture of 520 parts ( 4 moles) of isooctyl alcohol and 559.8 parts (9.33
moles) of isopropyl alcohol is prepared and heated to 60 C. at which time
672.5
parts (3.03 moles) of phosphorus pentasulfide are added in portions while 15
stirring. The reaction then is maintained at 60 -65 C. for about one hour and
filtered. The filtrate is the desired phosphorodithioic acid.
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An oil slurry of 188.6 parts (4 moles) of zinc oxide and 144.2 parts of
mineral oil is prepared, and 1145 parts of the above-prepared
phosphorodithioic acid
are added in portions while maintaining the mixture at about 70 C. After all
of the
acid is charged, the mixture is heated at 80 C. for 3 hours. The reaction
mixture
then is stripped of water to 110 C. The residue is filtered through a filter
aid, and
the filtrate is an oil solution (10% mineral oil) of the desired product
containing
9.99% zinc, 19.55% sulfur and 9.33% phosphorus.
Example (C)-8
A phosphorodithioic acid is prepared by the general procedure of Example
(C)-4 utilizing 260 parts ( 2 moles) of isooctyl alcohol, 480 parts (8 moles)
of
isopropyl alcohol, and 504 parts (2.27 moles) of phosphorus pentasulfide. The
phosphorodithioic acid (1094 parts, 3.84 moles) is added to an oil slurry
containing
181 parts (4.41 moles) of zinc oxide and 135 parts of mineral oil over a
period of 30
minutes. The mixture is heated to 80C. and maintained at this temperature for
3
hours. After stripping to 100C. and 19 mm. Hg., the mixture is filtered twice
through a filter aid, and the filtrate is an oil solution (10% mineral oil) of
the zinc
salt containing 10.06% zinc, 9.04% phosphorus, and 19.2% sulfur.
Example (C)-9
Isopropyl alcohol (410 parts, 6.8 moles) and 590 parts (4.5 moles) 2-
ethylhexyl alcohol are charged to a reactor and heated to 50 C. Phosphorus
pentasulfide (541 parts, 2.4 moles) is added under a nitrogen sweep. The
addition is
complete in 1.5 hours at a reaction temperature of from 50-65 C. The contents
are
stirred for 2 hours and filtered at 55 C. to give the desired
phosphorodithioic acid.
A reactor is charged with 145 parts (3.57 equivalents) of zinc oxide and 116
parts oil. Stirring is begun and added is 1000 parts (3.24 equivalents) of the
above
obtained phosphorodithioic acid over a 1 hour period beginning at room
temperature. The addition causes an exotherm to 52 C. The contents are heated
to
80 C. and maintained at this temperature for 2 hours. The contents are then
vacuum
stripped to 100 C. at 22 millimeters mercury. Added is 60 parts oil and the
contents
are filtered to give the desired product containing 12% oil,. 9.5% zinc, 18.5%
sulfur
and 8.6% phosphorus.
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Ex3mple (C)-10
Following the procedure of Example (C)-9, a phosphorodithioic acid is
prepared by reacting 1000 parts of an alcohol mixture comprising 46.8% weight
isopropyl alcohol and 53.2% weight 4-methyl-2-pentanol, and 642 parts (2.89
moles) phosphorus pentasulfide. To 1000 parts of this acid is added 56 parts
diluent
oil and 157.5 parts (1.9 moles) zinc oxide. Additional oil is added (28.6
parts) and
the contents are filtered to give a product containing 9% oil, 10.0%
phosphorus,
11.05 % zinc and 21% sulfur.
Other Additives
Additive-concentrates and lubricating oil compositions of this invention may
contain other additives. The use of such additives is optional and the
presence
thereof in the compositions of this invention will depend on the particular
use and
level of performance required. Thus the other additive may be included or
excluded.
One or more zinc salts of dithiophosphoric acids other than those described
herein as component (C) may be present in a minor amount to provide additional
extreme pressure, anti-wear and anti-oxidancy performance.
Other additives that may optionally be used in the lubricating oils of this
invention include, for example, auxiliary dispersants, viscosity improvers,
oxidation
inhibitors, corrosion inhibitors, pour point depressants, extreme pressure
agents,
anti-wear agents, color stabilizers, friction modifiers, and anti-foam agents.
The above-illustrated other additives are well known in the art and are
described in numerous patents and piublications. They may each be present. in
lubricating compositions at a concentration of as little as 0.001% by weight,
usually
ranging from about 0.01% to about 20% by weight. In most instances, when used,
each contributes from about 0.1% to about 10% by weight, more often up to
about
5% by weight.
Additive Concentrates
Lubricating oil compositions of this invention may be prepared by directly
adding each ingredient to the oil of lubricating viscosity. Preferably,
however, they
are usually supplied as an additive concentrate wherein the additives, usually
a
mixture of two or more thereof, are diluted with a substantially inert,
normally liquid
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least about 20% by weight of additives, often as much as 80% by weight.
Additive
concentrates are prepared by mixing together the desired components, often at
elevated temperatures, usually less than 150 C, often no more, than about 130
C,
frequently no more than about 100 C.
The following example illustrates a lubricating oil composition used in the
method of this invention:
Example I
An engine lubricating oil composition is prepared by combining 10 parts of
an additive concentrate containing 57.5% of the dispersant of Example (B)-13,
9.2
parts of the zinc dithiophosphate of Example (C)-10, 2.52 parts of
di(nonylphenyl)
amine, 7 parts sulfurized C12_18 olefin, 5 parts 2,6-di tertiary butyl-4-
(propylene
tetramer) phenol, 4.6 parts of the product of Example (A)-2, 6.8 parts of the
product
of Example (A)-1, 0.09 parts of a kerosene solution of a silicone antifoam
agent, and
sufficient mineral oil to make 100 parts additive concentrate, with 0.13 parts
of a
polymethacrylate pour point depressant, 0.74% of an ethylene-propylene polymer
viscosity improver and a mineral oil basestock (Chevron RLOP 100N) to make a
total of 100 parts of lubricating oil composition.
Comparative Example I
An engine lubricating oil composition, identical in every respect to that of
Example I is prepared except 6.8 parts of the product of Example (A)-1 in the
additive concentrate is replaced (equal TBN basis) with 5.2 parts of a 68% in
oil
solution of magnesium. overbased alkyl benzene sulfonate.
Comparative Exam lp e II
An engine lubricating oil composition, identical in every respect to that of
Example I is prepared except the 4.6 parts of the product of Example (A)-2 is
replaced (equal TBN basis) with an additional 6.9 parts (total 13.7 parts) of
the
product of Example (A)-1.
Fuel consumption and tailpipe emissions of engines lubricated with
lubricants of Example I and comparative Example I were measured using the
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procedure described in Part 86 of Title 40 of the Code of Federal Regulations,
entitled `Protection of the Environment', published by the U. S. Government
Printing Office (1996). Briefly, the procedure involves operating a test
vehicle using
the Federal Test Procedure (FTP) cycle, an emission certification test
procedure used
for light duty vehicles employing a Clayton Model ECE-50 chassis dynamometer.
Exhaust sampling was conducted using a constant volume sampler. The
emissions are analyzed and reported.
Fuel consumption is measured using volumetric and gravimetric procedures.
During testing, fuel is supplied to the engine from a container.
It was found that both fuel consumption and NOR emissions were reduced
employing the lubricant of Example I, a lubricant of the instant invention.
The data in the following table illustrate the surprising effect of the
lubricant of the instant invention compared to a comparative lubricant. NOX
emissions are reported in grams per mile.
Lubricant I Comparative Lubricant I
% Reduction in Fuel 2.41 1.48
Consumption over Baseline
NOX Emissions:
3-Bag Composite * 0.22 0.26
Cold Transient (Bag 1) $ 0.48 0.52
Stabilized (Bag 2) 0.19 0.19
Hot Transient (Bag 3) t 0.14 0.20
* Statistically significant @ 98% confidence interval
$ Statistically significant @ 80% confidence interval
t Statistically significant @ 99% confidence interval
It has also surprisingly been discovered that combustion chamber deposits
formed during operation with the all calcium detergent system of Comparative
Example II are removed using the calcium and sodium detergent system of
Example
I following operation with the lubricant of Comparative Example 2. After
12,500
miles using the lubricant of Comparative Example 2, heavy piston crown
deposits
are observed. The lubricant is changed to that of Example I. After only 500
miles of
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operation with the lubricant of Example I, a noticeable reduction in the
amount of
piston crown deposits is observed. After a total of 12,500 miles using the
lubricant
of Example 1, piston crown deposits are further reduced.
It is known that some of the materials described above may interact in the
final formulation, so that the components of the final formulation may be
different
from those that are initially added. For instance, metal ions (of, e.g., a
detergent) can
migrate to other acidic sites of other molecules. The products formed thereby,
including the products formed upon employing the composition of the present
invention in its intended use, may not susceptible of easy description.
Nevertheless,
all such modifications and reaction products are included within the scope of
the
present invention; the present invention encompasses the composition prepared
by
admixing the components described above.
Each of the documents referred to above is incorporated herein by reference.
Except in the examples, or where otherwise explicitly indicated, all numerical
quantities in this description specifying amounts of materials, reaction
conditions,
molecular weights, number of carbon atoms, and the like, are to be understood
as
modified by the word "about". Unless otherwise indicated, each chemical or
composition referred to herein should be interpreted as being a commercial
grade
material which may contain the isomers, by-products, derivatives, and other
such
materials which are normally understood to be present in the commercial grade.
However, the amount of each chemical component is presented exclusive of any
solvent or diluent oil which may be customarily present in the commercial
material,
unless otherwise indicated. It is to be understood that the upper and lower
amount,
range, and ratio limits set forth herein may be independently combined..
While the invention has been explained in relation to its preferred
embodiments, it is. to be understood that various modifications thereof will
become
apparent to those skilled in the art upon reading the disclosure. Therefore,
it is to be
understood that the invention disclosed herein is intended to cover such
modifications as fall within the scope of the appended claims.
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