Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
Lubricant for Two-Stroke Cycle Engines
BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to an engine lubricant,
particularly for
two-stroke cycle engines, and to combustible compositions for fueling two-
stroke cycle
engines.
[0002] Two-stroke cycle engines are widely used for portable power
equipment and
also represent an important portion of the engines used in transportation,
particularly in
the developing regions of the world. The lubricants required for the operation
of two-
stroke cycle engines are, in some designs, mixed with the liquid fuel, and
this fuel-lubricant
mixture is typically passed through the crankcase and, ultimately, to the
combustion
chambers, where the entire fuel-lubricant composition is burned. Combustion of
the
lubricant can generate high particulate emissions. The particulate emissions
emanating
from conventional two-cycle fuel-lubricant combustion generally comprise
organic carbon
particulates of various sizes and number profiles. As global constraints on
particulate
emissions become tighter, the use of two-cycle engines may come under
increasing
scrutiny. One approach to complying with tighter emissions demands is to
reduce the use
and reliance on two-cycle engines. An alternative approach is to employ rather
expensive
catalysts to react with and reduce particle emissions. As noted, the use of
catalysts can add
cost to engine manufacture and operation and are susceptible to degradation by
ash-
containing additives in lubricant compositions. It would, therefore, be
desirable to provide
lubricant compositions and fuel-lubricant mixtures that, during operation of
two-cycle
engines lubricated and fueled, respectively, thereby, generate reduced
particulate
emissions, in relation to one of at least reduced particulate mass, total
organic or elemental
carbon, or particle number, and preferably more than one of reduced
particulate mass, total
organic or elemental carbon, or particle number, while maintaining engine
performance,
lubricity, and cleanliness.
SUMMARY OF THE INVENTION
[0003] The disclosed technology provides a lubricant composition
comprising:
a. 5 wt. % to 35 wt. % of an oil of lubricating viscosity,
b. greater than 50 wt. % to 90 wt. % of a hydrocarbon solvent; and
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c. at least one additive selected from (i) a dispersant and (ii) a friction
modifier.
[0004] In some embodiments, the lubricant composition may comprise 5 to
25 wt. %,
or 5 to 20 wt. %, or 5 to 15 wt. %, or 5 to 10 wt. % of an oil of lubricating
viscosity.
[0005] In some embodiments, the oil of lubricating viscosity may be
selected from any
of a Group I, II, III, IV or V base oil and blends thereof
[0006] In still further embodiments, a lubricant composition may
comprise 60 to
90 wt. %, or 65 to 90 wt. % of a hydrocarbon solvent.
[0007] In certain embodiments, the hydrocarbon solvent may be selected
from one or
more of aromatic type hydrocarbon solvents, aliphatic type hydrocarbon
solvents,
naphthenic type hydrocarbon solvents or various blends thereof.
[0008] The hydrocarbon solvent in certain embodiments may have a
boiling point of
between about 140 C (284 F) and about 350 C (662 F). The hydrocarbon solvent
in
certain embodiments may have a flash point of between about 40 C (104 F) and
about
140 C (284 F).
[0009] In some embodiments, the dispersant may include a Mannich¨type
dispersant
and a succinimide-type dispersant.
[0010] In some embodiments, the weight percent ratio of dispersant to
oil of
lubricating viscosity may be 1:6 to 1:2.5.
[0011] The disclosed technology further provides a combustible mixture for
fueling a
two-cycle engine comprising a lubricating composition admixed with a liquid
fuel
composition at a ratio of 1:60 to 1:40, or about 1:50 by volume, wherein the
lubricating
composition comprises:
a. from 5 wt. % to 35 wt. % of an oil of lubricating viscosity,
b. from 60 wt. % to 90 wt. of a hydrocarbon solvent;
c. from 0.02 wt. % to 10 wt. % of a dispersant
d. from 0.1 wt. % to 5 wt. % of at least one friction modifier, and
e. optionally, a detergent.
[0012] The disclosed technology also provides a method of lubricating
an internal
combustion engine, such as a two-stroke cycle engine, comprising supplying
thereto the
lubricant composition.
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[0013] The disclosed technology also provides a method of fueling an
internal
combustion engine, such as a two-stroke cycle engine, comprising supplying
thereto the
combustible mixture.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Various preferred features and embodiments will be described below
by way
of non-limiting illustration.
[0015] One component of the disclosed technology, which in all
instances of the
present invention will be a minor portion of the lubricant composition, is an
oil of
lubricating viscosity, which may be referred to as a base oil. The base oil
may be selected
from any of the base oils in Groups I-V of the American Petroleum Institute
(API) Base
Oil Interchangeability Guidelines, namely
Base Oil Category Sulfur (%) Saturates (%) Viscosity Index
Group I >0.03 and/or <90 80 to 120
Group II <0.03 and >90 80 to 120
Group III <0.03 and >90 >120
Group IV All polyalphaolefins (PA0s)
Group V All others not included in Groups I, II, III or IV
Groups I, II and III are mineral oil base stocks. The oil of lubricating
viscosity can include
natural or synthetic oils and mixtures thereof Mixtures of mineral oil and
synthetic oils,
e.g., polyalphaolefin oils and/or polyester oils, may be used. In some
embodiments of the
present invention, the base oil will be a Group I, II, or III base oil, and in
some
embodiments it will be a mixture of base oils comprising a Group I, II, or III
base oil and
at least one of a Group IV or V oil. In some embodiments, the base oil may be
substantially
free of a Group I, or Group II or Group III or Group IV or Group V base oil.
[0016] Natural oils include animal oils and vegetable oils (e.g. 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 also useful oils of
lubricating
viscosity. Oils of lubricating viscosity derived from coal or shale are also
useful.
[0017] Synthetic oils include hydrocarbon oils and halosubstituted
hydrocarbon oils
such as polymerized and interpolymerized olefins and mixtures thereof,
alkylbenzenes,
polyphenyl, alkylated diphenyl ethers, and alkylated diphenyl sulfides and
their
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derivatives, analogs and homologues thereof Alkylene oxide polymers and
interpolymers
and derivatives thereof, and those where terminal hydroxyl groups have been
modified by,
e.g., esterification or etherification, are other classes of synthetic
lubricating oils.
[0018] Other suitable synthetic lubricating oils include esters of
dicarboxylic acids and
those made from C5 to C12 monocarboxylic acids and polyols or polyol ethers.
More
specifically, esters useful as synthetic oils may comprise esters of
dicarboxylic acids (e.g.,
phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids,
maleic acid,
azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer,
malonic acid, alkyl malonic acids, and alkenyl malonic acids) with any of a
variety of
alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol,
ethylene glycol, diethylene glycol monoether, and propylene glycol). Further,
esters
useful as synthetic oils may also include those made from C5 to C20
monocarboxylic acids
and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol, and tripentaerythritol.
[0019] Still other synthetic lubricating oils may include liquid esters of
phosphorus-
containing acids, polymeric tetrahydrofurans, silicon-based oils such as poly-
alkyl-,
polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils, and silicate oils.
[0020] Other synthetic oils include those produced by Fischer-Tropsch
reactions,
typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one
embodiment
oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as
well as
other gas-to-liquid oils.
[0021] Unrefined, refined and rerefined oils, either natural or
synthetic (as well as
mixtures thereof) of the types disclosed hereinabove can be used. 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 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. Rerefined oils often are additionally processed
to remove
spent additives and oil breakdown products.
[0022] The base oils, and particularly the synthetic ester oils, will
typically have a
kinematic viscosity at 100 C (KV 100) of at least 2.7 mm25-1 (cSt) (or at
least 3 cSt) (or at
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least 6 cSt). Base oils may typically have a boiling point in the range of
about 350 C to
about 800 C and/or a flash point greater than about 150 C.
[0023] In
all embodiments of the lubricant compositions, the total base oil, namely,
the total of all Group I-V oils in the lubricant composition, will constitute
a minor portion
(less than 50 percent by weight (also referred to as wt. %)) of the lubricant
composition,
with a major portion (greater than 50 wt. %) of the lubricant being a solvent
(as discussed
in further detail below). In
fact, particularly useful lubricating compositions
demonstrating excellent performance with low particulate emissions may have a
total
amount of oil of lubricating viscosity (including diluent or carrier oils
present in the
additional components referenced below) of less than 35 wt. %, or less than 25
wt. % or
wt. %, or even less than 15 wt. % or 10 wt. % of the lubricant composition. In
some
embodiments, the total amount of oil of lubricating viscosity may be from 5 to
35 wt. %
or 5 to 25 wt. % or 5 to 20 wt. % or 5 to 15 wt. % of the lubricant
composition.
[0024] A
second component of the lubricant composition is a solvent. The solvent is
15 typically a hydrocarbonaceous (or hydrocarbon) solvent, that is, one
which exhibits
principally hydrocarbon character, even though relatively small numbers of
heteroatoms
may be present in the molecule. The solvent may be a hydrocarbon and may have
predominantly aromatic character or non-aromatic (e.g., alkane) character. The
solvent
may comprises less than 20 percent by weight aromatic components and/or may be
20 substantially free from polynuclear aromatic components.
[0025]
The solvent may be characterized by a KV 100 of less than 2.5 cSt, or less
than
2.0 or 1.5 or 1.0 cSt. Particularly useful are solvents having a boiling point
range of about
140 C (284 F) to about 350 C (662 F). The hydrocarbon solvent in certain
embodiments
may have a flash point of between about 40 C (104 F) and about 140 C (284 F).
[0026] Examples of useful solvents may include kerosene, hydrotreated
kerosene,
middle distillate fuels, isoparaffinic and naphthenic aliphatic hydrocarbon
solvents,
dimers, and higher oligomers of propylene butene and similar olefins as well
as paraffinic
and aromatic hydrocarbon solvents and mixtures thereof Such solvents may
contain
functional groups other than carbon and hydrogen and may include alcohols,
esters, ethers,
.. ketones, and aldehyde solvents and blends thereof Alcohol solvents may
include such
alcohols as methanol, ethanol and butanol. Particularly useful are aliphatic
solvents,
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including the solvent sold under the trademark "Exxsol D8041)" by Exxon
Chemical
Company.
[0027] As referenced above, the solvent or solvent blend will
constitute the major
portion of the lubricant compositions. The amount of solvent in a fully
formulated
lubricant of the disclosed technology will, accordingly, be greater than 50
wt. %, or, in
some embodiments, greater than 60 wt. % or 70 wt. %, or even 80 wt. % or 90
wt. % of
the lubricant composition. In some embodiments, the amount of hydrocarbon
solvent will
be from greater than 50 wt. % to 95 wt. % or 60 wt. % to 90 wt. % or 70 wt. %
to 90 wt. %
or 75 wt. % to 90 wt. %.
[0028] In other embodiments, the ratio of solvent to total base oil in the
lubricant
composition may be from 15:1 to 1.5:1 or 15:1 to 2:1 or 15:1 to 4:1 or 15:1 to
6:1.
[0029] The lubricating compositions of the present invention will
include at least one
dispersant. Dispersants in general are well known in the field of lubricants
and include
primarily what are known as ashless dispersants and polymeric dispersants.
Ashless
.. dispersants are so-called because, as supplied, they do not contain metal
and thus do not
normally contribute to sulfated ash when added to a lubricant. However they
may, of
course, interact with ambient metals if they are added to a lubricant which
includes metal-
containing species. Ashless dispersants are characterized by a polar group
attached to a
relatively high molecular weight hydrocarbon chain.
[0030] The lubricant compositions of the present invention may include at
least one of
a Mannich-type dispersant, a succinimide-type dispersant or a phenolic-type
dispersant.
In some embodiments, the lubricant may include a Mannich-type and a
succinimide-type
dispersant. In still other embodiments, the lubricant may include a Mannich-
type and a
succinimide-type and a phenolic-type dispersant.
[0031] A Mannich-type dispersant, which may also be referred to herein as a
Mannich
dispersant, is a reaction product of a hydrocarbyl-substituted phenol, an
aldehyde, and an
amine or ammonia. The hydrocarbyl substituent of the hydrocarbyl-substituted
phenol can
have 10 to 400 carbon atoms, in another instance 30 to 180 carbon atoms, and
in a further
instance 10 or 40 to 110 carbon atoms. This hydrocarbyl substituent can be
derived from
an olefin or a polyolefin. Useful olefins include alpha-olefins and branched
alpha-olefins,
such as ethylene, propylene, isobutylene, 1-butene, 1-decene, etc. which are
commercially
available.
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[0032] Useful polyolefins which can form the hydrocarbyl substituent
can be prepared,
for instance, by polymerizing olefin monomers by well-known polymerization
methods
and are also commercially available. The olefin monomers include monoolefins,
including
monoolefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene,
isobutylene, and 1-decene. An especially useful monoolefin source is a C4
refinery stream
having a 35 to 75 weight percent butene content and a 30 to 60 weight percent
isobutene
content. Useful olefin monomers also include diolefins such as isoprene and
1,3-
butadiene. Olefin monomers can also include mixtures of two or more
monoolefins, of
two or more diolefins, or of one or more monoolefins and one or more
diolefins. Useful
polyolefins include polyisobutylenes having a number average molecular weight
of 140 to
5000, in another instance of 400 to 2500, and in a further instance of 140 or
500 to 1500.
The polyisobutylene can have a vinylidene double bond content of 5 to 69%, in
a second
instance of 50 to 69%, and in a third instance of 50 to 95%. The polyolefin
can be a
homopolymer prepared from a single olefin monomer or a copolymer prepared from
a
mixture of two or more olefin monomers. Also possible as the hydrocarbyl
substituent
source are mixtures of two or more homopolymers, two or more copolymers, or
one or
more homopolymers and one or more copolymers. The foregoing description of
suitable
hydrocarbyl groups or polyolefin groups is also applicable to the hydrocarbyl
substituent
of the succinimide dispersant, described in detail below.
[0033] The hydrocarbyl-substituted phenol which is used to prepare the
Mannich
dispersant can be prepared by alkylating phenol with an olefin or polyolefin
described
above, such as a polyisobutylene or polypropylene, using well-known alkylation
methods.
[0034] The aldehyde used to form the Mannich dispersant can have 1 to
10 carbon
atoms, and is generally formaldehyde or a reactive equivalent thereof such as
formalin or
paraformaldehyde.
[0035] The amine used to form the Mannich dispersant can be a monoamine
or a
polyamine, including alkylene polyamine, other aliphatic and aromatic mono-
and
polyamines, alkanolamines having one or more hydroxyl groups and mixtures
thereof.
Useful amines include ethanolamine, diethanolamine, methylamine,
dimethylamine,
ethylenediamine, dimethylaminopropylamine, diethylenetriamine and 2-(2-
aminoethyl-
amino)ethanol. The Mannich dispersant can be prepared by reacting a
hydrocarbyl-
substituted phenol, an aldehyde, and an amine as described in U.S. Patent No.
5,697,988.
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In one embodiment, the Mannich reaction product is prepared from an
alkylphenol derived
from a polyisobutylene, formaldehyde, and an amine that is a primary
monoamine, a
secondary monoamine, or an alkylenediamine, in particular, ethylenediamine or
dimethylamine. In one embodiment, the alkylphenol may be prepared from a high-
vinylidene polyisobutene, having, e.g., greater than 50, greater than 70 or
greater than 75
percent terminal vinylidene groups (i.e., such percentage of polyisobutylene
molecules
having vinylidene end groups; that is, mole percentage of polyisobutylene
molecules
having a terminal vinylidene group.) The foregoing description of the amine is
also
applicable to the description of the amine used in preparing the succinimide
dispersant,
described below.
[0036] In one embodiment the Mannich dispersant comprises the reaction
product of
a hydrocarbyl-substituted phenol, formaldehyde or a reactive equivalent of
formaldehyde,
and a primary or secondary amine. In one embodiment the Mannich dispersant
comprises
the reaction product of a polyisobutene-substituted phenol, formaldehyde or a
reactive
equivalent of formaldehyde, and dimethylamine.
[0037] The amount of the Mannich dispersant employed in the lubricant
composition
may be in the range of 0.1 to 5 wt. % of the lubricant composition. In other
embodiments
it may be present at 0.15 to 3.0 wt. %, or 0.2 to 3.0 wt. %, or 0.5 to 3.0 wt.
%, or 1.0 to
2.0 wt. % of the lubricant composition.
[0038] A second type of dispersant that may be present in the lubricant
compositions
is a succinimide-type dispersant. In one embodiment, the succinimide
dispersant is a
condensation product of hydrocarbyl-substituted succinic anhydride or a
reactive
equivalent thereof (e.g., an anhydride, ester, or acid halide), with a
polyethylene
polyamine. Succinimide dispersants may generally be viewed as comprising a
variety of
chemical structures including typically
0 0
N¨[R2-NFlix-R2-
where each Rl is independently an alkyl group, frequently a polyisobutylene
group with a
molecular weight (M.) of 500-5000 based on the polyisobutylene precursor, and
R2 are
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alkylene groups, commonly ethylene (C2H4) groups. Such molecules are commonly
derived from reaction of an alkenyl acylating agent with a polyamine, and a
wide variety
of linkages between the two moieties is possible beside the simple imide
structure shown
above, including a variety of amides and quaternary ammonium salts. In the
above
structure, the amine portion is shown as an alkylene polyamine, although other
aliphatic
and aromatic mono- and polyamines may also be used. Also, a variety of modes
of linkage
of the le groups onto the imide structure are possible, including various
cyclic linkages.
The ratio of the carbonyl groups of the acylating agent to the nitrogen atoms
of the amine
may be 1:0.5 to 1:3, and in other instances 1:1 to 1:2.75 or 1:1.5 to 1:2.5.
Succinimide
dispersants are more fully described in U.S. Patents 4,234,435 and 3,172,892
and in EP
0355895.
[0039] Succinimide dispersants may also be described as being prepared
from
hydrocarbyl-substituted succinic acylating agent which are, in turn, prepared
by the
so-called "chlorine" route or by the so-called "thermal" or "direct
alkylation" route. These
routes are described in detail in published application US 2005-0202981,
paragraphs 0014
through 0017. A direct alkylation or low-chlorine route is also described in
U.S. Patent
6,077,909; refer to column 6 line 13 through col. 7 line 62 and column 9 lines
10 through
col. 10 line 11. Illustrative thermal or direct alkylation processes involve
heating a
polyolefin, typically at 180 to 250 C, with maleic anhydride under an inert
atmosphere.
Either reactant may be in excess. If the maleic anhydride is present in
excess, the excess
may be removed after reaction by distillation. These reactions may employ, as
the
polyolefin, high vinylidene polyisobutylene, that is, having greater than 50,
70, or 75%
terminal vinylidene groups (a and f3 isomers). In certain embodiments, the
succinimide
dispersant may be prepared by the direct alkylation route. In other
embodiments it may
comprise a mixture of direct alkylation and chlorine-route dispersants.
[0040] The succinimide dispersant will be one which is capable of
providing a
relatively large quantity of nitrogen to the lubricant. The nitrogen will be
nitrogen atoms
that are a part of the amine component or the condensed amide or imide groups
of the
dispersant. That is, it will impart at least 40 parts per million by weight of
nitrogen to the
.. lubricant, and in some embodiments at least 70 or 100 or 130 or 150 parts
per million, and
up to, for example, 1000 or 900 or 800 or 600 parts per million. These amounts
will be
determined by both the amount of the succinimide dispersant in the lubricant
formulation
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and the amount of nitrogen within the given dispersant. Thus, certain of the
succinimide
dispersants of the present technology are comparatively high in nitrogen
content, i.e., at
least 3 wt. % of the succinimide dispersant or at least 4 wt. % or at least
4.4 wt. %, and up
to 6 or 5.5 or 5 wt. %.
[0041] Such high nitrogen dispersants are, in certain embodiments,
characterized as
having a basicity, which may be referred to as base number or total base
number (TBN)
according to ASTM D2896, due to the presence of basic amine functionality. The
present
succinimide dispersant may thus have a TBN of at least 90 or 100 or 110 and up
to, for
instance, 160 or 140 or 120. Other suitable TBN ranges may be 60 to 160 or 70
to 140 or
80 to 120. Such values are to be calculated on the basis of an oil-free
dispersant, as will
be evident to the skilled person. In certain applications, the succinimide
dispersant may
be borated.
[0042] The amount of the succinimide dispersant employed in the
lubricant
composition may be in the range of 0.1 to 5 wt. % of the lubricant
composition. In other
embodiments it may be present at 0.15 to 3.0 wt. %, or 0.2 to 3.0 wt. %, or
0.5 to 3.0 wt. %,
or 1.0 to 2.0 wt. %.
[0043] The combined amount of the Mannich dispersant and the
succinimide
dispersant may be in the range of 0.2 to 10 wt. % of the lubricant
composition. In other
embodiments, 0.5 to 10 wt. %, or 1 to 8 wt. %, or 2 to 6 wt. %, or 2 to 5 wt.
%. The relative
amounts of the Mannich dispersant and the succinimide dispersant, expressed as
a weight
ratio, may be 80:20 to 20:80 or alternatively 70:30 to 30:70 or 65:35 to
45:55.
[0044] Other dispersants may also be present, if desired. They may be
lower nitrogen-
content dispersants than the above-described succinimide dispersant, or they
may have
shorter or longer hydrocarbyl chains, or they may have other functional
groups. One such
dispersant may be a condensation product of a fatty hydrocarbyl monocarboxylic
acylating
agent, such as a fatty acid, with an amine. The fatty acid may contain 10 to
26 carbon
atoms (e.g., 12 to 24 or 14 to 20 or 16 to 18). An example is isostearic acid.
The amine
may be a polyethylene polyamine such as tetraethylene pentamine (TEPA). The
condensation product may be an amide or an imidazoline. Other dispersants
include high
molecular weight esters. These materials are similar to the above-described
succinimides
except that they may be seen as having been prepared by reaction of a
hydrocarbyl
acylating agent and a polyhydric aliphatic alcohol such as glycerol,
pentaerythritol, or
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sorbitol. Other dispersants include polymeric dispersant additives, also
referred to as
dispersant viscosity modifiers, which are generally hydrocarbon-based polymers
containing polar functionality to impart dispersancy characteristics to the
polymer.
[0045] Either one or both or all of the dispersants may be post-treated
with any of a
variety of agents to impart desirable properties thereto, while retaining, in
some
embodiments, a relatively high TBN for the succinimide dispersant. Such post-
treatment
includes reaction with urea, thiourea, dimercaptothiadiazoles, carbon
disulfide, aldehydes,
ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides,
nitriles, epoxides,
boron compounds such as boric acid, phosphorus compounds, or mixtures thereof
References detailing such treatment are listed in U.S. Patent 4,654,403.
[0046] When present, these other dispersants may be present in amounts
from
.01 wt. % to about 2 wt. %.
[0047] In certain embodiments of the present invention, lubricant
compositions may
have a ratio of total dispersant to total base oil (from all component sources
in the lubricant
composition) of from 1:6 to 1:2.5.
[0048] The lubricating compositions of the present invention may
further comprise at
least one friction modifier, which may be an ashless or ash containing
friction modifier.
Ashless and ash-containing friction modifiers are well known to those skilled
in the art. A
useful list of friction modifiers are included in U.S. Pat. No. 4,792,410.
U.S. Pat.
No. 5,110,488 discloses metal salts of fatty acids and especially zinc salts,
useful as
friction modifiers. A list of friction modifiers includes fatty acid amides,
fatty epoxides,
borated fatty epoxides, fatty amines, glycerol esters, borated glycerol
esters, alkoxylated
fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids,
sulfurized olefins,
fatty imidazolines, condensation products of carboxylic acids and polyalkylene-
polyamines, amide, ester or imide derivatives of hydroxy-carboxylic acids,
metal salts of
alkyl salicylates, amine salts of alkylphosphoric acids and mixtures thereof.
[0049] Representatives of each of these types of friction modifiers are
known and are
commercially available.
[0050] Borated fatty epoxides are known from Canadian Patent No.
1,188,704. These
oil-soluble boron containing compositions are prepared by reacting at a
temperature from
about 80 C to about 250 C, at least one of boric acid or boron trioxide with
at least one
fatty epoxide having the formula
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0
_________________________________________ CR3R4
wherein each of le, R2, le and R4 is hydrogen or an aliphatic radical, or any
two thereof
together with the epoxy carbon atom or atoms to which they are attached, form
a cyclic
radical. The fatty epoxide preferably contains at least 8 carbon atoms.
[0051] The borated fatty epoxides can be characterized by the method for
their
preparation which involves the reaction of two materials. Reagent A can be
boron trioxide
or any of the various forms of boric acid including metaboric acid (HB02),
orthoboric acid
(H3B03) and tetraboric acid (H2B407). Boric acid, and especially orthoboric
acid, is
preferred. Reagent B can be at least one fatty epoxide having the above
formula. In the
formula, each of the R groups is most often hydrogen or an aliphatic radical
with at least
one being a hydrocarbyl or aliphatic radical containing at least 6 carbon
atoms. The molar
ratio of reagent A to reagent B is generally 1:0.25 to 1:4. Ratios of 1:1 to
1:3 are preferred,
with about 1:2 being an especially preferred ratio. The borated fatty epoxides
can be
prepared by merely blending the two reagents and heating them at temperature
of 80 to
250 C, preferably 100 to 200 C, for a period of time sufficient for reaction
to take place.
If desired, the reaction may be effected in the presence of a substantially
inert, normally
liquid organic diluent. During the reaction, water is evolved and may be
removed by
distillation.
[0052] Non-borated fatty epoxides, corresponding to "Reagent B" above,
are also
useful as friction modifiers.
[0053] Borated amines are generally known from U.S. Pat. No. 4,622,158.
Borated
amine friction modifiers (including borated alkoxylated fatty amines) are
conveniently
prepared by the reaction of a boron compounds, as described above, with the
corresponding amines. The amine can be a simple fatty amine or hydroxy
containing
tertiary amines.
[0054] The borated amines can be prepared by adding the boron reactant,
as described
above, to an amine reactant and heating the resulting mixture at a 50 to 300
C, preferably
100 C to 250 C or 150 C to 230 C, with stirring. The reaction is continued
until by-
product water ceases to evolve from the reaction mixture indicating completion
of the
reaction.
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[0055]
Among the amines useful in preparing the borated amines are commercial
alkoxylated fatty amines known by the trademark "ETHOMEEN" and available from
Akzo Nobel. Representative examples of these ETHOMEENTm materials is
ETHOMEENTm C/12 (bis[2-hydroxyethyl]cocoamine); ETHOMEENTm C/20
(polyoxyethylene[10]cocoamine); ETHOMEENTm S/12 (bis[2-hydroxyethyl]soyamine);
ETHOMEENTm T/12 (bis[2-hydroxyethyl]tallowamine); ETHOMEENTm T/15
(polyoxyethylene-[5]tallowamine); ETHOMEENTm 0/12 (bi s[2-hydroxyethyl]oley1 -
amine); ETHOMEENTm 18/12 (bis[2-hydroxyethyl]octadecyl amine);
and
ETHOMEENTm 18/25 (polyoxyethylene[15]octadecyl amine). Fatty amines and
ethoxylated fatty amines are also described in U.S. Pat. No. 4,741,848.
[0056]
The alkoxylated fatty amines, and fatty amines themselves (such as
oleylamine) are generally useful as friction modifiers in this invention. Such
amines are
commercially available.
[0057]
Both borated and unborated fatty acid esters of glycerol can be used as
friction
modifiers. The borated fatty acid esters of glycerol are prepared by borating
a fatty acid
ester of glycerol with boric acid with removal of the water of reaction.
Preferably, there is
sufficient boron present such that each boron will react with from 1.5 to 2.5
hydroxyl
groups present in the reaction mixture. The reaction may be carried out at a
temperature in
the range of 60 C to 135 C, in the absence or presence of any suitable organic
solvent such
as methanol, benzene, xylenes, toluene, or oil.
[0058]
Fatty acid esters of glycerol themselves can be prepared by a variety of
methods
well known in the art. Many of these esters, such as glycerol monooleate and
glycerol
tallowate, are manufactured on a commercial scale. The useful esters are oil-
soluble and
are preferably prepared from C8 to C22 fatty acids or mixtures thereof such as
are found in
natural products and as are described in greater detail below. Fatty acid
monoesters of
glycerol are preferred, although, mixtures of mono and diesters may be used.
For example,
commercial glycerol monooleate may contain a mixture of 45% to 55% by weight
monoester and 55% to 45% diester.
[0059]
Fatty acids can be used in preparing the above glycerol esters; they can also
be
used in preparing their metal salts, amides, and imidazolines, any of which
can also be
used as friction modifiers. Preferred fatty acids are those containing 6 to 24
carbon atoms,
preferably 8 to 18. The acids can be branched or straight-chain, saturated or
unsaturated.
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Suitable acids include 2-ethylhexanoic, decanoic, oleic, stearic, isostearic,
palmitic,
myristic, palmitoleic, linoleic, lauric, and linolenic acids, and the acids
from the natural
products tallow, palm oil, olive oil, peanut oil, corn oil, and Neat's foot
oil. A particularly
preferred acid is oleic acid. Preferred metal salts include zinc and calcium
salts. Examples
are overbased calcium salts and basic oleic acid-zinc salt complexes which can
be
represented by the general formula Zn4Oleate301. Preferred amides are those
prepared by
condensation with ammonia or with primary or secondary amines such as
diethylamine
and diethanolamine. Fatty imidazolines are the cyclic condensation product of
an acid with
a diamine or polyamine such as a polyethylenepolyamine. The imidazolines are
generally
represented by the structure
_
R'
where R is an alkyl group and R' is hydrogen or a hydrocarbyl group or a
substituted
hydrocarbyl group, including ¨(CH2CH2NH),¨ groups. In a preferred embodiment
the
friction modifier is the condensation product of a C8 to C24 fatty acid with a
polyalkylene
polyamine, and in particular, the product of isostearic acid with
tetraethylenepentamine.
The condensation products of carboxylic acids and polyalkyleneamines may
generally be
imidazolines or amides.
[0060] Sulfurized olefins may be used as friction modifiers. A
particularly preferred
sulfurized olefin is one which is prepared in accordance with the detailed
teachings of U.S.
Pat. Nos. 4,957,651 and 4,959,168. Described therein is a cosulfurized mixture
of two or
more reactants selected from the group consisting of (1) at least one fatty
acid ester of a
polyhydric alcohol, (2) at least one fatty acid, (3) at least one olefin, and
(4) at least one
fatty acid ester of a monohydric alcohol.
[0061] Reactant (3), the olefin component, comprises at least one
olefin. This olefin is
preferably an aliphatic olefin, which usually will contain 4 to 40 carbon
atoms, preferably
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from 8 to 36 carbon atoms. Terminal olefins, or alpha-olefins, are preferred,
especially
those having from 12 to 20 carbon atoms. Mixtures of these olefins are
commercially
available, and such mixtures are contemplated for use in this invention.
[0062] The cosulfurized mixture of two or more of the reactants, is
prepared by
reacting the mixture of appropriate reactants with a source of sulfur. The
mixture to be
sulfurized can contain 10 to 90 parts of reactant (1), or 0.1 to 15 parts by
weight of reactant
(2); or 10 to 90 parts, often 15 to 60 parts, more often 25 to 35 parts by
weight of reactant
(3), or 10 to 90 parts by weight of reactant (4). The mixture, in the present
invention,
includes reactant (3) and at least one other member of the group of reactants
identified as
reactants (1), (2) and (4). The sulfurization reaction generally is effected
at an elevated
temperature with agitation and optionally in an inert atmosphere and in the
presence of an
inert solvent. The sulfurizing agents useful in the process of the present
invention include
elemental sulfur, which is preferred, hydrogen sulfide, sulfur halide, sodium
sulfide and a
mixture of hydrogen sulfide and sulfur or sulfur dioxide. Typically often 0.5
to 3 moles of
sulfur are employed per mole of olefinic bonds.
[0063] Metal salts of alkyl salicylates include calcium and other salts
of long chain
(e.g. C12 to C16) alkyl-substituted salicylic acids.
[0064] Friction modifiers may include derivatives of (or a compound
derived from) a
hydroxy-carboxylic acid, prepared or preparable by reaction of the acid group
and/or the
alcohol group of the hydroxy-carboxylic acids to form esters, amides, and
imides and
mixtures of multiple such functionalities.
[0065] Suitable hydroxy-carboxylic acids may include monohydroxy
monocarboxylic
acids, polyhydroxy monocarboxylic acids, monohydroxy polycarboxylic acids and
polyhydroxy polycarboxylic acids and may be exemplified by citric acid,
tartaric acid,
lactic acid, malic acid, glycolic acid, hydroxy-propionic acid,
hydroxyglutaric acid,
oligomers thereof, or mixtures thereof The derivative of (or compound derived
from) a
hydroxy-carboxylic acid includes amide, ester or imide derivatives of a
hydroxy-
carboxylic acid, or mixtures thereof Typically, the derivative of a hydroxy-
carboxylic acid
may be a derivative of a hydroxy- polycarboxylic acid such as tartaric acid.
[0066] In one embodiment the amide, ester or imide derivative of a hydroxy-
carboxylic acid may be at least one of hydroxy-carboxylic acid di- ester, a
hydroxy-
carboxylic acid di-amide, a hydroxy-carboxylic acid mono- imide, a hydroxy-
carboxylic
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acid di-imide, a hydroxy-carboxylic acid ester- amide, a hydroxy-carboxylic
acid ester-
imide, and a hydroxy-carboxylic acid imide-amide. In one embodiment the amide,
ester or
imide derivative of a hydroxy-carboxylic acid may be at least one of the group
consisting
of a hydroxy-carboxylic acid di-ester, a hydroxy-carboxylic acid di-amide, and
a hydroxy-
carboxylic acid ester-amide.
[0067] Examples of a suitable a hydroxy-carboxylic acid include In one
embodiment
the amide, ester or imide derivative of a hydroxy-carboxylic acid may be
derived from
tartaric acid, citric acid, hydroxy-succinic acid, dihydroxy mono-acids, mono-
hydroxy
diacids, or mixtures thereof In one embodiment the amide, ester or imide
derivative of a
hydroxy-carboxylic acid includes a derivative or (or compound derived from)
tartaric acid
or citric acid. In one embodiment the amide, ester or imide derivative of a
hydroxy-
carboxylic acid includes a compound derived from tartaric acid.
[0068] The derivative of a hydroxy-carboxylic acid may be selected from
the group
consisting of a hydroxy-carboxylic acid di-ester, a hydroxy- carboxylic acid
di-amide, a
hydroxy-carboxylic acid imide, a hydroxy- carboxylic acid di-imide, a hydroxy-
carboxylic
acid ester-amide, a hydroxy- carboxylic acid ester-imide, and a hydroxy-
carboxylic acid
imide-amide. The derivative of a hydroxy-carboxylic acid may be selected from
the group
consisting of a hydroxy-carboxylic acid imide, a hydroxy-carboxylic acid di-
imide, a
hydroxy-carboxylic acid ester-imide, and a hydroxy-carboxylic acid imide-
amide.
[0069] The derivative of a hydroxy-carboxylic acid may be selected from the
group
consisting of a hydroxy-carboxylic acid imide and a hydroxy- carboxylic acid
di-imide.
[0070] The derivative of a hydroxy-carboxylic acid may be derivative of
tartaric acid,
an imide derivative of citric acid, or mixtures thereof.
[0071] The derivative of a hydroxy-carboxylic acid may be imide
derivative of tartaric
acid, an imide derivative of citric acid, or mixtures thereof In one
embodiment the
derivative of a hydroxy-carboxylic acid is either an ester or imide. The ester
derivative of
a hydroxy-carboxylic acid may be a tartrate. The imide derivative of a hydroxy-
carboxylic
acid may be a tartrimide.
[0072] In one embodiment the derivative of (or compound derived from) a
hydroxy-
carboxylic acid may be imide derivative of a hydroxy-carboxylic acid. US
Patent
Applications US 60/939949 (filed May 24, 2007), now W02008/147704, and US
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60/939952 (filed May 24, 2007), now WO 2008/147700, disclose suitable hydroxy-
carboxylic acid compounds, and methods of preparing the same.
[0073] Canadian Patent 1 183 125; US Patent Publication numbers
2006/0183647 and
US-2006-0079413; US Patent Application number 60/867402 (now W02008/067259);
and British Patent 2 105 743 A, all disclose examples of suitable tartaric
acid derivatives.
[0074] The amount of the friction modifier employed in the lubricant
composition may
be in the range of 0.1 to 5 wt. % of the lubricant composition. In other
embodiments it
may be present at 0.15 to 3.0 wt. %, or 0.2 to 3.0 wt. %, or 0.5 to 3.0 wt. %,
or 1.0 to
2.0 wt. % of the lubricant composition.
[0075] In some embodiments of the present invention, mixtures of ash
containing and
ashless friction modifiers may be employed. In some embodiments, the lubricant
composition may be substantially free of ashless friction modifiers. In yet
other
embodiments, the lubricant composition may be substantially free of ash-
containing
friction modifiers.
[0076] The lubricant composition may also contain a polymer such as an
olefin
polymer, as for example polyisobutene. Generally suitable polymers are
relatively low
molecular weight materials, having a molecular weight (number average) of 5000
or less,
such as 500 to 3000 or 1000 to 2500. Occasionally, however, higher molecular
weight
olefin polymers have been used in two-cycle lubricants; see, for example, U.S.
patent
5,741,764. Such polymers may be hydrogenated to remove most or all of any
remaining
ethylenic unsaturation. If an olefin copolymer, such as a low molecular weight
polyisobutylene is present, it may be present in an amount of 0.1 to 3 wt. %
or 0.1 to
2 wt. % or 0.2 to 2.0 wt. % of the lubricant composition.
[0077] Another material which may be present is a hydrocarbyl-
substituted phenol.
This may be a similar material to that used in the preparation of the Mannich
dispersant,
above, and its description as recited there will be applicable for this
component as well.
In one embodiment, the hydrocarbyl-substituted phenol may be a polyisobutylene-
substituted phenol, and the polyisobutylene group may have a number average
molecular
weight of 300 to 3000 or 500 to 2000 or 750 to 1600 or about 1000. Derivatives
of the
hydrocarbyl-substituted phenol may also be used, including the reaction
products of the
hydrocarbyl-substituted phenol with an amine such as an alkylene polyamine,
other
aliphatic and aromatic mono- and polyamines, alkanolamines having one or more
hydroxyl
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groups and mixtures thereof, or an epoxide. The hydrocarbyl phenol, if it is
present, may
be present, in an amount of up to 10 wt. %, such as 0.2 to 5 wt. % or 0.5 to 4
wt. % or 1.0
to 2.0 wt. % of the lubricant composition.
[0078] The lubricant composition may also contain a detergent. The
detergent may be
an ashless detergent or an ash containing detergent, such as a metal-
containing detergent.
Detergents are often overbased materials, otherwise referred to as overbased
or superbased
salts. These are generally single phase, homogeneous Newtonian systems
characterized
by a metal content in excess of that which would be present for neutralization
according
to the stoichiometry of the metal and the particular acidic organic compound
reacted with
the metal. The overbased materials are prepared by reacting an acidic material
(typically
an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a
mixture
comprising an acidic organic compound, a reaction medium comprising at least
one inert,
organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for said acidic
organic material,
a stoichiometric excess of a metal base, and a promoter such as a phenol or
alcohol.
[0079] The acidic organic material will normally have a sufficient number
of carbon
atoms to provide a degree of solubility in oil. The amount of excess metal is
commonly
expressed in terms of metal ratio. The term "metal ratio" is the ratio of the
total equivalents
of the metal to the equivalents of the acidic organic compound. A neutral
metal salt has a
metal ratio of one. A salt having 4.5 times as much metal as present in a
normal salt will
have metal excess of 3.5 equivalents, or a ratio of 4.5.
[0080] Such overbased materials are well known to those skilled in the
art. Patents
describing techniques for making basic salts of alkylaromatic sulfonic acids,
carboxylic
acids, phenols, phosphonic acids, and mixtures of any two or more of these
include U.S.
Patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186;
3,384,585;
3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109. Yet other
detergents are
referred to as salixarate detergents. These include overbased materials
prepared from
salicylic acid (which may be unsubstituted) with a hydrocarbyl-substituted
phenol, such
entities being linked through ¨CH2¨ or other alkylene bridges. It is believed
that the
salixarate derivatives have a predominantly linear, rather than macrocyclic,
structure,
although both structures are intended to be encompassed by the term
"salixarate".
Salixarate derivatives and methods of their preparation are described in
greater detail in
U.S. patent number 6,200,936 and PCT Publication WO 01/56968.
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[0081] In certain embodiments the detergent may be an overbased
sulfonate, phenate,
salicylate, or salixarate detergent. In certain embodiments it may comprise an
overbased
calcium phenate detergent. The phenols useful in making phenate detergents can
be
represented by (10)a-Ar-(OH)b, where le is an aliphatic hydrocarbyl group of 4
to 400 or
6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms; Ar is an aromatic group
such as
benzene, toluene or naphthalene; a and b are each at least one, the sum of a
and b being up
to the number of displaceable hydrogens on the aromatic nucleus of Ar, such as
1 to 4 or
1 to 2. There is typically an average of at least 8 aliphatic carbon atoms
provided by the
R' groups for each phenol compound. Phenate detergents are also sometimes
provided as
sulfur-bridged species.
[0082] While the metal salt of the phenate detergent is typically
calcium, the metal
compounds useful in making the basic metal salts are more generally any Group
1 or
Group 2 metal compounds (CAS version of the Periodic Table of the Elements).
Examples
include alkali metals such as sodium, potassium, lithium, copper, magnesium,
calcium,
barium, zinc, and cadmium. In one embodiment the metals are sodium, magnesium,
or
calcium. The anionic portion of the basic metal compound can be hydroxide,
oxide,
carbonate, borate, or nitrate.
[0083] The ash containing detergent may be present in the lubricant
composition in an
amount 0.1 to 10 wt. % of the lubricant composition, or 0.5 to 5 wt. % of the
lubricant
composition, or even 0.8 to 2.2 wt. %. In certain embodiments a metal-
containing
detergent may contribute at least about 0.1 total base number, or at least 0.3
or 0.4 or 0.6
TBN to the lubricant composition, and in some embodiments up to 3 or 2 or 1
TBN. In
other embodiments, the metal-containing detergent may be present in an amount
to deliver
at least 0.01 percent sulfated ash to the composition. The detergent may be
present in an
amount to deliver 0.01 to 0.12 percent sulfated ash or, alternatively, 0.05 to
0.1 percent, or
even 0.06 to 0.09 percent.
[0084] The lubricant compositions of the present invention may comprise
an ashless
detergent. The ashless (or metal-free) detergent may comprise a basic salt of
a quaternary
pnictogen compound. By basic salt, it is meant that the quaternary pnictogen
compound
provides base number (measured as total base number TBN by ASTM D2896 and/or
ASTM D4739) to the lubricating composition.
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[0085] The ashless detergents differ from conventional metal-based
detergents in that
they are metal free or substantially metal free or contain a lower amount of
metal that
would be expected based on the amount of TBN that they deliver. Alternatively
expressed,
they do not contribute metal ions to lubricants in which they are added, or
contribute less
metal ions than would be expected on the amount of TBN that they deliver. In
certain
embodiments the detergents are metal free, although they may be mixed with
other
components, such as other detergents that do contain metal, while still, in
themselves,
being metal free. By the term "substantially metal free" is meant a detergent
that contains
only a contaminant or a trace amount of a metal, an amount that may in many
circumstances be ignored. For instance, such a detergent may contain less than
5% or less
than 3 or 1% metal by weight.
[0086] In place of some or all of the metal ion of the detergent, the
materials of the
present invention will contain one or more quaternary non-metallic pnictogen
cations.
Pnictogens are the elements in column 15 (or Group Va) of the periodic table,
the column
headed by nitrogen. The non-metallic pnictogens include nitrogen and
phosphorus.
[0087] Quaternary nitrogen or phosphorus compounds are known.
Ordinarily nitrogen
is a trivalent element, forming three covalent bonds to hydrogen or carbon
atoms in
ammonia or amines: NHxR3,, where R is a group linked to the nitrogen atom
through a
carbon atom of the R group. Quaternary nitrogen compounds, on the other hand,
comprise
a quaternary ammonium ion and a counterion (e.g., hydroxide, halide),
represented by the
general formula
NR4+ X-
where, each R independently represents a suitable hydrocarbyl group, and X-
represents
one equivalent of an anionic counterion, which may include fractional
equivalents of
polyanionic species (e.g. a half mole of carbonate, i.e. 1/2 CO2-). Quaternary
phosphonium
ions may be similarly represented (PR4+). In such materials, the nitrogen (or
phosphorus)
has four substantially non-ionizable covalent bonds to carbon atoms. The
quaternary atoms
are permanently charged and are comparatively unaffected by the pH of the
medium. They
are thus distinguished from ordinary ammonium or phosphonium ions or
protonated
amines, which materials contain up to three substantially non-ionizable
covalent bonds to
carbon and one or more acidic hydrogen atoms or protons associated with the
nitrogen or
phosphorus atom. The present quaternary ions will not contribute acidity to
the detergent,
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as would be titratable as TAN by ASTM D 664A. The basic ashless detergents of
the
present technology will thus be free from acidic protons in the sense that
they will have
the general structure NR4+X" rather than HNR3+X", in the case of nitrogen.
However, the
detergent molecules overall may (or may not) contain other acidic hydrogen
that is
titratable as TAN, on other portions of the detergent than the cation, that
is, on the anionic
substrate portion. An example of a titratable hydrogen might be on a phenolic
OH group
or bicarbonate (HCO3-). In certain embodiments, however, the detergent as a
whole will
be substantially free from acidic protons, having a TAN of less than 10 or
less than 5 or
less than 3 or less than 1, on an oil free basis.
[0088] It is not intended that each of the four bonds of the nitrogen or
phosphorus must
necessarily be directed to a separate carbon atom: The 4 R groups are not
necessary
different carbon groups. Thus two of the bonds may be directed to the same
carbon atom
in a double-bonded structure or as delocalized bonds within an aromatic ring.
Examples
of such include pyridinium ions and imidazolium ions.
[0089] Many quaternary salt compounds are known. Quaternary ammonium salts,
for
instance, are commercially available and may be prepared by the reaction of
ammonia or
an amine with an alkyl halide as the complete alkylation product. Certain
quaternary
phosphonium salts may be prepared by the reaction of phosphine with aldehydes,
e.g.,
tetrakis(hydroxymethyl)phosphonium chloride. Examples of quaternary ammonium
compounds include tetrahydrocarbyl ammonium salts with hydrocarbyl groups such
as
methyl, ethyl, propyl, butyl, benzyl, and mixtures thereof In another
embodiment, up to
three of the R groups in the quaternary NR4+ structure may be such hydrocarbyl
groups
and one or more groups may be a hydroxy-substituted hydrocarbyl group such as
a
hydroxyalkyl group, or an amine-substituted hydrocarbyl group. Examples of
quaternary
.. ammonium salts containing a hydroxyalkyl group, and methods for their
synthesis, are
disclosed in U.S. Pat. No. 3,962,104, Swietlik et al.; see column 1 line 16
through
column 2 line 49; column 8 lines 13 through 49, and the Examples. In certain
embodiments, the quaternary ammonium compound is derived from a monoamine,
i.e. a
tertiary amine having only a single amino group, i.e. having no additional
amine nitrogen
.. atoms in any of the three hydrocarbyl groups or substituted hydrocarbyl
groups attached
to the tertiary amine nitrogen. In certain embodiments there are no additional
amine
nitrogen atoms in any of the hydrocarbyl groups or substituted hydrocarbyl
groups
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attached to the central nitrogen in the quaternary ammonium ion. Further
examples of
quaternary ammonium compounds include tetraethylammonium hydroxide or halide
and
tetrabutylammonium hydroxide or halide and such biological materials as
choline
chloride, HOCH2CH2N(CH3)3C1. Any such materials may provide the cation for the
present detergents.
[0090] The anion portion of the detergent may be an organic anion
having at least one
aliphatic hydrocarbyl group of sufficient length to impart oil solubility to
the detergent.
Suitable aliphatic hydrocarbyl groups, if they are in the form of a
substituent on an
aromatic ring (as in alkylphenates or alkylbenzenesulfonates) may contain 4 to
400 carbon
atoms, or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms. The anionic
portion of the
detergent may thus be any of the anions derived from the acidic organic
materials that are
used to prepare conventional detergents. As mentioned above, these include
sulfonic acids,
providing sulfonate detergents with sulfonate anions, carboxylic acids,
providing
carboxylate detergents with carboxylate anions, phenols, providing phenate
detergents
with phenate anions, hydrocarbyl-substituted salicylic acids, providing
salicylate
detergents with salicylate anions, phosphonic acids, providing phosphonate
detergents, as
well as salixarate, calixarate, and saligenin detergents, and mixtures
thereof. In certain
embodiments the ashless detergents may be sulfonates or salicylates, and in
other
embodiments, sulfonates.
[0091] The anion portion of the ashless detergent may be an acylated
(co)polymer.
Acylated (co)polymers include (co)polymers containing or functionalized with
at least one
carboxylic acid group, carboxylic anhydride, or mixtures thereof Acylated
polymers
include polyolefins that have been grafted or otherwise functionalized with
one or more
a,13-unsaturated acylating agents. Suitable polyolefins include (co)polymers
of ethylene,
propylene, butene, isobutylene, higher alpha-olefins, butadiene, isoprene, and
combinations thereof. In one embodiment, the acylated copolymer is a
polyisobutylene
having a number average molecular weight (Mn) of 400 to 3000 (as measured
versus
polystyrene standards) functionalized with at least 1 and up to 2 succinic
acid groups or
functional equivalents (e.g. succinic anhydride). In one embodiment, the
acylated
copolymer is a copolymer of ethylene and at least one higher alpha olefin,
wherein the
olefin copolymer has Mn of between 5000 Daltons and 100,000 Daltons or between
15,000
Daltons and 60,000 Daltons (as measured by GPC against polystyrene standards).
In one
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embodiment, the acylated copolymer is a copolymer of ethylene and propylene; a
copolymer of ethylene, propylene and butene; a copolymer of ethylene and
butene; or
combinations thereof.
[0092] The acylated copolymer may be a poly(meth)acrylate (PMA)
containing at
least one of (meth)acrylic acid moieties, other acylated monomers that
copolymerize
readily with (meth)acrylates, or combinations thereof In one embodiment, the
poly(meth)acrylate contains at least 2 weight percent (meth)acrylic acid
moiety, either by
direct incorporation of (meth)acrylic acid monomers during polymerization or
by partial
hydrolysis of the polymethacrylate after polymerization is complete. PMA's are
prepared
from mixtures of methacrylate monomers having different alkyl groups. The
alkyl groups
may be either straight chain or branched chain groups containing from 1 to 24
carbon
atoms. Other acylated monomers that may co-polymerize with (meth)acrylates
include
maleic acid, maleic anhydride, fumaric acid, cinnamic acid, caffeic acid,
esters of the
preceding acids, and combinations thereof.
[0093] The anion portion of the ashless detergent may further include an
inorganic
anion, especially the conjugate base of inorganic protic acids. Inorganic
anions include
borate, sulfate, phosphate, nitrate, carbonate, bicarbonate, hydroxide, and
combinations
thereof. In one embodiment, the ashless detergent comprises a quaternary
pnictogen salt
of an inorganic base such as carbonate, bicarbonate, hydroxide, or mixtures
thereof
[0094] The ashless quaternary pnictogen detergent may be a mixture of both
organic
and inorganic anions salts; that is, the quaternary pnictogen cation would be
present in
excess of the amount necessary to effect a stoichiometric neutral salt with
the organic
anion. In such cases, the ashless detergent may be understood to be overbased.
Degree of
overbasing (or "base ratio") can be calculated as the ratio of cation
equivalents (herein
described as a quaternary pnictogen cation) to organic anion equivalents; a
neutral salt of
[tetraalkylammonium] [alkylbenzenesulfonate] can be seen as having a base
ratio of 1Ø
In one embodiment, the ashless detergent comprising a quaternary pnictogen
salt of an
organic anion is overbased. The ashless detergents of the present invention
may thus, in
certain embodiments, have a base ratio of 1.1, 1.5 or 2 or 3 or 7, up to 40 or
25 or 20 or
10.
[0095] Overbased ashless detergents may be obtained by a process
analogous to the
process for preparing overbased metal-containing detergents, while considering
the
23
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important differences required to obtain the present materials. That is, the
present
detergents may be prepared by reacting a mixture comprising an acidic organic
compound
or substrate, as described above, with a molar excess, that is, a
stoichiometric excess, of a
basic quaternary pnictogen compound, optionally in an inert reaction medium or
organic
solvent such as mineral oil, naphtha, toluene, or xylene. Optionally an
additional acidic
material may be present, such as oxo acid, e.g., carbon dioxide, to form a
carbonate or
bicarbonate, and optionally a small amount of a promoter (e.g. an alkanol of
one to twelve
or one to six carbon atoms such as methanol, ethanol, or amyl alcohol, or an
alkylated an
alkylated phenol such as heptylphenol, octylphenol, or nonylphenols) may be
present.
[0096] The presence of the oxo acid may assist in incorporation of larger
quantities of
base, through formation of, in the case of carbon dioxide, colloidal carbonate
of the base.
Suitable oxo anions which may become a part of the overbased detergent include
carbonate, bicarbonate, borate, hydroxide, nitrate, phosphate, sulfate, and
carboxylate,
such as oxalate, tartrate, citrate, succinate, and acetate ions. The
carboxylate anions may
contain 8 or fewer or 6 or fewer or 5 or fewer or 3 or 2 or 1 carbon atom(s).
Also included
may be ions derived from I3-keto esters and diketones. The oxo anions may be
derived
from inorganic acids, e.g., carbonate or bicarbonate ions.
[0097] In one embodiment, the ashless detergent may at least one of an
alkylbenzene
sulfonate detergent, a phenate detergent, a sulfur-coupled detergent, a
salicylate detergent,
an aliphatic carboxylic acid detergent, overbased compositions of said
detergents, or
mixtures thereof
[0098] The ashless detergent may have a TBN of at least 35 mg KOH/g as
measured
by ASTM D2896. In one embodiment the ashless detergent may have a TBN of at
least
50 mg KOH/g, or at least 75 mg KOH/g, or at least 95 mg KOH/g (reported on an
oil-free
basis, i.e., excluding any diluent oil).
[0099] The ashless detergent may be present in the lubricant
composition in an amount
0.1 to 10 wt. % of the lubricant composition, or 0.5 to 5 wt. % of the
lubricant composition,
or even 0.8 to 2.2 wt. %. In some embodiments, the ashless quaternary
pnictogen detergent
may be present in the lubricating composition in amount to deliver total base
number
(TBN) at least 1.5 mg KOH/g to the composition, or at least 2.3, or 3.0 up to
12, or even
4.4 up to 8.5 mg KOH/g to the lubricating composition (as measured by ASTM
D2896).
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[0100] The total amount of the detergent, if present, may in certain
embodiments be
up to 10 wt. % or 5 wt. % e.g., 0.01 to 5 wt. % or 0.01 to 3 wt. % or 0.5 to 3
wt. % or 0.5
to 2.0 wt. %.
[0101] In certain embodiments, the present lubricant composition is not
an ash-free
lubricant; that is, the detergent may be an ash-containing detergent,
containing 0.01 to 0.12
percent sulfated ash or, alternatively, 0.05 to 0.1 percent, or even 0.06 to
0.09 percent,
which ash may be provided by the metal-containing detergent or detergents or
in whole or
in part from other sources such as zinc salts (e.g., zinc
dialkyldithiophosphates),
molybdenum compounds, or titanium compounds.
[0102] In some embodiments of the present invention, mixtures of ash
containing and
ashless detergents may be employed. In some embodiments, the lubricant
composition
may be substantially free of ashless detergents. In yet other embodiments, the
lubricant
composition may be substantially free of ash-containing detergents.
[0103] A further component of the present lubricant compositions may
include a
surfactant, in an amount up to about 5 wt. % or up to about 4 wt. % or from
about 0.05 to
about 5 wt. % or about 0.05 to about 4 wt. %. The surfactant may comprise an
oil soluble
polyalkylene glycol, which may be a homopolymer or a copolymer, typically a
copolymer.
[0104] The lubricant composition may include a polyether fluidizer
component
comprising a polyether, a polyetheramine, or mixtures thereof The polyether of
the present
invention can be represented by the formula RO[CH2CH(R1)0]H where R is a
hydrocarbyl group; Rl is selected from the group consisting of hydrogen, alkyl
groups of
1 to 14 carbon atoms, and mixtures thereof; and x is a number from 2 to 50.
The
hydrocarbyl group R is a univalent hydrocarbon group, has one or more carbon
atoms, and
includes alkyl and alkyl-phenyl groups having 7 to 30 total carbon atoms, such
as 9 to 25
total carbon atoms, or 11 to 20 total carbon atoms. The repeating oxyalkylene
units may
be derived from ethylene oxide, propylene oxide, or butylene oxide. The number
of
oxyalkylene units x may be 10 to 35, or 18 to 27. The polyether of the present
invention
can be prepared by various well-known methods including condensing one mole of
an
alcohol or alkylphenol with two or more moles of an alkylene oxide, mixture of
alkylene
oxides, or with several alkylene oxides in sequential fashion, usually in the
presence of a
base catalyst. U.S. Pat. No. 5,094,667 provides reaction conditions for
preparing a
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polyether. Suitable polyethers are commercially available from Dow Chemicals,
Huntsman, ICI and include the Actaclearg series from Bayer.
[0105] The polyetheramine of the present technology can be represented,
in certain
embodiments, by the formula R[OCH2CH(R1)].A, where R is a hydrocarbyl group as
described above for polyethers; le is selected from the group consisting of
hydrogen, alkyl
groups of 1 to 14 carbon atoms, and mixtures thereof; n is a number from 2 to
50; and A
is selected from the group consisting of ¨OCH2CH2CH2NR2R2 and ¨NR3R3 where
each
R2 is independently hydrogen or a hydrocarbyl group of one or more carbon
atoms, and
each R3 is independently hydrogen, a hydrocarbyl group of one or more carbon
atoms, or
¨[R4N(R5)]pR6 where R4 is C2_C10 alkylene, R5 and R6 are independently
hydrogen or a
hydrocarbyl group of one or more carbon atoms, and p is a number from 1 to 7.
The
polyetheramine may be derived from ethylene oxide, propylene oxide, or
butylene oxide.
The number of oxyalkylene units n in the polyetheramine may be 10 to 35, or 18
to 27.
The polyetheramine of the present technology can be prepared by various well
known
methods. A polyether derived from an alcohol or alkylphenol as described above
can be
condensed with ammonia, an amine or a polyamine in a reductive amination to
form a
polyetheramine as described in European Publication No. EP 310875.
Alternatively, the
polyether can be condensed with acrylonitrile and the nitrile intermediate
hydrogenated to
form a polyetheramine as described in U.S. Pat. No. 5,094,667. Suitable
polyetheramines
include those where A is ¨OCH2CH2CH2NH2. Polyetheramines are commercially
available in the Techrong series from Chevron and in the Jeffamine series
from
Huntsman.
[0106] In one embodiment, the polyether may be represented by the
formula le¨(-
0¨R2¨)n¨R3 wherein le is a hydrocarbyl group of 10 to 24 (or 12 to 15) carbon
atoms,
each R2 is independently an alkylene group of 2 to 6 (or 3 to 4) carbon atoms,
n is 10 to 30
(or 18 to 26), and R3 is H or an alkyl group or ¨CH2CH2NH2 or ¨CH2CH2CH2NH2 or
¨
CH2CHRNH2, where R is an alkyl group (especially, methyl or ethyl), e.g., ¨
CH2CH(CH3)NH2, or where together le and R3 may represent an alkylene group so
as to
form a cyclic ether. A suitable polyether, which may also be described as a
polyether
fluidizer, may comprise a reaction product of one unit of (that is, derived
from) a hydroxy-
containing hydrocarbon and two or more units of (that is, derived from) an
alkylene oxide,
wherein the hydroxy-containing hydrocarbon contains 1 to 50 carbon atoms and
the
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alkylene group of the alkylene oxide contains 2 to 6 carbon atoms, wherein the
reaction
product is optionally further reacted with acrylonitrile and hydrogenated to
provide a
terminal amino group.
[0107] The polyether or polyetheramine of the present technology may
have a number
average molecular weight of 300 or 350 to 5000, in another instance of 400 to
3500, and
in further instances of 450 to 2500 and 1000 to 2000.
[0108] The polyether (or polyether fluidizer) may be present in the
lubricant
composition in an amount of 0.01 or 0.05 or 0.1 or 0.3 or 0.5 to 5 wt. %, or
0.8 to 4 wt. %
or 1 to 3 wt. % or 0.1 to 3 wt. % or 1.5 to 2.5 wt. %, e.g., about 2 wt. %
[0109] Other conventional components may also be present, including pour
point
depressants; viscosity index modifiers; metal deactivators; antioxidants; rust
inhibitors,
corrosion inhibitors, high pressure additives, anti-wear additives, and
antifoam agents.
Any of these materials can be present or can be eliminated, if desired.
[0110] The lubricant compositions formed as described above may, in
some
embodiments comprise only ash-free components, and thus be characterized as
ash-free
lubricant compositions. In other embodiments, one or more components may
contribute
ash to the lubricant composition. The total ash content of the lubricant
composition may
be less than 2000 parts per million (ppm) or less than 1500 ppm, or 1000 ppm,
or 500 ppm,
or 250 ppm or 100 ppm.
[0111] The lubricant compositions may have a sulfur content of less than
500 ppm or
400 ppm or 200 ppm or 100 ppm. In some embodiments, the lubricant composition
may
be substantially free of sulfur containing components.
[0112] The components of the present invention can be prepared by
mixing the
indicated components directly, or by preparing one or more of the components
in the form
of a concentrate, to which other components (such as oil or solvent) can
subsequently be
added.
[0113] The present lubricant may be supplied to an engine in any of a
variety of ways,
depending at least in part on the design of the engine. It may be supplied
along with the
fuel, either by injection into the fuel stream or by premixing the lubricant
into the bulk
fuel.
[0114] Regarding the fuel, any of a variety of fuels may be used. The
fuel is normally
a liquid at ambient conditions e.g., room temperature (20 to 30 C). The fuel
may be a
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hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture thereof. The fuel into
which the
lubricant composition for a two-cycle engine is mixed is commonly, but not
necessarily,
gasoline as defined by ASTM specification D4814. In one embodiment, the fuel
is a
gasoline, and in other embodiments, the fuel is a leaded gasoline or a
nonleaded gasoline.
The nonhydrocarbon fuel can be an oxygen-containing composition, often
referred to as
an oxygenate, which can include an alcohol, an ether, a ketone, an ester of a
carboxylic
acid, a nitroalkane, or a mixture thereof. The nonhydrocarbon fuel can
include, for
example, methanol, ethanol, propanol, butanol, methyl t-butyl ether, methyl
ethyl ketone,
transesterified oils and/or fats from plants and animals such as rapeseed
methyl ester and
soybean methyl ester, and nitromethane. In some embodiments, the fuel can have
an
oxygenate content on a weight basis of 15 percent by weight, or 25 percent by
weight, or
50 percent by weight, or 65 percent by weight, or 85 percent by weight, or 90
percent by
weight. Mixtures of hydrocarbon and nonhydrocarbon fuels can include, for
example,
gasoline and methanol and/or ethanol, diesel fuel and ethanol, and diesel fuel
and a
transesterified plant oil such as rapeseed methyl ester, fuels referred to as
E85 or M85, and
fuels referred to as AlCoolTM. In one embodiment, mixtures of hydrocarbon and
nonhydrocarbon fuels can be defined by ASTM D-5798-99. In one embodiment, the
fuel
comprises a blend of ethanol and gasoline having a ratio from 10:90 to 90:10,
or 15:85 to
90:10, or 25:75 to 90:10. In an embodiment, the fuel can be an emulsion of
water in a
hydrocarbon fuel, in a nonhydrocarbon fuel, or a mixture thereof The lubricant
may be
blended into the liquid fuel in an amount or ratio of 1:200 to 1:25 by volume,
or 1:60 to
1:40, or about 1:50 (e.g., about 2% lubricant by volume). In certain
embodiments of the
present inventions, the lubricant composition, when blended into the liquid
fuel in an
amount or ratio of about 1:50, delivers a base oil to liquid fuel ratio of
about 1:125 to
1:500, or 1:150 to 1:400, or 1:200 to 1:350 by volume.
[0115] It is accordingly within the scope of the present technology to
provide a
combustible mixture for fueling an engine, such as a two cycle engine, that
comprises a
lubricant composition as described admixed with a liquid fuel at a ratio of
1:60 to 1:40, or
about 1:50 by volume.
[0116] In combustible mixtures of the present technology, the ratio of the
oil of
lubricating viscosity to liquid fuel may be 1:125 to 1:500, or 1:150 to 1:400,
or 1:200 to
1:350 by volume, while demonstrating excellent performance and reduced
particulate
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matter in at least one of total particulate mass, particulate number, total
organic carbon or
elemental carbon, or particulate size.
[0117] The lubricant and/or the combustible mixture formed using the
lubricant
composition of the present technology may be profitably employed in a two-
stroke cycle
engine. Such engines are commonly used in lawn and garden equipment, portable
contractor equipment such as pumps and electrical generators, low-cost
transportation
vehicles, such as mopeds, as well as commercial and recreational vehicles
including
motorcycles, outboard engines (for boats and marine vehicles), snowmobiles,
and
personal watercraft vehicles. In some larger recreational applications as in
outboard
engines, engines with a displacement of 2,000 to 3,000cm3 generate
approximately
150 kW (201 hp). 2-stroke cycle engines can also be found in very small
applications,
such as in power tools like weed trimmers or chain saws. These smaller engines
typically
output up to 10 hp or up to 5 hp or 1 to 10 hp or 1 to 5 hp or 5 to 10 hp. The
engine may
have a cylinder displacement of 20 to 80 cm3. In some embodiments, therefore,
the
engines may have a power output of less than 150 kW, such as less than 100 or
less than
50 or less than 20 kW; or 0.1 to 15 kW or 0.5 to 10 kW or 1-5 kW, and
optionally a
cylinder displacement of 10 to 300 cm3, or 15-100 or 20-80 cm3.
[0118] The amount of each chemical component described is presented
exclusive of
any solvent or diluent oil, which may be customarily present in the commercial
material,
that is, on an active chemical basis, unless otherwise indicated. However,
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.
[0119] 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 or anionic 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 be 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.
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EXAMPLES
[0120] A series of lubricant compositions is prepared according to the
formulations in
Table 1 and tested in a Stihl FS 460C two-stroke cycle brush cutter engine,
45.6 cm'
engine displacement, running on gasoline-lubricant mixtures (1:50 admixture of
lubricant
and fuel (unadditized gasoline)). Preparation of the engine for each test
involves draining
(as necessary) any existing fuel/oil mixture and replacing the fuel filter. A
portion of the
fuel/oil candidate is run in the engine at idle for 15 minutes followed by a
wide open
throttle for 15 minutes. The remaining fuel/oil is drained and the fuel filter
is again
changed. A new portion of the fuel/oil mixture is then put into the engine in
preparation
for the test.
[0121] The test consists of two stages: an idle portion and a full
throttle portion. The
engine is operated at the idle condition for 15 minutes. During the last 5
minutes, data on
emissions from the engine is collected. The engine is then operated at the
full throttle
condition for 15 minutes. During the last 5 minutes, data on emissions from
the engine is
collected. This idle/full throttle sequence is repeated four times (for a
total of five data
collections in each of idle and full throttle operation).
[0122] Collection of particulates was undertaken employing a device
similar to the
Solid Particle Sampling System described in SAE Technical Paper No. 2007-01-
0307,
entitled "Sampling System for Solid and Volatile Exhaust Particle Size, Number
and Mass
Emissions". For purposes of the particulate collection herein, the Solid
Particle Sampling
System was dissimilar to the system described in the referenced SAE Technical
Paper in
that the 2T engine exhaust was coupled to a full-flow dilution tunnel, instead
of a micro-
dilution tunnel as depicted. Particle mass was measured using a Sierra BG3
partial flow
sampling system from Sierra Instruments, Inc. Particle number and size were
measured
using a TSI Engine Exhaust Particle Sizer (EEPS) available from TSI.
[0123] Particulate matter was evaluated with respect to total
particulate mass and
particulate number.
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Table 1
Amounts, % by weight* Comp 1 Ex 1 Ex 2 Ex 3
Oil' Balance to Balance Balance Balance to
100% to 100% to 100% 100%
Solventb -- 66.67 80.00 80.00
Polyolefin-substituted phenol 2.00 0.67 0.40 2.00
Friction Modifier (GMO) 0.50 0.17 0.10 0.50
Mannich dispersant' 1.91 0.64 0.38 1.91
Succinimide dispersant' 1.91 0.64 0.38 1.91
* on an oil free basis.
a. Base oil plus diluent oils from other additives.
b. Exxsol D-80 aliphatic hydrocarbon solvent from Exxon.
c. Product of polyisobutylene phenol, formaldehyde, and dimethylamine.
d. 4.7% N content.
t400 --------------------------------------------------
1,200 =,
1
1.000 --
u.
1
'''...
tka
2
a. moo ..
,
0.400 --
-
:
IMMELear#V ::-;:;iik '.. .:-.:1477:7717771
k\. aillM;470144 '.::::::: ::.V.: 1::* iI:::::
1:.;= :=X ;;;i:(:=:,;;
0.000 .. l,N.µ. It .-i:--1- -ti: ++44
OH
gi Comp 1 IE Ex 1 0 Ex 2 E3 Ex 3
Graph 1 - Particulate Matter Emissions (Mass)
31
CA 03021039 2018-10-12
WO 2017/184688 PCT/US2017/028289
1.80E+14 ..........................................
1.60E+14 ..
140E+14 --
.5.
1,20E+14
i J
c 1,00E+14
0
t) \\11Earirel
a.1 48.00E+13 .. EtV
E
6,00E+13 .. \ Luallihaer
Z
T
4.4
m ---------------- \\*111initagagnal et., 2.00E+13
7.0 k1/4\.\\\ 134:111
-45 0,00E+00 .. man=
Oil
f
f
n Comp 1 E0 Ex I. n Ex 2 El Ex 3
Graph 2 - Solid Particle Number (Post-Oxidation Catalyst)
[0124] The results depicted in Graphs 1 and 2 demonstrate that the
lubricant formulas
of the disclosed technology provided fuel lubricant compositions that operated
the
exemplary two-cycle engines with a significant reduction in both overall mass
of particle
emissions and total particle number. The same was achieved with no noticeable
reduction
in engine performance, cleanliness, or power output.
[0125] Each of the documents referred to above is incorporated herein
by reference.
The mention of any document is not an admission that such document qualifies
as prior
art or constitutes the general knowledge of the skilled person in any
jurisdiction. 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". It is to be understood that the upper and lower amount, range, and
ratio limits set
forth herein may be independently combined. Similarly, the ranges and amounts
for each
element of the invention can be used together with ranges or amounts for any
of the other
elements. As used herein, the expression "consisting essentially of' permits
the inclusion
of substances that do not materially affect the basic and novel
characteristics of the
composition under consideration. As used herein, the expression "substantially
free of'
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means that none of the described materials is intentionally present, but does
not exclude
small or trace amounts present due to its presence in other materials as an
impurity and/or
byproduct.
[0126] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is
used in its ordinary sense, which is well-known to those skilled in the art.
Specifically, it
refers to a group having a carbon atom directly attached to the remainder of
the molecule
and having predominantly hydrocarbon character. Examples of hydrocarbyl groups
include hydrocarbon substituents, including aliphatic, alicyclic, and aromatic
substituents;
substituted hydrocarbon substituents, that is, substituents containing non-
hydrocarbon
groups which, in the context of this invention, do not alter the predominantly
hydrocarbon
nature of the substituent; and hetero substituents, that is, substituents
which similarly have
a predominantly hydrocarbon character but contain other than carbon in a ring
or chain. A
more detailed definition of the term "hydrocarbyl substituent" or "hydrocarbyl
group" is
found in paragraphs [0137] to [0141] of published application US 2010-0197536.
33
