U.S. patent application number 11/572867 was filed with the patent office on 2008-05-29 for lubricating compositions.
Invention is credited to W. Preston Barnes, Stephen J. Cook, Richard Leahy, Alexandra Mayhew.
Application Number | 20080121206 11/572867 |
Document ID | / |
Family ID | 35116067 |
Filed Date | 2008-05-29 |
United States Patent
Application |
20080121206 |
Kind Code |
A1 |
Leahy; Richard ; et
al. |
May 29, 2008 |
Lubricating Compositions
Abstract
A method of lubricating an internal combustion engine with a
power output of at least 1600 kilowatts, with a lubricating
composition, the method comprising: (1) monitoring one or more
performance characteristics of the engine; (2) selecting an
additive package to provide a desired TBN level to a lubricating
composition to modify the performance characteristics of the
engine; (3) combining the additive package of step (2) with (a) a
component having a viscosity of about 2 mm.sup.2/s to 12
mm.sup.2/s, comprising a light neutral base oil, and optionally (b)
a component having a viscosity of above 12 mm.sup.2/s to about 40
mm.sup.2/s, comprising heavy neutral base oil or a brightstock, to
form a lubricating composition; and (4) supplying the lubricating
composition of step (3) to the engine.
Inventors: |
Leahy; Richard; (Hessle,
GB) ; Mayhew; Alexandra; (Branston, GB) ;
Barnes; W. Preston; (Concord, OH) ; Cook; Stephen
J.; (Heage, GB) |
Correspondence
Address: |
THE LUBRIZOL CORPORATION;ATTN: DOCKET CLERK, PATENT DEPT.
29400 LAKELAND BLVD.
WICKLIFFE
OH
44092
US
|
Family ID: |
35116067 |
Appl. No.: |
11/572867 |
Filed: |
July 22, 2005 |
PCT Filed: |
July 22, 2005 |
PCT NO: |
PCT/US05/26309 |
371 Date: |
January 9, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60592356 |
Jul 29, 2004 |
|
|
|
60660650 |
Mar 11, 2005 |
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Current U.S.
Class: |
123/196R |
Current CPC
Class: |
C10M 2215/28 20130101;
C10M 2209/084 20130101; C10N 2030/06 20130101; C10N 2040/252
20200501; C10M 2205/026 20130101; C10N 2030/02 20130101; C10N
2060/14 20130101; C10M 167/00 20130101; C10N 2020/04 20130101; C10N
2030/04 20130101; C10M 2207/028 20130101; C10M 169/045 20130101;
C10M 2219/044 20130101; C10M 2219/046 20130101; C10M 2223/045
20130101; C10N 2030/52 20200501; C10M 169/048 20130101; C10N
2020/02 20130101; C10N 2010/04 20130101; C10M 163/00 20130101; C10M
171/02 20130101; C10M 2215/28 20130101; C10N 2060/14 20130101; C10M
2215/28 20130101; C10N 2060/14 20130101 |
Class at
Publication: |
123/196.R |
International
Class: |
F01M 9/02 20060101
F01M009/02 |
Claims
1. A method of lubricating an internal combustion engine with a
power output of at least 1600 kilowatts, with a lubricating
composition, the method comprising: (1) monitoring one or more
performance characteristics of the engine; (2) selecting an
additive package to provide a desired TBN level to a lubricating
composition to modify the performance characteristics of the
engine; (3) combining the additive package of step (2) with (a) a
component having a viscosity of about 2 mm.sup.2/s to 12
mm.sup.2/s, comprising a light neutral base oil, and optionally (b)
a component having a viscosity of above 12 mm.sup.2/s to about 40
mm.sup.2/s, comprising heavy neutral base oil or a brightstock, to
form a lubricating composition; and (4) supplying the lubricating
composition of step (3) to the engine; wherein the lubricating
composition has a total base number of at least 10 mg KOH/g; and
wherein the component comprising the light neutral base oil is
supplied from an oil reservoir available to said internal
combustion engine.
2. The method of claim 1, wherein the total base number of the
lubricating composition is about 30 or higher.
3. The method of claim 1, wherein the internal combustion engine
has a power output of at least about 3000 kilowatts.
4. The method of claim 1, wherein the internal combustion engine is
a 2-stroke marine diesel engine.
5. The method of claim 1, wherein the light neutral base oil is
provided from a new or used crankcase system oil.
6. The method of claim 1, wherein the total base number of the
lubricating composition is 30 mg KOH/g or higher.
7. The method of claim 1, wherein the one or more characteristics
of the engine comprise wear, engine load, variation in TBN,
deposits, or corrosion.
8. The method of claim 1, wherein said reservoir is a day tank or
cylinder oil service tank or a storage tank.
9. The method of claim 1, wherein the additive package of step (2)
is combined with a base oil in a blender.
10. The method of claim 1 wherein the additive package of step (2)
further comprises at least one performance additive comprising a
polymeric thickener, a dispersant, an antiwear agent, a detergent
or mixtures thereof.
11. The method of claim 10, wherein the polymeric thickener
comprises polyisobutylene with a weight average molecular weight Mw
of more than about 8000 to about 25,000 or a poly(meth)acrylate
with a weight average molecular weight Mw of about 20,000 to about
300,000.
12. The method of claim 10, wherein the detergent comprises a
sulphonate, a phenate or mixtures thereof.
13. The method of claim 10, wherein the dispersant comprises a
polyisobutylene succinimide.
14. The method of claim 10, wherein the antiwear agent comprises a
metal hydrocarbyl dithiophosphate.
15. The method of claim 1, wherein the light neutral base oil is
present at about 50 to about 99.9 weight percent of the lubricating
composition; the heavy neutral base oil or brightstock is present
at about 0.01 to about 25 weight percent of the lubricating
composition; and at least one performance additive is present at
about 0.01 to about 25 weight percent of the lubricating
composition.
16. The use of a system oil additised with an additive package to
make a cylinder lubricant.
17. The use of the system oil of claim 16, as a cylinder lubricant
in a 2-stroke marine diesel engine.
18. The use of the system oil of claim 16, wherein the system oil
is from used crankcase system oil.
Description
[0001] This application claims priority from U.S. 60/592,356, 20
Jul. 2004 and U.S. 60/660,650, 11 Mar. 2005.
FIELD OF INVENTION
[0002] The present invention relates to a method of lubricating an
internal combustion engine by monitoring engine performance and
adding an additive package accordingly. The invention further
relates to a composition suitable for the method.
BACKGROUND OF THE INVENTION
[0003] It is known to add various additives to an oil of
lubricating viscosity for diesel or gasoline engines, for instance,
a 2-stroke engine, to reduce wear and improve cleanliness. In
diesel engines an oil of lubricating viscosity is used particularly
to reduce wear of cylinder liners and piston rings. Often engine
operating temperatures and pressures are sufficient to break down
the film of the oil of lubricating viscosity on the internal walls
of the cylinder, and increased wear and decreased engine
cleanliness due to deposits occurs.
[0004] In many 2-stroke engines, especially marine diesel engines
or stationary power diesel engines, there are two lubricating
compositions. One composition is a system oil of viscosity
generally less than 12 mm.sup.2/s which is used to lubricate the
crankcase of the 2-stroke engines and has a low Total Base Number
(TBN). The system oil is normally unsuitable for lubricating
cylinder liners and piston rings because of its low TBN and low
viscosity. The second lubricating composition used in a 2-stroke
engine has a higher viscosity and TBN and is suitable for
lubricating cylinder liners and piston rings. This is sometimes
referred to as a cylinder oil. (All viscosities reported herein are
kinematic viscosity measured at 100.degree. C., unless otherwise
specified).
[0005] Further, in 2-stroke engines associated with marine vessels
or stationary power stations, typical fully formulated lubricating
compositions suitable for lubricating cylinder liners and piston
rings have a total base number of 70 to 80. However, due to
variations in sulphur content of fuel, the amount of TBN required
varies as amount of base required to neutralise sulphuric acid
produced during combustion changes. The presence of excessive
amounts of unreacted compounds in an additive package providing
TBN, e.g., detergents, can contribute to the formation of deposits.
To overcome differences in the sulphur content of fuel, two or more
lubricating compositions with differing TBN are independently
available for use. One lubricating composition has TBN of 40 to 50
suitable for low sulphur containing fuel, whereas the second
lubricating composition has a TBN of 70 or more and is used for
higher sulphur containing fuel.
[0006] Increased amounts of deposits and contaminants from cylinder
wear are known to contaminate system oil and/or other unused oil
suitable for lubricating the cylinder liners and piston rings. When
contaminated, the system oil and/or oil suitable for lubricating
the cylinder liners and piston rings needs to be replenished to
prevent contaminants having a detrimental effect on
performance.
[0007] When the system oil is contaminated to levels exceeding
those defined in CIMAC guidelines titled "Guidelines for the
Lubrication of Two-Stroke Crosshead Diesel Engines," (page 42,
section 8, 1997), it is removed from the crankcase and replenished
with fresh system oil. The removed system oil is typically stored
in a sludge tank until it undergoes waste management treatment.
[0008] US Patent Application 2003/0196632 A1 discloses a method to
employ instrumentation to effectuate variation in lubricant flow
rate in response to actual engine conditions. The method regularly
monitors one or more engine parameters with instruments such as XRF
or IR for base number measurement. The measured engine parameters
are used to calculate the feed rate of lubricant to the engine.
[0009] US Patent Application 2003/0159672 A1 discloses a method of
regularly monitoring one or more engine parameters of an all-loss
lubricating system and calculating from the engine parameters an
amount of a secondary fluid that is required to be added to base
fluid to create a modified base lubricant that is applied to the
engine during operations.
[0010] US Patent Application 2003/0183188 A1 discloses a device and
a process for real time optimizing engine lubricating oil
properties in response to actual operating conditions. The process
includes on-line modification of lubricant properties by repeatedly
measuring a system that recirculates a base lubricant and one or
more system condition parameters at a location of interest. The
process then calculates an amount of secondary fluid to add to the
lubricant followed by mixing the base fluid with the secondary
fluid creating a modified base lubricant and applying to a location
of interest.
[0011] International Application WO 99/64543 A1 discloses diesel
cylinder oil having a viscosity of 15 to 27 mm.sup.2/s (or cSt), a
viscosity index of at least 95 and a TBN of at least 40 mg KOH/g.
The oil is a neutral base stock of no more than 725 SUS viscosity
at 100.degree. C. and 2 to 15 wt % of the oil a liquid
polyisobutylene with a viscosity of 1500 to 8000 mm.sup.2/s (cSt)
at 100.degree. C.
[0012] Therefore it would be advantageous to provide a lubricating
composition and method of imparting the lubricating composition
with the correct properties to control deposit formation, wear and
reduced waste treatment costs. The present invention provides a
lubricating composition and a method of imparting a lubricating
composition with such properties using a selected additive package
to control deposit formation or wear.
SUMMARY OF THE INVENTION
[0013] In one embodiment the present invention provides a method of
lubricating an internal combustion engine with a power output of at
least 1600 kilowatts, with a lubricating composition, the method
comprising: [0014] (1) monitoring one or more performance
characteristics of the engine; [0015] (2) selecting an additive
package to provide a desired TBN level to a lubricating composition
to modify the performance characteristics of the engine; [0016] (3)
combining the additive package of step (2) with (a) a component
having a viscosity of 2 mm.sup.2/s to 12 mm.sup.2/s, comprising a
light neutral base oil, and optionally (b) a component having a
viscosity of above 12 mm.sup.2/s to 35 mm.sup.2/s or 40 mm.sup.2/S,
comprising heavy neutral base oil or a brightstock, to form a
lubricating composition; and [0017] (4) supplying the lubricating
composition of step (3) to the engine,
[0018] wherein the lubricating composition has a total base number
of at least 10 mg KOH/g; and the component comprising the light
neutral base oil is supplied from an oil reservoir available to
said internal combustion engine.
[0019] In one embodiment the invention further provides a method of
lubricating an internal combustion engine with a power output of at
least 1600 kilowatts, with a lubricating composition, the method
comprising contacting (that is, lubricating or supplying) the
internal combustion engine with a lubricating composition
comprising: [0020] (a) a 2 mm.sup.2/S to 12 mm.sup.2/s light
neutral base oil; [0021] (b) 0 to 20 weight percent of a heavy
neutral base oil or a brightstock with a viscosity above 12
mm.sup.2/s to 40 mm.sup.2/s; and [0022] (c) at least one
performance additive comprising: a polymeric thickener, a
dispersant, an antiwear agent, a detergent or mixtures thereof;
wherein the polymeric thickener, when present, has a weight average
molecular weight (Mw) of more than 8000 and is present in an amount
to provide a total viscosity of the composition of 12 mm.sup.2/s to
29 mm.sup.2/s; the dispersant or detergent when present imparts
basicity to said lubricating composition; and the composition has a
total base number of at least about 10 mg KOH/g.
[0023] In one embodiment the invention further provides a
lubricating composition comprising: [0024] (a) a 2 mm.sup.2/s to 12
mm.sup.2/s light neutral base oil; [0025] (b) a heavy neutral base
oil or a brightstock with a viscosity of above 12 mm.sup.2/s to 35
mm.sup.2/s or 40 mm.sup.2/s; and [0026] (c) at least one
performance additive comprising: a polymeric thickener, a
dispersant, an antiwear agent, a detergent or mixtures thereof;
wherein the polymeric thickener when present has a weight average
molecular weight (Mw) of more than 8000 and is present in an amount
to provide a total viscosity of the composition of 12 mm.sup.2/s or
15 mm.sup.2/s to 26.1 mm.sup.2/s or 29 mm.sup.2/s; the dispersant
or detergent when present imparts basicity to said lubricating
composition; and the composition has a total base number of at
least 10 mg KOH/g.
DETAILED DESCRIPTION OF THE INVENTION
[0027] The present invention provides a method for lubricating an
internal combustion engine as described above.
[0028] As used herein all viscosity measurements of the light
neutral base oil of heavy neutral base all are at 100.degree. C.
and quoted in units of mm.sup.2/s (or cSt).
[0029] In one embodiment the heavy neutral base oil or brightstock
has a viscosity of above 12 mm.sup.2/s to 35 mm.sup.2/s and in
another embodiment a viscosity of above 12 mm.sup.2/s to 40
mm.sup.2/s.
[0030] In one embodiment total viscosity of the lubricating
composition is 12 mm.sup.2/s or 15 mm.sup.2/s to 26.1 mm.sup.2/s
and in another embodiment 12 mm.sup.2/s or 15 mm.sup.2/s to 21.9
mm.sup.2/s. Typically the lubricating composition with a total
viscosity of 12 mm.sup.2/s or 15 mm.sup.2/s to 26.1 mm.sup.2/s is
an SAE 60 grade, and an SAE 50 grade lubricating composition has a
viscosity of 12 mm.sup.2/s or 15 mm.sup.2/s to 21.9 mm.sup.2/s.
[0031] The performance characteristics of an engine which may be
monitored include wear, engine load, variation in TBN, deposits, or
corrosion, and these may be monitored directly or indirectly. It is
to be understood that the term "monitoring performance
characteristics of the engine" not only includes mechanical or
power output measurements, but it further includes chemical or
physical properties of the lubricating oil in the engine. Wear may
be measured by a number of techniques including determining the
metal or metal oxide particles present in scrape down lubricant
from a cylinder liner. Other examples of monitoring engine
performance include measuring the sulphur content of the fuel, the
load of an engine and TBN of the lubricant. A more detailed
description of possible techniques for monitoring performance
characteristics of an engine is disclosed in US Patent Application
2003/0159672.
[0032] The selection of an additive package to provide a desired
TBN level to a lubricating composition may be determined by
analyzing fuel properties such as sulphur content or other
performance characteristics described above. In one embodiment when
the sulphur content of the fuel is low (often less than 4 wt % of
the fuel) the amount of TBN required to neutralise acids produced
during combustion, e.g., sulphuric acid, is reduced and the
additive package may contain less detergent. The TBN provided by
the additive package is typically provided in large part by the
presence in the package of an overbased detergent, described in
greater detail below. In one embodiment the sulphur content of the
fuel is high (often over 4 wt % of the fuel) and as a consequence
the amount of TBN required from detergent may be higher.
[0033] The total base number (TBN) of the lubricating composition
in one embodiment is 30 or higher, in another embodiment 40 or
higher, in another embodiment 50 or higher, in another embodiment
60 or higher, in another embodiment 65 or higher and in another
embodiment 70 or higher. Examples of the TBN of the lubricating
composition include 40, 50, 60, 65, 70, 80 or 100.
[0034] The selected additive package of step (2) is combined with a
base oil defined above by known methods such as in a blender. In
one embodiment the blender is typically located in situ available
relative to an internal combustion engine, which will typically
have a power output of at least 1600 kilowatts. In one embodiment
the internal combustion engine has a power output of at least 2000
kilowatts, in another embodiment at least 3000 kilowatts and in
another embodiment at least 4700 kilowatts.
[0035] The lubricating composition of step (3) in one embodiment is
supplied to the combustion engine directly from a "day tank" (or
cylinder oil service tank) and in another embodiment from a storage
tank.
[0036] In one embodiment the invention provides a lubricating
composition comprising: [0037] (a) a 2 mm.sup.2/s to 12 mm.sup.2/s
light neutral base oil; [0038] (b) a heavy neutral base oil or a
brightstock with a viscosity of above 12 mm.sup.2/s to 40
mm.sup.2/s; and [0039] (c) at least one performance additive
comprising: a polymeric thickener, a dispersant, an antiwear agent,
a detergent or mixtures thereof; wherein the polymeric thickener
when present has a weight average molecular weight (Mw) of more
than 8000 and is present in an amount to provide a total viscosity
of the composition of 15 mm.sup.2/s to 29 mm.sup.2/s; the
dispersant or detergent, when present, imparts basicity to said
lubricating composition; and the composition has a total base
number of at least 10 mg KOH/g.
[0040] In one embodiment the invention further provides a
lubricating composition comprising:
[0041] (a) a 2 mm.sup.2/s to 12 mm.sup.2/s light neutral base
oil;
[0042] (b) a heavy neutral base oil or a brightstock with a
viscosity above 12 mm.sup.2/s to 40 mm.sup.2/s;
[0043] (c) a polymeric thickener; and
[0044] (d) at least one performance additive comprising: a
dispersant, an antiwear agent, a detergent or mixtures thereof;
wherein the polymeric thickener has a weight average molecular
weight (Mw) of more than 8000 and is present in an amount to
provide a total viscosity of the composition of 15 mm.sup.2/s to 29
mm.sup.2/s; the dispersant or detergent when present imparts
basicity to said lubricating composition; and the composition has a
total base number of at least 10 mg KOH/g.
[0045] In one embodiment the invention provides a lubricating
composition comprising:
[0046] (a) a 2 mm.sup.2/s to 12 mm.sup.2/s light neutral base
oil;
[0047] (b) 0 to 20 weight percent of a heavy neutral base oil or a
brightstock with a viscosity above 12 mm.sup.2/s to 40
mm.sup.2/s;
[0048] (c) a polymeric thickener; and
[0049] (d) at least one performance additive comprising: a
dispersant, an antiwear agent, a detergent or mixtures thereof;
wherein the polymeric thickener has a weight average molecular
weight (Mw) of more than 8000 and is present in an amount to
provide a total viscosity of the lubricating composition of 15
mm.sup.2/s to 29 mm.sup.2/s (or viscosity grade ranging from SAE 30
to SAE 60 (typically SAE 50)); the dispersant or detergent when
present imparts basicity to said lubricating composition; and the
composition has a total base number of at least 10 mg KOH/g.
[0050] In one embodiment the invention employs oil of lubricating
viscosity with a 2 mm.sup.2/s to 12 mm.sup.2/s (typically with an
SAE 30 grade) light neutral base oil and optionally a heavy neutral
base oil or a brightstock with a viscosity above 12 mm.sup.2/s to
40 mm.sup.2/s. Such oils include natural and synthetic oils, oil
derived from hydrocracking, hydrogenation, and hydrofinishing,
unrefined, refined and re-refined oils and mixtures thereof.
Hydrotreated naphthenic oils are also known and can be used, as
well as oils prepared by a Fischer-Tropsch gas-to-liquid synthetic
procedure as well as other gas-to-liquid oils. In one embodiment
the dispersant mixture of the present invention is useful when
employed in a gas-to-liquid oil.
[0051] The source of the light neutral base oil in one embodiment
is a new or used crankcase system oil from a 2-stroke engine or
fresh from a system oil tank without further processing. In one
embodiment the used system oil is additised with an additive
package to make it useful as a cylinder lubricant. In one
embodiment the used system oil is additised with an additive
package to prolong oil life or improve performance of the system
oil based on the monitoring data of step (1).
[0052] When present, the heavy neutral base oil or brightstock, in
one embodiment, is used oil from a sump used to lubricate the
internal combustion engine.
[0053] In one embodiment the lubricating composition is an SAE 50
grade lubricant.
[0054] The light neutral base oil is present in one embodiment from
40 to 99.9, in another embodiment 50 to 99.9, in another embodiment
60 to 99.9 and in another embodiment 70 to 99.9 weight percent of
the lubricating composition.
[0055] The heavy neutral base oil or brightstock is present in one
embodiment from 0 to 35, in another embodiment 0 to 30, in another
embodiment 0.01 to 25 and in another embodiment 0.05 to 20 weight
percent of the lubricating composition. In one embodiment the heavy
neutral base oil is present from 1 to 25 or 5 to 20 weight percent
of the lubricating composition.
[0056] In several other embodiments the amount of heavy neutral
base oil or brightstock is present from 0 to 20 weight percent, or
0 to 10 weight percent of 0 to 5 weight percent of the lubricating
composition. In one embodiment the amount of heavy neutral base oil
or brightstock is zero weight percent.
Performance Additives
[0057] Optionally the lubricating composition includes at least one
performance additive selected from the group consisting of metal
deactivators, polymeric thickeners, dispersants, antioxidants,
antiwear agents, corrosion inhibitors, antiscuffing agents, extreme
pressure agents, foam inhibitors, demulsifiers, friction modifiers,
pour point depressants and mixtures thereof. Typically,
fully-formulated lubricating oil will contain one or more of these
performance additives.
[0058] The total combined amount of the optional performance
additives present in one embodiment from 0 or 0.01 to 25, in
another embodiment 0 or 0.01 to 20, in another embodiment 0 or 0.01
to 15 and in another embodiment 0.05 or 0.1 or 0.5 to 10 weight
percent of the lubricating composition.
The Polymeric Thickener
[0059] The polymeric thickener includes styrene-butadiene rubbers,
ethylene-propylene copolymers, hydrogenated styrene-isoprene
polymers, hydrogenated radical isoprene polymers,
poly(meth)acrylate acid esters, polyalkyl styrenes, polyolefins
(such as polyisobutylene), polyalkylmethacrylates and esters of
maleic anhydride-styrene copolymers. In one embodiment the
polymeric thickener is free of polyisobutylene; and in another
embodiment the polymeric thickener is a polyisobutylene. In one
embodiment the polymeric thickener is poly(meth)acrylate.
[0060] The polymeric thickener in several embodiments has a weight
average molecular weight (Mw) of more than 8000, or 8400 or more,
at least 10,000, or at least 15,000, or at least 25,000 or at least
35,000. The polymeric thickener generally has no upper limit on Mw,
however in one embodiment the Mw is less than 2,000,000 in another
embodiment less than 500,000 and in another embodiment less than
150,000. Examples of suitable ranges of Mw include in one
embodiment 12,000 to 1,000,000, in another embodiment 20,000 to
300,000 and in another embodiment 30,000 to 75,000.
[0061] If a polyisobutylene polymeric thickener is present, the
weight average molecular weight (Mw) may be more than 8000, or 8400
or more, at least 10,000 to 15,000 or 25,000. Examples of a
suitable range include more than 8000 to 25,000 or 8400 to
15,000.
[0062] The polymeric thickener in one embodiment is present from 0
or 0.01 to 15 and in another embodiment 0.05 to 10 weight percent
of the lubricating composition.
Antiwear Agent
[0063] In one embodiment of the invention the lubricating
composition further comprises an antiwear agent such as a metal
hydrocarbyl dithiophosphate. Examples of a metal hydrocarbyl
dithiophosphate include zinc dihydrocarbyl dithiophosphates (often
referred to as ZDDP, ZDP or ZDTP). Examples of suitable zinc
hydrocarbyl dithiophosphates compounds include the reaction
product(s) of butyl/pentyl, heptyl, octyl, and/or nonyl
dithiophosphoric acid zinc salts or mixtures thereof.
[0064] In an alternative embodiment the antiwear agent is ashless,
i.e., the antiwear agent is metal-free (prior to mixture with other
components). In one embodiment the metal-free antiwear agent is an
amine salt. The ashless antiwear agent often contains an atom
including sulphur, phosphorus, boron or mixtures thereof.
Detergent
[0065] The invention optionally includes a detergent such as an
overbased sulphonate detergent. The sulphonate detergent of the
composition includes compounds represented by the formula:
(R.sup.1).sub.k-A-SO.sub.3M (I)
wherein each R.sup.1 is a hydrocarbyl group in one embodiment
containing 6 to 40 carbon atoms, in another embodiment 8 to 35
carbon atoms and in another embodiment 12 to 30 carbon atoms; A may
be independently a cyclic or acyclic divalent or multivalent
hydrocarbon group; M is hydrogen, a valence of a metal ion, an
ammonium ion or mixtures thereof; and k is an integer of 0 to 5,
for example 0, 1, 2, 3, 4, 5. In one embodiment k is 1, 2 or 3, in
another embodiment 1 or 2 and in another embodiment 1. In one
embodiment M is hydrogen and is present on less than 30%, in
another embodiment less than 20%, in another embodiment less than
10% and in another embodiment less than 5% of the available M
entities, the balance of the M entities being a metal or ammonium
ion.
[0066] In one embodiment k is 1 and R.sup.1 is a branched alkyl
group with 6 to 40 carbon atoms. In one embodiment k is 1 and
R.sup.1 is a linear alkyl group with 6 to 40 carbon atoms.
[0067] Examples of suitable sulphonic acids capable of forming the
overbased sulphonate detergent include polypropene benzene
sulphonic acid, undecyl benzene sulphonic acid, dodecyl benzene
sulphonic acid, tridecyl benzene sulphonic acid, tetradecyl benzene
sulphonic acid, pentadecyl benzene sulphonic acid, hexadecyl
benzene sulphonic acid and mixtures thereof. In one embodiment the
sulphonic acid includes tridecyl benzene sulphonic acid, tetradecyl
benzene sulphonic acid, octadecyl benzene sulphonic acid,
tetraeicosyl benzene sulphonic acid or mixtures thereof. In one
embodiment of the invention the sulphonic acid is a polypropene
benzene sulphonic acid, where the polypropene contains 18 to 30
carbon atoms.
[0068] In one embodiment of the invention the sulphonate components
are calcium polypropene benzenesulphonate and calcium monoalkyl and
dialkyl benzenesulphonates wherein the alkyl groups contain at
least 10 or 12 carbons, for example 11, 12, 13, 14, 15, 18, 24 or
30 carbon atoms.
[0069] When M is a valence of a metal ion, the metal may be
monovalent, divalent, trivalent or mixtures of such metals. When
monovalent, the metal M includes an alkali metal such as lithium,
sodium, or potassium, and when divalent, the metal M includes an
alkaline earth metal such as magnesium, calcium or barium. In one
embodiment the metal is an alkaline earth metal. In one embodiment
the metal is calcium.
[0070] When A is cyclic hydrocarbon group, suitable groups include
phenylene or fused bicyclic groups such as naphthylene, indenylene,
indanylene, bicyclopentadienylene or mixtures thereof. In one
embodiment A comprises a benzene ring.
[0071] When A is an acyclic divalent hydrocarbon group, the carbon
chain may be linear or branched. In one embodiment A is an acyclic
linear hydrocarbon group.
[0072] The overbased sulphonate detergent in one embodiment has a
TBN (total base number) of at least 350, in another embodiment at
least 400, in another embodiment at least 425, in another
embodiment at least 450 and in another embodiment at least 475. In
one embodiment the overbased sulphonate detergent has a TBN of 400
or 500.
[0073] The sulphonate detergent is present in one embodiment at 0.1
to 35, in another embodiment 2 to 30, in another embodiment 5 to 25
and in another embodiment 10 to 25 weight percent of the
lubricating composition.
Overbasing the Sulphonate Detergent
[0074] In one embodiment the sulphonate detergent is overbased.
Overbased materials, otherwise referred to as overbased or
superbased salts, are generally single phase, homogeneous Newtonian
systems characterised by a metal content in excess of that which
would be present for neutralisation 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, often carbon dioxide) with a mixture comprising an acidic
organic compound, a reaction medium comprising at least one organic
solvent and promoter such as phenol or a mixture of alcohols. A
mixture of alcohols typically contains methanol and at least one
alcohol with 2 to 7 carbon atoms, and may contain 50-60 mole
percent methanol. The acidic organic material (substrate) 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 to substrate ratio. The term "metal to
substrate ratio" or "metal ratio" is the ratio of the total
equivalents of the metal to the equivalents of the substrate. An
overbased sulphonate detergent in one embodiment has a metal ratio
of 12.5:1 to 40:1, in another embodiment 13.5:1 to 40:1, in another
embodiment 14.5:1 to 40:1, in another embodiment 15.5:1 to 40:1 and
in another embodiment 16.5:1 to 40:1. Furthermore the overbased
detergent often has a low in-process viscosity and a low final
viscosity.
[0075] A sulphonate detergent with 500 TBN and its preparation are
disclosed in U.S. Pat. No. 5,792,732. In Example 2 thereof, a 500
TBN all-linear alkylbenzene sulphonate is prepared by reacting an
alkyl benzene sulphonate from Witco Corp. (now known as Crompton)
with Ca(OH).sub.2 and CaO in n-heptane and methanol and bubbling
with CO.sub.2. It is also reported in the aforementioned patent
(col. 5) that a 500 TBN overbased sulphonate containing highly
branched alkylbenzene sulphonate is available from Witco Corp. (now
known as Crompton) as Petronate.RTM. C-500. Another method for
preparing an overbased sulphonate detergent of high metal ratio is
disclosed in U.S. Pat. No. 6,444,625 (see, for instance, column 3,
bottom). The latter process includes providing a sulphonic acid to
a reactor, adding a lime reactant for neutralization and
overbasing, adding a lower aliphatic C.sub.1 to C.sub.4 alcohol and
a hydrocarbon solvent, and carbonating the process mixture with
carbon dioxide during which process the exotherm of the reaction is
maintained between 27.degree. C. and 57.degree. C. Alternatively, a
high metal-ratio detergent may be prepared by using a mixture of
short chain alcohols, with or without a hydrocarbon solvent,
conducting the addition of lime reactants and carbon dioxide in
multiple iterations, and, if desired the process of adding lime and
carbon dioxide and of removal of volatile materials may be
repeated. The overbased sulphonate detergent in the present
invention may be used alone or with other overbased sulphonates. In
one embodiment the sulphonate detergent is in a mixture with other
sulphonate detergents. Alternatively a 500 TBN sulphonate detergent
may be prepared by the process shown in Preparative Example
S-1.
Preparative Example S-1
[0076] A sample of a 500 TBN sulphonate detergent is prepared using
a vessel with flange and clip, overhead stirrer with paddle and
polytetrafluoroethylene (PTFE) stirrer gland, Dean Stark trap and
double surface condenser, a mantle/thermocouple temperature
controller system, the equipment from just above the mantle to just
below the condenser being covered with glass wool. The vessel is
charged with 35.1 parts by weight of C.sub.16-C.sub.24 alkylbenzene
sulphonic acid and 31.8 parts by weight of mineral oil (SN 150) and
heated to 30.degree. C. The reactor is charged through a port with
11.6 parts by weight of alcohols containing methanol and a mixture
of iso-butanol/amyl alcohol. The weight ratio of methanol to the
mixture of iso-butanol/amyl alcohol is 1.31. The reactor is charged
with 14.9 parts by weight of calcium hydroxide and the mixture is
heated to 54.degree. C. at which temperature carbon dioxide is
added to form a carbonated product. The carbonated product is
further treated three more times with similar (or equal) portions
of calcium hydroxide and carbon dioxide. Water is removed by
stripping before repeating the addition of alcohol, calcium
hydroxide and carbon dioxide two times. The product is stripped and
filtered.
[0077] Optionally the lubricating composition further includes a
phenate detergent. The phenate detergent is known and includes
neutral and overbased metal salts of a sulphur-containing phenate,
a non-sulphurised phenate or mixtures thereof. Suitable metal salts
are the same as those described for the sulphonate detergent.
[0078] The phenate detergent in one embodiment has a TBN from 30 to
450, in another embodiment 30 to 350 or 290, in another embodiment
40 to 265, in another embodiment 50 to 190 and in another
embodiment 70 to 175. In one embodiment the sulphur containing
phenate detergent has a TBN of 150, in another embodiment a TBN of
225 and in another embodiment 250.
[0079] Other suitable detergent compounds include a salicylate,
carboxylate, phosphate, salixarate or mixtures thereof.
Dispersant
[0080] The invention optionally further includes a dispersant. The
dispersant is known and includes an ash-containing dispersant or an
ashless-type dispersant, "ashless" dispersant being so named
because, prior to mixing with other components of the lubricant,
they do not contain metals which form sulfated ash. After
admixture, of course, they may acquire metal ions from other
components; but they are still commonly referred to as "ashless
dispersants." The dispersant may be used alone or in combination
with other dispersants. In one embodiment the ashless dispersant
does not contain ash-forming metals. Ashless type dispersants are
characterised by a polar group attached to a relatively high
molecular weight hydrocarbon chain. Typical ashless dispersants
include a N-substituted long chain hydrocarbon succinimide such as
alkenyl succinimide. Examples of N-substituted long chain alkenyl
succinimides include polyisobutylene succinimide with number
average molecular weight of the polyisobutylene substituent in one
embodiment from 350 to 5000, and in another embodiment 500 to 3000.
Succinimide dispersants and their preparation are disclosed, for
instance in U.S. Pat. No. 4,234,435. Succinimide dispersants are
typically the imide formed from a polyamine, typically a
poly(ethyleneamine).
[0081] In one embodiment the invention the dispersant is derived
from polyisobutylene, an amine and zinc oxide to form a
polyisobutylene succinimide complex with zinc.
[0082] In one embodiment the dispersant is derived from half ester,
ester or salts of a long chain hydrocarbon acylating agent such as
long chain alkenyl succinic acid/anhydride.
[0083] Another class of ashless dispersant is Mannich bases.
Mannich dispersants are the reaction products of alkyl phenols with
aldehydes (especially formaldehyde) and amines (especially
polyalkylene polyamines). The alkyl group typically contains at
least 30 carbon atoms.
[0084] The dispersant may also be post-treated by conventional
methods by a reaction with any of a variety of agents. Among these
are urea, thiourea, dimercaptothiadiazole or derivatives thereof,
carbon disulphide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, maleic anhydride,
acrylonitrile, epoxides, boron compounds, and phosphorus
compounds.
[0085] In one embodiment of the invention the dispersant is borated
using a variety of agents selected from the group consisting of the
various forms of boric acid (including metaboric acid, HBO.sub.2,
orthoboric acid, H.sub.3BO.sub.3, and tetraboric acid,
H.sub.2B.sub.4O.sub.7), boric oxide, boron trioxide, and alkyl
borates.
[0086] The borated dispersant may be prepared by blending the boron
compound and the N-substituted long chain alkenyl succinimides and
heating them at a suitable temperature in one embodiment from
80.degree. C. to 250.degree. C., in another embodiment 90.degree.
C. to 230.degree. C. and in another embodiment 100.degree. C. to
210.degree. C., until the desired reaction has occurred. The molar
ratio of the boron compounds to the N-substituted long chain
alkenyl succinimides is typically 10:1 to 1:4, in another
embodiment 4:1 to 1:3, and in another embodiment about 1:2. An
inert liquid may be used in performing the reaction. The liquid may
include toluene, xylene, chlorobenzene, dimethylformamide and
mixtures thereof.
[0087] Other performance additives may be used, such as an
antioxidant including a diphenylamine, a hindered phenol, a
molybdenum dithiocarbamate, a sulphurised olefin and mixtures
thereof (in one embodiment the lubricating composition is free of
an antioxidant); corrosion inhibitors including octylamine
octanoate; condensation products of dodecenyl succinic acid or
anhydride and a fatty acid such as oleic acid with a polyamine;
metal deactivators including derivatives of benzotriazoles,
1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or
2-alkyldithiobenzothiazoles; foam inhibitors including copolymers
of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl
acetate; demulsifiers including trialkyl phosphates, polyethylene
glycols, polyethylene oxides, polypropylene oxides and (ethylene
oxide-propylene oxide) polymers; pour point depressants including
esters of maleic anhydride-styrene, polymethacrylates,
polyacrylates or polyacrylamides; and friction modifiers including
fatty acid derivatives such as amines, esters, epoxides, fatty
imidazolines, condensation products of carboxylic acids and
polyalkylene-polyamines and amine salts of alkylphosphoric
acids.
Process
[0088] The invention also includes a process to prepare a
lubricating composition, comprising mixing:
[0089] (a) a 2 mm.sup.2/s to 12 mm.sup.2/s light neutral base
oil;
[0090] (b) a heavy neutral base oil or a brightstock with a
viscosity above 12 mm.sup.2/s to 40 mm.sup.2/s; and
[0091] (c) at least one performance additive comprising: a
polymeric thickener, a dispersant, an antiwear agent, a detergent
or mixtures thereof;
wherein the polymeric thickener has a weight average molecular
weight (Mw) of more than 8000 and is present in an amount to
provide a total viscosity of the composition of 12 mm.sup.2/s or 15
mm.sup.2/s to 29 mm.sup.2/s; the dispersant or detergent when
present imparts basicity to said lubricating composition; and the
composition has a total base number of at least 10 mg KOH/g.
[0092] The mixing conditions include a temperature in one
embodiment from 15.degree. C. to 130.degree. C., in another
embodiment 20.degree. C. to 120.degree. C. and in another
embodiment 25.degree. C. to 110.degree. C.; and for a period of
time in one embodiment from 30 seconds to 48 hours, in another
embodiment 2 minutes to 24 hours, and in other embodiments 5
minutes to 16 hours or 20 minutes to 4 hours; and at pressures in
one embodiment from 86 kPa to 270 kPa (650 mm Hg to 2000 mm Hg), in
another embodiment 92 kPa to 200 kPa (690 mm Hg to 1500 mm Hg), and
in another embodiment 95 kPa to 130 kPa (715 mm Hg to 1000 mm
Hg).
[0093] The process optionally includes mixing other performance
additives as described above. The optional performance additives
may be added sequentially, separately or as a concentrate. In one
embodiment the composition is a concentrate.
INDUSTRIAL APPLICATION
[0094] The lubricating composition of the present invention is
useful for an internal combustion engine, for example stationary
combustion engine, such as a power station combustion engine; a
diesel fuelled engine, a gasoline fuelled engine, a natural gas
fuelled engine or a mixed gasoline/alcohol fuelled engine. In one
embodiment the internal combustion engine is a 4-stroke and in
another embodiment a 2-stroke engine. In one embodiment the diesel
fuelled engine is a marine diesel engine.
[0095] In one embodiment of the invention provides a method for
lubricating an internal combustion engine, comprising supplying
thereto a lubricant comprising the composition as described herein.
The use of the composition may impart one or more of TBN control,
cleanliness properties, antiwear performance and deposit
control.
[0096] In one embodiment the invention provides a method for
lubricating a 2-stroke marine diesel cylinder comprising:
lubricating said 2-stroke marine diesel cylinder with a lubricating
composition comprising:
[0097] (a) a 2 mm.sup.2/S to 12 mm.sup.2/s light neutral base
oil;
[0098] (b) 0 to 20 weight percent of a heavy neutral base oil or a
brightstock with a viscosity above 12 mm.sup.2/s to 40
mm.sup.2/s;
[0099] (c) a polymeric thickener; and
[0100] (d) at least one performance additive comprising: a
dispersant, an antiwear agent, a detergent or mixtures thereof;
wherein the polymeric thickener has a weight average molecular
weight (Mw) of more than 8000 and is present in an amount to
provide a total viscosity of the lubricating composition of 12
mm.sup.2/s or 15 mm.sup.2/s to 29 mm.sup.2/s (or viscosity grade
ranging from SAE 40 to SAE 60); the dispersant or detergent when
present imparts basicity to said lubricating composition; and the
composition has a total base number of at least 10 mg KOH/g.
[0101] The following examples provide an illustration of the
invention. These examples are non exhaustive and are not intended
to limit the scope of the invention.
EXAMPLES
[0102] All additive components used in Preparative Examples 1-7 are
commercially available from The Lubrizol Corporation. All
performance additives used in the examples quote the weight percent
as supplied, including the conventional amount of diluent oil.
Preparative Example 1
System Oil Composition (P1)
[0103] A system oil is prepared having a TBN of 1-15, containing 1
wt % dispersant, 0.5 wt % ZDDP, 6 wt % of 250 TBN phenate
detergent, 0.5 wt % of neutral sulphonate detergent and base oil
containing light solvent neutral oil and brightstock. The system
oil composition has a viscosity of 11 mm.sup.2/s.
Preparative Example 2
System Oil Composition (P2)
[0104] A System Oil is prepared having a TBN of 2-7, containing 0.5
wt % dispersant, 0.3 wt % ZDDP, 1.0 wt % of 250 TBN phenate
detergent, 1.2 wt % of neutral sulphonate detergent, 0.2 wt % of an
anti-oxidant and base oil containing 4.8 wt % of Exxon 150 light
neutral base oil and 92.2 wt % of Exxon 600 light neutral base
stock. The system oil composition has a viscosity of 11
mm.sup.2/s.
Preparative Example 3
SAE 50 Lubricating Oil Composition (P3)
[0105] A core lubricating oil composition is prepared having a TBN
of 3-30, containing 1.5 wt % dispersant, 0.5 wt % of ZDDP, 12 wt %
of 250 TBN phenate, and base oil containing solvent neutral oil and
brightstock. The core lubricating oil composition has a viscosity
of 19.5 mm.sup.2/s.
Preparative Example 4
SAE 50 Lubricating Oil Composition (P4)
[0106] A core lubricating oil composition is prepared having a TBN
of 4-10, containing 1 wt % of borated dispersant, 6.5 wt % of 250
TBN phenate, and base oil containing solvent neutral oil and
brightstock. The core lubricating oil composition has a viscosity
of 19.5 mm.sup.2/s.
Preparative Example 5
High TBN Composition (P5)
[0107] A high TBN composition is prepared from a 200 TBN
concentrate of 50 wt % of 400 TBN overbased sulphonate detergent
and 50 wt % of 500 SN basestock.
Preparative Example 6
High TBN Composition (P6)
[0108] A high TBN composition is prepared from a 400 TBN
concentrate of 80 wt % of 500 TBN overbased sulphonate detergent
and 20 wt % of 500 SN basestock.
Preparative Example 7
Polymeric Thickener Composition (P7)
[0109] Preparative Example 7 is a polymethacrylate viscosity index
improver with a weight average molecular weight, Mw of 10.sup.5 to
106.
Examples 1-10
[0110] Examples 1-10 are prepared by blending portions of
preparative examples 1-7 as shown: [0111] Weight Percentage of
Preparative Examples 1-7
TABLE-US-00001 [0111] Example TBN P1 P2 P3 P4 P5 P6 P7 EX 1 40 94 6
EX 2 40 97.3 2.7 EX 3 40 84 16 EX 4 40 92 8 EX 5 40 90.3 6.7 3 EX 6
70 76.5 23.5 EX 7 70 89 11 EX 8 70 68 32 EX 9 70 84.5 15.5 EX 10 70
82.5 14.5 3
Example 11
EX11
[0112] A lubricating composition is prepared from 79.4 wt % of
fresh system oil from Preparative Example 2, 2.6 wt % of 150 TBN
phenate detergent, 15 wt % of 400 TBN sulphonate detergent, 0.8 wt
% of borated dispersant and 2.2 wt % of the product of Preparative
Example 7. The lubricating composition has TBN of 67.2, and a
viscosity of 18.1 mm.sup.2/S.
Example 12
EX12
[0113] A lubricating composition is prepared with 40.3 wt % of
fresh system oil from Preparative Example 2, 40.3 wt % of used
system oil containing contaminants from an engine stuffing box (a
stuffing box is fitted to a crankcase to separate system oil from
used cylinder oil) from Preparative Example 2. The used system oil
is originally derived from the system oil of Preparative Example 2.
The lubricating composition further contains 2.5 wt % of 150 TBN
phenate detergent, 14.2 wt % of 400 TBN sulphonate detergent, 0.7
wt % of borated dispersant and 2 wt % of the product of Preparative
Example 7. The lubricating composition has TBN of 67.2, and a
viscosity of 18.1 mm.sup.2/s.
Example 13
EX13
[0114] A lubricating composition is prepared with 81.7 wt % of used
system oil containing contaminants from an engine stuffing box. The
used system oil is originally derived from the system oil of
Preparative Example 2. The lubricating composition further contains
2.3 wt % of 150 TBN phenate detergent, 13.4 wt % of 400 TBN
sulphonate detergent, 0.7 wt % of borated dispersant and 1.9 wt %
of the product of Preparative Example 7. The lubricating
composition has TBN of 66.2, and a viscosity of 17.8
mm.sup.2/s.
Reference Example 1
RF1
[0115] Reference Example is the same as Example 11, except the
compound of preparative Example 7 is absent. Furthermore the system
oil is replaced with 55 wt % of Exxon 600N base oil and 23.7 wt %
of Exxon 150 brightstock base oil. The Reference Examples has TBN
of 68.9, and a viscosity of 18.7 mm.sup.2/s.
Reference Example 2
RF2
[0116] Reference Example is the same as Example 11, except the
compound of preparative Example 7 is absent and ZDDP is present at
0.5 wt %. Furthermore the system oil is replaced with 55.9 wt % of
Exxon 600N base oil and 23.8 wt % of Exxon 150 brightstock base
oil. The Reference Examples has TBN of 68.9, and a viscosity of
18.7 mm.sup.2/s.
Test 1: Cameron Plint Wear Test
[0117] The Cameron Plint TE-77.TM. is a reciprocating wear tester.
In this test a steel ball upper specimen is reciprocated against a
steel flat lower specimen. The lubricant sample is initially
treated with 3.5 wt % sulphuric acid. The Cameron Plint is then
charged with 10 ml of the sample and heated to 50.degree. C. and
held for 20 minutes. The sample is then subject to a load of 240 N
over two minutes while at the same time reciprocation is started at
10 Hz over 15 mm stroke length. The sample is then heated to
350.degree. C. at 2.degree. C. per minute and then held at
temperature for 3 hours. At the end of the test the onset of film
failure is measured. The onset of film failure is determined by the
temperature at which the oil film as measured by the contact
potential first falls to 80% of its starting value. The results
obtained by testing the lubricants of the indicated Examples are as
shown:
TABLE-US-00002 Example Temperature of Onset of Film Failure
(.degree. C.) EX11 320 EX12 300 EX13 290 RF1 250 RF2 240
[0118] The analysis of the experimental data obtained indicates
that presence of the additive package of the invention provides one
or more of TBN control, cleanliness properties, antiwear
performance and deposit control to a system oil.
Examples 14 to 26
[0119] Examples 14 to 26 contain 2 wt % of various polymethacrylate
polymeric thickeners, 1.5 wt % of a succinimide dispersant, 7 wt %
of a brightstock base oil, between 67.4 and 72.3 wt % of a light
neutral base oil and a detergent package. The detergent package in
Examples 14 to 22 contains a mixture of sulphonate detergents with
a TBN ranging from 350 to 500 TBN. Examples 23 to 26 contain a
mixture of sulphonate and phenate detergents.
[0120] Reference Example 3 (RF3) is a commercially available marine
diesel cylinder lubricant.
Test 2: Panel Coker
[0121] Approximately 233 g of sample is placed in a 250 ml Panel
Coker apparatus and heated to 325.degree. C. The sample is splashed
against a metal plate for 15 seconds and then baked for 45 seconds.
The splashing and baking cycle is continued for approximately 3
hours. The sample is cooled to room temperature and the amount of
deposits left on the metal plate is weighed. The results obtained
by testing the lubricants of the indicated Examples are as
shown:
TABLE-US-00003 Example Deposits (mg) RF3 121.0 EX14 43.2 EX15 23.7
EX16 77.3 EX17 57.7 EX18 45.7 EX19 106.2 EX20 41.1 EX21 78.7 EX22
101.8 EX23 27.4 EX24 55.3 EX25 22.6 EX26 62.8
[0122] In summary the results of the Panel Coker test demonstrate
that the composition of the invention has reduced deposit formation
than a conventional marine diesel cylinder lubricant.
[0123] While the invention has been explained, it is to be
understood that various modifications thereof will become apparent
to those skilled in the art upon reading the specification.
Therefore, it is to be understood that the invention disclosed
herein is intended to cover such modifications as fall within the
scope of the appended claims.
[0124] 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. Similarly, the
ranges and amounts for each element of the invention may be used
together with ranges or amounts for any of the other elements. As
used herein any member of a genus (or list) may be excluded from
the claims.
[0125] 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
[0126] (i) hydrocarbon substituents, that is, aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, and aromatic-, aliphatic-, and alicyclic-substituted
aromatic substituents, as well as cyclic substituents wherein the
ring is completed through another portion of the molecule (e.g.,
two substituents together form a ring);
[0127] (ii) 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 (e.g., halo (especially
chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto,
nitro, nitroso, and sulfoxy);
[0128] (iii) hetero substituents, that is, 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, and encompass substituents as pyridyl, furyl,
thienyl and imidazolyl. In general, no more than two, or no more
than one, non-hydrocarbon substituent will be present for every ten
carbon atoms in the hydrocarbyl group; typically, there will be no
non-hydrocarbon substituents in the hydrocarbyl group.
[0129] 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. 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.
* * * * *