U.S. patent application number 14/389010 was filed with the patent office on 2015-04-02 for bearing lubricants for pulverizing equipment.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Edward S. Akucewich, Frank M. Cooney, Matthew R. Sivik, James N. Vinci.
Application Number | 20150094243 14/389010 |
Document ID | / |
Family ID | 48096330 |
Filed Date | 2015-04-02 |
United States Patent
Application |
20150094243 |
Kind Code |
A1 |
Vinci; James N. ; et
al. |
April 2, 2015 |
Bearing Lubricants For Pulverizing Equipment
Abstract
The invention relates to a method of lubricating the bearings of
solid fuel pulverizers, for example, coal pulverizers. The method
involves supplying to the bearings a lubricating composition
designed to have superior performance compared to conventional coal
pulverizer bearing lubricants. The invention also provides a
bearing lubricant for a coal pulverizer as well as its use in coal
pulverizing equipment to improve the service life and/or durability
of bearings in coal pulverizing equipment. The invention also
provides an additive composition for use in a bearing lubricant for
a coal pulverizer, as well as the use of the additive composition
to improve the service life and/or performance of the bearing
lubricant.
Inventors: |
Vinci; James N.; (Mayfield
Heights, OH) ; Akucewich; Edward S.; (Chesterland,
OH) ; Sivik; Matthew R.; (Broadview Heights, OH)
; Cooney; Frank M.; (Wixom, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
48096330 |
Appl. No.: |
14/389010 |
Filed: |
April 1, 2013 |
PCT Filed: |
April 1, 2013 |
PCT NO: |
PCT/US2013/034754 |
371 Date: |
September 29, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61619970 |
Apr 4, 2012 |
|
|
|
Current U.S.
Class: |
508/287 |
Current CPC
Class: |
C10M 2205/0265 20130101;
C10M 141/10 20130101; C10M 2223/043 20130101; C10M 2205/0285
20130101; C10M 2217/043 20130101; C10N 2040/02 20130101; C10M
2223/04 20130101; C10M 2223/049 20130101; C10M 2215/042 20130101;
C10M 2203/1006 20130101; C10M 2219/00 20130101; C10N 2030/06
20130101; C10M 2215/28 20130101; C10M 2215/28 20130101; C10N
2060/14 20130101; C10M 2215/28 20130101; C10N 2060/14 20130101 |
Class at
Publication: |
508/287 |
International
Class: |
C10M 141/10 20060101
C10M141/10 |
Claims
1. A method of lubricating the bearings of a solid fuel pulverizer
comprising the steps of: I. supplying to said bearings a lubricant
composition comprising: (a) an oil of lubricating viscosity; (b) a
phosphorus-containing compound; and (c) a nitrogen-containing
dispersant; and wherein the lubricant composition optionally
further comprises: (d) a sulfur-containing compound.
2. The method of claim 1 wherein the oil of lubricating viscosity
comprises a mineral base oil.
3. The method of claim 2 wherein the oil of lubricating viscosity
comprises a synthetic base oil.
4. The method of claim 1 wherein the phosphorus-containing compound
comprises an alkyl phosphite, a phosphoric acid ester, an amine
salt of a phosphoric acid ester, or some combination thereof.
5. The method of claim 1 wherein the nitrogen-containing dispersant
comprises: a polyetheramine; a borated succinimide dispersant; a
non-borated succinimide dispersant; a Mannich dispersant comprising
the reaction product of a dialkylamine, an aldehyde and a
hydrocarbyl substituted phenol; or any combination thereof.
6. The method of claim 5 wherein the nitrogen-containing dispersant
comprises a non-borated succinimide dispersant derived from an
aromatic amine.
7. The method of claim 1 wherein the lubricant composition further
comprises: (d) a sulfur-containing compound.
8. The method of claim 1 wherein the phosphorus-containing compound
comprises an alkyl phosphite and the nitrogen-containing dispersant
comprises a non-borated succinimide dispersant.
9. The method of claim 1 wherein the phosphorus-containing compound
is present in the lubricant composition from 0.01 to 5.0 percent by
weight; and wherein the nitrogen-containing dispersant is present
in the lubricant composition from 0.01 to 4.0 percent by
weight.
10. A bearing lubricant for a solid fuel pulverizer comprising: (a)
an oil of lubricating viscosity; (b) a phosphorus-containing
compound; and (c) a nitrogen-containing dispersant.
11. The bearing lubricant of claim 10 wherein the
phosphorus-containing compound comprises an alkyl phosphite, a
phosphoric acid ester, an amine salt of a phosphoric acid ester, or
some combination thereof.
12. The bearing lubricant of claim 10 wherein the
nitrogen-containing dispersant comprises: a polyetheramine; a
borated succinimide dispersant; a non-borated succinimide
dispersant; a Mannich dispersant comprising the reaction product of
a dialkylamine, an aldehyde and a hydrocarbyl substituted phenol;
or any combination thereof.
13. The bearing lubricant of claim 10 wherein the
phosphorus-containing compound is present in the lubricant
composition from 0.01 to 5.0 percent by weight; and wherein the
nitrogen-containing dispersant is present in the lubricant
composition from 0.01 to 4.0 percent by weight.
14. The bearing lubricant of claim 10 wherein the bearing lubricant
further comprises: (d) a sulfur-containing compound.
15. The use of a lubricant composition to improve the service life
or durability of bearings in solid fuel pulverizing equipment, said
lubricant composition comprising: (a) an oil of lubricating
viscosity; (b) a phosphorus-containing compound; and (c) a
nitrogen-containing dispersant.
Description
FIELD OF THE INVENTION
[0001] The invention relates to a method of lubricating the
bearings of solid fuel pulverizers, for example, coal pulverizers.
The method involves supplying to the bearings a lubricating
composition designed to have superior performance compared to
conventional coal pulverizer bearing lubricants. The invention also
provides a bearing lubricant for a coal pulverizer as well as its
use in coal pulverizing equipment to improve the service life
and/or durability of bearings in coal pulverizing equipment. The
invention also provides an additive composition for use in a
bearing lubricant for a coal pulverizer, as well as the use of the
additive composition to improve the service life and/or performance
of the bearing lubricant.
BACKGROUND OF THE INVENTION
[0002] Pulverizers are well known for the reduction of the particle
size of solid fuel to allow for combustion of the solid fuel in a
furnace. A pulverizer employs some combination of impact, attrition
and crushing to reduce a solid fuel to a particular particle size.
Several types of pulverizer mills can be employed for the
pulverization of the solid fuel, for example, coal, to a
particulate size appropriate for firing in a furnace. These can
include ball-tube mills, impact mills, attrition mills, ball race
mills, and ring roll or bowl mills. Most typically, however, bowl
mills with integral classification equipment are employed for the
pulverization of the solid fuel to allow for transport, drying and
direct firing of the pulverized fuel entrained in an air stream.
There is an on-going need to improve the mill loading and roll life
of the bearings of these pulverizers.
[0003] Another factor which deteriorates roll life of the bearings
in addition to increased mill loading includes solid fuel dust,
such as coal dust, for example, which flows into and contaminates
the bearings as well as the lubricant. Typically, pulverizers have
an interface between the rotatable assembly and stationary shaft
that is exposed to atmospheric conditions and a differential
pressure across the assembly allows the coal dust, for example, to
flow into the assembly housing the bearings. The ingress of coal at
this interface, which allows the shaft to extend there through and
rotate with respect to the journal assembly, contaminates the
lubricant and journal bearings thus deteriorating the roll life of
the journal bearings.
[0004] Some approaches involve complicated mechanical seals and
expensive new equipment designed to reduce the amount of dust
ingress. However, these solution do nothing for the current
equipment already in use.
[0005] Therefore, there remains a need for a method, and a
lubricant, and an additive package that increases bearing roll life
in these pulverisers, which facilitates increased mill loading and
prevents damage from contamination of the bearings, thus allowing
more effective use of existing equipment without the need for
costly refits and modifications.
SUMMARY OF THE INVENTION
[0006] The invention provides a method of lubricating the bearings
of a solid fuel pulverizer. The method involved supplying to the
bearings a lubricating composition designed to have superior
performance compared to conventional solid fuel pulverizer bearing
lubricants. The lubricating composition is designed to have
improved dust loading capability, in other words, the lubricant is
designed to perform better and/or last longer than conventional
lubricants in the harsh conditions seen in pulverizers, including
conditions related to large amounts of dust in the environment,
which does get worked into the lubricant. The invention also
provides a bearing lubricant for a pulverizer as well as its use in
pulverizing equipment to improve the service life and/or durability
of bearings in pulverizing equipment. The invention also provides
an additive composition for use in a bearing lubricant for a
pulverizer, as well as the use of the additive composition to
improve the service life and/or performance of the bearing
lubricant. In some embodiments, the solid fuel pulverizer described
herein is a coal pulverizer.
[0007] The lubricating composition of the invention includes (a) an
oil of lubricating viscosity, (b) a phosphorus-containing compound,
and (c) a nitrogen-containing dispersant, where the
phosphorus-containing compound and the nitrogen-containing
dispersant work together to allow for better performance in the
pulverizer bearing lubricant. In some embodiments, the compositions
further include (d) a sulfur-containing compound.
[0008] In some embodiments, the invention deals with mineral base
oil lubricants. In other embodiments, the invention deals with
synthetic base oil lubricants.
[0009] The invention provides for various phosphorus-containing
compound including an alkyl phosphite, a phosphoric acid ester, an
amine salt of a phosphoric acid ester, or some combination thereof.
In some embodiments, the phosphorus-containing compound comprises
an alkyl phosphite.
[0010] The invention provides for various nitrogen-containing
dispersants including a polyetheramine, a borated succinimide
dispersant, a non-borated succinimide dispersant, a Mannich
dispersant comprising the reaction product of (i) a dialkylamine,
(ii) an aldehyde and (iii) a hydrocarbyl substituted phenol, as
well as any combination of the various nitrogen-containing
dispersants. In some embodiments, the nitrogen-containing
dispersant comprises a non-borated succinimide dispersant. The
invention further provides for a lubricant containing an alkyl
phosphite and a non-borated succinimide dispersant.
[0011] In any of these embodiments, the phosphorus-containing
compound may be present in the lubricant composition from 0.25 or
0.5 up to 2.0 or 1.0 percent by weight and the nitrogen-containing
dispersant is present in the lubricant composition from 0.1 or 0.5
up to 2.0 or 1.0 percent by weight, on an oil free basis, which may
also be described herein is on an actives basis.
DETAILED DESCRIPTION OF THE INVENTION
[0012] Various features and embodiments of the invention will be
described below by way of non-limiting illustration.
The Pulverizer and Method of Lubrication
[0013] The pulverizers suitable for use with the present invention
are not overly limited. Pulverizers may generally be described as
devices employable for purposes of effecting the grinding of
materials. More specifically, the prior art is replete with
examples of various types of apparatus that have been used to
effect the grinding of many different kinds of materials. In this
regard, in many instances discernible differences of a structural
nature can be found to exist between individual pulverizers. The
existence of such differences is, in turn, attributable for the
most part to the diverse functional requirements that are
associated with the individual applications in which pulverizers
are designed to be employed. For instance, in the selection of the
particular type of pulverizer that is to be utilized for a specific
application, one of the principal factors to consider is that of
the nature of the material that is to be ground in the apparatus.
Coal is one such material wherein there is a need to grind it in
order to render it suitable for use in certain applications.
Furthermore, fossil fuel fired power generation systems represent
one such application in which it is desired to employ coal, as the
source of fuel, and wherein a requirement exists to grind, i.e.,
pulverize, the coal to render it suitable for use for this purpose,
i.e., for use in a coal-fired power generation system. Thus, in
some embodiments, the pulverizers used with the invention are coal
pulverizers.
[0014] In some embodiments, the pulverizers of the invention may
include a feeder for feeding solid fuel to the pulverizer, an
apparatus for pulverizing the solid fuel, a distribution system for
distributing the solid fuel after the pulverization thereof, a
furnace in which the solid fuel is to be burned and the requisite
controls for effecting the proper operation of the solid fuel-fired
power generation system. Of particular interest here the apparatus
for pulverizing the solid fuel, for example, coal.
[0015] In some embodiments, the pulverizer of the present invention
is a bowl mill. A bowl mill may essentially consists of a body
portion in which a grinding table is mounted for rotation, a
plurality of grinding rollers that coact with the grinding table to
effect the grinding of solid fuel interposed there between, solid
fuel supply means for feeding to the interior of the bowl mill the
solid fuel that is to be pulverized, and air supply means for
supplying to the interior of the bowl mill the air required in the
operation of the latter. In accordance with the mode of operation
of such a bowl mill, the solid fuel, which enters the bowl mill, is
pulverized by virtue of the coaction of the grinding rollers with
the grinding table. After being pulverized, the solid fuel
particles are thrown outwardly by centrifugal force whereby the
particles are fed into a stream of air that is entering the bowl
mill. The stream of air, which now contains pulverized solid fuel
particles, flows through a tortuous path that is established in
part by the positioning within the bowl mill of a suitably
supported deflector means. As the stream of air and solid fuel
particles flows along the aforementioned tortuous path, the sharp
turns contained therein effects the separation of the coarse solid
fuel particles from the air stream. These coarse solid fuel
particles are then suitably returned to the grinding table for
further pulverization while the fine solid fuel particles are
carried through the bowl mill in the air stream, and exit therefrom
along with the air. Each bowl mill will typically also have
bearings, for example, upper bearings and lower bearings associated
with the grinding rollers with the grinding table and/or their
mounts.
[0016] Each pulverizer will typically also have a lubrication
system for supplying lubricant to its beatings, including the upper
and lower bearings of a bowl mill described, but all the various
bearing that may be found in the various types of pulverizers used
in the field.
[0017] The present invention provides a lubricant composition for
the bearings of a solid fuel pulverizer and also provides a method
of lubricating the bearings of a coal pulverizer by supplying to
said bearings the described lubricant composition. The lubricant
compositions useful in the invention are described below.
[0018] In some embodiments, the method of the invention involves
supplying the described lubricant composition to a coal pulverizer.
In some embodiments, the method of the invention involves supplying
the described lubricant composition to a bowl mill pulverizer. In
some embodiments, the method of the invention involves supplying
the described lubricant composition to a bowl mill coal pulverizer.
In some embodiments, the method of the invention involves supplying
the described lubricant composition to the upper bearings of the
pulverizer. In some embodiments, the method of the invention
involves supplying the described lubricant composition to the lower
bearings of the pulverizer. In some embodiments, the method of the
invention involves supplying the described lubricant composition to
the upper and lower bearings of the pulverizer, or even all of the
bearings in the pulverizer.
The Lubricant Composition
[0019] The invention includes a bearing lubricating composition
made up of (a) an oil of lubricating viscosity, (b) a
phosphorus-containing compound, and (c) a nitrogen-containing
dispersant, where the phosphorus-containing compound and the
nitrogen-containing dispersant work together to allow for better
performance in the pulverizer bearing lubricant. The invention also
provides an additive composition for use in a bearing lubricant for
a pulverizer made up of (a) an optional diluent which may be an oil
of lubricating viscosity or solvent, and (b) a
phosphorus-containing compound, and (c) a nitrogen-containing
dispersant, where the phosphorus-containing compound and the
nitrogen-containing dispersant work together to allow for better
performance in the pulverizer bearing lubricant. In some
embodiments, the compositions further include (d) a
sulfur-containing compound.
[0020] In some embodiments, the lubricant composition contains from
0.01 to 5.0, or from 0.25 to 5.0, or from 0.5 to 5.0, or from 0.5
to 4.0, from 0.75 to 3.0, from 0.9 to 2.0, or from 1 to 2, or even
1 or 2 percent by weight of a phosphorus-containing compound, on an
actives basis (meaning no diluent oil or solvent is includes,
rather the components are considered on a neat basis). In some
embodiments, the lubricant composition contains a
phosphorus-containing compound in an amount sufficient to deliver
from 0.01 to 5.0, or from 0.025 to 0.5 or from 0.025 to 0.25, or
from 0.05 to 0.1 percent by weight phosphorus to the overall
lubricant composition.
[0021] In some embodiments, the lubricant composition contains from
0.01 or 0.1 or 0.25 to 10 or 5 or 4, or from 0.01 or 0.1 or 0.25 to
5, or from 0.1 to 1.0, or from 0.4 to 2.0 or 2.5, or from 0.5 to
2.0 percent by weight of a nitrogen-containing dispersant on an
actives basis.
[0022] In some embodiments, the phosphorus-containing compound and
the nitrogen-containing dispersant are present in the lubricant
composition in a ratio from 1:10 to 10:1, or from 1:4 to 4:1, or
from 1:2 to 4:1, or from 1:1 to 3:1, or even about 2:1, where the
ratio is a weight ratio considered on an actives free basis. In
some embodiments, the phosphorus-containing compound and the
nitrogen-containing dispersant are present in the lubricant
composition in a ratio from 0.5:1 to 4:1, or from and/or to about
0.5:1, 1:1, 1.2:1, 2:1 or 4:1, where the ratio is a weight ratio
considered on an oil free basis.
The Oil of Lubricating Viscosity
[0023] One component of the compositions of the invention is an oil
of lubricating viscosity, which can be present in a major amount,
for a lubricant composition, or in a concentrate forming amount,
for a concentrate and/or additive composition.
[0024] Suitable oils include natural and synthetic lubricating oils
and mixtures thereof. In a fully formulated lubricant, the oil of
lubricating viscosity is generally present in a major amount (i.e.,
an amount greater than 50 percent by weight). Typically, the oil of
lubricating viscosity is present in an amount of 75 to 95 percent
by weight, and often greater than 80 percent by weight of the
overall composition.
[0025] The base oil component generally makes up 100 parts by
weight (pbw) of the overall composition with the pbw ranges for the
other components being provided with this 100 pbw of base oil in
mind. In other embodiments, the pbw ranges of the various
components, including the base oils, are provided such that the
total of the pbw of all components is 100, and thus the pbw values
are equivalent to percent by weight values. The pbw ranges provided
for the various components described below may be taken either way,
however, in most embodiments they are to be read so as to be
equivalent to percent by weight values.
[0026] The oil of lubricating viscosity may include natural and
synthetic oils, oil derived from hydrocracking, hydrogenation, and
hydrofinishing, unrefined, refined and refined oils or mixtures
thereof. Unrefined oils are those obtained directly from a natural
or synthetic source generally without (or with little) 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. Purification
techniques are known in the art and include solvent extraction,
secondary distillation, acid or base extraction, filtration,
percolation and the like. Re-refined oils are also known as
reclaimed or reprocessed oils, and are obtained by processes
similar to those used to obtain refined oils and often are
additionally processed by techniques directed to removal of spent
additives and oil breakdown products.
[0027] Natural oils useful as the oil of lubricating viscosity
include animal oils, vegetable oils (e.g., castor oil, lard oil),
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 and
oils derived from coal or shale or mixtures thereof.
[0028] Synthetic oils of lubricating viscosity include hydrocarbon
oils such as polymerized and interpolymerised olefins (e.g.,
polybutylenes, polypropylenes, propyleneisobutylene copolymers);
poly(1-hexenes), poly(1-octenes), poly(1-decenes), and mixtures
thereof; alkyl-benzenes (e.g., dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g.,
biphenyls, terphenyls, alkylated polyphenyls); alkylated biphenyl
ethers and alkylated biphenyl sulfides and the derivatives, analogs
and homologs thereof or mixtures thereof. In some embodiments, the
oil of lubricating viscosity used in the invention is a synthetic
oil that includes polymerized polyisobutylene, and in some
embodiments, the oil of lubricating viscosity used in the invention
is a synthetic oil that includes polymerized polyisobutylene and a
polyalphaolefin).
[0029] Another synthetic oil of lubricating viscosity include
polyol esters other than the hydrocarbyl-capped polyoxyalkylene
polyol as disclosed herein, dicarboxylic esters, liquid esters of
phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl
phosphate, and the diethyl ester of decane phosphonic acid), or
polymeric tetrahydrofurans. Synthetic conventional oil of
lubricating viscosity also include those produced by
Fischer-Tropsch reactions and typically may be hydroisomerised
Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil
of lubricating viscosity may be prepared by a Fischer-Tropsch
gas-to-liquid synthetic procedure as well as other gas-to-liquid
oils.
[0030] Oils of lubricating viscosity may further be defined as
specified in the American Petroleum Institute (API) Base Oil
Interchangeability Guidelines. The five base oil groups are as
follows: Group I (sulfur content >0.03 percent by weight, and/or
<90 percent by weight saturates, viscosity index 80-120); Group
II (sulfur content .ltoreq.0.03 percent by weight and .gtoreq.90
percent by weight saturates, viscosity index 80-120); Group III
(sulfur content .ltoreq.0.03 percent by weight and .gtoreq.90
percent by weight saturates, viscosity index .gtoreq.120); Group IV
(all polyalphaolefins, or PAO, such as PAO-2, PAO-4, PAO-5, PAO-6,
PAO-7 or PAO-8); and Group V. The oil of lubricating viscosity
includes API Group I, Group II, Group III, Group IV, Group V oil or
mixtures thereof. In one embodiment, the oil of lubricating
viscosity is an API Group I, Group II, Group III, Group IV oil or
mixtures thereof. Alternatively, the oil of lubricating viscosity
is often an API Group II, Group III or Group IV oil or mixtures
thereof.
[0031] In some embodiments, the lubricating oil component of the
present invention includes a Group II or Group III base oil, or a
combination thereof. These are classifications established by the
API (American Petroleum Institute). Group III oils contain <0.03
percent sulfur and >90 percent saturates and have a viscosity
index of >120. Group II oils have a viscosity index of 80 to 120
and contain <0.03 percent sulfur and >90 percent saturates.
The oil can also be derived from the hydroisomerization of wax,
such as slack wax or a Fischer-Tropsch synthesized wax. Such
"Gas-to-Liquid" oils are typically characterized as Group III.
[0032] The compositions of the present invention may include some
amount of Group I base oils, and even Group IV and Group V base
oils. Polyalphaolefins are categorized as Group IV. Group V
encompasses "all others". However, in some embodiments, the
lubricating oil component of the invention contains no more than
20, 10, 5, or even 1 percent by weight Group I base oil. These
limits may also apply to Group IV or Group V base oils. In other
embodiments, the lubricating oil present in the compositions of the
invention is at least 60, 70, 80, 90, or even 95 percent by weight
Group II and/or Group III base oil. In some embodiments, the
lubricating oil present in the compositions of the invention is
essentially only Group II and/or Group III base oil, where small
amounts of other types of base oils may be present but not in
amounts that significantly impact the properties or performance of
the overall composition.
[0033] In some embodiments, the compositions of the invention
include some amount of Group I and/or Group II base oils. In other
embodiments, the compositions of the invention are lubricating
compositions where the oil of lubricating viscosity is primarily
Group I and/or Group II base oils, or even essentially Group I
and/or Group II base oils, or even exclusively Group I and/or Group
II base oils.
[0034] In some embodiments, the compositions of the invention
include some amount of Group I and/or Group II base oils. In other
embodiments, the compositions of the invention are lubricating
compositions where the oil of lubricating viscosity is primarily
Group I and/or Group II base oils, or even essentially Group I
and/or Group II base oils, or even exclusively Group I and/or Group
II base oils.
[0035] The various described oils of lubricating viscosity may be
used alone or in combinations. The oil of lubricating viscosity is
used in the range of about 70 percent by weight to about 99 percent
by weight, and in another embodiment, in the range of about 75
percent by weight to about 98 percent by weight, in another
embodiment in the range of about 88 percent by weight to about 97
percent by weight of the lubricant.
The Phosphorus-Containing Compound
[0036] The compositions useful in the invention include a
phosphorus-containing compound.
[0037] In some embodiments, the phosphorus-containing compound is a
phosphite. Suitable phosphites include those having at least one
hydrocarbyl group with 4 or more, or 8 or more, or 12 or more,
carbon atoms. Typical ranges for the number of carbon atoms on the
hydrocarbyl group include 8 to 30, or 10 to 24, or 12 to 22, or 14
to 20, or 16 to 18. The phosphite may be a mono-hydrocarbyl
substituted phosphite, a di-hydrocarbyl substituted phosphite, or a
tri-hydrocarbyl substituted phosphite.
[0038] In one embodiment, the phosphite is sulphur-free i.e., the
phosphite is not a thiophosphite.
[0039] The phosphite having at least one hydrocarbyl group with 4
or more carbon atoms may be represented by the formulae:
##STR00001##
wherein at least one of R.sup.3, R.sup.4 and R.sup.5 may be a
hydrocarbyl group containing at least 4 carbon atoms and the other
may be hydrogen or a hydrocarbyl group. In one embodiment, both
R.sup.3, R.sup.4 and R.sup.5 are hydrocarbyl groups. The
hydrocarbyl groups may be alkyl, cycloalkyl, aryl, acyclic or
mixtures thereof. In the formula with all three groups R.sup.3,
R.sup.4 and R.sup.5, the compound may be a tri-hydrocarbyl
substituted phosphite i.e., R.sup.3, R.sup.4 and R.sup.5 are all
hydrocarbyl groups.
[0040] Alkyl groups may be linear or branched, typically linear,
and saturated or unsaturated, typically saturated. Examples of
alkyl groups for R.sup.3, R.sup.4 and R.sup.5 include octyl,
2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl,
nonadecyl, eicosyl or mixtures thereof.
[0041] In some embodiments, the phosphorus-containing compound is
an amine salt of a phosphate hydrocarbon ester (i.e., an amine salt
of a hydrocarbon ester of phosphoric acid). The amine salt of a
phosphate hydrocarbon ester may be derived from an amine salt of a
phosphate. The amine salt of the phosphate hydrocarbon ester may be
represented by the formula:
##STR00002##
Wherein: R.sup.3 and R.sup.4 may be independently hydrogen or
hydrocarbon typically containing 4 to 40, or 6 to 30, or 6 to 18,
or 8 to 18 carbon atoms, with the proviso that at least one is a
hydrocarbon group; and R.sup.5, R.sup.6, R.sup.7 and R.sup.8 may be
independently hydrogen or a hydrocarbyl group, with the proviso
that at least one is a hydrocarbyl group. The hydrocarbon groups of
R.sup.3 and/or R.sup.4 may be linear, branched, or cyclic.
[0042] Examples of a hydrocarbon group for R.sup.3 and/or R.sup.4
include straight-chain or branched alkyl groups include methyl,
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl and octadecyl. Additional examples include 2-ethylhexl,
4-methyl-2-pentyl, and isopropyl.
[0043] Examples of a cyclic hydrocarbon group for R.sup.3 and/or
R.sup.4 include cyclopentyl, cyclohexyl, cycloheptyl,
methylcyclopentyl, dimethylcyclopentyl, methylcyclopentyl,
dimethylcyclopentyl, methylethylcyclopentyl, diethyl-cyclopentyl,
methylcyclohexyl, dimethylcyclohexyl, methyl ethylcyclohexyl,
diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl,
methylethyl-cycloheptyl, and diethylcycloheptyl.
[0044] In one embodiment, the phosphate may be an amine salt of a
mixture of monoalkyl and dialkyl phosphoric acid esters. The
monoalkyl and dialkyl groups may be linear or branched.
[0045] The amine salt of a phosphate hydrocarbon ester may be
derived from an amine such as a primary amine, a secondary amine, a
tertiary amine, or mixtures thereof. The amine may be aliphatic, or
cyclic, aromatic or non-aromatic, typically aliphatic. In one
embodiment, the amine includes an aliphatic amine such as a
tertiary-aliphatic primary amine.
[0046] Examples of suitable primary amines include ethylamine,
propylamine, butylamine, 2-ethylhexylamine,
bis-(2-ethylhexyl)amine, octylamine, and dodecylamine, as well as
such fatty amines as n-octylamine, n-decylamine, n-dodecylamine,
n-tetradecylamine, n-hexadecylamine, n-octadecylamine and
oleylamine. Other useful fatty amines include commercially
available fatty amines such as "Armeen.RTM." amines (products
available from Akzo Chemicals, Chicago, Ill.), such as Armeen C,
Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD,
wherein the letter designation relates to the fatty group, such as
coco, oleyl, tallow, or stearyl groups.
[0047] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine,
dihexylamine, diheptylamine, methyl ethylamine, ethylbutylamine,
N-methyl-1-amino-cyclohexane, Armeen.RTM. 2C and ethylamylamine.
The secondary amines may be cyclic amines such as piperidine,
piperazine and morpholine.
[0048] Examples of tertiary amines include tri-n-butylamine,
tri-n-octylamine, tri-decylamine, tri-laurylamine,
tri-hexadecylamine, and dimethyloleylamine (Armeen.RTM. DMOD).
[0049] In one embodiment, the amines are in the form of a mixture.
Examples of suitable mixtures of amines include (i) a tertiary
alkyl primary amine with 11 to 14 carbon atoms, (ii) a tertiary
alkyl primary amine with 14 to 18 carbon atoms, or (iii) a tertiary
alkyl primary amine with 18 to 22 carbon atoms. Other examples of
tertiary alkyl primary amines include tert-butylamine,
tert-hexylamine, tert-octylamine (such as 1,1-dimethylhexylamine),
tert-decylamine (such as 1,1-dimethyloctylamine), tertdodecylamine,
tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine,
tert-tetracosanylamine, and tert-octacosanylamine.
[0050] In one embodiment, a useful mixture of amines is
"Primene.RTM. 81R" or "Primene.RTM. JMT." Primene.RTM. 81R and
Primene.RTM. JMT (both produced and sold by Rohm & Haas) are
mixtures of C11 to C14 tertiary alkyl primary amines and C18 to C22
tertiary alkyl primary amines respectively.
[0051] The amine salt of a phosphate hydrocarbon ester may be
prepared as is described in U.S. Pat. No. 6,468,946. Column 10,
lines 15 to 63 describes phosphoric acid esters formed by reaction
of phosphorus compounds, followed by reaction with an amine to form
an amine salt of a phosphate hydrocarbon ester. Column 10, line 64,
to column 12, line 23, describes preparative examples of reactions
between phosphorus pentoxide with an alcohol (having 4 to 13 carbon
atoms), followed by a reaction with an amine (typically
Primene.RTM. 81-R) to form an amine salt of a phosphate hydrocarbon
ester.
[0052] Suitable phosphorus-containing compounds also include
hydrocarbyl amine salts of dialkyldithiophosphoric acid. Examples
of hydrocarbyl amine salts of dialkyldithiophosphoric acid are
represented by the formula:
##STR00003##
wherein R.sup.26 and R.sup.27 are independently branched or linear
alkyl groups. R.sup.26 and R.sup.27 contain about 3 to about 30,
preferably about 4 to about 25, more preferably about 5 to about
20, and most preferably about 6 to about 19 carbon atoms. R.sup.23,
R.sup.24 and R.sup.25 are as described above.
[0053] In some embodiments, the hydrocarbyl amine salts of
dialkyldithiophosphoric acid include but are not limited to the
reaction product(s) of diheptyl or dioctyl or dinonyl
dithiophosphoric acids with ethylenediamine, morpholine or Primene
81R or mixtures thereof.
[0054] The phosphorus-containing compound may be present at 0.01
percent by weight to 5 percent by weight, or 0.1 percent by weight
to 3 percent by weight, or 0.2 percent by weight to 1.5 percent by
weight, or 0.25 percent by weight to 1 percent by weight, or 0.5
percent by weight to 1 percent by weight of the described
composition.
The Nitrogen-Containing Dispersant
[0055] The compositions useful in the invention include a
nitrogen-containing dispersant, which in some embodiments is a
hydrocarbyl substituted nitrogen containing additive. Suitable
hydrocarbyl substituted nitrogen containing additives for use in
the present invention includes additives sometimes referred to as
ashless dispersants. Dispersants in general are well known in the
field of lubricants and fuel (though often these additives are
referred to as fuel detergents when used in fuel applications).
Suitable materials include primarily what is 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 once 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. Examples of such materials include succinimide
dispersants, Mannich dispersants, and borated derivatives
thereof.
[0056] Mannich dispersants, sometimes referred to as a Mannich base
dispersant or Mannich detergents, are the 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, 30 to 180, 10 or 40 to 110 carbon atoms.
This hydrocarbyl substituent can be derived from an olefin or a
polyolefin, such as 1-decene, which are commercially available.
[0057] The 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.
[0058] 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.
[0059] 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.
[0060] The amine used to form the Mannich dispersant can be a
monoamine or a polyamine, including those materials described below
for the succinimide dispersants, including alkanolamines having one
or more hydroxyl groups. Useful amines include ethanolamine,
diethanolamine, methylamine, dimethylamine, ethylenediamine,
dimethylaminopropylamine, diethylenetriamine and
2-(2-amino-ethylamino)ethanol. The Mannich dispersant can be
prepared by reacting a hydrocarbyl-substituted phenol, an aldehyde,
and an amine as described in U.S. Pat. No. 5,697,988. 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.) The foregoing description of the amine is
also applicable to the description of the amine used in preparing
the succinimide dispersant, described below.
[0061] 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.
[0062] 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.
[0063] Another suitable hydrocarbyl substituted nitrogen containing
additive is a succinimide dispersant, which may also be referred to
as a succinimide fuel detergent. 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 an amine such as a
polyethylene polyamine. Succinimide dispersants may generally be
viewed as comprising a variety of chemical structures including
typically
##STR00004##
where each R.sup.1 is independently an alkyl group, frequently a
polyisobutylene group with a molecular weight (M.sub.n) of 500-5000
based on the polyisobutylene precursor, and R.sup.2 are alkylene
groups, commonly ethylene (C.sub.2H.sub.4) 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, including those described above and
below. Also, a variety of modes of linkage of the R.sup.1 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. Pat. Nos. 4,234,435
and 3,172,892 and in EP 0355895.
[0064] 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. Pat. No. 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.degree. 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, in some embodiments alpha
vinylidene end groups. 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.
[0065] Any of these additives may be post-treated with any of a
variety of agents to impart desirable properties thereto. 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. Pat. No. 4,654,403.
[0066] Additional suitable hydrocarbyl substituted nitrogen
containing additives include acylated amines, hydrocarbyl
substituted amines, or mixtures thereof.
[0067] Suitable acylated amines include reaction products of one or
more carboxylic acylating agent and one or more amine. The
carboxylic acylating agents include C.sub.8-30 fatty acids,
C.sub.14-20 isoaliphatic acids, C.sub.18-44 dimer acids, addition
dicarboxylic acids, trimer acids, addition tricarboxylic acids, and
hydrocarbyl substituted carboxylic acylating agents, including
those described above. Dimer acids are described in U.S. Pat. Nos.
2,482,760, 2,482,761, 2,731,481, 2,793,219, 2,964,545, 2,978,468,
3,157,681, and 3,256,304. Suitable amines may be any of those
described above, in some embodiments a polyamine, such as an
alkylenepolyamine or a condensed polyamine. Acylated amines, their
intermediates and methods for preparing the same are described in
U.S. Pat. Nos. 3,219,666; 4,234,435; 4,952,328; 4,938,881;
4,957,649; 4,904,401; and 5,053,152.
[0068] The hydrocarbyl substituted nitrogen containing additive may
also be a hydrocarbyl-substituted amine. These
hydrocarbyl-substituted amines are well known to those skilled in
the art. These amines are disclosed in U.S. Pat. Nos. 3,275,554;
3,438,757; 3,454,555; 3,565,804; 3,755,433; and 3,822,289.
Typically, hydrocarbyl substituted amines are prepared by reacting
olefins and olefin polymers, including the above polyalkenes and
halogenated derivatives thereof, with amines (mono- or polyamines).
The amines may be any of the amines described herein, and in some
embodiments is an alkylenepolyamine.
[0069] Examples of hydrocarbyl substituted amines include ethylene
polyamines such as diethylenetriamine; poly(propylene)amine;
N,N-dimethyl-N-poly(ethylene/propylene)amine, (50:50 mole ratio of
monomers); polybutene amine; N,N-di(hydroxyethyl)-N-polybutene
amine; N-(2-hydroxypropyl)-N-polybutene amine;
N-polybutene-aniline; N-polybutenemorpholine;
N-poly(butene)ethylenediamine;
N-poly(propylene)trimethylenediamine;
N-poly(butene)diethylenetriamine;
N',N'-poly(butene)tetraethylenepentamine;
N,N-dimethyl-N'-poly(propylene)-1,3-propylenediamine and the
like.
[0070] In some embodiments, the hydrocarbyl substituted nitrogen
containing additives described above are borated. Any of the
additives described herein may be borated, generally prepared by
the reaction of the additive with a boron-containing compound, for
example, boric acid.
[0071] In one embodiment, the boron compound is a borated
dispersant. Typically, the borated dispersant contains from about
0.1% to about 5%, or from about 0.5% to about 4%, or from 0.7% to
about 3% by weight boron. In one embodiment, the borated dispersant
is a borated acylated amine, such as a borated succinimide
dispersant. Borated dispersants are described in U.S. Pat. Nos.
3,000,916; 3,087,936; 3,254,025; 3,282,955; 3,313,727; 3,491,025;
3,533,945; 3,666,662 and 4,925,983. In one embodiment, the boron
compound is an alkali or mixed alkali metal and alkaline earth
metal borate. These metal borates are generally hydrated
particulate metal borates which are known in the art. Alkali metal
borates include mixed alkali and alkaline metal borates. These
metal borates are available commercially. Representative patents
disclosing suitable alkali and alkali metal and alkaline earth
metal borates and their methods of manufacture include U.S. Pat.
Nos. 3,997,454; 3,819,521; 3,853,772; 3,907,601; 3,997,454; and
4,089,790.
[0072] Hydrocarbyl substituted nitrogen containing additives
described above can also be post-treated by reaction with any of a
variety of agents besides borating agents. Among these are urea,
thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes,
ketones, carboxylic acids, hydrocarbon-substituted succinic
anhydrides, nitriles, epoxides, and phosphorus compounds.
References detailing such treatment are listed in U.S. Pat. No.
4,654,403.
[0073] The amines used in the preparation of the hydrocarbyl
substituted nitrogen containing additives described above may be
polyamines. Suitable polyamines include aliphatic, cycloaliphatic,
heterocyclic and aromatic polyamines. Examples of the polyamines
include alkylene polyamines, hydroxy containing polyamines, aryl
polyamines, and heterocyclic polyamines.
[0074] Alkylene polyamines are represented by the formula:
(H)(R.sub.5)N-(Alkylene-N).sub.n--(R.sub.5)(R.sub.5)
wherein n has an average value from 1, or about 2 to about 10, or
to about 7, or to about 5, and the "Alkylene" group has from 1, or
about 2 to about 10, or to about 6, or to about 4 carbon atoms.
Each R.sub.5 is independently hydrogen, or an aliphatic or
hydroxy-substituted aliphatic group of up to about 30 carbon
atoms.
[0075] Such alkylenepolyamines include methylenepolyamines,
ethylenepolyamines, butylenepolyamines, propylenepolyamines,
pentylenepolyamines, etc. The higher homologs and related
heterocyclic amines such as piperazines and
N-aminoalkyl-substituted piperazines are also included. Specific
examples of such polyamines are ethylenediamine, diethylenetriamine
(DETA), triethylenetetramine (TETA), tris-(2-aminoethyl)amine,
propylenediamine, trimethylenediamine, tripropylenetetramine,
tetraethylenepentamine, hexa-ethyleneheptamine,
pentaethylenehexamine, etc.
[0076] Higher homologs obtained by condensing two or more of the
above-noted alkylene amines are similarly useful as are mixtures of
two or more of the aforedescribed polyamines.
[0077] Ethylenepolyamines, such as those mentioned above, are
useful. Such polyamines are described in detail under the heading
Ethylene Amines in Kirk Othmer's "Encyclopedia of Chemical
Technology", 2d Edition, Vol. 7, pages 22-37, Interscience
Publishers, New York (1965). Such polyamines are most conveniently
prepared by the reaction of ethylene dichloride with ammonia or by
reaction of an ethylene imine with a ring opening reagent such as
water, ammonia, etc. These reactions result in the production of a
complex mixture of polyalkylenepolyamines including cyclic
condensation products such as the aforedescribed piperazines.
Ethylenepolyamine mixtures are also useful.
[0078] Other useful types of polyamine mixtures are those resulting
from stripping of the above-described polyamine mixtures to leave
as residue what is often termed "polyamine bottoms". In general,
alkylenepolyamine bottoms can be characterized as having less than
two, usually less than 1% (by weight) material boiling below about
200.degree. C. A typical sample of such ethylene polyamine bottoms
obtained from the Dow Chemical Company of Freeport, Tex. designated
"E-100" has a specific gravity at 15.6.degree. C. of 1.0168, a
percent nitrogen by weight of 33.15 and a viscosity at 40.degree.
C. of 121 centistokes. Gas chromatography analysis of such a sample
contains about 0.93% "Light Ends" (most probably DETA), 0.72% TETA,
21.74% tetraethylene pentamine and 76.61% pentaethylenehexamine and
higher (by weight). These alkylenepolyamine bottoms include cyclic
condensation products such as piperazine and higher analogs of
diethylenetriamine, triethylenetetramine and the like. These
alkylenepolyamine bottoms can be reacted solely with the acylating
agent or they can be used with other amines, polyamines, or
mixtures thereof.
[0079] Another useful polyamine is a condensation reaction between
at least one hydroxy compound with at least one polyamine reactant
containing at least one primary or secondary amino group. The
hydroxy compounds are in some embodiment's polyhydric alcohols and
amines. The polyhydric alcohols are described above. In some
embodiments, the hydroxy compounds are polyhydric amines.
Polyhydric amines include any of the above-described monoamines
reacted with an alkylene oxide (e.g., ethylene oxide, propylene
oxide, butylene oxide, etc.) having two to about 20, or to about
four carbon atoms. Examples of polyhydric amines include
tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane,
2-amino-2-methyl-1,3-propanediol,
N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine, and
N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, and in some
embodiments tris(hydroxymethyl)aminomethane (THAM).
[0080] In another embodiment, the polyamines are hydroxy-containing
polyamines. Hydroxy-containing polyamine analogs of
hydroxymonoamines, particularly alkoxylated alkylenepolyamines
(e.g., N,N(diethanol)ethylenediamine) may also be used. Such
polyamines may be made by reacting the above-described
alkylenepolyamines with one or more of the above-described alkylene
oxides. Similar alkylene oxide-alkanolamine reaction products may
also be used such as the products made by reacting the
aforedescribed primary, secondary or tertiary alkanolamines with
ethylene, propylene or higher epoxides in a 1:1 to 1:2 molar ratio.
Reactant ratios and temperatures for carrying out such reactions
are known to those skilled in the art.
[0081] Specific examples of alkoxylated alkylene polyamines include
N-(2-hydroxyethyl)ethylenediamine,
N,N-bis(2-hydroxyethyl)ethylenediamine,
1-(2-hydroxyethyl)piperazine, mono(hydroxypropyl)substituted
tetraethylenepentamine, N-(3-hydroxybutyl)tetraethylene diamine,
etc. Higher homologs obtained by condensation of the
above-illustrated hydroxy-containing polyamines through amino
groups or through hydroxy groups are likewise useful. Condensation
through amino groups results in a higher amine accompanied by
removal of ammonia while condensation through the hydroxy groups
results in products containing ether linkages accompanied by
removal of water. Mixtures of two or more of any of the aforesaid
polyamines are also useful.
[0082] In another embodiment, the amine is a heterocyclic
polyamine. The heterocyclic polyamines include aziridines,
azetidines, azolidines, pyridines, pyrroles, indoles, piperidines,
imidazoles, piperazines, isoindoles, purines, morpholines,
thiomorpholines, N-aminoalkylmorpholines,
N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N,N'-di
aminoalkylpiperazines, azepines, azocines, azonines, azecines and
tetra-, di- and perhydro derivatives of each of the above and
mixtures of two or more of these heterocyclic amines. In some
embodiments, the heterocyclic amines are the saturated 5- and
6-membered heterocyclic amines containing only nitrogen, oxygen
and/or sulfur in the hetero ring, especially the piperidines,
piperazines, thiomorpholines, morpholines, pyrrolidines, and the
like. Piperidine, aminoalkyl-substituted piperidines, piperazine,
aminoalkyl-substituted piperazines, morpholine,
aminoalkyl-substituted morpholines, pyrrolidine, and
aminoalkyl-substituted pyrrolidines. Usually the aminoalkyl
substituents are substituted on a nitrogen atom forming part of the
hetero ring. Specific examples of such heterocyclic amines include
N-aminopropylmorpholine, N-amino-ethylpiperazine, and
N,N'-diaminoethylpiperazine. Hydroxy heterocyclic polyamines are
also useful. Examples include N-(2-hydroxyethyl)cyclohexylamine,
3-hydroxycyclopentylamine, para-hydroxyaniline,
N-hydroxyethylpiperazine, and the like.
[0083] The amines used in the preparation of the hydrocarbyl
substituted nitrogen containing additives described above may also
be amines having at least 4 aromatic groups, at least one
--NH.sub.2 functional group, and at least 2 secondary or tertiary
amino groups.
[0084] Suitable amines having at least 3 aromatic groups, at least
one --NH.sub.2 functional group, and at least 2 secondary or
tertiary amino groups may be represented by the formula:
##STR00005##
wherein independently each variable may be defined as follows:
R.sup.1 may be hydrogen or a C.sub.1-5 alkyl group (typically
hydrogen); R.sup.2 may be hydrogen or a C.sub.1-5 alkyl group
(typically hydrogen); U may be an aliphatic, alicyclic or aromatic
group, with the proviso that when U is aliphatic, the aliphatic
group may be linear or branched alkylene group containing 1 to 5,
or 1 to 2 carbon atoms; and w may be 1 to 10, or 1 to 4, or 1 to 2
(typically 1).
[0085] Suitable amines having at least 3 aromatic groups, at least
one --NH.sub.2 functional group, and at least 2 secondary or
tertiary amino groups may be represented by the formula:
##STR00006##
wherein independently each variable may be defined as follows:
R.sup.1 may be hydrogen or a C.sub.1-5 alkyl group (typically
hydrogen); R.sup.2 may be hydrogen or a C.sub.1-5 alkyl group
(typically hydrogen); U may be an aliphatic, alicyclic or aromatic
group, with the proviso that when U is aliphatic, the aliphatic
group may be linear or branched alkylene group containing 1 to 5,
or 1 to 2 carbon atoms; and w may be 1 to 10, or 1 to 4, or 1 to 2
(typically 1).
[0086] Alternatively, the amines may also be represented by the
formula:
##STR00007##
wherein each variable U, R.sup.1, and R.sup.2 are the same as
described above and w is 0 to 9 or 0 to 3 or 0 to 1 (typically
0).
[0087] Examples of suitable amines having at least 3 aromatic
groups may be represented by any of the following formulae:
##STR00008##
[0088] In one embodiment, the amine having at least 3 aromatic
groups may include mixtures of compounds represented by the
formulae disclosed above. A person skilled in the art will
appreciate that these compounds may also react with the aldehyde
described below to form acridine derivatives. In addition to such
compounds, a person skilled in the art will also appreciate that
other acridine structures may be possible where the aldehyde reacts
with other benzyl groups bridged with the >NH group. Any or all
of the N-bridged aromatic rings are capable of such further
condensation and perhaps aromatization.
[0089] Examples of suitable amines having at least 3 aromatic
groups may be bis[p-(p-aminoanilino)phenyl]-methane,
2-(7-amino-acridin-2-ylmethyl)-N-4-{4-[4-(4-amino-phenylamino)-benzyl]-ph-
enyl}-benzene-1,4-diamine,
N.sup.4-{4-[4-(4-amino-phenylamino)-benzyl]-phenyl}-2-[4-(4-amino-phenyla-
mino)-cyclohexa-1,5-dienylmethyl]-benzene-1,4-diamine,
N-[4-(7-amino-acridin-2-ylmethyl)-phenyl]-benzene-1,4-diamine, or
mixtures thereof.
[0090] In one embodiment, the amine having at least 3 aromatic
groups may be bis[p-(p-aminoanilino)phenyl]-methane,
2-(7-amino-acridin-2-ylmethyl)-N-4-{4-[4-(4-amino-phenylamino)-benzyl]-ph-
enyl}-benzene-1,4-diamine or mixtures thereof.
[0091] The amine having at least 3 aromatic groups may be prepared
by a process comprising reacting an aldehyde with an amine
(typically 4-aminodiphenylamine). The resultant amine may be
described as an alkylene coupled amine having at least 3 aromatic
groups, at least one --NH.sub.2 functional group, and at least 2
secondary or tertiary amino groups.
[0092] In some embodiments, the hydrocarbyl substituted nitrogen
containing additives are succinimide dispersants. In some
embodiments, the hydrocarbyl substituted nitrogen containing
additives are non-borated succinimide dispersants. In some
embodiments, the succinimide dispersants are derived from an alkyl
aryl amine, polyethylene polyamines, or some combination thereof.
In some embodiments, the succinimide dispersants are derived from a
hydrocarbyl-substituted succinic anhydride or acid (a reactive
equivalent thereof e.g., an ester, acid halide, etc.) where the
hydrocarbyl-substituted succinic anhydride contains a
polyisobutylene group with a molecular weight from 500 to 3000, or
from 1600 to 3000, or from 1000 to 2000.
[0093] Suitable hydrocarbyl substituted nitrogen containing
additives also include quaternary ammonium salts, also referred to
as quaternary ammonium salt detergents and/or dispersants. Examples
of suitable quaternary ammonium salts include (i) imide quaternary
ammonium salts, (ii) Mannich quaternary ammonium salts, (iii)
polyalkene substituted amine quaternary ammonium salts, (iv) amide
quaternary ammonium salts, (v) ester quaternary ammonium salts,
(vi) polyester quaternary ammonium salts, or (vii) any combination
thereof.
[0094] These various types of quaternary ammonium salts may be
prepared in any number of ways but generally are prepared by
reacting a non-quaternized nitrogen-containing compound with a
quaternizing agent. Each of the different types of quaternary
ammonium salts described uses a different non-quaternized
nitrogen-containing compound in its preparation, but generally the
non-quaternized nitrogen-containing compound contains a tertiary
nitrogen capable of being quaternized (or a primary or secondary
nitrogen atom that can be alkylated to a tertiary nitrogen that can
then be quaternized) and a hydrocarbyl substituent group. The
non-quaternized compounds are typically detergents and/or
dispersants themselves, put once converted to quaternary ammonium
salts, can provide improved performance.
[0095] The hydrocarbyl substituent groups of the quaternary
ammonium salt detergents and/or dispersants, and/or of the
non-quaternized nitrogen-containing compounds from which they are
prepared, are not overly limited and may be any of the hydrocarbyl
substituent groups derived herein.
[0096] Each of the quaternary ammonium salts described above is
prepared using a quaternizing agent. Suitable quaternizing agents
are not overly limited so long as they are able to convert the
tertiary nitrogen of the non-quaternized precursor to a quaternized
nitrogen. Suitable quaternizing agents include dialkyl sulfates,
benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl
epoxides, esters of certain polycarboxylic acids, or mixtures
thereof. Any of the these agents, including the hydrocarbyl
epoxides and hydrocarbyl substituted carbonates, may be used in
combination with an acid, for example acetic acid. Suitable acids
include carboxylic acids, such as acetic acid, propionic acid,
2-ethylhexanoic acid, and the like. In some embodiments, including,
for example, the amide quaternary ammonium salts, the quaternizing
agents, including the hydrocarbyl epoxides and hydrocarbyl
substituted carbonates, are used without the addition of such an
acid. In some embodiments, particularly when no acid is used, some
amount of water is present during the reaction.
[0097] In some embodiments, the quaternizing agent can be a
hydrocarbyl epoxides, as represented by the following formula:
##STR00009##
wherein R.sup.15, R.sup.16, R.sup.17 and R.sup.18 can be
independently H or a C.sub.1-50 hydrocarbyl group. Examples of
suitable hydrocarbyl epoxides include: styrene oxide, ethylene
oxide, propylene oxide, butylene oxide, stilbene oxide, C.sub.2-50
epoxides, or combinations thereof.
[0098] With regards to the amide quaternary ammonium salt described
above, the presence of the amide group and its impact on the rest
of the structure allows the salt to be "self-salting" and thus not
requiring of a separate anion assuming the structure also includes
at least one other acid group. For example, when hydrocarbyl
substituted succinic anhydrides, and similar materials are used to
prepare the non-quaternized nitrogen-containing compounds, the
resulting quaternary ammonium salt can have an amide group and an
acid group, where the acid group becomes the counter anion for the
quaternized nitrogen or the resulting amide quaternary ammonium
salt. These materials may be described as betaines. The preparation
of these quaternary ammonium salts is typically marked by the use
of an alkylene oxide quaternizing agent, or a similar agent,
without the addition of a separate acid.
[0099] In another embodiment, the quaternizing agent can be an
ester of a carboxylic acid or an ester of a polycarboxylic acid. In
some embodiments, the quaternizing agent includes dimethyl oxalate,
methyl 2-nitrobenzoate and methyl salicylate.
[0100] In some embodiments, the quaternary ammonium salt is a
quaternized polymer formed by polymerizing the condensation product
of a hydrocarbyl-substituted acylating agent and a compound having
an oxygen or nitrogen atom capable of condensing the acylating
agent wherein the condensation product has at least one tertiary
amino group, or even polymerizing the hydrocarbyl-substituted
acylating agent which is then reacted with a compound having an
oxygen or nitrogen atom. One or more of the tertiary amino groups
on the polymer may then be quaternized using the methods described
herein resulting in a quaternized polymer.
[0101] Any of the quaternary ammonium salts described above may be
derived in the presence of a protic solvent. In some embodiments,
the process used to prepare these additives is substantially free
of to free of methanol. In one embodiment, the protic solvent
includes compounds that contain 1 or more hydroxyl functional
groups, and may include water. In some embodiments, the protic
solvent is water.
[0102] Additional details on quaternary ammonium salts, examples
thereof and methods of making the same can be found in U.S. Pat.
Nos. 7,951,211 and 7,906,470, US published applications US
2008/0113890, US 2012/0010112, and US 2011/0315107, and
international publications WO 2010/132259, WO 2010/097624, and WO
2011/095819.
[0103] The nitrogen containing dispersant may be a polyetheramine.
In some embodiments, the polyetheramine can include compounds
having two or more consecutive ether groups and at least one
primary, secondary or tertiary amine group where the amine nitrogen
has some basicity. The polyetheramines of this invention can
include poly(oxyalkylene) amines having a sufficient number of
repeating oxyalkylene units to render the poly(oxyalkylene)amine
soluble in a normally liquid fuel, such as, in hydrocarbons boiling
in a gasoline or diesel fuel range and blends of hydrocarbon fuel
with non-hydrocarbon fuel. Generally, poly(oxyalkylene)amines
having at least 5 oxyalkylene units are suitable for use in the
present invention.
[0104] Poly(oxyalkylene)amines can include:
hydrocarbylpoly(oxyalkylene)-amines,
hydrocarbylpoly(oxyalkylene)polyamines,
hydropoly(oxyalkylene)-amines, hydropoly(oxyalkylene)polyamines,
and derivatives of polyhydric alcohols having at least two
poly(oxyalkylene)amine and/or poly(oxyalkylene) polyamine chains on
the molecule of the derivative.
[0105] In one embodiment, the poly(oxyalkylene)amine for use in the
invention is represented by the formula:
R.sup.6O(A.sup.2O).sub.mR.sup.7NR.sup.8R.sup.9
wherein R.sup.6 is a hydrocarbyl group of 1 to 50 carbon atoms, or
8 to 30 carbon atoms; A.sup.2 is an alkylene group having 2 to 18
carbon atoms and in some embodiments 2 to 6 carbon atoms; m is a
number from 1 to 50; R.sup.7 is an alkylene group having 2 to 18
carbon atoms or in some embodiments 2 to 6 carbon atoms; and
R.sup.8 and R.sup.9 are independently hydrogen, a hydrocarbyl group
or --[R'N(R'')]nR''' wherein R' is an alkylene group having 2 to 6
carbon atoms, R'' and R''' are independently hydrogen or a
hydrocarbyl group, and n is a number from 1 to 7.
[0106] In another embodiment, the poly(oxyalkylene)amine of the
present invention can be represented by the formula:
R.sup.10O[CH.sub.2CH(CH.sub.2CH.sub.3)O].sub.ZCH.sub.2CH.sub.2CH.sub.2NH-
.sub.2
wherein R.sup.10 is an aliphatic group or alkyl-substituted phenyl
group of 8 to 30 carbon atoms; and Z is a number from 12 to 30. In
yet another embodiment, the poly-(oxyalkylene)amine of the present
invention can be represented by the formula above wherein R.sup.10
is
CH.sub.3CH(CH.sub.3)[CH.sub.2CH(CH.sub.3)].sub.2CH(CH.sub.3)CH.sub.2CH.su-
b.2-- and Z is a number from 16 to 28. Poly(oxyalkylene)amines of
the present invention can have a molecular weight in the range from
300 to 5,000.
[0107] The polyetheramines of the present invention can be prepared
by using the polyethers described above as intermediates and
converting them to polyetheramines. The polyether intermediates can
be converted to polyetheramines by several methods. The polyether
intermediate can be converted to a polyetheramine by a reductive
amination with ammonia, a primary amine or a polyamine as described
in U.S. Pat. Nos. 5,112,364 and 5,752,991. In one embodiment, the
polyether intermediate can be converted to a polyetheramine via an
addition reaction of the polyether to acrylonitrile to form a
nitrile which is then hydrogenated to form the polyetheramine. U.S.
Pat. No. 5,264,006 provides reaction conditions for the
cyanoethylation of the polyether with acrylonitrile and the
subsequent hydrogenation to form the polyetheramine. In yet another
embodiment, the polyether intermediate or poly(oxyalkylene) alcohol
is converted to the corresponding poly(oxyalkylene) chloride via a
suitable chlorinating agent followed by displacement of chlorine
with ammonia, a primary or secondary amine, or a polyamine as
described in U.S. Pat. No. 4,247,301.
[0108] The mixed alkoxylates of the present invention may also
include an alkoxylated fatty amine, which can include amines
represented by the formula:
##STR00010##
wherein R.sup.11 is a hydrocarbyl group having 4 to 30 carbon
atoms, A.sup.3 and A.sup.4 are vicinal alkylene groups, and the sum
of x and y is an integer that is at least 1. The hydrocarbyl group
is a univalent radical of carbon atoms that is predominantly
hydrocarbon in nature, but can have nonhydrocarbonaceous
substituent groups and can have heteroatoms. The hydrocarbyl group
R.sup.11 can be an alkyl or alkylene group of 4 to 30 carbon atoms,
or 10 to 22 carbon atoms. The vicinal alkylene groups A.sup.3 and
A.sup.4 can be the same or different and include:
ethylene(--CH.sub.2--), propylene (--CH.sub.2CH.sub.2CH.sub.2--)
and butylene (--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--) having the
carbon to nitrogen and carbon to oxygen bonds on adjacent or
neighboring carbon atoms. Examples of alkoxylated fatty amines can
include: diethoxylated tallowamine, diethoxylated oleylamine,
diethoxylated stearylamine, and the diethoxylated amine from
soybean oil fatty acids. Alkoxylated fatty amines are commercially
available from Akzo under the Ethomeen.RTM. series.
[0109] The nitrogen-containing compound may be present at 0.01
percent by weight to 5 percent by weight, or 0.1 percent by weight
to 3 percent by weight, or 0.2 percent by weight to 1.5 percent by
weight, or 0.25 percent by weight to 1 percent by weight, or 0.5
percent by weight to 1 percent by weight of the described
composition.
The Sulfur-Containing Compound
[0110] In some embodiments, the bearing lubricant of invention, or
the methods using the same, may also include (d) a
sulfur-containing compound.
[0111] Suitable sulfur-containing compounds include sulfurized
olefins. Any the olefins described herein for other components are
also suitable olefins from which sulfurized olefins may be
prepared. In some examples, the sulfur-containing compound is a
sulfurized olefin derived from isobutylene, butylene, propylene,
ethylene, or some combination thereof. In some examples, the
sulfur-containing compound is a sulfurized olefin derived any of
the natural oils or synthetic oils described above, or even some
combination thereof. For example, the sulfurized olefin may be
derived from vegetable oil.
[0112] When present, the sulfur-containing compound may be present
at 0.01 percent by weight to 5 percent by weight, or 0.1 percent by
weight to 3 percent by weight, or 0.2 percent by weight to 1.5
percent by weight, or 0.25 percent by weight to 1 percent by
weight, or 0.5 percent by weight to 1 percent by weight of the
described composition.
Additional Additives
[0113] Optionally, the lubricating compositions of the invention
include one or more additional additives, which may be selected
from the group including: a foam inhibitor, a demulsifier, a pour
point depressant, an antioxidant, a dispersant other than those
described above, a metal deactivator (such as a copper
deactivator), an antiwear agent other than those described above,
extreme pressure agent, viscosity modifiers, or mixtures thereof.
The optional additives may each be present in the range from 50,
75, 100 or even 150 ppm up to 5, 4, 3, 2 or even 1.5 percent by
weight, or from 75 ppm to 0.5 percent by weight, from 100 ppm to
0.4 percent by weight, or from 150 ppm to 0.3 percent by weight,
where the percent by weight values are with regards to the overall
lubricating oil composition. However, it is noted that some
optional additives, including viscosity modifying polymers, which
may alternatively be considered as part of the base fluid, may be
present in higher amounts including up to 30, 40, or even 50% by
weight when considered separate from the base fluid. The optional
additives may be used alone or mixtures thereof.
[0114] Antifoams, also known as foam inhibitors, are known in the
art and include but are not limited to organic silicones and
non-silicon foam inhibitors. Examples of organic silicones include
dimethyl silicone and polysiloxanes. Examples of non-silicon foam
inhibitors include but are not limited to polyethers, polyacrylates
and mixtures thereof as well as copolymers of ethyl acrylate,
2-ethylhexylacrylate, and optionally vinyl acetate. In some
embodiments, the antifoam is a polyacrylate. Antifoams may be
present in the composition from 0.001 to 0.012 or 0.004 pbw or even
0.001 to 0.003.
[0115] Demulsifiers are known in the art and include but are not
limited to derivatives of propylene oxide, ethylene oxide,
polyoxyalkylene alcohols, alkyl amines, amino alcohols, diamines or
polyamines reacted sequentially with ethylene oxide or substituted
ethylene oxides or mixtures thereof. Examples of demulsifiers
include polyethylene glycols, polyethylene oxides, polypropylene
oxides, (ethylene oxide-propylene oxide) polymers and mixtures
thereof. In some embodiments, the demulsifiers is a polyether.
Demulsifiers may be present in the composition from 0.002 to 0.012
pbw.
[0116] Pour point depressants are known in the art and include but
are not limited to esters of maleic anhydride-styrene copolymers,
polymethacrylates; polyacrylates; polyacrylamides; condensation
products of haloparaffin waxes and aromatic compounds; vinyl
carboxylate polymers; and terpolymers of dialkyl fumarates, vinyl
esters of fatty acids, ethylene-vinyl acetate copolymers, alkyl
phenol formaldehyde condensation resins, alkyl vinyl ethers and
mixtures thereof.
[0117] The compositions of the invention may also include a rust
inhibitor, other than some of the additive described above.
Suitable rust inhibitors include hydrocarbyl amine salts of
dialkyldithiophosphoric acid, hydrocarbyl amine salts of
hydrocarbyl arenesulphonic acid, fatty carboxylic acids or esters
thereof, an ester of a nitrogen-containing carboxylic acid, an
ammonium sulfonate, an imidazoline, mono-thio phosphate salts or
esters, or any combination thereof; or mixtures thereof.
[0118] Examples of hydrocarbyl amine salts of
dialkyldithiophosphoric acid of the invention include but are not
limited to those described above, as well as the reaction
product(s) of diheptyl or dioctyl or dinonyl dithiophosphoric acids
with ethylenediamine, morpholine or Primene 81R or mixtures
thereof. Suitable hydrocarbyl amine salts of hydrocarbyl
arenesulphonic acids used in the rust inhibitor package of the
invention are represented by the formula:
##STR00011##
wherein Cy is a benzene or naphthalene ring. R.sup.28 is a
hydrocarbyl group with about 4 to about 30, preferably about 6 to
about 25, more preferably about 8 to about 20 carbon atoms. z is
independently 1, 2, 3, or 4 and most preferably z is 1 or 2.
R.sup.23, R.sup.24 and R.sup.25 are as described above.
[0119] Examples of hydrocarbyl amine salts of hydrocarbyl
arenesulphonic acid of the invention include but are not limited to
the ethylenediamine salt of dinonylnaphthalene sulfonic acid.
[0120] Examples of suitable fatty carboxylic acids or esters
thereof include glycerol monooleate and oleic acid. An example of a
suitable ester of a nitrogen-containing carboxylic acid includes
oleyl sarcosine.
[0121] The rust inhibitors may be present in the range from
0.02-0.2, from 0.03 to 0.15, from 0.04 to 0.12, or from 0.05 to 0.1
pbw of the lubricating oil composition. The rust inhibitors of the
invention may be used alone or in mixtures thereof.
[0122] The lubricating compositions of the invention may also
include a metal deactivator. Metal deactivators are used to
neutralise the catalytic effect of metal for promoting oxidation in
lubricating oil. Suitable metal deactivators include but are not
limited to triazoles, tolyltriazoles, a thiadiazole, or
combinations thereof, as well as derivatives thereof. Examples
include derivatives of benzotriazoles other than those described
above, benzimidazole, 2-alkyldithiobenzimidazoles,
2-alkyldithiobenzothiazoles,
2-(N,N'-dialkyldithio-carbamoyl)benzothiazoles,
2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles,
2,5-bis(N,N'-dialkyldithiocarbamoyl)-1,3,4-thiadiazoles,
2-alkyldithio-5-mercapto thiadiazoles or mixtures thereof. These
additives may be used from 0.01 to 0.25 percent by weight in the
overall composition.
[0123] In some embodiments, the metal deactivator is a hydrocarbyl
substituted benzotriazole compound. The benzotriazole compounds
with hydrocarbyl substitutions include at least one of the
following ring positions 1- or 2- or 4- or 5- or 6- or
7-benzotriazoles. The hydrocarbyl groups contain about 1 to about
30, preferably about 1 to about 15, more preferably about 1 to
about 7 carbon atoms, and most preferably the metal deactivator is
5-methylbenzotriazole used alone or mixtures thereof.
[0124] The metal deactivators may be present in the range from
0.001 to 0.1, from 0.01 to 0.04 or from 0.015 to 0.03 pbw of the
lubricating oil composition. Metal deactivators may also be present
in the composition from 0.002 or 0.004 to 0.02 pbw. The metal
deactivator may be used alone or mixtures thereof.
[0125] Antioxidants may also be present including (i) an alkylated
diphenylamine, and (ii) a substituted hydrocarbyl mono-sulfide. In
some embodiments, the alkylated diphenylamines of the invention are
bis-nonylated diphenylamine and bis-octylated diphenylamine. In
some embodiments, the substituted hydrocarbyl monosulfides include
n-dodecyl-2-hydroxyethyl sulfide, 1-(tert-dodecylthio)-2-propanol,
or combinations thereof. In some embodiments, the substituted
hydrocarbyl monosulfide is 1-(tert-dodecylthio)-2-propanol.
[0126] The antioxidant package may also include sterically hindered
phenols. Examples of suitable hydrocarbyl groups include but are
not limited to 2-ethylhexyl or n-butyl ester, dodecyl or mixtures
thereof. Examples of methylene-bridged sterically hindered phenols
include but are not limited to 4,4'-methylene-bis(6-tert-butyl
o-cresol), 4,4'-methylene-bis(2-tert-amyl-o-cresol),
2,2'-methylene-bis(4-methyl-6-tert-butylphenol),
4,4'-methylene-bis(2,6-di-tertbutylphenol) or mixtures thereof.
[0127] In some embodiments, the compositions of the invention are
essentially free of, or even completely free of alkylated phenols,
alkaryl amines, or both, or contain them at not more than 2.0
percent by weight, 1.0 percent by weight, or even 0.5 percent by
weight where the percent by weight values refer to the total amount
of alkylated phenols and/or alkaryl amines present in the overall
lubricant.
EXAMPLES
[0128] The invention will be further illustrated by the following
examples, which set forth particularly advantageous embodiments.
While the examples are provided to illustrate the invention, they
are not intended to limit it.
Example Set 1
[0129] A set of examples of coal pulverizer lubricant compositions
is prepared. The formulations of the examples are summarized in the
table below in percent by weight, with the phosphorus-containing
compound and nitrogen containing dispersant listed on an actives
basis:
TABLE-US-00001 TABLE 1 Ex 1 Ex 2 Ex 3 Ex 9.sup.5 COMP COMP COMP Ex
4 Ex 5 Ex 6 Ex 7 Ex 8 COMP Base 99.26 97.80 98.6 95.55 96.87 96.45
97.81 96.66 NA Medium.sup.1 Phosphorus- 0 1.47 0 1.87 1.93 0.95
0.97 1.43 NA containing compound.sup.2 Nitrogen 0 0 1.21 1.87 0.48
1.89 0.49 1.19 NA Containing Dispersant.sup.3 Additional 0.74 0.73
0.73 0.70 0.72 0.71 0.73 0.72 NA Additives.sup.4 .sup.1The base
medium is a mixture of polyalphaolefin (Group IV) base oil and
polyisobutylene base oil. The same base medium is used in each
example unless otherwise noted, and on a PBW basis is present in
the same amount in each example. Differences in the percent by
weight listed for each example is solely due the different amounts
of the phosphorus-containing compound and nitrogen containing
dispersant that are in each example. .sup.2The
phosphorus-containing compound in the examples is an alkenyl
phosphite. .sup.3The nitrogen containing dispersant in the examples
is a succinimide dispersant. .sup.4The same additional additive
package is used for each example, and on a PBW basis is present in
the same amount in each example. Differences in the percent by
weight listed for each example is solely due the different amounts
of the phosphorus-containing compound and nitrogen containing
dispersant that are in each example. .sup.5Example 9 is a
commercially available lubricant marketed for this application. The
formulation of the lubricant is not known and so the material is
included only as an example of the conventional lubricants
commercially available for this application.
[0130] Each of the example lubricants is tested in a procedure that
simulates the harsh conditions seen in the bearings of pulverizers,
and specifically coal pulverizers. Coal dust is added to the
example lubricant to simulate the contamination that occurs in the
field and the impact on lubricant performance is measured to
demonstrate the examples ability to provide acceptable performance
under those conditions. The test uses a high load KRL type tester
and a SNR 32008.C test bearing. The test procedure involves the
following steps: [0131] (1) Clean a new test bearing in an
ultrasonic bath with toluene for 15 minutes. Rinse with textile
spirits and allow the bearing to dry. [0132] (2) Obtain the start
of test bearing weight to the tenth of a milligram. [0133] (3)
Place bearing in the test head of the KRL type tester. [0134] (4)
Add 0.9 percent by weight coal dust to the example lubricant. Mix
the lubricant and coal dust well using a high speed shaker and then
fill the test head with 30 ml of the coal dust contaminated example
lubricant. [0135] (5) Install test head into the KRL type tester.
[0136] (6) Run the test conditions outlined in Table 2, which are
designed to simulate the harsh conditions and manner of operation
experienced in the bearings of pulverizers:
TABLE-US-00002 [0136] TABLE 2 Speed Load Temp Time Phase (rpm) (kg)
(Degrees C.) (hrs) Break In 150 800 90 1 Break In 300 800 90 1
Break In 430 800 90 2 Break In 150 1600 90 1 Break In 300 1600 90 1
Break In 430 1600 90 2 Break In 150 2400 90 1 Break In 300 2400 90
1 Test 430 2400 90 48
[0137] (7) At the end of test remove, save, and label the example
lubricant. [0138] (8) Clean the test bearing by rinsing with
textile spirits and then clean the bearing in ultrasonic bath with
toluene for 15 minutes. Rinse again with textile spirits and allow
the bearing to dry. [0139] (9) Obtain the end of test bearing
weight to the tenth of a milligram. [0140] (10) Determine weight
loss from the start and end of test weights and analyze the end of
test example lubricant for the amount of wear metals.
[0141] The results from the testing of the example lubricants are
summarized in the table below:
TABLE-US-00003 TABLE 3 Ex 1 Ex 2 Ex 3 Ex 9.sup.4 COMP COMP COMP Ex
4 Ex 5 Ex 6 Ex 7.sup.2 Ex 8.sup.3 COMP Total Weight 8.7 15.6 9.9
8.9 4.9 9.5 8.2 14.1 22.6 Loss (mg).sup.1 Iron in 172 266 229 322
337 293 128 294 770 Lubricant (ppm) .sup.1For the total weight
loss, the lower the value the better the performance of the
lubricant. Total weight loss is the more important result presented
above in regards to evaluating lubricant performance. .sup.2The
results shown for Example 7 are the average of two test results.
.sup.3The results shown for Example 8 are the average of three test
results. .sup.4The results shown for Example 9 are the average of
four test results.
[0142] The results show that the pulverizer bearing lubricants of
the present invention, and the methods of using the same, can
provide significant performance under the harsh conditions seen by
pulverizer bearings. The described lubricants and methods are
particularly advantageous compared to the current commercially
available options for these applications.
Example Set 2
[0143] A second set of examples of coal pulverizer lubricant
compositions is prepared without adding any additional additives.
The formulations of the examples are summarized in the table below
in percent by weight, with the phosphorus-containing compound and
nitrogen containing dispersant listed on an actives basis:
TABLE-US-00004 TABLE 4 Ex 10.sup.5 Ex 12 Ex 16 Ex 17 COMP Ex
11.sup.5 COMP Ex 13 Ex 14 Ex 15 COMP COMP Ex 18 Base NA NA 100
99.26 94.44 98.53 99.01 99.50 99.63 Medium.sup.1 Phosphorus- NA
0.50 0.00 0.50 3.70 0.98 0.99 0.00 0.25 containing compound.sup.2
Nitrogen NA 0.25 0.00 0.25 1.85 0.49 0.00 0.50 0.12 Containing
Dispersant.sup.3 Additional NA 0.00 0.00 0.00 0.00 0.00 0.00 0.00
0.00 Additives.sup.4 .sup.1The base medium is a mixture of
polyalphaolefin (Group IV) and polyisobutylene base oil. The same
base medium is used in each example unless otherwise noted. See
footnote 1 in Table 1 above. .sup.2The phosphorus-containing
compound in the examples is an alkenyl phosphite. .sup.3The
nitrogen containing dispersant in the examples is a succinimide
dispersant. .sup.4No additional additives are added to these
examples. .sup.5Example 10 is a commercially available lubricant
marketed for this application. The formulation of the lubricant is
not known and so the material is included only as an example of the
conventional lubricants commercially available for this
application. Example 11 is the same commercially available
lubricant but now top treated with the additive combination of the
present invention.
[0144] The examples of Table 4 are evaluated in the same test
procedure described above. The results are summarized in the table
below:
TABLE-US-00005 TABLE 5 Ex 10.sup.2 Ex 12.sup.3 Ex 16 Ex 17 COMP Ex
11 COMP Ex 13 Ex 14 Ex 15 COMP COMP Ex 18 Total Weight 22.6 21.5
8.7 8.7 11.4 11.3 4.7 13.3 4.2 Loss (mg).sup.1 Iron in 770 177 172
124 258 156 449 222 123 Lubricant (ppm) .sup.1For the total weight
loss, the lower the value the better the performance of the
lubricant. Total weight loss is the more important result presented
above in regards to evaluating lubricant performance. .sup.2The
results shown for Example 10 are the average of three test results.
.sup.3The results shown for Example 11 are the average of four test
results.
[0145] The results show that the pulverizer bearing lubricants of
the present invention, and the methods of using the same, can
provide significant performance under the harsh conditions seen by
pulverizer bearings. The described lubricants and methods are
particularly advantageous compared to the current commercially
available options for these applications.
[0146] In particular, it is noted that the inventive examples
(Examples 13, 14, 15, and 18) all have better weight loss results
than the conventional and un-additized lubricants (Examples 10 and
12). Example 16 has a good weight loss result but the amount of
iron in the lubricant at end of test is far too high. Likewise,
Example 17 has a reasonable, but still high, amount of iron, but
has high weight loss. In contrast, the inventive examples give a
good balance of results in both areas. Furthermore, the top treated
commerical example (Example 12) showed significant improvement as
well, when the present invention was applied to it.
[0147] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
indicated, all numerical quantities in this description specifying
amounts, reaction conditions, molecular weights, number of carbon
atoms, etc., are to be understood as modified by the word "about."
Unless otherwise indicated, all percent and formulation values are
on a weight basis. Unless otherwise indicated, all molecular
weights are number average molecular weights. 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, 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 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.
* * * * *