U.S. patent application number 14/200930 was filed with the patent office on 2015-07-16 for natural oil derivative based thickener components used in grease compositions and processes for making such compositions.
This patent application is currently assigned to ELEVANCE RENEWABLE SCIENCES, INC.. The applicant listed for this patent is ELEVANCE RENEWABLE SCIENCES, INC.. Invention is credited to Paul A. Bertin.
Application Number | 20150197702 14/200930 |
Document ID | / |
Family ID | 50514039 |
Filed Date | 2015-07-16 |
United States Patent
Application |
20150197702 |
Kind Code |
A1 |
Bertin; Paul A. |
July 16, 2015 |
NATURAL OIL DERIVATIVE BASED THICKENER COMPONENTS USED IN GREASE
COMPOSITIONS AND PROCESSES FOR MAKING SUCH COMPOSITIONS
Abstract
A grease composition is disclosed, having from 50 to 99 weight
percent of a lubricating base oil, from 1 to 30 weight percent of a
thickener component including one or more of (i) one or more
natural oil derivatives selected from the group consisting of
triglycerides, diglycerides, monoglycerides, or oligomers
therefrom, fatty acid methyl esters and corresponding fatty acids,
salts, and dibasic esters therefrom, and C.sub.10-C.sub.15 esters,
C.sub.15-C.sub.18 esters, or C.sub.+ diesters, or diesters
therefrom, (ii) one or more carboxylic acids and/or derivatives
thereof, and (iii) one or more of a metal base compound, and from 1
to 15 weight percent of one or more optional additives. Processes
for making grease compositions are also disclosed.
Inventors: |
Bertin; Paul A.; (Western
Springs, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ELEVANCE RENEWABLE SCIENCES, INC. |
Woodridge |
IL |
US |
|
|
Assignee: |
ELEVANCE RENEWABLE SCIENCES,
INC.
Woodridge
IL
|
Family ID: |
50514039 |
Appl. No.: |
14/200930 |
Filed: |
March 7, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61927606 |
Jan 15, 2014 |
|
|
|
Current U.S.
Class: |
508/512 |
Current CPC
Class: |
C10N 2050/10 20130101;
C10N 2040/02 20130101; C10M 117/06 20130101; C10N 2020/02 20130101;
C10M 2203/1006 20130101; C10M 2207/1276 20130101; C10N 2010/02
20130101; C10N 2030/26 20200501; C10M 117/00 20130101; C10M
2207/1296 20130101; C10M 2207/2825 20130101; C10M 117/04 20130101;
C10M 2207/401 20130101; C10M 2207/1285 20130101; C10M 2205/0285
20130101; C10N 2010/04 20130101 |
International
Class: |
C10M 117/06 20060101
C10M117/06 |
Claims
1. A grease composition comprising: (a) from 50 to 99 weight
percent of a lubricating base oil, (b) from 1 to 30 weight percent
of a thickener component comprising one or more of (i) one or more
natural oil derivatives selected from the group consisting of
triglycerides, diglycerides, monoglycerides, or oligomers
therefrom, fatty acid methyl esters and corresponding fatty acids,
salts, and dibasic esters therefrom, and C.sub.10-C.sub.15 esters,
C.sub.15-C.sub.18 esters, or C.sub.18+ esters, or diesters
therefrom, (ii) one or more carboxylic acids and/or derivatives
thereof, and (iii) one or more of a metal base compound; and (c)
from 1 to 15 weight percent of one or more optional additives.
2. The grease composition of claim 1, wherein the lubricating base
oil comprises a mineral oil, a synthetic oil, a natural oil, or a
natural oil derivative, individually or in combinations
thereof.
3. The grease composition of claim 2, wherein the lubricating base
oil comprises a polyalphaolefin base oil.
4. The grease composition of claim 1, wherein the dibasic esters
comprise octadecanedioic acid dimethyl esters.
5. The grease composition of claim 1, wherein the one or more
carboxylic acids and/or derivatives thereof comprises a
C.sub.2-C.sub.36 mono-, di-, tri-, and/or poly-carboxylic acid
and/or derivative thereof.
6. The grease composition of claim 5, wherein the C.sub.2-C.sub.36
mono-, di-, tri-, and/or poly- carboxylic acid and/or derivative
thereof comprises a hydroxy-substituted, aliphatic, cyclic,
alicyclic, aromatic, branched, saturated, unsaturated , or
heteroatom substituted, carboxylic acid or ester derivative
thereof.
7. The grease composition of claim 1, wherein the C.sub.2-C.sub.36
mono-, di-, tri-, and/or poly- carboxylic acid and/or derivative
thereof comprises a C.sub.12-C.sub.24 hydroxy carboxylic acid or
C.sub.12-C.sub.24 hydroxy ester derivative of such acids.
8. The grease composition of claim 7, wherein the C.sub.12-C.sub.24
hydroxy carboxylic acid or ester derivative of such acids is
12-hydroxystearic acid and ester derivatives.
9. The grease composition of claim 8, wherein the C.sub.12-C.sub.24
hydroxy carboxylic acid ester derivative is 12-hydroxystearate.
10. The grease composition of claim 1, wherein said metal base
compound is a metal hydroxide selected from the group consisting of
calcium hydroxide, strontium hydroxide, lithium hydroxide, sodium
hydroxide, potassium hydroxide, and magnesium hydroxide.
11. The grease composition of claim 1, wherein said optional
additives are selected from the group consisting of: metal
deactivators, antioxidants, antiwear agents, rust inhibitors,
viscosity modifiers, extreme pressure agents, and corrosion
inhibitors.
12. A grease composition comprising: (a) about 75 to 85 weight
percent of a lubricating base oil comprising a polyalphaolefin base
oil, (b) about 15 to 25 weight percent of a thickener component
comprising one or more of (i) one or more natural oil derivatives
comprising esters comprise octadecanedioic acid dimethyl esters,
(ii) one or more carboxylic acids comprising 12-hydroxystearic
acid, and (iii) one or more of a metal base compound comprising
lithium hydroxide; and (c) from 1 to 15 weight percent of one or
more optional additives selected from the group consisting of metal
deactivators, antioxidants, antiwear agents, rust inhibitors,
viscosity modifiers, extreme pressure agents, and corrosion
inhibitors.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] A claim of priority for this application under 35 U.S.C.
.sctn.119(e) is hereby made to the following U.S. provisional
patent application: U.S. Ser. No. 61/927,606 filed Jan. 15, 2014;
and this application is incorporated herein by reference in its
entirety.
FIELD OF THE INVENTION
[0002] This application relates to natural oil derivative based
thickener components used in grease compositions and processes for
making such compositions.
BACKGROUND OF THE INVENTION
[0003] A wide variety of greases have been developed over the years
comprising a number of different formulations with a wide variation
in associated properties. An important component found in greases
is the thickening agent, which is often at least one metal soap,
and differences in grease formulations have often involved this
ingredient. Soap thickened greases constitute a significant segment
by far of the commercially available greases worldwide. Simple soap
greases, which are salts of long chain fatty acids and a
neutralizing agent, are probably the most predominant type of
grease in use today, with lithium 12-hydroxystearate being the
thickener most often used. Complex soap greases, which generally
comprise metal salts of a mixture of organic acids have also come
into widespread use, particularly because of the various property
advantages such type greases can possess (i.e. dropping points at
least 20.degree. C. higher than their corresponding simple soap
greases).
[0004] We have found that the incorporation of certain natural oil
derivatives as a thickener component in complex greases provides
for greases with reduced processing times and improved yields.
SUMMARY OF THE INVENTION
[0005] In one aspect, a grease composition is disclosed. The grease
composition comprises from 50 to 99 weight percent of a lubricating
base oil, and from 1 to 30 weight percent of a thickener component.
The thickener component comprises one or more of (i) one or more
natural oil derivatives selected from the group consisting of
triglycerides, diglycerides, monoglycerides, or oligomers
therefrom, fatty acid methyl esters and corresponding fatty acids,
salts, and dibasic esters therefrom, and C.sub.10-C.sub.15 esters,
C.sub.15-C.sub.18 esters, or C.sub.18+ esters, or diesters
therefrom, (ii) one or more carboxylic acids and/or derivatives
thereof, and (iii) one or more of a metal base compound. In some
embodiments, the natural oil derivative comprises octadecanedioic
acid methyl esters. The grease composition may further comprise
from 1 to 15 weight percent of one or more optional additives.
DETAILED DESCRIPTION OF THE INVENTION
[0006] The present application relates to natural oil based grease
compositions and processes for making such compositions.
[0007] As used herein, the singular forms "a," "an," and "the"
include plural referents unless the context clearly dictates
otherwise. For example, reference to "a substituent" encompasses a
single substituent as well as two or more substituents, and the
like.
[0008] As used herein, the terms "for example," "for instance,"
"such as," or "including" are meant to introduce examples that
further clarify more general subject matter. Unless otherwise
specified, these examples are provided only as an aid for
understanding the applications illustrated in the present
disclosure, and are not meant to be limiting in any fashion.
[0009] As used herein, the following terms have the following
meanings unless expressly stated to the contrary. It is understood
that any term in the singular may include its plural counterpart
and vice versa.
[0010] As used herein, the term "natural oil" may refer to oil
derived from plants or animal sources. The term "natural oil"
includes natural oil derivatives, unless otherwise indicated.
Examples of natural oils include, but are not limited to, vegetable
oils, algae oils, animal fats, tall oils, derivatives of these
oils, combinations of any of these oils, and the like.
Representative non-limiting examples of vegetable oils include
canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil,
olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean
oil, sunflower oil, linseed oil, palm kernel oil, tung oil,
jatropha oil, mustard oil, camelina oil, pennycress oil, hemp oil,
algal oil, and castor oil. Representative non-limiting examples of
animal fats include lard, tallow, poultry fat, yellow grease, and
fish oil. Tall oils are by-products of wood pulp manufacture. In
certain embodiments, the natural oil may be refined, bleached,
and/or deodorized. In some embodiments, the natural oil may be
partially or fully hydrogenated. In some embodiments, the natural
oil is present individually or as mixtures thereof.
[0011] As used herein, the term "natural oil derivatives" may refer
to the compounds or mixture of compounds derived from the natural
oil using any one or combination of methods known in the art. Such
methods include metathesis, saponification, transesterification,
esterification, interesterification, hydrogenation (partial or
full), isomerization, amidation, oxidation, and reduction,
individually or in combinations thereof. Representative
non-limiting examples of natural oil derivatives include gums,
phospholipids, waxes (e.g. non-limiting examples such as
hydrogenated metathesized natural oil waxes and amidated
hydrogenated metathesized natural oil waxes), soapstock, acidulated
soapstock, distillate or distillate sludge, fatty acids and fatty
acid alkyl ester (e.g. non-limiting examples such as 2-ethylhexyl
ester), hydroxy substituted variations thereof of the natural oil.
For example, the natural oil derivative may be a fatty acid methyl
ester ("FAME") derived from the glyceride of the natural oil. In
some embodiments, a feedstock includes canola or soybean oil, as a
non-limiting example, refined, bleached, and deodorized soybean oil
(i.e., RBD soybean oil). Soybean oil typically comprises about 95%
weight or greater (e.g., 99% weight or greater) triglycerides of
fatty acids. Major fatty acids in the polyol esters of soybean oil
include saturated fatty acids, as a non-limiting example, palmitic
acid (hexadecanoic acid) and stearic acid (octadecanoic acid), and
unsaturated fatty acids, as a non-limiting example, oleic acid
(9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid),
and linolenic acid (9,12,15-octadecatrienoic acid). In one
embodiment, one particular natural oil derivative is hydrogenated
castor oil, which is the glyceride of 12-hydroxystearic acid. In
some embodiments, hydrogenation and saponification of castor oil
yields 12-hydroxystearic acid, which is then reacted with lithium
hydroxide or lithium carbonate to give high performance grease. In
some embodiments, natural oil derivatives may arise from bottoms
streams from a metathesis reactor, or from bottoms streams of
downstream separation units from a metathesis reactor. Such bottoms
streams may be primarily esters, where such esters may include
triglycerides, diglycerides, monoglycerides, or oligomers
therefrom, or fatty acid methyl esters ("FAME") and corresponding
fatty acids, salts, and dibasic esters therefrom, or
C.sub.10-C.sub.15 esters, C.sub.15-C.sub.18 esters, or C.sub.18+
esters, or diesters therefrom, wherein such esters may occur as
free esters or in combinations thereof. In some embodiments, such
esters are preferably monoglycerides and/or fatty acid methyl
esters. In some embodiments, such bottoms streams may include
octadecanedioic acid methyl esters (ODDAME).
[0012] As used herein, the term "metathesis" or "metathesizing"
refers to the reacting of a feedstock in the presence of a
metathesis catalyst to form a metathesized product or "metathesized
natural oil" comprising a new olefinic compound. Metathesizing may
refer to cross-metathesis (a.k.a. co-metathesis), self-metathesis,
ring-opening metathesis, ring-opening metathesis polymerizations
("ROMP"), ring-closing metathesis ("RCM"), and acyclic diene
metathesis ("ADMET"). As a non-limiting example, metathesizing may
refer to reacting two triglycerides present in a natural oil
feedstock (self-metathesis) in the presence of a metathesis
catalyst, wherein each triglyceride has an unsaturated
carbon-carbon double bond, thereby forming a "natural oil oligomer"
having a new mixture of olefins and esters that may comprise one or
more of: metathesis monomers, metathesis dimers, metathesis
trimers, metathesis tetramers, metathesis pentamers, and higher
order metathesis oligomers (e.g., metathesis hexamers). Examples of
metathesis compositions, processes, and products are reported in R.
L. Pederson, Commercial Applications of Ruthenium Metathesis
Processes; in "Handbook of Metathesis"; Vol. 2; R. H. Grubbs Ed.;
Wiley-VCH Weinheim, Germany; 2003; pp. 491 to 510 (ISBN No.
3-527-30616-1). Of note, both intra- and inter-molecular
cross-metathesis of unsaturated fatty acid glycerides in soybean
oil results in long chain (e.g. C18 or higher) latent diacids.
[0013] As used herein, the term "metathesized natural oil" refers
to the product formed from the metathesis reaction of a natural oil
in the presence of a metathesis catalyst to form a mixture of
olefins and esters comprising one or more of: metathesis monomers,
metathesis dimers, metathesis trimers, metathesis tetramers,
metathesis pentamers, and higher order metathesis oligomers (e.g.,
metathesis hexamers). In certain embodiments, the metathesized
natural oil has been partially to fully hydrogenated, forming a
"hydrogenated metathesized natural oil." In certain embodiments,
the metathesized natural oil is formed from the metathesis reaction
of a natural oil comprising more than one source of natural oil
(e.g., a mixture of soybean oil and palm oil). In other
embodiments, the metathesized natural oil is formed from the
metathesis reaction of a natural oil comprising a mixture of
natural oils and natural oil derivatives.
[0014] As used herein, the term "dropping point," "drop point," or
"melting point" are terms that may refer to the temperature at
which the grease begins to melt. The drop point may be measured
using ASTM-D127-08, ASTM D2265, or the Mettler Drop Point FP80
system, incorporated by reference herein.
[0015] As used herein, the term "needle penetration" may refer to
the relative hardness of the grease composition. The needle
penetration may be measured using ASTM-D1321-02a, incorporated by
reference herein.
[0016] As used herein, the term "cone penetration" may refer to the
measurement of the solidity of the grease. Penetration is the
depth, in tenths of millimeters, to which a standard cone sinks
into the grease under prescribed conditions. Thus higher
penetration numbers indicate softer grease, since the cone has sunk
deeper into the sample.
Grease Composition
[0017] The elements of a lubricating grease composition are
generally divided among three parts: lubricating base oil,
thickener, and additives. In general, the roles of these three
parts is that the base oil carries out the main role of
lubrication, the thickener structures the lubricating base oil into
a semi-solid, and the additives impart additional functionality to
the lubricating base oil and/or thickener, such as corrosion or
oxidation resistance.
Lubricating Base Oil
[0018] The lubricating base oil employed in the grease composition
can be any of the conventionally used lubricating oils, and is
preferably a mineral oil, a synthetic oil or a blend of mineral and
synthetic oils, or in some cases, natural oils and natural oil
derivatives, all individually or in combinations thereof. Mineral
lubricating oil base stocks used in preparing the greases can be
any conventionally refined base stocks derived from paraffinic,
naphthenic and mixed base crudes. The lubricating base oil may
include polyolefin base stocks, of both polyalphaolefin (PAO) and
polyinternal olefin (PIO) types. Oils of lubricating viscosity
derived from coal or shale are also useful.
[0019] Examples of synthetic oils include hydrocarbon oils such as
polymerized and interpolymerized 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 diphenyl
ethers and alkylated diphenyl sulfides and the derivatives, analogs
and homologs thereof.
[0020] Alkylene oxide polymers and interpolymers and derivatives
thereof where the terminal hydroxyl groups have been modified by
esterification, and etherification, constitute another class of
known synthetic lubricating oils that can be used. These are
exemplified by the oils prepared through polymerization of ethylene
oxide or propylene oxide, the alkyl and aryl ethers of these
polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol
ether having a number average molecular weight of 1000, diphenyl
ether of polyethylene glycol having a molecular weight of 500-1000,
diethyl ether of polypropylene glycol having a molecular weight of
1000-1500) or mono- and polycarboxylic esters thereof, for example,
the acetic acid esters, mixed C.sub.3-8 fatty acid esters, or the
C.sub.13 Oxo acid diester of tetraethylene glycol.
[0021] Another suitable class of synthetic lubricating oils that
can be used comprises the esters of dicarboxylic acids (e.g.,
phthalic acid, succinic acid, alkyl succinic acids, alkenyl
succinic acids, maleic acid, azelaic acid, suberic acid, sebacic
acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid,
alkyl malonic acids, and alkenyl malonic acids) with a variety of
alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol,
2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether,
and propylene glycol). Specific examples of these esters include
dibutyl adipate, di-(2-ethylhexyl) sebacate, di-n-hexyl fumarate,
dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl
phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl
diester of linoleic acid dimer, and the complex ester formed by
reacting one mole of sebacic acid with two moles of tetraethylene
glycol and two moles of 2-ethylhexanoic acid. Esters useful as
synthetic oils also include those made from C.sub.5 to C.sub.12
monocarboxylic acids and polyols such as neopentyl glycol,
trimethylol propane, and pentaerythritol, or polyol ethers such as
dipentaerythritol, and tripentaerythritol.
[0022] Silicon-based oils such as the polyalkyl-, polyaryl-,
polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils
comprise another useful class of synthetic lubricants (e.g.,
tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)
silicate, tetra-(4-methylhexyl) silicate,
tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2-pentoxy)
disiloxane, poly(methyl) siloxanes, and poly-(methylphenyl)
siloxanes). Other synthetic lubricating oils include liquid esters
of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl
phosphate, and the diethyl ester of decane phosphonic acid), and
polymeric tetrahydrofurans.
[0023] Unrefined, refined and re-refined oils, either natural or
synthetic (as well as mixtures of two or more of any of these) of
the type disclosed hereinabove can be used as the lubricating base
oil in the grease composition. Unrefined oils are those obtained
directly from a natural or synthetic source without further
purification treatment. For example, a shale oil obtained directly
from retorting operations, a petroleum oil obtained directly from
primary distillation or ester oil obtained directly from an
esterification process and used without further treatment would be
an unrefined oil. 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. Many such purification
techniques are known to those skilled in the art such as solvent
extraction, secondary distillation, acid or base extraction,
filtration, percolation, re-refined oils are obtained by processes
similar to those used to obtain refined oils applied to refined
oils which have been already used in service. Such re-refined oils
are also known as reclaimed or reprocessed oils and often are
additionally processed by techniques directed to removal of spent
additives and oil breakdown products.
[0024] Oils of lubricating viscosity can also be defined as
specified in the American Petroleum Institute (API) Base Oil
Interchangeability Guidelines. The five base oil groups are as
follows:
TABLE-US-00001 Base Oil Category Sulfur (%) Saturates (%) Viscosity
Index Group I >0.03 and/or <90 80-120 Group II .ltoreq.0.03
and .gtoreq.90 80-120 Group III > Group IV All polyalphaolefins
(PAOs) Group V All others not included in Groups I, II, III, or
IV
[0025] Groups I, II, and III are mineral oil base stocks. In some
embodiments, the oil of lubricating viscosity is a Group I, II,
III, IV, or V oil or mixtures thereof.
[0026] The lubricating base oil is present in a "major amount,"
meaning greater than about 50 weight percent of the grease
composition, preferably in the range 50 to 99 weight percent of the
grease composition, preferably 60 to 95 weight percent of the
grease composition, more preferably 70 to 92 weight percent of the
grease composition and most preferably 75 to 90 weight percent of
the grease composition. In general these lubricating oils have a
viscosity in the range of 15 to 220, preferably 30 to 150 cSt at
40.degree. C., and a viscosity index in the range of 30 to 170,
preferably 30 to 140.
Thickener
[0027] Another component in the subject grease composition is a
thickener which serves to increase the consistency of the
composition. In some embodiments, the thickener generally comprises
one or more of the following: (i) one or more natural oil
derivatives selected from the group consisting of triglycerides,
diglycerides, monoglycerides, or oligomers therefrom, fatty acid
methyl esters and corresponding fatty acids, salts, and dibasic
esters therefrom, and C.sub.10-C.sub.15 esters, C.sub.15-C.sub.18
esters, or C.sub.18+ esters, or diesters therefrom, (ii) one or
more carboxylic acids and/or derivatives thereof, and (iii) one or
more of a metal base compound.
[0028] The thickener may be present in a "minor amount," meaning
less than about 50 weight percent of the grease composition,
preferably in the range of 1 to 30 weight percent of the grease
composition, and more preferably 5 to 20 weight percent of the
grease composition, and most preferably 10 to 20 weight percent of
the grease composition. Generally, the function of the thickener is
to provide a physical matrix which holds the lubricating base oil
in a solid structure until operating conditions initiate
viscoelastic flow.
A. Natural Oil Derivatives
[0029] In some embodiments, the thickener may have a component
comprising a natural oil derivative, wherein such derivative arises
from bottoms streams from a metathesis reactor, or from bottoms
streams of downstream separation units from a metathesis reactor.
Such bottoms streams may be primarily esters, where such esters may
include triglycerides, diglycerides, monoglycerides, or oligomers
therefrom, or fatty acid methyl esters ("FAME") and corresponding
fatty acids, salts, and dibasic esters therefrom, or
C.sub.10-C.sub.15 esters, C.sub.15-C.sub.15 esters, or C.sub.18+
esters, or diesters therefrom, wherein such esters may occur as
free esters or in combinations thereof. In some embodiments, such
esters are preferably monoglycerides and/or fatty acid methyl
esters.
[0030] In some embodiments, the fatty acid methyl esters may
include C.sub.10-C.sub.17 methyl esters, non-limiting examples of
which include methyl 9-decenoate ("9-DAME"), methyl 10-undecenoate
("10-UDAME"), and methyl 9-dodecenoate ("9-DDAME"), respectively,
and their corresponding fatty acids (via hydrolysis) would be
9-decenoic acid ("9DA"), 9-undecenoic acid ("9UDA"), and
9-dodecenoic acid ("9DDA"). In some embodiments, the methyl esters
may be derived from 9-tridecenoic acid, 9-tetradecenoic acid,
9-pentadecenoic acid, 9-hexadecenoic acid, 9-heptadecenoic acid,
and the like. In some embodiments, the fatty acid may be a C18
diacid such as 9-octadecenedioic acid (9-ODDA), which can be
generated by the metathesis of 9DA and/or 9DDA. The 9-ODDA may be
hydrolyzed to its corresponding acid, octadecanedioic acid
(ODDA).
[0031] In some embodiments, the bottoms stream may include
diesters, including a C18 diester such as dimethyl
9-octadecenedioate (9-ODDAME), which can be generated by the
self-metathesis of methyl oleate. The 9-ODDAME could be produced
by: (i) cross-metathesis of 9-DAME with 9-DDAME to form cis/trans
9-ODDAME and 1-butene; (ii) cross-metathesis of 9-DAME with 9-UDAME
to form cis/trans 9-ODDAME and 1-propene; (iii) self-metathesis of
9-DDAME to form cis/trans 9-ODDAME and 3-hexene; and (iv)
self-metathesis of 9-UDAME to form cis/trans 9-ODDAME and 2-butene.
The 9-ODDAME may undergo hydrogenation to yield its saturated
counterpart, octadecanedioic acid methyl esters (ODDAME). In some
embodiments, the ODDAME may be at least 50% w/w purity, or at least
70% w/w purity, or at least 80% w/w purity, or at least 95% w/w
purity.
[0032] Metathesis is a catalytic reaction generally known in the
art that involves the interchange of alkylidene units among
compounds containing one or more double bonds {e.g., olefinic
compounds) via the formation and cleavage of the carbon-carbon
double bonds. Metathesis may occur between two like molecules
(often referred to as self-metathesis) and/or it may occur between
two different molecules (often referred to as cross-metathesis).
Self-metathesis may be represented schematically as shown in
Equation I.
R.sup.1--CH=CH--R.sup.2+R.sup.1--CH=CH--R.sup.2R.sup.1--CH.dbd.CH--R.sup-
.1+R.sup.2--CH=CH--R.sup.2 (I)
[0033] wherein R.sup.1 and R.sup.2 are organic groups.
[0034] Cross-metathesis may be represented schematically as shown
in Equation II.
R.sup.1--CH=CH--R.sup.2+R.sup.3--CH=CH--R.sup.4R.sup.1--CH=CH--R.sup.3+R-
.sup.1--CH=CH--R.sup.4+R.sup.2--CH=CH--R.sup.3+R.sup.2--CH=CH--R.sup.4+R.s-
up.1--CH=CH--R.sup.1+R.sup.2--CH=CH--R.sup.2+--CH=CH--R.sup.3+R.sup.4--CH=-
CH--R.sup.4 (II)
[0035] wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are organic
groups.
[0036] In one embodiment, the hydrogenated metathesized natural oil
based wax may be produced by the steps of: (a) providing a
metathesis composition; (b) providing a metathesis catalyst
comprising a transition metal; (c) metathesizing at least a portion
of the metathesis composition in the presence of the metathesis
catalyst to form a first composition comprising one or more
metathesis products and transition metal; (d) hydrogenating at
least a portion of the first composition in the presence of a
hydrogenation catalyst to form a second composition comprising one
or more hydrogenated metathesis products, transition metal, and
hydrogenation catalyst; and (e) removing at least a portion of the
hydrogenation catalyst from the second composition, wherein the
removal of the hydrogenation catalyst removes at least a portion of
the transition metal of the metathesis catalyst from the second
composition.
[0037] In some embodiments, the metathesis compositions comprise
polyol esters of unsaturated fatty acids. The polyol esters
typically comprise one or more of monoacylglycerides,
diacylglycerides, and triacylglycerides. The polyol esters are
derived, for example, from natural oils. In one embodiment, the
metathesis composition is refined, bleached, and deodorized (i.e.,
RBD) soybean oil. The metathesis compositions may include esters of
the fatty acids provided by the oils and fats and molecules with a
single hydroxy site such as fatty acid methyl esters.
[0038] As used herein, "polyol esters" refers to esters produced
from polyols. Polyols may include more than two hydroxyl groups.
These polyols may comprise from two to about 10 carbon atoms, and
may comprise from two to six hydroxyl groups, but other numbers of
carbon atoms and/or hydroxyl groups are possible as well. The
polyols may contain two to four hydroxyl moieties. Non-limiting
examples of polyols include glycerin, 1,2-propanediol,
1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,
2-ethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl
glycol, 2,2,4-trimethyl-1,3-pentanediol, trimethylolpropane (TMP),
sorbitol and pentaerythritol. Very commonly, the polyol esters
employed herein are esters of glycerin, e.g., triacylglycerides, or
esters of a mixture of glycerin and one or more other polyols.
[0039] The polyol ester component may include a partial fatty acid
ester of one or more polyols and/or a polyol which is fully
esterified with fatty acids ("complete polyol fatty acid ester").
Examples of complete polyol fatty acid esters include
triacylglycerides, propylene glycol diesters and tetra esters of
pentaerythritol. Examples of suitable polyol partial esters include
fatty acid monoglycerides, fatty acid diglycerides and sorbitan
partial esters (e.g., diesters and triesters of sorbitan). In some
embodiments, the polyol may include from 2 to 6 carbon atoms and 2
to 6 hydroxyl groups. Examples of suitable polyols include
glycerol, trimethylolpropane, ethylene glycol, propylene glycol,
pentaerythritol, sorbitan and sorbitol.
[0040] In some embodiments, the natural oil derivatives may arise
from bottoms streams from a metathesis reactor, or from bottoms
streams of downstream separation units from a metathesis reactor.
Such bottoms streams may be primarily esters, where such esters may
include triglycerides, diglycerides, monoglycerides, or oligomers
therefrom, or fatty acid methyl esters ("FAME") and corresponding
fatty acids, salts, and dibasic esters therefrom, or
C.sub.10-C.sub.15 esters, C.sub.15-C.sub.18 esters, or C.sub.18+
esters, or diesters therefrom, wherein such esters may occur as
free esters or in combinations thereof. In some embodiments, such
esters are preferably monoglycerides and/or fatty acid methyl
esters. In some embodiments, such bottoms streams may include
octadecanedioic acid methyl esters (ODDAME).
[0041] The term "metathesis catalyst" includes any catalyst or
catalyst system that catalyzes a metathesis reaction. Any known or
future-developed metathesis catalyst may be used, individually or
in combination with one or more additional catalysts. Non-limiting
exemplary metathesis catalysts and process conditions are described
in PCT/US2008/009635, pp. 18-47, incorporated by reference herein.
A number of the metathesis catalysts as shown are manufactured by
Materia, Inc. (Pasadena, Calif.). Additional exemplary metathesis
catalysts include, without limitation, metal carbene complexes
selected from the group consisting of molybdenum, osmium, chromium,
rhenium, and tungsten. The term "complex" in this context refers to
a metal atom, such as a transition metal atom, with at least one
ligand or complexing agent coordinated or bound thereto. Such a
ligand typically is a Lewis base in metal carbene complexes useful
for alkyne or alkene-metathesis. Typical examples of such ligands
include phosphines, halides and stabilized carbenes. Some
metathesis catalysts may employ plural metals or metal co-catalysts
(e.g., a catalyst comprising a tungsten halide, a tetraalkyl tin
compound, and an organoaluminum compound). An immobilized catalyst
can be used for the metathesis process. An immobilized catalyst is
a system comprising a catalyst and a support, the catalyst
associated with the support. Exemplary associations between the
catalyst and the support may occur by way of chemical bonds or weak
interactions (e.g. hydrogen bonds, donor acceptor interactions)
between the catalyst, or any portions thereof, and the support or
any portions thereof. Support is intended to include any material
suitable to support the catalyst. Typically, immobilized catalysts
are solid phase catalysts that act on liquid or gas phase reactants
and products. Exemplary supports are polymers, silica or alumina.
Such an immobilized catalyst may be used in a flow process. An
immobilized catalyst can simplify purification of products and
recovery of the catalyst so that recycling the catalyst may be more
convenient.
[0042] The metathesis process can be conducted under any conditions
adequate to produce the desired metathesis products. For example,
stoichiometry, atmosphere, solvent, temperature and pressure can be
selected to produce a desired product and to minimize undesirable
byproducts. The metathesis process may be conducted under an inert
atmosphere. Similarly, if the olefin reagent is supplied as a gas,
an inert gaseous diluent can be used. The inert atmosphere or inert
gaseous diluent typically is an inert gas, meaning that the gas
does not interact with the metathesis catalyst to substantially
impede catalysis. For example, particular inert gases are selected
from the group consisting of helium, neon, argon, nitrogen and
combinations thereof.
[0043] Similarly, if a solvent is used, the solvent chosen may be
selected to be substantially inert with respect to the metathesis
catalyst. For example, substantially inert solvents include,
without limitation, aromatic hydrocarbons, such as benzene,
toluene, xylenes, etc.; halogenated aromatic hydrocarbons, such as
chlorobenzene and dichlorobenzene; aliphatic solvents, including
pentane, hexane, heptane, cyclohexane, etc.; and chlorinated
alkanes, such as dichloromethane, chloroform, dichloroethane,
etc.
[0044] In certain embodiments, a ligand may be added to the
metathesis reaction mixture. In many embodiments using a ligand,
the ligand is selected to be a molecule that stabilizes the
catalyst, and may thus provide an increased turnover number for the
catalyst. In some cases the ligand can alter reaction selectivity
and product distribution. Examples of ligands that can be used
include Lewis base ligands, such as, without limitation,
trialkylphosphines, for example tricyclohexylphosphine and tributyl
phosphine; triarylphosphines, such as triphenylphosphine;
diarylalkylphosphines, such as, diphenylcyclohexylphosphine;
pyridines, such as 2,6-dimethylpyridine, 2,4,6-trimethylpyridine;
as well as other Lewis basic ligands, such as phosphine oxides and
phosphinites. Additives may also be present during metathesis that
increase catalyst lifetime.
[0045] Any useful amount of the selected metathesis catalyst can be
used in the process. For example, the molar ratio of the
unsaturated polyol ester to catalyst may range from about 5:1 to
about 10,000,000:1 or from about 50:1 to 500,000:1.
[0046] The metathesis reaction temperature may be a
rate-controlling variable where the temperature is selected to
provide a desired product at an acceptable rate. The metathesis
temperature may be greater than -40.degree. C., may be greater than
about -20.degree. C., and is typically greater than about 0.degree.
C. or greater than about 20.degree. C. Typically, the metathesis
reaction temperature is less than about 150.degree. C., typically
less than about 120.degree. C. An exemplary temperature range for
the metathesis reaction ranges from about 20.degree. C. to about
120.degree. C.
[0047] The metathesis reaction can be run under any desired
pressure. The total pressure may be selected to be greater than
about 10 kPa, in some embodiments greater than about 30 kPa, or
greater than about 100 kPa. Typically, the reaction pressure is no
more than about 7000 kPa, in some embodiments no more than about
3000 kPa. An exemplary pressure range for the metathesis reaction
is from about 100 kPa to about 3000 kPa.
[0048] In some embodiments, the metathesis reaction is catalyzed by
a system containing both a transition and a non-transition metal
component. The most active and largest number of catalyst systems
are derived from Group VI A transition metals, for example,
tungsten and molybdenum.
C. Carboxylic Acids and Derivatives
[0049] The carboxylic acid has about 2 to about 36, preferably
about 6 to about 24, more preferably about 9 to about 20 carbon
atoms, and mono-, di-, tri-, and/or poly-acid variants,
hydroxy-substituted variants, aliphatic, cyclic, alicyclic,
aromatic, branched, aliphatic- and alicyclic-substituted aromatic,
aromatic-substituted aliphatic and alicyclic groups, saturated and
unsaturated variants, and heteroatom substituted variants thereof.
In some embodiments, the mono- or di-esters or poly-esters of these
acids thereof may be used. Non-limiting examples of such carboxylic
acids include lauric acid, azelaic acid, myristic acid, palmitic
acid, arachic acid, behenic acid, lignoceric acid, oleic acid,
linoleic acid, linolenic acid, capric acid, lignoceric acid,
decenoic acid, undecenoic acid, dodecenoic acid, ricinoleic acid,
myristoleic acid, palmitoleic acid, gadoleic acid, elaidic acid,
cis-eicosenoic acid, erucic acid, nervonic acid, 2,4-hexadienoic
acid, linoleic acid, 12-hydroxy tetradecanoic acid, 10-hydroxy
tetradeconoic acid, 12-hydroxy hexadecanoic acid, 8-hydroxy
hexadecanoic acid, 12-hydroxy icosanic acid, 16-hydroxy icosanic
acid 11,14-eicosadienoic acid, linolenic acid,
cis-8,11,14-eicosatrienoic acid, arachidonic acid,
cis-5,8,11,14,17-eicosapentenoic acid,
cis-4,7,10,13,16,19-docosahexenoic acid, all-trans-retinoic acid,
lauroleic acid, eleostearic acid, licanic acid, citronelic acid,
nervonic acid, abietic acid, abscisic acid, octanedioic acid,
nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid),
undecanedioic acid, dodecanedioic acid, tridecanedioic acid,
tetradecanedioic acid, pentadecanoic acid and mixtures thereof. In
some embodiments, azelaic acid is a preferred carboxylic acid. In
some embodiments, naphthenic acids and mixtures thereof, such as
are obtainable from various petroleum sources, may be used. Other
non-limiting examples, such as hydroxystearic, hydroxy-ricinoleic,
hydroxybehenic and hydroxypalmitic acids may be used, preferably
hydroxystearic acid or esters of these acids such as 9-hydroxy-,
10-hydroxy- or 12-hydroxy-stearic acid, and most preferably
12-hydroxystearic acid.
D. Metal Base Compound
[0050] In the metal base compound, the metals themselves can be
selected from alkali metals or alkaline earth metals, such as,
without limitation, beryllium, magnesium, calcium, lithium, sodium,
potassium, strontium and barium; transition metals, without
limitation, such as titanium, vanadium, chromium, manganese, iron,
cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium,
silver, cadmium, tungsten and mercury; and other metals such as
aluminum, gallium, tin, iron, lead, and lanthanoid metals, all
individually or in combinations thereof. Said metals are more
preferably selected from lithium, sodium, magnesium, aluminum,
calcium, zinc and barium. Examples of carboxylic acid metal salts
which may be conveniently used in the present invention are metal
salts of any combination of a mono- or poly-carboxylic; branched
alicyclic, cyclic, cycloalkyl, or linear, saturated or unsaturated,
mono- or poly-hydroxy substituted or unsubstituted carboxylic acid,
acid chloride or the ester of said carboxylic acid with an alcohol
such as an alcohol of about 1 to about 5 carbon atoms. As for the
base compound, the alkoxides, oxides, hydroxides, carbonates,
chlorides, and mixtures thereof of any of the aforementioned metals
are found to be especially useful. In some embodiments, hydroxides
of these aforementioned metals are preferred, and calcium
hydroxide, strontium hydroxide, magnesium hydroxide, sodium
hydroxide, and lithium hydroxide are more preferred. The metal
hydroxide is a mono- or di- or tri-valent metal or a mixture
thereof. In one embodiment the metal hydroxide is lithium hydroxide
monohydrate and can be solid or aqueous, although aqueous is
preferred.
[0051] In some embodiments, the metal base, usually a metal
hydroxide, such as lithium hydroxide or in its more commonly
available form of lithium hydroxide monohydrate, is reacted with a
carboxylic acid, usually 12-hydroxystearic acid, or with a
carboxylic acid derivative, usually 12-hydroxystearate or
hydrogenated castor oil, to form a metallic (lithium) soap. This
reaction is most often carried out in the lubricating base oil with
water also being present. The water is added to act as a reaction
solvent if the acid is used. If the carboxylic acid derivative is
used, the water acts both as reaction solvent and reactant, the
latter effect being necessary for the hydrolytic cleavage of the
ester linkages in the 12-hydroxystearate or the hydrogenated castor
oil. In some embodiments, the lithium hydroxide is reacted with two
or more carboxylic acids, such as 12-hydroxystearic acid and
azelaic acid, to form a metallic (lithium) soap.
Optional Grease Additives
[0052] Various optional additives may be incorporated into the
grease compositions of this invention, for the particular service
intended. Such optional additives that may commonly be used
include: metal deactivators, antioxidants, antiwear agents, rust
inhibitors, viscosity modifiers, extreme pressure agents, corrosion
inhibitors, and other additives recognized in the art to perform a
particular function or functions. Such additives may be present in
the range of 1 to 15 weight percent of the grease composition, and
more preferably 3 to 10 weight percent of the grease
composition.
[0053] Metal deactivators may include derivatives of
benzotriazoles, benzimidazole, 2-alkyldithiobenz-imidazoles,
2-alkyldithiobenzothiazoles,
2-(N,N-dialkyldithiocarbamoyl)-benzothiazoles,
2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles,
2,5-bis(N,N-dialkyldithio-carbamoyl)-1,3,4-thiadiazoles,
2-alkyldithio-5-mercapto thiadiazoles or mixtures thereof.
Antioxidants may include a variety of chemical types including
phenate sulfides, phosphosulfurized terpenes, sulfurized esters,
aromatic amines, and hindered phenols. Antiwear agents may include
a metal thiophosphate, especially a zinc dialkyldithiophosphate; a
phosphoric acid ester or salt thereof; a phosphite; and a
phosphorus-containing carboxylic ester, ether, or amide. Rust
inhibitors may include metal sulfonates such as calcium sulfonate
or magnesium sulfonate, amine salts of carboxylic acids such as
octylamine octanoate, condensation products of dodecenyl succinic
acid or anhydride and a fatty acid such as oleic acid with a
polyamine, e.g. a polyalkylene polyamine such as
triethylenetetramine, and half esters of alkenyl succinic acids in
which the alkenyl radical contains 8 to 24 carbon atoms with
alcohols such as polyglycols.
[0054] Viscosity modifiers may include polymeric materials
including styrene-butadiene rubbers, ethylene-propylene copolymers,
polyisobutenes, hydrogenated styrene-isoprene polymers,
hydrogenated radical isoprene polymers, polymethacrylate acid
esters, polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl
conjugated diene copolymers, polyolefins, polyalkylmethacrylates,
esters of maleic anhydride-styrene copolymers and mixtures thereof.
Extreme Pressure (EP) Agents may include agents that are soluble in
the oil include a sulfur or chlorosulfur EP agent, a chlorinated
hydrocarbon EP agent, or a phosphorus EP agent, or mixtures
thereof. Examples of such EP agents are chlorinated wax, organic
sulfides and polysulfides, such as benzyldisulfide,
bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized
sperm oil, sulfurized methyl ester of oleic acid, sulfurized
alkylphenol, sulfurized dipentene, sulfurized terpene, and
sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons,
such as the reaction product of phosphorus sulfide with turpentine
or methyl oleate, phosphorus esters such as the dihydrocarbon and
trihydrocarbon phosphites, i.e., dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphite, pentylphenyl phosphite;
dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite
and polypropylene substituted phenol phosphite, metal
thiocarbamates, such as zinc dioctyldithiocarbamate and barium
heptylphenol diacid, such as zinc dicyclohexyl phosphorodithioate
and the zinc salts of a phosphorodithioic acid combination may be
used. Corrosion inhibitors may include: mercaptobenzothiazole,
barium dinonylnaphthalene sulfonate, glycerol monooleate, sodium
nitrite, and imidazolines of tetraethylenepentamine, among
others.
Uses/Applications for the Grease Compositions
[0055] The grease compositions described herein are useful for
lubricating, sealing and protecting mechanical components such as
gears, axles, bearings, shafts, hinges and the like. Such
mechanical components are found in automobiles, trucks, bicycles,
steel mills, mining equipment, railway equipment including rolling
stock, aircraft, boats, construction equipment and numerous other
types of industrial and consumer machinery. The grease compositions
described herein may be used in various applications, including,
but not limited to, lubricating surface mining machinery (pins and
bushings, open gears in large electric shovels), constant velocity
joints (CV joints), ball bearings, journal bearings, high speed low
load machinery lubrication, low speed-high load machinery
lubrication, conveyor belt bearings lubrication, gears lubrication,
open gears lubrication, curve and flange rail lubrication, traction
motor gear lubrication, high temperature highly corrosive media
lubrication, wheel bearing lubrication of motor vehicles and
trucks, journal bearing lubrication of freight and high speed
trains, paper machinery lubrication, lawn and garden machinery
lubrication, pipe dope anti seize lubrication, automotive tie rod
ends, roof, seating and steering mechanism lubrication, jacks and
landing gear equipment lubrication, continuous caster and hot mills
bearing lubrication, lubrication of garage door mechanisms and oven
chain lubrication.
Grease Preparation
[0056] Greases can be manufactured in several consistencies as
defined by National Lubricating Grease Institute (N.L.G.I.) as
described in ASTM Method D-217 for Cone Penetration of Lubricating
Greases. Adjusting the lubricating base oil, thickener component,
and additive content will permit the manufacture of various grades
of greases.
[0057] As is well known in the art, greases are sold in various
grades depending upon the softness of the grease. The softer the
grease, the more fluid the grease. For example, very soft greases
sold under the designation NLGI 0 have a cone penetration number
from about 355 to 385, those having a cone penetration range of 310
to 340 are designated NLGI 1 and the most widely sold greases have
a cone penetration range of 265 to 295 and are designated NLGI 2.
Table 1 below shows the various NLGI grades for greases.
TABLE-US-00002 TABLE 1 NLGI Grades for greases NLGI Grade Worked
Cone Penetration (ASTM D 217) @ 77.degree. F. 000 445-475 00
400-430 0 355-385 1 310-340 2 265-295 3 220-250 4 175-205 5 130-160
6 85-115
[0058] Since there are a variety of different greases with varying
formulations and properties and since such properties can be
altered, sometimes significantly, by changes in process conditions
and apparatus, a great deal of flexibility is needed in the process
equipment for manufacturing greases. Because of the desired
flexibility and because many greases are specialty type greases
made in small amounts, most grease manufacturing has been of the
batch type.
[0059] Batch processing generally comprises the use of one or more
large kettles that may be equipped with, for example, paddle
agitation, stirring, heating, external recirculation systems
capable of pumping the contents from the bottom of the kettle to
the top, and combinations thereof. As used herein, the terms kettle
and vessel may be used interchangeably. The kettles that may be
utilized herein may be of a size generally in a range of from 500
liters to 20,000 liters, preferably in a range of from 2,000 liters
to 15,000 liters, and more preferably in a range of from 3,000
liters to 10,000 liters. Examples of suitable kettles include open
kettles and pressurized kettles. An example grease kettle is
equipped with stirring, heating, and an external recirculation
system, capable of pumping the contents from the bottom of the
kettle to the top. The kettles may have heating means, cooling
means, paddle type stirrers, gear-type circulation pumps,
circulation line, back pressure shear valve in said circulation
line, colloid mill, product filter, and other associated piping,
valves, instrumentation, etc. required for the commercial
manufacture of grease. The grease may also be passed through a
grease mill again to obtain a further improvement in yield and
appearance, where such mills may include a Morehouse mill, a
Charlotte mill, and a Gaulin homogenizer.
[0060] Another type of batch processor sometimes used is a
Stratco.RTM. mixer which has a different internal mixing
configuration. In this equipment, the material is circulated by an
impeller located at the bottom of the vessel, where it is possible
to obtain rapid circulation and thorough mixing.
[0061] In some embodiments, the grease compositions described
herein may also encompass complex greases. Complex greases are
formed by reaction of a metal-containing reagent with two or more
acids. One of the acids is (i) a hydroxy carboxylic acid or
reactive derivative thereof, such as a C9-C24 hydroxystearic acid,
preferably 9-hydroxy, 10-hydroxy, or 12-hydroxystearic acid, or the
mono- or di-esters or poly-esters thereof, and (ii) one or more
natural oil derivatives selected from the group consisting of
triglycerides, diglycerides, monoglycerides, or oligomers
therefrom, fatty acid methyl esters and corresponding fatty acids,
salts, and dibasic esters therefrom, and C.sub.10-C.sub.15 esters,
C.sub.15-C.sub.18 esters, or C.sub.18+ esters, or diesters
therefrom. As a control experiment, a dicarboxylic acid, such as
one or more straight or branched chain C.sub.2 -C.sub.12
dicarboxylic acids, examples of which may include oxalic, malonic,
succinic, glutaric, adipic, suberic, pimelic, azelaic,
dodecanedioic and sebacic acids, preferably azelaic acid, or the
mono- or di-esters or poly-esters thereof, was used. Optionally, an
additional hydroxy carboxylic acid may be utilized, where such acid
has from 3 to 14 carbon atoms and can be either an aliphatic acid
such as lactic acid, 6-hydroxy decanoic acid, 3-hydroxybutanoic
acid, 4-hydroxybutanoic acid, etc. or an aromatic acid such as
parahydroxybenzoic acid, salicylic acid, 2-hydroxy-4-hexylbenzoic
acid, meta hydroxybenzoic acid, 2,5-dihydroxybenzoic acid;
2,6-dihydroxybenzoic acid; 4-hydroxy-3-methoxybenzoic acid, etc. or
a hydroxyaromatic aliphatic acid such as orthohydroxyphenyl,
metahydroxyphenyl, or parahydroxyphenyl acetic acid. A
cycloaliphatic hydroxy acid such as hydroxy cyclopentyl carboxylic
acid or hydroxynaphthenic acid could also be used. There is no
absolute industry standard defining the dropping point of a complex
grease. However, it is often accepted that minimum dropping points
of about 260.degree. C. are displayed by complex greases.
Generally, a complex grease is one which displays a dropping point
significantly higher, typically at least about 20.degree. C.
higher, than the corresponding simple metal soap grease.
[0062] To prepare the complex greases described herein, the various
thickener components (one or more of: carboxylic acids, and/or
natural oil derivative, and metal base) are added to a lubricating
base oil, and this mixture is charged to a kettle, mixer, or
equivalent vessel. Preferably, these thickener components are
12-hydroxystearic acid, octadecanedioic acid methyl esters
(ODDAME), lithium hydroxide monohydrate, and the lubricating base
oil is PAO 6. In a first stage, a portion of PAO 6 and all
12-hydroxystearic acid were added to a vessel and heated to
80.degree. C. (176.degree. F.) until a homogeneous melt formed.
Lithium hydroxide monohydrate (1 equiv) was mixed with deionized
water and gently heated. This metal base was then added to the oil
solution under constant mechanical stirring and heated to about
100.degree. C. (212.degree. F.) for about 1 hour to complete
neutralization. In a second stage, ODDAME was then added to the
vessel followed by additional lithium hydroxide monohydrate (2.05
equiv) necessary to saponify this dibasic ester. The reaction was
gradually heated to 200.degree. C. (392.degree. F.) to complete
lithium soap thickener formation and facilitate dehydration and
evaporation of methanol.
[0063] Thereafter, the mixture is then transferred to a finishing
kettle or equivalent vessel for cooling. This cooling may be
assisted by incorporating additional lubricating base oil into the
mixture. Mixing can be continued until the grease reaches ambient
temperatures. After about 90 minutes into this cooling phase, the
heat is removed, and at about 1 hour thereafter, optional grease
additives may be added to the finishing kettle. The grease may be
finished by homogenization at 6000 psi.
[0064] In some embodiments, a thickener component may arise from
bottoms streams from a metathesis reactor, or from bottoms streams
of downstream separation units from a metathesis reactor, and may
include bottoms streams such as octadecanedioic acid methyl esters
(ODDAME). Upon saponification during processing with a metal
hydroxides such as lithium hydroxide, ODDAME will yield the
dilithium salt of octadecanedioic acid (ODDA). Venting of methanol
byproduct during soap formation is acceptable in grease processes
as the methyl ester of 12-HSA is used in continuous grease
production facilities.
[0065] FIG. 2 below illustrates a representative reaction between
ODDAME and 12-HSA.
##STR00001##
[0066] Of note, ODDA has a melting point between azelaic and
sebacic acids and is about 1.5 times more oil soluble than azelaic
acid. The expected benefits of an ODDAME complexing agent over
azelaic acid include increased solvency in nonpolar synthetic base
oil (i.e. PAO), improved water resistance of the final grease,
differentiated additive loading if fiber packing is more porous,
and high temperature performance. The improved oil solubility of
ODDAME may enable complex grease processing at lower temperatures.
Beyond lithium complex greases, ODDAME may also favorably impact
aluminum and calcium complex grease products. Table 1A below
compares the melting points and oil solubilities (Log P values) of
common grease complexing agents with ODDA.
TABLE-US-00003 TABLE 1A Physical properties of common grease
complexing agents and ODDA. Diacid Structure Mp (.degree. C.) Log P
Adipic (C6) ##STR00002## 153 1.68 Azelaic (C9) ##STR00003## 108
2.01 Sebacic (C10) ##STR00004## 134 2.12 ERS ODDA (C18)
##STR00005## 125 3.00
[0067] While the invention as described may have modifications and
alternative forms, various embodiments thereof have been described
in detail. It should be understood, however, that the description
herein of these various embodiments is not intended to limit the
invention, but on the contrary, the intention is to cover all
modifications, equivalents, and alternatives falling within the
spirit and scope of the invention as defined by the claims.
Further, while the invention will also be described with reference
to the following non-limiting examples, it will be understood, of
course, that the invention is not limited thereto since
modifications may be made by those skilled in the art, particularly
in light of the foregoing teachings.
EXAMPLES
Example 1
[0068] A two stage reaction process was used to prepare a lithium
12-hydroxystearate complex grease using Sample A, which was a 71%
w/w purity ODDAME. The first stage of the reaction consisted of
reacting a stoichiometric amount of lithium hydroxide monohydrate
with 12-hydroxystearic acid. In the second stage, the required
amount of metal base was reacted with Sample A. The grease
formulation was 20% thickener and 80% PAO-6. The thickener
composition was 73% lithium hydroxystearate and 27% dilithium salt
of Sample A, as further described below:
[0069] Batch size: 2500 grams
[0070] 2500 g.times.0.20=500 g of thickener
TABLE-US-00004 Thickener Composition Ingredient Moles 500 g .times.
0.73 = 365 g Li 12-OH Stearate 365/305.9 = 1.19 500 g .times. 0.27
= 135 g Sample A FW (formula weight)/MW Ingredient Moles (molecular
weight) Grams LiOH--H2O 1.19 41.9 49.9 12-HSA 1.19 300 357.9 Li
12-OH Stearate 305.9
[0071] Preparation of dilithium salt of Sample A
2LiOH--H2O+HOCO--(CH.sub.2).times.--COOH=Li-(Sample A)-Li +2H2O
[0072] MW of Sample A based on saponification value is 223
g/mole
[0073] 135 g/223 g mole-1=0.6 mole
TABLE-US-00005 Ingredient Moles FW/MW g LiOH--H2O 0.6 .times. 2 =
1.2 41.9 50 Sample A 0.6 223 134
[0074] A portion of the PAO-6 was added to the grease making vessel
along with all of the 12-HSA. The vessel contents where heated to
approximately 175.degree. F. or enough to completely melt the fatty
acid. The LiOH--H2O was mixed with approximately 100 ml of DI
(deionized) water and gently heated. The metal base was then added
to the oil and fatty acid solution with constant mechanical
stirring.
[0075] After approximately 1 hour, Sample A was added to the vessel
followed by the required amount of metal base. The temperature was
gradually raised to approximately 390.degree. F., to complete the
formation of the thickener and to dehydrate the grease. The grease
batch was allowed to cool and was subsequently homogenized at 6000
psi.
[0076] The chemical and physical properties of the grease were
determined as reported in Table 2 below.
TABLE-US-00006 TABLE 2 Property Method Result Color Visual
Off-White Appearance Visual Smooth Po (unworked penetration) ASTM
D217 284 P60 (worked penetration) ASTM D217 308, 306 P10k (worked
penetration) ASTM D217 303 DP (dropping point) ASTM D2265
498.degree. F. Oil Separation ASTM D6084 0.31% 24 h at 212.degree.
F. PDSC, 302.degree. F., pure dry O2 ASTM D5483 Minor exotherm at
37.19 at 500 psi minutes
Example 2
[0077] A two stage reaction process was used to prepare a lithium
12-hydroxystearate complex grease using Sample B, which was 82% w/w
purity ODDAME. The first stage of the reaction consisted of
reacting a stoichiometric amount of lithium hydroxide monohydrate
with 12-hydroxystearic acid. In the second stage, the required
amount of metal base was reacted with Sample B. The grease
formulation was 20% thickener and 80% PAO-6.
[0078] A portion of the PAO-6 was added to the grease making vessel
along with all of the 12-HSA. The vessel contents where heated to
approximately 175.degree. F. or enough to completely melt the fatty
acid. The LiOH--H2O was mixed with approximately 100 ml of DI
(deionized) water and gently heated. The base was then added to the
oil and fatty acid solution with constant mechanical stirring.
After approximately 1 hour, Sample B was added to the vessel
followed by the required amount of base. The temperature was
gradually raised to approximately 390.degree. F., to complete the
formation of the thickener and to dehydrate the grease. The grease
batch was allowed to cool and was subsequently homogenized at 6000
psi.
[0079] The chemical and physical properties of the grease were
determined as reported in Table 3 below.
TABLE-US-00007 TABLE 3 Property Method Result Color Visual
Off-White Appearance Visual Smooth Po (unworked penetration) ASTM
D217 244 P60 (worked penetration) ASTM D217 271 P10K (worked
penetration) ASTM D217 315 Dropping Point ASTM D2265
>500.degree. F. Oil Separation, 24 h at 212.degree. F. ASTM
D6084 0.00% PDSC at 302.degree. F. ASTM D5483 Minor exotherm at
60.18 minutes Water Washout @ 175.degree. F. ASTM D1264 9.63%
Example 3
[0080] A two stage reaction process was used to prepare a lithium
12-hydroxystearate complex grease using Sample C, which was a 98%
w/w purity ODDAME. The first stage of the reaction consisted of
reacting a stoichiometric amount of lithium hydroxide monohydrate
with 12-hydroxystearic acid. In the second stage, the required
amount of metal base was reacted with Sample C. The grease
formulation was 20% thickener and 80% PAO-6.
[0081] A portion of the PAO-6 was added to the grease making vessel
along with all of the 12-HSA. The vessel contents where heated to
approximately 175.degree. F. or enough to completely melt the fatty
acid. The LiOH--H2O was mixed with approximately 100 ml of DI
(deionized) water and gently heated. The base was then added to the
oil and fatty acid solution with constant mechanical stirring.
[0082] After approximately 1 hour, Sample C was added to the vessel
followed by the required amount of base. The temperature was
gradually raised to approximately 392.degree. F., to complete the
formation of the thickener and to dehydrate the grease. The grease
batch was allowed to cool and was subsequently homogenized at 6000
psi.
[0083] The chemical and physical properties of the grease were
determined as reported in Table 4 below.
TABLE-US-00008 TABLE 4 Property Method Result Color Visual White
Appearance Visual Smooth Po (unworked ASTM D217 282 penetration)
P60 (worked ASTM D217 291 penetration) P10K (worked ASTM D217 347
penetration) Dropping Point ASTM D2265 489.degree. F. Oil
Separation, 24 h at ASTM D6084 0.00% 212.degree. F. PDSC at
302.degree. F. ASTM D5483 Minor exotherm at 108.31 minutes
Example 4
Control
[0084] A two stage reaction process was used to prepare a lithium
12-hydroxystearate complex grease using azelaic acid, as a control.
The first stage of the reaction consisted of reacting a
stoichiometric amount of lithium hydroxide monohydrate with
12-hydroxystearic acid. In the second stage, the required amount of
metal base was reacted with azelaic acid. Ten percent additional
PAO-6 was added to the grease formulated with azelaic acid. The
grease formulation was 18% thickener and 82% PAO-6.
[0085] A portion of the PAO-6 was added to the grease making vessel
along with all of the 12-HSA. The vessel contents where heated to
approximately 175.degree. F. or enough to completely melt the fatty
acid. The LiOH--H2O was mixed with approximately 100 ml of DI
(deionized) water and gently heated. The base was then added to the
oil and fatty acid solution with constant mechanical stirring.
[0086] After approximately 1 hour, azelaic acid was added to the
vessel followed by the required amount of base. The temperature was
gradually raised to approximately 392.degree. F., to complete the
formation of the thickener and to dehydrate the grease. The grease
batch was allowed to cool and was subsequently homogenized at 6000
psi.
[0087] The chemical and physical properties of the grease were
determined as reported in Table 5 below.
TABLE-US-00009 TABLE 5 Property Method Result Color Visual Grayish
Appearance Visual Smooth but less smooth than other samples Po
(unworked penetration) ASTM D217 245 P60 (worked penetration) ASTM
D217 259 P10K (worked penetration) ASTM D217 324 Dropping Point
ASTM D2265 >500.degree. F. Oil Separation, 24 h at 212.degree.
F. ASTM D6084 0.00% PDSC at 302.degree. F. ASTM D5483 Minor
exotherm at 39.23 minutes Water Washout @ 175.degree. F. ASTM D1264
18.01%
[0088] Complex grease samples with similar consistencies as in
Sample B and azelaic acid (Examples 2 and 4, respectively) were
tested for water resistance properties via ASTM D1264. The method
measures the amount of grease removed from a bearing under exposure
to a constant water stream. Significantly, grease prepared from
Sample B had a nearly two-fold improved response at 9.63% compared
to the azelaic standard at 18.01%, consistent with the reduced
water solubility of the long-chain dibasic ester (ODDAME)
complexing agent.
* * * * *