Note: Descriptions are shown in the official language in which they were submitted.
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NATURAL OIL BASED GREASE COMPOSITIONS AND PROCESSES FOR
MAKING SUCH COMPOSITIONS
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] A claim of priority for this application under 35 U.S.C. 119(e)
is hereby
made to the following U.S. provisional patent application: U.S. Serial No.
61/774,760
filed March 8, 2013; and this application is incorporated herein by reference
in its
entirety.
BACKGROUND
[0002] 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 C higher than their corresponding simple soap
greases).
[0003] We have found that the incorporation of hydrogenated metathesized
natural oils and their derivatives as a thickener component in simple and
complex
greases provides for greases with reduced processing times and improved
yields.
SUMMARY
[0004] 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, (ii) one or
more
hydrogenated metathesized natural oils and/or natural oil derivatives, (iii)
one or
more amidated metathesized natural oils and/or natural oil derivatives, (iv)
one or
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more carboxylic acids and/or derivatives thereof, and (v) one or more of a
metal
base compound. In
some embodiments, the one or more hydrogenated
metathesized natural oils and/or natural oil derivatives comprises a
hydrogenated
metathesized soybean oil based wax. The grease composition may further
comprise
from 1 to 15 weight percent of one or more optional additives.
[0005] In
another aspect, a process for preparing a simple grease composition
is disclosed. The process comprises adding from 1 to 30 weight percent of a
thickener component comprising one or more of (i) one or more natural oil
derivatives, (ii) one or more hydrogenated metathesized natural oils and/or
natural
oil derivatives, (iii) one or more amidated metathesized natural oils and/or
natural oil
derivatives, (iv) one or more carboxylic acids and/or derivatives thereof, to
from 50 to
99 weight percent of a lubricating base oil, and charging this mixture to a
kettle,
mixer or equivalent vessel. This mixture is then heated to a temperature
between
about 140 F to 200 F for approximately 30-60 minutes, in order to dissolve
the one
or more carboxylic acids and/or derivatives thereof into the lubricating base
oil. One
or more of a metal base compound is then charged to this mixture in an amount
slightly in excess of the stoichiometric amount required to neutralize the one
or more
carboxylic acids and/or derivatives thereof. The mixture is then maintained at
a
temperature between about 190 F to about 270 F for approximately 30-90
minutes
to complete the neutralization and to effect a substantial dehydration of the
mixture.
This mixture is then heated to about 350 F to about 430 F for up to
approximately
60 minutes. Thereafter, the mixture is cooled with the assistance of
incorporating an
additional amount of the lubricating base oil and the removal of heat, to
yield the
grease composition. Optionally, from 1 to 15 weight percent of one or more
additives may be added to the grease composition.
[0006] In
another aspect, a process for preparing a complex grease
composition is disclosed. The process comprises adding from 1 to 30 weight
percent of a thickener component comprising one or more of (i) one or more
natural
oil derivatives, (ii) one or more hydrogenated metathesized natural oils
and/or
natural oil derivatives, (iii) one or more amidated metathesized natural oils
and/or
natural oil derivatives, (iv) two or more carboxylic acids and/or derivatives
thereof, to
from 50 to 99 weight percent of a lubricating base oil, and charging this
mixture to a
kettle, mixer or equivalent vessel. This mixture is then heated to a
temperature
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between about 140 F to 200 F for approximately 30-60 minutes, in order to
dissolve the two or more carboxylic acids and/or derivatives thereof into the
lubricating base oil. One or more of a metal base compound is then charged to
this
mixture in an amount slightly in excess of the stoichiometric amount required
to
neutralize the two or more carboxylic acids and/or derivatives thereof. The
mixture is
then maintained at a temperature between about 190 F to about 270 F for
approximately 30-90 minutes to complete the neutralization and to effect a
substantial dehydration of the mixture. This mixture is then heated to about
350 F to
about 430 F for up to approximately 60 minutes. Thereafter, the mixture is
cooled
with the assistance of incorporating an additional amount of the lubricating
base oil
and the removal of heat, to yield the grease composition. Optionally, from 1
to 15
weight percent of one or more additives may be added to the grease
composition.
DETAILED DESCRIPTION
[0007] The present application relates to natural oil based grease
compositions and processes for making such compositions.
[0008] 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.
[0009] 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.
[0010] 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.
[0011] 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,
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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.
[0012] 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.
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[0013] 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.
[0014] 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.
[0015] 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
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melt. The drop point may be measured using ASTM-D127-08 or the Mettler Drop
Point FP80 system, incorporated by reference herein.
[0016] 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.
[0017] 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
[0018] 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
[0019] 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.
[0020]
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,
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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.
[0021] 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 Cm fatty acid esters, or the C13 Oxo acid diester of
tetraethylene
glycol.
[0022] 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 C5 to C12 monocarboxylic acids and polyols such as neopentyl glycol,
trimethylol propane, and pentaerythritol, or polyol ethers such as
dipentaerythritol,
and tripentaerythritol.
[0023] 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-
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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.
[0024]
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.
[0025]
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:
Base Oil
Category Sulfur (%) Saturates (%) Viscosity Index
Group I >0.03 and/or <90 80-120
Group ll 0.03 and 90 80-120
Group III >
Group IV All polyalphaolefins (PA05)
Group V All others not included in Groups I, II, Ill, or IV
[0026]
Groups I, II, and III are mineral oil base stocks. In some embodiments,
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the oil of lubricating viscosity is a Group I, II, III, IV, or V oil or
mixtures thereof.
[0027] 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 C., and a viscosity index in the range of
30 to
170, preferably 30 to 140.
Thickener
[0028] Another component in the subject grease composition is a thickener
which serves to increase the consistency of the composition. The thickener
generally comprises multiple components, which may include one or more of the
following: (i) one or more natural oil derivatives, such as hydrogenated
natural oils,
(ii) one or more hydrogenated metathesized natural oils and/or natural oil
derivatives,
(iii) one or more amidated metathesized natural oils and/or natural oil
derivatives, (iv)
one or more carboxylic acids, such as 12-hydroxystearic acid (12-HSA) and
azelaic
acid, and derivatives thereof, and (v) one or more of a metal base compound,
such
as metal oxide, metal hydroxide, or metal carbonate, or mixtures thereof.
[0029] 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 and Hydrogenated Metathesized Natural Oils
[0030] The natural oil derivatives may include one or more hydrogenated
natural oils. Such hydrogenated natural oils may include: hydrogenated
vegetable
oil, hydrogenated algae oil, hydrogenated animal fat, hydrogenated tall oil,
hydrogenated derivatives of these oils, and mixtures thereof. In one
embodiment,
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the hydrogenated vegetable oil is hydrogenated canola oil, hydrogenated
rapeseed
oil, hydrogenated coconut oil, hydrogenated corn oil, hydrogenated cottonseed
oil,
hydrogenated olive oil, hydrogenated palm oil, hydrogenated peanut oil,
hydrogenated safflower oil, hydrogenated sesame oil, hydrogenated soybean oil,
hydrogenated sunflower oil, hydrogenated linseed oil, hydrogenated palm kernel
oil,
hydrogenated tung oil, hydrogenated jatropha oil, hydrogenated mustard oil,
hydrogenated camelina oil, hydrogenated pennycress oil, hydrogenated castor
oil,
hydrogenated derivatives of these oils, and mixtures thereof. In
another
embodiment, the hydrogenated natural oil is a hydrogenated animal fat such as
hydrogenated lard, hydrogenated tallow, hydrogenated poultry fat, hydrogenated
fish
oil, hydrogenated derivatives of these oils, and mixtures thereof. In
some
embodiments, the hydrogenated natural oil is hydrogenated castor oil.
[0031] In
some embodiments, the thickener may have a component
comprising a hydrogenated metathesized natural oil or a natural oil derivative
thereof, such as a hydrogenated metathesized natural oil based wax. In many
instances, the natural oil is metathesized and hydrogenated to modify the
physical
properties of the natural oil such that it forms a wax. Representative
examples of
hydrogenated metathesized natural oils include hydrogenated metathesized
vegetable oil, hydrogenated metathesized algae oil, hydrogenated metathesized
animal fat, hydrogenated metathesized tall oil, hydrogenated metathesized
derivatives of these oils, and mixtures thereof. In
one embodiment, the
hydrogenated metathesized vegetable oil is hydrogenated metathesized canola
oil,
hydrogenated metathesized rapeseed oil, hydrogenated metathesized coconut oil,
hydrogenated metathesized corn oil, hydrogenated metathesized cottonseed oil,
hydrogenated metathesized olive oil, hydrogenated metathesized palm oil,
hydrogenated metathesized peanut oil, hydrogenated metathesized safflower oil,
hydrogenated metathesized sesame oil, hydrogenated metathesized soybean oil,
hydrogenated metathesized sunflower oil, hydrogenated metathesized linseed
oil,
hydrogenated metathesized palm kernel oil, hydrogenated metathesized tung oil,
hydrogenated metathesized jatropha oil, hydrogenated metathesized mustard oil,
hydrogenated metathesized camelina oil, hydrogenated metathesized pennycress
oil, hydrogenated metathesized castor oil, hydrogenated metathesized
derivatives of
these oils, and mixtures thereof. In
another embodiment, the hydrogenated
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metathesized natural oil is a hydrogenated metathesized animal fat such as
hydrogenated metathesized lard, hydrogenated metathesized tallow, hydrogenated
metathesized poultry fat, hydrogenated metathesized fish oil, hydrogenated
metathesized derivatives of these oils, and mixtures thereof. In one
embodiment,
the natural oil is a hydrogenated metathesized soybean oil ("HMSBO"). In one
embodiment, S-55 is a hydrogenated metathesized soybean oil available from
Elevance Renewable Sciences, Woodridge, IL. In one embodiment the HMSBO has
a drop point of about 54 C (129 F), a congeal point of about 52 C (126 F) and
a
needle penetration of about 13 dmm. In another embodiment, the natural oil is
a
hydrogenated metathesized soybean oil that has been vacuum stripped to remove
paraffins. In particular, this vacuum stripped version of HMSBO, S-60, is a
hydrogenated metathesized soybean oil available from Elevance Renewable
Sciences, Woodridge, IL. In one embodiment, this vacuum stripped HMSBO has a
drop point of about 54 C (129 F) and a needle penetration of about 1.4 dmm.
For
the purposes of this document, this vacuum stripped HMSBO shall also be
included
in the general definition of HMSBO.
[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.
(I) R1-CH=cH-R2+ 1_ 1-< - CH=cH-R2,, 1-< -1_
CH=cH_Ri + R2_cH=CH-R2
wherein R1 and R2 are organic groups.
[0033] Cross-metathesis may be represented schematically as shown in
Equation II.
(II) R1-CH=CH-R2+ R3-CH=CH-R44-*
R1-CH=CH-R3 + R1-CH=cH-R4. + 2_ 1-< - CH=CH-R3 + R2-CH=CH-R4
+ R1-CH=cH_Ri + 2_ 1-< - CH=CH-R2+ R3-CH=CH-R3+ R4-CH=CH-R4
wherein R1, R2, R3, and R4 are organic groups.
[0034] In one embodiment, the hydrogenated metathesized natural oil based
wax may be produced by the steps of: (a) providing a metathesis
composition;(b)
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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.
[0035] 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.
[0036] 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-trimethy1-1,3-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.
[0037] 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.
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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.
[0038] In some embodiments, the polyol esters are metathesized and
hydrogenated to form wax compositions. For example, in one embodiment,
refined,
bleached and deodorized (RBD) soybean oil is self-metathesized in the presence
of
a metathesis catalyst to form a metathesis product. The resulting metathesis
product is then hydrogenated without first removing the metathesis catalyst to
form a
hydrogenated metathesis product in the form of a wax. In some embodiments, the
metathesis product is steam stripped and/or vacuum stripped in order to remove
or
reduce hydrocarbon impurities. For example, the metathesis product may be
distilled
in order to remove or reduce hydrocarbons having a molecular weight of about
200
gram/mole or less or to remove or reduce hydrocarbons having a molecular
weight
of about 300 grams/mole or less. The stripping may be accomplished by sparging
the mixture in a vessel, typically agitated, by contacting the mixture with a
gaseous
stream in a column that may contain typical distillation packing (e.g., random
or
structured), or evaporating the lights in an evaporator such as a wiped film
evaporator. Typically, stripping will be conducted at reduced pressure and at
temperatures ranging from about 100 C. to 250 C. The temperature may depend,
for example, on the level of vacuum used, with higher vacuum allowing for a
lower
temperature and allowing for a more efficient and complete separation of
volatiles.
In one embodiment, the hydrogenated metathesized natural oil is a hydrogenated
metathesized soybean oil that is vacuum stripped to remove paraffins. In
particular,
S-60 is a hydrogenated metathesized soybean oil available from Elevance
Renewable Sciences, in Woodridge, IL. In some embodiments, the hydrogenated
metathesized natural oil and/or 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"), or C10_C15 esters,
C15-C18
esters, or C18+ esters, or diesters therefrom, wherein such esters may occur
as free
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esters or in combinations thereof. In some embodiments, such esters are
preferably
monoglycerides and/or fatty acid methyl esters.
[0039] 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, CA). 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" 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.
[0040] 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
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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.
[0041] 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.
[0042] 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.
[0043] 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.
[0044] 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 C., may be greater
than
about -20 C., and is typically greater than about 0 C. or greater than about
20 C.
Typically, the metathesis reaction temperature is less than about 150 C.,
typically
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less than about 120 C. An exemplary temperature range for the metathesis
reaction
ranges from about 20 C. to about 120 C.
[0045] 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.
[0046] 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.
[0047] In some embodiments, the metathesis composition is thereafter
hydrogenated with one or more hydrogenation catalysts. Such hydrogenation
catalysts may comprise, for example, nickel, copper, palladium, platinum,
molybdenum, iron, ruthenium, osmium, rhodium, or iridium. Combinations of
metals
may also be used. Useful catalyst may be heterogeneous or homogeneous. In some
embodiments, the catalysts are supported nickel or sponge nickel type
catalysts.
[0048] In some embodiments, the hydrogenation catalyst comprises nickel
that has been chemically reduced with hydrogen to an active state (i.e.,
reduced
nickel) provided on a support. In some embodiments, the support comprises
porous
silica (e.g., kieselguhr, infusorial, diatomaceous, or siliceous earth) or
alumina. The
catalyst are characterized by a high nickel surface area per gram of nickel.
[0049] In some embodiments, the particles of supported nickel catalyst
are
dispersed in a protective medium comprising hardened triacylglyceride, edible
oil, or
tallow. In an exemplary embodiment, the supported nickel catalyst is dispersed
in the
protective medium at a level of about 22 wt. % nickel.
[0050] In some embodiments, the supported nickel catalysts are of the
type
reported in U.S. Pat. No. 3,351,566 (Taylor et al.), incorporated herein by
reference
in its entirety. These catalyst comprise solid nickel-silica having a
stabilized high
nickel surface area of 45 to 60 sq. meters per gram and a total surface area
of 225 to
300 sq. meters per gram. The catalysts are prepared by precipitating the
nickel and
silicate ions from solution such as nickel hydrosilicate onto porous silica
particles in
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such proportions that the activated catalyst contains 25 to 50 wt. % nickel
and a total
silica content of 30 to 90 wt %. The particles are activated by calcining in
air at 600
to 900 F, then reducing with hydrogen.
[0051] Useful catalysts having a high nickel content are described in EP
0 168
091, incorporated herein by reference in its entirety, wherein the catalyst is
made by
precipitation of a nickel compound. A soluble aluminum compound is added to
the
slurry of the precipitated nickel compound while the precipitate is maturing.
After
reduction of the resultant catalyst precursor, the reduced catalyst typically
has a
nickel surface area of the order of 90 to 150 sq. m per gram of total nickel.
The
catalysts have a nickel/aluminum atomic ratio in the range of 2 to 10 and have
a total
nickel content of more than about 66% by weight.
[0052] Useful high activity nickel/alumina/silica catalysts are described
in EP 0
167 201, incorporated herein by reference in its entirety. The reduced
catalysts have
a high nickel surface area per gram of total nickel in the catalyst.
[0053] Useful nickel/silica hydrogenation catalysts are described in U.S.
Pat.
No. 6,846,772, incorporated herein by reference in its entirety. The catalysts
are
produced by heating a slurry of particulate silica (e.g. kieselguhr) in an
aqueous
nickel amine carbonate solution for a total period of at least 200 minutes at
a pH
above 7.5, followed by filtration, washing, drying, and optionally
calcination. The
nickel/silica hydrogenation catalysts are reported to have improved filtration
properties.
[0054] Also useful are high surface area nickel/alumina hydrogenation
catalysts, for example as reported in U.S. Pat. No. 4,490,480, incorporated
herein by
reference in its entirety. These catalysts typically have a total nickel
content of 5 to
40% by weight.
[0055] Commercial examples of supported nickel hydrogenation catalysts
include those available under the trade designations "NYSOFACT", "NYSOSEL",
and "NI 5248 D" (from Englehard Corporation, Iselin, N.H.). Additional
supported
nickel hydrogenation catalysts include those commercially available under the
trade
designations "PRICAT 9910", "PRICAT 9920", "PRICAT 9908", "PRICAT 9936, and
"PRICAT 9925" (from Johnson Matthey Catalysts, Ward Hill, Mass.).
[0056] Hydrogenation may be carried out in a batch or in a continuous
process and may be partial hydrogenation or complete hydrogenation. In a
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representative batch process, a vacuum is pulled on the headspace of a stirred
reaction vessel and the reaction vessel is charged with soybean oil (e.g., RBD
soybean oil). The soybean oil may be heated to a desired temperature.
Typically, the
temperature ranges from about 50 C. to 350 C., for example, about 100 C. to
300
C. or about 150 C. to 250 C. The desired temperature may vary, for example,
with
hydrogen gas pressure. Typically, a higher gas pressure will require a lower
temperature. In a separate container, the hydrogenation catalyst is weighed
into a
mixing vessel and is slurried with a small amount of soybean oil. When the
soybean
oil reaches the desired temperature, the slurry of hydrogenation catalyst is
added to
the reaction vessel. Hydrogen gas is then pumped into the reaction vessel to
achieve
a desired pressure of FL gas. Typically, the H, gas pressure ranges from about
15 to
3000 psig, for example, about 40 to about 100 psig. As the gas pressure
increases,
more specialized high-pressure processing equipment may be required. Under
these
conditions the hydrogenation reaction begins and the temperature is allowed to
increase to the desired hydrogenation temperature, where it is maintained by
cooling
the reaction mass, for example, with cooling coils. Typically, the
hydrogenation
temperature ranges from about 20 C. to about 250 C., for example, about 100
C.
or greater, or about 120 C. to about 220 C. When the desired degree of
hydrogenation is reached, the reaction mass is cooled to the desired
filtration
temperature.
[0057] The amount of hydrogenation catalysts is typically selected in
view of a
number of factors including, for example, the type of hydrogenation catalyst
used,
the amount of hydrogenation catalyst used, the degree of unsaturation in the
metathesis product, the desired rate of hydrogenation, the desired degree of
hydrogenation (e.g., as measure by iodine value (IV)), the purity of the
reagent, and
the FL gas pressure. In some embodiments, the hydrogenation catalyst is used
in an
amount of about 10 wt. % or less, for example, about 5 wt. % or less or about
1 wt.
% or less.
[0058] After hydrogenation, the used hydrogenation catalyst is removed
from
the hydrogenated metathesized product using known techniques such as
filtration. In
some embodiments, the hydrogenation catalyst is removed using a plate and
frame
filter such as those commercially available from Sparkle Filters, Inc., Conroe
Tex. In
some embodiments, the filtration is performed with the assistance of pressure
or a
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vacuum. In order to improve filtering performance, a filter aid may be used. A
filter
aid may be added to the metathesized product directly or it may be applied to
the
filter. Representative examples of filtering aids include diatomaceous earth,
silica,
alumina, and carbon. Typically, the filtering aid is used in an amount of
about 10 wt.
% or less, for example, about 5 wt. % or less or about 1 wt. (:)/0 or less.
Other filtering
techniques and filtering aids may also be employed to remove the used
hydrogenation catalyst. In other embodiments the hydrogenation catalyst is
removed
using centrifugation followed by decantation of the product.
[0059] After filtering, the hydrogenated metathesis products typically
contain
less than about 100 ppm of the metathesis catalyst transition metal. In other
embodiments, the hydrogenated metathesis products contain less than about 10
ppm of the metathesis catalyst transition metal. In still other embodiments,
the
hydrogenated metathesis products contain less than about 1 ppm of the
metathesis
catalyst transition metal, for example, about 0.9 ppm or less, about 0.8 ppm
or less,
about 0.7 ppm or less, about 0.6 ppm or less, about 0.5 ppm or less, about 0.4
ppm
or less, about 0.3 ppm or less, or about 0.1 ppm or less. In exemplary
embodiments,
the metathesis catalyst is a ruthenium-based catalyst and the hydrogenated
metathesis product contains less than about 0.1 ppm ruthenium.
[0060] In some embodiments, hydrogenated metathesized oil is a mixture of
compounds of at least two general types: paraffinic compounds and
triglycerides of
long-chain mono-carboxylic and di-carboxylic acids and oligomers thereof. The
paraffinic compounds typically do not react under any fat splitting conditions
and exit
the reaction unaltered. Depending on the application, the paraffinic compounds
can
be partly or fully removed (stripped). Triglycerides and oligomers thereof are
reacted
with water or OFI1H+ giving mainly free fatty acids corresponding to the
hydrogenated metathesized oil fatty acid profile (mono- and di-acids) and
glycerol
leaving small amounts of partially hydrolyzed hydrogenated metathesized oil
composed of diglycerides, monoglycerides, and oligomers thereof.
[0061] In some embodiments, the metathesized natural oil may be
epoxidized.
The metathesized natural oil may be epoxidized via any suitable peroxyacid.
Peroxyacids (peracids) are acyl hydroperoxides and are most commonly produced
by the acid-catalyzed esterification of hydrogen peroxide. Any peroxyacid may
be
used in the epoxidation reaction. Examples of hydroperoxides that may be used
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include, but are not limited to, peracetic acid, performic acid, m-
dichloroperbenzoic
acid, tert-butylhydroperoxide, triphenylsilylhydroperoxide,
cumylhydroperoxide, and
hydrogen peroxide.
B. Amidated Metathesized Natural Oils
[0062] In
some embodiments, the thickener may have a component
comprising an amidated hydrogenated metathesized natural oil or natural oil
derivative, such as an amidated hydrogenated metathesized natural oil based
wax.
A number of valuable amide wax compositions may be prepared by reacting an
amine with an ester-functional group of a metathesized natural oil in the
presence of
a basic catalyst or heat to form an amidated metathesized natural oil. This
reaction
may generate amidated metathesized natural oil compositions having unique
properties over other forms of amide waxes, natural oils, or metathesized
natural
oils. Such unique properties may include a higher drop point, higher congeal
point,
improved hardness, improved malleability, improved emulsifiability, improved
functionality, improved viscosity, and/or improved compatibility with other
materials
(such as triglyceride oils and waxes, polyamides, stearic acid, ethylene vinyl
acetate
copolymers, tackifier resins, and paraffins in low concentration). In
certain
embodiments, it is possible to tailor the range of certain properties (such as
drop
point or hardness) by modifying the amount or type of amine used in the
reaction
with the metathesized natural oil.
[0063] In
certain embodiments, the metathesized natural oil in the amidated
metathesized natural oil composition has been "hydrogenated" (i.e., full or
partial
hydrogenation of the unsaturated carbon-carbon bonds in the metathesized
natural
oil) in the presence of a hydrogenation catalyst to form a hydrogenated
metathesized
natural oil. In one embodiment, the natural oil is partially hydrogenated
before it is
subjected to the metathesis reaction. In another embodiment, the natural oil
is
metathesized prior to being subjected to partial or full hydrogenation. Any
known or
future-developed hydrogenation catalysts may be used, alone or in combination
with
one or more additional catalysts. Non-limiting exemplary hydrogenation
catalysts
were described previously in this document.
Representative examples of
hydrogenated metathesized natural oils were described previously in this
document.
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[0064] The
amine compound(s) selected for the reaction with the
metathesized natural oil may be ammonia or a compound containing one or more
primary or secondary amino groups. In certain embodiments, the amine is a mono-
substituted amine having one non-hydrogen substituted group (such as an alkyl,
aryl
group, alkyl-amino group, or aryl-amino group), a di-substituted amine having
two
non-hydrogen substituted groups, an amino-alcohol, or a combination thereof.
In
certain non-limiting embodiments, the amine is a mono-substituted or di-
substituted
amine such as: methylamine, dimethylamine, ethylamine, diethylamine,
propylamine,
dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine,
hexylamine,
dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, or a
mixture
thereof. In other non-limiting embodiments, the amine is an amino-alcohol such
as:
methanolamine, dimethanolamine, ethanolamine, diethanolamine, propanolamine,
dipropanolamine, butanolamine, dibutanolamine, pentanolamine, dipentanolamine,
hexanolamine, dihexanolamine, heptanolamine, diheptanolamine, octanolamine,
dioctanolamine, aniline, or a mixture thereof. In yet other non-limiting
embodiments,
the amine is a diamine such as: ethylenediamine (1,2-ethanediamine), 1,3-
propanediamine, 1,4-butanediamine (putrescine), 1,5-pentanediamine, 1,6-
hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,3-
bis(aminomethyl)cyclohexane, meta-xylenediamine, 1,8-naphthalenediamine, p-
phenylenediamine, N-(2-aminoethyl)-1,3-propanediamine, or a mixture thereof.
In
yet other non-limiting embodiments, the amine is a triamine or tetramine such
as:
diethylenetriamine, dipropylenetriamine, dibutylenetriamine,
dipentylenetriamine,
dihexylenetriamine, diheptylenetriamine, dioctylenetriamine, spermidine,
melamine,
triethylenetetramine, tripropylenetetramine,
tributylenetetramine,
tripentylenetetramine, trihexylenetetramine,
triheptylenetetramine,
trioctylenetetramine, hexamine, or a mixture thereof. In another embodiment,
the
amine is an imidazole or oxazolidine.
[0065] In
one embodiment, the amine is selected from the group consisting of:
ethanolamine, diethanolamine, diethylamine, ethylenediamine (1,2-
ethanediamine),
hexamethyleneamine, and mixtures thereof. In one embodiment, the amine is
ethylenediamine. In another embodiment, the amine is diethanolamine. In some
embodiments, HMSBO may be fractionally amidated with diethanol amine to
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generate an emulsifying amidated wax, A100, available from Elevance Renewable
Sciences, in Woodridge, IL.
[0066] In certain embodiments, the amine is a polar compound that is
useful
for forming a hydrous amidated metathesized natural oil composition. The
hydrous
composition is capable of being water dispersible and improving the viscosity
of the
wax composition. Non-limiting examples of polar amines include amino-alcohols
such as: methanolamine, dimethanolamine, ethanolamine, diethanolamine,
propanolamine, dipropanolamine, butanolamine, dibutanolamine, pentanolamine,
dipentanolamine, hexanolamine, dihexanolamine, heptanolamine, diheptanolamine,
octanolamine, dioctanolamine, aniline, or mixtures thereof.
[0067] In other embodiments, the amine is a non-polar compound that is
useful for forming an anhydrous amidated metathesized natural oil composition.
Such anhydrous compositions may be capable of improving the hardness and drop
point of the wax composition.
[0068] In one embodiment, the amount of amine present in the amine-
metathesized natural oil reaction is between approximately 0.1 percent by
weight
and 30 percent by weight of the metathesized natural oil present. In other
embodiments, the amount of basic catalyst is between approximately 0.1 percent
by
weight and 10 percent by weight of the metathesized natural oil or between
approximately 1 percent by weight and 15 percent by weight of the metathesized
natural oil. Alternatively, the amount of amine added to the reaction can be
expressed in terms of the ratio of amine equivalents in the amine to ester
equivalents
in the metathesized natural oil. In one embodiment, the ratio of amine
equivalents to
ester equivalents is between approximately 1:100 and approximately 10:1. In
another embodiment, the ratio of amine equivalents to ester equivalents is
between
approximately 1:10 and approximately 5:1. In other embodiments, the ratio of
amine
equivalents to ester equivalents is approximately 1:3, approximately 2:3,
approximately 1:2, or approximately 1:1.
[0069] The basic catalyst that may be used to improve the reaction rate
of the
amine-metathesized natural oil reaction is a basic compound generally known to
a
person of skill in the art. In certain embodiments, the basic catalyst is
sodium
carbonate, lithium carbonate, sodium methanolate, potassium hydroxide, sodium
hydride, potassium butoxide, potassium carbonate, or a mixture thereof. In
certain
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embodiments, the basic catalyst may be added to the reaction between the amine
and metathesized natural oil in dry form or dissolved in water.
[0070] In other embodiments, the reaction rate of the amine-metathesized
natural oil reaction is improved by heating the amine-metathesized natural oil
mixture
(with or without a basic catalyst present) to at least 100 C, at least 120 C,
at least
140 C, at least 160 C, or between approximately 100 C and approximately 200 C.
[0071] In one embodiment, the amount of basic catalyst added to the
reaction
is between approximately 1 percent by weight and 10 percent by weight of the
metathesized natural oil present. In other embodiments, the amount of basic
catalyst is between approximately 0.1 percent by weight and 1.0 percent by
weight of
the metathesized natural oil or between approximately 0.01 percent by weight
and
0.1 percent by weight of the metathesized natural oil. In another embodiment,
the
amount of basic catalyst is approximately 0.5 percent by weight of the
metathesized
natural oil.
[0072] In one embodiment, the amine-metathesized natural oil reaction is
conducted in a nitrogen or other inert atmosphere. In certain embodiments, the
reaction is conducted under atmospheric conditions and the reactor temperature
is
between approximately 80-250 C, between approximately 120-180 C, or between
approximately 120-160 C. In certain embodiments, the reactor temperature is
held
for approximately 1-24 hours, approximately 4-24 hours, approximately 1 hour,
approximately 2 hours, approximately 4 hours, or approximately 6 hours.
[0073] In certain embodiments, following the amine-metathesized natural
oil
reaction, the product mixture is vacuum pumped for at least 30 minutes or at
least 1
hour to separate the water, any unreacted amine, and/or glycerol from the
amidated
metathesized natural oil product. In another embodiment, paraffin byproduct
from
the metathesis and hydrogenation reactions can be separated from the amidated
metathesized natural oil product.
[0074] In certain embodiments, when the metathesized natural oil is
reacted
with at least one amine in the presence of the basic catalyst or heat, the
ester
functionality is replaced by an amine to form an amidated metathesized natural
oil
comprising molecules having the following structures:
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0 0 iR2
II II
R1- /C-X1- X2¨ C ¨ N
\
R3
and
R4 0
\ 11
N¨C¨X3
/
R5
wherein Ri is selected from the group consisting of:
- 0¨CH2
R6 R8
/ / I
- N - N
HC
¨0¨R10
\ \ I
R7 , R9 , and H2C-0¨R11
wherein R2, R3,R4, R5, R6, R7, Rg, and R9 are independently selected from the
group
consisting of hydrogen, alcohols, alkyls, aryls, alkyl-amines, and aryl-
amines,
wherein Rio and Rii are independently selected from the group consisting of:
0 0
0
11 11 II
hydrogen, - C¨x4¨X6¨C¨R1 , and - C¨X6 , and
wherein Xi, X2, X31 X4, X5, and X6 are independently selected from the group
consisting of Cg - C28 saturated or unsaturated alkyl chains from either a
fatty acid of
a natural oil, or a derivative thereof formed by a metathesis reaction.
[0075] In certain embodiments, R2, R3, R41 R51 R6, R7, Rg, and R9 may
form at
least one amine selected from the group consisting of: methylamine,
dimethylamine,
ethylamine, diethylamine, propylamine, dipropylamine, butylamine,
dibutylamine,
pentylamine, dipentylamine, hexylamine, dihexylamine, heptylamine,
diheptylamine,
octylamine, dioctylamine, methanolamine, dimethanolamine, ethanolamine,
diethanolamine, propanolamine, dipropanolamine, butanolamine, dibutanolamine,
pentanolamine, dipentanolamine, hexanolamine, dihexanolamine, heptanolamine,
diheptanolamine, octanolamine, dioctanolamine, aniline, ethylenediamine (1,2-
ethanediamine), 1,3-propanediamine, 1,4-butanediamine (putrescine), 1,5-
pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,3-
bis(aminomethyl)cyclohexane, meta-xylenediamine, 1,8-naphthalenediamine, p-
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phenylenediamine, N-(2-aminoethyl)-1,3-propanediamine,
diethylenetriamine,
dipropylenetriamine, dibutylenetriamine, dipentylenetriamine,
dihexylenetriamine,
diheptylenetriamine, dioctylenetriamine, spermidine, melamine,
triethylenetetramine,
tripropylenetetramine, tributylenetetramine,
tripentylenetetramine,
trihexylenetetramine, triheptylenetetramine,
trioctylenetetramine, hexamine,
imidazole, oxazolidine, or mixtures thereof.
[0076] In
one embodiment, the amidated metathesized natural oil comprises a
"diacid functionality" [e.g., -(C=0)-Xi-X2-(C=0)-]. In
another embodiment, the
amidated metathesized natural oil contains the diacid functionality and a
glycerol
backbone of the metathesized natural oil.
[0077] In
certain embodiments, in addition to the amidated metathesized
natural oil product, the reaction between the metathesized natural oil and
amine
produces a hydroxy-metathesis oligomer co-product having the following
structure:
H¨R12
wherein R12 is:
- O¨CH2
I
HC¨O¨R13
I
H2C¨O¨R14
wherein R13 and R14 are independently selected from the group consisting of:
II II 110 0
0
hydrogen, - C¨X7¨X8¨C¨R12, and - C¨x9
wherein X7, X8, and X9 are independently selected from the group consisting of
C8 -
C28 saturated or unsaturated alkyl chains from either a fatty acid of a
natural oil, or a
derivative thereof formed by a metathesis reaction.
C. Carboxylic Acids and Derivatives
[0078] 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
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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
[0079] 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
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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.
[0080] 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
[0081] 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
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percent of the grease composition, and more preferably 3 to 10 weight percent
of the
grease composition.
[0082]
Metal deactivators may include derivatives of benzotriazoles,
benzimidazole, 2-alkyldithiobenz-imidazoles, 2-alkyldithiobenzothiazoles, 2-
(N,N-
dialkyldithiocarbamoy1)-benzothiazoles, 2,5-bis(alkyl-dithio)-1,3,4-
thiadiazoles, 2,5-
bis(N,N-dialkyldithio-carbamoyI)-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 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.
[0083]
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 DieIs-
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
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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
[0084] 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 castor and hot mills bearing lubrication,
lubrication
of garage door mechanisms and oven chain lubrication.
GREASE PREPARATION
[0085] 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,
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thickener component, and additive content will permit the manufacture of
various
grades of greases.
[0086] 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.
NLGI Grade Worked Cone Penetration (ASTM D 217) @ 77 F
000 445-475
00 400-430
o 355-385
1 310-340
2 265-295
3 220-250
4 175-205
130-160
6 85-115
Table 1. NLGI Grades for greases
[0087] 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.
[0088] 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. 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
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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.
[0089] Another type of batch processor sometimes used is a Stratco@ 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.
[0090] To prepare the simple greases described herein, the various
thickener
components (one or more of: carboxylic acids, hydrogenated natural oil, and/or
hydrogenated metathesized natural oil derivative) are added to a lubricating
base oil,
and this mixture is charged to a kettle, mixer, or equivalent vessel.
Preferably, these
thickener components are naphthenic acid, 12-hydroxystearic acid, hydrogenated
castor oil, and hydrogenated metathesized soybean oil (S60), and the
lubricating
base oil is a naphthenic pale oil. These materials are then stirred and heated
to a
temperature between about 140 F to 200 F for approximately 30-60 minutes, in
order to dissolve one or more of the acids into the lubricating base oil. The
metal
base, usually a metal hydroxide such as lithium hydroxide is then charged to
the
vessel, usually in an amount slightly in excess of the stoichiometric amount
required
to neutralize the acid. The temperature at this stage is usually between about
190 F
to about 270 F., preferably between about 240 F to about 260 F, for a
period of
time (approximately 30-90 minutes) sufficient to complete the neutralization
and to
effect a substantial dehydration of the mixture, i.e., the removal of 70 to
100% of the
water, by venting. After venting the water vapor, heating of the mixture is
resumed
and increased to about 350 to about 430 F, preferably between about 390 F
to
about 410 F, and maintained at that level for about 15 minutes to about 1
hour to
ensure optimum soap crystallization, dispersing of the acid into the mixture,
and
improved yields. This increase in temperature (or "cookout") is effected as
rapidly as
possible to save time and to minimize oxidation.
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[0091] Thereafter, the mixture is then transferred to a finishing kettle
or
equivalent vessel for cooling. This cooling is 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.
[0092] 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) a dicarboxylic acid, such as one or
more
straight or branched chain C2 -C12 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. 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 C are
displayed by complex greases. Generally, a complex grease is one which
displays
a dropping point significantly higher, typically at least about 20 C higher,
than the
corresponding simple metal soap grease.
[0093] To prepare the complex greases described herein, the various
thickener components (one or more of: carboxylic acids, hydrogenated natural
oil,
and/or hydrogenated natural oil derivative) are added to a lubricating base
oil, and
this mixture is charged to a kettle, mixer, or equivalent vessel. Preferably,
these
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thickener components are naphthenic acid, 12-hydroxystearic acid, azelaic
acid, and
hydrogenated metathesized soybean oil (S60), and the lubricating base oil is a
naphthenic pale oil. These materials are then stirred and heated to a
temperature
between about 140 F to 200 F for approximately 30-60 minutes, in order to
dissolve one or more of the acids into the lubricating base oil. The
metal base,
usually a metal hydroxide such as lithium hydroxide is then charged to the
vessel, is
then added to convert the azelaic acid to its dilithium soap (dilthium
azelate) usually
in an amount slightly in excess of the stoichiometric amount required to
neutralize
both acid groups of the azelaic acid. The temperature at this stage is usually
between about 190 F to about 270 F, preferably between about 240 F to about
260 F, for a period of time (approximately 30-90 minutes) sufficient to
complete the
neutralization and to effect a substantial dehydration of the mixture, i.e.,
the removal
of 70 to 100% of the water, by venting. After venting the water vapor, heating
of the
mixture is resumed and increased to about 350 to about 430 F, preferably
between about 390 F to about 410 F, and maintained at that level for about
15
minutes to about 1 hour to ensure optimum soap crystallization, dispersing of
the
acid into the mixture, and improved yields. This increase in temperature (or
"cookout") is effected as rapidly as possible to save time and to minimize
oxidation.
[0094]
Thereafter, the mixture is then transferred to a finishing kettle or
equivalent vessel for cooling. This cooling is 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.
[0095] In
some embodiments, the S60 component of the thickener serves to
liberate long chain (i.e. C18 and higher) dicarboxylate salts, carboxylate
salts, and
glycerol upon exposure to metal hydroxides during grease processing, thus
serving
as a latent grease complexing agent. Also, since the S60 component will often
react
in a similar manner to hydrogenated castor oil, simple greases may achieve
some
complex character under standard processing conditions (3 hours). The
inclusion of
S60 into simple grease compositions would allow for lower processing
temperatures
and increased production capacity without compensating simple grease
performance.
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[0096] To illustrate the chemistry involved in this application, a
representative
reaction between S60 and lithium hydroxide is shown below:
0
ortvµ
(( 0
0
0 0
0\/\kCI(n Li0 13.15
+
0 0
OLi
lII 0 LION 0
+ 0
0 0
Li0
0 0
0 0 +
glycerol
0 0
[0097] In many instances, neutralization of conventional organic
dicarboxylic
acids (i.e, azelaic acid) used in the preparation of complex greases
necessitates
additional water removal, whereas dicarboxylate salts generated from S60
saponification release glycerol which is tolerated, and often included in most
grease
formulations. Carboxylate salts formed from S60 upon treatment with alkali are
proposed to enhance grease thickener structuring and enable batch processing
temperatures lower than the melt point of 12-hydroxystearic acid (-400 F)
used to
thicken simple lithium grease. Reduced thickener kettle reaction temperatures
may
reduce processing time and increase grease throughput depending on the
manufacturing protocol.
[0098] 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.
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EXAMPLES
EXAMPLE 1
[0099] In a 100 gallon Stratco mixer vessel, various thickener
components
were added. In this step, naphthenic acid (0.2% by weight), 12-hydroxystearic
acid
(4.9% by weight), hydrogenated castor oil (1.9% by weight), and S60 (1% by
weight), were added to Pale Oil 750 (lubricating base oil), and melted into
the
lubricating base oil at 170 F and mixed. After 50 minutes, aqueous lithium
hydroxide
was charged to the vessel, and the mixture heated to about 250 F to a nearly
fluid
consistency, to saponify and neutralize this mixture. Thereafter, water vapor
was
vented upon reaction completion, and heating was increased to about 380 F to
completely disperse the lithium 12-HSA into the mixture. This mixture was then
transferred to a finishing kettle, at a period between 60 and 90 minutes from
the start
of the experiment, an additional amount of lubricating base oil was added
dropwise
for dilution. At about 90 minutes, the heat was removed, and at about 1 hour
thereafter, optional additives were charged to the finishing kettle, and
cooling
resumed until the end of the experiment at 4 hours.
[00100] It was determined that the inclusion of S60 in the thickener
matrix at
1% by weight yielded an NLGI grease (ASTM 60 stroke worked penetration =288,
280), with a higher drop point than simple lithium greases (415 F vs. 385 F).
EXAMPLE 2
[00101] In a 100 gallon Stratco mixer vessel, various thickener
components
were added. In this step, naphthenic acid (0.34% by weight), 12-hydroxystearic
acid
(7.32% by weight), azelaic acid (2.4% by weight), and S60 (1.5% by weight),
were
added to Pale Oil 750 (lubricating base oil), and melted into the lubricating
base oil
at 170 F and mixed. After 50 minutes, aqueous lithium hydroxide was charged to
the vessel, and the mixture heated to about 250 F to a nearly fluid
consistency, to
saponify and neutralize this mixture. Thereafter, water vapor was vented upon
reaction completion, and heating was increased to about 350 F to completely
disperse the lithium 12-HSA and azelaic acid into the mixture. This mixture
was then
transferred to a finishing kettle, at a period between 60 and 90 minutes from
the start
of the experiment, an additional amount of lubricating base oil was added
dropwise
for dilution. At about 90 minutes, the heat was removed, and at about 1 hour
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thereafter, optional additives were charged to the finishing kettle, and
cooling
resumed until the end of the experiment at 4 hours.
[00102] It was determined that the inclusion of S60 in the thickener
matrix at
1.5% by weight yielded a complex grease (NLGI grade 2 - 60 stroke
unworked/worked cone penetration = 267, 262; 10,000 stroke - 270 dmm, 100,000
stroke - 293 dmm; Timken 50 lb pass; drop point 514 F).
EXAMPLE 3
[00103] In an open kettle, various thickener components were added. In
this
step, one or more components, such as naphthenic acid , 12-hydroxystearic
acid,
hydrogenated castor oil, and S60, in the percentages by weight shown in Table
2
below , were added to Pale Oil 750 (lubricating base oil), and melted into the
lubricating base oil at 170 F and mixed. After 50 minutes, aqueous lithium
hydroxide
was charged to the vessel, and the mixture heated to about 250 F to a nearly
fluid
consistency, to saponify and neutralize this mixture. Thereafter, water vapor
was
vented upon reaction completion, and heating was increased to about 380 F to
completely disperse the lithium 12-HSA into the mixture. This mixture was then
transferred to a finishing kettle, at a period between 60 and 90 minutes from
the start
of the experiment, an additional amount of lubricating base oil was added
dropwise
for dilution. At about 90 minutes, the heat was removed, and at about 1 hour
thereafter, optional additives were charged to the finishing kettle, and
cooling
resumed until the end of the experiment at 4 hours.
[00104] The quantities of the lubricating base oil, thickener components,
reaction conditions, and material properties of the finished simple grease and
complex grease products are shown in Table 2.
Exp. Formu- 12-HSA H. Naphthenic Azelaic Total S60 Final
Drop Cone
# lation (A) Castor Acid (%w/w) Acid Thickener
(%w/w) Reaction Point Penetr.
(%w/w) (G) (%w/w) (%w/w) Temp (F) (F)
(dmm)
(%w/w)
1 A 4.91 1.92 0.16 0.00 6.99 0 400 386 279
2 A 4.91 1.92 0.16 0.00 6.99 1 400 406 300
3 A 4.91 1.92 0.16 0.00 6.99 0 350 rt na
4 A 4.91 1.92 0.16 0.00 6.99 1 350 369 324
A 4.91 1.92 0.16 0.00 6.99 1.5 350 367 311
6 A 4.91 1.92 0.16 0.00 6.99 2 350 371 470
7 A 6.18 2.32 0.16 0.00 8.66 0 350 341 450
36
CA 02899369 2015-07-24
WO 2014/138613 PCT/US2014/021863
8 A 7.30 2.70 0.16 0.00 10.16 0 350 379 243
9 B 6.83 0.00 0.16 0.00 6.99 1 380 392 322
B 6.83 0.00 0.16 0.00 6.99 0 350 rt
na
11 B 6.83 0.00 0.16 0.00 6.99 1 350 rt na
12 B 6.83 0.00 0.16 0.00 6.99 1.5 350
rt na
13 B 6.83 0.00 0.16 0.00 6.99 2 350 366
464
14 C 7.32 0 0.34 2.4 10.06 1.5 350 514 267
TABLE 2. Simple and complex grease composition properties
[00105] Compared to control experiment 3, inclusion of S60 at 1%
(experiment
4) and 1.5% (experiment 5) enabled grease formation at near NLGI Grade 2
specification at 350 F. At 2% S60 (experiment 6), the grease was extremely
soft,
suggesting a threshold level had been exceeded. Control (experiment 7) showed
that the increased relative amount of 12-hydroxystearic acid and hydrogenated
castor oil in the thickener (about 8% by weight) did not allow processing at
350 F.
Control (experiment 8) showed that the increased relative amount of 12-
hydroxystearic acid and hydrogenated castor oil in the thickener (about 10% by
weight) produced a harder grease at NLGI Grade 3 specification. A pilot scale
run at
350 F for experiment 5 yielded at NLGI specification grease (drop point of
378 F,
unworked/worked cone penetration of 326/324 dmm). A pilot scale run at 350 F
for
experiment 14 successfully yielded a complex grease at 350 F. Experiment 9
also
showed that a simple grease may be made without the inclusion of hydrogenated
castor oil, which produced a grease at NLGI Grade 1 specifications.
37
