U.S. patent application number 14/531566 was filed with the patent office on 2015-02-26 for maleanized ester derivatives.
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 Bertin, Jonathan Brekan, Amy Dalby, Stephen A. Di Biase, Zhe Wang.
Application Number | 20150057204 14/531566 |
Document ID | / |
Family ID | 52480908 |
Filed Date | 2015-02-26 |
United States Patent
Application |
20150057204 |
Kind Code |
A1 |
Brekan; Jonathan ; et
al. |
February 26, 2015 |
Maleanized Ester Derivatives
Abstract
This disclosed invention relates to a maleinated ester
derivative derived from an unsaturated linear aliphatic carboxylic
acid methyl ester, maleic anhydride, and a monohydric alcohol.
Lubricants and functional fluids containing the maleinated esters
are disclosed.
Inventors: |
Brekan; Jonathan;
(Woodridge, IL) ; Di Biase; Stephen A.;
(Woodridge, IL) ; Wang; Zhe; (Woodridge, IL)
; Dalby; Amy; (Woodridge, IL) ; Bertin; Paul;
(Woodridge, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Elevance Renewable Sciences, Inc. |
Woodridge |
IL |
US |
|
|
Assignee: |
Elevance Renewable Sciences,
Inc.
Woodridge
IL
|
Family ID: |
52480908 |
Appl. No.: |
14/531566 |
Filed: |
November 3, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14202337 |
Mar 10, 2014 |
|
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14531566 |
|
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61776952 |
Mar 12, 2013 |
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Current U.S.
Class: |
508/496 ;
554/121 |
Current CPC
Class: |
C10M 2205/0285 20130101;
C10N 2020/02 20130101; C10M 129/78 20130101; Y02P 20/582 20151101;
C10M 129/72 20130101; C10M 2207/281 20130101; C10M 2203/1006
20130101; C10N 2030/06 20130101; C10M 2203/1025 20130101; C10N
2030/04 20130101; C07C 69/34 20130101; C10M 159/12 20130101; C10N
2020/081 20200501; C10M 2203/1025 20130101; C10N 2020/02 20130101;
C10M 2203/1025 20130101; C10N 2020/02 20130101 |
Class at
Publication: |
508/496 ;
554/121 |
International
Class: |
C10M 129/72 20060101
C10M129/72 |
Claims
1. A composition comprising a triester compound of the following
formula ##STR00006## wherein each R is independently a C.sub.3-12
alkyl.
2. The composition of claim 1, wherein each R is independently
C.sub.5-10 alkyl
3. The composition of claim 1, wherein each R is independently
propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl,
dodecyl, 2-methylbutyl, 3-methylbutyl, or a branched C.sub.10
alkyl.
4. The composition of claim 3, wherein each R is pentyl.
5. The composition of claim 3, wherein each R is decyl.
6. The composition of claim 3, wherein each R is 3-methylbutyl.
7. The composition of claim 3, wherein each R is 2-methylbutyl.
8. The composition of claim 3, wherein each R is a branched
C.sub.10 alkyl.
9. The composition of claim 3, wherein each R is hexyl.
10. The composition of claim 3, wherein each R is octyl.
11. The composition of claim 1, wherein the composition is a
lubricant composition.
12. The composition of claim 11, wherein the composition further
comprises one or more additional base oils selected from the group
consisting of an API Group I base oil, an API Group II base oil, an
API Group III base oil, an API Group IV base oil, an API Group V
base oil, and combinations thereof.
13. The composition of claim 12, wherein the composition comprises
the triester compound in an amount ranging from 1 to 75 percent by
weight, based on the total weight of the composition.
14. The composition of claim 13, wherein the composition comprises
the triester compound in an amount ranging from 5 to 60 percent by
weight, based on the total weight of the composition.
15. The composition of claim 12, further comprising a dispersant, a
detergent, or a combination thereof.
16. The composition of claim 12, further comprising a pour point
depressant.
17. The composition of claim 12, further comprising a viscosity
modifier.
18. The composition of claim 12, further comprising an anti-foam
agent.
19. The composition of claim 12, further comprising a
thickener.
20. The composition of claim 12, further comprising additives
selected from the group consisting of: corrosion-inhibiting agents,
oxidation-inhibiting agents, pour point depressing agents, extreme
pressure agents, antiwear agents, viscosity index improvers,
friction modifiers, hindered amines, phenolic inhibitors,
sulfurized inhibitors, antioxidants, metal cutting additives,
antimicrobial additives, color stabilizers, viscosity modifiers,
demulsifiers, seal swelling agents, anti-foam agents, and any
combinations thereof.
Description
[0001] The present application is a continuation-in-part of U.S.
patent application Ser. No. 14/202,337, filed Mar. 10, 2014, which
claims the benefit of priority of U.S. Provisional Application No.
61/776,952, filed Mar. 12, 2013. Both of the aforementioned
applications are hereby incorporated by reference as though fully
set forth herein in their entirety.
TECHNICAL FIELD
[0002] This invention relates to maleinized ester derivatives and,
more particularly, to maleinized ester derivatives derived from
unsaturated linear aliphatic carboxylic acid methyl esters, maleic
anhydride, and monohydric alcohols. The invention relates to
lubricants and functional fluids containing the maleinized ester
derivatives.
BACKGROUND
[0003] Synthetic lubricants may be used in passenger car motor
oils, heavy-duty diesel engine oils, marine and railroad engine
lubricants, automatic transmission fluids, hydraulic fluids, gear
oils, and industrial lubricants, such as metalworking fluids and
lubricating greases.
SUMMARY
[0004] The purpose of these synthetic lubricants is to provide
improved friction and wear control, rapid dissipation of heat, and
the dissolution of and/or facilitating the removal of
service-related contaminants. Achieving a proper balance between
various performance characteristics is an important consideration
in selecting a synthetic lubricant for a particular application.
For example, polyolefin based lubricants typically exhibit good
low-temperature properties, high viscosity index, and excellent
thermal stability, but poor solvency. As a result, these lubricants
tend to be inadequate without the presence of additional polar base
stock-containing components. Conversely, polar base
stock-containing lubricants, such as those based on synthetic
esters and vegetable oils, typically exhibit good solvency and high
surface affinity. However, these lubricants tend to be inadequate
with respect to resistance to wear. The problem, therefore, is to
provide a synthetic lubricant that exhibits both good solvency and
good resistance to wear reduction characteristics. This invention
provides a solution to this problem.
[0005] This invention relates to a composition comprising a
maleinized ester derivative made by the reaction of: (i) an
unsaturated linear aliphatic carboxylic acid methyl ester
comprising a linear hydrocarbon chain of about 8 to about 18 carbon
atoms, or about 10 to about 14 carbon atoms, or about 12 carbon
atoms; maleic anhydride; and a monohydric alcohol of 3 to about 12
carbon atoms, or 3 to about 10 carbon atoms, or 3 to about 8 carbon
atoms, or about 5 to about 10 carbon atoms, or about 5 carbon
atoms; wherein the maleinized ester derivative comprises at least
two proximal ester groups and another ester group, the proximal
ester groups and the another ester group containing straight chain
alkyl groups of 3 to about 12 carbon atoms, or 3 to about 8 carbon
atoms, or about 5 carbon atoms; the proximal ester groups being
separated from the another ester group by at least about 8 carbon
atoms, or at least about 9 carbon atoms, or at least about 10
carbon atoms.
[0006] When counting the number of carbon atoms separating two
ester groups, the carbonyl atoms of each ester group are included.
For example, two proximal ester groups formed on a maleic anhydride
group are separated by two carbon atoms, but when including the
carbonyl atoms of the ester group, the proximal ester groups are
separated by four carbon atoms. Similarly, when counting the number
of carbon atoms between a proximal ester group and the another
ester group, the carbonyl atoms of each ester group are
included.
[0007] The monohydric alcohol may be linear or branched. In an
advantageous embodiment of the invention, the monohydric alcohol
comprises one or more linear alcohols.
[0008] In any of the above-indicated embodiments, the unsaturated
linear aliphatic carboxylic acid methyl ester is reacted with the
maleic anhydride to form a maleinized unsaturated carboxylic acid
methyl ester, and the maleinized unsaturated carboxylic acid methyl
ester is reacted with the monohydric alcohol to form the maleinized
ester derivative.
[0009] In any of the above-indicated embodiments, prior to the
reaction with the monohydric alcohol, the maleinized carboxylic
acid methyl ester comprises a methyl ester group and a maleic
anhydride group, the reaction with the monohydric alcohol
comprising an esterification reaction with the maleic anhydride
group and a transesterification reaction with the methyl ester
group.
[0010] In any of the above-indicated embodiments, prior to the
reaction with the monohydric alcohol, the maleinized carboxylic
acid methyl ester comprises a methyl ester group and two maleic
anhydride groups, the reaction with the monohydric alcohol
comprising an esterification reaction with the maleic anhydride
groups and a transesterification reaction with the methyl ester
group.
[0011] In any of the above-indicated embodiments, the maleinized
ester derivative comprises a mono-triester.
[0012] In any of the above-indicated embodiments, the maleinized
ester derivative comprises a mixture of a mono-triester and a
di-triester.
[0013] In any of the above-indicated embodiments, the maleinized
ester is biodegradable.
[0014] In any of the above-indicated embodiments, the maleinized
ester derivative is biodegradable.
[0015] In any of the above-indicated embodiments, the maleinized
ester derivative contains one or more carbon-carbon double bonds,
the carbon-carbon double bonds being hydrogenated to form saturated
carbon bonds.
[0016] In any of the above-indicated embodiments, the unsaturated
linear aliphatic carboxylic acid methyl ester comprises methyl
8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate, methyl
9-dodecenoate, methyl 9-octadecenoate, or a mixture of two or more
thereof.
[0017] In any of the above-indicated embodiments, the monohydric
alcohol comprises 1-propanol, 1-butanol, 1-pentanol, 1-hexanol,
1-heptanol, 1-octanol, 1-decanol, 1-undecanol, 1-dodecanol,
2-methyl butanol, 3-methyl butanol, a C.sub.10 branched alcohol, or
a mixture of two or more thereof.
[0018] In any of the above-indicated embodiments, the unsaturated
linear aliphatic carboxylic acid methyl ester comprises methyl
9-dodecenoate and the monohydric alcohol comprises 1-pentanol.
[0019] In any of the above-indicated embodiments, the unsaturated
linear aliphatic carboxylic acid methyl ester is derived from a
natural product. The natural product may comprise vegetable oil,
algae oil, fungus oil, animal oil, animal fat, sucrose, lactose,
glucose, fructose, canola oil, rapeseed oil, coconut oil, corn oil,
cottonseed oil, olive oil, palm oil, peanut oil, safflower oil,
sesame oil, soybean oil, sunflower seed oil, tall oil, linseed oil,
palm kernel oil, tung oil, jatropha oil, mustard oil, camellina
oil, pennycress oil, castor oil, coriander oil, almond oil, wheat
germ oil, bone oil, lard, tallow, poultry fat, algae oil, yellow
grease, fish oil, sugar cane, sugar beet, corn syrup, or a mixture
of two or more thereof.
[0020] In some embodiments, the disclosure provides compositions
comprising a triester compound of the following formula
##STR00001##
wherein each R is independently a C.sub.3-12 alkyl. In some
embodiments, each R is independently C.sub.5-10 alkyl. In some
embodiments, each R is independently propyl, butyl, pentyl, hexyl,
heptyl, octyl, decyl, undecyl, dodecyl, 2-methylbutyl,
3-methylbutyl, or a branched C.sub.10 alkyl. In some embodiments,
each R is pentyl. In some other embodiments, each R is decyl. In
some other embodiments, each R is 3-methylbutyl. In some other
embodiments, each R is 2-methylbutyl. In some other embodiments,
each R is branched C.sub.10 alkyl. In some other embodiments, each
R is hexyl. In some other embodiments, each R is octyl.
[0021] These compositions may be useful as additives as well as
base stocks for lubricant compositions and/or functional fluid
compositions. Because these compositions may be derived from
natural products, they may be classified as renewable materials.
This technology may be referred to as "green" technology.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is a flow sheet illustrating a process within the
scope of the invention for reacting an unsaturated linear aliphatic
carboxylic acid methyl ester with maleic anhydride to form a
maleinized unsaturated carboxylic acid methyl ester. The maleinized
unsaturated carboxylic acid methyl ester may be referred to as a
maleinized ester intermediate.
[0023] FIG. 2 is a flow sheet illustrating a process within the
scope of the invention for esterifying a maleinized unsaturated
carboxylic acid methyl ester (or maleinized ester
intermediate).
[0024] FIG. 3 is a chart showing conversions for the maleinization
of methyl 9-dodecenoate at reaction temperatures of 195.degree. C.,
205.degree. C., 215.degree. C. and 230.degree. C. over a reaction
period of 12 hours.
[0025] FIG. 4 is a chart showing acid value plots for reactions of
maleinized methyl 9-dodecenoate with 1-pentanol.
[0026] FIG. 5 is a schematic illustration of the test apparatus
used in Example 9.
DETAILED DESCRIPTION
[0027] All ranges and ratio limits disclosed in the specification
and claims may be combined in any manner. It is to be understood
that unless specifically stated otherwise, references to "a," "an,"
and/or "the" may include one or more than one, and that reference
to an item in the singular may also include the item in the
plural.
[0028] The phrase "and/or" should be understood to mean "either or
both" of the elements so conjoined, i.e., elements that are
conjunctively present in some cases and disjunctively present in
other cases. Other elements may optionally be present other than
the elements specifically identified by the "and/or" clause,
whether related or unrelated to those elements specifically
identified unless clearly indicated to the contrary. Thus, as a
non-limiting example, a reference to "A and/or B," when used in
conjunction with open-ended language such as "comprising" can
refer, in one embodiment, to A without B (optionally including
elements other than B); in another embodiment, to B without A
(optionally including elements other than A); in yet another
embodiment, to both A and B (optionally including other elements);
etc.
[0029] The word "or" should be understood to have the same meaning
as "and/or" as defined above. For example, when separating items in
a list, "or" or "and/or" shall be interpreted as being inclusive,
i.e., the inclusion of at least one, but also including more than
one, of a number or list of elements, and, optionally, additional
unlisted items. Only terms clearly indicated to the contrary, such
as "only one of" or "exactly one of," or may refer to the inclusion
of exactly one element of a number or list of elements. In general,
the term "or" as used herein shall only be interpreted as
indicating exclusive alternatives (i.e. "one or the other but not
both") when preceded by terms of exclusivity, such as "either,"
"one of," "only one of," or "exactly one of."
[0030] The phrase "at least one," in reference to a list of one or
more elements, should be understood to mean at least one element
selected from any one or more of the elements in the list of
elements, but not necessarily including at least one of each and
every element specifically listed within the list of elements and
not excluding any combinations of elements in the list of elements.
This definition also allows that elements may optionally be present
other than the elements specifically identified within the list of
elements to which the phrase "at least one" refers, whether related
or unrelated to those elements specifically identified. Thus, as a
non-limiting example, "at least one of A and B" (or, equivalently,
"at least one of A or B," or, equivalently "at least one of A
and/or B") can refer, in one embodiment, to at least one,
optionally including more than one, A, with no B present (and
optionally including elements other than B); in another embodiment,
to at least one, optionally including more than one, B, with no A
present (and optionally including elements other than A); in yet
another embodiment, to at least one, optionally including more than
one, A, and at least one, optionally including more than one, B
(and optionally including other elements); etc.
[0031] The transitional words or phrases, such as "comprising,"
"including," "carrying," "having," "containing," "involving,"
"holding," and the like, are to be understood to be open-ended,
i.e., to mean including but not limited to.
[0032] The term "ester group" refers to a chemical group wherein a
carbonyl is adjacent to an ether linkage. The ester group may be
represented by the formula --COOR, wherein R is an alkyl group.
[0033] The term "proximal ester groups" refers to ester groups
attached to the same compound and positioned within no more than
about four carbon atoms from each other. The ester groups formed by
the esterification of a maleic anhydride group may be referred to
as proximal ester groups.
[0034] The term "another ester group" refers to an ester group
attached to a compound that also contains two or more proximal
ester groups, the another ester group not being one of the proximal
ester groups.
[0035] The term "maleinized ester" refers to a product made by the
reaction of an unsaturated carboxylic acid methyl ester with maleic
anhydride. The maleinized ester may be referred to as a maleinized
ester intermediate.
[0036] The term "maleinized ester derivative" refers to a product
made by the reaction of a maleinized ester with a monohydric
alcohol.
[0037] The term "unsaturated linear aliphatic carboxylic acid
methyl ester" refers to a compound represented by the formula
R--COOCH.sub.3, wherein R is an unsaturated linear aliphatic
hydrocarbon group (e.g., an alkenyl group). Examples of the
unsaturated linear aliphatic carboxylic acid methyl esters that may
be used include methyl 8-nonenoate, methyl 9-decenoate, methyl
10-undecenoate, methyl 9-dodecenoate, methyl 9-octadecenoate, or a
mixture of two or more thereof.
[0038] The term "maleic anhydride" refers to a compound represented
by the formula C.sub.2H.sub.2(CO).sub.2O. Maleic anhydride is the
acid anhydride of maleic acid.
[0039] The term "monohydric alcohol" refers to a compound
represented by the formula ROH, wherein R is a aliphatic
hydrocarbon (e.g., alkyl) group. R may be branched or linear. In an
advantageous embodiment, R is linear. Examples of the monohydric
alcohols that may be used include 1-propanol, 1-butanol,
1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol,
1-undecanol, 1-dodecanol, 2-methyl butanol, 3-methyl butanol, a
C.sub.10 branched alcohol, or a mixture of two or more thereof.
[0040] The term "natural product" is used herein to refer to
products of nature, including natural oil, carbohydrates, and the
like.
[0041] The term "natural oil" refers to oils or fats derived from
plants or animals. The term "natural oil" includes natural oil
derivatives, unless otherwise indicated, and such natural oil
derivatives may include one or more natural oil derived unsaturated
carboxylic acids or derivatives thereof. The natural oils may
include vegetable oils, algae oils, fungus oils, animal oils or
fats, tall oils, derivatives of these oils, combinations of two or
more of these oils, and the like. The natural oils may include, for
example, canola oil, rapeseed oil, coconut oil, corn oil,
cottonseed oil, olive oil, palm oil, peanut oil, safflower oil,
sesame oil, soybean oil, sunflower seed oil, linseed oil, palm
kernel oil, tung oil, jatropha oil, mustard oil, camellina oil,
pennycress oil, castor oil, coriander oil, almond oil, wheat germ
oil, bone oil, lard, tallow, poultry fat, yellow grease, fish oil,
mixtures of two or more thereof, and the like. The natural oil
(e.g., soybean oil) may be refined, bleached and/or deodorized.
[0042] The natural product may comprise a refined, bleached and/or
deodorized natural oil, for example, a refined, bleached, and/or
deodorized soybean oil (i.e., RBD soybean oil). Soybean oil may
comprises about 95% by weight or greater (e.g., 99% weight or
greater) triglycerides of fatty acids. The fatty acids in the
soybean oil may include saturated fatty acids, including palmitic
acid (hexadecanoic acid) and stearic acid (octadecanoic acid), and
unsaturated fatty acids, including oleic acid (9-octadecenoic
acid), linoleic acid (9, 12-octadecadienoic acid), and linolenic
acid (9,12,15-octadecatrienoic acid).
[0043] The term "carbohydrate" is used herein to refer to a class
of compounds with the empirical formula C.sub.m(H.sub.2O).sub.n
that comprise carbon, hydrogen and oxygen atoms, with a
hydrogen:oxygen ratio of 2:1. An example is deoxyribose which has
the empirical formula C.sub.5H.sub.10O.sub.4. The carbohydrates
include the saccharides. The saccharides may include:
monosaccharides, disaccharides, oligosaccharides, and
polysaccharides. The monosaccharides and disaccharides may be
referred to as sugars. The sugars, which may be in the form of
crystalline carbohydrates, may include sucrose, lactose, glucose,
fructose, fruit sugar, and the like. These may be obtained from
sugar cane, sugar beet, corn syrup, and the like.
[0044] The term "biodegradable" refers to a material that degrades
to form CO.sub.2 and water.
[0045] The term "metathesis reaction" refers to a catalytic
reaction which involves the interchange of alkylidene units among
compounds containing one or more carbon-carbon 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 between two
different molecules (often referred to as cross-metathesis).
[0046] The term "metathesis catalyst" refers to any catalyst or
catalyst system that catalyzes a metathesis reaction.
Maleinized Ester
[0047] The maleinized ester may be formed by the reaction of an
unsaturated linear aliphatic carboxylic acid methyl ester with
maleic anhydride. The maleinized ester may be referred to as a
maleinized ester intermediate. The maleinized ester derivative may
be formed by reaction of the maleinized ester with a monohydric
alcohol.
[0048] The unsaturated linear aliphatic carboxylic acid methyl
ester may comprise an unsaturated linear aliphatic hydrocarbon
chain (e.g., an alkenyl chain) of from about 8 to about 18 carbon
atoms, or from about 10 to about 14 carbon atoms, or from about 10
to about 12 carbons, or about 12 carbon atoms, with one or more
carbon-carbon double bonds in the hydrocarbon chain. The
unsaturated linear aliphatic carboxylic acid methyl ester may be
monounsaturated or polyunsaturated with, for example, from 1 to
about 4, or 1 to about 3, or 1 or 2, or 1 carbon-carbon double
bonds. When the hydrocarbon chain contains more than one
carbon-carbon double bond, it may be partially hydrogenated to form
a mono-unsaturated compound prior to being maleinized.
[0049] The unsaturated linear aliphatic carboxylic acid methyl
ester may comprise methyl 8-nonenoate, methyl 9-decenoate, methyl
10-undecenoate, methyl 9-dodecenoate, methyl 9-octadecenoate, or a
mixture of two or more thereof.
[0050] The unsaturated linear aliphatic carboxylic acid methyl
ester may be derived from one or more natural products, including
natural oil, carbohydrates, and the like. The unsaturated linear
aliphatic carboxylic acid methyl ester may be derived from an
estolide. The unsaturated linear aliphatic carboxylic acid methyl
ester may be derived from a polyol ester, for example, a
monoglyceride, diglyceride, triglyceride, or a mixture of two or
more thereof.
[0051] The natural product may comprise one or more oils or fats
derived from plants and/or animals. The natural oils may include
vegetable oils, algae oils, fungus oils, animal oils or fats, tall
oils, derivatives of these oils, combinations of two or more of
these oils, and the like. The natural product may comprise one or
more carbohydrates. The natural products may include sucrose,
lactose, glucose, fructose, canola oil, rapeseed oil, coconut oil,
corn oil, cottonseed oil, olive oil, palm oil, peanut oil,
safflower oil, sesame oil, soybean oil, sunflower seed oil, linseed
oil, palm kernel oil, tung oil, jatropha oil, mustard oil,
camellina oil, pennycress oil, castor oil, tall oil, coriander oil,
almond oil, wheat germ oil, bone oil, lard, tallow, poultry fat,
yellow grease, fish oil, bone oil, mixtures of two or more thereof,
and the like. The natural product may be a natural oil (e.g.,
soybean oil) which is refined, bleached and/or deodorized.
[0052] The natural product may comprise soybean oil. Soybean oil
may comprise unsaturated glycerides, for example, in many
embodiments about 95% weight or greater (e.g., 99% weight or
greater) triglycerides. Major fatty acids making up soybean oil may
include saturated fatty acids, palmitic acid (hexadecanoic acid)
and stearic acid (octadecanoic acid), and unsaturated fatty acids,
oleic acid (9-octadecenoic acid), linoleic acid (9,
12-octadecadienoic acid), and linolenic acid
(9,12,15-octadecatrienoic acid). Soybean oil may be a highly
unsaturated vegetable oil with many of the triglyceride molecules
having at least two unsaturated fatty acids. The soybean oil may be
refined, bleached and/or deodorized.
[0053] The unsaturated linear aliphatic carboxylic acid methyl
ester may be derived from a natural product using a metathesis
reaction process. Metathesis is a catalytic reaction that involves
an interchange of alkylidene units among compounds containing one
or more carbon-carbon double bonds (i.e., olefinic compounds). The
reaction mechanism involves cleavage and formation of carbon-carbon
double bonds. Metathesis can occur between two of the same
molecules (often referred to as self-metathesis) and/or it can
occur between two different molecules (often referred to as
cross-metathesis). The self-metathesis process may comprise
reacting a natural product such as a natural oil or natural oil
derived unsaturated carboxylic acid and/or ester in the presence of
a metathesis catalyst to form a metathesized natural product.
[0054] The cross-metathesis process may comprise reacting a natural
product such as a natural or natural oil derivative with another
olefinic compound in the presence of a metathesis catalyst to form
a product mixture containing the desired unsaturated carboxylic
acid methyl ester. The another olefinic compound may be a natural
product, natural oil, natural oil derivative or a short chain
olefin. The short chain olefin may comprise an alpha olefin, an
internal olefin, or a mixture thereof. The internal olefin may be
symmetric or asymmetric. The olefin may comprise one or more of
ethene, propene, 2-butene, 3-hexene, 4-octene, 2-pentene, 2-hexene,
2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene,
4-nonene, ethylene, 1-propene, 1-butene, 1-pentene, 1-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
1-octadecene, 1-eicosene, or a mixture of two or more thereof.
[0055] The catalyst used in the metathesis reaction may be any
catalyst or catalyst system which catalyzes the metathesis
reaction. The metathesis catalyst may be used, alone or in
combination with one or more additional catalysts. Exemplary
metathesis catalysts may include metal carbene catalysts based upon
transition metals, for example, ruthenium, molybdenum, osmium,
chromium, rhenium, and/or tungsten. Examples of metathesis
catalysts and process conditions are described in US 2011/0160472,
incorporated by reference herein in its entirety, except that in
the event of any inconsistent disclosure or definition from the
present specification, the disclosure or definition herein shall be
deemed to prevail. A number of the metathesis catalysts described
in US 2011/0160472 are presently available from Materia, Inc.
(Pasadena, Calif.).
[0056] In some embodiments, the metathesis catalyst includes a
Grubbs-type olefin metathesis catalyst and/or an entity derived
therefrom. In some embodiments, the metathesis catalyst includes a
first-generation Grubbs-type olefin metathesis catalyst and/or an
entity derived therefrom. In some embodiments, the metathesis
catalyst includes a second-generation Grubbs-type olefin metathesis
catalyst and/or an entity derived therefrom. In some embodiments,
the metathesis catalyst includes a first-generation
Hoveyda-Grubbs-type olefin metathesis catalyst and/or an entity
derived therefrom. In some embodiments, the metathesis catalyst
includes a second-generation Hoveyda-Grubbs-type olefin metathesis
catalyst and/or an entity derived therefrom. In some embodiments,
the metathesis catalyst includes one or a plurality of the
ruthenium carbene metathesis catalysts sold by Materia, Inc. of
Pasadena, Calif. and/or one or more entities derived from such
catalysts. Representative metathesis catalysts from Materia, Inc.
for use in accordance with the present teachings include but are
not limited to those sold under the following product numbers as
well as combinations thereof: product no. C823 (CAS no.
172222-30-9), product no. C848 (CAS no. 246047-72-3), product no.
C601 (CAS no. 203714-71-0), product no. C627 (CAS no. 301224-40-8),
product no. C571 (CAS no. 927429-61-6), product no. C598 (CAS no.
802912-44-3), product no. C793 (CAS no. 927429-60-5), product no.
C801 (CAS no. 194659-03-9), product no. C827 (CAS no. 253688-91-4),
product no. C884 (CAS no. 900169-53-1), product no. C833 (CAS no.
1020085-61-3), product no. C859 (CAS no. 832146-68-6), product no.
C711 (CAS no. 635679-24-2), product no. C933 (CAS no.
373640-75-6).
[0057] In some embodiments, the metathesis catalyst includes a
molybdenum and/or tungsten carbene complex and/or an entity derived
from such a complex. In some embodiments, the metathesis catalyst
includes a Schrock-type olefin metathesis catalyst and/or an entity
derived therefrom. In some embodiments, the metathesis catalyst
includes a high-oxidation-state alkylidene complex of molybdenum
and/or an entity derived therefrom. In some embodiments, the
metathesis catalyst includes a high-oxidation-state alkylidene
complex of tungsten and/or an entity derived therefrom. In some
embodiments, the metathesis catalyst includes molybdenum (VI). In
some embodiments, the metathesis catalyst includes tungsten (VI).
In some embodiments, the metathesis catalyst includes a molybdenum-
and/or a tungsten-containing alkylidene complex of a type described
in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,
4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem.
Rev., 2009, 109, 3211-3226, each of which is incorporated by
reference herein in its entirety, except that in the event of any
inconsistent disclosure or definition from the present
specification, the disclosure or definition herein shall be deemed
to prevail.
[0058] The product produced by the metathesis reaction may comprise
one or more unsaturated carboxylic acids and/or esters. These may
include glycerides and free fatty acids and/or esters. The acids
and/or esters may be used as a source for the unsaturated
carboxylic acid methyl esters of the present invention. In an
embodiment, further processing may target, for example,
C.sub.8-C.sub.18 fatty acid methyl esters. These may include methyl
8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate, methyl
9-dodecenoate, methyl 9-octadecenoate, or a mixture of two or more
thereof.
[0059] The natural product and/or natural product derived
unsaturated carboxylic acid and/or ester may be partially
hydrogenated prior to undergoing the metathesis reaction. Multiple
unsaturated bonds within a polyunsaturated reactant provide
multiple reaction sites. Multiple reaction sites may increase the
chemical identity of the reaction products, which in turn may
increase the complexity of the product composition. Multiple
reaction sites within the reactants may also increase catalyst
demand for the reaction. These factors may increase the overall
complexity and inefficiency of the reaction process. More efficient
reaction processes that can reduce catalyst demand and reduce
complexity of the reaction product compositions may be provided by
partially hydrogenating polyunsaturated reactants in the starting
material prior to conducting the metathesis reaction process.
[0060] The unsaturated linear aliphatic carboxylic acid methyl
esters may be partially hydrogenated prior to being reacted with
the maleic anhydride to form the maleinized esters.
[0061] The hydrogenation reactions, as well as the metathesis
reactions, and catalysts for such reactions, that may be used are
described in more detail in U.S. patent publication
2012-0264664A1.
[0062] The reaction between the unsaturated linear aliphatic
carboxylic acid methyl ester and the maleic anhydride to form the
maleinized ester may be a thermal reaction conducted without a
catalyst, or it may be a catalytic reaction. The catalyst may
comprise a dialkylperoxide, or a Lewis acid such as AlCl.sub.3. The
reaction temperature may be in the range from about 100.degree. C.
to about 300.degree. C., or from about 150.degree. C. to about
250.degree. C., or from about 195.degree. C. to about 240.degree.
C., or about 220.degree. C. to about 240.degree. C., or about
230.degree. C. Lab studies for the maleinization of methyl
9-dodecenoate at reaction temperatures of 195.degree. C.,
205.degree. C., 215.degree. C. and 230.degree. C. are shown in FIG.
3. A useful temperature for the maleinization of methyl
9-dodecenoate is 230.degree. C. with a reaction time of 8
hours.
[0063] The molar ratio of equivalents of the unsaturated linear
aliphatic carboxylic acid methyl ester to equivalents of the maleic
anhydride may be from about 0.5:1 to about 4:1, or from about 1:1
to about 2:1. The weight of an equivalent of an unsaturated linear
aliphatic carboxylic acid methyl ester as well as maleic anhydride
is dependent on the number of carbon-carbon double bonds in the
molecular structure of the compounds. For example, one mole of an
unsaturated linear aliphatic carboxylic acid methyl ester having
one carbon-carbon double bond in its molecular structure would have
an equivalent weight equal to its molecular weight. Maleic
anhydride, with one carbon-carbon double bond, has a equivalent
weight equal to its molecular weight.
[0064] The amount of catalyst added to the reaction, when used, may
be up to about 15 percent by weight of the unsaturated linear
aliphatic carboxylic acid methyl ester, or from about 5 to about 15
percent by weight, or from about 5 to about 10 percent by
weight.
[0065] The reaction may be conducted in an inert atmosphere, for
example, a nitrogen atmosphere. The time of reaction may range from
about 1 to about 24 hours, or from about 6 to about 18 hours, or
from about 10 to about 16 hours, or about 8 hours.
[0066] Following the reaction, the product mixture may be subjected
to isolation of the crude material. The crude material may be
subjected to a vacuum to separate undesired volatile materials from
the product which may be referred to as a maleinized ester.
[0067] The maleinized ester may comprise the product made by the
reaction of maleic anhydride with an unsaturated linear aliphatic
carboxylic acid methyl ester comprising methyl 8-nonenoate, methyl
9-decenoate, methyl 10-undecenoate, methyl 9-dodecenoate, methyl
9-octadecenoate, or a mixture of two or more thereof.
[0068] The maleinization of an unsaturated linear aliphatic
carboxylic acid methyl ester to form a maleinized ester within the
scope of the invention is shown below. The specific reaction that
is shown is for the maleinization of methyl 9-dodecenoate. Some
di-maleinization of the mono-maleinized materials may occur by the
addition of a second maleic anhydride molecule to the
mono-maleinized material. This reaction may produce about 3-5 wt %
of the di-maleinized material in the reaction mixture. Isomers for
the ene reaction that are believed to form are shown, however the
9,10 di-substitution may not occur for steric hindrance reasons and
the isomer shown with a terminal double bond may be energetically
unlikely.
##STR00002##
Maleinized Ester Derivative
[0069] The maleinized ester derivative of the invention may be made
by reacting the above-indicated maleinized ester with a monohydric
alcohol. The monohydric alcohol may be linear or branched. In an
advantageous embodiment, the alcohol is linear. The monohydric
alcohol may contain 3 to about 12 carbon atoms, or 3 to about 10
carbon atoms, or 3 to about 8 carbon atoms, or about 5 to about 10
carbon atoms, or about 5 carbon atoms. The monohydric alcohol may
comprise 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol,
1-octanol, 1-decanol, 1-undecanol, 1-dodecanol, 2-methyl butanol,
3-methyl butanol, a C.sub.10 branched alcohol, or a mixture of two
or more thereof.
[0070] The ratio of C.dbd.O groups in the maleinized ester to --OH
groups in the monohydric alcohol may be from about 1 to about 6, or
from about 1 to about 3, or from about 1 to about 2, or about
1.
[0071] The reaction between the maleinized ester and the monohydric
alcohol may be carried out in the presence of a catalyst. The
catalyst may be a Lewis acid or a Bronsted acid. These may include
one or more sulfonic acids. The catalyst may comprise methane
sulfonic acid. The reaction may be enhanced by heating the reaction
mixture to a temperature in the range from about 100.degree. C. to
about 250.degree. C., or from about 100.degree. C. to about
200.degree. C., or from about 150.degree. C. to about 200.degree.
C., or from about 160.degree. C. to about 170.degree. C.
[0072] The amount of catalyst added to the reaction may be from
about 0.5 percent by weight to about 10 percent by weight of the
maleinized ester, or from about 2 to about 4 percent by weight, or
3 percent by weight.
[0073] The reaction may be conducted in an inert atmosphere, for
example, a nitrogen atmosphere. The time of reaction may range from
about 4 to about 12 hours, or from about 6 to about 12 hours, or
from about 8 to about 10 hours.
[0074] The reaction may be conducted at a pressure above
atmospheric pressure, for example, in a stainless steel reactor
with a back-pressure regulator. The internal pressure of the
reaction may range from a gauge pressure of about 0 to about 60
psig (about 0 to about 414 kilopascals), or from about 30 to about
50 psig (about 207 to about 345 kilopascals), or about 45 psig
(about 310 kilopascals).
[0075] The maleinized ester derivative formed by the reaction of
the maleinized ester with the monohydric alcohol may comprise a
triester. The triester may comprise a mono-triester, or a mixture
of a mono-triester and a di-triester. The maleinized ester
derivative can have up to three ester groups on the mono-maleinized
molecules and up to five ester groups on the di-maleinized
molecules.
[0076] The mechanism for the reaction of the maleinized ester with
the monohydric alcohol may involve three reactions. The first
reaction takes place with the anhydride ring opening and forming a
half ester which includes an ester group and a free carboxylic acid
group. The free carboxylic acid group then reacts with the alcohol
and forms a diester. In addition, transesterification of the methyl
ester group with the monohydric alcohol results in the formation of
a triester. Representative structures for the reaction of
maleinized methyl 9-dodecenoate and 1-pentanol are shown below.
##STR00003##
[0077] The initial ring opening reaction with the monohydric
alcohol may produce no byproducts. The esterification of the
carboxylic acid with the monohydric alcohol is a reversible
reaction and produces water as a byproduct. The water is removed in
order to shift the equilibrium to the ester and reduce the overall
acidity of the product. The transesterification of the methyl ester
with the monohydric alcohol produces methanol as a byproduct. This
reaction is also reversible. The methanol is removed in order to
drive the reaction towards the monohydric alcohol ester. The
esterification and transesterification reactions may be driven to
completion by using an excess of the monohydric alcohol and by
removing the byproducts of reaction, water and methanol.
[0078] The progress of the reaction may be monitored by measuring
the acid value (AV) of the reaction mixture. For example, AV plots
for the reaction of maleinized methyl 9-dodecenoate and 1-pentanol
are shown in FIG. 4.
[0079] The maleinized ester derivatives formed by the reaction of
maleinized esters with monohydric alcohols may be partially or
fully hydrogenated to accommodate end use requirements. The
hydrogenation process that may be used is described in U.S. patent
publication 2012-0264664A1.
Lubricants and Functional Fluids
[0080] The lubricant and/or functional fluid compositions of the
invention may comprise one or more of the above-identified
maleinized ester derivatives. These derivatives may be useful as
viscosity modifiers, solubility improvers, performance boosters,
and the like, as well as base oils. These derivatives, when used as
base oils, may be referred to as functional base oils. These
derivatives may be blended with one or more conventional base
oils.
[0081] The lubricant compositions may be effective as engine oil or
crankcase lubricating oils for spark-ignited and
compression-ignited internal combustion engines, including
automobile and truck engines, two-stroke cycle engines, aviation
piston engines, marine and diesel engines, stationary gas engines,
and the like. The lubricant compositions may comprise engine oils.
The functional fluids may comprise a driveline fluid such as an
automatic transmission fluid, manual transmission fluid, transaxle
lubricant, fluid for continuously variable transmissions, dual
clutch automatic transmission fluid, farm tractor fluid, fluids for
hybrid vehicle transmission, or gear oil. The functional fluid may
comprise a metal-working lubricant, hydraulic fluid, or other
lubricating oil or grease composition.
[0082] The maleinated ester derivatives may be biodegradable and
may be used as functional base oils. The functional base oil may
have a kinetic viscosity (ASTM D-445) in the range from about 2 to
about 1000 cSt at 100.degree. C., or from about 2 to about 500, or
from about 2 to about 100, or from about 4 to about 10 cSt. The
base oil may have a viscosity up to about 35 cSt at 100.degree. C.,
or in the range from about 3 to about 35 cSt, or in the range from
about 5 to about 35 cSt at 100.degree. C.
[0083] The functional base oil may have a viscosity index (ASTM
D2270) in the range from about 120 to about 250, or from about 130
to about 170.
[0084] The functional base oil may have a pour point (ASTM D97) in
the range from about -20 to about -70.degree. C., or from about -30
to about -45.degree. C., or about -40.degree. C.
[0085] The functional base oil may have an aniline point (ASTM
D611) in the range from about 25 to about 120.degree. C., or from
about 50 to about 100.degree. C.
[0086] The functional base oil may have oxidation induction time
(ASTM D6186) at 210.degree. C. in the range from about 1 to about
10 minutes, or from about 1 to about 3 minutes, or from about 5 to
about 10 minutes.
[0087] The functional base oil may have an oxidation onset
temperature (ASTM E2009) in the range from about 170.degree. C. to
about 220.degree. C., or from about 190.degree. C. to about
210.degree. C.
[0088] The cold crank simulator viscosity test values (ASTM D5293)
for the functional base oil may be in the range from about 13000 to
about 9500 cP, or from about 7000 to about 9500 cP, at a
temperature of -15.degree. C.; or in the range from about 7000 to
about 6600 cP, or from about 1000 to about 6200 cP, at a
temperature of -35.degree. C.
[0089] The evaporation loss (ASTM D5293) for the functional base
oils may be in the range from about 5 to about 15%, or from about 4
to about 7%.
[0090] The functional base oils may exhibit enhanced values for
high temperature shear stability, fuel economy, deposit control,
oxidative stability, thermal stability, and the like.
[0091] The functional base oil may be used alone as the base oil or
may be blended with an American Petroleum Institute (API) Group I,
II, III, IV or V base oil, a natural oil, an estolide fluid, or a
mixture of two or more thereof. Examples of the natural oil may
include soybean oil, rapeseed oil, and the like. The blended base
oil may contain from about 1% to about 75%, or from about 5% to
about 60% by weight of the maleinized ester derivative.
[0092] The API Group I-V base oils have the following
characteristics:
TABLE-US-00001 Base Oil Category Sulfur (%) Saturates (%) Viscosity
Index Group I >0.03 and/or <90 80 to 120 Group II
.ltoreq.0.03 and .gtoreq.90 80 to 120 Group III .ltoreq.0.03 and
.gtoreq.90 .gtoreq.120 Group IV All polyalphaolefins (PAO) Group V
All others not included in Groups I, II, III, or IV
The Group I-Ill base oils are mineral oils.
[0093] The base oil may be present in the lubricant or functional
fluid composition at a concentration of greater than about 60% by
weight based on the overall weight of the lubricant or functional
fluid composition, or greater than about 65% by weight, or greater
than about 70% by weight, or greater than about 75% by weight.
[0094] When the maleinated ester derivatives are blended with
polyalphaolefins to make up the base oil, the maleinated ester
derivatives may comprise from about 10% to about 80%, or from about
20% to about 60%, or about 30% by weight of the base oil.
[0095] The polyalphaolefins blended with the maleinated ester
derivates to make up the functional base oil may comprise any API
Group IV polyalphaolefin. These may include poly(1-hexene),
poly(1-octene), poly(1-decene), mixtures of two or more thereof,
and the like. The polyalphaolefin may comprise a PAO-4, PAO-8,
PAO-12, PAO-20, or a mixture of two or more thereof. The term
"PAO-4" refers to a polyalphaolefin with a kinematic viscosity at
100.degree. C. of about 4 (typically about 3 to 5) mm.sup.2/s as
determined by Test Method GB/T265. The term "PAO-8" refers to a
polyalphaolefin with a kinematic viscosity at 100.degree. C. of
about 8 (typically about 7 to 9) mm.sup.2/s. The term "PAO-12"
refers to a polyalphaolefin with a kinematic viscosity at
100.degree. C. of about 12 (typically about 11 to 13) mm.sup.2/s.
The term "PAO-20" refers to a polyalphaolefin with a kinematic
viscosity at 100.degree. C. of about 20 mm.sup.2/s.
[0096] The lubricant or functional fluid may further comprise one
or more dispersants and/or detergents. The dispersant may be
present in the lubricant or functional fluid composition at a
concentration in the range from about 0.01 to about 20% by weight,
or from about 0.1 to about 15% by weight based on the weight of the
lubricant or functional fluid. The detergent may be present in the
lubricant or functional fluid composition at a concentration in the
range from about 0.01% by weight to about 50% by weight, or from
about 1% by weight to about 30% by weight based on the weight of
the lubricant or functional fluid composition. The detergent may be
present in an amount suitable to provide a TBN (total base number)
in the range from about 2 to about 100 to the lubricant
composition, or from about 3 to about 50. TBN is the amount of acid
(perchloric or hydrochloric) needed to neutralize all or part of a
material's basicity, expressed as milligrams of KOH per gram of
sample.
[0097] The detergent may include one or more overbased materials
prepared by reacting an acidic material (typically an inorganic
acid or lower carboxylic acid, such as carbon dioxide) with a
mixture comprising an acidic organic compound, a reaction medium
comprising at least one inert, organic solvent (mineral oil,
naphtha, toluene, xylene, etc.) for said acidic organic material, a
stoichiometric excess of a metal base, and a promoter such as a
calcium chloride, acetic acid, phenol or alcohol. The acidic
organic material may have a sufficient number of carbon atoms to
provide a degree of solubility in oil. The metal may be zinc,
sodium, calcium, barium, magnesium, or a mixture of two or more
thereof. The metal ratio may be from an excess of 1 to about 40, or
in the range from about 1.1 to about 40. These detergents may
include overbased sulfonates, overbased phenates, mixtures thereof,
and the like.
[0098] The dispersant that may be used may include any dispersant
known in the art which may be suitable for the lubricant or
functional fluid compositions of this invention. These may
include:
[0099] (1) Reaction products of carboxylic acids (or derivatives
thereof), with nitrogen containing compounds such as amines,
hydroxy amines, organic hydroxy compounds such as phenols and
alcohols, and/or basic inorganic materials. These may be referred
to as carboxylic dispersants. These may include succinimide
dispersants, such as polyisobutenylsuccinimide.
[0100] (2) Reaction products of relatively high molecular weight
aliphatic or alicyclic halides with amines, for example,
polyalkylene polyamines. These may be referred to as "amine
dispersants."
[0101] (3) Reaction products of alkylphenols with aldehydes (e.g.,
formaldehyde) and amines (e.g., polyalkylene polyamines), which may
be referred to as "Mannich dispersants."
[0102] (4) Products obtained by post-treating the carboxylic, amine
or Mannich dispersants with such reagents as urea, thiourea, carbon
disulfide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, nitriles, epoxides,
boron compounds, phosphorus compounds or the like.
[0103] (5) Interpolymers of oil-solubilizing monomers such as decyl
methacrylate, vinyl decyl ether and high molecular weight olefins
with monomers containing polar substituents, e.g., aminoalkyl
acrylates or acrylamides and poly-(oxyethylene)-substituted
acrylates. These may be referred to as "polymeric dispersants."
[0104] The lubricant or functional fluid composition may further
comprise one or more additional functional additives, including,
for example, one or more corrosion-inhibiting agents,
oxidation-inhibiting agents, pour point depressing agents, extreme
pressure (EP) agents, antiwear agents, viscosity index (VI)
improvers, friction modifiers (e.g., fatty friction modifiers),
hindered amine, phenolic and/or sulfurized inhibitors,
antioxidants, metal cutting additives (e.g., sulfur chloride),
antimicrobial additives, color stabilizers, viscosity modifiers
(e.g., ethylene propylene diene (EPDM) viscosity modifiers),
demulsifiers, seal swelling agents, anti-foam agents, mixtures of
two or more thereof, and the like.
[0105] Extreme pressure (EP) agents and corrosion and
oxidation-inhibiting agents which may be included in the lubricants
and/or functional fluids of the invention, may include chlorinated
aliphatic hydrocarbons such as chlorinated wax; organic sulfides
and polysulfides such as benzyl disulfide,
bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl
ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene,
and sulfurized terpene; phosphosulfurized hydrocarbons such as the
reaction product of a phosphorus sulfide with turpentine or methyl
oleate, phosphorus esters including principally dihydrocarbyl and
trihydrocarbyl phosphites such as dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphite, pentylphenyl phosphite,
dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite,
dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite,
polypropylene (molecular weight 500)-substituted phenyl phosphite,
diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such
as zinc dioctyldithiocarbamate, and barium heptylphenyl
dithiocarbamate; Group II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithioate, zinc dioctyl phosphorodithioate,
barium di(heptylphenyl)phosphorodithioate, cadmium dinonyl
phosphorodithioate, and the zinc salt of a phosphorodithioic acid
produced by the reaction of phosphorus pentasulfide with an
equimolar mixture of isopropyl alcohol and n-hexyl alcohol.
[0106] Many of the above-mentioned extreme pressure agents and
corrosion-oxidation inhibitors may also serve as antiwear agents.
Zinc dialkyl phosphorodithioates are examples of such
multifunctional additives.
[0107] Pour point depressants may be used to improve low
temperature properties of the oil-based compositions. Examples of
useful pour point depressants may include polymethacrylates;
polyacrylates; polyacrylamides; condensation products of
haloparaffin waxes and aromatic compounds; vinyl carboxylate
polymers; and terpolymers of dialkyl fumarates, vinyl esters of
fatty acids, alkyl vinyl ethers, or mixtures of two or more
thereof.
[0108] The viscosity modifiers may include one or more
polyacrylates, polymethacrylates, polyolefins, and/or
styrene-maleic ester copolymers.
[0109] Anti-foam agents may be used to reduce or prevent the
formation of stable foam. The anti-foam agents may include
silicones, organic polymers, and the like.
[0110] The lubricant or functional fluid may include one or more
thickeners to provide the lubricant or functional fluid with a
grease-like consistency. The thickener may comprise lithium
hydroxide, lithium hydroxide monohydrate, or a mixture thereof. The
thickener may comprise 9-decenoic acid diol.
[0111] The functional additives may be added directly to the
lubricant or functional fluid composition. Alternatively, the
additives may be diluted with a substantially inert, normally
liquid organic diluent such as mineral oil, naphtha, benzene,
toluene or xylene, to form an additive concentrate, which may then
be added to the lubricant and/or functional fluid. The functional
additives may include the maleinized ester derivatives of the
invention. These concentrates may contain from about 0.1 to about
99%, or from about 10% to about 90% by weight, of one or more of
the additives. The remainder of the concentrate may comprise the
substantially inert normally liquid diluent.
[0112] The following examples are provided to illustrate the
invention.
EXAMPLE 1
[0113] 0.355 kg (4.03 mol) 1-pentanol is charged to a reaction
flask that is equipped with a thermocouple, addition funnel,
nitrogen inlet, magnetic stirrer, and short-path distillation
bridge. The alcohol is heated to 110.degree. C. and methanesulfonic
acid (1.5 mL, 70% aqueous solution) is added. Maleinized methyl
9-dodecenoate (0.32 kg, AV=420 mg KOH/g) is added dropwise using
the addition funnel. The term "AV" refers to acid value. A reaction
occurs. A terniary mixture of water, methanol and pentanol is
removed via distillation. After the addition of the methyl
9-dodecenoate is completed the resulting reaction mixture is heated
to 120.degree. C. for an additional hour. The AV is monitored to
observe the reaction progress, which is about 20. The temperature
is further increased to remove excess 1-pentanol and obtain an
AV<2. The reaction mixture is allowed to cool to room
temperature and vacuum (2 torr) is applied to remove residual water
and alcohol. The temperature is stepwise increased to 160.degree.
C. to remove all volatiles. The remaining ester product is filtered
over a bed of silica (1 inch (2.54 cm) fritted funnel) by applying
vacuum. The filtration yields a golden to amber oil. The amount of
desired product is 0.38 kg (71% yield). KV (100.degree. C.)=5.0
cSt; KV (40.degree. C.)=24.73 cSt; and viscosity index
(VI)=128.
EXAMPLE 2
[0114] Maleinized methyl 9-dodecenoate (50 g, 0.16 mol), 1-decanol
(90.2 g, 0.58 mol), p-toluenesulfonic acid (1.5 g, 0.008 mol) and
50 milliliters (ml) of toluene are added to a one-liter,
three-necked round-bottom flask at 23.degree. C. under an air
atmosphere. The flask is fitted with a thermocouple temperature
regulator with heating mantle, Dean-Stark trap with condenser, and
a stopper with a nitrogen needle inlet. Nitrogen gas is passed
through the needle inlet into the head space of the apparatus (flow
rate=2.5 ft.sup.3/hr (70.8 liters/hr)) for 10 minutes. The
temperature is increased to 115.degree. C. After 60 minutes, the
temperature is increased to 120.degree. C. After an additional 90
minutes, the temperature is increased to 130.degree. C.
Approximately 12.8 ml of distillate is collected in the Dean-Start
trap. An aliquot of the reaction mixture is taken at 4 hours into
the reaction and measured for AV=2.3 mg KOH/g. The reaction mixture
is stirred for another 2.5 hours (total reaction time 6.5 hours).
The heating source is removed and the reaction mixture is allowed
to cool to ambient temperature. Ethyl acetate (200 ml) is used to
wash the reaction mixture using a separatory funnel. The resulting
organic layer is washed with a NaOH solution (0.97 g NaOH in 480 ml
H.sub.2O) followed by washing with a saturated NaCl solution three
times. The resulting organic solution is concentrated by a rotorary
evaporator (5 Torr, 60.degree. C.) to remove ethyl acetate and
excess alcohol. A triester product is separated from residual
alcohol and water by vacuum distillation (2 Torr, 25.degree. C. to
135.degree. C.). The triester product is in the form of a clear
dark amber oil. Analysis of the product indicates a mass of 112 g;
a yield of 94%; KV (100.degree. C.)=8.05 cSt; KV (40.degree.
C.)=44.4 cSt; and viscosity index (VI)=152.
EXAMPLE 3
[0115] Maleinized methyl 9-dodecenoate (100 g, 0.32 mol),
3-methylbutanol (125 g, 1.42 mol), p-toluenesulfonic acid (3 g,
0.015 mol) and 100 milliliters (ml) of toluene are added to a
one-liter, three-necked round-bottom flask at 23.degree. C. under
an air atmosphere. The flask is fitted with a thermocouple
temperature regulator with heating mantle, Dean-Stark trap with
condenser, and a stopper with a nitrogen needle inlet. Nitrogen gas
is passed through the needle inlet into the head space of the
apparatus (flow rate=2.5 ft.sup.3/hr (70.8 liters/hr)) for 10
minutes. The temperature is increased to 115.degree. C. After 60
minutes, the temperature is increased to 120.degree. C. After an
additional 90 minutes, the temperature is increased to 130.degree.
C. Approximately 12.8 ml of distillate is collected in the
Dean-Start trap. An aliquot of the reaction mixture is taken at 4
hours into the reaction and measured for AV with the result being a
AV of 7.6. The reaction mixture is stirred for another 2.5 hours
(total reaction time 6.5 hours). The heating source is removed and
the reaction mixture is allowed to cool to ambient temperature.
Ethyl acetate (200 ml) is used to wash the reaction mixture using a
separatory funnel. The resulting organic layer is washed with a
NaOH solution (0.97 g NaOH in 480 ml H.sub.2O) followed by washing
with a saturated NaCl solution three times. The resulting organic
solution is concentrated by a rotorary evaporator (5 Torr,
60.degree. C.) to remove ethyl acetate and excess alcohol. A
triester product is separated from residual alcohol and water by
vacuum distillation (2 Torr, 25.degree. C. to 135.degree. C.). The
triester product is in the form of a clear dark amber oil. Analysis
of the product indicates a mass of 147.9 g; a yield of 88%; KV
(100.degree. C.)=5.8 cSt; KV (40.degree. C.)=33.5 cSt; and
viscosity index (VI)=115.
EXAMPLE 4
[0116] 0.741 kg (8.4 mol) 2-methylbutanol is charged to a reaction
flask that is equipped with a thermocouple, addition funnel,
nitrogen inlet, magnetic stirrer, and short-path distillation
bridge. The alcohol is heated to 110.degree. C. and methanesulfonic
acid (3.0 mL, 70% aqueous solution) is added. Maleinized methyl
9-dodecenoate (0.8 kg, AV=420 mg KOH/g) is added dropwise using the
addition funnel. A reaction occurs. A terniary mixture of water,
methanol, and reactant alcohol is removed via distillation. After
the addition is completed the resulting reaction mixture is heated
to 120.degree. C. for an additional hour. The AV is monitored to
observe the reaction progress, which is about 20. The temperature
is further increased to remove excess 2-methylbutanol and obtain an
AV<2. The reaction mixture is allowed to cool to room
temperature and vacuum (2 torr) is applied to remove residual water
and alcohol. The temperature is stepwise increased to 160.degree.
C. to remove all volatiles. The remaining ester product is filtered
over a bed of silica (1 inch (2.54 cm), fritted funnel) by applying
vacuum. The filtration yields a golden to amber oil. The amount of
desired product is 0.877 kg (65% yield). KV (100.degree. C.)=5.99
cSt; KV (40.degree. C.)=37.58 cSt; and viscosity index
(VI)=102.
EXAMPLE 5
[0117] Maleinized methyl 9-dodecenoate (100 g, 0.32 mol), Exxal10
((C.sub.10 branched alcohol from ExxonMobil), 179.2 g, 1.13 mol),
p-toluenesulfonic acid (3 g, 0.015 mol) and 100 milliliters (ml) of
toluene are added to a one-liter, three-necked round-bottom flask
at 23.degree. C. under an air atmosphere. The flask is fitted with
a thermocouple temperature regulator with heating mantle,
Dean-Stark trap with condenser, and a stopper with a nitrogen
needle inlet. Nitrogen gas is passed through the needle inlet into
the head space of the apparatus (flow rate=2.5 ft.sup.3/hr (70.8
liters/hr)) for 10 minutes. The temperature is increased to
115.degree. C. After 60 minutes, the temperature is increased to
120.degree. C. After an additional 90 minutes, the temperature is
increased to 130.degree. C. Approximately 12.8 ml of distillate is
collected in the Dean-Start trap. An aliquot of the reaction
mixture is taken at 4 hours into the reaction and measured for AV
with the result being a TAN of 7.6. The reaction mixture is stirred
for another 2.5 hours (total reaction time 6.5 hours). The heating
source is removed and the reaction mixture is allowed to cool to
ambient temperature. Ethyl acetate (200 ml) is used to wash the
reaction mixture using a separatory funnel. The resulting organic
layer is washed with a NaOH solution (0.97 g NaOH in 480 ml
H.sub.2O) followed by washing with a saturated NaCl solution three
times. The resulting organic solution is concentrated by a rotorary
evaporator (5 Torr, 60.degree. C.) to remove ethyl acetate and
excess alcohol. A triester product is separated from residual
alcohol and water by vacuum distillation (2 Torr, 25.degree. C. to
135.degree. C.). The triester product is in the form of a clear
dark amber oil. Analysis of the product indicates a mass of 149 g;
a yield of 63%; KV (100.degree. C.)=10.4 cSt; KV (40.degree.
C.)=79.9 cSt; and viscosity index (VI)=113.
[0118] Samples of products from Examples 1 to 5 are tested for
viscosity index or VI (ASTM D2270) with the results indicated in
Table 1.
TABLE-US-00002 TABLE 1 Example Alcohol Viscosity Index 1 1-Pentanol
128 2 1-Decanol 152 3 3-Methylbutanol 115 4 2-Methylbutanol 102 5
Exxal 10 (C.sub.10 branched 113 alcohol)
EXAMPLE 6
[0119] Maleinized methyl 9-dodecenoate is made by the reaction of
methyl 9-dodecenoate and maleic anhydride via an "Ene" reaction.
The maleinized methyl 9-dodecenoate is then reacted with 1-pentanol
in the presence of methane sulfonic acid in an
esterification/transesterification reaction to form a mixture of a
mono-triester and a di-triester. The following reactants and
catalyst are used:
TABLE-US-00003 Name CAS # Methyl 9-dodecenoate 39202-17-0 Maleic
anhydride 108-31-6 1-Pentanol 71-41-0 Methanesulfonic acid
75-75-2
Step 1:
[0120] The apparatus for conducting the maleinization reaction
process includes a reactor, stripper and filter. A flow sheet for
the process is shown in FIG. 1. A fresh feed containing methyl
9-dodecenoate and maleic anhydride is added to the reactor, heated
to 75-90.degree. C. and agitated to melt the maleic anhydride and
mix it into the methyl 9-dodeconate. The reaction temperature is
220.degree. C.-240.degree. C. The pressure in the reactor is
approximately 30 psig (206.8 kilopascals). The reaction mixture is
stripped in the stripper at a temperature of 200.degree. C. and a
pressure of <2 Torr. The desired product, which is in the form
of a maleinized ester intermediate, is separated from the unreacted
reactants (and some intermediate), and filtered. The unreacted
reactants are recycled to the reactor. A material balance for Step
1 of the process is as follows (all numerical values being in
kilograms):
TABLE-US-00004 Fresh Feed Recycle Product Methyl 9-dodecenoate
519.7 168.2 8.4 Maleic anhydride 256.3 120 -- Mono-maleinized --
28.9 730 methyl 9-dodecenoate Di-maleinized methyl -- -- 35.6
9-dodecenoate
Step 2:
[0121] The esterification reaction process is conducted using the
process illustrated in FIG. 2. The apparatus for conducting the
esterification process includes a reactor and a stripper. The
reactor is setup with an overhead system able to collect 5-10
liters of overhead condensate. The process includes three separate
reactions, namely, an anhydride ring opening reaction, an
esterification reaction with the maleic anhydride group, and a
transesterification reaction where the 1-pentanol replaces the
methyl ester group. 1-Pentanol (31.0 Kg) and methanesulfonic acid
(0.253 Kg) are loaded into the reactor and heated to 110.degree. C.
with agitation. The maleinized ester intermediate from Step 1 (27.3
Kg) is added over a 30 minute period. After the maleinized ester
intermediate is added, the reactor is closed up and the nitrogen
sparge is set at 140 ml/min. The internal pressure is controlled
and regulated at 45 psig (310 kilopascals). The temperature of the
reactor is increased to 160.degree. C. After the reactor reaches
160.degree. C., the pressure is slowly reduced until the overhead
condensation rate is approximately 2 liters per minute. The
pressure is continually decreased to meet the above overhead
condensate flow rate. Every hour from time zero, reactor samples
are taken to measure for AV. The pressure is continually decreased
until it reaches 0 psig (0 kilopascals gauge pressure). At
approximately, 3 hours the pressure is 0 psig (0 kilopascals) and
TAN is equal to 5 mg KOH/g or below. An additional 6 L of pentanol
and 0.253 Kg of methanesulfonic acid are added and the reaction
pressure is increased to 20 psig (138 kilopascals) or adjusted to
maintain an overhead flow rate of 2 L per minute. The pressure is
decreased slowly to maintain that flow rate until the pressure is 0
psig (0 kilopascals). At this point the temperature is increased to
170.degree. C. The reaction is terminated when the TAN is below 3
mg KOH/g. The reaction mixture is stripped at 175.degree. C. and
<2 Torr to separate unreacted pentanol (268.9 Kg) and
methanesulfonic acid (about 1 Kg) from the esterified product. The
esterified product contains 41.5 Kg of a triester of the maleinized
methyl 9-dodeconate.
[0122] The triester comprises a mixture of positional and olefin
isomers. The major component (.about.95%), a mono-triester, of this
material is comprised of a triester in isomeric form. Two proximal
ester groups are separated from a third ester group by an
unsaturated carbon chain of C.sub.11 to C.sub.14 in length. The
proximal ester groups are separated by a C.sub.4 saturated carbon
chain. The minor component (.about.5%), a di-triester, comprises
five ester groups, where four proximal esters are separated from
the fifth ester groups by an unsaturated carbon chain of C.sub.11
to C.sub.16 in length. The alkyl portions of the ester groups have
the structure nC.sub.5H.sub.12. These structures are shown
below.
##STR00004##
EXAMPLE 7
[0123] The triester from Example 6 is subjected to a hydrogenation
reaction using a transition metal, hydrogenation catalyst. The
carbon-carbon double bonds are converted to saturated carbon bonds
with the hydrogenation reaction. The resulting structures are shown
below.
##STR00005##
EXAMPLE 8
[0124] A triester derived from maleinized methyl 9-dodecenoate and
1-pentanol is blended with a polyalphaolefin base stock and an
antioxidant to form a lubricating oil composition. This formulation
is subjected to a Sequence IIIG Engine Test with the results
showing improved average weighted piston deposit values. This
indicates that fewer deposits are forming leading to a cleaner
running engine. The lubricating oil formulation that is used is a
SAE Viscosity 0W-20 oil which contains the following
ingredients:
TABLE-US-00005 Wt % Triester derived from maleinized methyl 9- 30.0
dodecenoate and 1-pentanol PAO-4 polyalphaolefin 69.5 Irganox L57
(octylated/butylated 0.5 diphenylamine antioxidant from Ciba
Specialty Chemicals)
[0125] The Sequence IIIG Test is an industry standard fired-engine,
dynamometer lubricant test for evaluating automotive engine oils
for certain high-temperature performance characteristics, including
oil thickening, varnish deposition, oil consumption, and engine
wear. Such oils include both single viscosity grade and
multi-viscosity grade oils that are used in spark-ignition,
gasoline-fueled engines, as well as diesel engines.
[0126] The Sequence IIIG Test utilizes a 1996 General Motors
Powertrain 3800 Series II, water-cooled, 4 cycle, V-6 engine as the
test apparatus. The Sequence IIIG test engine is an overhead valve
design (OHV) and uses a single camshaft operating both intake and
exhaust valves via pushrods and hydraulic valve lifters in a
sliding-follower arrangement. The engine uses one intake and one
exhaust valve per cylinder. Induction is handled by a modified GM
port fuel injection system setting the air-to-fuel ratio at 15:1.
The test engine is overhauled prior to each test, during which
critical engine dimensions are measured and rated or measured parts
(pistons, camshaft, valve lifters, etc.) are replaced.
[0127] The Sequence IIIG Test consists of a 10-minute operational
check, followed by 100 hours of engine operation at moderately high
speed, load, and temperature conditions. The 100-hour segment is
broken down into five 20-hour test segments. Following the
10-minute operational check and each 20-hour segment, oil samples
are drawn from the engine. The kinematic viscosities of the 20-hour
segment samples are compared to the viscosity of the 10-minute
sample to determine the viscosity increase of the test oil. The
results are indicated below.
TABLE-US-00006 Average Viscosity Average Weighted Increase Cam +
Lifter Piston Deposits (%) Wear (.mu.m) (merits) Original Results
69.51 51.4 5.46 Transformed Results .sup.B 4.241471 3.9396 Industry
Correction Factor 0.000000 0.0000 0.0000 Corrected Transformed
4.241471 3.9396 Severity Adjustment -0.497540 0.3594 0.4102 Final
Transformed Result 3.743931 4.2990 Final Original Unit Result 42.3
73.6 5.87 Oil Consumption Hours, h .sup.C 100 Maximum Cam + Lifter
Wear, .mu.m 69 Average Oil Ring Plugging, % 0 Average Piston
Varnish, merits 9.70 Oil Consuption, L 2.71 Number of Cold-Stuck
Rings 0 Number of Hot-Stuck Rings 0 .sup.B Viscosity Increase uses
LN (PVIS), Average Cam + Lifter Wear uses LN (ACLW), Weighted
Piston Deposits does not use a transformation .sup.C Test hours at
which Oil Consumption is calculated .sup.D Non-Reference Oil Tests
Only Viscosity Increase Data (cSt at 40.degree. C.) Hours Viscosity
Change Percent New Oil 42.13 Initial .sup.B 40.97 20 44.18 3.21
7.84 40 46.77 5.80 14.16 60 49.94 8.97 21.89 80 54.14 13.17 32.15
100 69.45 28.48 69.51 Results of ICP Analysis of Used Oil .sup.C
Hours Iron Copper Lead Initial 8 2 2 20 61 30 31 40 118 35 36 60
172 34 38 80 250 39 43 100 357 43 68 .sup.A 8000 cSt is the Maximum
Allowable Viscosity .sup.B at the End of Leveling Run .sup.C Units
are in ppm (parts per million). Camshaft Valve Cam and Lifter
Number Lobe, .mu.m Lifter, .mu.m Wear, .mu.m 1 1 49 50 2 3 38 41 3
3 46 49 4 11 48 59 5 3 47 50 6 8 45 53 7 3 44 47 8 5 47 52 9 5 49
54 10 5 43 48 11 7 38 45 12 12 57 69 Maximum 12 57 69 Minimum 1 38
41 Average 6 46 51.4 Oil Ring Land Piston Deposit, Merits % Chipped
1 8.65 0 2 5.82 0 3 3.32 0 4 1.90 0 5 6.73 0 6 8.07 0 Average 5.75
0.00 % Oil Ring Ring Sticking .sup.A Piston Plugging Hot-Stuck
Rings Cold Stuck Rings 1 0 N N 2 0 N N 3 0 N N 4 0 N N 5 0 N N 6 0
N N Total 0 0 Average 0 .sup.A Possible Values T = Top Compression
Ring B = Bottom Compression Ring O = Oil Ring N = None Grooves,
merits Lands, merits Undercrown, 1 2 3 2 3 merits Piston 1 3.89
7.27 9.45 5.62 8.66 2.82 Piston 2 3.54 4.85 8.69 2.17 5.82 2.24
Piston 3 4.37 1.03 9.02 0.99 3.32 1.67 Piston 4 0.75 0.74 8.20 0.71
1.90 1.33 Piston 5 0.75 3.73 8.93 0.85 6.73 1.94 Piston 6 1.97 3.10
9.31 1.62 8.07 2.19 WF 0.05 0.10 0.20 0.15 0.30 0.10 Note: These
are Unweighted Ratings. Piston Skirt Varnish, merits Thrust
Anti-Thrust Average Piston 1 9.95 10.00 9.98 Piston 2 9.11 10.00
9.56 Piston 3 9.71 9.91 9.81 Piston 4 8.71 9.95 9.33 Piston 5 9.57
9.90 9.74 Piston 6 9.52 10.00 9.76 Average 9.43 9.96 9.70 WF 0.10
PSVAVx = (PSTx + PSVAx)2 Where x = Number of Piston PSVTAV =
Average of Six Thrust Piston Skirt Ratings PSVAAV = Average of Six
Anti-Thrust Piston Skirt Rating APV = Average of All 12 Piston
Ratings. Total Weighted Deposits, merits Piston 1 7.53 Piston 2
5.65 Piston 3 4.42 Piston 4 3.49 Piston 5 5.51 Piston 6 6.13 WPDX =
(WF*G1Px) + (WF*G2Px) + WF*G3Px) = (WF*L2P) + (WF*ORLDx) =
(WF*UCPx) + (WF*PSVAVx) Where: x = Number of Piston WF =
Appropriate Weighting Factor (WF) for Part, From Table Average
Weighted Piston 5.46 Deposits, merits WPD = (WPD1 + WPD2 + WPD3 +
WPD4 + WPD5 + WPD6)/6
EXAMPLE 9
[0128] A maleinized ester derivative in the form of hydrogenated
1-pentyl triester of maleinated-9-dodecene methyl ester
(hereinafter the "test substance") is evaluated for aerobic
biodegradability in water containing mineral salts and activated
sludge. The activated sludge is taken from a wastewater treatment
plant and is used as a source of microbial inoculum. The objectives
of the study are: 1) to evaluate the biodegradability
(mineralization to CO.sub.2 production) potential of the test
substance in an aerobic, aqueous medium; and 2) to determine the
mineralization potential of a reference chemical in order to assess
the viability of the test inoculum.
[0129] The test substance is in the form of a slight yellow oily
liquid. It has the molecular formula C.sub.32H.sub.60O.sub.6, and a
carbon content of 71.07%.
[0130] The reference substance is sodium benzoate, CAS No.
532-32-1. The molecular formula is C.sub.6H.sub.5COONa. The
chemical purity of the reference substance is 99.9%.
[0131] The reagent water is purified, deionized and filtered.
[0132] Approximately one liter of activated sludge is used as the
microbial inoculum. The sludge is collected from the Columbia
Wastewater Plant in Columbia, Mo. This plant treats predominately
domestic sewage.
[0133] An aqueous mineral salts medium provides essential mineral
nutrients and trace elements necessary to sustain the inoculum
throughout the test period. The mineral salts medium is prepared by
addition of reagent grade salts to reagent water. The mineral salts
include salts of K, Na, NH.sub.4, Ca, Mg and Fe. The pH of the
mineral salts medium is 7.27.
[0134] Each test system consists of a 5-L Pyrex carboy (reaction
flask or vessel) containing a 3.0 L test solution volume comprised
of mineral salts medium, prepared microbial inoculum, reagent
water, and the appropriate test and/or reference substance
additions. Outside air is passed through a pre-trap containing 500
mL of approximately 5 N KOH. The air is then passed through
approximately 500 mL of reagent water to humidify the air, as well
as to prevent contamination of the flasks from the KOH pre-trap.
The CO.sub.2-free and humidified air is then passed through the
reaction flasks. This is shown in FIG. 5.
[0135] The CO.sub.2-free air is introduced into each flask by
positive pressure, and the flow rates (50-100 mL/minute) are
measured and adjusted using flow meters. The outlet from each flask
is connected to three CO.sub.2 absorber gas-washing traps in
series, each filled with 100 mL of 0.2 N KOH solution. These traps
capture the CO.sub.2 evolved from the reaction flasks. A magnetic
stir bar is placed in each flask. The flasks are placed on
insulated magnetic stir plates and stirred throughout the duration
of the study. The test systems are kept in the dark (except for
sampling and maintenance) in a temperature-controlled environmental
chamber set at 22.degree. C. Temperature of the chamber is
continuously measured using a Rees Scientific temperature
monitoring system.
[0136] The activated sludge is homogenized in a blender at a medium
speed for two minutes. The homogenized sludge is allowed to settle
for 30 to 60 minutes then filtered through glass wool. A volume of
30 mL of the filtrate is used as the inoculum for each reaction
flask.
[0137] The suspended solids concentration in each filtered solution
is determined by filtering three 10 mL aliquots of sludge through
pre-weighed Whatman glass-fiber filter pads, followed by drying on
a Mettler HR73P halogen moisture analyzer. The increase in weight
of the filter pads is used to determine the suspended solids level.
The suspended solids concentration of the prepared activated sludge
is determined in the triplicate aliquots to be 0.4, 0.2, and 0.4
g/L, which corresponds to a mean of 0.3 g/L. The total
concentration of suspended solids in each reaction flask (30 mL of
inoculum to 3,000 mL of test medium) is 3 mg/L.
[0138] A 1.00-mg/mL stock solution of the reference substance is
prepared by weighing 500.8 mg of sodium benzoate into a 500-mL
Class A volumetric flask, correcting for purity (99.9%), and
bringing the solution to volume with reagent water. The solution is
stored refrigerated when not in use.
[0139] One day prior to dosing, six test systems are assembled.
Each 5-L carboy receives 2,400 mL of mineral salts medium and 30 mL
of the prepared activated sludge. Stirring and aeration with
CO.sub.2-free air at approximately 90 mL/minute is started for each
flask. The flasks are allowed to aerate overnight to purge the
systems of CO.sub.2 before initiation of the test (dosing on Day
0).
[0140] Duplicate control systems are prepared by adding 570 mL of
reagent water to the 5-L carboys. The final volume is 3,000 mL.
[0141] Duplicate test substance systems are prepared by adding 570
mL of reagent water and approximately 42.2 mg (dosed
gravimetrically) of the test substance to two of the 5-L carboys.
The nominal concentration of carbon from the test substance in the
final volume of 3,000 mL of solution is 10 mg C/L.
[0142] The reference substance system is prepared by adding 467 mL
of reagent water and 103 mL of the 1.00-mg/mL reference substance
stock solution to a 5-L carboy. The nominal concentration of carbon
from the reference substance in the final volume of 3,000 mL of
solution is 20 mg C/L.
[0143] The toxicity control system is prepared by adding 467 mL of
reagent water, 103 mL of the 1.00-mg/mL reference substance stock
solution, and approximately 42.2 mg (dosed gravimetrically) of the
test substance to a 5-L carboy. The nominal concentration of carbon
from the toxicity system in the final volume of 3,000 mL of
solution is 30 mg C/L.
[0144] After all additions, each of the reaction flasks are
connected to a series of three traps containing 100 mL of 0.2 N
KOH. Aeration and stirring of the flasks are continued. Flow meters
connected to the test systems are adjusted to facilitate airflow at
50-100 mL/min. The bubbling of air and stirring in each flask, as
well as the bubbling in each trap, confirms the constant
aeration.
[0145] Approximately one hour after dosing, approximately 80 mL of
each test solution are removed, and the pH of each of the test
solution is measured. One sample is filtered with a 0.45-.mu.m
nylon filter (sample for dissolved organic carbon (DOC) analysis)
and both samples are deposited into autosampler bottles, which are
stored refrigerated until analysis for dissolved organic carbon
(DOC) and inorganic carbon (IC) concentrations.
[0146] The CO.sub.2 produced in the test systems is trapped in the
0.2 N KOH solutions, which are then analyzed for inorganic carbon
(IC) content. Samples of the KOH solutions are collected for
CO.sub.2 analysis on Days 0, 2, 6, 9, 12, 15, 19, and 29. For each
sampling day, aliquots of the KOH solution from the trap nearest
each flask are placed into appropriately labeled glass autosampler
vials. The vials are filled leaving no headspace, capped using
Teflon septa, the caps wrapped in parafilm, and stored at room
temperature until analysis. For each sample day, the remaining KOH
solution in this trap is discarded and replaced with 100 mL of a
fresh 0.2 N KOH solution. The refilled trap is then rotated to the
position farthest from the carboy, and the other two traps are
moved forward (nearer to the carboy) one position.
[0147] The test is terminated after 28 days of incubation. The pH
of each test solution is measured on Day 28 of the test. After
sampling the test solutions, 1 mL of concentrated HCl is added to
each test solution to drive carbonates and the remaining CO.sub.2
from solution. The flasks are then re-sealed and allowed to aerate
overnight. On Day 29, samples are taken from the test carboys for
IC analysis, duplicate aliquots of each trap are for IC analysis,
and the traps are not refilled with 0.2 N KOH.
[0148] Bacterial plate counts are performed on the prepared
activated sludge prior to initiation and each replicate reaction
flask solution at Day 28. A dilution series of each sample is
prepared in sterile, pH 7.2, phosphate-buffered water at 10.sup.-2,
10.sup.-3, 10.sup.-4, 10.sup.-5, and 10.sup.-6. Duplicate 1-mL
aliquots of each dilution are directly analyzed by plate counting
methods patterned after methods described in Standard Methods for
the Examination of Water and Wastewater. (See, American Public
Health Association (APHA), American Water Works Association (AWWA),
and Water Environment Federation (WEF). 1998. Standard Methods for
the Examination of Water and Wastewater, 20.sup.th Edition, Part
9215 B, Pour Plate Method). The bacterial growth medium is Plate
Count Agar (Difco Laboratories). The plates of inocula are
incubated at 26.+-.2.degree. C. for five to six days before
counting the number of colonies on plates with fewer than 300
colonies. The number of colonies at the dilution coming closest to
300 colonies is used to calculate colony forming units (CFU)/mL for
each sample.
[0149] DOC and IC analyses are conducted using a Teledyne Fusion
Persulfate TOC (Total Organic Carbon) Analyzer. DOC is conducted
using the TOC mode. Inorganic carbon analyses is conducted using
the IC mode.
[0150] For IC and DOC analysis, three injections of each sample are
made. The mean, SD, and CV are calculated for each sample. The mean
value is reported as the carbon content of the sample in mg
C/L.
[0151] Primary standards for total carbon (TC) analyses are made
using potassium hydrogen phthalate prepared in HPLC-grade water.
Primary standards for inorganic carbon (IC) analyses are made using
sodium bicarbonate prepared in HPLC-grade water. Dilutions of the
TC and IC primary standards are used as working standards to
calibrate each carbon analyzer. A second set of the IC primary
standard and dilutions is prepared and used as standards to check
the performance of the carbon analyzers during each analysis. All
dilutions of primary standards are prepared using HPLC-grade water.
The HPLC-grade water that is used is manufactured by Fisher.
[0152] Calculations are performed using Microsoft Office Excel.
Values are not rounded during the calculations. Final results are
assigned by simple rounding (i.e., digits 0-4 round down and digits
5-9 round up).
[0153] The carbon analyzer calculates inorganic carbon
concentrations automatically as mg C/L, based on comparison to
carbon standard solutions. The mg C/trap at each sampling point for
each flask is calculated as follows:
( Calculated mg C / L from TOC analyzer ) .times. ( 0.1 L volume of
gas - washing bottles ) = ( mg C trap ) ##EQU00001##
For the control systems, the evolved mg CO.sub.2 is calculated as
follows:
[ ( mg C / L from trap ) - ( mg C / L from freshly prepared KOH ) ]
.times. ( CO 2 wt . C wt . ) .times. ( 0.1 L volume of gas washing
bottles ) = ( evolved mg CO 2 ) ##EQU00002##
The carbon to carbon dioxide factor used is 3.664 [from 44.01
(CO.sub.2)/12.01 (C)]. The cumulative evolved mg CO2 is then
calculated for each control flask by summing values from successive
days.
[0154] For flasks receiving test or reference substance, the net mg
C produced is calculated for each sample point as follows:
mg Cr trap - mg C I B trap = Net mg C trap ##EQU00003##
[0155] where:
[0156] mg C.sub.T/trap=calculated mg C/trap value for the test or
reference flask
[0157] mg C.sub.IB/trap=average calculated mg C/trap value for the
control flasks
[0158] Percent theoretical CO2 (% ThCO2) production from each test
and reference system is calculated as follows:
Cumulative Net Trapped Carbon ( mg C ) Applied Theoretical Carbon (
mg C ) .times. 100 = % Th CO 2 ##EQU00004##
[0159] The volume of test and reference solutions after DOC
sampling at initiation is 2.92 L (from the 3,000 mL total volume,
approximately 80 mL (two autosampler bottles for DOC and IC
analysis) are removed after dosing.
[0160] The applied theoretical carbon in the reference substance
systems is calculated based on the volume of reference substance
solution added to the reaction flask, the concentration of the
reference substance solution, the percent carbon of the reference
substance, and the total volume of testing medium in the reaction
flask. The applied carbon for the reference substance system is
calculated as follows.
Applied ThCO 2 Test Substance = [ 103 mL .times. 1.00 mg / mL
.times. 58.34 % C .times. 2.92 L ] 3.00 L = 58.5 mg C
##EQU00005##
[0161] The applied theoretical carbon in the test substance systems
is calculated based on the mass of test substance added to the
reaction flask, the percent carbon of the test substance, the
percent purity of the test substance, and the total volume of
testing medium in the reaction flask. The applied theoretical
carbon for the test substance replicate A flask is calculated as
follows.
Applied ThCO 2 Reference Substance = [ 42.5 mg .times. 71.07 %
.times. 100 % .times. 2.92 L ] 3.00 L = 29.54 mg C ##EQU00006##
[0162] The applied theoretical carbon in the toxicity control
systems is calculated based on the mass of test substance added to
the reaction flask, the percent carbon of the test substance, the
percent purity of the test substance, and the total volume of
testing medium in the reaction flask in addition to the volume of
reference substance solution added to the reaction flask, the
concentration of the reference substance solution, the percent
carbon of the reference substance, and the total volume of testing
medium in the reaction flask. The applied theoretical carbon for
the toxicity control is equal to that of the reference substance
system and the test substance system combined, for a total of 87.7
mg C.
[0163] The percent DOC removed from each test and reference
substance system is calculated and determined as follows:
[ 1 - ( T 28 - BL 28 T 0 - BL 0 ) ] .times. 100 = % DOC Removed
##EQU00007##
[0164] where:
[0165] T.sub.0, T.sub.28=DOC (mg C/L) measured from the test or
reference flask reaction solutions at Days 0 and 28
[0166] BL.sub.0, BL.sub.28=Average DOC (mg C/L) measured from the
control flask reaction solutions at Days 0 and 28
[0167] The pH of the control solutions are 7.66 and 7.62 at study
initiation and 7.50 and 7.56 at termination for replicates A and B,
respectively. The pH of the test substance solutions are 7.72 and
7.60 at study initiation and 7.65 and 7.58 at termination for
replicates A and B, respectively. The pH of the reference substance
system increases from 7.61 at study initiation to 7.84 at study
termination. The pH of the toxicity control system is 7.64 at study
initiation and 7.77 at study termination. All pH values are
suitable for biological systems
[0168] The average temperature of the environmental chamber ranges
from 21.06 to 21.91.degree. C. during the test duration.
[0169] At study initiation, DOC in the control solutions is not
detected. At study termination, the mean DOC concentration of the
control solutions is not detected.
[0170] At study initiation, DOC concentration in the test substance
replicates is not detected. The mean corrected DOC concentrations
of the test substance solutions at termination is 3.35 mg C/L. The
test substance is insoluble in water, so the result showing minimal
to no DOC at initiation is expected. The increase in DOC
concentration from Day 0 to Day 28 is likely due to the
insolubility of the test substance in water (that is, more test
substance likely went into solution while stirring over time).
Consequently, DOC removal cannot be calculated for the test
substance.
[0171] At study initiation, the corrected DOC concentration of the
reference substance solution is 21.0 mg C/L, which confirms the
dose rate of 20 mg C/L. The corrected DOC concentration of the
reference substance solution at termination is 0.00 mg C/L,
corresponding to 100% DOC removal.
[0172] At study initiation, the corrected DOC concentration of the
toxicity control is 21.4 mg C/L, which is consistent with the above
(i.e. 20 mg C/L of reference substance and test substance being
insoluble so contributing no DOC). The corrected DOC concentration
of the toxicity control at termination is 3.65 mg C/L.
[0173] At study initiation, the IC concentrations of the control
solutions are 0.0133 and 0.0501 mg C/L for replicates A and B,
respectively. The measured IC concentration of the test substance
solutions at initiation is 0.5690 and 0.0000 mg C/L for replicates
A and B, respectively. After adjustment for control IC
concentrations, the average IC concentration for the test substance
solutions is 0.25 mg C/L. This value corresponds to 2.53% of the
total carbon (TC). The IC concentration of the reference substance
solution at initiation, after adjustment for the mean of the
control, is 0.79 mg C/L or 3.79% of the TC concentration. The IC
concentration of the toxicity control solution at initiation, after
adjustment for the mean of the control, is 0.54 mg C/L or 1.76% of
the TC concentration. These results show that inorganic carbon does
not significantly contribute to background levels of carbon in the
test systems.
[0174] The bacterial plate counts prior to initiation show that the
prepared activated sludge contains 9.2.times.10.sup.4 CFU/mL. The
results of bacterial plate counts at study termination show that
the controls contain 2.2.times.10.sup.4 CFU/mL for replicate A and
2.0.times.10.sup.4 CFU/mL for replicate B. The test treatment
replicates A and B contain 2.4.times.10.sup.4 and
3.7.times.10.sup.4 CFU/mL, respectively. The reference substance
treatment contains 1.4.times.10.sup.4 CFU/mL. The toxicity control
contains 1.7.times.10.sup.4 CFU/mL. This microbial evaluation data
suggests the test substance has no significant effect on the
population of microbes, and the microbial populations in the
inoculum are viable.
[0175] CO.sub.2 evolved from the control system is 236.8 and 146.7
mg CO.sub.2, by Day 29 of the study for replicate A and B,
respectively. These values are corrected for the background
CO.sub.2 present in the fresh KOH solutions. The goal of the
control systems are to provide the background CO.sub.2 values
resulting from the endogenous CO.sub.2 evolution from the microbial
inoculum. The total mg CO.sub.2 evolved from the control system is
divided by 3 (liters of solution per flask) to give mg CO.sub.2/L.
The total mg CO.sub.2 evolved from the control system, 191.7 mg
CO.sub.2 (63.9 mg CO.sub.2/L) is higher than 40 mg CO.sub.2/L,
however is still within the upper limit indicated in the protocol
(<70 mg CO.sub.2/L or 210 mg CO.sub.2/flask).
[0176] The test substance exhibits mean % ThCO.sub.2 values of
15.8% and 71.6% (after correction for background CO2 from the
controls) at Day 9 and Day 19 of the study, respectively. The test
substance exhibits % ThCO.sub.2 values of 63.8% for replicate A and
79.4% for replicate B at Day 19 of the study, and the replicates
are within 20% of each other at the end of the 10-day window. Since
biodegradation values exceeds 60% ThCO.sub.2 within a 10 day
window, these results indicate that the test substance may be
classified as readily biodegradable
[0177] The reference substance exhibits a % ThCO.sub.2 value of
67.2% on Day 9 of the study. The value through Day 29 of the study
is 73.7% ThCO.sub.2. The results from Day 9 (67.2% ThCO.sub.2
evolved) indicate greater than 60% ThCO.sub.2 evolved in the first
9 days of the test. These results indicate that the inoculum is
viable according to the criteria outlined in the applicable testing
guideline.
[0178] The toxicity control, sodium benzoate plus the test
substance, exhibit a % ThCO.sub.2 value of 47.5% on Day 6 of the
study. The value through Day 29 of the study is 72.8% ThCO.sub.2.
Since the biodegradation value is greater than 25% ThCO.sub.2 by
day 6, the test substance can be assumed to not be inhibitory.
[0179] The mean percent theoretical CO.sub.2 produced by the test
substance is 15.8% by Day 9 of the study and 71.6% by Day 19 of the
study. Since the biodegradation value exceeds 60% ThCO.sub.2 within
a 10-day window, the test substance can be classified as readily
biodegradable.
[0180] The percent theoretical CO.sub.2 produced by the reference
substance is 67.2% by Day 9 of the study, confirming the inoculum
is viable. The percent theoretical CO.sub.2 produced by the
toxicity control is 47.5% by Day 6 of the study, confirming the
triester is not inhibitory.
[0181] While the invention has been explained in relation to
various embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein includes any such
modifications that may fall within the scope of the appended
claims.
EXAMPLE 10
[0182] Maleinized methyl 9-dodecenoate (200 g), 1-decanol (470 g),
methane-sulfonic acid (1.9 g) are added to a one-liter,
three-necked round-bottom flask at 23.degree. C. under an air
atmosphere. The flask is fitted with a thermocouple temperature
regulator with heating mantle, Dean-Stark trap with condenser, and
a stopper with a nitrogen needle inlet. Nitrogen gas is passed
through the needle inlet into the head space of the apparatus (flow
rate=2.5 ft.sup.3/hr (70.8 liters/hr)) for 10 minutes. The
temperature is increased to 150.degree. C. After 2 hours an aliquot
of the reaction mixture is taken and measured for AV=7.6 mg KOH/g.
The reaction mixture is stirred for another 4 hours (total reaction
time 6 hours). The reaction was sampled and measured for AV=2.9 mg
KOH/g. The heating source is removed and the reaction mixture is
allowed to cool to ambient temperature. The reaction mixture is
subjected to vacuum distillation (2 Torr, 25.degree. C. to
175.degree. C.) to removed residual decanol, methanol, and water.
The residual crude triester product is passed through a pad of
basic alumina oxide to isolate the unsaturated product as a clear
brown oil. KV (100.degree. C.)=6.88 cSt; KV (40.degree. C.)=33.97
cSt; viscosity index (VI)=167, TGA NOACK Volatility=5.8%. The
unsaturated material is subjected to hydrogenation (3 wt% nickel on
silica; 250 psi, 175.degree. C., 1000 RPM) for 4 hours. The
catalyst was removed by filtration to provide the final product has
a yellow oil KV (100.degree. C.)=6.8 cSt; KV (40.degree. C.)=34.05
cSt; viscosity index (VI)=163, TGA NOACK Volatility=7%; and pour
point -30.degree. C.
* * * * *