U.S. patent application number 15/157449 was filed with the patent office on 2016-09-08 for esters for use as a base stock in lubricant applications.
This patent application is currently assigned to Trent University. The applicant listed for this patent is Trent University. Invention is credited to Laziz Bouzidi, Stephen Augustine DiBiase, Shaojun Li, Ali Mahdevari, Suresh Narine, Syed Q.A. Rizvi.
Application Number | 20160257901 15/157449 |
Document ID | / |
Family ID | 45809606 |
Filed Date | 2016-09-08 |
United States Patent
Application |
20160257901 |
Kind Code |
A1 |
Narine; Suresh ; et
al. |
September 8, 2016 |
Esters for Use as a Base Stock in Lubricant Applications
Abstract
This invention relates to base ester compounds and complex ester
compounds that can be used as a base stock for lubricant
applications or a base stock blend component for use in a finished
lubricant or for particular applications, and methods of making the
same. The base ester compounds and complex esters described herein
comprise dimer and/or trimer esters, and their respective branched
derivatives.
Inventors: |
Narine; Suresh;
(Peterborough, CA) ; Li; Shaojun; (Peterborough,
CA) ; Mahdevari; Ali; (Peterborough, CA) ;
Bouzidi; Laziz; (Peterborough, CA) ; DiBiase; Stephen
Augustine; (River Forest, IL) ; Rizvi; Syed Q.A.;
(Painesville, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Trent University |
Peterborough |
|
CA |
|
|
Assignee: |
Trent University
Peterborough
CA
|
Family ID: |
45809606 |
Appl. No.: |
15/157449 |
Filed: |
May 18, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14259575 |
Apr 23, 2014 |
9359571 |
|
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15157449 |
|
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|
13026268 |
Feb 13, 2011 |
8741822 |
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14259575 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10N 2020/02 20130101;
C10M 105/36 20130101; C10N 2050/10 20130101; C10N 2040/20 20130101;
C10N 2040/08 20130101; C07C 69/66 20130101; C10M 2207/2825
20130101; C10N 2070/00 20130101; C10M 2207/301 20130101; C10M
2207/2815 20130101; C10M 105/40 20130101; C10N 2040/24 20130101;
C07C 69/34 20130101; C10M 105/34 20130101; C10N 2030/68 20200501;
C10N 2030/08 20130101; C10N 2030/02 20130101; C10M 2207/30
20130101; C10N 2040/26 20130101; C10N 2030/10 20130101; C10N
2040/22 20130101; C10N 2030/66 20200501; C10M 105/42 20130101; C10M
2207/28 20130101; C10N 2040/25 20130101; C10N 2040/30 20130101;
C07C 69/00 20130101; C10M 2207/2805 20130101; C10M 2207/301
20130101; C10N 2020/02 20130101; C10M 2207/301 20130101; C10N
2020/065 20200501; C10M 2207/301 20130101; C10N 2020/071 20200501;
C10M 2207/301 20130101; C10N 2020/065 20200501; C10M 2207/301
20130101; C10N 2020/071 20200501; C10M 2207/301 20130101; C10N
2020/02 20130101 |
International
Class: |
C10M 105/34 20060101
C10M105/34; C10M 105/36 20060101 C10M105/36 |
Claims
1. A lubricant base stock composition comprising a base ester
having the formula (III) ##STR00005## wherein n1=between 0 and 8;
wherein n2=between 0 and 8; wherein m1=between 5 and 9; and wherein
m2=between 5 and 9.
2. The lubricant base stock composition of claim 1, wherein the
composition has a melt onset of between about 15.degree. C. down to
about -19.degree. C.
3. The lubricant base stock composition of claim 1, wherein the
composition has a dynamic viscosity at 100.degree. C. of between
about 1.0 mPascal Seconds and about 7.5 mPascal Seconds.
4. The lubricant base stock composition of claim 1, wherein the
composition has a dynamic viscosity at 40.degree. C. of between
about 1.7 mPascal Seconds and about 28.0 mPascal Seconds.
5. The lubricant base stock composition of claim 1, wherein the
composition has a crystallization onset of between about 26.degree.
C. down to about -20.degree. C.
6. A lubricant composition comprising the lubricant base stock of
claim 1 and one or more additives selected from the group
consisting of detergents, antiwear agents, antioxidants, metal
deactivators, extreme pressure (EP) additives, dispersants,
viscosity index improvers, pour point depressants, corrosion
protectors, friction coefficient modifiers, colorants, antifoam
agents, and demulsifiers.
7. The lubricant composition of claim 6, wherein the lubricant
composition is used in an application selected from the group
consisting of two-cycle engine oils, hydraulic fluids, drilling
fluids, greases, compressor oils, cutting fluids, milling fluids,
and emulsifiers for metalworking.
8. A lubricant base stock composition comprising a base ester
having the formula (IV): ##STR00006## wherein n1=between 0 and 8;
wherein n2=between 0 and 8; wherein m1=between 5 and 9; wherein
m2=between 5 and 9; and wherein k1=k2=5.
9. The lubricant base stock composition of claim 8, wherein the
composition has a melt onset of about 22.degree. C.
10. The lubricant base stock composition of claim 8, wherein the
composition has a dynamic viscosity at 100.degree. C. of about 7.1
mPascal Seconds.
11. The lubricant base stock composition of claim 8, wherein the
composition has a dynamic viscosity at 40.degree. C. of about 25.4
mPascal Seconds.
12. The lubricant base stock composition of claim 8, wherein the
composition has a crystallization onset of about 19.degree. C.
13. A lubricant composition comprising the lubricant base stock of
claim 8 and one or more additives selected from the group
consisting of detergents, antiwear agents, antioxidants, metal
deactivators, extreme pressure (EP) additives, dispersants,
viscosity index improvers, pour point depressants, corrosion
protectors, friction coefficient modifiers, colorants, antifoam
agents, and demulsifiers.
14. The lubricant composition of claim 13, wherein the lubricant
composition is used in an application selected from the group
consisting of two-cycle engine oils, hydraulic fluids, drilling
fluids, greases, compressor oils, cutting fluids, milling fluids,
and emulsifiers for metalworking.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a divisional application of U.S.
patent application Ser. No. 14/259,575, filed Apr. 23, 2014, which
is a divisional application of U.S. patent application Ser. No.
13/026,268 filed Feb. 13, 2011. Both of the foregoing priority
applications are hereby incorporated by reference as though set
forth herein in their entireties.
FIELD OF THE INVENTION
[0002] This application relates to base ester compounds and complex
ester compounds that can be used as a base stock or a base stock
blend component for use in lubricant applications, and methods of
making the same.
BACKGROUND OF THE INVENTION
[0003] Lubricants are widely used to reduce friction between
surfaces of moving parts and thereby reduce wear and prevent damage
to such surfaces and parts. Lubricants are composed primarily of a
base stock and one or more lubricant additives. The base stock is
generally a relatively high molecular weight hydrocarbon. In
applications where there is a large amount of pressure applied to
moving parts, lubricating compositions composed only of hydrocarbon
base stock tend to fail and the parts become damaged. To make
lubricants, such as motor oils, transmission fluids, gear oils,
industrial lubricating oils, metal working oils, etc., one starts
with a lubricant grade of petroleum oil from a refinery, or a
suitable polymerized petrochemical fluid. Into this base stock,
small amounts of additive chemicals are blended therein to improve
material properties and performance, such as enhancing lubricity,
inhibiting wear and corrosion of metals, and retarding damage to
the fluid from heat and oxidation. As such, various additives such
as oxidation and corrosion inhibitors, dispersing agents, high
pressure additives, anti-foaming agents, metal deactivators and
other additives suitable for use in lubricant formulations, can be
added in conventional effective quantities. It has long been known
that synthetic esters can be used both as a base stock and as an
additive in lubricants. By comparison with the less expensive, but
environmentally less safe mineral oils, synthetic esters were
mostly used as base oils in cases where the viscosity/temperature
behavior was expected to meet stringent demands. The increasingly
important issues of environmental acceptance and biodegradability
are the drivers behind the desire for alternatives to mineral oil
as a base stock in lubricating applications. Synthetic esters may
be polyol esters, polyalphaolefins (PAO), and triglycerides found
in natural oils. Of key importance to natural oil derived
lubricants are physical properties, such as improved low
temperature properties, improved viscosity at the full range of
operating conditions, improved oxidative stability (meaning removal
of double bonds in the case of natural oil derived materials), and
improved thermal stability.
[0004] Various prior art efforts have attempted to describe esters
for use in biolubricant applications, examples of which include
U.S. Patent Application No. 2009/0198075 titled Synthesis of
Diester Based Biolubricants from Epoxides ("Ref. 1"); Synthesis and
Physical Properties of Potential Biolubricants Based on Ricinoleic
Acid, by Linxing Yao et al., Journal of the American Oil Chemists'
Society 87, 2010, 937-945 ("Ref. 2); Melting Points and Viscosities
of Fatty Acid Esters that are Potential Targets for Engineered
Oilseed, by Linxing Yao et al., Journal of the American Oil
Chemists' Society 85, 2008, 77-82 ("Ref. 3"); Diesters from Oleic
Acid: Synthesis, Low Temperature Properties and Oxidation
Stability, by Bryan R. Moser et al. Journal of the American Oil
Chemists' Society 84, 2007, 675-680 ("Ref. 4"); Oleic Acid
Diesters: Synthesis, Characterization and Low-Temperature
Properties, by Jumat Salimon et al., European Journal of Scientific
Research 32(2), 2009, 216-229 ("Ref. 5"); U.S. Pat. No. 6,018,063
titled Biodegradable Oleic Estolide Ester Base Stocks and
Lubricants ("Ref. 6"); and Oleins as a Source of Estolides for
Biolubricant Applications, by L. A. Garcia-Zapateiro et. al.,
Grasas Y Aceites, 61(2), 2010, 171-174 ("Ref. 7") (collectively,
the "cited prior art"). However, none of the cited prior art
references describe improved physical properties to the broad
extent of the present invention.
SUMMARY OF THE INVENTION
[0005] In one aspect of the invention, a lubricant base stock
composition is disclosed, comprising a complex ester having the
formula (I):
##STR00001##
wherein n1=between 0 and 8; wherein n2=between 0 and 8; wherein
m1=between 5 and 9; wherein m2=between 5 and 9; wherein W=OH or
OCOR, wherein X=OH or OCOR, wherein Y=OCOR or OH; wherein Z=OH or
OCOR, and in groups W, X, Y, and Z, R=CiHj, wherein i is 2 or
greater and j is 5 or greater.
[0006] In another aspect of the invention, a lubricant base stock
composition is disclosed comprising a complex ester having the
formula (II):
##STR00002##
[0007] wherein n1=between 0 and 8; wherein n2=between 0 and 8;
wherein m1=between 5 and 9; wherein m2=between 5 and 9; wherein
k1=k2=5 or greater; wherein P=OH or OCOR, wherein Q=OH or OCOR,
wherein S=OCOR or OH; wherein T=OH or OCOR, wherein U=OH or OCOR,
wherein V=OH or OCOR, and in groups P, Q, S, T, U, and V, R=CiHj,
wherein i is 2 or greater and j is 5 or greater.
[0008] In another aspect of the invention, a process for preparing
a complex ester is disclosed, comprising the steps of: (a) reacting
a fatty carboxylic acid having from between about 3 to 36 carbon
atoms and a fatty alcohol having between about 8 to about 24 carbon
atoms, in the presence of a base, a condensing agent, and a
solvent, at temperature between about 4 and 50.degree. C. for about
4 to 36 hours, to produce a base ester; (b) epoxidizing the base
ester with a peroxyacid and a solvent at temperature between about
4 and 50.degree. C. for about 4 to 36 hours to produce an epoxide;
(c) reacting the epoxide with another fatty carboxylic acid having
from between about 3 to 36 carbon atoms, at temperatures between
about 50 and 150.degree. C. for about 4 to 36 hours in a
nitrogenous atmosphere, to produce said complex ester.
[0009] In another aspect of the invention, a process for preparing
a complex ester comprising the steps of: (a) reacting a fatty
carboxylic acid having from between about 3 to 36 carbon atoms and
a metathesis catalyst, at temperature between about 30 and
70.degree. C. for about 4 to 36 hours, then purified via a solvent
to produce a diacid product; (b) reacting said diacid product with
fatty alcohol having between about 8 to about 24 carbon atoms, in
the presence of a base, a condensing agent, and a solvent, at a
temperature between about 4 and 50.degree. C. for about 4 to 36
hours, to produce a base ester; (b) epoxidizing the base ester with
a peroxyacid and a solvent at temperature between about 4 and
50.degree. C. for about 4 to 36 hours to produce an epoxide; (c)
reacting the epoxide with another fatty carboxylic acid having from
between about 3 to 36 carbon atoms, at temperatures between about
50 and 150.degree. C. for about 4 to 36 hours in a nitrogenous
atmosphere, to produce said complex ester.
[0010] In another aspect of the invention, a lubricant base stock
composition is disclosed comprising a base ester having the formula
(III):
##STR00003##
wherein n1=between 0 and 8; wherein n2=between 0 and 8; wherein
m1=between 5 and 9; and wherein m2=between 5 and 9.
[0011] In another aspect of the invention, a lubricant base stock
composition is disclosed comprising a base ester having the formula
(IV):
##STR00004##
wherein n1=between 0 and 8; wherein n2=between 0 and 8; wherein
m1=between 5 and 9; wherein m2=between 5 and 9; and wherein
k1=k2=5.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 depicts the synthesis of dimer esters of the present
invention.
[0013] FIG. 2 depicts a scheme for epoxidation of alkene of the
present invention.
[0014] FIG. 3 depicts a scheme for the ring opening esterification
of epoxides of the present invention.
[0015] FIG. 4 depicts the synthesis of dimer ester branched
compounds of the present invention.
[0016] FIG. 4A depicts a generalized structure for the base dimer
ester of the present invention.
[0017] FIG. 4B depicts a generalized structure for the dimer ester
branched derivatives of the present invention.
[0018] FIG. 5 depicts the base trimer esters and their branched
compounds of the present invention.
[0019] FIG. 5A depicts a generalized structure for the base trimer
esters of the present invention.
[0020] FIG. 5B depicts a generalized structure for the trimer ester
branched derivatives of the present invention.
[0021] FIG. 6 depicts the synthesis of Compound A and its branched
derivatives of the present invention.
[0022] FIG. 7 depicts the synthesis of Compound B and its branched
derivatives of the present invention.
[0023] FIG. 8 depicts the synthesis of Compound C and its branched
derivatives of the present invention.
[0024] FIG. 9 depicts the synthesis of Compound D and its branched
derivatives of the present invention.
[0025] FIG. 10 depicts the synthesis of Compound E and its branched
derivatives of the present invention.
[0026] FIG. 11 depicts the synthesis of Compound F and its branched
derivatives of the present invention.
[0027] FIG. 12 depicts the synthesis of Compound G and its branched
derivatives of the present invention.
[0028] FIG. 13 depicts the synthesis of (E)-didec-9-enyl
octadec-9-enedioate (Compound H) of the present invention.
[0029] FIG. 14 depicts the synthesis of Compound H branched
derivatives of the present invention.
[0030] FIG. 15 depicts a general synthesis of branched esters of
the present invention.
[0031] FIG. 16 depicts the ring-opening reaction of the epoxide of
Compound G of the present invention.
[0032] FIG. 17 depicts the ring-opening reaction of the epoxide of
Compound E of the present invention.
[0033] FIG. 18 depicts the ring-opening reaction of the epoxide of
Compound H of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0034] The present application relates to the compositions and
methods for synthesis of base ester compounds and complex ester
compounds for use as a base stock for lubricant applications, or a
base stock blend component for use in a finished lubricant
composition, or for particular applications. As used herein, base
ester compounds may refer to dimer esters and/or trimer esters,
where esters shall be understood to include mono-, di-, tri-,
tetra-, and higher esters, as applicable. As used herein, complex
esters refers to the respective branched derivatives of dimer
esters, and/or the respective branched derivatives of trimer esters
or diesters, or combinations of the respective branched derivatives
of dimer esters and/or the respective branched derivatives of
trimer esters and/or their respective branched derivatives. As used
herein, the dimer esters, trimer esters or diesters, and the
respective branched derivatives of either of these may at times be
referred to generally as compounds, derivatives and/or samples.
[0035] The base esters and complex esters in accordance with the
present invention may constitute a lubricant base stock
composition, or a base stock blend component for use in a finished
lubricant composition, or they may be mixed with one or more
additives for further optimization as a finished lubricant or for a
particular application. Suitable applications which may be utilized
include, but are not limited to, two-cycle engine oils, hydraulic
fluids, drilling fluids, greases, compressor oils, cutting fluids,
milling fluids, and as emulsifiers for metalworking fluids.
Suitable non-limiting examples of additives may include detergents,
antiwear agents, antioxidants, metal deactivators, extreme pressure
(EP) additives, dispersants, viscosity index improvers, pour point
depressants, corrosion protectors, friction coefficient modifiers,
colorants, antifoam agents, demulsifiers and the like. The base
esters and complex esters in accordance with the present invention
may also have alternative chemical uses and applications, as
understood by a person skilled in the art. The content of the base
esters and complex esters of the present invention will typically
be present from about 0.1 to about 100% by weight, preferably about
25 to about 100% by weight, and most preferably from about 50 to
about 100% by weight of a finished lubricant composition.
[0036] The dimer esters were prepared at room temperature
(typically between 17-27.degree. C.) by reacting a fatty carboxylic
acid (or its acid halide, preferably an acid chloride created by
reacting a fatty carboxylic acid with a chlorinating agent, such as
thionyl chloride, phosphorus trichloride, oxalylchloride or
phosphorus pentachloride) and a fatty alcohol with a condensing
agent and a catalyst. The trimer esters, and in some embodiments,
trimer diesters, were prepared, at room temperatures, by reacting
an aliphatic dicarboxylic acid, preferably a diacid (or its acid
halide, preferably an acid chloride created by reacting an
aliphatic dicarboxylic acid with a chlorinating agent, such as
thionyl chloride, phosphorus trichloride, or phosphorus
pentachloride) with a fatty alcohol with a condensing agent and a
catalyst. Also in some embodiments, the dimer and trimer esters may
be prepared via a metathesis route.
[0037] The condensing agent typically is a carbodiimide, generally
represented by the formula: R.sup.1N.dbd.C.dbd.NR.sup.2 wherein
R.sup.1 and R.sup.2 are alkyl groups containing from 1 to about 18
carbon atoms, cycloalkyl groups containing 5 to about 10 carbon
atoms and aryl groups, which term includes alkaryl and arylalkyl
groups, containing 5 to about 18 carbon atoms. Non-limiting
examples of such carbodiimides are dimethyl carbodiimide,
diisopropyl carbodiimide, diisobutyl carbodiimide, dioctyl
carbodiimide, tert-butyl isopropyl carbodiimide, dodecyl isopropyl
carbodiimide, dicylohexyl carbodiimide, diphenyl carbodiimide,
di-o-tolyl carbodiimide, bis(2, 6-diethylphenyl) carbodiimide,
bis(2, 6-diisopropylphenyl carbodiimide, di-beta-naphthyl
carbodiimide, benzyl isoopropyl carbodiimide, phenyl-o-tolyl
carbodiimide and preferably, dicyclohexylcarbodiimide (DCC).
[0038] The catalyst may comprise a base, with non-limiting examples
such as a triethyl amine, tripropyl amine, tributyl amine, pyridine
and 4-dimethylamino pyridine or other pyridine derivative, and
preferably, 4-dimethylaminopyridine (DMAP).
[0039] The solvent used in the esterification and/or epoxidation of
the present invention may be chosen from the group including but
not limited to aliphatic hydrocarbons (e.g., hexane and
cyclohexane), organic esters (i.e. ethyl acetate), aromatic
hydrocarbons (e.g., benzene and toluene), ethers (e.g., dioxane,
tetrahydrofuran, ethyl ether, tert-butyl methyl ether), halogenated
hydrocarbons (e.g., methylene chloride and chloroform), and
preferably, chloroform.
[0040] The fatty carboxylic acid is derived from a natural oil,
with non-limiting examples such as canola oil, rapeseed oil,
coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut
oil, safflower seed oil, sesame seed oil, soybean oil, sunflower
oil, linseed oil, palm kernel oil, tung oil, jojoba oil, jatropha
oil, mustard oil, camellina oil, pennycress oil, hemp oil, algal
oil, castor oil, lard, tallow, poultry fat, yellow grease, fish
oil, tall oils, and mixtures thereof. Optionally, the natural oil
may be partially and/or fully hydrogenated, and may also be
refined, bleached, and/or deodorized. Suitable fatty carboxylic
acids of natural oils include, but are not limited to, aliphatic,
saturated, unsaturated, straight chain or branched fatty acids
having 3 to 36 carbon atoms, such as propionic acid, caproic acid,
caprylic acid, capric acid, caproleic acid (9-decenoic acid),
lauric acid, nonanoic acid, myristic acid, palmitic acid, oleic
acid, linoleic acid, linolenic acid, stearic acid, arachic acid,
erucic acid and behenic acid.
[0041] The alcohol is typically a fatty alcohol of between 8 and 24
carbon atoms. The fatty alcohols are meant herein to include
monohydric and polyhydric fatty alcohols, particularly those
containing 8 to 24 carbon atoms exhibiting straight-chain or
branched-chain structure, which are saturated or unsaturated
(containing one or more carbon-carbon double bonds). Non-limiting
examples of fatty alcohols include oleic, linolenic, linolenic,
lauric, caproic, erucic, myristic and palmitic alcohols, as well as
mixtures of any of the foregoing fatty alcohols. In some
embodiments, the fatty alcohol may be an unsaturated primary
alcohol such as 9-decen-1-ol, which is derived from 9-decenoic
acid.
[0042] Following the above esterification, the base esters were
epoxidized via any suitable peroxyacid. Peroxyacids (peracids) are
acyl hydroperoxides and are most commonly produced by the
acid-catalyzed esterification of hydrogen peroxide. Any peroxyacid
may be used in the epoxidation reaction. The peroxyacids may be
formed in-situ by reacting a hydroperoxide with the corresponding
acid, such as formic or acetic acid. Examples of hydroperoxides
that may be used include, but are not limited to, hydrogen
peroxide, tert-butylhydroperoxide, triphenylsilylhydroperoxide,
cumylhydroperoxide, and preferably, hydrogen peroxide. Other
commercial organic peracids may also be used, such as benzoyl
peroxide, and potassium persulfate. Commonly used solvents in the
epoxidation of the present invention may be chosen from the group
including but not limited to aliphatic hydrocarbons (e.g., hexane
and cyclohexane), organic esters (i.e. ethyl acetate), aromatic
hydrocarbons (e.g., benzene and toluene), ethers (e.g., dioxane,
tetrahydrofuran, ethyl ether, tert-butyl methyl ether), halogenated
hydrocarbons (e.g., methylene chloride and chloroform), and
preferably, methylene chloride.
[0043] Following epoxidation, the addition of any suitable fatty
carboxylic acids, typically having between 3 and 36 carbon atoms,
preferably, propionic or nonanoic acid, was utilized to produce
branched compounds, with further details as described later in this
document.
[0044] In certain embodiments (compounds E, F, G, and H, and their
branched derivatives), the fatty carboxylic acid derived from the
natural oil may be metathesized in the presence of a metathesis
catalyst. Metathesis is a catalytic reaction that involves the
interchange of alkylidene units among compounds containing one or
more double bonds (i.e., olefinic compounds) via the formation and
cleavage of the carbon-carbon double bonds.
[0045] The metathesis catalyst in this reaction may include any
catalyst or catalyst system that catalyzes a metathesis reaction.
Any known metathesis catalyst may be used, alone or in combination
with one or more additional catalysts. Non-limiting exemplary
metathesis catalysts and process conditions are described in
PCT/US2008/009635, pp. 18-47, incorporated by reference herein. A
number of the metathesis catalysts as shown are manufactured by
Materia, Inc. (Pasadena, Calif.).
[0046] With regards to compounds E, F, G, and H, and their branched
derivatives, 9-decenoic acid may be formed by the cross-metathesis
of oleic acid or methyl oleate, found in or derived from natural
oils, with ethene, propene, butene, hexene, and/or a higher
alpha-olefin which produces 9-decenoic acid (or the corresponding
ester of decenoic acid if an ester (e.g., the methyl ester) of
oleic acid is employed), and 1-decene. The cross-metathesis of
oleic acid or methyl oleate with ethene, propene, butene and/or a
higher alpha-olefin is carried out in the presence of a metathesis
catalyst under suitable metathesis reaction conditions. Also, in
some embodiments, compounds E, F, G and H may be prepared by
cross-metathesis from compound A and an olefin having a terminal
carbon double bond (such as those described in the preceding
sentence). Generally, cross metathesis may be represented
schematically as shown in Equation I:
R.sup.1--CH.dbd.CH--R.sup.2+R.sup.3--CH.dbd.CH--R.sup.4.revreaction.R.su-
p.1--CH.dbd.CH--R.sup.3+R.sup.1--CH.dbd.CH--R.sup.4+R.sup.2--CH.dbd.CH--R.-
sup.3+R.sup.2--CH.dbd.CH--R.sup.4+R.sup.1--CH.dbd.CH--R.sup.1+R.sup.2--CH.-
dbd.CH--R.sup.2+R.sup.3--CH.dbd.CH--R.sup.3+R.sup.4--CH.dbd.CH--R.sup.4
(I) [0047] wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are
organic groups.
[0048] In some embodiments, compound H may be prepared by
self-metathesis via compound G (metathesis occurring between two of
the same molecules, in this case, compound G). Generally,
self-metathesis may be represented schematically as shown in
Equation II below.
R.sup.1--CH.dbd.CH--R.sup.2+R.sup.1--CH.dbd.CH--R.sup.2.revreaction.R.su-
p.1--CH.dbd.CH--R.sup.1+R.sup.2--CH.dbd.CH--R.sup.2 (II) [0049]
wherein R.sup.1 and R.sup.2 are organic groups.
[0050] In some embodiments, the 9-decenoic acid may be reduced to
9-decen-1-ol using a typical reducing agent under conditions known
to a person skilled in the art. The reducing agent is typically a
hydride reagent such as lithium aluminum hydride and boron hydrides
such as sodium borohydride, diborane, and 9-borabicyclo [3.3.1]
nonane (9-BBN); preferably, the reducing agent is lithium aluminum
hydride. In the alternative, an ester of the 9-decenoic acid, such
as methyl 9-decenoate, may be hydrogenated into 9-decen-1-ol with a
hydrogen containing gas and in the presence of a catalyst system,
under hydrogenation conditions known to a person skilled in the
art. The 9-decen-1-ol may be reacted with a suitable fatty
carboxylic acid or its acid chloride as stated below for specific
compounds.
[0051] A non-limiting listing of representative dimer esters
produced by the process of this invention is listed below in Table
1.
TABLE-US-00001 TABLE 1 Dimer Esters and their branched derivatives
synthesized (the column headed "Structure" refers to the structures
shown in FIGS. 1, 4, and 4A). Com- pounds Name Structure A
Octadec-9-enoic acid octadec-9-enyl ester n1 = n2 = 8 m1 = m2 = 5 B
Docos-13-enoic acid octadec-9-enyl ester n1 = n2 = 8 m1 = 9; m2 = 5
C Docos-13-enoic acid docos-13-enyl ester n1 = n2 = 8 m1 = m2 = 9 D
Octadec-9-enoic acid docos-13-enyl ester n1 = n2 = 8 m1 = 5; m2 = 9
E octadec-9-enyl dec-9-enoate n1 = 0; n2 = 8 m1 = m2 = 5 F
dec-9-enyl oleate n1 = 8; n2 = 0 m1 = m2 = 5 G dec-9-enyl
dec-9-enoate n1 = n2 = 0 m1 = m2 = 5 A2
9(10)-hydroxy-10(9)-(propionyloxy)octa- n1 = n2 = 8 decyl
9(10)-hydroxy-10(9)- m1 = m2 = 5 (propionyloxy)octadecanoate R =
C.sub.2H.sub.5 A2-II 9(10)-hydroxy-10(9)-(nonanoyloxy)octa- n1 = n2
= 8 decyl 9(10)-hydroxy-10(9)- m1 = m2 = 5
(nonanoyloxy)octadecanoate R = C.sub.8H.sub.17 A3
1-(9(10)-hydroxy-10(9)- n1 = n2 = 8
(propionyloxy)octadecanoyloxy)octadecane- m1 = m2 = 5
9,10-diyldipropionate or/and 1-(9(10)- R = C.sub.2H.sub.5
hydroxy-10(9)-(propionyloxy)octadecyloxy)-
1-oxooctadecane-9,10-diyl dipropionate A4 1-(9,10- n1 = n2 = 8
bis(propionyloxy)octadecanoyloxy)octadec- m1 = m2 = 5 ane-9,10-diyl
dipropionate R = C.sub.2H.sub.5 B2
10(9)-hydroxy-9(10)-(propionyloxy)octa- n1 = n2 = 8 decyl
13(14)-hydroxy-14(13)- m1 = 9; m2 = 5 (propionyloxy)docosanoate R =
C.sub.2H.sub.5 B3 22-(10(9)-hydroxy-9(10)- n1 = n2 = 8
(propionyloxy)octadecyloxy)-22-oxo- m1 = 9; m2 = 5
docosane-9,10-diyl dipropionate or/and R = C.sub.2H.sub.5
1-(13(14)-hydroxy-14(13)-(propionyl-
oxy)docosanoyloxy)octadecane-9,10-diyl dipropionate B4 1-(13,14- n1
= n2 = 8 bis(propionyloxy)docosanoyloxy)octa- m1 = 9; m2 = 5
decane-9,10-diyl dipropionate R = C.sub.2H.sub.5 C2
13(14)-hydroxy-14(13)-(propionyl- n1 = n2 = 8 oxy)docosyl
13(14)-hydroxy-14(13)- m1 = m2 = 9 (propionyloxy)docosanoate R =
C.sub.2H.sub.5 C2-II 13(14)-hydroxy-14(13)-(nonanoyl- n1 = n2 = 8
oxy)docosyl 13(14)-hydroxy-14(13)- m1 = m2 = 9
(nonanoyloxy)docosanoate R = C.sub.8H.sub.17 C3
22-(13(14)-hydroxy-14(13)- n1 = n2 = 8
(propionyloxy)docosyloxy)-22-oxodocosane- m1 = m2 = 9 9,10-diyl
dipropionate or/and 22-(13(14)- R = C.sub.2H.sub.5
hydroxy-14(13)-(propionyloxy)docosanoyl- oxy)docosane-9,10-diyl
dipropionate C4 22-(13,14- n1 = n2 = 8
bis(propionyloxy)docosanoyloxy)docosane- m1 = m2 = 9 9,10-diyl
dipropionate R = C.sub.2H.sub.5 D2
14(13)-hydroxy-13(14)-(propionyl- n1 = n2 = 8 oxy)docosyl
9(10)-hydroxy-10(9)- m1 = 5; m2 = 9 (propionyloxy)octadecanoate R =
C.sub.2H.sub.5 D3 22-(9(10)-hydroxy-10(9)- n1 = n2 = 8
(propionyloxy)octadecanoyloxy)docosane- m1 = 5; m2 = 9 9,10-diyl
dipropionate or/and 1-(14(13)- R = C.sub.2H.sub.5
hydroxy-13(14)-(propionyloxy)docosyloxy)- 1-oxooctadecane-9,10-diyl
dipropionate D4 1-(13,14-bis(propionyloxy)docosyloxy)-1- n1 = n2 =
8 oxooctadecane-9,10-diyl dipropionate m1 = 5; m2 = 9 R =
C.sub.2H.sub.5 E2-1 10(9)-hydroxy-9(10)-(propionyl- n1 = 0; n2 = 8
oxy)octadecyl m1 = m2 = 5 9-hydroxy-10-(propionyloxy)decanoate R =
C.sub.2H.sub.5 E2-2 10(9)-hydroxy-9(10)-(propionyl- n1 = 0; n2 = 8
oxy)octadecyl m1 = m2 = 5 10-hydroxy-9-(propionyloxy)decanoate R =
C.sub.2H.sub.5 E3 10-(10(9)-hydroxy-9(10)- n1 = 0; n2 = 8
(propionyloxy)octadecyloxy)-10-oxodecane- m1 = m2 = 5 1,2-diyl
dipropionate R = C.sub.2H.sub.5 E4 1-(9,10- n1 = 0; n2 = 8
bis(propionyloxy)decanoyloxy)octadecane- m1 = m2 = 5 9,10-diyl
dipropionate R = C.sub.2H.sub.5 F2-1
9-hydroxy-10-(propionyloxy)decyl 9(10)- n1 = 8; n2 = 0
hydroxy-10(9)-(propionyloxy)octadecanoate m1 = m2 = 5 R =
C.sub.2H.sub.5 F2-2 10-hydroxy-9-(propionyloxy)decyl 9(10)- n1 = 8;
n2 = 0 hydroxy-10(9)-(propionyloxy)octadecanoate m1 = m2 = 5 R =
C.sub.2H.sub.5 F3 10-(9(10)-hydroxy-10(9)- n1 = 8; n2 = 0
(propionyloxy)octadecanoyloxy)decane-1,2- m1 = m2 = 5 diyl
dipropionate R = C.sub.2H.sub.5 F4
1-(9,10-bis(propionyloxy)decyloxy)-1- n1 = 8; n2 = 0
oxooctadecane-9,10-diyl dipropionate m1 = m2 = 5 R = C.sub.2H.sub.5
G2-1 9-hydroxy-10-(propionyloxy)decyl 9- n1 = n2 = 0
hydroxy-10-(propionyloxy)decanoate m1 = m2 = 5 R = C.sub.2H.sub.5
G2-2 10-hydroxy-9-(propionyloxy)decyl 9- n1 = n2 = 0
hydroxy-10-(propionyloxy)decanoate m1 = m2 = 5 or/and
9-hydroxy-10-(propionyloxy)decyl R = C.sub.2H.sub.5
10-hydroxy-9-(propionyloxy)decanoate G3-1 10-(9-hydroxy-10- n1 = n2
= 0 (propionyloxy)decanoyloxy)decane-1,2-diyl m1 = m2 = 5
dipropionate or/and 10-(9-hydroxy-10- R = C.sub.2H.sub.5
(propionyloxy)decyloxy)-10-oxodecane-1,2- diyl dipropionate G3-2
10-(10-hydroxy-9- n1 = n2 = 0
(propionyloxy)decanoyloxy)decane-1,2-diyl m1 = m2 = 5 dipropionate
or/and 10-(10-hydroxy-9- R = C.sub.2H.sub.5
(propionyloxy)decyloxy)-10-oxodecane-1,2- diyl dipropionate G4
10-(9,10-bis(propionyloxy)decanoyloxy)dec- n1 = n2 = 0 ane-1,2-diyl
dipropionate m1 = m2 = 5 R = C.sub.2H.sub.5
TABLE-US-00002 TABLE 2 Trimer Esters and their branched derivatives
synthesized (the column headed "Structure" refers to the structures
shown in FIGS. 5 and 5A). Com- pounds Name Structure H
E-didec-9-enyl octadec-9-enedioate n1 = n2 = 0; m1 = m2 = 5; k1 =
k2 = 5 H3 1-(9(10)-hydroxy-10(9)-(propionyloxy)decyl) n1 = n2 = 0;
18-(10(9)-hydroxy-9(10)-(propionyloxy)decyl)- m1 = m2 = 5;
9(10)-hydroxy-10(9)-(propionyloxy)octadec- k1 = k2 = 5 anedioate R
= C.sub.2H.sub.5 H4 1-(9,10-bis(propionyloxy)decyl) 18-(9(10)- n1 =
n2 = 0; hydroxy-10(9)-(propionyloxy)decyl) 10(9)- m1 = m2 = 5;
hydroxy-9(10)-(propionyloxy)octadec- k1 = k2 = 5 anedioate R =
C.sub.2H.sub.5 H5 Bis (9,10-bis(propionyloxy)decyl)9(10)- n1 = n2 =
0; hydroxy-10(9)-(propionyloxy)octadec- m1 = m2 = 5; andioate k1 =
k2 = 5 R = C.sub.2H.sub.5 H6 Bis
(9,10-bis(propionyloxy)decyl)9,10-bis n1 = n2 = 0;
(propionyloxy)octadecanedioate m1 = m2 = 5; k1 = k2 = 5 R =
C.sub.2H.sub.5
[0052] The dimer esters presented were prepared by two general
procedures described in FIG. 1, with specifics described for each
compound A-G described later below:
[0053] Procedure 1:
[0054] To a solution of fatty alcohol (typically 1-100 mmol,
preferably 5-50 mmol, and most preferably, 10 mmol) in Chloroform
(typically 1-100 mL, preferably 10-50 mL, and most preferably, 20
mL), fatty acid (typically 1-100 mmol, preferably 5-50 mmol, and
most preferably 10.1 mmol), 4-dimethylaminopyridine (typically
1-100 mmol, preferably 5-50 mmol, and most preferably 10 mmol) was
added. To this reaction mixture in an ice bath,
dicyclohexyl-carbodiimide (typically 1-100 mmol, preferably 5-50
mmol, and most preferably 11 mmol) in Chloroform was added slowly
and the reaction was stirred at a temperature (typically between
4-50.degree. C., preferably between 12-33.degree. C., and most
preferably between 17-27.degree. C.) overnight. The precipitated
dicyclohexylurea was removed by filtration. The organic phase was
then washed sequentially with water, 5% HCl, 4% NaHCO3, water. The
solvents were roto-evaporated and the residue was purified by
column chromatography with Ethyl Acetate/Hexane to give a colorless
oil.
[0055] Procedure 2:
[0056] To a solution of fatty alcohol (typically 1-100 mmol,
preferably 5-50 mmol, and most preferably 10 mmol) in chloroform
(typically 1-100 mL, preferably 10-50 mL, and most preferably 30
mL), acyl chloride (typically 1-100 mmol, preferably 5-50 mmol, and
most preferably 10 mmol) was added. Pyridine (typically 1-100 mmol,
preferably 5-50 mmol, and most preferably 12 mmol) was then added
to the reaction solution drop wise. The reaction mixture was
stirred at a temperature (typically between 4-50.degree. C.,
preferably between 12-33.degree. C., and most preferably between
17-27.degree. C.) overnight. The reaction mixture was then diluted
with another amount of Chloroform (typically 1-300 mL, preferably
100-200 mL, and most preferably 160 mL). The organic layer was
washed with water (3.times.50 mL), followed by 5% HCl (2.times.50
mL), water (2.times.50 mL), 4% NaHCO.sub.3 (2.times.50 mL) and
water (3.times.50 mL). The organic layer was dried over
Na.sub.2SO.sub.4. After chloroform was removed, the residue was
purified by column chromatography with Ethyl acetate/Hexane to give
a colorless oil.
[0057] The synthesis of the esters were followed by epoxidation
with peroxyacid which was formed from formic acid and hydrogen
peroxide in situ to give epoxides (FIG. 2) with CH.sub.2Cl.sub.2
(methylene chloride) used as solvent. Compared to the reaction
without CH.sub.2Cl.sub.2, epoxidation with CH.sub.2Cl.sub.2 as a
solvent was faster with fewer side-products, since CH.sub.2Cl.sub.2
improves the solubility of the reagents in the reaction.
Epoxidations of compounds E, F and G, with terminal double bonds,
were slower (.about.36 hours as opposed to .about.5 hours for the
epoxidations of compounds A, B, C and D) because the alkyl group on
the carbon double bond in compounds A, B and C can increase the
rate of epoxidation.
[0058] To a stirred solution of ester (typically 1-100 mmol,
preferably 5-50 mmol, and most preferably 10 mmol) and formic acid
(typically 1-100 mmol, preferably 20-80 mmol, and most preferably
60 mmol) in CH.sub.2Cl.sub.2 (typically 1-100 mL, preferably 5-50
mL, and most preferably 10 mL) at 4.degree. C., H.sub.2O.sub.2
(typically 1-100 mmol, preferably 5-70 mmol, and most preferably 44
mmol) was slowly added. The reaction proceeded at a temperature
(typically between 4-50.degree. C., preferably between
12-33.degree. C., and most preferably between 17-27.degree. C.)
with vigorous stirring for 4-36 hrs. After removal of the aqueous
phase, additional CH.sub.2Cl.sub.2 (30 mL) was added to the organic
phase, which was washed sequentially with water (2.times.20 mL),
saturated aqueous NaHCO.sub.3 (2.times.10 mL) and brine (2.times.20
mL), then dried on Na.sub.2SO.sub.4, filtered, and concentrated.
The residue was purified by column chromatography with Ethyl
acetate/Hexane to give white crystals.
I. Synthesis of Dimer and Trimer Esters and Branched Derivatives of
Dimer and Trimer Esters
[0059] The addition of carboxylic acids to the epoxides by
ring-opening esterification was accomplished to give branched
compounds without need for either a further catalyst or further
solvent as shown in FIGS. 2 and 3. The reactions with 2-branched
compounds as main products were carried out at typically between
50-150.degree. C., preferably between about 70-120.degree. C., and
most preferably at about 95.degree. C., but those with 3- and
4-branched compounds were carried out at typically between
60-160.degree. C., preferably between about 80-140.degree. C., and
most preferably at about 120.degree. C., where water produced in
the reactions was partially removed.
[0060] For branched compounds derived from compounds A, B, C and D,
no effort to distinguish the regiochemistry
(9-alkanonate-10-hydroxy-oactadecanoate versus the equally likely
alkyl 10-alkanoate-9-9hydroxyoctadecanoate regio-isomer) or the
stereochemistry (S, or R at C9 and C10) of the polyol esters was
made due to the laborious chromatography required and the economics
involved at potentially larger commercial scales. However, for
those branched compounds derived from compounds E, F and G, in
consideration of the fact that the position of hydroxyl group or
carboxyl acid branch at the chain end would have significant
influence on their properties, and since the differences in their
polarity makes them easier to separate, the regio-isomers (but not
stereo-isomers) were separated.
[0061] To the epoxidation products above, (typically 1-100 mmol,
preferably 5-50 mmol, and most preferably 10 mmol), propionic acid
or nonanoic acid (typically 1-400 mmol, preferably 100-300 mmol,
and most preferably 220 mmol) was added. The reaction was carried
out under an N.sub.2 atmosphere and heated to typically between
50-150.degree. C., preferably between about 70-120.degree. C., and
most preferably at 95.degree. C. and stirred at 95.degree. C. for
typically between about 4 to 36 hours, preferably 10-20 hours, and
most preferably 16 hours. To achieve 3 or 4 branches in the
compounds, the reaction temperature was raised to typically between
60-160.degree. C., preferably between about 80-140.degree. C., and
most preferably at 120.degree. C. The resulting products were
poured into 200 mL of water and extracted with Ethyl acetate
(2.times.50 mL). The organic phase was washed sequentially by water
(2.times.100 mL), saturated aqueous NaHCO.sub.3 (2.times.100 mL)
and brine (2.times.200 mL), dried on Na.sub.2SO.sub.4, and
concentrated. The residue was purified by column chromatography
with Ethyl Acetate/Hexane.
[0062] The dimer ester branched derivatives were prepared by the
synthesis shown in FIG. 4. The respective dimer esters are depicted
by the generalized structure in FIG. 4A, wherein n1=between 0 and
8; wherein n2=between 0 and 8; wherein m1=between 5 and 9; and
wherein m2=between 5 and 9.
[0063] In a generalized manner, the syntheses of the dimer ester
branched compounds yields a compound as depicted in FIG. 4B,
wherein n1 is between 0 and 8; wherein n2 is between 0 and 8;
wherein m1 is between 5 and 9; wherein m2 is between 5 and 9;
wherein W is OH or OCOR, wherein X is OH or OCOR, wherein Y is OCOR
or OH; wherein Z is OH or OCOR, and in groups W, X, Y, and Z,
R=CiHj, wherein i is 2 or greater and j is 5 or greater.
[0064] The trimer esters presented (Compound H) and its branched
derivatives are depicted as shown in FIG. 5. The respective base
trimer ester is depicted by the generalized structure in FIG. 5A,
wherein n1=between 0 and 8; wherein n2=between 0 and 8; wherein
m1=between 5 and 9; wherein m2=between 5 and 9; and wherein
k1=k2=5.
[0065] In a generalized manner, the syntheses of the trimer ester
branched compounds yields a compound as depicted in FIG. 5B,
wherein n1 is between 0 and 8; wherein n2 is between 0 and 8;
wherein m1 is between 5 and 9; wherein m2 is between 5 and 9;
wherein k1=k2=5 or greater; wherein P=OH or OCOR; wherein Q=OH or
OCOR; wherein S=OCOR or OH; wherein T=OH or OCOR; wherein U=OH or
OCOR; wherein V=OH or OCOR, and in groups P, Q, S, T, U, and V,
R=CiHj, wherein i is 2 or greater and j is 5 or greater.
[0066] The compounds presented in Table 1 and Table 2 above were
characterized with a combination of nuclear magnetic resonance
(1H-NMR), high performance liquid chromatography (HPLC), and/or
mass spectrometry (MS), as shown in Table 3 below.
TABLE-US-00003 TABLE 3 Characterization of Compounds Com-
Characterization methods pounds 1H-NMR HPLC-Fid MS A Yes No No B
Yes No No C Yes No No D Yes No No E Yes No No F Yes No No G Yes No
No A2 Yes No No A2-II Yes No No A3 Yes No No A4 Yes No No B2 Yes No
No B3 Yes No No B4 Yes No No C2 Yes No No C2-II Yes No No C3 Yes No
No C4 Yes No No D2 Yes Yes No D3 Yes No No D4 Yes Yes No E2-1 Yes
Yes Yes E2-2 Yes Yes No E3 Yes Yes No E4 Yes Yes No F2-1 Yes Yes No
F2-2 Yes Yes No F3 Yes Yes Yes F4 Yes Yes Yes G2-1 Yes Yes No G2-2
Yes No Yes G3-1 Yes Yes Yes G3-2 Yes No No G4 Yes Yes No H Yes No
No H3 Yes Yes Yes H4 Yes Yes Yes H5 Yes Yes Yes H6 Yes Yes Yes
[0067] The synthesis of the individual dimer and trimer esters,
their epoxides, and their branched derivatives, are provided
below:
Octadec-9-enoic acid octadec-9-enyl ester (Compound A)
[0068] Compound A was prepared from Oleoyl chloride and ( )eyl
alcohol in the presence of pyridine following the general procedure
discussed before and as shown in FIG. 6. Pure compound A was a
colorless oil obtained by column chromatography with Ethyl
acetate/Hexane=1:30. Reaction conditions for branched derivative
compounds A2, A3, and A4 are also shown below.
[0069] Yield: 98.5%
[0070] 1H-NMR in CDCl.sub.3 (ppm): 5.4 (4, m), 4.1 (2, t), 2.3 (2,
t), 2.1-2.0 (8, m), 1.7-1.56 (4, m), 1.44-1.20 (42, m), 0.86-0.76
(6, t)
[0071] Purity: >95%
Docos-13-enoic acid octadec-9-enyl ester (Compound B)
[0072] Compound B was prepared from Erucic acid and Oleyl alcohol
in the presence of DCC and DMAP following the general procedure
discussed before and as shown in FIG. 7. Pure compound B was a
colorless oil obtained by column chromatography with Ethyl
acetate/Hexane=1:40. Reaction conditions for branched derivative
compounds B2, B3, and B4 are also shown below.
[0073] Yield: 91.8%
[0074] 1H-NMR in CDCl.sub.3 (ppm), 5.4 (4, m), 4.1 (2, t), 2.3 (2,
t), 2.1-2.0 (8, m), 1.7-1.56 (4, m), 1.44-1.20 (50, m), 0.86-0.76
(6, t)
[0075] Purity: >95%
Docos-13-enoic acid docos-13-enyl ester (Compound C)
[0076] Compound C was prepared from Erucic acid and Erucic alcohol
with presence of DCC and DMAP following the general procedure
discussed before and as shown in FIG. 8. Pure compound C was a
colorless oil obtained by column chromatography with Ethyl
acetate/Hexane=1:40. Reaction conditions for branched derivative
compounds C2, C3, and C4 are also shown below.
[0077] Yield: 95%
[0078] 1H-NMR in CDCl.sub.3 (ppm), 5.4 (4, m), 4.1 (2, t), 2.3 (2,
t), 2.1-2.0 (8, m), 1.7-1.56 (4, m), 1.44-1.20 (58, m), 0.86-0.76
(6, t)
[0079] Purity: >95%
Octadec-9-enoic acid docos-13-enyl ester (Compound D)
[0080] Compound D was prepared from Oleoyl chloride and Erucic acid
following the general procedure discussed before and as shown in
FIG. 9. Pure compound D was a colorless oil obtained by column
chromatography with Ethyl acetate/Hexane=1:40. Reaction conditions
for branched derivative compounds D2, D3, and D4 are also shown
below.
[0081] Yield: 94.5%
[0082] 1H-NMR in CDCl.sub.3 (ppm), 5.4 (4, m), 4.1 (2, t), 2.3 (2,
t), 2.1-2.0 (8, m), 1.7-1.56 (4, m), 1.44-1.20 (50, m), 0.86-0.76
(6, t)
[0083] Purity: >95%
Octadec-9-enyl dec-9-enoate (Compound E)
[0084] Compound E was prepared from Oleyl alcohol and 9-decenoic
acid following the general procedure previously discussed and shown
in FIG. 10. Pure compound E was a colorless oil obtained by column
chromatography with Ethyl acetate/Hexane=1:40.
[0085] Yield: 96%
[0086] 1H-NMR in CDCl.sub.3 (ppm), 5.8 (1, m), 5.4 (2, m), 5.0 (2,
dd), 4.1 (2, t), 2.3 (2, t), 2.0 (6, m), 1.6 (4, m), 1.4-1.2 (30,
m), 0.9 (3, t)
[0087] Purity: >95%
Dec-9-enyl oleate (Compound F)
[0088] Compound F was prepared from Oleoyl chloride and
9-decen-1-ol following the general procedure already discussed and
shown in FIG. 11. Pure compound F was a colorless oil obtained by
column chromatography with Ethyl acetate/Hexane=1:40.
[0089] Yield: 97.5%
[0090] 1H-NMR in CDCl.sub.3 (ppm), 5.8 (1, m), 5.4 (2, m), 5.0 (2,
dd), 4.1 (2, t), 2.3 (2, t), 2.0 (6, m), 1.6 (4, m), 1.4-1.2 (30,
m), 0.9 (6, t)
[0091] Purity: >95%
Dec-9-enyl dec-9-enoate (Compound G)
[0092] Compound G was prepared from 9-decen-1-ol and 9-decenoic
acid following the general procedure already discussed and shown in
FIG. 12. Pure compound G was a colorless oil by column
chromatography with Ethyl acetate/Hexane=1:50.
[0093] Yield: 92.7%
[0094] 1H-NMR in CDCl.sub.3 (ppm), 5.8 (2, m), 5.0 (4, dd), 4.0 (2,
t), 2.3 (2, t), 2.0 (4, m), 1.6 (4, m), 1.4-1.2 (18, m)
[0095] Purity: >95%
8-(3-octyloxiran-2-yl) octyl 8-(3-octyloxiran-2-yl) octanoate
(Epoxides of A)
[0096] Epoxide was prepared from compound A with H.sub.2O.sub.2 and
Formic acid as shown in FIG. 6. Pure compound was obtained by
column chromatography with Ethyl acetate/Hexane=1:30.
[0097] Yield: 70%
[0098] 1H-NMR in CDCl.sub.3 (ppm): 4.1 (2, t), 2.9 (4, Br), 2.3 (2,
t), 2.1-2.0 (8, m), 1.7-1.6 (4, m), 1.5-1.20 (42, m), 0.86-0.76 (6,
t)
[0099] Purity: >95%
8-(3-octyloxiran-2-yl) octyl 12-(3-octyloxiran-2-yl) dodecanoate
(Epoxide of B)
[0100] Epoxide was prepared from compound B with H.sub.2O.sub.2 and
Formic acid with CH.sub.2Cl.sub.2 as a solvent as shown in FIG. 7.
Pure compound was obtained by column chromatography with Ethyl
acetate/Hexane=1:20.
[0101] Yield: 75%
[0102] 1H-NMR in CDCl.sub.3 (ppm), 4.1 (2, t), 2.9 (4, br), 2.3 (2,
t), 2.1-2.0 (8, m), 1.7-1.56 (4, m), 1.44-1.20 (50, m), 0.86-0.76
(6, t)
[0103] Purity: >95%
12-(3-octyloxiran-2-yl) dodecyl 12-(3-octyloxiran-2-yl) dodecanoate
(Epoxide of C)
[0104] Epoxide was prepared from compound C with H.sub.2O.sub.2 and
Formic acid and the mixture of Hexane (20 mL) and Ethyl acetate (10
mL) as solvent (Shown in FIG. 8). Pure compound was obtained by
column chromatography with Ethyl acetate/Hexane=1:20 as white
solid.
[0105] Yield: 73%
[0106] 1H-NMR in CDCl.sub.3 (ppm), 4.1 (2, t), 2.9 (4, br), 2.3 (2,
t), 2.1-2.0 (8, m), 1.7-1.56 (4, m), 1.44-1.20 (58, m), 0.86-0.76
(6, t)
[0107] Purity: >95%
12-(3-octyloxiran-2-yl)dodecyl 8-(3-octyloxiran-2-yl)octanoate
(Epoxide of D)
[0108] Epoxide was prepared from compound D with H.sub.2O.sub.2 and
Formic acid with CH.sub.2Cl.sub.2 as solvent (shown in FIG. 9).
Pure compounds was obtained by column chromatography with Ethyl
acetate/Hexane=1:30 as white solid.
[0109] Yield: 72.7%
[0110] 1H-NMR in CDCl.sub.3 (ppm), 4.1 (2, t), 2.9 (4, br), 2.3 (2,
t), 2.1-2.0 (8, m), 1.7-1.56 (4, m), 1.44-1.20 (50, m), 0.86-0.76
(6, t)
[0111] Purity: >95%
8-(3-octyloxiran-2-yl)octyl 8-(oxiran-2-yl)octanoate (Epoxide of
E)
[0112] Epoxide was prepared from compound E with H.sub.2O.sub.2 and
Formic acid with CH.sub.2Cl.sub.2 as solvent and at room
temperature for 28 hours (shown in FIG. 10). Pure compounds was
obtained by column chromatography with Ethyl acetate/Hexane=1:10 as
colorless oil.
[0113] Yield: 75.6%
[0114] 1H-NMR in CDCl.sub.3 (ppm), 4.1 (2, t), 2.9 (3, br), 2.8 (1,
t), 2.5 (1, t) 2.3 (2, t), 1.6-1.2 (40, m), 0.9 (3, t)
[0115] Purity: >95%
8-(oxiran-2-yl)octyl 8-(3-octyloxiran-2-yl)octanoate (Epoxide of
F)
[0116] Epoxide was prepared from compound F with H.sub.2O.sub.2 and
Formic acid with CH.sub.2Cl.sub.2 as solvent and at room
temperature for 48 hours (shown in FIG. 11). Pure compounds was
obtained by column chromatography with Ethyl acetate/Hexane=1:10 as
colorless oil.
[0117] Yield: 71.4%
[0118] 1H-NMR in CDCl.sub.3 (ppm), 4.1 (2, t), 2.9 (3, br), 2.8 (1,
t), 2.5 (1, t) 2.3 (2, t), 1.6-1.2 (40, m), 0.9 (3, t)
[0119] Purity: >95%
8-(oxiran-2-yl)octyl 8-(oxiran-2-yl)octanoate (Epoxide of G)
[0120] Epoxide was prepared from compound F with H.sub.2O.sub.2 and
Formic acid with CH.sub.2Cl.sub.2 as solvent and at room
temperature for 48 hours (shown in FIG. 12). Pure compounds was
obtained by column chromatography with Ethyl acetate/Hexane=1:10 as
colorless oil.
[0121] Yield: 72%
[0122] 1H-NMR in CDCl.sub.3 (ppm), 4.0 (2, t), 3.0 (2, br), 2.7 (2,
t), 2.5 (2, t), 2.3 (2, t), 1.6-1.2 (27, m)
[0123] Purity: >95%
Branched Derivatives of Compound A
[0124] Branched compound A derivatives were prepared from epoxide
of compound A and propionic acid (or nonanoic acid for A2-II) at
95.degree. C. for A2 and A3 or 120.degree. C. for A3 and A4 (Shown
in FIG. 6).
9(10)-hydroxy-10(9)-(propionyloxy) octadecyl
9(10)-hydroxy-10(9)-(propionyloxy) octadecanoate (A2)
[0125] Pure compound A2 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:10.
[0126] Yield: 89.5%
[0127] 1H-NMR in CDCl.sub.3 (ppm), 4.8 (2, m), 4.1 (2, t), 3.7-3.5
(2, m), 2.4-2.2 (6, m), 1.5-1.2 (46, m), 1.1 (6, t), 0.8 (6, t)
[0128] Purity>95%
9(10)-hydroxy-10(9)-(nonanoyloxy) octadecyl
9(10)-hydroxy-10(9)-(nonanoyloxy) octadecanoate (A2-II)
[0129] Pure compound A2-II was given as colorless oil by column
chromatography with Ethyl Acetate/Hexane=1:10.
[0130] Yield: 64%
[0131] 1H-NMR in CDCl.sub.3 (ppm), 4.8 (2, m), 4.1 (2, t), 3.7-3.5
(2, m), 2.4-2.2 (6, m), 1.6 (16, m), 1.5-1.2 (62, m), 0.8 (12,
t)
[0132] Purity: >95%
1-(9(10)-hydroxy-10(9)-(propionyloxy) octadecanoyloxy)
octadecane-9,10-diyldipropionate or/and
1-(9(10)-hydroxy-10(9)-(propionyloxy)
octadecyloxy)-1-oxooctadecane-9,10-diyl dipropionate (A3)
[0133] Pure compound A3 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:6.
[0134] Yield: 30.6% A4+38.2% A3 at 120.degree. C.
[0135] 1H-NMR in CDCl.sub.3 (ppm), 5.0 (2, m), 4.8 (1, m), 4.0 (2,
t), 3.6 (1, m), 2.4-2.2 (8, m), 1.8-1.2 (55, m), 1.1 (9, t), 0.8
(6, t)
[0136] Purity: >95%
1-(9,10-bis(propionyloxy)octadecanoyloxy)octadecane-9,10-diyl
dipropionate (A4)
[0137] Pure compound A4 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:10.
[0138] Yield: 30.6% A4+38.2% A3 at 120.degree. C.
[0139] 1H-NMR in CDCl.sub.3 (ppm), 5.0 (4, m), 4.0 (2, t), 2.4-2.2
(10, m), 1.7-1.5 (6, m), 1.4-1.2 (48, m), 1.1 (12, t), 0.8 (6,
t)
[0140] Purity: >95%
Branched Derivatives of Compound B:
[0141] Branched Compound B derivatives were prepared from the
epoxide of compound B and propionic acid at 95.degree. C. for B2
and B3 or 120.degree. C. for B3 and B4 (shown FIG. 7).
10(9)-hydroxy-9(10)-(propionyloxy) octadecyl
13(14)-hydroxy-14(13)-(propionyloxy) docosanoate (B2)
[0142] Pure compound B2 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:8.
[0143] Yield: 47.8% B2+29% B3 at 95.degree. C.; 46% B2+35.7%
B3+11.3% B4 at 120.degree. C. 1H-NMR in CDCl.sub.3 (ppm), 4.8 (2,
m), 4.0 (2, t), 3.6 (2, br), 2.3 (4, q), 2.2 (2, t), 1.8-1.5 (10,
m), 1.5-1.2 (56, m), 1.1 (6, t), 0.8 (6, t)
[0144] Purity: >95%
22-(10(9)-hydroxy-9(10)-(propionyloxy)octadecyloxy)-22-oxodocosane-9,10-di-
yl dipropionate or/and
1-(13(14)-hydroxy-14(13)-(propionyloxy)docosanoyloxy)octadecane-9,10-diyl
dipropionate (B3)
[0145] Pure compound B3 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:10.
[0146] Yield: 47.8% B2+29% B3 at 95.degree. C., 46% B2+35.7%
B3+11.3% B4 at 120.degree. C.
[0147] 1H-NMR in CDCl.sub.3 (ppm), 5.0 (2, m), 4.8 (1, m), 4.0 (2,
t), 3.6 (1, br), 2.4-2.2 (8, m), 1.7-1.2 (63, m), 1.1 (9, t), 0.8
(6, t)
[0148] Purity: >95%
1-(13, 14-bis (propionyloxy)docosanoyloxy)octadecane-9,10-diyl
dipropionate (B4)
[0149] Pure compound B4 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:10.
[0150] Yield: 46% B2+35.7% B3+11.3% B4 at 120.degree. C.
[0151] 1H-NMR in CDCl.sub.3 (ppm), 4.8 (4, m), 3.6 (2, t), 2.2-2.0
(10, m), 1.4-1.2 (12, br), 1.1-0.9 (50, m), 0.8 (12, t), 0.6 (6,
t)
[0152] Purity: >95%
Branched Derivatives of Compound C:
[0153] Branched Compound C derivatives were prepared from epoxide
of compound C and propionic acid (or nonanoic acid for C2-II) at
95.degree. C. for compounds C2 and C3 or 120.degree. C. for C3 and
C4 (shown in FIG. 8).
13(14)-hydroxy-14(13)-(propionyloxy)docosyl
13(14)-hydroxy-14(13)-(propionyloxy)docosanoate (C2)
[0154] Pure compound C2 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:8.
[0155] Yield: 71.6% C2 and 17.9% C3 at 95.degree. C.
[0156] 1H-NMR in CDCl.sub.3 (ppm), 4.8 (2, m), 4.1 (2, t), 3.6 (2,
br), 2.4 (4, q), 2.3 (2, t), 1.6 (10, br), 1.5-1.2 (62, m), 1.1 (6,
t), 0.9 (6, t)
[0157] Purity: >95%
13(14)-hydroxy-14(13)-(nonanoyloxy)docosyl
13(14)-hydroxy-14(13)-(nonanoyloxy)docosanoate (C2-II)
[0158] Yield: 87.1%
[0159] 1H-NMR in CDCl.sub.3 (ppm), 4.8 (2, m), 4.1 (2, t), 3.6 (2,
br), 2.4-2.3 (6, t), 1.6 (12, br), 1.5-1.2 (86, m), 0.9 (12, t)
[0160] Purity: >95%
22-(13(14)-hydroxy-14(13)-(propionyloxy)docosyloxy)-22-oxodocosane-9,10-di-
yl dipropionate or/and
22-(13(14)-hydroxy-14(13)-(propionyloxy)docosanoyloxy)docosane-9,10-diyld-
ipropionate (C3)
[0161] Pure compound C3 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:10.
[0162] Yield: 71.6% C2 and 17.9% C3 at 95.degree. C., 44.8%
C4+39.7% C3 at 120.degree. C.
[0163] 1H-NMR in CDCl.sub.3 (ppm), 5.0 (2, m), 4.8 (1, m), 4.0 (2,
t), 3.5 (1, br), 2.4-0.22 (8, m), 1.6-1.2 (71, m), 1.1 (9, t), 0.8
(6, t)
[0164] Purity: >95%
22-(13,14-bis(propionyloxy)docosanoyloxy)docosane-9,10-diyldipropionate
(C4)
[0165] Pure compound C4 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:10.
[0166] Yield: 44.8% C4+39.7% C3 at 120.degree. C.
[0167] 1H-NMR in CDCl.sub.3 (ppm), 5.0 (4, m), 4.0 (2, t), 2.4-2.2
(10, m), 1.6-1.4 (12, br), 1.4-1.2 (58, m), 1.1 (12, t), 0.8 (6,
t)
[0168] Purity: >95%
Branched Derivatives of Compound D:
[0169] Branched Compound D derivatives were prepared from the
epoxide of compound D and propionic acid at 95.degree. C. for D2
and D3 or 120.degree. C. for D3 and D4 (shown in FIG. 9).
14(13)-hydroxy-13(14)-(propionyloxy)docosyl
9(10)-hydroxy-10(9)-(propionyloxy)octadecanoate (D2)
[0170] Pure compound D2 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:8.
[0171] Yield: 77.8% D2+9.5% D3 at 95.degree. C.
[0172] 1H-NMR in CDCl.sub.3 (ppm), 4.8 (2, m), 4.0 (2, t), 3.6 (2,
br), 2.3 (4, q), 2.2 (2, t), 1.8-1.5 (10, m), 1.5-1.2 (54, m), 1.1
(6, t), 0.8 (6, t)
[0173] Purity: >95%
22-(9(10)-hydroxy-10(9)-(propionyloxy)octadecanoyloxy)docosane-9,10-diyl
dipropionate or/and
1-(14(13)-hydroxy-13(14)-(propionyloxy)docosyloxy)-1-oxooctadecane-9,10-d-
iyl dipropionate (D3)
[0174] Pure compound D3 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:10.
[0175] Yield: 77.8% D2+9.5% D3 at 95.degree. C., 42.8% D4+48.5% D3
at 120.degree. C.
[0176] 1H-NMR in CDCl.sub.3 (ppm), 5.0 (2, m), 4.8 (1, m), 4.0 (2,
t), 3.6 (1, br), 2.4-2.2 (8, m), 1.7-1.2 (63, m), 1.1 (9, t), 0.8
(6, t)
[0177] Purity: >95%
1-(13,14-bis(propionyloxy)docosyloxy)-1-oxooctadecane-9,10-diyl
dipropionate (D4)
[0178] Pure compound D4 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:10.
[0179] Yield: 42.8% D4+48.5% D3 at 120.degree. C.
[0180] 1H-NMR in CDCl.sub.3 (ppm), 4.8 (4, m), 3.6 (2, t), 2.2-2.0
(10, m), 1.4-1.2 (12, br), 1.1-0.9 (50, m), 0.8 (12, t), 0.6 (6,
t)
[0181] Purity: >95%
Branched Derivatives of Compound E:
[0182] Branched Compound E derivatives were prepared from the
epoxide of compound E and propionic acid at 95.degree. C. for E2
and E3 or 120.degree. C. for E3 and E4 (shown in FIG. 10).
10(9)-hydroxy-9(10)-(propionyloxy)octadecyl
9-hydroxy-10-(propionyloxy)decanoate (E2-1)
[0183] Pure compound E2-1 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:4.
[0184] Yield: 26% g E3+58% E2-M at 95.degree. C. (E2-M meaning a
70:30 wt:wt mixture of E2-1 and E2-2 by HPLC).
[0185] 1H-NMR in CDCl.sub.3 (ppm), 5.0-4.8 (1, m), 4.2 (1, d), 4.1
(2, t), 4.0 (1, dd), 3.8 (1, m), 3.7-3.5 (2, m), 2.4 (4, m), 2.2
(2, t), 1.6-1.2 (41, m), 1.1 (6, m), 0.8 (3, t)
[0186] MS (+Na+), 623.7
[0187] Purity: >95%
10(9)-hydroxy-9(10)-(propionyloxy)octadecyl
10-hydroxy-9-(propionyloxy)decanoate (E2-2)
[0188] Pure compound E2-2 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:4.
[0189] Yield: 26% g E3+58% E2-M at 95.degree. C.
[0190] 1H-NMR in CDCl.sub.3 (ppm), 5.0-4.8 (1, m), 4.2 (1, d), 4.1
(2, t), 4.0 (1, dd), 3.8 (1, m), 3.7-3.5 (2, m), 2.4 (4, m), 2.2
(2, t), 1.6-1.2 (41, m), 1.1 (6, m), 0.8 (3, t)
[0191] Purity: 94.3%
10-(10(9)-hydroxy-9(10)-(propionyloxy)octadecyloxy)-10-oxodecane-1,2-diyl
dipropionate (E3)
[0192] Pure compound E3 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:6 to 1:3.
[0193] Yield: 26% g E3+58% E2-M at 95.degree. C., 32.5% E4+21.5%
E3+33.7% E2 at 120.degree. C.
[0194] 1H-NMR in CDCl.sub.3 (ppm), 5.1 (1, m), 4.8 (1, m), 4.2 (1,
d), 4.0 (3, m), 3.6 (3, br), 2.3 (8, m), 1.7-1.2 (41, m), 1.1 (9,
m), 0.8 (3, t)
[0195] Purity: >95%
1-(9,10-bis(propionyloxy)decanoyloxy)octadecane-9,10-diyl
dipropionate (E4)
[0196] Pure compound E4 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:6.
[0197] Yield: 32.5% E4+21.5% E3+33.7% E2 at 120.degree. C.
[0198] 1H-NMR in CDCl.sub.3 (ppm), 5.1 (1, m), 5.0 (2, m), 4.2 (1,
d), 4.0 (3, m), 2.3 (10, m), 1.7-1.5 (10, m), 1.4-1.2 (30, m), 1.1
(12, m), 0.8 (3, t) Purity: >95%
Branched Derivatives of Compound F:
[0199] Branched Compound F derivatives were prepared from the
epoxide of compound F and propionic acid at 95.degree. C. for F2
and F3 or 120.degree. C. for F3 and F4 (shown in FIG. 11).
9-hydroxy-10-(propionyloxy)decyl
9(10)-hydroxy-10(9)-(propionyloxy)octadecanoate (F2-1)
[0200] Pure compound F2-1 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:4.
[0201] Yield: 19.8% F3+64.3% F2-M from 3.2 g
[0202] 1H-NMR in CDCl.sub.3 (ppm), 5.0-4.8 (1, m), 4.2 (1, d), 4.1
(2, t), 4.0 (1, dd), 3.8 (1, m), 3.7-3.5 (2, m), 2.4 (4, m), 2.2
(2, t), 1.6 (8, m), 1.6-1.2 (33, m), 1.1 (6, m), 0.8 (3, t)
[0203] Purity: >95%
10-hydroxy-9-(propionyloxy)decyl
9(10)-hydroxy-10(9)-(propionyloxy)octadecanoate (F2-2)
[0204] Pure compound F2-2 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:4.
[0205] Yield: 19.8% F3+64.3% F2-M
[0206] 1H-NMR in CDCl.sub.3 (ppm), 5.0-4.8 (1, m), 4.2 (1, d), 4.1
(2, t), 4.0 (1, dd), 3.8 (1, m), 3.7-3.5 (2, m), 2.4 (4, m), 2.2
(2, t), 1.6 (8, m), 1.6-1.2 (33, m), 1.1 (6, m), 0.8 (3, t)
[0207] Purity: >95%
10-(9(10)-hydroxy-10(9)-(propionyloxy)octadecanoyloxy)decane-1,2-diyl
dipropionate (F3)
[0208] Pure compound F3 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:6.
[0209] Yield: 19.8% F3+64.3% F2-M at 95.degree. C., 51.3% F4+30% F3
at 120.degree. C.
[0210] 1H-NMR in CDCl.sub.3 (ppm), 5.1 (1, m), 4.8 (1, m), 4.2 (1,
d), 4.0 (3, m), 3.7 (3, br), 2.3 (8, m), 1.6 (8, m), 1.5-1.2 (33,
m), 1.1 (9, m), 0.8 (3, t) MS (+Na+), 679.3
[0211] Purity: >95%
1-(9,10-bis(propionyloxy)decyloxy)-1-oxooctadecane-9,10-diyl
dipropionate (F4)
[0212] Pure compound F4 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:6.
[0213] Yield: 51.3% F4+30% F3 at 120.degree. C.
[0214] 1H-NMR in CDCl.sub.3 (ppm), 5.1 (1, m), 5.0 (2, m), 4.2 (1,
d), 4.0 (3, m), 2.3 (10, m), 1.7-1.4 (10, m), 1.4-1.2 (30, m), 1.1
(12, m), 0.8 (3, t)
[0215] MS(+Na+) 735.6
[0216] Purity: >95%
Branched Derivatives of Compound G:
[0217] Branched compound G derivatives were prepared from the
epoxide of compound G and propionic acid at 95.degree. C. for G2
and G3 or 120.degree. C. for G3 and G4 (shown in FIG. 12).
9-hydroxy-10-(propionyloxy)decyl
9-hydroxy-10-(propionyloxy)decanoate (G2-1)
[0218] Pure compound G2-1 was given as white solid by column
chromatography with Ethyl acetate/Hexane=1:2.
[0219] Yield: 47.7% G3+51.2% G2-M at 95.degree. C.
[0220] 1H-NMR in CDCl.sub.3 (ppm), 4.9 (1, br), 4.2 (2, d), 4.0 (2,
m), 3.9 (2, dd), 3.8 (2, br), 3.7-3.6 (1, m), 2.4 (4, m), 2.2 (2,
t), 1.6 (5, m), 1.5 (4, m), 1.4-1.2 (17, m), 1.1 (6, t)
[0221] Purity: >95%
10-hydroxy-9-(propionyloxy)decyl
9-hydroxy-10-(propionyloxy)decanoate or/and
9-hydroxy-10-(propionyloxy)decyl
10-hydroxy-9-(propionyloxy)decanoate (G2-2)
[0222] Pure compound G2-2 was given as white solid by column
chromatography with Ethyl acetate/Hexane=1:2.
[0223] Yield: 47.7% G3+51.2% G2-M at 95.degree. C.
[0224] 1H-NMR in CDCl.sub.3 (ppm), 4.9 (1, br), 4.2 (2, d), 4.0 (2,
m), 3.9 (2, dd), 3.8 (2, br), 3.7-3.6 (1, m), 2.4 (4, m), 2.2 (2,
t), 1.6 (5, m), 1.5 (4, m), 1.4-1.2 (17, m), 1.1 (6, t) MS(+Na+):
511.3
[0225] Purity: >95%
10-(9-hydroxy-10-(propionyloxy)decanoyloxy)decane-1,2-diyl
dipropionate or/and
10-(9-hydroxy-10-(propionyloxy)decyloxy)-10-oxodecane-1,2-diyl
dipropionate (G3-1)
[0226] Pure compound G3-1 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:3.
[0227] Yield: 47.7% G3+51.2% G2-M at 95.degree. C., 57.2% G4+21.5%
G3 at 120.degree. C. 1H-NMR in CDCl.sub.3 (ppm), 5.1 (1, br), 4.2
(1, d), 4.1 (1, d), 4.0 (2, m), 3.9 (2, dd), 3.8 (1, br), 2.3 (8,
m), 1.7-1.2 (27, m), 1.1 (9, m)
[0228] Purity: >95%
10-(10-hydroxy-9-(propionyloxy)decanoyloxy)decane-1,2-diyl
dipropionate or/and
10-(10-hydroxy-9-(propionyloxy)decyloxy)-10-oxodecane-1,2-diyl
dipropionate (G3-2)
[0229] Pure compound G3-2 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:3.
[0230] Yield: 47.7% G3+51.2% G2-M at 95.degree. C., 57.2% G4+21.5%
G3 at 120.degree. C. 1H-NMR in CDCl.sub.3 (ppm), 5.1 (1, br), 4.2
(1, d), 4.1 (1, d), 4.0 (2, m), 3.9 (2, dd), 3.8 (1, br), 2.3 (8,
m), 1.7-1.2 (27, m), 1.1 (9, m)
[0231] Purity: >95%
10-(9, 10-bis(propionyloxy)decanoyloxy)decane-1,2-diyl dipropionate
(G4)
[0232] Pure compound G4 was given as colorless oil by column
chromatography with Ethyl acetate/Hexane=1:5.
[0233] Yield: 57.2% G4+21.5% G3 at 120.degree. C.
[0234] 1H-NMR in CDCl.sub.3 (ppm), 5.1 (2, m), 4.2 (2, d), 4.0 (4,
m), 2.3 (10, m), 1.6 (7, m), 1.5 (18, m) 1.1 (12, m)
[0235] Purity: >95%
Synthesis of (E)-didec-9-enyl octadec-9-enedioate and its branched
compounds (Compound H)
Materials:
[0236] Oleic acid (90%), Grubbs metathesis catalyst (2.sup.nd
generation catalyst), 9-decen-1-ol, Propionic acid, Chloroform,
Dichloromethane, N,N'-Dicyclohexylcarbodiimide (DCC),
4-Dimethylaminopyridine (DMAP), Formic acid, hydrogen peroxide were
purchased from Sigma-Aldrich. Hexane and Ethyl Acetate from ACP
Chemical Int. (Montreal, Quebec, Canada) were used without further
treatment. The synthesis procedure for compound H is shown in FIG.
13.
[0237] E-didec-9-enyl octadec-9-enedioate was prepared from
9-decen-1-ol and 1,18-Octadec-9-enedioic acid which was prepared
from Oleic acid by metathesis reaction with Grubbs catalyst
(2.sup.nd generation).
Synthesis of 1,18-Octadec-9-enedioic acid
[0238] Oleic acid (76 g (270 mmol)) was transferred into a 250 ml
three-necked round bottomed flask and stirred at a temperature
typically between 10-100.degree. C., preferably between about
30-70.degree. C., and most preferably at 45.degree. C. under
nitrogen gas for 0.5 h. Grubbs metathesis catalyst 2.sup.nd
generation (85 mg) was added. The reaction mixture was stirred at
45.degree. C. for around 5 min, at which point diacid
(1,18-Octadec-9-enedioic acid) began to be precipitated from the
reaction mixture. The reaction was kept at this temperature for 24
hours and then it was quenched with ethyl vinyl ether (15 ml), and
excess ether was removed under reduced pressure. The residue was
purified by recrystallization from ethyl acetate and hexane (1:2)
to give 29.75 g of product as a white solid.
[0239] Yield: 72%
[0240] .sup.1H-NMR in DMSO-d6 (ppm): 12 (2H, s, --COOH), 5.3 (2H,
t, --CH.dbd.CH--), 2.2 (4H, m, --CH2-COOH), 1.9 (4H, m,
--CH2-CH.dbd.), 1.4 (4H, m, --CH2-CH2-COOH), 1.3-1.2 (18H, m,
CH2)
[0241] Purity: >95%
Synthesis of (E)-didec-9-enyl octadec-9-enedioate (H)
[0242] To the solution of 1,18-Octadec-9-enedioic acid (15.6 g, 50
mmol) and 9-decen-1-01 (23.4 g, 150 mmol) in CHCl.sub.3 at around
0.degree. C., DMAP (12.2 g, 100 mmol) was added, followed by slow
addition of DCC (22.7 g, 110 mmol). The reaction mixture was
allowed to be warmed to room temperature and kept overnight. The
mixture was filtered to remove solid. The filtrate was concentrated
on a rotary evaporator. The residue was purified by flash
chromatography using Ethyl acetate/Hexane (1:40) to give 28 g of
product as a colorless oil.
[0243] .sup.1H-NMR in CDCl.sub.3 (ppm): 5.8 (2H, m, .dbd.CH--), 5.4
(2H, t, --CH.dbd.CH--), 5.0-4.8 (4H, dd, CH2=), 4.0 (4, t,
--CH2-O), 2.3 (4H, t, O.dbd.C--CH2-), 2.1-1.8 (8H, m,
.dbd.CH--CH2-), 1.6 (8H, m, --CH2-CH2-O--), 1.4-1.2 (36, m,
--CH2-)
[0244] Purity: >95%
Epoxidation of H (FIG. 14)
[0245] To a stirred solution of ester (2.7 g, 4.56 mmol) and formic
acid (2.2 g, 9 mmol) in 3 mL CH.sub.2Cl.sub.2 at 4.degree. C.,
H.sub.2O.sub.2 (30%) (3.4 g, 6.6 mmol) was slowly added. The
reaction proceeded at room temperature with vigorous stirring for
48 hrs. After removal of the water phase, more CH.sub.2Cl.sub.2 (10
mL) was added to organic phase, which was washed sequentially with
water (2.times.20 mL) sat. aq NaHCO.sub.3 (2.times.10 mL) and brine
(2.times.20 mL), dried on Na.sub.2SO.sub.4, filtered, and
concentrated on a rotary evaporator. The residue was purified by
column chromatography with Ethyl acetate/Hexane=1:4 to give 2.1 g
of white solid.
[0246] Yield: 72%
[0247] .sup.1H-NMR in CDCl.sub.3 (ppm): 4.0 (4H, t, --CH2-O--), 2.9
(2H, m), 2.7 (2H, t), 2.6 (2H, t), 2.4 (2H, dd), 2.3 (4H, t,
O.dbd.C--CH2-), 1.7-1.2 (52H, m)
[0248] Purity: >95%
Synthesis of Branched Compounds of Compound H (FIG. 14)
[0249] The branched compounds below are referred to as H3
(3-branched), H4 (4-branched), H5 (5-branched), and H6
(6-branched). To the epoxidation products above (1.6 g, 4.7 mmol),
15.47 mmol propionic acid was added. The reaction was carried out
under an N.sub.2 atmosphere and heated to typically between
50-150.degree. C., preferably between about 70-120.degree. C., and
most preferably at 95.degree. C. and stirred at 95.degree. C. for
typically between about 4 to 36 hours, preferably 10-20 hours, and
most preferably 16 hours. To achieve 5 or 6 branches in the
compounds, the reaction temperature was raised to typically between
60-160.degree. C., preferably between about 80-140.degree. C., and
most preferably at 120.degree. C. The resulting products were
poured into 10 ml of water and extracted with Ethyl acetate
(2.times.10 mL). The organic phase was washed sequentially by water
(2.times.10 mL), sat. aq NaHCO.sub.3 (2.times.10 mL) and brine
(2.times.20 mL), dried on Na.sub.2SO.sub.4, then filtered and
concentrated on a rotary evaporator. The residue was purified by
column chromatography with Ethyl Acetate/Hexane (1:1 for H3, 1:2
for H4, 1:3 for H5 and 1:4 for H6).
[0250] Yield: 37.5% H3+43.8% H4+11.5% H5 at 95.degree. C., and
43.7% H5+38.4% H6 at 120.degree. C. .sup.1H-NMR in CDCl.sub.3
(ppm)
1-(9(10)-hydroxy-10(9)-(propionyloxy)decyl)
18-(10(9)-hydroxy-9(10)-(propionyloxy)decyl)-9(10)-hydroxy-10(9)-(propion-
yloxy)octadecanedioate (H3)
[0251] 5.1-4.8 (2H, m), 4.3-4.1 (2H, dd), 4.0 (4H, t), 4.0-3.9 (2H,
dd), 3.8 (1H, m), 3.7-3.5 (2H, m), 2.4-2.2 (10H, m), 1.9 (3H, br,
--OH), 1.6-1.2 (52H, m), 1.2-1.0 (9H, t, --CH3). MS(M+Na.sup.+):
881.5
[0252] Purity: >95%
1-(9,10-bis(propionyloxy)decyl)
18-(9(10)-hydroxy-10(9)-(propionyloxy)decyl)
10(9)-hydroxy-9(10)-(propionyloxy)octadecanedioate (H4)
[0253] 5.2-4.8 (3H, m), 4.3-4.1 (2H, dd), 4.0 (4H, m), 4.0-3.9 (1,
dd), 3.8 (1H, m), 3.7-3.5 (2H, m), 2.4-2.2 (12H, m), 1.9 (2H, br,
--OH), 1.7-1.2 (52H, m), 1.1 (12H, m, --CH3).
[0254] MS(M+Na.sup.+): 937.6
[0255] Purity: >95%
Bis
(9,10-bis(propionyloxy)decyl)9(10)-hydroxy-10(9)-(propionyloxy)octadec-
andioate (H5)
[0256] 5.2-4.7 (3H, m), 4.2 (2H, dd), 4.0 (6H, m), 3.6 (1H, m), 2.3
(14H, m), 1.6-1.4 (16, m), 1.4-1.2 (36H, m), 1.1 (15, m)
[0257] MS(M+Na.sup.+): 993.9
[0258] Purity: >95%
Bis (9,10-bis(propionyloxy)decyl)9,10-bis
(propionyloxy)octadecanedioate (H6)
[0259] 5.1 (2H, m), 4.9 (2H, m), 4.2 (2, dd), 4.0 (6H, q), 2.3
(16H, m), 1.7-1.4 (16H, m), 1.4-1.2 (36H, m), 1.1 (18, m)
[0260] MS(M+Na.sup.+): 1049.9
[0261] Purity: >95%
Composition of Crude Samples
[0262] Several compounds described herein are crude samples, as in
they are mixtures of existing branched derivatives of a dimer
and/or trimer ester. Compounds E95, F95, G95, and H95 are the crude
samples of compounds E F, G, and H, respectively. These are
mixtures of branched compounds of compounds E F, G, and H,
respectively, which were prepared from their epoxides and propionic
acid at 95.degree. C. Reaction time for these compounds was 24
hours. Similarly, compounds E120, F120, and G120 are crudes of
compounds E, F, and G, respectively, prepared at 120.degree. C. for
24 hours. H120A is the crude sample of compound H prepared at
120.degree. C. for 16 hours. H120 B is the crude sample of compound
H prepared at 120.degree. C. for 26 hours. As referred to at a
later point in this application, H120C is the crude sample of
compound H prepared at 120.degree. C. for 26 hours, and H120-20H is
the crude sample of compound H prepared at 120.degree. C. for 20
hours. The Table 4 below summarizes the specific compositions of
the above crude samples. Also in Table 4 below, "NI" means "not
identified."
TABLE-US-00004 TABLE 4 Compositions of H branched compounds (%)
Name H3 H4 H5 H6 NI water H95 (26 hours) 37.48 43.83 11.69 0 7 --
H120A (16 hours) 6.31 39.66 35.82 6.14 3.72 8 H120B (26 Hours) 0
7.12 33.7 38.43 20.75 -- 120A Dry 7.23 43.11 38.94 6.67 4.05 --
Compositions of E branched compounds Name E2 E3 E4 NI -- -- E95
88.06 11.39 -- -- -- -- E120 6.46 77.83 15.7 -- -- -- Compositions
of G branched compounds Name G2 G3 G4 NI -- -- G95 30.66 56.97 12
-- -- -- G120 3.5 44.52 51.08 -- -- -- Compositions of F branched
compounds Name F2 F3 F4 NI -- -- F95 85.43 12.82 -- 1.75 -- -- F120
39.12 53.01 4.28 3.60 -- --
Study of Time and Temperature Dependence of the Ring-Opening
Reaction of Epoxides by Propionic Acid
[0263] Exhaustive efforts were made to synthesize pure samples of
the base esters A-H and their individual branched derivatives, so
as to understand the influence of structure on lubrication and low
temperature fluidity properties. In this section, the mixture of
branched products arising out of the epoxide of certain base esters
(compounds E, G, and H), was studied by controlling the temperature
of the ring-opening reaction and quenching the reaction at various
time periods (as generically shown in FIG. 15).
[0264] By managing the degree of ring opening, the structure of the
complex ester mixture is altered so that the low temperature
properties of the fluids are adjusted to best fit various
applications. Due to their asymmetric structures and terminal
epoxide rings, the ring-opening esterification of compounds E, G,
and H derivatives are complex. In order to optimize the reaction
conditions and better control the ring-opening esterification, so
as to produce an optimized mixture of structures in the complex
ester mixture which then delivers unique functionality for specific
applications, it is important to understand the time-temperature
dependence of the reaction.
Materials:
[0265] Compounds E, G, and H were prepared from Oleic acid,
9-decenoic acid and 9-decen-1-ol as detailed above; Propionic acid,
H.sub.2O.sub.2, and Formic acid were purchased from Sigma-Aldrich.
FIGS. 16-18 show the reactions that were being performed, to
varying degrees, for compounds E, G, and H.
Method:
[0266] The epoxides were prepared from esters of E, G, and H,
followed by ring-opening reactions with propionic acid using
solvent-free conditions, as described above. The reactions were
carried out at 95.degree. C. and 120.degree. C. for 24 hours and at
140.degree. C. for 8 hours. HPLC-ELSD was used to monitor the
ring-opening reactions.
[0267] The samples were measured on Waters e2695 HPLC with Waters
2424 ELS Detector and C18 column (5 um 4.6.times.150 mm). The
mobile phase was mixture of 85% ACN: 15% water with a flow rate of
1 mL/min. The individual pure branched derivatives were first used
as standards, so that the complex mixtures could be analyzed with
confidence.
[0268] The following Tables 5 through 13 show the evolution of the
various branched species of several base esters with time at the
various temperatures. These complex mixtures were also analyzed for
lubricating and low temperature fluidity and the structure-function
relationships examined, separately below.
[0269] Tables 5 through 13: Time-Temperature dependence of ring
opening reactions
TABLE-US-00005 TABLE 5 Composites of ring-opening of epoxide of G
at 95.degree. C. Time (hours) G2 G3 G4 SM G1R 0.00 100.00 1.00 3.14
0.00 0.00 58.63 38.23 2.00 20.25 0.00 0.00 21.51 58.23 4.00 64.71
5.57 0.00 5.57 29.70 6.00 81.26 8.08 0.00 0.00 10.66 8.00 79.35
16.73 0.00 3.64 11.00 69.94 27.82 1.23 0.67 13.00 61.69 35.52 2.13
0.26 24.00 30.66 56.97 12.00
TABLE-US-00006 TABLE 6 Composites of ring-opening of epoxide of G
at 120.degree. C. Time (hours) G2 G3 G4 SM G1R 0.00 100.00 1.00
27.63 16.96 0.00 16.91 54.97 2.00 73.54 18.63 0.00 7.25 18.63 4.00
66.16 31.58 1.85 0.41 6.00 44.11 48.82 7.06 8.00 29.00 57.26 13.66
11.00 13.52 57.18 29.00 24.00 0.69 21.34 76.38
TABLE-US-00007 TABLE 7 Composites of ring-opening of epoxide of G
at 140.degree. C. Time (hours) G2 G3 G4 SM G1R 0.00 100.00 0.50
51.92 6.27 41.46 1.00 82.14 7.28 7.28 2.00 68.41 29.89 1.39 0.17
3.00 45.12 49.11 5.59 4.00 33.01 56.70 10.13 5.00 24.68 58.99 16.16
6.00 14.96 58.04 26.80 7.00 4.73 45.94 49.13 8.50 3.50 44.52
51.08
TABLE-US-00008 TABLE 8 Composites of ring-opening of epoxide of H
at 95.degree. C. Time(hours) H3 H4 H5 H2R H1R SM 0.00 100.00 1.00
11.30 88.70 2.00 0.26 40.83 6.23 52.68 3.00 2.03 51.13 19.07 27.77
5.00 11.56 37.00 43.49 7.95 7.00 26.25 2.76 18.08 46.89 6.03 9.00
40.93 6.69 8.45 39.89 3.96 13.00 55.18 16.31 3.76 20.44 4.31 26.00
37.48 43.84 11.48 3.28 7.90 2.26
TABLE-US-00009 TABLE 9 Composites of ring-opening of epoxide of H
at 120.degree. C. Time (hours) H3 H4 H5 H6 H2R H1R SM 0.00 100.00
1.00 8.20 40.28 42.74 8.78 2.00 40.06 4.88 42.29 8.69 4.08 3.00
59.50 14.43 18.51 2.64 4.29 5.00 50.58 36.29 5.23 3.19 2.22 2.48
7.00 30.80 49.95 14.95 0.96 2.19 1.14 9.00 20.83 50.30 23.62 2.54
2.72 12.00 9.16 41.74 37.44 6.13 24.00 9.46 46.53 33.65 26.00 7.12
43.70 38.43
TABLE-US-00010 TABLE 10 Composites of ring-opening of epoxide of H
at 140.degree. C. Time (hours) H3 H4 H5 H6 H1R H2R SM 0.00 100.00
0.50 2.86 36.22 54.11 6.82 1.00 61.51 38.49 1.50 81.74 9.70 8.56
2.00 73.78 23.71 2.51 3.00 59.59 40.41 4.00 37.82 59.91 2.26 5.00
25.59 66.87 6.48 6.00 20.81 70.13 9.06 7.00 15.70 68.76 14.11 0.91
8.00 10.20 67.08 19.66 1.89 24.00 12.09 52.74
TABLE-US-00011 TABLE 11 Composites of ring-opening of epoxide of E
at 95.degree. C. Time(hours) E2 E3 E4 E1R1 E1R1 SM 0.00 100.00 1.00
1.09 18.09 5.00 75.70 2.00 13.71 44.17 11.09 31.03 4.00 57.75 33.68
6.22 2.34 6.00 81.04 17.34 1.62 8.00 91.64 1.53 6.83 10.00 95.15
2.44 2.42 12.00 95.27 4.73 24.00 88.06 11.39
TABLE-US-00012 TABLE 12 Composites of ring-opening of epoxide of E
at 120.degree. C. E2 E3 E4 E1R1 E1R2 SM 0.00 100.00 0.50 13.12
43.04 9.82 34.02 1.00 68.50 27.85 3.65 2.00 95.91 4.20 3.00 97.52
2.48 4.00 94.21 5.79 6.00 87.99 12.00 8.00 69.72 30.28 10.00 59.35
40.65 12.00 44.31 55.02 0.67 24.00 6.46 77.83 15.70
TABLE-US-00013 TABLE 13 Composites of ring-opening of epoxide of E
at 140.degree. C. Time(hours) E2 E3 E4 E1R1 E1R2 SM 0.00 100.00
0.50 82.47 19.54 0.00 1.00 100.00 1.50 96.45 3.55 2.00 91.43 8.57
3.00 74.33 25.66 4.00 61.90 48.10 6.00 20.70 74.80 4.50 7.50 9.63
81.50 8.87
II. Experimental Methods--Measurement of Physical Properties
[0270] For the synthesized dimer esters and trimer esters
(compounds A-H), and their respective branched derivatives
described above, the following describes the experimental methods
utilized to measure physical properties of the aforesaid
compounds.
Differential Scanning calorimetry
[0271] The cooling and heating profiles of all compounds were
carried out using a Q200 model DSC (TA Instruments, DE, USA)
equipped with a refrigerated cooling system (RCS 90, TA
Instrument).
[0272] Approximately 5.0-10.0 (.+-.0.1) mg of fully melted and
homogenously mixed sample was placed in an aluminum DSC pan which
was then hermetically sealed. An empty aluminum pan was used as a
reference and the measurements were performed under a nitrogen flow
of 50 mL/min.
[0273] The "TA Universal Analysis" software coupled with a
published method (Use of first and second derivatives to accurately
determine key parameters of DSC thermographs in lipid
crystallization studies. Thermochimica Acta, 2005. 439(1-2): p.
94-102, Bouzidi et al., 2005) was used to analyze the data and
extract the main characteristics of the peaks (temperature at
maximum heat flow, T.sub.m; onset temperature, T.sub.On; offset
temperature, TO.sub.ff; enthalpy, .DELTA.H; and full width at half
maximum, FWHM). The temperature window over which a thermal event
occurs is defined as the absolute value of the difference between
T.sub.Off and T.sub.On of that event. It is labeled .DELTA.T.sub.C
for crystallization and .DELTA.T.sub.M for melting. The
characteristics of the shoulders when present were estimated using
a simple decomposition of the signal into its obvious main
components. The positions in this case were estimated using the
first and second derivatives of the differential heat flow.
[0274] The samples were subjected to cooling profiles which allow
for comparison between the different techniques used. The samples
were heated to 50.degree. C. and held for 5 min, a temperature and
a time over which crystal memory is erased, and then cooled at a
constant rate of 3.0.degree. C./min, to a finish temperature of
-90.degree. C., where it was held isothermally for a 5 min. The
sample was then reheated at a constant rate of 3.0.degree. C./min
to 70.degree. C. to obtain the melting profile.
[0275] In some instances (E2-2, E2-M, F2-1, F2-2, F3, F4), a
0.1.degree. C./min cooling rate was used. The sample in this case
was heated to 90.degree. C. and held for 5 min and then cooled at
the constant rate down to -90.degree. C. where the sample was held
isothermally for 5 min then reheated to 90.degree. C. at a constant
rate of 3.0.degree. C./min to obtain the heating profile.
Thermo Gravimetric Analysis
[0276] The TGA measurements were carried out on a TGA Q500 (TA
Instruments, DE, USA) equipped with a TGA heat exchanger (P/N
953160.901). Approximately 8.0-15.0 mg of fully melted and
homogenously mixed sample was loaded in the open TGA platinum pan.
The sample was heated from 25 to 600.degree. C. under dry nitrogen
at a constant heating rate of 3.degree. C./min. The TGA
measurements were performed under a nitrogen flow of 40 mL/min for
balance purge flow and 60 mL/min for sample purge flow. All the
samples were run in triplicate.
[0277] The samples which were run by TGA are: A, B, C, D, A2, C2,
E2 G4, H5, H6, E, F, G, E95, E120, F95, F120, G95, G120, G140, H95,
H120A, and H120B.
Viscosity Measurement
[0278] Sample viscosities were measured on a computer-controlled
rheometer, AR2000ex, equipped with a standard AR Series Peltier
Plate and Peltier AR series Concentric Cylinder (TA Instruments,
DE, USA). The circulating fluid heat exchange medium was provided
either by a TA heat exchanger (TA P/N 953/160.901) or a temperature
controlled circulating water bath (Julabo F25, Allentown, Pa.). The
AR Series Peltier Plate has a 80-mm diameter hardened chrome
surface and can provide a continuous temperature range of
-20.degree. C. to 180.degree. C. when used with circulating water
at 1.degree. C. and -40.degree. C. to 160.degree. C. when an
appropriate circulating fluid at -20.degree. C. is used. The AR
Series Peltier concentric cylinder can provide a continuous
temperature range of 0.degree. C. to 100.degree. C. when used with
circulating water at 1.degree. C. and -40.degree. C. to 100.degree.
C. when an appropriate circulating fluid at -20.degree. C. is used.
The internal resolution of both systems is 0.01.degree. C. The AR
Series plate and cylinder offer typical heating rates of up to 50
and 13.degree. C./min, respectively and a temperature accuracy of
0.1.degree. C.
[0279] The experiments were performed under an air bearing pressure
at 27 psi. A 40-mm 2.degree. steel cone (SIN 511406.901) geometry
was used for testing high viscosity materials and a standard-size
recessed-end concentric cylinder (stator inner radius 15 mm and
rotor outer radius 14 mm, SIN 545023.001) for low viscosity
materials. Approximately 0.59 mL and 6.65 mL of fully melted and
homogenously mixed sample was used in the parallel plate and
concentric cylinder geometry, respectively. Circulating water at
0.degree. C. in the TA heat exchanger and 6.degree. C. in the
circulating bath were used and temperatures as low as -10.degree.
C. and as high as 120.degree. C. were easily obtained with an
accuracy of 0.1.degree. C.
[0280] Viscosities of samples were measured from temperatures above
each sample's melting point up to 110.degree. C. The measurements
were performed using 3 methods: 1. Shear rate/share stress curves,
2. Constant Temperature Rate, Constant shear rate procedure, and 3.
Peak hold procedure. The viscosities measured viscosities were
found in good agreement within experimental uncertainty.
Shear Rate/Share Stress Curves (Increasing and Decreasing Shear
Rate)
[0281] The procedure was carried out by controlling shear rate, and
measurements were performed in 10.degree. C. steps. The shear rate
range was optimized for torque (lowest possible is 10 .mu.Nm) and
velocity (maximum supplier suggested of 40 rad/s). At each
measurement temperature, the lowest shear rate accessible was
determined by controlling the lowest torque available compatible
with the temperature, and the highest shear rate was determined by
increasing the applied torque to a level where the maximum
suggested velocity is reached. Typical optimization results are
summarized in Table 14 below.
TABLE-US-00014 TABLE 14 Typical optimized shear rate limits for
different temperatures of measurements. Temperature shear rate
(s.sup.-1) (.degree. C.) Lower limit Upper limit 110 100 1200 100
50 1200 90 10 1200 80 10 1200 70 10 1200 60 1 1200 50 1 1200 40 1
1200 30 0.5 1200 20 0.1 1200 10 0.1 700 0 0.01 700 -10 0.01 500
[0282] We have used three (3) available shear rate/share stress
procedures to determine viscosity:
Continuous Ramp Procedure:
[0283] The sample was first heated to 110.degree. C. and
equilibrated for 5 min and a continuous ramp procedure was
initiated from 110.degree. C. down to the melting temperature by
10.degree. C. steps. The procedure is repeated for each temperature
with 5 min equilibration time at each temperature. Shear rate was
increased from lower to upper shear rate according to Table 14.
Duration was 10 min in the log mode and sampling was 20 point per
decade. G4 was also run with decreasing shear rate to allow for
comparison.
Steady State Flow Procedure:
[0284] This procedure was used for a limited number of samples
(which are E2-2, E95, E120, F95, F120, G95, G120, H95, H120A,
H120A_dry, H120B, H3, H4, H5 and H6) for comparison and
optimization purposes. The sample was also heated to 110.degree. C.
and equilibrated for 5 min and the continuous ramp procedure was
initiated down to the melting temperature by 5.degree. C. steps.
The procedure is repeated for each temperature with 5 min
equilibration time at each temperature. Increasing shear rate from
the lower limit to the upper limit was used in the linear mode with
25 s.sup.-1 steps and sampling period of 1 min.
Step Flow Procedure
[0285] The step flow procedure was only used for one sample (G3-1).
The sample was first measured at its melting point (0.degree. C.)
then at increasing temperatures (10.degree. C. steps). The sample
was equilibrated for 5 min at the measurement temperature and then
subjected to the step flow procedure using 20 sampling points per
decade, a constant time of 30 s, and average last 10 seconds. Shear
rate was increased from its lower to its upper limit according to
Table 14.
Constant Temperature Rate Procedure
[0286] In order to speed up data collection, cooling and heating
rate procedures were tested and compared to the shear rate/shear
stress procedure. The sample was quickly heated to 110.degree. C.
and equilibrated at this temperature for 5 min then cooled down at
a constant rate (3.0.degree. C./min) to its melting temperature. A
constant shear rate of 200 s.sup.-1 was chosen as it was the lowest
common shear rate which yielded a constant viscosity in the range
applied (Newtonian behavior--characterized by having a shear stress
that is linearly proportional to the shear strain rate) as
determined from the continuous ramp procedure. Sampling points were
recorded every 1.degree. C. All other measurement conditions were
kept constant.
[0287] Some samples (E2-2, F2-2, G3-1, H120B) were run using
decreasing temperature ramp at the same conditions. Other samples
(E2-2, G3-1, E95, E120, F120, G95, G120, H95, H120A, H120A_dry,
H120B, H3, H4, H5 and H6) were run at decreasing temperature using
a rate of 1.0.degree. C./min. G3-1 was also run at increasing
temperature using a rate of 1.0.degree. C./min.
Peak Hold Procedure
[0288] The peak hold procedure is an alternative to the constant
rate procedure. It also uses a fixed shear rate and is based on the
equilibration and holding of the sample at a set temperature,
measurement of viscosity and subsequent stepping the temperature
for another equilibration, holding and measurement. This procedure
was used only for one sample (G3-1) and was found comparable and
therefore was not employed further. The procedure was started at
the sample melting point (-1.degree. C.) and 3 C steps with 5 min
equilibration and 10 min duration time. A shear rate of 200
s.sup.-1 was used.
III. Properties of the Compounds of this Invention
[0289] The dimer and trimer esters and their branched derivatives
of the present invention exhibit improved viscosity at the full
range of operating conditions, improved oxidative stability
(meaning removal of double bonds in the case of natural oil derived
materials), and improved thermal stability. In particular, we have
discovered that in the branched derivatives, branching the
hydrocarbon backbone in an asymmetrical fashion greatly improves
low temperature performance, and has improved fluidity at low
temperatures in an unexpected manner. These aspects are described
in further detail below.
[0290] Table 15 below shows the crystallization onsets, onsets and
offsets of melt (all in .degree. C.), and dynamic viscosities at
0.degree. C., 20.degree. C., 40.degree. C., and 100.degree. C. (in
m-Pascal-seconds, or mPa.$), of all the compounds created in this
invention.
TABLE-US-00015 TABLE 15 Crystallization onsets, onsets and offsets
of melt (all in .degree. C.), and dynamic viscosities at 0.degree.
C., 20.degree. C., 40.degree. C., and 100.degree. C. (in mPa s), of
all the compounds created in this invention. Final Crystallization
Melting Melting Viscosity Viscosity Viscosity Viscosity Onset Onset
Offset at at at at Sample (.degree. C.) STD (.degree. C.) STD
(.degree. C.) STD 0.degree. C. 20.degree. C. 40.degree. C.
100.degree. C. A -0.69 0.26 -12.29 0.05 10.01 0.07 90 29.8 16.0 5.2
A2 -37.67 1.02 -57.81 0.36 -40.27 0.16 12210 1706.0 391.1 27.5
A2-II -27.40 0.35 -20.32 0.32 29.18 0.34 N/A N/A N/A N/A A3 -48.70
1.09 -68.57 0.04 -53.55 0.51 3850 712.0 199.5 20.8 A4 -55.00 5.44
-72.71 0.40 -61.99 0.10 1876 407.4 129.9 17.0 B 15.20 1.57 0.58
0.09 16.84 0.84 Not Liquid 40.7 20.9 5.9 B2 -34.66 0.07 -32.87 0.03
50.36 1.24 13000 1846.0 426.0 29.8 B3 -43.02 0.05 -57.54 0.28
-34.74 0.55 3970 710.9 236.3 23.3 B4 -50.90 3.50 -72.14 0.04 -39.58
1.22 2192 479.3 152.1 19.9 C 25.97 0.93 14.84 0.40 30.42 0.74 Not
Liquid Not Liquid 28.0 7.5 C2 -14.79 0.10 -12.01 0.15 51.99 0.05
15030 2156.0 500.8 33.5 C2-II -5.03 0.59 -4.35 0.59 3.88 0.15 N/A
N/A N/A N/A C3 -36.10 0.36 -35.37 0.83 -4.99 0.23 3912 78.0 227.2
24.3 C4 -50.00 0.80 -70.43 0.07 -12.49 0.15 2512 559.8 177.9 29.5 D
14.41 3.01 2.77 0.15 23.55 2.35 Not Liquid 40.3 21.0 5.9 D2 -37.90
0.04 -41.15 0.04 -28.21 0.32 13860 1959.0 451.5 30.7 D3 -51.50 0.50
-66.38 2.15 -39.37 1.49 4092 777.6 221.8 22.8 D4 -50.10 5.00 -71.17
0.04 -61.42 0.00 2330 507.3 160.3 19.8 E -13.35 0.14 -13.61 0.21
-6.47 0.08 Not Liquid 7.5 4.8 2.2 E2-1 -25.56 4.05 -67.54 0.06
27.48 0.22 4648 824.6 221.0 26.8 E2-2 -36.14 0.73 -62.39 0.20
-51.23 0.55 7414 1175.0 289.7 23.2 E2-M -42.26 1.32 -62.86 0.16
-25.67 0.04 7279 1188 300.6 28.6 E3 -50.83 1.83 -75.23 0.50 -60.08
0.70 2044 424 130.4 16.0 E4 -36.84 25.00 -76.09 0.13 -68.94 0.16
1012 241.6 83.6 13.1 F -5.79 0.02 -19.53 0.00 5.81 0.24 Not Liquid
9.049 5.7 2.3 F2-1 -14.74 0.09 -67.22 0.34 41.60 0.03 5939 1010
260.2 21.8 F2-2 -40.91 1.26 -61.04 0.31 -50.77 0.39 5003 877 232.0
29.6 F2-M -28.58 0.47 -63.05 0.48 32.90 0.30 5792 984.7 255.9 22.1
F3 -56.84 1.68 -77.17 1.22 -61.34 0.69 2013 419.3 129.6 17.3 F4
-47.05 20.00 -84.92 0.19 -74.34 0.73 698 179.7 66.4 11.6 G -19.47
0.77 -18.30 0.11 -14.70 0.28 Not Liquid 2.409 1.7 1.0 G2-1 36.76
1.79 -80.35 0.54 54.66 0.02 Not Liquid Not Liquid 170.2 19.0 G2-2
-8.08 0.03 -73.68 0.98 29.16 0.24 N/A N/A N/A N/A G2-M 19.28 0.20
-24.48 0.71 43.41 0.17 Not Liquid Not Liquid 183.3 21.5 G3-1 -21.77
0.18 -78.56 0.76 -15.60 0.07 928 224.2 78.3 11.3 G3-2 -50.63 0.98
-73.39 0.05 -37.22 0.34 N/A N/A N/A N/A G3-M -33.85 0.21 -74.73
0.20 -25.46 0.21 1523 341.6 113.2 16.0 G4 No crystallization up to
-90 .degree. C. 379 105.8 43.4 7.9 H 18.76 1.10 22.27 0.12 24.94
0.40 Not Liquid Not Liquid 25.4 7.1 H3 -26.71 0.10 -61.49 0.13
33.96 0.64 23350 3304.0 773.0 56.1 H4 -34.73 2.94 -64.37 0.12 29.66
0.50 9575 1589.0 420.1 38.9 H5 -51.78 0.36 -68.10 0.21 12.35 0.35
4691 891.7 260.3 28.3 H6 -49.80 0.82 -71.10 0.36 -20.34 1.24 3399
684.7 210.3 27.5 E95 -1.95 0.05 -67.96 0.05 16.41 0.11 3363 627.9
177.9 21.0 E120 -10.02 0.07 -72.74 0.16 -2.29 0.81 1796 385.7 121.3
N/A F95 -33.83 0.16 -66.35 0.06 28.32 0.34 Not Liquid 721.3 198.8
20.8 F120 -53.44 0.42 -69.94 0.32 -24.75 0.15 2751 538.2 157.7 17.2
G95 -8.73 0.47 -76.68 0.41 7.97 0.43 1853 408.2 133.4 18 G120
-44.38 0.34 -78.41 0.01 -23.71 0.37 833.1 203.7 73.2 12 H95 -25.90
0.37 -63.33 0.34 13.47 0.44 N/A 2189 554.6 45.3 H120A -56.52 2.48
-74.74 0.09 -64.64 0.79 6999 1259 346.5 36.06 H120A -43.57 2.09
-66.48 0.21 -58.21 0.19 7823 1371 378.4 36.7 Dry H120B -49.71 1.97
-68.11 0.05 -59.75 0.09 5752 1064 306.8 32.4 N/A= Not
Available.
[0291] Several of the compounds in this invention have superior
melt onsets compared to the cited prior art efforts. The onsets of
melt, and dynamic viscosities at 40.degree. C. and 100.degree. C.
are reported for the cited prior art efforts below in Table 16, for
which such information is available. In Table 16, "N/R" means "not
reported" for that particular reference.
TABLE-US-00016 TABLE 16 Cited prior art properties Best dynamic
Best dynamic Prior Best Melt viscosity at 40.degree. C. viscosity
at 100.degree. C. Art Onset(.degree. C.) (in m Pa s) (in m Pa s)
Ref. 1 -20 N/R 3 (Kinematic (pour Point) Viscosity in cSt) Ref. 2
-50 16.5 3.46 (Melting point) (calculated) Ref. 3 -37.7 8.6 N/R
Ref. 4 -42 N/R N/R (Pour Point) Ref. 5 -56 N/R N/R Ref. 6 -43 679
58.6 Ref. 7 N/R 400.5 43.9
[0292] In addition, none of the cited prior art documents provide
details of the offsets of melt for their respective compounds. The
offsets of melt are important because they establish at what
temperature the particular compound is completely free of solid
material, and is a much more sensitive measurement because of this
than pour point or cloud point.
[0293] Several of the compounds described in this invention have
superior low-temperature fluidity properties, meeting one of the
major requirements for natural oil derived lubricants. Low
temperature properties are important for lubricant pumpability,
filterability, and fluidity as well as cold cranking and startup.
Furthermore, the onsets of melt demonstrated by the compounds of
this invention are as low as -80.degree. C., besting the cited
prior art references in this aspect. Therefore, one improved
utility of the compounds of this invention is improved low
temperature fluidity or low temperature crystallization.
[0294] Table 15 also recites the viscosity at 100.degree. C. of all
the compounds described in this invention. If one compares these
viscosity measurements with those of the cited prior art, it is
clear that the viscosities of the compounds described by this
invention span a much larger range, and many are as high as and
higher than the highest viscosities of the cited prior art at
100.degree. C. Furthermore, with the range of viscosities at
100.degree. C. of the compounds described in the invention which
have onsets of melt equivalent to or less than -40.degree. C., one
can see that the range of viscosities at 100.degree. C. which also
have superior low temperature fluidity is competitive with the
highest recorded viscosities of the cited prior art and offers a
much larger viscosity range at this temperature. Furthermore, with
the range of viscosities at 40.degree. C. of the compounds
described in this invention which have onsets of melt equivalent to
or less than -40.degree. C., one can see that the viscosities of
compounds in this invention which melt at or below -40.degree. C.
are vastly superior to the viscosities of the majority of the
compounds of the cited prior art, and such compounds outperform the
estolide technology in low temperature fluidity in the cited prior
art.
[0295] It should also be mentioned that all of the compounds
described in this invention are Newtonian (characterized by having
a shear stress that is linearly proportional to the shear strain
rate) from sub-zero temperatures to 100.degree. C., and that we
have been able to develop predictive models which relate the
structure of the compounds to their viscosities.
[0296] Therefore, another improved utility of these compounds that
is claimed is vastly improved viscosity ranges with enhanced low
temperature fluidity.
Oxidative Stability
[0297] Another important area for improvement of natural oil
derived lubricants relate to their oxidative instability due to the
presence of carbon-carbon double bonds. It should be noted that all
of the branched compounds in this invention are completely devoid
of double bonds. They inherently therefore are significantly
improved in terms of oxidative stability compared to natural oil
derived compounds with remaining double bonds. As commonly
understood in the art, oxidative stability defines durability of a
lubricant and its ability to maintain functional properties during
its use. Therefore, another improved utility that is being claimed
is improved oxidative stability.
Thermal Stability
[0298] Another important area for improvement for natural oil
derived lubricants is in their thermal stability. Thermal
Gravimetric Analysis for certain compounds described in this
invention (compounds A, B, C, D, E, F, G, A2, C2, E2, G4, H5, H6,
H95, H120A, E95, E120, F95, F120, G95, G120 and G140 have been run
by TGA) shows that the thermal stability of these compounds were
surprisingly high, with these compositions having thermal stability
between about 300.degree. C. through about 390.degree. C. Below in
Table 17 shows degradation temperatures and associated weight loss
values of the compounds run by TGA.
TABLE-US-00017 TABLE 17 Degradation temperatures and associated
weight loss values of the compounds run by TGA. T1 Loss1 T2 Loss2
T3 Loss3 Sample (.degree. C.) (%) (.degree. C.) (%) (.degree. C.)
(%) A -- -- 317 81 -- -- B -- -- 322 84 -- -- C -- -- 350 76 -- --
D -- -- 329 85 -- -- E -- -- 259 81 -- -- F -- -- 260 82 -- -- G --
-- 197 81 -- -- A2 -- -- 327 62 414 99 C2 -- -- 391 66 G4 -- -- 324
63 415 99 H5 -- -- 345 45 423 92 H6 -- -- 343 41 424 93 E95 -- --
305 58 -- -- E120 -- -- 309 58 -- -- F95 -- -- 313 54 -- -- F120 --
-- 319 56 -- -- G95 290 46 345 84 415 98 G120 295 10 306 56 415 98
G140 289 53 346 89 413 98 H95 221 2 345 39 423 91 H120A -- -- 350
39 443 87 H120B 220 4 342 39 423 90
Hydrolytic Stability
[0299] Another important area for improvement for natural oil
derived lubricants is in their hydrolytic stability. In table 18
below, the tested samples exhibit hydrolytic stability for up to 26
hours:
TABLE-US-00018 TABLE 18 Hydrolytic Stability Room Temp. 60.degree.
C. for 26 h Sample pH.sup.1 pH.sup.1 A2 3.8 3.6 H120 3.8 3.6 H120C
3.4 3.2 H120-20H 3.3 3.2 .sup.1For the pH tests, 3 g of sample were
mixed with 7 g DI H.sub.2O in scintillation vials. The pH of the
aqueous layer was then measured with a Mettler Toledo pH probe
using a two-point calibration. The room temperature pH samples were
mixed by briefly shaking the vials in hand, while the 60.degree. C.
samples were mixed in a shaker.
[0300] The foregoing detailed description and accompanying figures
have been provided by way of explanation and illustration, and are
not intended to limit the scope of the appended claims. Many
variations in the present embodiments illustrated herein will be
apparent to one of ordinary skill in the art, and remain within the
scope of the appended claims and their equivalents.
* * * * *