U.S. patent application number 17/482080 was filed with the patent office on 2022-03-17 for synthetic esters derived from high stability oleic acid.
This patent application is currently assigned to Quaker Chemical Corporation. The applicant listed for this patent is Quaker Chemical Corporation. Invention is credited to Nico BROEKHOF, Lex Herrendorf.
Application Number | 20220081635 17/482080 |
Document ID | / |
Family ID | |
Filed Date | 2022-03-17 |
United States Patent
Application |
20220081635 |
Kind Code |
A1 |
BROEKHOF; Nico ; et
al. |
March 17, 2022 |
SYNTHETIC ESTERS DERIVED FROM HIGH STABILITY OLEIC ACID
Abstract
The present invention is directed to a composition comprising a
synthetic ester having a fatty acid mixture including: oleic acid
in amount of at least about 85 wt % of the fatty acid mixture;
linoleic acid in an amount of about 3 wt % of the fatty acid
mixture or less; and linolenic acid in an amount of about 0.5 wt %
of the fatty acid mixture or less.
Inventors: |
BROEKHOF; Nico; (Uithoorn,
NL) ; Herrendorf; Lex; (Uithoorn, NL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Quaker Chemical Corporation |
Wilmington |
DE |
US |
|
|
Assignee: |
Quaker Chemical Corporation
Wilmington
DE
|
Appl. No.: |
17/482080 |
Filed: |
September 22, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15573721 |
Nov 13, 2017 |
11155761 |
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PCT/US16/33056 |
May 18, 2016 |
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17482080 |
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62163922 |
May 19, 2015 |
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International
Class: |
C10M 101/04 20060101
C10M101/04; C07C 67/08 20060101 C07C067/08 |
Claims
1.-14. (canceled)
15. A method of preparing a synthetic ester, the method comprising
reacting a fatty acid mixture with an alcohol, wherein the fatty
acid mixture comprises: a. oleic acid in amount of at least about
85 wt % of the fatty acid mixture; b. linoleic acid in an amount of
about 3 wt % of the fatty acid mixture or less; and c. linolenic
acid in an amount of about 0.5 wt % of the fatty acid mixture or
less.
16. The method of claim 15, wherein the oleic acid is a high
stability oleic acid.
17. The method of claim 15, wherein the alcohol is selected from
the group consisting of: trimethylol propane (TMP), neopentyl
glycol (NPG), pentaerythritol (PE), 2-butyl-2-ethyl-1,3-propanediol
(BEPD), 2,2,4-trimethyl-1,3-propanediol (TMPD), polyglycerol,
2,2-diethyl-1,3-propanediol, 1,3,-propanediol, 1,2-propanediol,
1,4-butanediol, 1,4-butenediol, 1,4-butynediol, 1,6-hexanediol,
1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-, 1,3-, 1,4-, 1,8-,
2,4-, 2,7-, and 4,5-octanediol, tricyclodecane dimethanol (TCD),
1,4-cyclohexanedimethanol, 1,12-dodecanediol,
2-methyl-2,4-pentanediol, 2-methyl-1,3-propanediol (MPD),
2-methyl-1,2-propanediol, 2-hydroxyethoxy-ethan-2-ol, dipropylene
glycol (3 isomer mixture), di-pentaerythritol, tri-pentaerythritol,
di-trimethylolpropane (di-TMP), triethylene glycol, tri-propylene
glycol, tetraethylene glycol, tetrapropylene glycol, polyethylene
glycol (PEG, 1\4W 200-1.000.000 g/mol), polypropylene glycol (PPG,
MW 200-10.000 g/mol), ethylene glycol, 1,2,-, 1,3-, 2,3-butanediol,
1,1-, 1,3-, 1,4-, 2,3-, 2,4-pentanediol, 2-butene-1,2-diol,
2-butene-1,4-diol, 2-methyl-1,5-pentanediol,
2,4-dimethyl-2,4-pentanediol, 2,2-diethyl-1,4-butanediol,
2-pentene-1,5-diol, 2-propyl-1,3-butanediol, 1,4-hexanediol,
1,6-hexanediol, 5-methyl-1,2-hexanediol, 1-phenyl-1,2-ethanediol,
2-phenyl-1,2-propanediol, 1,6-diphenyl-1,6-hexanediol,
1,2-diphenyl-1,2-ethanediol, tris(2-hydroxyethyl)isocyanurate
(THEIC), poly-tetrahyfrofuran (poly-THF, MW 250, 650, 1000, 1400,
1800 and 2000 g/mol), 2-ethyl-1,3-hexanediol (EHD), EO-PO block
copolymers, EO-PO-EO block copolymers, PO-EO block copolymers,
PO-EO-PO block copolymers, 1,2-pentanediol,
4-methyl-1,4-hexanediol, 3,3-dimethyl-1,6-hexanediol,
2,4-dimethyl-3-hexene-2,5-diol, 2,3-, 2,4-, 2,5-, 3,4-hexanediol,
1,2,3,6-hexanetetrol, 2-heptene-1,6-diol,
5-ethyl-3-methyl-2,4-heptanediol, 2-methyl-2-octene-1,4-diol,
2,4,4,5,5,7-hexamethyl-3,6-octanediol,
2,7-dimethyl-4-octane-2,7-diol,
2-butyl-4-ethyl-3-methyl-1,3-octanediol, 1,9-nonanediol, 1,2-,
1,10-decanediol, 5-decyne-4,7-diol, 5,8-diethyl-6,7-dodecanediol,
9-octadecene-1,12-diol, 9,10,1,12-octadecanediol, 1,9-,
1,11-undecanediol, 1,13-tridecanediol, 1,2-tetradecanediol, 1,2-,
1,16-hexadecanediol, 1,2-, 1,12-octadecanediol,
2-isobutyl-1,3-propanediol, 2-ethyl-1,3-propanediol,
2-ethyl-1,3-butanediol, 2,2-diethyl-1,4-butanediol,
2,2,3,3,-tetramethyl-1,4-butanediol, bisphenol A, hydrogenated
bisphenol A, ortho,meta, para-xylene-alpha, alpha diols,
3,6-dimethyl-ortho-xylene-alpha,alpha-diol,
alpha,alpha-dimethyl-para-xylene-alpha,alpha diol,
1,6-diphenyl-1,6-hexanediol;
2-ethyl-2-(hydroxymethyl)-1,3-propanediol ethoxylates (TMP-EOx
where x ranges from 1 to 100 moles of EO),
2-ethyl-2-(hydroxymethyl)-1,3-propanediol propoxylates (TMP-POx,
where x ranges from 1-100 moles of PO),
2-ethyl-2-(hydroxymethyl)-1,3-propanediol (random) alkoxylates
(TMP-EOx-POy, TMP-EOx-POy-EOx, TMP-POx-EOy, TMP-POx-EOy-POx, where
x and y range from 1-100 moles both for E0 and PO),
2-ethyl-2-(hydroxymethyl)-1,3-propanediol butoxylate (TMP-BuOx,
where x ranges from 1-25 moles of BuO (butyleneoxide)),
2,2-dimethyl-1,3-propanediol ethoxylates (NPG-EOx, where x ranges
from 1 to 100 moles of EO), 2,2-dimethyl-1,3-propanediol
propoxylates (NPG-PDx, where x ranges from 1 to 100 moles of PO),
2,2-dimethyl-1,3-propanediol (random) alkoxylates (NPG-EOx-POy,
NPG-POx-EOy, NPG-EOx-POy-EOx, NPG-POx-EOy-POx where x and y range
from 1 to 100 moles for both EO and PO),
2,2-dimethyl-1,3-propanediol butoxylate (NPG-BuOx, where x ranges
from 1 to 25 moles of BuO), 2,2-bis(hydroxymethyl)-1,3-propanediol
ethoxylates (penta EOx, where x ranges from 1-100 moles of EO),
2,2-bis(hydroxymethyl)-1,3-propanediol propoxylates (penta POx,
where x ranges from 1-100 moles of propyleneoxide (PO)),
2,2-bis(hydroxymethyl)-1,3-propanediol (random) alkoxylates (penta
EOx-POy where x and y range from 1-100 moles of EO and PO),
2,2-bis(hydroxymethyl)-1,3-propanediol EOx-POy-EOx (penta
EOx-POy-EOx, where x and y range from 1-100 moles of EO and PO),
2,2-bis(hydroxymethyl)-1,3-propanediol butoxylates (penta BuOx,
where x ranges from 1-25 moles of butyleneoxide),
2-butyl-2-ethyl-1,3-propanediol (BEPD) ethoxylates (BEPD-EOx, where
x ranges from 1-100 moles of EO), 2-butyl-2-ethyl-1,3-propanediol
propoxylates (BEPD-POx, where x ranges from 1-100 moles of PO),
2-butyl-2-ethyl-1,3-propanediol (random) alkoxylates (BEPD-EOx-POy,
BEPD-EOx-POy-EOx, BEPD-POx-EOy-POx, where x ranges from 1-100 moles
of E0 and PO), and 2-butyl-2-ethyl-1,3-propanediol butoxylates
(BEPD-BuOx, where x ranges from 1-25 moles of butyleneoxide).
18. The method of claim 15, wherein the alcohol is selected from
the group consisting of neo pentyl glycol (NPG), trimethylol
propane (TMP), penta-erythritol (PE), di-TMP, di-PE, 2-ethyl
hexanol, butyl ethyl propane diol (BEPD), trimethyl propanediol
(TMPD), propylene glycol, and combinations thereof.
19. The method of claim 15, wherein the alcohol is selected from
the group consisting of neo pentyl glycol, trimethylol propane, and
penta-erythritol.
20. The method of claim 15, wherein the alcohol is trimethylol
propane.
21. The method of claim 15, wherein the linolenic acid is present
in an amount of about 0.2 wt % of the fatty acid mixture or
less.
22. The method of claim 15, wherein a composition comprising the
synthetic ester meets standards for fire resistance according to
Factory Mutual Approvals Class Number 6930, April 2009.
23. The method of claim 15, wherein a composition comprising the
synthetic ester maintains oxidative stability for about 2,500 hours
or greater according to ASTM D943.
24. The method of claim 15, wherein a composition comprising the
synthetic ester exhibits a pour point temperature of about
-10.degree. C. or less.
25. The method of claim 15, wherein the fatty acid mixture is
derived from cleaving of a high stability algal oil sourced from
genetically modified algae.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Patent Application No. 62/163,922 filed May 19, 2015, entitled
"Synthetic Esters Derived from High Stability Oleic Acid,"
incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
[0002] Triglycerides obtained from vegetable or animal sources are
known to be used as base oil for lubricant formulations. These
natural triglycerides often show poor hydrolytic stability as well
as limited low temperature properties such as pour point and cold
test stability. The present invention relates to synthetic esters
prepared from, for example, an algal-derived triglyceride such as
high stability algal oil from Solazyme Inc., which may provide
excellent oxidation stability as well as improved low temperature
properties and hydrolytic stability as compared to the
corresponding triglycerides, making them suitable for a range of
industrial lubricants.
SUMMARY OF THE INVENTION
[0003] According to some embodiments, the present invention relates
to a composition comprising a synthetic ester having a fatty acid
mixture comprising: oleic acid in amount of at least about 85 wt %
of the fatty acid mixture; linoleic acid in an amount of about 3 wt
% of the fatty acid mixture or less; and linolenic acid in an
amount of about 0.5 wt % of the fatty acid mixture or less. In some
embodiments, the linolenic acid is present in an amount of about
0.2 wt % of the fatty acid mixture or less.
[0004] In some embodiments, the synthetic ester is derived from
high stability oleic acid. In some embodiments, the synthetic ester
is derived from high stability algal oil.
[0005] In certain embodiments, the composition includes alcohol. In
some embodiments the alcohol includes neo pentyl glycol (NPG),
trimethylol propane (TMP), penta-erythritol (PE), di-TMP, di-PE,
2-ethyl hexanol, butyl ethyl propane diol (BEPD), trimethyl
propanediol (TMPD), and/or propylene glycol.
[0006] In some embodiments, the composition meets standards for
fire resistance according to Factory Mutual Approvals Class Number
6930, April 2009. In some embodiments, the composition maintains
oxidative stability for about 2,500 hours or greater according to
ASTM D943. In some embodiments, the composition exhibits a pour
point temperature of about -10.degree. C. or less.
[0007] In certain embodiments, the composition is a lubricant or a
hydraulic fluid.
[0008] According to some embodiments, the present invention relates
to a method of preparing a synthetic ester, comprising esterifying
high stability oleic acid to produce a synthetic ester having a
fatty acid mixture comprising: oleic acid in amount of at least
about 85 wt % of the fatty acid mixture; linoleic acid in an amount
of about 3 wt % of the fatty acid mixture or less; and linolenic
acid in an amount of about 0.5 wt % of the fatty acid mixture or
less.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0009] The foregoing summary, as well as the following detailed
description of certain embodiments of the invention will be better
understood when read in conjunction with the following exemplary
embodiments and the appended drawings.
[0010] FIG. 1 is graph showing the varying acid number of esters
including certain additives.
[0011] FIG. 2 is a graph showing the varying viscosity of esters
including certain additives.
DETAILED DESCRIPTION OF THE INVENTION
[0012] Compositions and methods of the present invention relate to
synthetic esters derived from high stability oleic acid, which may
be manufactured from high stability algal oil. In some embodiments,
the synthetic esters have unique lubricant properties such as
exceptional oxidation stability and/or improved low temperature
properties as compared to the corresponding triglycerides.
[0013] Tailored triglycerides, e.g. obtained via genetically
engineered plant seeds such as High Oleic Sunflower or High Oleic
Canola, or genetically modified Algae, such as that manufactured by
Solazyme, have been used in the past as a base oil for lubricant
formulations. Specific triglycerides may provide beneficial
properties such as oxidation stability, however, they may exhibit
drawbacks such as limited low temperature properties including pour
point and/or cold test stability.
[0014] Surprisingly, it has been found that a synthetic ester
prepared from a triglyceride having a unique fatty acid
distribution, such as high stability algal oil, may provide
desirable lubricant properties including exceptional oxidation
stability and superior low temperature properties compared with the
corresponding triglyceride.
[0015] In some embodiments, the present invention relates to
synthetic esters containing a) fatty acid mixtures with an oleic
acid content of about 85 wt %, a linoleic acid content of about
.ltoreq.3 wt % and a linolenic acid content of about .ltoreq.0.5 wt
% relative to the mixture, b) alcohols, and c) as desired,
polyfunctional carboxylic acids. Embodiments of the present
invention also relate to industrial lubricants, such as hydraulic
fluids, based on these esters.
[0016] Triglyceride
[0017] Compositions and methods of some embodiments of the present
invention relate to triglycerides having a certain fatty acid
distribution. In some embodiments, a suitable triglyceride may
include high stability algal oil, such as that produced by Solazyme
Inc.
[0018] In some embodiments, a suitable triglyceride may include a
fatty acid mixture having oleic acid in amount of at least about 85
wt % of the fatty acid mixture; linoleic acid in an amount of about
3 wt % of the fatty acid mixture or less; and/or linolenic acid in
an amount of about 0.5 wt % of the fatty acid mixture or less.
[0019] In some embodiments, a suitable triglyceride includes a
fatty acid mixture having oleic acid in an amount of at least about
80 wt % of the fatty acid mixture; at least about 82 wt % of the
fatty acid mixture; at least about 84 wt % of the fatty acid
mixture; at least about 85 wt % of the fatty acid mixture; at least
about 86 wt % of the fatty acid mixture; about 80 wt % to about 92
wt % of the fatty acid mixture; about 82 wt % to about 90 wt % of
the fatty acid mixture; about 84 wt % to about 88 wt % of the fatty
acid mixture; about 85 wt % to about 87 wt % of the fatty acid
mixture; about 80 wt % of the fatty acid mixture; about 82 wt % of
the fatty acid mixture; about 84 wt % of the fatty acid mixture;
about 86 wt % of the fatty acid mixture; about 88 wt % of the fatty
acid mixture; about 90 wt % of the fatty acid mixture; or about 92
wt % of the fatty acid mixture.
[0020] In some embodiments, a suitable triglyceride includes a
fatty acid mixture having linoleic acid in an amount of about 5 wt
% of the fatty acid mixture or less; about 4 wt % of the fatty acid
mixture or less; about 3 wt % of the fatty acid mixture or less;
about 2 wt % of the fatty acid mixture or less; about 1 wt % of the
fatty acid mixture or less; about 0.7 wt % of the fatty acid
mixture or less; about 0.5 wt % of the fatty acid mixture or less;
about 0.1 wt % to about 5 wt % of the fatty acid mixture; about 0.1
wt % to about 4 wt % of the fatty acid mixture; about 0.1 wt % to
about 3 wt % of the fatty acid mixture; about 0.1 wt % to 2 wt % of
the fatty acid mixture; about 0.1 wt % to about 1.5 wt % of the
fatty acid mixture; about 0.1 wt % to about 1 wt % of the fatty
acid mixture; about 0.2 wt % to about 0.8 wt % of the fatty acid
mixture; about 0.2 wt % to about 0.6 wt % of the fatty acid
mixture; about 0.1 wt % of the fatty acid mixture; about 0.2 wt %
of the fatty acid mixture; about 0.3 wt % of the fatty acid
mixture; about 0.4 wt % of the fatty acid mixture; about 0.5 wt %
of the fatty acid mixture; about 0.6 wt % of the fatty acid
mixture; about 0.8 wt % of the fatty acid mixture; about 1 wt % of
the fatty acid mixture; about 1.5 wt % of the fatty acid mixture;
about 2 wt % of the fatty acid mixture; about 3 wt % of the fatty
acid mixture; about 4 wt % of the fatty acid mixture; or about 5 wt
% of the fatty acid mixture.
[0021] In some embodiments, a suitable triglyceride includes a
fatty acid mixture having linolenic acid in an amount of about 3 wt
% of the fatty acid mixture or less; about 2 wt % of the fatty acid
mixture or less; about 1 wt % of the fatty acid mixture or less;
about 0.7 wt % of the fatty acid mixture or less; about 0.5 wt % of
the fatty acid mixture or less; about 0.4 wt % of the fatty acid
mixture or less; about 0.3 wt % of the fatty acid mixture or less;
about 0.2 wt % of the fatty acid mixture or less; about 0.1 wt % of
the fatty acid mixture or less; about 0 wt % to about 5 wt % of the
fatty acid mixture; about 0.1 wt % to about 5 wt % of the fatty
acid mixture; about 0 wt % to about 4 wt % of the fatty acid
mixture; about 0 wt % to about 3 wt % of the fatty acid mixture;
about 0 wt % to 2 wt % of the fatty acid mixture; about 0 wt % to
about 1.5 wt % of the fatty acid mixture; about 0 wt % to about 1
wt % of the fatty acid mixture; about 0 wt % to about 0.8 wt % of
the fatty acid mixture; about 0 wt % to about 0.6 wt % of the fatty
acid mixture; about 0 wt % to about 0.4 wt % of the fatty acid
mixture; about 0 wt % to about 0.2 wt % of the fatty acid mixture;
about 0.1 wt % to about 4 wt % of the fatty acid mixture; about 0.1
wt % to about 3 wt % of the fatty acid mixture; about 0.1 wt % to 2
wt % of the fatty acid mixture; about 0.1 wt % to about 1.5 wt % of
the fatty acid mixture; about 0.1 wt % to about 1 wt % of the fatty
acid mixture; about 0.2 wt % to about 0.8 wt % of the fatty acid
mixture; about 0.2 wt % to about 0.6 wt % of the fatty acid
mixture; about 0.1 wt % of the fatty acid mixture; about 0.2 wt %
of the fatty acid mixture; about 0.3 wt % of the fatty acid
mixture; about 0.4 wt % of the fatty acid mixture; about 0.5 wt %
of the fatty acid mixture; about 0.6 wt % of the fatty acid
mixture; about 0.8 wt % of the fatty acid mixture; about 1 wt % of
the fatty acid mixture; about 1.5 wt % of the fatty acid mixture;
about 2 wt % of the fatty acid mixture; about 3 wt % of the fatty
acid mixture; about 4 wt % of the fatty acid mixture; or about 5 wt
% of the fatty acid mixture.
[0022] In some embodiments, a suitable triglyceride includes a
fatty acid mixture having palmitoleic acid in an amount of about 5
wt % of the fatty acid mixture or less; about 4 wt % of the fatty
acid mixture or less; about 3 wt % of the fatty acid mixture or
less; about 2 wt % of the fatty acid mixture or less; about 1 wt %
of the fatty acid mixture or less; about 0.7 wt % of the fatty acid
mixture or less; about 0.5 wt % of the fatty acid mixture or less;
about 0.1 wt % to about 5 wt % of the fatty acid mixture; about 0.1
wt % to about 4 wt % of the fatty acid mixture; about 0.1 wt % to
about 3 wt % of the fatty acid mixture; about 0.1 wt % to 2 wt % of
the fatty acid mixture; about 0.1 wt % to about 1.5 wt % of the
fatty acid mixture; about 0.1 wt % to about 1 wt % of the fatty
acid mixture; about 0.2 wt % to about 0.8 wt % of the fatty acid
mixture; about 0.2 wt % to about 0.6 wt % of the fatty acid
mixture; about 0.1 wt % of the fatty acid mixture; about 0.2 wt %
of the fatty acid mixture; about 0.3 wt % of the fatty acid
mixture; about 0.4 wt % of the fatty acid mixture; about 0.5 wt %
of the fatty acid mixture; about 0.6 wt % of the fatty acid
mixture; about 0.8 wt % of the fatty acid mixture; about 1 wt % of
the fatty acid mixture; about 1.5 wt % of the fatty acid mixture;
about 2 wt % of the fatty acid mixture; about 3 wt % of the fatty
acid mixture; about 4 wt % of the fatty acid mixture; or about 5 wt
% of the fatty acid mixture.
[0023] In some embodiments, a suitable triglyceride includes a
fatty acid mixture having palmitic acid in an amount of about 4 wt
% to about 14 wt % of the fatty acid mixture; about 6 wt % to about
12 wt % of the fatty acid mixture; about 8 wt % to about 10 wt % of
the fatty acid mixture; about 4 wt % of the fatty acid mixture;
about 6 wt % of the fatty acid mixture; about 8 wt % of the fatty
acid mixture; about 9 wt % of the fatty acid mixture; about 10 wt %
of the fatty acid mixture; about 12 wt % of the fatty acid mixture;
or about 14 wt % of the fatty acid mixture.
[0024] In some embodiments, a suitable triglyceride includes a
fatty acid mixture having stearic acid in an amount of about 1 wt %
to about 6 wt % of the fatty acid mixture; about 2 wt % to about 5
wt % of the fatty acid mixture; about 3 wt % to about 4 wt % of the
fatty acid mixture; about 1 wt % of the fatty acid mixture; about 2
wt % of the fatty acid mixture; about 3 wt % of the fatty acid
mixture; about 4 wt % of the fatty acid mixture; about 5 wt % of
the fatty acid mixture; or about 6 wt % of the fatty acid
mixture.
[0025] Fatty Acid
[0026] The fatty acids in the triglyceride can be obtained by
standard techniques known to those skilled in the art. For example,
HSAO triglyceride may be split into glycerol and fatty acid (HSAO
fa), which may be converted to many synthetic esters, including,
neo pentyl glycol or NPG-ester, trimethylol propane or TMP-ester
and penta-erythritol or PE-ester.
[0027] Alcohols
[0028] In some embodiments, a synthetic ester of the present
invention comprises alcohol. In some embodiments, the fatty acids
obtained from the triglyceride are converted with alcohol to
prepare a synthetic ester. Selection of a suitable alcohol may
provide improved properties, such as low temperature properties, of
the synthetic ester in comparison to the corresponding
triglyceride.
[0029] In some embodiments, alcohols that may be used for
esterification include, but are not limited to neo pentyl glycol
(NPG), trimethylol propane (TMP), and/or penta-erythritol (PE). In
some embodiments, complex esters may be prepared by using, for
example, dimer acid, adipic acid, and/or dodecanoic acid.
[0030] In some embodiments, suitable alcohols may include
isopropanol, neo pentyl glycol (NPG), trimethylol propane (TMP),
penta-erythritol (PE), di-TMP, di-PE, 2-ethyl hexanol, butyl ethyl
propane diol (BEPD), trimethyl propanediol (TMPD), and/or propylene
glycol.
[0031] In some embodiments, suitable alcohols may include
2-ethyl-2-(hydroxymethyl)-1,3-propanediol (trimethylol propane,
TMP), 2,2-dimethyl-1,3-propanediol (neopentyl glycol, NPG),
2,2-bis(hydroxymethyl)-1,3-propanediol (pentaerythritol, penta),
2-butyl-2-ethyl-1,3-propanediol (BEPD),
2,2,4-trimethyl-1,3-propanediol (TMPD), polyglycerine,
2,2-diethyl-1,3-propanediol, 1,3-propanediol, 1,2-propanediol
(propylene glycol), 1,6-hexanediol, 1,4-butanediol, 1,4-butenediol,
1,4-butynediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-,
1,3-, 1,4-, 1,8-, 2,4-, 2,7-, and 4,5-octanediol, tricyclodecane
dimethanol (octahydro-4,7-methano-1-H-indenedimethanol, TCD Alcohol
DM), 1,4-cyclohexanedimethanol
(1,4-bis-(hydroxymethyl)-cyclohexane), 1,12-dodecanediol,
2-methyl-2,4-pentanediol (hexylene glycol),
2-methyl-1,3-propanediol (MPD), 2-methyl-1,2-propanediol,
2-hydroxyethoxy-ethan-2-ol (diethylene glycol), dipropylene glycol
(3 isomer mixture), di-pentaerythritol, tri-pentaerythritol,
di-trimethylolpropane (di-TMP), triethylene glycol, tri-propylene
glycol, tetraethylene glycol, tetrapropylene glycol, polyethylene
glycol (PEG, MW 200-1.000.000 gram/mol), polypropylene glycol (PPG,
MW 200 10.000 gram/mol), ethane-1,2-diol (ethylene glycol), 1,2,-,
1,3-, 2,3-butanediol, 1,1-, 1,3-, 1,4-, 2,3- and 2,4-, pentanediol,
2-butene-1,2-diol, 2-butene-1,4-diol, 2-methyl-1,5-pentanediol,
2,4-dimethyl-2,4-pentanediol, 2,2-diethyl-1,4-butanediol,
2-pentene-1,5-diol, 2-propyl-1,3-butanediol, 1,4-hexanediol,
1,6-hexanediol, 5-methyl-1,2-hexanediol, 1-phenyl-1,2-ethanediol,
2-phenyl-1,2-propanediol, 1,6-diphenyl-1,6-hexanediol,
1,2-diphenyl-1,2-ethanediol, tris(2-hydroxyethyl)isocyanurate
(THEIC), poly-tetrahyfrofuran (poly-THF, MW 250, 650, 1000, 1400,
1800 and 2000), 2-ethyl-1,3-hexanediol (EHD), EO-PO block
copolymers, EO-PO-EO block copolymers, PO-EO block copolymers,
PO-EO-PO block copolymers (so called "reverse" types),
1,2-pentanediol, 4-methyl-1,4-hexanediol,
3,3-dimethyl-1,6-hexanediol, 2,4-dimethyl-3-hexene-2,5-diol, 2,3-,
2,4-, 2,5-, and 3,4-hexanediol, 1,2,3,6-hexanetetrol,
2-heptene-1,6-diol, 5-ethyl-3-methyl-2,4-heptanediol,
2-methyl-2-octene-1,4-diol, 2,4,4,5,5,7-hexamethyl-3,6-octanediol,
2,7-dimethyl-4-octane-2,7-diol,
2-butyl-4-ethyl-3-methyl-1,3-octanediol, 1,9-nonanediol, 1,2- and
1,10-decanediol, 5-decyne-4,7-diol, 5,8-diethyl-6,7-dodecanediol,
9-octadecene-1,12-diol, 9,10 and 1,12-octadecanediol, 1,9- and
1,11-undecanediol, 1,13-tridecanediol, 1,2-tetradecanediol, 1,2-
and 1,16-hexadecanediol, 1,2- or 1,12-octadecanediol,
2-Isobutyl-1,3-propanediol, 2-ethyl-1,3-propanediol,
2-ethyl-1,3-butanediol, 2,2-diethyl-1,4-butanediol,
2,2,3,3,-tetramethyl-1,4-butanediol, bisphenol A, hydrogenated
bisphenol A, ortho,meta or para-xylene-alpha, alpha diols,
3,6-dimethyl-ortho-xylene-alpha,alpha-diol,
alpha,alpha,-dimethyl-para-xylene-alpha,alpha diol,
1,6-diphenyl-1,6-hexanediol, alkanolamines such as: triethanolamine
(TEA), diethanolamine (DEA), N,N-dimethylaminoethanol,
N,N-diethylaminoethanol, N,N-dibutylaminoethanol,
N-phenyl-diethanolamine, N-methyl-diethanolamine,
di-isopropyl-ethanolamine (mixture of isomers);
2-ethyl-2-(hydroxymethyl)-1,3-propanediol ethoxylates (trimethylol
propane, TMP EO.sub.x where x ranges from 1 to 100 moles of EO),
2-ethyl-2-(hydroxymethyl)-1,3-propanediol propoxylates (Trimethylol
propane, TMP, PD.sub.x, where x ranges from 1-100 moles of PO),
2-Ethyl-2-(hydroxymethyl)-1,3-propanediol (random) Alkoxylates
(Trimethylol propane, TMP EO.sub.x-PO.sub.y, TMP
EO.sub.x-PO.sub.y-EO.sub.x, reverse types like TMP
PO.sub.x-EO.sub.y, TMP PO.sub.x-EO.sub.y-POx, where x and y range
from 1-100 moles both for ethylene oxide (EO) and propylene oxide
(PO), 2-ethyl-2-(hydroxymethyl)-1,3-propanediol butoxylate
(trimethylol propane, TMP BuO.sub.x, where x ranges from 1 25 moles
of butyleneoxide), 2,2-dimethyl-1,3-propanediol ethoxylates
(neopentyl glycol, NPG EO.sub.x, where x ranges from 1 to 100 moles
of EO), 2,2-dimethyl-1,3-propanediol propoxylates (neopentyl
glycol, NPG PD.sub.x, where x ranges from 1 to 100 moles of PO),
2,2-dimethyl-1,3-propanediol (random) alkoxylates (neopentyl
glycol, NPG EO.sub.x PO.sub.y, NPG PO.sub.x-EO.sub.y, NPG
EO.sub.x-PO.sub.y-EO.sub.x, reverse types like NPG
PO.sub.x-EO.sub.y-PD.sub.x where x and y range from 1 to 100 moles
for both ethylene oxide (EO) and propylene oxide (PO),
2,2-dimethyl-1,3-propanediol butoxylate (neopentyl glycol, NPG
BuO.sub.x, where x ranges from 1 to 25 moles of butyleneoxide),
2,2-bis(hydroxymethyl)-1,3-propanediol ethoxylates
(pentaerythritol, penta EO.sub.x, where x ranges from 1-100 moles
of EO), 2,2-bis(hydroxymethyl)-1,3-propanediol propoxylates
(pentaerythritol, penta PD.sub.x, where x ranges from 1-100 moles
of propyleneoxide (PO), 2,2-bis(hydroxymethyl)-1,3-propanediol
(random) alkoxylates (pentaerythritol, penta EO.sub.x-PO.sub.y
where x and y range from 1-100 moles of EO and PO),
2,2-bis(hydroxymethyl)-1,3-propanediol EO.sub.xPO.sub.y-EO.sub.x
(pentaerythritol, penta EO.sub.x-PO.sub.y-EO.sub.x, where x and y
range from 1-100 moles of EO and PO),
2,2-bis(hydroxymethyl)-1,3-propanediol butoxylates
(pentaerythritol, penta BuO.sub.x, where x ranges from 1-25 moles
of butyleneoxide), 2-butyl-2-ethyl-1,3-propanediol (BEPD)
ethoxylates (BEPD EO where x ranges from 1-100 moles of EO),
2-butyl-2-ethyl-1,3-propanediol (BEPD) propoxylates (BEPD PD.sub.x,
where x ranges from 1-100 moles of PO),
2-butyl-2-ethyl-1,3-propanediol (BEPD) (random) alkoxylates (BEPD
EOx-POy, BEPD EOx-POy-EOx, BEPD POx-EOy-POx, where x ranges from
1-100 moles of EO and PO), and/or 2-butyl-2-ethyl-1,3-propanediol
(BEPD) butoxylates (BEPD BuO.sub.x, where x ranges from 1-25 moles
of butyleneoxide).
[0032] Method
[0033] For example, HSAO triglyceride may be split into glycerol
and fatty acid (HSAO fa), which may be converted to many synthetic
esters, including, NPG-ester, TMP-ester and PE-ester. In some
embodiments, the fatty acids obtained from the triglyceride are
converted with alcohol to prepare a synthetic ester. These
synthetic esters can be obtained by standard techniques known to
those skilled in the art.
[0034] Product/Additional Components
[0035] In some embodiments, compositions comprising synthetic
esters of the present invention may be used for lubricants. In some
embodiments, compositions comprising synthetic esters of the
present invention may be used for hydraulic fluids. Synthetic
esters prepared according to embodiments of the present invention
are understood to have the same fatty acid distribution as the
corresponding triglyceride from which they were derived. In some
embodiments, the fatty acid distribution of the compositions
comprising synthetic esters of the present invention may be
associated with desirable lubricant properties.
[0036] Compositions including synthetic esters of the present
invention may include selected additional ingredients in suitable
amounts to achieve the desired result. In some embodiments,
compositions may include phenolic and/or aminic anti-oxidants,
extreme pressure additives, anti-wear additives, viscosity
modifiers, dewatering agents, emulsifiers, defoamers, and/or
wetting agents. Depending on the type of composition to be prepared
and the desired properties, some or all of the following components
may be included in suitable amounts:
TABLE-US-00001 Component Exemplary Amount Phenolic anti-oxidant
0.1-3.0 wt % Aminic anti-oxidant 0.1-3.0 wt % Extreme pressure
additive 0.05-1.0 wt % Anti-wear additive 0.05-1.0 wt % Viscosity
modifiers 0.0-10 wt % Dewatering agents 0.0-0.2 wt % Emulsifiers
0.0-10.0 wt % Defoamers 0.0-0.2 wt % Wetting agents 0.0-3.0 wt
%
[0037] In some embodiments, suitable phenolic antioxidants may
include alkylated monophenols, bis-hydroxyphenols, bisphenols, tris
and tetraphenolics, thioester antioxidants, aminic antioxidants,
and/or phosphite antioxidants.
[0038] In some embodiments, suitable alkylated monophenols may
include 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol,
2,6-di-tert-butyl-4-methylphenol (BHT), 2-tert-4,6-dimethylphenol,
di-sec-butylphenol, 2-sec-4-tert-butylphenol,
2,4-di-tert-amylphenol, 2,4-di-cumylphenol,
2,4,6-tri-tert-butylphenol, 2-tert-butylphenol,
(1,1-dimethyl)-4-methoxyphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-hydroxymethylphenol,
2,6-di-tert-butyl-4-iso-butylphenol,
2,6-di-octadecyl-4-methylphenol,
n-octadecyl-beta-4-hydroxy-3,5-di-tert-butylhydroxyphenyl)propionate,
isotridecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol,
3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester,
4,6-Bis(octylthiomethyl)-ortho-cresol,
2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazin-
e, and/or styrenated phenol (=mono or di or
tri-alphamethylbenzyl-phenol).
[0039] In some embodiments, suitable bis-hydroxyphenols may include
2-(1,1-dimethylethyl)-1,4-benzenediol,
2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone,
and/or 2,6-diphenyl-4-octadecyloxyphenol.
[0040] In some embodiments, suitable bisphenols may include
2,2-methylenebis-(6-tert-butyl-4-methylphenol),
2,2-methylenebis-(4-ethyl-6-tert-butylphenol),
4,4-methylenebis-(2,6-di-tert-butylphenol),
4,4-butylidenebis-(3-methyl-6-tert-butylphenol),
triethyleneglycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate-
], 2,2-methylenebis-[4-methyl-6-(alpha-methylcyclohexyl)-phenol],
2,2-methylenebis-(4-methyl-6-cyclohexylphenol),
2,2-methylenebis-(6-nonyl-4-methylphenol),
1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate],
4,4-thiobis(3-methyl-6-tert-butylphenol),
bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulphide,
2,2-thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
N.N-hexamethylene-bis-(3,5-di-tert-butyl-4-hydroxy)hydrocinnamide,
2,2-ethylidenebis-(4,6-di-tert-butylphenol),
1,2-bis[3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl]hydrazine,
2,2-methylenebis-(4,6-di-tert-butylphenol),
2,2-ethylidenebis-(4,6-di-tert-butylphenol),
2,2-ethylidenebis-(6-tert-butyl-para-isobutylphenol),
2,2-methylenebis-[6-(alpha-methylbenzyl)-4-nonylphenol,
4,4-methylenebis-(6-tert-butyl-2-methylphenol),
1,1-bis-(5-tert-butyl-4-hydroxy-2-methyl phenyl)butane,
2,6-di-(-3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
2,2-methylene-bis-(6-(1-methylcyclohexyl-para-cresol),
2,2-oxamidobis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate,
and/or 6,6-di-tert-butyl-2,2-thiobis-para-cresol.
[0041] In some embodiments, suitable tris and tetraphenolics may
include tris-(3,5-di-tert-butylhydroxybenzyl)isocyanurate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methan-
e, 1,1,1,-tris-(2-methyl-4-hydroxy-5-tert-butylphenol)butane,
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
3,3-bis-(3-tert-butyl-4-hydroxyphenyl)-ethylenebutyrate,
di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene,
di-[2-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl-
]terephtalate, butylated reaction product of p-cresol and
dicyclopentadiene.
[0042] In some embodiments, suitable thioester antioxidants may
include pentaerythrityl-tetrakis(3-laurylpropionate),
dilauryl-3,3-thiopropionate, distearyl-3,3-thiopropionate,
di-tridecyl-3,3-thiopropionate, di-myristyl-3,3-thiopropionate,
stearylthiopropionamide, bis[2-methyl-4-(3-n-C.sub.12-C.sub.14
alkylthiopropionyloxy)-5-tert-butylphenyl]sulphode, and/or
di-octadecyldisulphide.
[0043] In some embodiments, suitable aminic antioxidants may
include octyl/butyl-diphenylamine, p,p-bis-nonyl-diphenylamine,
N-phenyl-1-diphenylamine, N-phenyl-2-diphenylamine,
octylated-phenyl-alpha-naphtylamine, p,p-bis-octyl-diphenylamine,
polymerized 2,2,4-trimethyl-1,2-dihydroquinoline,
4,4-bis-(alpha,alpha-dimethylbenzyl)-diphenylamine, N,
N-di-2-naphtyl-p-phenylenediamine, N,N-diphenyl-p-phenylenediamine,
N-phenyl-N-isopropyl-p-phenylenediamine,
N-phenyl-N-(1,3-dimethylbutyl)-p-phenylenediamine,
N-(1-methylheptyl)-N-phenyl-p-phenylenediamine, mixed
diaryl-p-phenylenediamine (Wingstay 100),
N,N-di-sec-butyl-para-phenylenediamine,
N,N-di-iso-propyl-para-phenylenediamine,
N,N-bis-(1,4-dimethylpentyl)-para-phenylenediamine,
N,N-bis-(1-ethyl-3-methylpentyl)-para-phenylenediamine,
N,N-dicyclohexyl-para-phenylenediamine,
N,N-diphenyl-para-phenylenediamine,
N-isopropyl-N-phenyl-para-phenylenediamine,
N,N-di-sec-butyl-para-phenylenediamine,
N-cyclohexyl-N-phenyl-para-phenylenediamine,
N,N-dimethyl-N,N-di-sec-butyl-para-phenylenediamine, diphenylamine,
and/or 2,4-diaminodiphenyl methane.
[0044] In some embodiments, suitable phosphite antioxidants may
include tris-(2,4-di-tert-butylphenyl)-phosphite,
tris-(n-nonylphenyl)-phosphite, diphenyl-iso-octyl-phosphite,
diphenyl-isodecyl-phosphite, diphenyl-mono-tridecyl-phosphite,
phenyl-di-isodecyl-phosphite, tris-(2-ethylhexyl)-phosphite,
tris(isodecyl) phosphite, tris(tridecyl) phosphite,
tri-laurylthio-phosphite, tris-(mono & di nonylphenyl mixed)
phosphites, bis-(2,4-di-tert-butylphenyl) pentaerythritol, and/or
di stearylpentaerythritol diphosphite.
[0045] In some embodiments, a composition may include a yellow
metal passivator. In some embodiments, suitable yellow metal
passivators may include beznotriazole, tolutriazole, triazole,
2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole,
tetrahydrobenzotriazole, Irgamet 39.COPYRGT. (BASF), Irgamet
42.COPYRGT. (BASF), and/or Irgamet 30.COPYRGT. (BASF).
[0046] Use
[0047] In some embodiments, synthetic esters of the present
invention are prepared and/or formulated to provide improved
properties, such as low temperature properties, of the synthetic
ester in comparison to the corresponding triglyceride. Synthetic
esters prepared from a triglyceride having a unique fatty acid
distribution as described herein, such as high stability algal oil,
may provide desirable lubricant properties including exceptional
oxidation stability and superior low temperature properties
compared with the corresponding triglyceride. As a result, such
synthetic esters may be useful in metal lubricants and/or hydraulic
fluids, and metal lubricants and/or hydraulic fluid containing such
synthetic esters may exhibit improved properties as well.
[0048] In some embodiments, compositions including synthetic esters
of the present invention meet standards for fire resistance
according to Factory Mutual Approvals Class Number 6930, April
2009, which standard is incorporated by reference herein in its
entirety.
[0049] In some embodiments, compositions including synthetic esters
of the present invention maintain oxidative stability for about 750
hours or greater according to ASTM D943, which standard is
incorporated by reference herein in its entirety. In some
embodiments, compositions including synthetic esters of the present
invention maintain oxidative stability according to ASTM D943 for
about 200 hours or greater; about 250 hours or greater; about 300
hours or greater; about 350 hours or greater; about 400 hours or
greater; about 450 hours or greater; about 500 hours or greater;
about 550 hours or greater; about 600 hours or greater; about 650
hours or greater; about 700 hour or greater; about 750 hours or
greater; about 800 hours or greater; about 850 hours or greater;
about 900 hours or greater; about 950 hours or greater; about 1000
hours or greater; about 1100 hours or greater; about 1200 hours or
greater; about 1300 hours or greater; about 1400 hours or greater;
about 1500 hours or greater; about 1600 hours or greater; about
1700 hours or greater; about 1800 hours or greater; about 1900
hours or greater; about 2000 hours or greater; about 2100 hours or
greater; about 2200 hours or greater; about 2300 hours or greater;
about 2400 hours or greater; about 2500 hours or greater; about 200
hours to about 3000 hours; about 500 hours to about 3000 hours;
about 750 hours to about 3000 hours; about 750 hours to about 2500
hours; about 800 hours to about 2000 hours; about 1000 hours to
about 1800 hours; about 1200 hours to about 1600 hours; about 200
hours; about 800 hours; about 900 hours; about 1000 hours; about
1200 hours; about 1400 hours; about 1600 hours; about 1800 hours;
about 2000 hours; about 2200 hours; about 2400 hours; or about 2500
hours.
[0050] In some embodiments, compositions including synthetic esters
of the present invention exhibit a pour point temperature of about
-10.degree. C. or less. In some embodiments, compositions including
synthetic esters of the present invention exhibit a pour point
temperature of about 0.degree. C. or less; about -5.degree. C. or
less; about -10.degree. C. or less; about -15.degree. C. or less;
about -20.degree. C. or less; about -25.degree. C. or less; about
-30.degree. C. or less; about -35.degree. C. or less; about
-40.degree. C. or less; about -45.degree. C. or less; about
-50.degree. C. or less; about 0.degree. C.; about -5.degree. C.;
about -10.degree. C.; about -15.degree. C.; about -20.degree. C.;
about -25.degree. C.; about -30.degree. C.; about -35.degree. C.;
about -40.degree. C.; about -45.degree. C.; about -50.degree. C.;
about -10.degree. C. to about -70.degree. C.; about -10.degree. C.
to about -50.degree. C.; about -15.degree. C. to about -65.degree.
C.; about -20.degree. C. to about -60.degree. C.; about -25.degree.
C. to about -55.degree. C.; about -30.degree. C. to about
-50.degree. C.; or about -35.degree. C. to about -45.degree. C.
[0051] In some embodiments, compositions including synthetic esters
of the present invention exhibit a cloud point temperature of about
-10.degree. C. or less. In some embodiments, compositions including
synthetic esters of the present invention exhibit a pour point
temperature of about 0.degree. C. or less; about -5.degree. C. or
less; about -10.degree. C. or less; about -15.degree. C. or less;
about -20.degree. C. or less; about -25.degree. C. or less; about
-30.degree. C. or less; about -35.degree. C. or less; about
-40.degree. C. or less; about -45.degree. C. or less; about
-50.degree. C. or less; about 0.degree. C.; about -5.degree. C.;
about -10.degree. C.; about -15.degree. C.; about -20.degree. C.;
about -25.degree. C.; about -30.degree. C.; about -35.degree. C.;
about -40.degree. C.; about -45.degree. C.; about -50.degree. C.;
about -10.degree. C. to about -70.degree. C.; about -10.degree. C.
to about -50.degree. C.; about -15.degree. C. to about -65.degree.
C.; about -20.degree. C. to about -60.degree. C.; about -25.degree.
C. to about -55.degree. C.; about -30.degree. C. to about
-50.degree. C.; or about -35.degree. C. to about -45.degree. C.
[0052] As used throughout, the term "about" is understood to
mean.+-.10% of the value referenced. For example, "about 90" is
understood to literally mean 81 to 99.
[0053] The Oxidation Tests followed the following protocol:
[0054] Dry-TOST test: ASTM D 943, ISO 4263 [0055] Test sample: 330
ml [0056] Oxidation bath temperature 95.5.degree. C. (204.degree.
F.) [0057] O.sub.2 flow 3 liter/hour, 0.4 bar inlet pressure [0058]
Catalyst: Copper-Iron coil [0059] Initial measurement of acid
number and viscosity, t=0 situation [0060] Sampling at regular
intervals for AN and viscosity [0061] `Lifetime` (hrs) is reached
when the initial AN has increased with 2.0 mg KOH/g [0062]
Reproducibility (at tight variable control): .+-.5% (hrs) [0063]
Latest revision: Appearance rating of catalyst coil wires [0064]
Tests were performed without additives, and also with a fixed
(hydraulic fluid) additive package as set forth below, including:
[0065] 0.25% Aminic AO [0066] 0.50% Phenolic AO [0067] 0.10%
Cu-corrosion inhibitor [0068] 0.25% Thiophosphate AW additive
[0069] 0.05% Defoamer
[0070] Results of the Dry-TOST without additives are set forth in
the chart below:
TABLE-US-00002 Details 24 Details 48 hr check hr check Dry TOST
.DELTA.AN/ .DELTA.AN/ Lifetime Acidity .DELTA.Viscosity
.DELTA.Viscosity Product (hrs) (mg KOH/g) 40.degree. C. 40.degree.
C. HOAO <24 0.43 4.4/31 10/72 HSAO <24 0.06 2.6/19 8.7/51
TMPTO 31 1.38 2.2/35 6.4/71 Rapeseed Oil <24 0.19 3.3/36 6.3/113
HO <24 0.12 6.9/48 6.9/48 Sunflower
[0071] Results of the Dry-TOST with additives are set forth in the
chart below and FIG. 1 and FIG. 2:
TABLE-US-00003 Lifetime Product (hrs) HOAO + additives 176 HSAO +
additives 513 TMPTO + additives 438 Rapeseed Oil + additives <72
HO Sunflower + additives 113
[0072] High Oleic Algal Oil (HOAO) and High Stability Algal Oil
(HSAO) were evaluated in comparison to Trimethylolpropane
tri-oleate (TMPTO), Rapeseed Oil and High Oleic Sunflower Oil. The
test profile included: fatty acid distribution, viscosities/VI,
Flash- and Fire point, Cloud point, Pour point, and Cold test
(e.g., the temperature when solid after 24 hours, in 5.degree. C.
steps).
[0073] The viscosities and viscosity indices of the products are
set forth in the chart below:
TABLE-US-00004 Viscosity at Viscosity at Product 40.degree. C.
100.degree. C. VI HOAO 38.91 8.49 204 HSAO 40.32 8.64 200 TMPTO
46.44 9.44 193 Rapeseed Oil 35.01 8.06 215 HO Sunflower 39.57 8.57
203
[0074] The flash and fire point of the products are set forth in
the chart below:
TABLE-US-00005 Flash Point Fire Point Product (.degree. C.)
(.degree. C.) HOAO 326 362 HSAO 326 366 TMPTO 316 362 Rapeseed Oil
326 360 HO Sunflower 332 362
[0075] The cloud point, pour point and cold test of the products
are set forth in the chart below:
TABLE-US-00006 Cold Test Cloud Point Pour Point (.degree. C.)
(.degree. C.) (.degree. C.) 24 hrs/-5.degree. C. Product ISL MPP5G
ISL MPP5G steps HOAO -13 -24 Solid at -10 HSAO -14 -18 Solid at -10
TMPTO -26 -51 Liquid at -30 Rapeseed Oil -15 -21 Solid at -15 HO
Sunflower -13 -18 Solid at -10
[0076] In some embodiments, the following pour point depressants
were used, with the impact noted in the chart below:
TABLE-US-00007 Treat Rates (%) Pour Point Depressants Supplier
Recommended Actual Viscoplex 10-171 Evonik 0.25-0.5 0.25-5.0
Viscoplex 10-312 Evonik 0.25-0.5 0.25-0.5 Functional PPD-555
Functional Products 0.5-1.0 0.5-1.0 Functional PPD-557 Functional
Products 0.5-1.0 0.5-1.0 Lubrizol 3702 Lubrizol 0.2-2.0 0.2-2.0
Lubrizol 3715 Lubrizol 0.2-2.0 0.2-2.0
Pour point decrease: 5.degree. C. max (at 4-5% treat rate)
[0077] In some embodiments, HSAO-based Synthetic Esters, when
evaluated in hydraulic fluids, include the following non-optimized
additive package:
TABLE-US-00008 Cu-corrosion inhibitor 0.10 Mono-phenolic AO 0.50
Aminic AO 0.35 EP/AW-agent 0.25 Dewatering agent 0.02 Anti-foam
0.05
[0078] The properties of certain oleic acid types are set forth in
the charts below:
TABLE-US-00009 Fatty acid distributions of various Oleic acid types
Typical values Carbon chain Oleic acid HSAO fatty acid distribution
vegetable origin algal origin C 12 0.5 0.1 C 14 0.3 0.4 C 16 5.7
4.1 C 16:1 -- 0.1 C 18 2.1 3.4 C 18:1 78.8 88.8 C 18:2 11.8 1.8 C
18:3 0.1 0.2 C 20 0.3 0.3 C 20:1 0.5 0.5 Esters - Standard Oleic
Acid NPG-DO TMP-TO Penta-TO Parameters UOM Clear light Clear yellow
Clear yellow Appearance visual amber liquid to amber liquid liquid
Acid number mgKOH/g 0.4 1.1 1.4 Viscosity 40.degree. C. mm2/s 24.4
46.7 72.1 Viscosity 100.degree. C. mm2/s 5.84 9.3 13 Viscosity
index mm2/s 198 187 184 Pour point .degree. C. -21 -36 -21 Flash
point (COC) .degree. C. 262 315 314 Esters - HSAO Fatty Acid
NPG-VHOA TMP-VHOA Penta-VHOA Parameters UOM Clear light Clear
yellow Clear yellow Appearance visual yellow liquid liquid liquid
Acid number mgKOH/g 1.45 1.2 1.4 Viscosity 40.degree. C. mm2/s 25.7
47.5 68.3 Viscosity 100.degree. C. mm2/s 6.26 9.42 12.84 Viscosity
index mm2/s 210 187 191 Pour point .degree. C. -21 -27 -24 Flash
point (COC) .degree. C. 274 320 312
TABLE-US-00010 ISO 25 ISO 25 ISO 46 ISO 46 ISO 68 ISO 68 Raw
Material % % % % % % Dry-TOST Results NPG Di-HSAO ester 98.73
NPG-DO 98.73 TMP Tri-HSAO ester 98.73 TMP-TO 98.73 Penta Tetra-HSAO
ester 98.73 PETO 98.73 Additive package 1.27 1.27 1.27 1.27 1.27
1.27 Total, %: 100.00 100.00 100.00 100.00 100.00 100.00 Dry-TOST
test Acid Number (mg KOH/g) t = 0 hrs 2.10 1.45 2.05 1.94 2.03 1.81
t = 96 hrs 1.95 1.40 1.93 1.91 1.92 1.45 t = 144 hrs 1.88 1.34 1.82
1.88 1.84 1.49 t = 336 hrs 1.82 1.34 1.51 1.78 1.72 4.86 t = 480
hrs 1.68 16.4 1.54 1.75 1.40 -- t = 600 hrs 1.38 -- 1.42 14.1 1.40
-- t = 792 hrs Life time, hours 356 501 277 Ester overview for the
patent All esters made with Soleum Very High Oleic Acid (SVHOA)
NPG-Di SVHOA ester 98.73 NPG-DO 98.73 TMP-Tri-SVHOA ester 98.73
TMP-TO 98.73 Penta Tetra SVHOA ester 98.73 PETO 98.73 Tolutriazole
0.10 0.10 0.10 0.10 0.10 0.10 2,6-di-tert-Butylphenol 0.50 0.50
0.50 0.50 0.50 0.50 Irgalube 349* 0.25 0.25 0.25 0.25 0.25 0.25
Irganox L 57* 0.35 0.35 0.35 0.35 0.35 0.35 EO-PO Block copolymer
0.02 0.02 0.02 0.02 0.02 0.02 Clerol AMH 2* 0.05 0.05 0.05 0.05
0.05 0.05 Total, %: 100.00 100.00 100.00 100.00 100.00 100.00
Dry-TOST test Acidnumber, mgKOH/g: t = 0 hrs 2.10 1.45 2.05 1.94
2.03 1.81 t = 96 hrs 1.95 1.40 1.93 1.91 1.92 1.45 t = 144 hrs 1.88
1.34 1.82 1.88 1.84 1.49 t = 336 hrs 1.82 1.34 1.51 1.78 1.72 4.86
t = 480 hrs 1.68 16.4 1.54 1.75 1.40 -- t = 600 hrs 1.38 1.42 14.1
1.66 Lifetime, hours 356 501 277 *Irgalube 349 is a trade mark of
BASF/Ciba *Irganox L-57 is a trade mark of BASF/Ciba *Clerol AMH 2
is a trade mark of BASF/Ciba *NPG-DO, TMP-TO and PETO are esters
made in-house at Quaker Chemical B.V.
EXAMPLES
Example 1
[0079] Various triglycerides and esters were analyzed for fatty
acid distribution. The results are included in the chart below:
TABLE-US-00011 Fatty Acid Distribution (Typical values) Product C16
C16:1 C18 C18:1 C18:2 C18:3 Other HOAO 3.5 0 3.2 83.8 7.8 .4 1.3
High stability 8.8 0.4 3.3 86.2 0.4 0 0.9 algal oil TMPTO* 5.3 1.8
1.9 76.8 10.7 0 3.5 Rapeseed Oil 4.5 .2 2 63.9 18 8.6 2.8 HO
Sunflower 4.0 0.1 3.6 83.8 6.3 0.2 2 *Ester prepared from standard
oleic acid (not high stability algal oil); HOAO very similar to HO
Sunflower (as intended); Rapeseed oil: high unsaturation; HSAO:
high Oleic, but near-zero C18:2 and C18:3; TMPTO: relatively high
in C18:2.
[0080] It is understood that esters prepared from the triglycerides
listed above will have the same fatty acid distribution as the
corresponding triglyceride.
[0081] The test results above demonstrate the effectiveness of the
formulation in providing desirable levels of corrosion protection
and paint adhesion.
[0082] While illustrative embodiments and examples of the invention
are disclosed herein, it will be appreciated that numerous
modifications and other embodiments may be devised by those skilled
in the art and that these embodiments and examples are
non-limiting. For example, the features for the various embodiments
can be used in other embodiments. Therefore, it will be understood
that the appended claims are intended to cover all such
modifications and embodiments that come within the spirit and scope
of the present disclosure.
[0083] A number of references have been cited, the entire
disclosures of which are incorporated herein in their entirety by
reference.
* * * * *