U.S. patent application number 16/834862 was filed with the patent office on 2020-07-23 for wax ethers and related methods.
The applicant listed for this patent is International Flora Technologies, Ltd.. Invention is credited to Jeff Addy.
Application Number | 20200231524 16/834862 |
Document ID | / |
Family ID | 67984784 |
Filed Date | 2020-07-23 |
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United States Patent
Application |
20200231524 |
Kind Code |
A1 |
Addy; Jeff |
July 23, 2020 |
Wax Ethers and Related Methods
Abstract
Implementations of a method of forming a wax ether composition
may include: providing a batch of lipids, drying the batch of
lipids, and cooling the batch of lipids. The method may also
include dosing, with a catalyst, the batch of lipids at 0.1% to
0.3% by weight of the batch of lipids and dissolving the catalyst
in the batch of lipids to form a homogenous solution. The method
may include adding at least a molar equivalent of a hydrogen donor
to the homogenous solution. The method may include sealing and
maintaining the homogenous solution and hydrogen donor under
atmospheric pressure under reflux until a chemical reaction between
the homogenous solution and the hydrogen donor forms a product
comprising an ether.
Inventors: |
Addy; Jeff; (Chandler,
AZ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
International Flora Technologies, Ltd. |
Chandler |
AZ |
US |
|
|
Family ID: |
67984784 |
Appl. No.: |
16/834862 |
Filed: |
March 30, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16364033 |
Mar 25, 2019 |
10633318 |
|
|
16834862 |
|
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|
62648059 |
Mar 26, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 41/01 20130101;
B01J 27/08 20130101; C07C 41/01 20130101; C07C 43/04 20130101 |
International
Class: |
C07C 41/01 20060101
C07C041/01 |
Claims
1. A method of forming an ether composition, the method comprising:
providing a batch of lipids; drying the batch of lipids; dosing the
batch of lipids with a catalyst at 0.1% to 0.3% by weight of the
batch of lipids to form a homogenous solution; and sealing and
maintaining the homogenous solution and a hydrogen donor under
atmospheric pressure under reflux until a chemical reaction between
the homogenous solution and the hydrogen donor forms a product
comprising an ether.
2. The method of claim 1, wherein drying the batch of lipids
comprises heating the batch of lipids at 100 C under agitation and
vacuum.
3. The method of claim 1, further comprising cooling the batch of
lipids; dissolving the catalyst to form the homogenous solution;
and adding at least a molar equivalent of the hydrogen donor to the
homogenous solution.
4. The method of claim 1, further comprising removing a residue of
the hydrogen donor through one of vacuum distillation or physical
separation.
5. The method of claim 1, further comprising capturing and
redistributing the hydrogen donor using a condenser during the
chemical reaction.
6. The method of claim 1, wherein a product of the chemical
reaction comprises an iodine value of 52 and a melting point of 45
C.
7. The method of claim 1, wherein the hydrogen donor comprises
1,1,3,3-tetramethyldisiloxane (TMDS).
8. The method of claim 1, wherein the catalyst is a metal
halide.
9. A method of forming an ether composition, the method comprising:
providing a batch of triglycerides; drying the batch of
triglycerides; dosing the batch of triglycerides with a catalyst at
0.1% to 0.3% by weight of the batch of triglycerides to form a
homogenous solution; and sealing and maintaining the homogenous
solution and a hydrogen donor under atmospheric pressure under
reflux until a chemical reaction between the homogenous solution
and the hydrogen donor forms a product comprising an ether.
10. The method of claim 9, wherein drying the batch of
triglycerides comprises heating the batch of triglycerides at 100 C
under agitation and vacuum.
11. The method of claim 9, further comprising cooling the batch of
triglycerides to 5 C-10 C above a melting point of the batch of
triglycerides under agitation and vacuum.
12. The method of claim 9, further comprising removing a residue of
the hydrogen donor through one of vacuum distillation or physical
separation.
13. The method of claim 9, further comprising capturing and
redistributing the hydrogen donor using a condenser during the
chemical reaction.
14. The method of claim 9, further comprising adding at least a
molar equivalent of a hydrogen donor to the homogenous
solution.
15. A method of forming a wax ether composition, the method
comprising: providing a batch of wax esters; drying the batch of
wax esters; dosing with a catalyst, the batch of triglycerides at
0.1% to 0.3% by weight of the batch of wax esters to form a
homogenous solution; and sealing and maintaining the homogenous
solution and a hydrogen donor under atmospheric pressure under
reflux until a chemical reaction between the homogenous solution
and the hydrogen donor forms a product comprising an ether.
16. The method of claim 15, wherein the batch of wax esters
comprises wax esters comprising carbon chain lengths ranging from
C24 to C52.
17. The method of claim 15, wherein drying the batch of wax esters
comprises heating the batch of wax esters at 100 C under agitation
and vacuum.
18. The method of claim 15, further comprising cooling the batch of
wax esters to 5 C-10 C above a melting point of the batch of wax
esters under agitation and vacuum.
19. The method of claim 15, further comprising adding at least a
molar equivalent of hydrogen donor to the homogenous solution.
20. The method of claim 15, further comprising capturing and
redistributing the hydrogen donor using a condenser during the
chemical reaction.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation application of the
earlier U.S. Utility Patent Application to Jeff Addy entitled "Wax
Ethers and Related Methods," application Ser. No. 16/364,033, filed
Mar. 25, 2019, now pending, which claims the benefit of the filing
date of U.S. Provisional Patent Application 62/648,059, entitled
"Wax Ethers and Related Methods" to Jeff Addy et al. which was
filed on Mar. 26, 2018, the disclosure of each of which are hereby
incorporated entirely herein by reference.
BACKGROUND
1. Technical Field
[0002] Aspects of this document relate generally to wax ethers,
such as methods of forming wax ethers from lipids. More specific
implementations involve ether lipids sourced from botanical raw
materials.
2. Background
[0003] In organic chemistry, an ether is a carbon-containing
molecule that includes the ether functional group (--C--O--C--) in
part of its molecular structure.
SUMMARY
[0004] Implementations of a method of forming an ether composition
may include: providing a batch of lipids, drying the batch of
lipids, and cooling the batch of lipids. The method may also
include dosing, with a catalyst, the batch of lipids at 0.1% to
0.3% by weight of the batch of lipids and dissolving the catalyst
in the batch of lipids to form a homogenous solution. The method
may include adding at least a molar equivalent of a hydrogen donor
to the homogenous solution. The method may include sealing and
maintaining the homogenous solution and hydrogen donor under
atmospheric pressure under reflux until a chemical reaction between
the homogenous solution and the hydrogen donor forms a product
comprising an ether.
[0005] Implementations of methods of forming ether compositions may
include one, all, or any of the following:
[0006] Drying the batch of lipids may include heating the batch of
lipids at 100 C under agitation and vacuum.
[0007] Cooling the batch of lipids may include cooling the batch of
lipids to 5 C-10 C above the melting point of the lipids under
agitation and vacuum.
[0008] The method may further include removing a residue of the
hydrogen donor through one of vacuum distillation or physical
separation.
[0009] The method may further include capturing and redistributing
the hydrogen donor using a condenser during the chemical
reaction.
[0010] The batch of lipids may include wax esters or
triglycerides.
[0011] The hydrogen donor may include 1,1,3,3-Tetramethyldisiloxane
(TMDS).
[0012] The catalyst may be a metal halide.
[0013] Implementations of a method of forming an ether composition
may include: providing a batch of triglycerides, drying the batch
of triglycerides, and cooling the batch of triglycerides. The
method may also include dosing, with a catalyst, the batch of
triglycerides at 0.1% to 0.3% by weight of the batch of
triglycerides and dissolving the catalyst in the batch of
triglycerides to form a homogenous solution. The method may include
adding at least a molar equivalent of a hydrogen donor to the
homogenous solution. The method may include sealing and maintaining
the homogenous solution and the hydrogen donor under atmospheric
pressure under reflux until a chemical reaction between the
homogenous solution and the hydrogen donor is complete.
[0014] Implementations of methods of forming ether compositions may
include one, all, or any of the following:
[0015] Drying the batch of lipids may include heating the batch of
triglycerides at 100 C under agitation and vacuum.
[0016] Cooling the batch of triglycerides may include cooling the
batch of triglycerides to 5 C-10 C above the melting point of the
batch of triglycerides under agitation and vacuum.
[0017] The method may further include removing a residue of the
hydrogen donor through one of vacuum distillation or physical
separation.
[0018] The method may further include capturing and redistributing
the hydrogen donor using a condenser during the chemical
reaction.
[0019] A product of the chemical reaction may include an iodine
value of 52 and a melting point of 45 C.
[0020] Implementations of a method of forming a wax ether
composition may include: providing a batch of wax esters, drying
the batch of wax esters, and cooling the batch of wax esters. The
method also includes dosing, with a catalyst, the batch of wax
esters at 0.1% to 0.3% by weight of the batch of wax esters and
dissolving the catalyst in the batch of wax esters to form a
homogenous solution. The method includes adding at least a molar
equivalent of a hydrogen donor to the homogenous solution. The
method includes sealing and maintaining the homogenous solution and
the hydrogen donor under atmospheric pressure under reflux until a
chemical reaction between the homogenous solution and the hydrogen
donor forms a product comprising an ether.
[0021] Implementations of methods of forming ether compositions may
include one, all, or any of the following:
[0022] The batch of wax esters may include wax esters having carbon
chain lengths ranging from C24 to C52.
[0023] Drying the batch of wax esters may include heating the batch
of wax esters at 100 C under agitation and vacuum.
[0024] Cooling the batch of wax esters may include cooling the
batch of wax esters to 5C-10 C above the melting point of the batch
of wax esters under agitation and vacuum.
[0025] The method may further include removing a residue of the
hydrogen donor through one of vacuum distillation or physical
separation.
[0026] The method may further include capturing and redistributing
the hydrogen donor using a condenser during the chemical
reaction.
[0027] The foregoing and other aspects, features, and advantages
will be apparent to those artisans of ordinary skill in the art
from the DESCRIPTION and DRAWINGS, and from the CLAIMS.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Implementations will hereinafter be described in conjunction
with the appended drawings, where like designations denote like
elements, and:
[0029] FIG. 1 is a graph illustrating carbon chain length
distributions between reactants and products from an implementation
of a method of forming wax ethers;
[0030] FIG. 2 is a graph illustrating carbon chain length
distributions between a wax ester product marketed under the
tradename FLORAESTERS.RTM. 70 as a reactant and the resulting ether
derivative in an implementation of a method of forming wax ethers;
and
[0031] FIG. 3 is a graph comparing the percentage of 1-nonanol and
iodine values of products of an implementation of a method of
forming wax ethers.
DESCRIPTION
[0032] This disclosure, its aspects and implementations, are not
limited to the specific components, assembly procedures or method
elements disclosed herein. Many additional components, assembly
procedures and/or method elements known in the art consistent with
the intended methods of forming wax ethers will become apparent for
use with particular implementations from this disclosure.
Accordingly, for example, although particular implementations are
disclosed, such implementations and implementing components may
comprise any shape, size, style, type, model, version, measurement,
concentration, material, quantity, method element, step, and/or the
like as is known in the art for such wax ethers, and implementing
components and methods, consistent with the intended operation and
methods.
[0033] In various implementations, lipids that are classified as
wax-esters can be derivatized into different compounds. During a
reduction reaction, ester functional groups on the reactant are
reduced to ethers. Under specific conditions, points of
unsaturation on the ethers may also cleave to form low-boiling
point carbon chains with functional groups of alkanes, alkenes,
ketones, and aldehydes. In various implementations of methods
disclosed in this document, a catalyst is used to carry out the
reduction reaction. In various implementations, the method may
employ a catalyst such as, by non-limiting example, a metal halide
such as, by non-limiting example, gallium bromide (GaBr3) in
combination with a hydrogen donor such as, by non-limiting example,
1,1,3,3-tetramethyldisiloxane (TMDS).
[0034] Implementations of a method of forming wax ethers from wax
esters may employ a batch reaction process. In a particular
implementation of the process, the method includes providing a
batch of lipids (input material) and drying the batch of lipids at
100 C under constant agitation and full vacuum until substantially
all water has evaporated from the material. The batch of lipids are
then be cooled to 5 C-10 C above the melting point of the lipid
while the batch of lipids is still under agitation and vacuum.
Vacuuming of the batch of lipids is stopped and the catalyst is
then dosed at 0.1% to 0.3% by weight of the lipid, depending on the
input material. In various implementations of a method of forming
wax ethers, triglycerides or other similar material may be used as
the input material. After the catalyst has dissolved and the
solution is homogenous, a molar equivalent plus about 0-10% excess
of TMDS or other hydrogen donor on a molar basis is added to the
reactor. A molar equivalent, as used herein, is an amount of a
substance that will supply the reaction with one mole of hydrogen
protons. In various implementations, however, other hydrogen donor
reactants other than TMDS or in combination with TMDS may be added
to the reactor.
[0035] After addition of the catalyst and the hydrogen donor
reactant, the reactor is then sealed and maintained under
atmospheric pressure under reflux until the reaction is complete.
In various implementations, the time for completion of the reaction
may last around 30 minutes. In other implementations, the reaction
may take more than 30 minutes or less than 30 minutes depending on
the particular reactants involved. During the reaction, a condenser
is used to capture and redistribute the TMDS, or other hydrogen
donor, as needed. The reaction is determined to be complete when
TMDS is no longer detectably being condensed out of the condenser.
Following a determination that the reaction is completed, any
residual TMDS or other hydrogen donor and any polysiloxanes in the
liquid phase are then removed through, by non-limiting example,
vacuum distillation, physical separation, or phase separation. The
vacuum distillation may be performed at an elevated temperature,
such as between about 100 C to about 250 C depending on the degree
of polymerization of the polysiloxanes. The degree of
polymerization may be determined by the amount of residual TMDS,
the amount of catalyst used, and the reaction time. Following
separation of the remaining unreacted hydrogen donor, the catalyst
may be deactivated by various refining processes such as, by
non-limiting example, a brine wash, treatment with an absorbent
material such as activated carbon, silica, bleaching earth, or
other process capable of deactivating and/or removing the catalyst
material. In various implementations, catalyst deactivation may be
performed before or after removal of the residual TMDS and/or the
polysiloxanes.
[0036] The reaction, including conversion, ether/ester
distribution, and identification for the wax-ether product, may be
monitored through observing the saponification (SAP) value measured
using the official method of the American Oil Chemists' Society
file name Cd 3-25 (AOCS Cd 3-25). The saponification value is the
amount of alkali necessary to saponify a definite quantity of the
test sample. It is expressed as the number of milligrams of
potassium hydroxide (KOH) required to saponify 1 gram of the test
sample. In the examples of reactions disclosed herein, the reaction
was also monitored with an Agilent 6890 Gas Chromatograph (GC) with
a 5973N Mass Spectrometer using electron ionization (EI) equipped
with a cool-on column inlet. The source temperature was maintained
at 250 C and the quadrupole temperature was maintained at 150 C.
The column used was a Restek RTX-65TG, 30 m, 250 .mu.m diameter,
and 0.1 .mu.m film thickness. Temperature programming on the GC was
initiated at 60 C for 1 minute and increased to 350 C at 4 C/min,
holding at 350 C for 5 min. Gas flowrate was maintained at 1 mL/min
using research grade helium. The mass spectral database National
Institute of Standards and Technology (NIST) 12 (NIST
Thermophysical Properties of Pure Fluids Database: Version 3.0) was
utilized for identification when available. Various AOCS standard
procedures were used to evaluate additional properties of the wax
ethers, such as AOCS Cd 8-53 for peroxide value, AOCS Ci 4-91 for
acid value, AOCS Cd 1-25 for iodine value, AOCS Cc 18-80 for
dropping point, and Cd 12b-92 for oxidative stability index
(OSI).
[0037] In particular implementations, the reaction may begin using
wax esters as the reactants. The wax ester species include
esterified fatty acids and fatty alcohols with chain lengths from
C14 to C26 with varying degrees of unsaturation that may form
complete wax esters ranging from C24 to C52. Also included may be
those esterified fatty acids and fatty alcohols used to produce
transesterified products like those marketed under the tradenames
FLORAESTERS.RTM. 15, FLORAESTERS.RTM. 20, FLORAESTERS.RTM. 30,
FLORAESTERS.RTM. 60, or FLORAESTERS.RTM. 70 by International Flora
Technologies, LTD. of Chandler, Ariz. Examples of such
corresponding fatty alcohols and fatty esters that may be used in
various implementations corresponding with the aforementioned
tradenamed products are included in Table 1 (below).
TABLE-US-00001 TABLE 1 Wax Ester Alcohol Acid C36 Hexadecanyl
Eicosanoate Hexadecanyl (11Z)-Eicos-11-enoate (9Z)-Hexadec-9-enyl
Eicosanoate (9Z)-Hexadec-9-enyl (11Z)-Eicos-11-enoate Octadecanyl
Octadecanoate Octadecanyl (9Z)-Octadec-9-enoate (9Z)-Octadec-9-enyl
(9Z)-Octadec-9-enoate Eicosanyl Hexadecanoate Eicosanyl
(9Z)-Hexadec-9-enoate (11Z)-Eicos-11-enyl Hexadecanoate
(11Z)-Eicos-11-enyl (9Z)-Hexadec-9-enoate C38 Hexadecanyl
Docosanoate Hexadecanyl (13Z)-Docos-13-enoate (9Z)-Hexadec-9-enyl
Docosanoate (9Z)-Hexadec-9-enyl (13Z)-Docos-13-enoate Octadecanyl
Eicosanoate Octadecanyl (11Z)-Eicos-11-enoate (9Z)-Octadec-9-enyl
Eicosanoate (9Z)-Octadec-9-enyl (11Z)-Eicos-11-enoate Eicosanyl
Octadecanoate Eicosanyl (9Z)-Octadec-9-enoate (11Z)-Eicos-11-enyl
Octadecanoate (11Z)-Eicos-11-enyl (9Z)-Octadec-9-enoate Docosanyl
Hexadecanoate Docosanyl (9Z)-Hexadec-9-enoate (13Z)-Docos-13-enyl
Hexadecanoate (13Z)-Docos-13-enyl (9Z)-Hexadec-9-enoate C40
Hexadecanyl Tetracosanoate Hexadecanyl (15Z)-Tetracos-15-enoate
(9Z)-Hexadec-9-enyl Tetracosanoate (9Z)-Hexadec-9-enyl
(15Z)-Tetracos-15-enoate Octadecanyl Docosanoate Octadecanyl
(13Z)-Docos-13-enoate (9Z)-Octadec-9-enyl Docosanoate
(9Z)-Octadec-9-enyl (13Z)-Docos-13-enoate Eicosanyl Eicosanoate
Eicosanyl (11Z)-Eicos-11-enoate (11Z)-Eicos-11-enyl
(11Z)-Eicos-11-enoate Docosanyl Octadecanoate Docosanyl
(9Z)-Octadec-9-enoate (13Z)-Docos-13-enyl Octadecanoate
(13Z)-Docos-13-enyl (9Z)-Octadec-9-enoate Tetracosanyl
Hexadecanoate Tetracosanyl (9Z)-Hexadec-9-enoate
(15Z)-Tetracos-15-enyl Hexadecanoate (15Z)-Tetracos-15-enyl
(9Z)-Hexadec-9-enoate C42 Octadecanyl Tetracosanoate Octadecanyl
(15Z)-Tetracos-15-enoate (9Z)-Octadec-9-enyl Tetracosanoate
(9Z)-Octadec-9-enyl (15Z)-Tetracos-15-enoate Eicosanyl Docosanoate
Eicosanyl (13Z)-Docos-13-enoate (11Z)-Eicos-11-enyl Docosanoate
(11Z)-Eicos-11-enyl (13Z)-Docos-13-enoate Docosanyl Docosanoate
Docosanyl (13Z)-Docos-13-enoate (13Z)-Docos-13-enyl
(13Z)-Docos-13-enoate Tetracosanyl Octadecanoate Tetracosanyl
(9Z)-Octadec-9-enoate (15Z)-Tetracos-15-enyl Octadecanoate
(15Z)-Tetracos-15-enyl (9Z)-Octadec-9-enoate C44 Eicosanyl
Tetracosanoate Eicosanyl (15Z)-Tetracos-15-enoate
(11Z)-Eicos-11-enyl Tetracosanoate (11Z)-Eicos-11-enyl
(15Z)-Tetracos-15-enoate Docosanyl Docosanoate Docosanyl
(13Z)-Docos-13-enoate (13Z)-Docos-13-enyl (13Z)-Docos-13-enoate
Tetracosanyl Eicosanoate Tetracosanyl (11Z)-Eicos-11-enoate
(15Z)-Tetracos-15-enyl Eicosanoate (15Z)-Tetracos-15-enyl
(11Z)-Eicos-11-enoate C46 Docosanyl Tetracosanoate Docosanyl
(15Z)-Tetracos-15-enoate (13Z)-Docos-13-enyl Tetracosanoate
(13Z)-Docos-13-enyl (15Z)-Tetracos-15-enoate Tetracosanyl
Docosanoate Tetracosanyl (13Z)-Docos-13-enoate
(15Z)-Tetracos-15-enyl Docosanoate (15Z)-Tetracos-15-enyl
(13Z)-Docos-13-enoate
[0038] These various reactants may be, in various implementations,
products of the transesterification of jojoba oil and hydrogenated
jojoba oil having varying iodine values. A reaction was done with
each of these wax ester reactants as described above, including the
same catalyst and hydrogen donor previously described. The
resulting product of the etherification reaction using these
reactants, an ether lipid, demonstrates distinctive properties that
were not present in the starting reactants. These properties are
summarized in Table 2 (below) for each of the respective wax ester
products versus the corresponding wax ether product. While many of
the physical properties of the wax ether product are similar to the
wax ester product, those for SAP value and oxidative stability
index (OSI) differ markedly. These characteristics may show parity
with shorter chain length ethers that are not jojoba derived, such
as mixtures containing C14-C26 fatty acids and fatty alcohols of
varying saturation. However, the difference in OSI value shows that
the wax ether product is more stable than the corresponding wax
ether product.
TABLE-US-00002 TABLE 2 Ether Floraesters Ether Floraesters Ether
Floraesters Ether Floraesters Test 20 20 30 30 60 60 70 70 PEROXIDE
VALUE 0 0 0 0 0 0 0 0 ACID VALUE 0.73 0.69 0.71 0.72 0.69 0.7 0.68
0.67 IODINE VALUE 61.72 65.33 55.28 57.66 42.87 43.29 0 0 SAP VALUE
1.2 91.3 0.9 92.4 0.7 93.1 1.2 93.7 DROPPING POINT 46.9 46 51.2
50.3 55.6 54.1 69.3 68.9 (.degree. C.) OSI (hrs) 138 115 139 122
151 136 220 180
[0039] In another implementation of a method of forming wax esters
from triglyceride input material, the transesterification product
of moringa oil and hydrogenated moringa oil was used as the
reactant under the same conditions described above, including using
the same catalyst and hydrogen donor. Conversion was monitored by
quantitating the triglyceride component using SAP value and normal
phase high pressure liquid chromatography (HPLC) using an Agilent
1160 HPLC with a quaternary pump and an Alltech 2000 ELSD detector
using 1.8 L/min nitrogen at 50 C. Separation was done with an
Agilent RX-SIL 4.6.times.50 mm, 1.8 .mu.m particle size column
maintained at 45 C. The mobile phase consisted of 100% hexane to
60% hexane/40% ethyl acetate over 15 minutes at 1 mL/min.
[0040] The difference in the various input materials in the
examples provided in this document did not have any observed effect
on reaction time as both wax esters and triglycerides of varying
degrees of saturation were observed to be fully converted within 30
minutes.
[0041] The most notable difference between the wax-ester and
triglyceride etherification products was that the triglycerol ether
showed a remarkable change in melting point compared to the
starting material despite maintaining a similar iodine value. The
transesterification product of moringa oil and hydrogenated moringa
with an iodine value of 52 had a melting point of 45 C, making it a
solid at room temperature. Unexpectedly, in contrast, the
triglycerol ether equivalent of the moringa oil had a primary solid
to liquid transition at 16 C, and resembled a milky liquid at room
temperature with the secondary transition from white to transparent
occurring at 42 C. This optical behavior of the liquid likely
indicates an "unstable" polymorphic property that is not observed
in the wax-ethers variants.
[0042] It is also notable that the iodine value as found in AOCS Cd
1-25 slightly decreases during the ether process indicating a
decrease in the concentration of double bonds present on the fatty
acid or fatty alcohol chains. Without being bound by any theory,
this appears to be due to an oxidation reaction that effectively
cleaves the chain at the double bond, forming a short chain ether
and alcohol. The oxidation of the double bond containing wax-esters
is apparent in the minor changes in carbon chain length
distributions between the reactants and products shown in the graph
of FIG. 1. The fatty acids and fatty alcohols in jojoba and moringa
oils have double bonds in the omega-9 position. The oxidative
cleavage at the omega-9 position yields the alcohol 1-nonanol, an
alcohol with 9 carbons and a distinct human.
[0043] The reaction also does not show a notable difference between
the carbon chain length distribution between the ether product or
the ester product when using input materials like those used to
produce FLORAESTERS.RTM. 70 which do not have double bonds as shown
in the graph of FIG. 2. Quantitative and qualitative analysis of
1-nonanol was done using the GC-MS method mentioned above. The
concentration of synthesized 1-nonanol decreases proportionally
across the products as the concentration of double bonds and iodine
value decreases as seen in the graph in FIG. 3. This behavior is
unexpected, as previous work indicates this observed side reaction
to form 1-nonanol does not occur and assumes the conversion is
limited to the reductive reaction of carboxylic acids or esters to
alcohols or ethers as described in PCT Application Publication No.
WO2013010747 to Metzger et al, entitled "Process For Reducing
Carboxylic Esters Or Carboxylic Lactones To The Corresponding
Ethers," filed Jun. 22, 2012, the entirety of which is hereby
incorporated by reference. Under previously mentioned reaction
conditions, the reducing agent is observed to simultaneously
oxidize alkenes to alcohols (1-nonanol) to a certain degree while
still reducing esters to ethers.
[0044] The foregoing indicates that for wax esters, the
etherification reaction disclosed herein appears to be nonspecific
and works to cleaves double bonds not limited to fatty acids or
fatty alcohols. Thus, it has been observed that inherent color
bodies, such as carotenoids and tocopherols in the reactants, also
undergo this oxidation process readily during the reaction. The
oxidation of the double bonds on these molecules removes the
optical activity of the molecules and renders the final product
devoid of color (optically clear). Referring to Table 3 (below),
the observed data contrasting the optical characteristics of the
ester and ether products, and including a sample which was spiked
with the addition of 500 ppm alpha-tocopherol in the input material
is illustrated. As indicated, the ether product, whether spiked or
not, was substantially optically clear following the process, as
both the tocopherols and beta carotene present in the reactants
were not detectable (noted as ND) after the reaction. This result
was also unexpected in view of the teachings of previous work. The
color and amount of color bodies of the final product was measured
using the Lovibond method as found in AOCS file Cc 13e-92 and an
Agilent 1160 HPLC with a quaternary pump and an Alltech 2000
Evaporative light scattering detector (ELSD) using 1.8 L/min
nitrogen at 40.degree. C. Separation was done with an Agilent
RX-SIL 4.6.times.50 mm, 1.8 .mu.m particle size column maintained
at 45.degree. C. The mobile phase included 98% hexane to 2%
isopropanol isocratically flowed for 15 minutes at 1 L/min. The
diode array detector (DAD) was set to monitor beta carotene at 475
nm and alpha tocopherol at 291 nm.
TABLE-US-00003 TABLE 3 Beta Tocopherol Carotene Lovi Color (ppm)
(ppm) Floraesters 20 4.2Y, 0.9R 127 43 Ethers 20 0.3Y, 0.2R ND ND
Floraesters 20 Spiked 4.8Y, 1.1R 721 76 Ether 20 Spiked 0.3Y, 0.3R
ND ND
[0045] An additional unexpected result, which was not disclosed or
taught in any previous work, relates to the effect of the
deactivation of these color bodies which serve as natural
antioxidants. It was observed that the deactivation of the color
bodies did not result in any reduction in the oxidative
stability--something clearly unexpected and novel. One would assume
that the lack of antioxidants would decrease the Oxidative
Stability Index using the method of AOCS file Cd 12b-92. However,
the additional surprisingly unexpected result of a significant
increase in OSI values was observed as previously illustrated in
Table 1 (above). Given that the natural antioxidants in the
reactant material were already oxidized in the reaction and could
not contributed to the OSI value at this point, the result that the
ether product exhibited much higher OSI was not predicted or a
predictable result in view of what is taught and disclosed in
previous work.
[0046] In various implementations, the distribution chain lengths
(C36, C38, C40, C42, C44, and C46) did not substantially change
during the conversion from a wax-ester to a wax-ether. In some
implementations, the ether products have a notable observed
increase in spreading properties on the skin. An additional
subjective property noted with the ether products is a "less
greasy" feel when compared to the FLORAESTERS starting materials.
An additional subjective property noted with implementations of the
ether products is a unique "film forming" property that is absent
in the ester products that is described as a "non-volatile
silicone" or "siliconeized" feel.
[0047] The feel test results for the ether products were
substantiated in a consumer test panel. The ether derivatives were
compared to dimethicone CS100, a commonly used silicone in cosmetic
applications. The materials were compared in a neat application. It
was found that ethers resembled dimethicone in spread, absorbency,
and feel immediately and post 30 minutes after application. The
ethers also displayed similar gloss, stickiness, slipperiness,
amount of residue, silkiness/smoothness, greasiness, and
moisturization of the skin when compared to dimethicone CS100. The
ability of the ether product to mimic a silicone's subjective
properties was unexpected, given the ether product does not contain
silicon in its chemical structure.
[0048] In places where the description above refers to particular
implementations of wax ethers and implementing components,
sub-components, methods and sub-methods, it should be readily
apparent that a number of modifications may be made without
departing from the spirit thereof and that these implementations,
implementing components, sub-components, methods and sub-methods
may be applied to other wax ethers.
* * * * *