U.S. patent application number 15/643955 was filed with the patent office on 2018-01-11 for lubricating members for razor cartridges comprising a metathesized unsaturated polyol ester.
The applicant listed for this patent is The Gillette Company LLC. Invention is credited to Joseph Jay Kemper, Safa Motlagh, Rajan Keshav Panandiker, Philip Andrew Sawin, Jeffrey John Scheibel, Beth Ann Schubert, Alison Fiona Stephens, Robert John Strife, LUKE ANDREW ZANNONI.
Application Number | 20180010060 15/643955 |
Document ID | / |
Family ID | 59351156 |
Filed Date | 2018-01-11 |
United States Patent
Application |
20180010060 |
Kind Code |
A1 |
ZANNONI; LUKE ANDREW ; et
al. |
January 11, 2018 |
LUBRICATING MEMBERS FOR RAZOR CARTRIDGES COMPRISING A METATHESIZED
UNSATURATED POLYOL ESTER
Abstract
The invention relates to a lubricating member for a razor
cartridge comprising a lipid phase comprising a lipophilic
structurant and a liquid phase, wherein said liquid phase comprises
a metathesized unsaturated polyol ester which can be manufactured
in a simple one batch process without thermal degradation and
exhibiting improved lubricating and skin care properties over a
sustained period.
Inventors: |
ZANNONI; LUKE ANDREW; (West
Chester, OH) ; Schubert; Beth Ann; (Mainville,
OH) ; Panandiker; Rajan Keshav; (West Chester,
OH) ; Kemper; Joseph Jay; (Cincinnati, OH) ;
Strife; Robert John; (West Chester, OH) ; Motlagh;
Safa; (Dayton, OH) ; Scheibel; Jeffrey John;
(Glendale, OH) ; Stephens; Alison Fiona;
(Maidenhead, GB) ; Sawin; Philip Andrew;
(Cincinnati, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Gillette Company LLC |
Boston |
MA |
US |
|
|
Family ID: |
59351156 |
Appl. No.: |
15/643955 |
Filed: |
July 7, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62359785 |
Jul 8, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 111/04 20130101;
C10M 105/40 20130101; A61K 8/894 20130101; C10N 2030/06 20130101;
C10M 109/02 20130101; C10M 2207/281 20130101; A61Q 9/02 20130101;
C10M 2207/0203 20130101; C10M 2209/0806 20130101; A61K 8/342
20130101; A61K 8/86 20130101; A61K 8/922 20130101; A61K 8/37
20130101; A61K 8/737 20130101; C10N 2020/04 20130101; C11D 3/2093
20130101 |
International
Class: |
C10M 105/40 20060101
C10M105/40 |
Claims
1. A lubricating member comprising, a) a liquid phase comprising a
metathesized unsaturated polyol ester, said metathesized
unsaturated polyol ester having one or more of the following
properties: (i) a weight average molecular weight of from about
5,000 Daltons to about 50,000 Daltons; (ii) an oligomer index from
greater than 0 to 1; (iii) an iodine value of from about 30 to
about 200; b) a lipophilic structurant; and c) Optionally a water
soluble polymer.
2. A lubricating member according to claim 1, wherein said
metathesized unsaturated polyol ester having a weight average
molecular weight of from about 5,000 Daltons to about 50,000
Daltons.
3. A lubricating member according to claim 1, wherein said
metathesized unsaturated polyol ester has an iodine value of from
about 30 to about 200.
4. A lubricating member comprising, a) a liquid phase comprising a
metathesized unsaturated polyol ester, said metathesized
unsaturated polyol ester having a weight average molecular weight
of from about 2,000 Daltons to about 50,000 Daltons; and one or
more of the following properties: (i) a free hydrocarbon content,
based on total weight of metathesized unsaturated polyol ester of
from about 0% to about 5%; (ii) an oligomer index from greater than
0 to 1; (iii) an iodine value of from about 8 to about 200; b) a
lipohilic structurant; and c) optionally a water soluble
polymer
5. A lubricating member according to claim 4, wherein said
metathesized unsaturated polyol ester has an iodine value of from
about 10 to about 200.
6. A lubricating member according to claim 4, wherein said
metathesized unsaturated polyol ester has an oligomer index from
about 0.001 to 1.
7. A lubricating member according to claim 1, wherein said
metathesized unsaturated polyol ester has a free hydrocarbon
content, based on total weight of metathesized unsaturated polyol
ester, of from about 0% to about 5%.
8. A lubricating member according to claim 1, said composition
comprising, based on total composition weight, from about 0.1% to
about 50% of said metathesized unsaturated polyol ester.
9. A lubricating member according to claim 1, wherein the
metathesized unsaturated polyol ester is metathesized at least
once.
10. A lubricating member according to claim 1, wherein said
metathesized unsaturated polyol ester is derived from a natural
polyol ester and/or a synthetic polyol ester, preferably said
natural polyol ester is selected from the group consisting of a
vegetable oil, a animal fat, a algae oil and mixtures thereof; and
said synthetic polyol ester is derived from a material selected
from the group consisting of ethylene glycol, propylene glycol,
glycerol, polyglycerol, polyethylene glycol, polypropylene glycol,
poly(tetramethylene ether) glycol, pentaerythritol,
dipentaerythritol, tripentaerythritol, trimethylolpropane,
neopentyl glycol, a sugar, preferably, sucrose, and mixtures
thereof.
11. A lubricating member according to claim 1, wherein said
metathesized unsaturated polyol ester is selected from the group
consisting of metathesized Abyssinian oil, metathesized Almond Oil,
metathesized Apricot Oil, metathesized Apricot Kernel oil,
metathesized Argan oil, metathesized Avocado Oil, metathesized
Babassu Oil, metathesized Baobab Oil, metathesized Black Cumin Oil,
metathesized Black Currant Oil, metathesized Borage Oil,
metathesized Camelina oil, metathesized Carinata oil, metathesized
Canola oil, metathesized Castor oil, metathesized Cherry Kernel
Oil, metathesized Coconut oil, metathesized Corn oil, metathesized
Cottonseed oil, metathesized Echium Oil, metathesized Evening
Primrose Oil, metathesized Flax Seed Oil, metathesized Grape Seed
Oil, metathesized Grapefruit Seed Oil, metathesized Hazelnut Oil,
metathesized Hemp Seed Oil, metathesized Jatropha oil, metathesized
Jojoba Oil, metathesized Kukui Nut Oil, metathesized Linseed Oil,
metathesized Macadamia Nut Oil, metathesized Meadowfoam Seed Oil,
metathesized Moringa Oil, metathesized Neem Oil, metathesized Olive
Oil, metathesized Palm Oil, metathesized Palm Kernel Oil,
metathesized Peach Kernel Oil, metathesized Peanut Oil,
metathesized Pecan Oil, metathesized Pennycress oil, metathesized
Perilla Seed Oil, metathesized Pistachio Oil, metathesized
Pomegranate Seed Oil, metathesized Pongamia oil, metathesized
Pumpkin Seed Oil, metathesized Raspberry Oil, metathesized Red Palm
Olein, metathesized Rice Bran Oil, metathesized Rosehip Oil,
metathesized Safflower Oil, metathesized Seabuckthorn Fruit Oil,
metathesized Sesame Seed Oil, metathesized Shea Olein, metathesized
Sunflower Oil, metathesized Soybean Oil, metathesized Tonka Bean
Oil, metathesized Tung Oil, metathesized Walnut Oil, metathesized
Wheat Germ Oil, metathesized High Oleoyl Soybean Oil, metathesized
High Oleoyl Sunflower Oil, metathesized High Oleoyl Safflower Oil,
metathesized High Erucic Acid Rapeseed Oil, and mixtures
thereof.
12. A lubricating member for a razor cartridge according to claim 1
comprising: from 20% to 90%, preferably from 20% to 80% by weight
of a lipid phase comprising, a) from 10% to 70% by weight of the
lubricating member of a lipophilic structurant or mixture thereof,
b) from 10% to 70% by weight of the lubricating member of a liquid
phase, wherein said liquid phase has a melting point below
45.degree. C., and wherein said lubricating member further
optionally comprises from 1% to 40% by weight of a water soluble
polymer or mixture thereof.
13. A lubricating member according to claim 12, wherein said
lipophilic structurant has a melting point of from 45.degree. C. to
less than 60.degree. C.
14. A lubricating member according to claim 12, wherein said
lipophilic structurant has a melting point of from 45.degree. C. to
5.degree. C. less than the melting point of said water soluble
polymer.
15. A lubricating member according to claim 12, wherein said at
least 90% of said water soluble polymer is in the form of discrete
particulates dispersed within said lipophilic structurant.
16. A lubricating member according to claim 12, wherein said water
soluble polymer has a melting point of 60.degree. C. or
greater.
17. A lubricating member for a razor cartridge according to claim
1, wherein said liquid phase comprises a component selected from
natural oil, synthetic oil, natural butters, triglycerides,
petrolatum, silicones and mixtures thereof.
18. A lubricating member for a razor cartridge according to claim
1, wherein said liquid phase comprises a material selected from
capric and or caprylic triglycerides, olive oil, shea butter, cocoa
butter, isopropyl isostearate, petrolatum, dimethicone, phenylated
silicones, silicone polyether block polymer and mixtures
thereof.
19. A lubricating member for a razor cartridge according to claim
18, wherein said liquid phase comprises a silicone polyether block
copolymer or mixtures thereof.
20. A lubricating member for a razor cartridge according to claim
1, wherein said liquid phase has a melting point of less than
40.degree. C., more preferably less than 30.degree. C., most
preferably 25.degree. C. or less.
21. A lubricating member for a razor cartridge according to claim
1, wherein said lipophilic structurant is selected from C14-C20
alcohols, microcrystalline wax, stearyloxytrimethylsilane and
mixtures thereof, and is preferably selected from cetyl alcohol,
stearyl alcohol or mixtures thereof.
22. A lubricating member for a razor cartridge according to claim
1, wherein said water soluble polymer comprises a polyethylene
oxide polymer.
23. A lubricating member for a razor cartridge according to claim
1, comprising from 25% to 35% of said lipophilic structurant, from
10% to 40% of said liquid phase and from 20% to 30% of said water
soluble polymer.
24. A lubricating member for a razor cartridge according to any
claim 1, wherein said member comprises less than 5% by weight,
preferably less than 1% by weight, more preferably is substantially
free of a water insoluble polymeric structurant.
25. A hair removal cartridge comprising a lubricating member
according to claim 1.
26. A method of manufacturing a lubricating member according to
claim 1, comprising the steps of: i) providing a particulate of
said water soluble polymer, ii) melting said lipophilic
structurant, iii) adding said liquid phase and mixing, iv) adding
said water soluble polymer particles to said melted lipophilic
structurant and liquid phase mixture and mixing, v) adding optional
ingredients and mixing, vi) transferring the resultant mixture into
a mould or container, and vii) optionally cooling to 25.degree. C.
Description
FIELD OF THE INVENTION
[0001] The invention relates to for razor cartridges comprising a
metathesized unsaturated polyol ester, a lipophilic structurant and
optionally a water soluble polymer.
BACKGROUND OF THE INVENTION
[0002] The use of shaving aids in combination with razor blades to
provide lubrication benefits during the shave is known. See e.g.,
U.S. Pat. No. 7,121,754; U.S. Pat. No. 6,298,558; U.S. Pat. No.
5,711,076; U.S. Pat. No. 5,134,775; U.S. Pat. No. 6,301,785, U.S.
2009/0223057, U.S. 2006/0225285, WO2007/031793 and U.S. Pat. No.
5,431,906. Such shaving aids typically comprise a water-insoluble
matrix material to provide structural integrity and a water-soluble
polymer, such as polyethylene oxide (polyox), in order to provide
lubrication during the shave once the water-soluble polymer forms a
solution with the water present during shaving. Since the
introduction of polyox as a shaving lubricant, however little
development has been made in the field, even though polyethylene
oxide polymers are not without limitations. There is a desire to
extend the benefits provided by shaving aids beyond lubrication to
also provide skin benefits during and after the shaving process.
Typically this would be achieved through the addition of skin care
oils and enabling deposition of them during the shaving process.
For example U.S. Pat. No. 6,442,839 and U.S. 2007/0110703 describe
the use of low levels of mineral and essential oils, butters, waxes
and silicones. The use of mineral oil to enhance the glide
performance is described in U.S. 2008/0060201. However the art also
discloses that the presence of oils results in a reduction of the
swelling and solubility of the shaving aid contained in water
insoluble polymer matrix. The ability of the shaving aid to swell
in contact with water is however believed to be the key mechanism
by which the lubrication benefit is delivered to the skin. Hence
this is not desirable, as it will negatively impact the overall
performance. Thus oils are typically avoided in the matrix.
[0003] Another limitation of such shaving aids is related to the
manufacturing process which typically involves an injection molding
or extrusion process step. These processes require the materials to
be conveyed through the process at elevated temperatures and shear.
The addition of oils in particular causes barrel slip and conveying
inconsistencies which is undesirable. These process temperatures
can also result in undesirable degradation of the oils.
[0004] Consequently there is still a need to provide a solid
shaving aid for razor cartridges comprising a liquid phase
contained therein exhibiting lubricating and skin care properties
over a sustained period which can be readily manufactured without
impacting performance due to thermal degradation of the ingredients
and which can accommodate additional additives to provide desirable
skin care benefits, especially in the liquid form such as oils, and
optionally a water soluble polymer.
[0005] A wide variety of skin care oils are available commercially.
One such desirable oil is metathesised unsaturated polyol esters.
The Applicants recognized that the problems with commercially
available metathesized unsaturated polyol esters lay in the
rheology of such materials as such rheology resulted in a range of
spreading that was insufficient with a first class of materials and
excessive spreading with a second class of materials. Thus, both
classes of commercially available materials exhibited insufficient
spreading leading to poor lubrication and feel during the shaving
process. Versions of metathesized unsaturated polyol esters are
disclosed that have the correct rheology. Such species of
metathesized unsaturated polyol esters provide unexpectedly
improved skin conditioning benefits after the shave and lubrication
during the shave. Additionally these materials are tolerant to the
wide range of conditions experienced during the shave such as the
high pH from shaving gels and foams and provide synergistic
benefits in the presence of cationic polymeric materials.
SUMMARY OF THE INVENTION
[0006] One aspect of the invention relates to a lubricating member
comprising:
a) a liquid phase comprising a metathesized unsaturated polyol
ester, said metathesized unsaturated polyol ester having one or
more of the following properties: (i) a weight average molecular
weight of from about 5,000 Daltons to about 50,000 Daltons; (ii) an
oligomer index from greater than 0 to 1; (iii) an iodine value of
from about 30 to about 200; and b) a lipophilic structurant c)
Optionally a water soluble polymer.
[0007] Another aspect of the invention relates to a lubricating
member comprising:
a) a liquid phase comprising a metathesized unsaturated polyol
ester, said metathesized unsaturated polyol ester having a weight
average molecular weight of from about 2,000 Daltons to about
50,000 Daltons; and one or more of the following properties: [0008]
(i) a free hydrocarbon content, based on total weight of
metathesized unsaturated polyol ester of from about 0% to about 5%;
[0009] (ii) an oligomer index from greater than 0 to 1; [0010]
(iii) an iodine value of from about 8 to about 200; and b) a
lipohilic structurant c) Optionally a water soluble polymer
[0011] Another aspect of the invention relates to a lubricating
member for use on a hair removal device, comprising from 20% to
90%, preferably from 20% to 80% by weight of a lipid phase said
lipid phase comprising:
a) from 10% to 70%, preferably from 10% to 60% by weight of a
lipophilic structurant. b) from 10% to 70% by weight of a liquid
phase, contained within said lipophilic structurant wherein said
liquid phase comprises a methathesized unsaturated polyol ester and
herein said lubricating member optionally further comprises from 1%
to 40% by weight of a water soluble polymer or mixture thereof.
[0012] Another aspect of the invention relates to a method of
manufacturing a lubricating member comprising the steps of: [0013]
i) Providing a particulate of said water soluble polymer; [0014]
ii) Melting said lipophilic structurant; [0015] iii) Adding said
liquid phase and mixing; [0016] iv) Optionally adding said water
soluble polymer particles to said melted lipophilic structurant and
liquid phase mixture and mixing; [0017] v) Adding other optional
ingredients and mixing; [0018] vi) Transferring the resultant
mixture into a mould or container; [0019] vii) Optionally cooling
to 25.degree. C. Unless stated otherwise all % are given as weight
% of the lubricating member.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0020] The terms "natural oils," "natural feedstocks," or "natural
oil feedstocks" may refer to oils derived from plants or animal
sources. The term "natural oil" includes natural oil derivatives,
unless otherwise indicated. The terms also include modified plant
or animal sources (e.g., genetically modified plant or animal
sources), unless indicated otherwise. Examples of natural oils
include, but are not limited to, vegetable oils, algae oils, fish
oils, animal fats, tall oils, derivatives of these oils,
combinations of any of these oils, and the like. Representative
non-limiting examples of vegetable oils include canola oil,
rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil,
palm oil, peanut oil, safflower oil, sesame oil, soybean oil,
sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha
oil, mustard oil, pennycress oil, camelina oil, and castor oil.
Representative non-limiting examples of animal fats include lard,
tallow, poultry fat, yellow grease, and fish oil. Tall oils are
by-products of wood pulp manufacture.
[0021] The term "natural oil derivatives" refers to derivatives
thereof derived from natural oil. The methods used to form these
natural oil derivatives may include one or more of addition,
neutralization, overbasing, saponification, transesterification,
esterification, amidification, hydrogenation, isomerization,
oxidation, alkylation, acylation, sulfurization, sulfonation,
rearrangement, reduction, fermentation, pyrolysis, hydrolysis,
liquefaction, anaerobic digestion, hydrothermal processing,
gasification or a combination of two or more thereof. Examples of
natural derivatives thereof may include carboxylic acids, gums,
phospholipids, soapstock, acidulated soapstock, distillate or
distillate sludge, fatty acids, fatty acid esters, as well as
hydroxy substituted variations thereof, including unsaturated
polyol esters. In some embodiments, the natural oil derivative may
comprise an unsaturated carboxylic acid having from about 5 to
about 30 carbon atoms, having one or more carbon-carbon double
bonds in the hydrocarbon (alkene) chain. The natural oil derivative
may also comprise an unsaturated fatty acid alkyl (e.g., methyl)
ester derived from a glyceride of natural oil. For example, the
natural oil derivative may be a fatty acid methyl ester ("FAME")
derived from the glyceride of the natural oil. In some embodiments,
a feedstock includes canola or soybean oil, as a non-limiting
example, refined, bleached, and deodorized soybean oil (i.e., RBD
soybean oil).
[0022] The term "free hydrocarbon" refers to any one or combination
of unsaturated or saturated straight, branched, or cyclic
hydrocarbons in the C.sub.2 to C.sub.22 range.
[0023] The term "metathesis monomer" refers to a single entity that
is the product of a metathesis reaction which comprises a molecule
of a compound with one or more carbon-carbon double bonds which has
undergone an alkylidene unit interchange via one or more of the
carbon-carbon double bonds either within the same molecule
(intramolecular metathesis) and/or with a molecule of another
compound containing one or more carbon-carbon double bonds such as
an olefin (intermolecular metathesis).
[0024] The term "metathesis dimer" refers to the product of a
metathesis reaction wherein two reactant compounds, which can be
the same or different and each with one or more carbon-carbon
double bonds, are bonded together via one or more of the
carbon-carbon double bonds in each of the reactant compounds as a
result of the metathesis reaction.
[0025] The term "metathesis trimer" refers to the product of one or
more metathesis reactions wherein three molecules of two or more
reactant compounds, which can be the same or different and each
with one or more carbon-carbon double bonds, are bonded together
via one or more of the carbon-carbon double bonds in each of the
reactant compounds as a result of the one or more metathesis
reactions, the trimer containing three bonded groups derived from
the reactant compounds.
[0026] The term "metathesis tetramer" refers to the product of one
or more metathesis reactions wherein four molecules of two or more
reactant compounds, which can be the same or different and each
with one or more carbon-carbon double bonds, are bonded together
via one or more of the carbon-carbon double bonds in each of the
reactant compounds as a result of the one or more metathesis
reactions, the tetramer containing four bonded groups derived from
the reactant compounds.
[0027] The term "metathesis pentamer" refers to the product of one
or more metathesis reactions wherein five molecules of two or more
reactant compounds, which can be the same or different and each
with one or more carbon-carbon double bonds, are bonded together
via one or more of the carbon-carbon double bonds in each of the
reactant compounds as a result of the one or more metathesis
reactions, the pentamer containing five bonded groups derived from
the reactant compounds.
[0028] The term "metathesis hexamer" refers to the product of one
or more metathesis reactions wherein six molecules of two or more
reactant compounds, which can be the same or different and each
with one or more carbon-carbon double bonds, are bonded together
via one or more of the carbon-carbon double bonds in each of the
reactant compounds as a result of the one or more metathesis
reactions, the hexamer containing six bonded groups derived from
the reactant compounds.
[0029] The term "metathesis heptamer" refers to the product of one
or more metathesis reactions wherein seven molecules of two or more
reactant compounds, which can be the same or different and each
with one or more carbon-carbon double bonds, are bonded together
via one or more of the carbon-carbon double bonds in each of the
reactant compounds as a result of the one or more metathesis
reactions, the heptamer containing seven bonded groups derived from
the reactant compounds.
[0030] The term "metathesis octamer" refers to the product of one
or more metathesis reactions wherein eight molecules of two or more
reactant compounds, which can be the same or different and each
with one or more carbon-carbon double bonds, are bonded together
via one or more of the carbon-carbon double bonds in each of the
reactant compounds as a result of the one or more metathesis
reactions, the octamer containing eight bonded groups derived from
the reactant compounds.
[0031] The term "metathesis nonamer" refers to the product of one
or more metathesis reactions wherein nine molecules of two or more
reactant compounds, which can be the same or different and each
with one or more carbon-carbon double bonds, are bonded together
via one or more of the carbon-carbon double bonds in each of the
reactant compounds as a result of the one or more metathesis
reactions, the nonamer containing nine bonded groups derived from
the reactant compounds.
[0032] The term "metathesis decamer" refers to the product of one
or more metathesis reactions wherein ten molecules of two or more
reactant compounds, which can be the same or different and each
with one or more carbon-carbon double bonds, are bonded together
via one or more of the carbon-carbon double bonds in each of the
reactant compounds as a result of the one or more metathesis
reactions, the decamer containing ten bonded groups derived from
the reactant compounds.
[0033] The term "metathesis oligomer" refers to the product of one
or more metathesis reactions wherein two or more molecules (e.g., 2
to about 10, or 2 to about 4) of two or more reactant compounds,
which can be the same or different and each with one or more
carbon-carbon double bonds, are bonded together via one or more of
the carbon-carbon double bonds in each of the reactant compounds as
a result of the one or more metathesis reactions, the oligomer
containing a few (e.g., 2 to about 10, or 2 to about 4) bonded
groups derived from the reactant compounds. In some embodiments,
the term "metathesis oligomer" may include metathesis reactions
wherein greater than ten molecules of two or more reactant
compounds, which can be the same or different and each with one or
more carbon-carbon double bonds, are bonded together via one or
more of the carbon-carbon double bonds in each of the reactant
compounds as a result of the one or more metathesis reactions, the
oligomer containing greater than ten bonded groups derived from the
reactant compounds.
[0034] As used herein, the terms "metathesize" and "metathesizing"
may refer to the reacting of a unsaturated polyol ester feedstock
in the presence of a metathesis catalyst to form a metathesized
unsaturated polyol ester product comprising a new olefinic compound
and/or esters. Metathesizing may refer to cross-metathesis (a.k.a.
co-metathesis), self-metathesis, ring-opening metathesis,
ring-opening metathesis polymerizations ("ROMP"), ring-closing
metathesis ("RCM"), and acyclic diene metathesis ("ADMET"). As a
non-limiting example, metathesizing may refer to reacting two
triglycerides present in a natural feedstock (self-metathesis) in
the presence of a metathesis catalyst, wherein each triglyceride
has an unsaturated carbon-carbon double bond, thereby forming an
oligomer having a new mixture of olefins and esters that may
comprise one or more of: metathesis monomers, metathesis dimers,
metathesis trimers, metathesis tetramers, metathesis pentamers, and
higher order metathesis oligomers (e.g., metathesis hexamers,
metathesis, metathesis heptamers, metathesis octamers, metathesis
nonamers, metathesis decamers, and higher than metathesis decamers
and above).
[0035] As used herein, the term "polyol" means an organic material
comprising at least two hydroxy moieties.
[0036] As used herein, the articles including "a" and "an" when
used in a claim, are understood to mean one or more of what is
claimed or described.
[0037] As used herein, the terms "include", "includes" and
"including" are meant to be non-limiting.
[0038] Unless otherwise noted, all component or composition levels
are in reference to the active portion of that component or
composition, and are exclusive of impurities, for example, residual
solvents or by-products, which may be present in commercially
available sources of such components or compositions.
[0039] All percentages and ratios are calculated by weight unless
otherwise indicated. All percentages and ratios are calculated
based on the total composition unless otherwise indicated.
[0040] It should be understood that every maximum numerical
limitation given throughout this specification includes every lower
numerical limitation, as if such lower numerical limitations were
expressly written herein. Every minimum numerical limitation given
throughout this specification will include every higher numerical
limitation, as if such higher numerical limitations were expressly
written herein. Every numerical range given throughout this
specification will include every narrower numerical range that
falls within such broader numerical range, as if such narrower
numerical ranges were all expressly written herein.
Compositions, Articles and Methods of Use
TABLE-US-00001 [0041] TABLE 1 Compositions Comp. No. Composition 1
A composition comprising, a) a metathesized unsaturated polyol
ester, said metathesized unsaturated polyol ester having one or
more of the following properties: (i) a weight average molecular
weight of from about 5,000 Daltons to about 50,000 Daltons, from
about 5,500 Daltons to about 50,000 Daltons, from about 5,500
Daltons to about 40,000 Daltons, or from about 6,000 Daltons to
about 30,000 Daltons; (ii) an oligomer index from greater than 0 to
1, from 0.001 to 1, 0.01 to 1, or from 0.05 to 1; (iii) an iodine
value of from about 30 to about 200, from about 30 to about 150,
from about 30 to about 120, or from about 50 to about 110. 2 In one
aspect of said composition 1 of Table 1, said metathesized
unsaturated polyol ester has the weight average molecular weight
property from a)(i) above. 3 In one aspect of said composition 1 of
Table 1, said metathesized unsaturated polyol ester has the
oligomer index property from a)(ii) above. 4 In one aspect of said
composition 1 of Table 1, said metathesized unsaturated polyol
ester has the iodine value property from a)(iii) above. 5 In one
aspect of said composition 1 of Table 1, said metathesized
unsaturated polyol ester has the property from a)(i) and from
a)(ii) above. 6 In one aspect of said composition 1 of Table 1,
said metathesized unsaturated polyol ester has the properties from
a)(i) and from a)(iii) above. 7 In one aspect of said composition 1
of Table 1, said metathesized unsaturated polyol ester has the
properties from a)(ii) and from a)(iii) above. 8 In one aspect of
said composition 1 of Table 1, said metathesized unsaturated polyol
ester has the properties from a)(i), a)(ii) and from a)(iii) above.
9 In one aspect, of compositions 1, 2, 3, 4, 5, 6, 7, and 8 of
Table 1, said metathesized unsaturated polyol ester has a free
hydrocarbon content, based on total weight of metathesized
unsaturated polyol ester, of from about 0% to about 5%, from about
0.1% to about 5%, from about 0.1% to about 4%, or from about 0.1 to
about 3%. 10 In one aspect of Table 1 Compositions 1, 2, 3, 4, 5,
6, 7, 8, and 9 the metathesized unsaturated polyol ester is
metathesized at least once. 11 In one aspect, of compositions 1, 2,
3, 4, 5, 6, 7, 8, 9 and 10 of Table 1, said composition comprises,
based on total composition weight, from about 0.1% to about 50%,
from about 0.5% to about 30%, or from about 1% to about 20% of said
metathesized unsaturated polyol ester.
TABLE-US-00002 TABLE 2 Compositions Comp. No. Composition 1 A
composition comprising: a) a metathesized unsaturated polyol ester,
said metathesized unsaturated polyol ester having a weight average
molecular weight of from about 2,000 Daltons to about 50,000
Daltons, from about 2,500 Daltons to about 50,000 Daltons, from
about 3,000 Daltons to about 40,000 Daltons, from about 3,000
Daltons to about 30,000 Daltons; and one or more of the following
properties: (i) a free hydrocarbon content, based on total weight
of metathesized unsaturated polyol ester, of from about 0% to about
5%, from about 0.1% to about 5%, from about 0.1% to about 4%, or
from about 0.1 to about 3%; (ii) an oligomer index from greater
than 0 to 1, from 0.001 to 1, 0.01 to 1, or from 0.05 to 1; (iii)
an iodine value of from about 8 to about 200, from about 10 to
about 200, from about 20 to about 150, from about 30 to about 120.
2 In one aspect of said composition 1 of Table 2, said metathesized
unsaturated polyol ester has the free hydrocarbon content property
from a)(i) above. 3 In one aspect of said composition 1 of Table 2,
said metathesized unsaturated polyol ester has the oligomer index
property from a)(ii) above. 4 In one aspect of said composition 1
of Table 2, said metathesized unsaturated polyol ester has the
iodine value property from a)(iii) above. 5 In one aspect of said
composition 1 of Table 2, said metathesized unsaturated polyol
ester has the property from a)(i) and from a)(ii) above. 6 In one
aspect of said composition 1 of Table 2, said metathesized
unsaturated polyol ester has the properties from a)(i) and from
a)(iii) above. 7 In one aspect of said composition 1 of Table 2,
said metathesized unsaturated polyol ester has the properties from
a)(ii) and from a)(iii) above. 8 In one aspect of said composition
1 of Table 2, said metathesized unsaturated polyol ester has the
properties from a)(i), a)(ii) and from a)(iii) above. 9 In one
aspect of Table 2 Compositions 1, 2, 3, 4, 5, 6, 7, and 8 the
metathesized unsaturated polyol ester is metathesized at least
once. 10 In one aspect, of compositions 1, 2, 3, 4, 5, 6, 7, and 9
of Table 2, said composition comprises, based on total composition
weight, from about 0.1% to about 50%, from about 0.5% to about 30%
or from about 1% to about 20% of said metathesized unsaturated
polyol ester.
[0042] In one aspect, Table 1 Compositions 1, 2, 3, 4, 5, 6, 7, 8,
9, 10 and 11; and Table 2 Compositions 1, 2, 3, 4, 5, 6, 7, 8, 9
and 10 the metathesized unsaturated polyol ester is derived from a
natural polyol ester and/or a synthetic polyol ester, in one
aspect, said natural polyol ester is selected from the group
consisting of a vegetable oil, an animal fat, an algae oil and
mixtures thereof; and said synthetic polyol ester is derived from a
material selected from the group consisting of ethylene glycol,
propylene glycol, glycerol, polyglycerol, polyethylene glycol,
polypropylene glycol, poly(tetramethylene ether) glycol,
pentaerythritol, dipentaerythritol, tripentaerythritol,
trimethylolpropane, neopentyl glycol, a sugar, in one aspect,
sucrose, and mixtures thereof.
[0043] In one aspect, Table 1 Compositions 1, 2, 3, 4, 5, 6, 7, 8,
9, 10 and 11; and Table 2 Compositions 1, 2, 3, 4, 5, 6, 7, 8, 9
and 10 the metathesized unsaturated polyol ester is selected from
the group consisting of metathesized Abyssinian oil, metathesized
Almond Oil, metathesized Apricot Oil, metathesized Apricot Kernel
oil, metathesized Argan oil, metathesized Avocado Oil, metathesized
Babassu Oil, metathesized Baobab Oil, metathesized Black Cumin Oil,
metathesized Black Currant Oil, metathesized Borage Oil,
metathesized Camelina oil, metathesized Carinata oil, metathesized
Canola oil, metathesized Castor oil, metathesized Cherry Kernel
Oil, metathesized Coconut oil, metathesized Corn oil, metathesized
Cottonseed oil, metathesized Echium Oil, metathesized Evening
Primrose Oil, metathesized Flax Seed Oil, metathesized Grape Seed
Oil, metathesized Grapefruit Seed Oil, metathesized Hazelnut Oil,
metathesized Hemp Seed Oil, metathesized Jatropha oil, metathesized
Jojoba Oil, metathesized Kukui Nut Oil, metathesized Linseed Oil,
metathesized Macadamia Nut Oil, metathesized Meadowfoam Seed Oil,
metathesized Moringa Oil, metathesized Neem Oil, metathesized Olive
Oil, metathesized Palm Oil, metathesized Palm Kernel Oil,
metathesized Peach Kernel Oil, metathesized Peanut Oil,
metathesized Pecan Oil, metathesized Pennycress oil, metathesized
Perilla Seed Oil, metathesized Pistachio Oil, metathesized
Pomegranate Seed Oil, metathesized Pongamia oil, metathesized
Pumpkin Seed Oil, metathesized Raspberry Oil, metathesized Red Palm
Olein, metathesized Rice Bran Oil, metathesized Rosehip Oil,
metathesized Safflower Oil, metathesized Seabuckthorn Fruit Oil,
metathesized Sesame Seed Oil, metathesized Shea Olein, metathesized
Sunflower Oil, metathesized Soybean Oil, metathesized Tonka Bean
Oil, metathesized Tung Oil, metathesized Walnut Oil, metathesized
Wheat Germ Oil, metathesized High Oleoyl Soybean Oil, metathesized
High Oleoyl Sunflower Oil, metathesized High Oleoyl Safflower Oil,
metathesized High Erucic Acid Rapeseed Oil, and mixtures
thereof.
Methods of Making Compositions
[0044] The compositions of the present invention can be formulated
into any suitable form and prepared by any process chosen by the
formulator, non-limiting examples of which are described in U.S.
Pat. No. 5,879,584 which is incorporated herein by reference. For
example, the metathesized unsaturated polyol esters can be combined
directly with the composition's other ingredients without
pre-emulsification and/or pre-mixing to form the finished products.
Alternatively, the metathesized unsaturated polyol esters can be
combined with surfactants or emulsifiers, solvents, suitable
adjuncts, and/or any other suitable ingredients to prepare
emulsions prior to compounding the finished products.
[0045] Suitable equipment for use in the processes disclosed herein
may include continuous stirred tank reactors, homogenizers, turbine
agitators, recirculating pumps, paddle mixers, plough shear mixers,
ribbon blenders, vertical axis granulators and drum mixers, both in
batch and, where available, in continuous process configurations,
spray dryers, and extruders. Such equipment can be obtained from
Lodige GmbH (Paderborn, Germany), Littleford Day, Inc. (Florence,
Ky., U.S.A.), Forberg AS (Larvik, Norway), Glatt Ingenieurtechnik
GmbH (Weimar, Germany), Niro (Soeborg, Denmark), Hosokawa Bepex
Corp. (Minneapolis, Minn., U.S.A.), Arde Barinco (New Jersey,
U.S.A.).
Lipid Phase
[0046] According to the invention the lubricating member is a solid
lubricating member at 25.degree. C. and may comprise from about 20%
to about 90% by weight, preferably from about 20% to about 80% by
weight of a lipid phase. The lipid phase comprises a lipophilic
structurant and a liquid phase contained within the lipophilic
structurant. The lipid phase comprises from about 10% to about 70%,
preferably from about 10% to 60%, more preferably from about 20% to
about 40%, even more preferably from about 25% to about 35% by
weight of the lubricating member of a lipophilic structurant.
[0047] The melting point of the lipophilic structurant is
preferably greater than 45.degree. C. to less than 60.degree. C.
and is thus preferably a solid at 25.degree. C. The melting point
is determined according to ASTM D5440-93. If the lipophilic
structurant comprises more than one material, the melting point is
determined for the resultant mixture as described hereinafter. In
one embodiment the lipophilic structurant has a melting point of
from about 45.degree. C. to about 5.degree. C. less than the
melting point of said water soluble polymer. The lipophilic
structurant is preferably water insoluble. It has been surprisingly
found that by providing a lipohilic structurant having a melting
point below 60.degree. C. enables both the ready addition of liquid
phase components and also water soluble polymers, which are
immiscible therein without melting of the water soluble polymer
during manufacture. The later thereby avoids thermal degradation
and thereby the lipophilic structurant provides a solid chassis at
room temperature (25.degree. C.) to contain the ingredient
components which also deliver lubrication to the skin and other
benefit agents during the shaving process. Moreover, the lipophilic
structurant also enhances skin feel benefits.
[0048] Suitable lipophilic structurants for use herein include C14
or greater, preferably C14 to C20, more preferably C16 to C18 chain
length fatty acyls such as fatty acids, fatty alcohols and esters,
triglycerides, waxes and mixtures thereof. Particularly preferred
are C14-C20 alcohols, in particular cetyl and stearyl alcohols and
mixtures thereof.
[0049] Suitable lipophilic structurants also include natural,
synthetic and silicone waxes. As used herein, the term "wax"
includes, but is not limited to, any material that is solid at
45.degree. C., preferably at 25.degree. C.; and are very slightly
soluble in water, preferably practically insoluble in water
according to the United States' Pharmacopeia (USP) definition in
31/NF 26 Vol. 2 General Notices, Page Xvii. According to that
definition, this means that 1000 to 10000 parts of water are needed
to dissolve 1 part solute and that more than 10,000 parts of water
are needed to dissolve 1 part solute respectively.
[0050] The lipophilic structurant and or lubricating member
preferably comprises less than 5%, preferably less than 1% by
weight and more preferably is substantially free of lathering soap
(i.e. salts of fatty acids such as C4-30 carboxylic acids) or
lathering surfactant. A lathering surfactant is defined as a
surfactant which when combined with water and mechanically agitated
generate a foam or later. Lathering surfactants include anionic and
amphoteric lathering surfactants and mixtures thereof. Anionic
lathering surfactants include sarcosinates, sulfates, sulfonate,
isethionate, taurates, phosphates, lactylates, glutamates, alkali
metal salts of fatty acids (i.e. soaps) having from 8 to 24
carbons, and mixtures thereof.
[0051] The wax may comprise natural wax, synthetic wax or mixtures
thereof. Natural waxes may be plant, animal or mineral derived.
Non-limiting examples of suitable natural waxes include Beeswax,
Copernicia Cerifera (Carnauba) Wax, Euphorbia Cerifera (Candelilla)
Wax, Jojoba Wax, Oryza Sativa (Rice) Bran Wax, Lemon peel wax,
Soybean wax, Sunflower wax and mixtures thereof.
[0052] Non-limiting examples of suitable synthetic waxes include
Hydrogenated Jojoba Wax, synthetic and siliconyl jojoba wax,
Hydrogenated Microcrystalline Wax, Microcrystalline Wax, synthetic,
siliconyl and Hydrogenated Rice Bran Wax, Ceresin, Ozokerite,
Paraffin, benhenyl beeswax, synthetic, siliconyl and hydrogenated
Beeswax, synthetic, hydrogenated and siliconyl Candelilla Wax,
synthetic, hydrogenated and siliconyl Carnauba, wax, synthetic,
hydrogenated and siliconyl lemon peel wax, synthetic, siliconyl and
hydrogenated soybean wax, synthetic, siliconyl and hydrogenated
sunflower wax and mixtures thereof. Preferred natural and synthetic
waxes are Beeswax, Microcrystalline wax, Candellila wax, Ozokerite,
and mixtures thereof.
[0053] Non-limiting examples of suitable silicone waxes include
Stearyoxy trimethylsilane such as DC580 wax, C30-45 alkyl methicone
available as DC AMS-C30 Cosmetic Wax, stearyoxymethyl silane
available as DC Silkywax 10, C24-54 alkyl methicone such as DC
ST-Wax 30, C30-45 Alkyldimethylsilyl, Polypropyl-silsesquioxane,
available as DC SW-8005 resin wax, and mixtures thereof.
[0054] Particularly preferred lipophilic structurants may be
selected from cetyl alcohol, stearyl alcohol, microcrystalline wax,
stearyloxy trimethylsilane and mixtures thereof.
Liquid Phase
[0055] The lubricating member may further comprise from about 10%
to about 70%, preferably from about 10% to about 60%, more
preferably from about 10% to about 40%, by weight of the
lubricating member of a liquid phase. In one embodiment the liquid
phase comprises a hydrophobic material or mixtures thereof. The
liquid phase may provide a number of in use benefits such as
lubrication, skin feel and cooling sensation. The liquid phase is
contained within the solid lubricating member by the lipophilic
structurant.
[0056] In one embodiment the liquid phase has a melting point of
45.degree. C. or less, preferably 40.degree. C. or less, even more
preferably 30.degree. C. or less, most preferably 25.degree. C. or
less. The melting point is determined according to ASTM D5440-93.
Preferably the liquid phase and the hydrophobic material is liquid
at 25.degree. C. The use of a liquid phase enables the materials to
be readily added to the lipophilic structurant upon melting
thereof. In another preferred embodiment the liquid phase
hydrophobic material or mixtures thereof may be very slightly
soluble and have a melting point of 45.degree. C. or less as
defined herein above and be miscible with one another. In another
embodiment the melting point of the mixture of liquid phase and the
lipophilic structurant is preferably from 45.degree. C. to
5.degree. C. less than the melting point of the water soluble
polymer.
[0057] The liquid phase comprises a metathesized unsaturated polyol
ester.
Metathesized Unsaturated Polyol Ester
[0058] Exemplary metathesized unsaturated polyol esters and their
starting materials are set forth in U.S. Patent Applications U.S.
2009/0220443 A1, U.S. 2013/0344012 A1 and US 2014/0357714 A1, which
are incorporated herein by reference. A metathesized unsaturated
polyol ester refers to the product obtained when one or more
unsaturated polyol ester ingredient(s) are subjected to a
metathesis reaction. 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.
Metathesis may occur between two of the same molecules (often
referred to as self-metathesis) and/or it may occur between two
different molecules (often referred to as cross-metathesis).
Self-metathesis may be represented schematically as shown in
Equation I.
R.sup.1--CH.dbd.CH--R.sup.2+R.sup.1--CH.dbd.CH--R.sup.2R.sup.1--CH.dbd.C-
H--R.sup.1+R.sup.2--CH.dbd.CH--R.sup.2 (I)
[0059] where R.sup.1 and R.sup.2 are organic groups.
[0060] Cross-metathesis may be represented schematically as shown
in Equation II.
R.sup.1--CH.dbd.CH--R.sup.2+R.sup.3--CH.dbd.CH--R.sup.4R.sup.1--CH.dbd.C-
H--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+20R.sup.3--CH.dbd.CH--R.sup.3+R.sup.4--CH.dbd.CH--R.sup.4
(II)
[0061] where R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are organic
groups.
[0062] When a polyol ester comprises molecules having more than one
carbon-carbon double bond, self-metathesis may result in
oligomerization or polymerization of the unsaturates in the
starting material. For example, Equation C depicts metathesis
oligomerization of a representative species (e.g., a polyol ester)
having more than one carbon-carbon double bond. In Equation C, the
self-metathesis reaction results in the formation of metathesis
dimers, metathesis trimers, and metathesis tetramers. Although not
shown, higher order oligomers such as metathesis pentamers,
hexamers, heptamers, octamers, nonamers, decamers, and higher than
decamers, and mixtures of two or more thereof, may also be formed.
The number of metathesis repeating units or groups in the
metathesized natural oil may range from 1 to about 100, or from 2
to about 50, or from 2 to about 30, or from 2 to about 10, or from
2 to about 4. The molecular weight of the metathesis dimer may be
greater than the molecular weight of the unsaturated polyol ester
from which the dimer is formed. Each of the bonded polyol ester
molecules may be referred to as a "repeating unit or group."
Typically, a metathesis trimer may be formed by the
cross-metathesis of a metathesis dimer with an unsaturated polyol
ester. Typically, a metathesis tetramer may be formed by the
cross-metathesis of a metathesis trimer with an unsaturated polyol
ester or formed by the cross-metathesis of two metathesis
dimers.
R.sup.1--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.3+R.sup.1--HC.dbd.CH--R.su-
p.2--HC.dbd.CH--R.sup.3R.sup.1--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.2--HC-
.dbd.--R.sup.3+(other products) (metathesis dimer)
R.sup.1--R.sup.2--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.3+R.sup.1--HC.dbd-
.CH--R.sup.2--HC.dbd.CH--R.sup.3R.sup.1--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.-
sup.2--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.3+(other product %)
(metathesis trimer)
R.sup.1--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.2--HC.-
dbd.CH--R.sup.3+R.sup.1--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.3R.sup.1--HC-
.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup.2--HC.dbd.CH--R.sup-
.2--HC.dbd.CH--R.sup.3+(other products) (metathesis tetramer)
Equation C
[0063] where R.sup.1, R.sup.2, and R.sup.3 are organic groups.
[0064] As a starting material, metathesized unsaturated polyol
esters are prepared from one or more unsaturated polyol esters. As
used herein, the term "unsaturated polyol ester" refers to a
compound having two or more hydroxyl groups wherein at least one of
the hydroxyl groups is in the form of an ester and wherein the
ester has an organic group including at least one carbon-carbon
double bond. In many embodiments, the unsaturated polyol ester can
be represented by the general structure (I):
##STR00001##
[0065] where n.gtoreq.1;
[0066] m.gtoreq.0;
[0067] p.gtoreq.0;
[0068] (n+m+p).gtoreq.2;
[0069] R is an organic group;
[0070] R' is an organic group having at least one carbon-carbon
double bond; and
[0071] R'' is a saturated organic group.
[0072] In many embodiments of the invention, the unsaturated polyol
ester is an unsaturated polyol ester of glycerol. Unsaturated
polyol esters of glycerol have the general structure (II):
##STR00002##
[0073] where --X, --Y, and --Z are independently selected from the
group consisting of:
--OH;--(O--C(.dbd.O)--R'); and --(O--C(.dbd.O)--R'');
[0074] where --R' is an organic group having at least one
carbon-carbon double bond and --R'' is a saturated organic
group.
[0075] In structure (II), at least one of --X, --Y, and --Z is
--(O--C(.dbd.O)--R').
[0076] In some embodiments, R' is a straight or branched chain
hydrocarbon having about 50 or less carbon atoms (e.g., about 36 or
less carbon atoms or about 26 or less carbon atoms) and at least
one carbon-carbon double bond in its chain. In some embodiments, R'
is a straight or branched chain hydrocarbon having about 6 carbon
atoms or greater (e.g., about 10 carbon atoms or greater or about
12 carbon atoms or greater) and at least one carbon-carbon double
bond in its chain. In some embodiments, R' may have two or more
carbon-carbon double bonds in its chain. In other embodiments, R'
may have three or more double bonds in its chain. In exemplary
embodiments, R' has 17 carbon atoms and 1 to 3 carbon-carbon double
bonds in its chain. Representative examples of R' include:
--(CH.sub.2).sub.7CH.dbd.CH--(CH.sub.2).sub.7--CH.sub.3;
--(CH.sub.1).sub.7CH.dbd.CH--CH.sub.2--CH.dbd.CH--(CH.sub.2).sub.4--CH.s-
ub.3; and
--(CH.sub.2).sub.7CH.dbd.CH--CH.sub.2--CH.dbd.CH--CH.sub.2--CH.dbd.CH--C-
H.sub.2--CH.sub.3.
[0077] In some embodiments, R'' is a saturated straight or branched
chain hydrocarbon having about 50 or less carbon atoms (e.g., about
36 or less carbon atoms or about 26 or less carbon atoms). In some
embodiments, R'' is a saturated straight or branched chain
hydrocarbon having about 6 carbon atoms or greater (e.g., about 10
carbon atoms or greater or about 12 carbon atoms or greater. In
exemplary embodiments, R'' has 15 carbon atoms or 17 carbon
atoms.
[0078] Sources of unsaturated polyol esters of glycerol include
synthesized oils, natural oils (e.g., vegetable oils, algae oils,
bacterial derived oils, and animal fats), combinations of these,
and the like. Recycled used vegetable oils may also be used.
Representative non-limiting examples of vegetable oils include
Abyssinian oil, Almond Oil, Apricot Oil, Apricot Kernel oil, Argan
oil, Avocado Oil, Babassu Oil, Baobab Oil, Black Cumin Oil, Black
Currant Oil, Borage Oil, Camelina oil, Carinata oil, Canola oil,
Castor oil, Cherry Kernel Oil, Coconut oil, Corn oil, Cottonseed
oil, Echium Oil, Evening Primrose Oil, Flax Seed Oil, Grape Seed
Oil, Grapefruit Seed Oil, Hazelnut Oil, Hemp Seed Oil, Jatropha
oil, Jojoba Oil, Kukui Nut Oil, Linseed Oil, Macadamia Nut Oil,
Meadowfoam Seed Oil, Moringa Oil, Neem Oil, Olive Oil, Palm Oil,
Palm Kernel Oil, Peach Kernel Oil, Peanut Oil, Pecan Oil,
Pennycress oil, Perilla Seed Oil, Pistachio Oil, Pomegranate Seed
Oil, Pongamia oil, Pumpkin Seed Oil, Raspberry Oil, Red Palm Olein,
Rice Bran Oil, Rosehip Oil, Safflower Oil, Seabuckthorn Fruit Oil,
Sesame Seed Oil, Shea Olein, Sunflower Oil, Soybean Oil, Tonka Bean
Oil, Tung Oil, Walnut Oil, Wheat Germ Oil, High Oleoyl Soybean Oil,
High Oleoyl Sunflower Oil, High Oleoyl Safflower Oil, High Erucic
Acid Rapeseed Oil, combinations of these, and the like.
Representative non-limiting examples of animal fats include lard,
tallow, chicken fat, yellow grease, fish oil, emu oil, combinations
of these, and the like. A representative non-limiting example of a
synthesized oil includes tall oil, which is a byproduct of wood
pulp manufacture. In some embodiments, the natural oil is refined,
bleached, and/or deodorized.
[0079] Other examples of unsaturated polyol esters include esters
such as those derived from ethylene glycol or propylene glycol,
polyethylene glycol, polypropylene glycol, or poly(tetramethylene
ether) glycol, esters such as those derived from pentaerythritol,
dipentaerythritol, tripentaerythritol, trimethylolpropane, or
neopentyl glycol, or sugar esters such as SEFOSE.RTM.. Sugar esters
such as SEFOSE.RTM. include one or more types of sucrose
polyesters, with up to eight ester groups that could undergo a
metathesis exchange reaction. Sucrose polyesters are derived from a
natural resource and therefore, the use of sucrose polyesters can
result in a positive environmental impact. Sucrose polyesters are
polyester materials, having multiple substitution positions around
the sucrose backbone coupled with the chain length, saturation, and
derivation variables of the fatty chains. Such sucrose polyesters
can have an esterification ("IBAR") of greater than about 5. In one
embodiment the sucrose polyester may have an IBAR of from about 5
to about 8. In another embodiment the sucrose polyester has an IBAR
of about 5-7, and in another embodiment the sucrose polyester has
an IBAR of about 6. In yet another embodiment the sucrose polyester
has an IBAR of about 8. As sucrose polyesters are derived from a
natural resource, a distribution in the IBAR and chain length may
exist. For example a sucrose polyester having an IBAR of 6, may
contain a mixture of mostly IBAR of about 6, with some IBAR of
about 5 and some IBAR of about 7. Additionally, such sucrose
polyesters may have a saturation or iodine value ("IV") of about 3
to about 140. In another embodiment the sucrose polyester may have
an IV of about 10 to about 120. In yet another embodiment the
sucrose polyester may have an IV of about 20 to 100. Further, such
sucrose polyesters have a chain length of about C.sub.12 to
C.sub.20 but are not limited to these chain lengths.
[0080] Non-limiting examples of sucrose polyesters suitable for use
include SEFOSE.RTM. 1618S, SEFOSE.RTM. 1618U, SEFOSE.RTM. 1618H,
Sefa Soyate IMF 40, Sefa Soyate LP426, SEFOSE.RTM. 2275,
SEFOSE.RTM. C1695, SEFOSE.RTM. C18:0 95, SEFOSE.RTM. C1495,
SEFOSE.RTM. 1618H B6, SEFOSE.RTM. 1618S B6, SEFOSE.RTM. 1618U B6,
Sefa Cottonate, SEFOSE.RTM. C1295, Sefa C895, Sefa C1095,
SEFOSE.RTM. 1618S B4.5, all available from The Procter and Gamble
Co. of Cincinnati, Ohio.
[0081] Other examples of suitable polyol esters may include but not
be limited to sorbitol esters, maltitol esters, sorbitan esters,
maltodextrin derived esters, xylitol esters, polyglycerol esters,
and other sugar derived esters.
[0082] Natural oils of the type described herein typically are
composed of triglycerides of fatty acids. These fatty acids may be
either saturated, monounsaturated or polyunsaturated and contain
varying chain lengths ranging from C.sub.8 to C.sub.30. The most
common fatty acids include saturated fatty acids such as lauric
acid (dodecanoic acid), myristic acid (tetradecanoic acid),
palmitic acid (hexadecanoic acid), stearic acid (octadecanoic
acid), arachidic acid (eicosanoic acid), and lignoceric acid
(tetracosanoic acid); unsaturated acids include such fatty acids as
palmitoleic (a C.sub.16 acid), and oleic acid (a C.sub.18 acid);
polyunsaturated acids include such fatty acids as linoleic acid (a
di-unsaturated C.sub.18 acid), linolenic acid (a tri-unsaturated
C.sub.18 acid), and arachidonic acid (a tetra-unsubstituted
C.sub.20 acid). The natural oils are further comprised of esters of
these fatty acids in random placement onto the three sites of the
trifunctional glycerine molecule. Different natural oils will have
different ratios of these fatty acids, and within a given natural
oil there is a range of these acids as well depending on such
factors as where a vegetable or crop is grown, maturity of the
vegetable or crop, the weather during the growing season, etc.
Thus, it is difficult to have a specific or unique structure for
any given natural oil, but rather a structure is typically based on
some statistical average. For example soybean oil contains a
mixture of stearic acid, oleic acid, linoleic acid, and linolenic
acid in the ratio of 15:24:50:11, and an average number of double
bonds of 4.4-4.7 per triglyceride. One method of quantifying the
number of double bonds is the iodine value (IV) which is defined as
the number of grams of iodine that will react with 100 grams of
oil. Therefore for soybean oil, the average iodine value range is
from 120-140. Soybean oil may comprise about 95% by weight or
greater (e.g., 99% weight or greater) triglycerides of fatty acids.
Major fatty acids in the polyol esters of soybean oil include
saturated fatty acids, as a non-limiting example, palmitic acid
(hexadecanoic acid) and stearic acid (octadecanoic acid), and
unsaturated fatty acids, as a non-limiting example, oleic acid
(9-octadecenoic acid), linoleic acid (9,12octadecadienoic acid),
and linolenic acid (9,12,15-octadecatrienoic acid).
[0083] In an exemplary embodiment, the vegetable oil is canola oil,
for example, refined, bleached, and deodorized canola oil (i.e.,
RBD canola oil). Canola oil is an unsaturated polyol ester of
glycerol that typically comprises about 95% weight or greater
(e.g., 99% weight or greater) triglycerides of fatty acids. Major
fatty acids in the polyol esters of canola oil include saturated
fatty acids, for example, palmitic acid (hexadecanoic acid) and
stearic acid (octadecanoic acid), and unsaturated fatty acids, for
example, oleic acid (9-octadecenoic acid), linoleic acid
(9,12-octadecadienoic acid), and linolenic acid
(9,12,15-octadecatrienoic acid). Canola oil is a highly unsaturated
vegetable oil with many of the triglyceride molecules having at
least two unsaturated fatty acids (i.e., a polyunsaturated
triglyceride).
[0084] In exemplary embodiments, an unsaturated polyol ester is
self-metathesized in the presence of a metathesis catalyst to form
a metathesized composition. Typically, after metathesis has
occurred, the metathesis catalyst is removed from the resulting
product. One method of removing the catalyst is treatment of the
metathesized product with clay. In many embodiments, the
metathesized composition comprises one or more of: metathesis
monomers, metathesis dimers, metathesis trimers, metathesis
tetramers, metathesis pentamers, and higher order metathesis
oligomers (e.g., metathesis hexamers). A metathesis dimer refers to
a compound formed when two unsaturated polyol ester molecules are
covalently bonded to one another by a self-metathesis reaction. In
many embodiments, the molecular weight of the metathesis dimer is
greater than the molecular weight of the individual unsaturated
polyol ester molecules from which the dimer is formed. A metathesis
trimer refers to a compound formed when three unsaturated polyol
ester molecules are covalently bonded together by metathesis
reactions. In many embodiments, a metathesis trimer is formed by
the cross-metathesis of a metathesis dimer with an unsaturated
polyol ester. A metathesis tetramer refers to a compound formed
when four unsaturated polyol ester molecules are covalently bonded
together by metathesis reactions. In many embodiments, a metathesis
tetramer is formed by the cross-metathesis of a metathesis trimer
with an unsaturated polyol ester. Metathesis tetramers may also be
formed, for example, by the cross-metathesis of two metathesis
dimers. Higher order metathesis products may also be formed. For
example, metathesis pentamers and metathesis hexamers may also be
formed. The self-metathesis reaction also results in the formation
of internal olefin compounds that may be linear or cyclic. If the
metathesized polyol ester is fully or partially hydrogenated, the
linear and cyclic olefins would typically be fully or partially
converted to the corresponding saturated linear and cyclic
hydrocarbons. The linear/cyclic olefins and saturated linear/cyclic
hydrocarbons may remain in the metathesized polyol ester or they
may be removed or partially removed from the metathesized polyol
ester using one or more known stripping techniques, including but
not limited to wipe film evaporation, falling film evaporation,
rotary evaporation, steam stripping, vacuum distillation, etc.
[0085] In some embodiments, the unsaturated polyol ester is
partially hydrogenated before being metathesized. For example, in
some embodiments, the unsaturated polyol ester is partially
hydrogenated to achieve an iodine value (IV) of about 120 or less
before subjecting the partially hydrogenated polyol ester to
metathesis.
[0086] In some embodiments, the unsaturated polyol ester may be
hydrogenated (e.g., fully or partially hydrogenated) in order to
improve the stability of the oil or to modify its viscosity or
other properties. Representative techniques for hydrogenating
unsaturated polyol esters are known in the art and are discussed
herein.
[0087] In some embodiments, the natural oil is winterized.
Winterization refers to the process of: (1) removing waxes and
other non-triglyceride constituents, (2) removing naturally
occurring high-melting triglycerides, and (3) removing high-melting
triglycerides formed during partial hydrogenation. Winterization
may be accomplished by known methods including, for example,
cooling the oil at a controlled rate in order to cause
crystallization of the higher melting components that are to be
removed from the oil. The crystallized high melting components are
then removed from the oil by filtration resulting in winterized
oil. Winterized soybean oil is commercially available from Cargill,
Incorporated (Minneapolis, Minn.).
[0088] In other embodiments, the metathesized unsaturated polyol
esters can be used as a blend with one or more fabric care benefit
agents and/or fabric softening actives.
[0089] Method of Making Metathesized Unsaturated Polyol Ester
[0090] The self-metathesis of unsaturated polyol esters is
typically conducted in the presence of a catalytically effective
amount of a metathesis catalyst. The term "metathesis catalyst"
includes any catalyst or catalyst system that catalyzes a
metathesis reaction. Any known or future-developed metathesis
catalyst may be used, alone or in combination with one or more
additional catalysts. Suitable homogeneous metathesis catalysts
include combinations of a transition metal halide or oxo-halide
(e.g., WOCl.sub.4 or WCl.sub.6) with an alkylating cocatalyst
(e.g., Me.sub.4Sn), or alkylidene (or carbene) complexes of
transition metals, particularly Ru or W. These include first and
second-generation Grubbs catalysts, Grubbs-Hoveyda catalysts, and
the like. Suitable alkylidene catalysts have the general
structure:
M[X.sup.1X.sup.2L.sup.1L.sup.2(L.sup.3).sub.n]=C.sub.m.dbd.C(R.sup.1)R.s-
up.2
[0091] Where M is a Group 8 transition metal, L.sup.1, L.sup.2, and
L.sup.3 are neutral electron donor ligands, n is 0 (such that
L.sup.3 may not be present) or 1, m is 0, 1, or 2, X.sup.1 and
X.sup.2 are anionic ligands, and R.sup.1 and R.sup.2 are
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups. Any two
or more of X.sup.1, X.sup.2, L.sup.1, L.sup.2, L.sup.3, R.sup.1 and
R.sup.2 can form a cyclic group and any one of those groups can be
attached to a support.
[0092] First-generation Grubbs catalysts fall into this category
where m=n=0 and particular selections are made for n, X.sup.1,
X.sup.2, L.sup.1, L.sup.2, L.sup.3, R.sup.1 and R.sup.2 as
described in U.S. Pat. Appl. Publ. No. 2010/0145086, the teachings
of which related to all metathesis catalysts are incorporated
herein by reference.
[0093] Second-generation Grubbs catalysts also have the general
formula described above, but L.sup.1 is a carbene ligand where the
carbene carbon is flanked by N, O, S, or P atoms, preferably by two
N atoms. Usually, the carbene ligand is part of a cyclic group.
Examples of suitable second-generation Grubbs catalysts also appear
in the '086 publication.
[0094] In another class of suitable alkylidene catalysts, L.sup.1
is a strongly coordinating neutral electron donor as in first- and
second-generation Grubbs catalysts, and L.sup.2 and L.sup.3 are
weakly coordinating neutral electron donor ligands in the form of
optionally substituted heterocyclic groups. Thus, L.sup.2 and
L.sup.3 are pyridine, pyrimidine, pyrrole, quinoline, thiophene, or
the like.
[0095] In yet another class of suitable alkylidene catalysts, a
pair of substituents is used to form a bi- or tridentate ligand,
such as a biphosphine, dialkoxide, or alkyldiketonate.
Grubbs-Hoveyda catalysts are a subset of this type of catalyst in
which L.sup.2 and R.sup.2 are linked. Typically, a neutral oxygen
or nitrogen coordinates to the metal while also being bonded to a
carbon that is .alpha.-, .beta.-, or .gamma.- with respect to the
carbene carbon to provide the bidentate ligand. Examples of
suitable Grubbs-Hoveyda catalysts appear in the '086
publication.
[0096] The structures below provide just a few illustrations of
suitable catalysts that may be used:
##STR00003##
[0097] An immobilized catalyst can be used for the metathesis
process. An immobilized catalyst is a system comprising a catalyst
and a support, the catalyst associated with the support. Exemplary
associations between the catalyst and the support may occur by way
of chemical bonds or weak interactions (e.g. hydrogen bonds, donor
acceptor interactions) between the catalyst, or any portions
thereof, and the support or any portions thereof. Support is
intended to include any material suitable to support the catalyst.
Typically, immobilized catalysts are solid phase catalysts that act
on liquid or gas phase reactants and products. Exemplary supports
are polymers, silica or alumina. Such an immobilized catalyst may
be used in a flow process. An immobilized catalyst can simplify
purification of products and recovery of the catalyst so that
recycling the catalyst may be more convenient.
[0098] In certain embodiments, prior to the metathesis reaction,
the unsaturated polyol ester feedstock may be treated to render the
natural oil more suitable for the subsequent metathesis reaction.
In one embodiment, the treatment of the unsaturated polyol ester
involves the removal of catalyst poisons, such as peroxides, which
may potentially diminish the activity of the metathesis catalyst.
Non-limiting examples of unsaturated polyol ester feedstock
treatment methods to diminish catalyst poisons include those
described in PCT/US2008/09604, PCT/US2008/09635, and U.S. patent
application Ser. Nos. 12/672,651 and 12/672,652, herein
incorporated by reference in their entireties. In certain
embodiments, the unsaturated polyol ester feedstock is thermally
treated by heating the feedstock to a temperature greater than
100.degree. C. in the absence of oxygen and held at the temperature
for a time sufficient to diminish catalyst poisons in the
feedstock. In other embodiments, the temperature is between
approximately 100.degree. C. and 300.degree. C., between
approximately 120.degree. C. and 250.degree. C., between
approximately 150.degree. C. and 210.degree. C., or approximately
between 190 and 200.degree. C. In one embodiment, the absence of
oxygen is achieved by sparging the unsaturated polyol ester
feedstock with nitrogen, wherein the nitrogen gas is pumped into
the feedstock treatment vessel at a pressure of approximately 10
atm (150 psig).
[0099] In certain embodiments, the unsaturated polyol ester
feedstock is chemically treated under conditions sufficient to
diminish the catalyst poisons in the feedstock through a chemical
reaction of the catalyst poisons. In certain embodiments, the
feedstock is treated with a reducing agent or a cation-inorganic
base composition. Non-limiting examples of reducing agents include
bisulfate, borohydride, phosphine, thiosulfate, and combinations
thereof.
[0100] In certain embodiments, the unsaturated polyol ester
feedstock is treated with an adsorbent to remove catalyst poisons.
In one embodiment, the feedstock is treated with a combination of
thermal and adsorbent methods. In another embodiment, the feedstock
is treated with a combination of chemical and adsorbent methods. In
another embodiment, the treatment involves a partial hydrogenation
treatment to modify the unsaturated polyol ester feedstock's
reactivity with the metathesis catalyst. Additional non-limiting
examples of feedstock treatment are also described below when
discussing the various metathesis catalysts.
[0101] In certain embodiments, a ligand may be added to the
metathesis reaction mixture. In many embodiments using a ligand,
the ligand is selected to be a molecule that stabilizes the
catalyst, and may thus provide an increased turnover number for the
catalyst. In some cases the ligand can alter reaction selectivity
and product distribution. Examples of ligands that can be used
include Lewis base ligands, such as, without limitation,
trialkylphosphines, for example tricyclohexylphosphine and tributyl
phosphine; triarylphosphines, such as triphenylphosphine;
diarylalkylphosphines, such as, diphenylcyclohexylphosphine;
pyridines, such as 2,6-dimethylpyridine, 2,4,6-trimethylpyridine;
as well as other Lewis basic ligands, such as phosphine oxides and
phosphinites. Additives may also be present during metathesis that
increase catalyst lifetime.
[0102] Any useful amount of the selected metathesis catalyst can be
used in the process. For example, the molar ratio of the
unsaturated polyol ester to catalyst may range from about 5:1 to
about 10,000,000:1 or from about 50:1 to 500,000:1. In some
embodiments, an amount of about 1 to about 10 ppm, or about 2 ppm
to about 5 ppm, of the metathesis catalyst per double bond of the
starting composition (i.e., on a mole/mole basis) is used.
[0103] In some embodiments, the metathesis reaction is catalyzed by
a system containing both a transition and a non-transition metal
component. The most active and largest number of catalyst systems
are derived from Group VI A transition metals, for example,
tungsten and molybdenum.
[0104] Multiple, sequential metathesis reaction steps may be
employed. For example, the metathesized unsaturated polyol ester
product may be made by reacting an unsaturated polyol ester in the
presence of a metathesis catalyst to form a first metathesized
unsaturated polyol ester product. The first metathesized
unsaturated polyol ester product may then be reacted in a
self-metathesis reaction to form another metathesized unsaturated
polyol ester product. Alternatively, the first metathesized
unsaturated polyol ester product may be reacted in a
cross-metathesis reaction with a unsaturated polyol ester to form
another metathesized unsaturated polyol ester product. Also in the
alternative, the transesterified products, the olefins and/or
esters may be further metathesized in the presence of a metathesis
catalyst. Such multiple and/or sequential metathesis reactions can
be performed as many times as needed, and at least one or more
times, depending on the processing/compositional requirements as
understood by a person skilled in the art. As used herein, a
"metathesized unsaturated polyol ester product" may include
products that have been once metathesized and/or multiply
metathesized. These procedures may be used to form metathesis
dimers, metathesis trimers, metathesis tetramers, metathesis
pentamers, and higher order metathesis oligomers (e.g., metathesis
hexamers, metathesis heptamers, metathesis octamers, metathesis
nonamers, metathesis decamers, and higher than metathesis
decamers). These procedures can be repeated as many times as
desired (for example, from 2 to about 50 times, or from 2 to about
30 times, or from 2 to about 10 times, or from 2 to about 5 times,
or from 2 to about 4 times, or 2 or 3 times) to provide the desired
metathesis oligomer or polymer which may comprise, for example,
from 2 to about 100 bonded groups, or from 2 to about 50, or from 2
to about 30, or from 2 to about 10, or from 2 to about 8, or from 2
to about 6 bonded groups, or from 2 to about 4 bonded groups, or
from 2 to about 3 bonded groups. In certain embodiments, it may be
desirable to use the metathesized unsaturated polyol ester products
produced by cross metathesis of an unsaturated polyol ester, or
blend of unsaturated polyol esters, with a C2-C100 olefin, as the
reactant in a self-metathesis reaction to produce another
metathesized unsaturated polyol ester product. Alternatively,
metathesized products produced by cross metathesis of an
unsaturated polyol ester, or blend of unsaturated polyol esters,
with a C2-C100 olefin can be combined with an unsaturated polyol
ester, or blend of unsaturated polyol esters, and further
metathesized to produce another metathesized unsaturated polyol
ester product.
[0105] The metathesis process can be conducted under any conditions
adequate to produce the desired metathesis products. For example,
stoichiometry, atmosphere, solvent, temperature, and pressure can
be selected by one skilled in the art to produce a desired product
and to minimize undesirable byproducts. The metathesis process may
be conducted under an inert atmosphere. Similarly, if a reagent is
supplied as a gas, an inert gaseous diluent can be used. The inert
atmosphere or inert gaseous diluent typically is an inert gas,
meaning that the gas does not interact with the metathesis catalyst
to substantially impede catalysis. For example, particular inert
gases are selected from the group consisting of helium, neon,
argon, nitrogen, individually or in combinations thereof.
[0106] In certain embodiments, the metathesis catalyst is dissolved
in a solvent prior to conducting the metathesis reaction. In
certain embodiments, the solvent chosen may be selected to be
substantially inert with respect to the metathesis catalyst. For
example, substantially inert solvents include, without limitation,
aromatic hydrocarbons, such as benzene, toluene, xylenes, etc.;
halogenated aromatic hydrocarbons, such as chlorobenzene and
dichlorobenzene; aliphatic solvents, including pentane, hexane,
heptane, cyclohexane, etc.; and chlorinated alkanes, such as
dichloromethane, chloroform, dichloroethane, etc. In one particular
embodiment, the solvent comprises toluene. The metathesis reaction
temperature may be a rate-controlling variable where the
temperature is selected to provide a desired product at an
acceptable rate. In certain embodiments, the metathesis reaction
temperature is greater than about -40.degree. C., greater than
about -20.degree. C., greater than about 0.degree. C., or greater
than about 10.degree. C. In certain embodiments, the metathesis
reaction temperature is less than about 150.degree. C., or less
than about 120.degree. C. In one embodiment, the metathesis
reaction temperature is between about 10.degree. C. and about
120.degree. C.
[0107] The metathesis reaction can be run under any desired
pressure. Typically, it will be desirable to maintain a total
pressure that is high enough to keep the cross-metathesis reagent
in solution. Therefore, as the molecular weight of the
cross-metathesis reagent increases, the lower pressure range
typically decreases since the boiling point of the cross-metathesis
reagent increases. The total pressure may be selected to be greater
than about 0.1 atm (10 kPa), in some embodiments greater than about
0.3 atm (30 kPa), or greater than about 1 atm (100 kPa). Typically,
the reaction pressure is no more than about 70 atm (7000 kPa), in
some embodiments no more than about 30 atm (3000 kPa). A
non-limiting exemplary pressure range for the metathesis reaction
is from about 1 atm (100 kPa) to about 30 atm (3000 kPa). In
certain embodiments it may be desirable to run the metathesis
reactions under an atmosphere of reduced pressure. Conditions of
reduced pressure or vacuum may be used to remove olefins as they
are generated in a metathesis reaction, thereby driving the
metathesis equilibrium towards the formation of less volatile
products. In the case of a self-metathesis of a natural oil,
reduced pressure can be used to remove C.sub.12 or lighter olefins
including, but not limited to, hexene, nonene, and dodecene, as
well as byproducts including, but not limited to cyclohexa-diene
and benzene as the metathesis reaction proceeds. The removal of
these species can be used as a means to drive the reaction towards
the formation of diester groups and cross linked triglycerides.
[0108] Hydrogenation:
[0109] In some embodiments, the unsaturated polyol ester is
partially hydrogenated before it is subjected to the metathesis
reaction. Partial hydrogenation of the unsaturated polyol ester
reduces the number of double bonds that are available for in the
subsequent metathesis reaction. In some embodiments, the
unsaturated polyol ester is metathesized to form a metathesized
unsaturated polyol ester, and the metathesized unsaturated polyol
ester is then hydrogenated (e.g., partially or fully hydrogenated)
to form a hydrogenated metathesized unsaturated polyol ester.
[0110] Hydrogenation may be conducted according to any known method
for hydrogenating double bond-containing compounds such as
vegetable oils. In some embodiments, the unsaturated polyol ester
or metathesized unsaturated polyol ester is hydrogenated in the
presence of a nickel catalyst that has been chemically reduced with
hydrogen to an active state. Commercial examples of supported
nickel hydrogenation catalysts include those available under the
trade designations "NYSOFACT".RTM., "NYSOSEL".RTM., and "NI 5248 D"
(from Englehard Corporation, Iselin, N.H.). Additional supported
nickel hydrogenation catalysts include those commercially available
under the trade designations "PRICAT 9910", "PRICAT 9920", "PRICAT
9908", "PRICAT 9936" (from Johnson Matthey Catalysts, Ward Hill,
Mass.).
[0111] In some embodiments, the hydrogenation catalyst comprising,
for example, nickel, copper, palladium, platinum, molybdenum, iron,
ruthenium, osmium, rhodium, or iridium. Combinations of metals may
also be used. Useful catalyst may be heterogeneous or homogeneous.
In some embodiments, the catalysts are supported nickel or sponge
nickel type catalysts.
[0112] In some embodiments, the hydrogenation catalyst comprises
nickel that has been chemically reduced with hydrogen to an active
state (i.e., reduced nickel) provided on a support. In some
embodiments, the support comprises porous silica (e.g., kieselguhr,
infusorial, diatomaceous, or siliceous earth) or alumina. The
catalysts are characterized by a high nickel surface area per gram
of nickel.
[0113] In some embodiments, the particles of supported nickel
catalyst are dispersed in a protective medium comprising hardened
triacylglyceride, edible oil, or tallow. In an exemplary
embodiment, the supported nickel catalyst is dispersed in the
protective medium at a level of about 22 wt. % nickel.
[0114] Hydrogenation may be carried out in a batch or in a
continuous process and may be partial hydrogenation or complete
hydrogenation. In a representative batch process, a vacuum is
pulled on the headspace of a stirred reaction vessel and the
reaction vessel is charged with the material to be hydrogenated
(e.g., RBD soybean oil or metathesized RBD soybean oil). The
material is then heated to a desired temperature. Typically, the
temperature ranges from about 50 deg. C. to 350 deg. C., for
example, about 100 deg. C. to 300 deg. C. or about 150 deg. C. to
250 deg. C. The desired temperature may vary, for example, with
hydrogen gas pressure. Typically, a higher gas pressure will
require a lower temperature. In a separate container, the
hydrogenation catalyst is weighed into a mixing vessel and is
slurried in a small amount of the material to be hydrogenated
(e.g., RBD soybean oil or metathesized RBD soybean oil). When the
material to be hydrogenated reaches the desired temperature, the
slurry of hydrogenation catalyst is added to the reaction vessel.
Hydrogen gas is then pumped into the reaction vessel to achieve a
desired pressure of H2 gas. Typically, the H2 gas pressure ranges
from about 15 to 3000 psig, for example, about 15 psig to 90 psig.
As the gas pressure increases, more specialized high-pressure
processing equipment may be required. Under these conditions the
hydrogenation reaction begins and the temperature is allowed to
increase to the desired hydrogenation temperature (e.g., about 120
deg. C. to 200 deg. C.) where it is maintained by cooling the
reaction mass, for example, with cooling coils. When the desired
degree of hydrogenation is reached, the reaction mass is cooled to
the desired filtration temperature.
[0115] The amount of hydrogenation catalysts is typically selected
in view of a number of factors including, for example, the type of
hydrogenation catalyst used, the amount of hydrogenation catalyst
used, the degree of unsaturation in the material to be
hydrogenated, the desired rate of hydrogenation, the desired degree
of hydrogenation (e.g., as measure by iodine value (IV)), the
purity of the reagent, and the H2 gas pressure. In some
embodiments, the hydrogenation catalyst is used in an amount of
about 10 wt. % or less, for example, about 5 wt. % or less or about
1 wt. % or less.
[0116] After hydrogenation, the hydrogenation catalyst may be
removed from the hydrogenated product using known techniques, for
example, by filtration. In some embodiments, the hydrogenation
catalyst is removed using a plate and frame filter such as those
commercially available from Sparkler Filters, Inc., Conroe Tex. In
some embodiments, the filtration is performed with the assistance
of pressure or a vacuum. In order to improve filtering performance,
a filter aid may be used. A filter aid may be added to the
metathesized product directly or it may be applied to the filter.
Representative examples of filtering aids include diatomaceous
earth, silica, alumina, and carbon. Typically, the filtering aid is
used in an amount of about 10 wt. % or less, for example, about 5
wt. % or less or about 1 wt. % or less. Other filtering techniques
and filtering aids may also be employed to remove the used
hydrogenation catalyst. In other embodiments the hydrogenation
catalyst is removed using centrifugation followed by decantation of
the product.
Additional Optional Liquid Phase Components
[0117] Suitable additional liquid phase components for use herein
include for example natural oils, synthetic oils, silicone oils,
petrolatum, triglycerides, butters or mixtures thereof. As used
herein, the term "oil" includes, but is not limited to any
non-aqueous substance that is very slightly soluble, preferably
practically insoluble in water according to the United States'
Pharmacopeia (USP) definition in 31/NF 26 Vol. 2 General Notices,
Page Xvii. According to that definition, means that 1000 to 10000
parts of water are needed to dissolve 1 part solute and that more
than 10,000 parts of water are needed to dissolve 1 part solute
respectively and is liquid at 25.degree. C. Petrolatum may be
considered as a lipophilic structurant or a liquid phase due to its
complex mixture of component materials. For the purposes of this
invention petrolatum is considered as a liquid phase component.
[0118] The oil may be selected from natural oil, synthetic oil,
silicone oil and mixtures thereof. Non-limiting examples of
suitable natural oils include Acetylated Castor Oil, Acetylated
Hydrogenated Castor Oil, Actinidia Chinensis (Kiwi), Seed Oil,
Adansonia Digitata Oil, Aleurites Moluccana Seed Oil, Anacardium
Occidentale (Cashew) Seed Oil, Arachis Hypogaea (Peanut) Oil,
Arctium Lappa Seed Oil, Argania Spinosa Kernel Oil, Argemone
Mexicana Oil, Avena Sativa (Oat) Kernel Oil, Bertholletia Excelsa
Seed Oil, Borago Officinalis Seed Oil, Brassica Campestris
(Rapeseed) Seed Oil, Calophyllum Tacamahaca Seed Oil, Camellia
Japonica Seed Oil, Camellia Kissi Seed Oil, Camellia Oleifera Seed
Oil, Canola Oil, Caprylic/Capric/Lauric Triglyceride,
Caprylic/Capric/Linoleic Triglyceride,
Caprylic/Capric/My-ristic/Stearic Triglyceride,
Caprylic/Capric/Stearic Triglyceride, Caprylic/Capric Triglyceride,
Carthamus Tinctorius (Hybrid Safflower) Seed Oil, Carthamus
Tinctorius (Safflower) Seed Oil, Carum Carvi (Caraway) Seed Oil,
Carya Illinoensis (Pecan) Seed Oil, Castor Oil Benzoate,
Chenopodium Quinoa Seed Oil, Cibotium Barometz Oil, Citrullus
Vulgaris (Watermelon) Seed Oil, Cocos Nucifera (Coconut) Oil, Cod
Liver Oil, Coffea Arabica (Coffee) Seed Oil, Coix Lacryma-Jobi
(Job's Tears) Seed Oil, Corylus Americana (Hazel) Seed Oil, Corylus
Avellana (Hazel) Seed Oil, Cucumis Sativus (Cucumber) Oil,
Cucurbita Pepo (Pumpkin) Seed Oil, Daucus Carota Sativa (Carrot)
Seed Oil, Elaeis Guineensis (Palm) Kernel Oil, Elaeis Guineensis
(Palm) Oil, Gossypium (Cotton) Seed Oil, Helianthus Annuus (Hybrid
Sunflower) Oil, Helianthus Annuus (Sunflower) Seed Oil, Hippophae
Rhamnoides Oil, Human Placental Lipids, Hydrogenated Canola Oil,
Hydrogenated Castor Oil, Hydrogenated Castor Oil Laurate,
Hydrogenated Castor Oil Triisostearate, Hydrogenated Coconut Oil,
Hydrogenated Cottonseed Oil, Hydrogenated C12-18 Triglycerides,
Hydrogenated Fish Oil, Hydrogenated Lard, Hydrogenated Menhaden
Oil, Hydrogenated Mink Oil, Hydrogenated Olive Oil, Hydrogenated
Orange Roughy Oil, Hydrogenated Palm Kernel Oil, Hydrogenated Palm
Oil, Hydrogenated Peanut Oil, Hydrogenated Rapeseed Oil,
Hydrogenated Shark Liver Oil, Hydrogenated Soybean Oil,
Hydrogenated Sunflower Seed Oil, Hydrogenated Tallow, Hydrogenated
Vegetable Oil, Isatis Tinctoria Seed Oil, Juglans Regia (Walnut)
Seed Oil, Lauric/Palmitic/Oleic Triglyceride, Umnanthes Alba
(Meadowfoam) Seed Oil, Unum Usitatissimum (Linseed) Seed Oil,
Lupinus Albus Seed Oil, Macadamia Integrifolia Seed Oil, Macadamia
Ternifolia Seed Oil, Maleated Soybean Oil, Mangifera Indica (Mango)
Seed Oil, Marmot Oil, Melaleuca Alternifolia (Tea Tree) Leaf Oil,
Melia Azadirachta Seed Oil, Melissa Officinalis (Balm Mint) Seed
Oil, Menhaden Oil, Mink Oil, Moringa pterygosperma Seed Oil,
Mortierella Oil, Neatsfoot Oil, Nelumbium Speciosum Flower Oil,
Nigella Sativa Seed Oil, Oenothera Biennis (Evening Primrose) Oil,
Olea Europaea (Olive) Fruit Oil, Olea Europaea (Olive) Husk Oil,
Orange Roughy Oil, Orbignya Cohune Seed Oil, Orbignya Oleifera Seed
Oil, Oryza Sativa (Rice) Bran Oil, Oryza Sativa (Rice) Germ Oil,
Ostrich Oil, Oxidized Corn Oil, Oxidized Hazel Seed Oil, Papaver
Orientale (Poppy) Seed Oil, Passiflora Edulis Seed Oil, Persea
Gratissima (Avocado) Oil, Pistacia Vera Seed Oil, Placental Lipids,
Prunus Amygdalus Amara (Bitter Almond) Kernel Oil, Prunus Amygdalus
Dulcis (Sweet Almond) Oil, Prunus Armeniaca (Apricot) Kernel Oil,
Prunus Avium (Sweet Cherry) Seed Oil, Prunus Cerasus (Bitter
Cherry) Seed Oil, Prunus Persica (Peach) Kernel Oil, Pyrus Malus
(Apple) Oil, Ribes Nigrum (Black Currant) Seed Oil, Ricinus
Communis (Castor) Seed Oil, Rosa Canina Fruit Oil, Rosa Moschata
Seed Oil, Salmon Oil, Salvia Hispanica Seed Oil, Santalum Album
(Sandalwood) Seed Oil, Sesamum Indicum (Sesame) Seed Oil, Shark
Liver Oil, Solanum Lycopersicum (Tomato) Seed Oil, Soybean Lipid,
Sphingolipids, Taraktogenos Kurzii Seed Oil, Telphairia Pedata Oil,
Vegetable Oil, Vitis Vinifera (Grape) Seed Oil, Zea Mays (Corn)
Germ Oil, Zea Mays (Corn) Oil, mineral oil and mixtures
thereof.
[0119] Suitable synthetic oils include hydrocarbons, esters,
alkanes, alkenes and mixtures thereof. Non-limiting examples
include isopropyl palmitate, isopropyl stearate, isohexadecane,
isododecane, polyglyceryl triisostearate and mixtures thereof.
[0120] Non-limiting examples of suitable silicone oils include
dimethicones (including partial esters of dimethicones and fatty
acids derived from natural/synthetic oils), cyclomethicones,
phenylated silicones, phenyl trimethicones, trimethyl pentaphenyl
trisiloxane, silicone polyether block copolymers and mixtures
thereof.
[0121] Suitable silicone polyether copolymers may comprise from
about 1% to 50%, by weight of polyethylene oxide, from about 20% to
about 90% by weight of polypropylene oxide and from about 1% to
about 20% by weight of silicone. Preferably the silicone polyether
copolymer comprises at least about 40%, more preferably at least
about 50%, most preferably at least about 60% by weight of
polypropylene oxide. In addition, the silicone polyether copolymer
preferably comprises at least about 10%, more preferably from at
least about 15%, most preferably from about 15% to 30% by weight of
polyethylene oxide. Furthermore, the silicone polyether block
copolymer comprises from 1% to 20%, preferably 10% to 20%, more
preferably about 15% by weight of silicone.
[0122] While silicone polyether block copolymers are known in the
art to provide a number of benefits such as foaming, defoaming,
wetting, deaeration and lubricity, it has been now been
surprisingly found that the selection of silicone block copolymers
having from 20% to 90% by weight of polypropylene oxide and from 1%
to 50% of polyethylene oxide unexpectedly further provide improved
lubrication whilst ensuring the required level of water dispersion
and or solubility verses silicone polyether block copolymers having
less or no polypropylene oxide and more polyethylene oxide.
Moreover, the use of such silicone block copolymers provides
improved adhesion to the skin verses alternative materials such as
copolymers of polyethylene oxide and polypropylene oxide.
Furthermore, the inclusion of 1% to 20% of silicone by weight of
the silicone polyether block copolymer surprisingly provides
desirable levels of lubrication despite being present at low levels
in the polymer.
[0123] The copolymers are block copolymers and may preferably have
a pendant graft structure. The silicone polyether block copolymer
preferably has a ratio of polyethylene oxide units to polypropylene
oxide units of from 3.0 to 0.1, preferably from 2.0 to 0.1, more
preferably from 0.6 to 0.25. The silicone polyether block copolymer
preferably has a ratio of polyethylene oxide units to polypropylene
oxide units to silicone units of from 20:65:15.
[0124] The silicone polyether copolymer may have a molecular weight
of from about 10000 to about 19000, more preferably from about
10000 to 15000. Suitable silicone polyether copolymers are
available from Momentive under the Silwets trademark products
including L7210, L7602, L7220, L7230, L7500, preferably L7210 and
L7602.
[0125] Non-limiting examples of commercially available silicone
oils include Dow Corning 200 fluid, Dow Corning 244, Dow Corning
245, Dow Corning 344, and Dow Corning 345, (commercially available
from Dow Corning Corp.); SF-1204 and SF-1202 Silicone Fluids
(commercially available from G.E. Silicones), GE 7207 and 7158
(commercially available from General Electric Co.); and SWS-03314
(commercially available from SWS Silicones Corp.), the Viscasil
series (sold by General Electric Company), SF 1075 methyl-phenyl
fluid (sold by General Electric Company) and 556 Cosmetic Grade
Fluid (sold by Dow Corning Corp.), Silshine 151 (sold by
Momentive), PH1555 and PH1560 (sold by Dow Corning) and Silwets
such as Silwets 7210, 7230 and 7220 (available from by
Momentive).
Suitable triglycerides, may have the following formula:
##STR00004##
wherein R, R' and R'' may be the same as or different from one or
both of the others, wherein each of R, R' and R'' is a fatty acid
and wherein the or each triglyceride is solid at 25.degree. C.
[0126] Suitable oils from which triglycerides may be formed from
include, but are not limited to, the oils listed herein. Suitable
fatty acids for formation of triglycerides include, but are not
limited to, Myristoleic acid, Palmitoleic acid, Sapienic acid,
Oleic acid, Linoleic acid, .alpha.-Linolenic acid, Arachidonic
acid, Eicosapentaenoic acid, Docosahexaenoic acid, Lauric acid
(C.sub.12), Myristic acid (C.sub.14), Palmitic acid (C.sub.16),
Stearic acid (C.sub.18), Arachidic acid (C.sub.20) and mixtures
thereof.
[0127] Specific sources of triglycerides suitable for inclusion
herein include Shea Butter, Theobroma Cacao (Cocoa) Seed Butter,
Cocoa Butter, Mangifera Indica (Mango) Seed Butter, Kokum Butter
and mixtures thereof. Particularly preferred are shea butter, cocoa
butter and mixtures thereof.
[0128] Preferred liquid phase components may be selected from
capric and or caprylic triglycerides, olive oil, shea butter, cocoa
butter, petrolatum, isopropyl isostearate, dimethicones, phenylated
silicones, silicone polyether block copolymers and mixtures
thereof. The silicone polyether block polymers are particularly
advantageous as they may facilitate the dispersion of the water
soluble polymer in the lipophilic structurant as discussed
hereinafter and may also improve lubrication.
Water Soluble Polymer
[0129] The lubricating member may further comprise from about 1% to
about 40% by weight, preferably from about 5% to about 40%, more
preferably from about 10% to about 30% and even more preferably
from about 20% to about 30% by weight of a water soluble
polymer.
[0130] Examples of suitable water soluble polymers suitable for use
herein include polyethylene oxide, polyvinyl pyrrolidone,
polyacrylamide, polyhydroxymethacrylate, polyvinyl imidazoline,
polyethylene glycol, polyvinyl alcohol,
polyhydroxyethymethacrylate, quaternary ammonium polymers, guars,
celluloses, modified celluloses and mixtures thereof. In some
embodiments the water soluble polymers may be selected from
polyethylene oxide, polyvinyl pyrrolidone, polyacrylamide,
polyhydroxymethacrylate, polyvinyl imidazoline, polyethylene
glycol, polyvinyl alcohol, polyhydroxyethymethacrylate, quaternary
ammonium polymers and mixtures thereof. In one embodiment, said
water soluble polymer is selected from the group consisting of
polyethylene oxide, polyethylene glycol, and mixtures thereof.
[0131] The preferred water soluble polymers are the polyethylene
oxides generally known as POLYOX (available from Union Carbide
Corporation) or ALKOX.RTM. (available from Meisei Chemical Works,
Kyoto, Japan). The water soluble polymer, (especially these
polyethylene oxides), may have average molecular weights of at
least about 20,000, preferably at least about 50,000, more
preferably at least about 100,000 or from about 100,000 to about 8
million, preferably about 300,000 to about 5 million, more
preferably from about 1 million to about 5 million, even more
preferably from about 2 million to about 4 million. One preferred
polyethylene oxide comprises a blend of about 40% to 80% of
polyethylene oxide having an average molecular weight of about 5
million (e.g. POLYOX COAGULANT) and about 60% to 20% of
polyethylene oxide having an average molecular weight of about
300,000 (e.g. POLYOX WSR-N-750). The polyethylene oxide blend may
also advantageously contain up to about 10% (for example about 5%)
by weight of a low molecular weight (i.e. MW<10,000)
polyethylene glycol such as PEG-100.
[0132] Suitable water soluble cationic polymers are, for example,
cationic cellulose derivatives, for example a quaternized
hydroxymethyl cellulose obtainable under the name UCARE POLYMER JR
400.RTM. from Dow, hydrophobized quaternized hydroxymethyl
cellulose, for example SOFTCAT.RTM. SL-5 from Dow, cationic
starches, copolymers of diallylammonium salts and acrylamides,
quaternized vinylpyrrolidone/vinyl imidazole polymers, for example
LUVIQUAT.RTM. (BASF), condensation products of polyglycols and
amines, quaternized collagen polypeptides, for example
lauryldimonium hydroxypropyl hydrolysed collagen
(LAMEQUAT.RTM.--L/Grunau), quaternised wheat polypeptides,
polyethyleneimine, cationic silicone polymers, for example
amidomethicones, copolymers of adipic acid and
Dimethylaminohydroxypropyldiethy-lenetriamine
(CARTARETIN.RTM./Clariant), copolymers of acrylic acid with
dimethyldiallylammo-nium chloride (MERQUAT.RTM. 550/Chemviron),
polyaminopolyamides, as described, for example, in FR-A-2 252840,
and the cross-linked water-soluble polymers thereof, cationic
chitin derivatives, for example of quaternised chitosan, optionally
distributed as microcrystals; condensation products of
dihaloalkyls, for example dibromobutane, with bisdialkylamines, for
example bisdimethylamino-1,3-propane, cationic guar gum, for
example JAGUAR.RTM. C-17 from Celanese or N-HANCE.RTM. 3196 from
Ashland, quaternised ammonium salt polymers, for example
MIRAPOL.RTM. A-15, MIRAPOL.RTM. AD-1, MIRAPOL.RTM. AZ-1 from
Miranol.
[0133] The water soluble polymer is preferably selected so that it
is solid at standard ambient temperature and pressure. The water
soluble polymer may thus have a melting point of 60.degree. C. or
greater, preferably 65.degree. C. or greater more preferably
70.degree. C. or greater. For embodiments comprising more than one
water soluble polymer the melting point of each component
preferably has a melting point of 60.degree. C. or greater,
preferably 65.degree. C. or greater more preferably 70.degree. C.
or greater. The melting point is determined according to ASTM
D5440-93.
[0134] In one embodiment of the invention the melting point of the
lipophilic structurant (or mixture, if present) is at least
5.degree. C., preferably at least 10.degree. C. less than the
melting point of the water soluble polymer, or from 5.degree. C. to
45.degree. C. less than the melting point of the water soluble
polymer.
[0135] In another embodiment the water soluble polymer is provided
in the form of particles, preferably discrete particles dispersed
within the lipophilic structurant. Preferably at least 90%, more
preferably at least 95% of said water soluble polymer is in the
form of discrete particulates dispersed within said lipophilic
structurant. These particulates may have an average particle size
of from 50 to 1250 microns, preferably less than 1000 microns. The
particles can be readily observed using scanning electron
microscopy techniques
[0136] While not being bound by theory it is believed that
lipophilic structurant having a melting point between about
45.degree. C. or greater than 45.degree. C. and less than
60.degree. C., enables the water insoluble materials to be melted
during the manufacturing process of the lubricating member in a
simple hot melt one batch process, but at temperatures which allow
the addition of thermally sensitive ingredients such as water
soluble polymers without these materials being melted. Moreover it
has been surprisingly found that the addition of the water soluble
polymer does not require that the polymer is in a liquid form or
that it is phase compatible with the lipophilic structurant. In
fact is has been surprisingly found that by selecting a water
soluble polymer having a melting point above the melting point of
the lipophilic structurant, the water soluble material may be added
in a solid form, as particulates which are dispersed throughout the
lipophilic structurant. It is believed that consequently the water
soluble material does not undergo any significant thermal
degradation during manufacture thereby increasing its efficacy as a
lubricant. Moreover using a particulate dispersion of the water
soluble polymer obsoletes the need for high temperature and high
shear process step during manufacture in order to incorporate
within the lipophilic structurant. The dispersion of the water
soluble polymer may be further improved by the incorporation of
silicone polyether block polymers as one of the components of the
liquid phase.
Water Insoluble Polymeric Structurant
[0137] The lubricating member may comprise less than 5% by weight
preferably less than 1% by weight, more preferably is substantially
free of a water insoluble polymeric structurant. Whilst not bound
by theory the structuring properties of the lubricating member of
the present invention are provided by the lipophilic structurant
and consequently additional water insoluble polymers are not
required. Such water insoluble polymeric structurants include
polyethylene (PE), polypropylene, polystyrene (PS),
butadiene-styrene copolymer (e.g. medium and high impact
polystyrene), polyacetal, acrylonitrile-butadiene-styrene
copolymer, ethylene vinyl acetate copolymer, polyurethane, and
blends thereof such as polypropylene/polystyrene blend or
polystyrene/impact polystyrene blend.
Optional Ingredients
[0138] In some embodiments, the lubricating material may comprise
any other ingredients commonly found in commercially available
shaving aid members. The lubricating member may therefore contain
other conventional shaving aid ingredients, such as low molecular
weight water-soluble release enhancing agents such as polyethylene
glycol (MW<10,000, e.g., 1-10% by weight PEG-100),
water-swellable release enhancing agents such as cross-linked
polyacrylics (e.g., 2-7% by weight), colorants, skin feel/care
actives, surfactants, soaps (including interrupted soaps),
antioxidants, preservatives, emollients, beard softeners,
astringents, medicinal agents, plasticizers, additional lubricants,
depilatories/keratolytic materials, tackifiers, skin-soothing
agents, fragrances, compatibilisers, anti-inflammatory agents,
antipruritic/counterirritant mater-ials, dyes, pigments etc. and
mixture thereof.
[0139] Other optional components may include skin active agents
such as, but not limited to oil soluble vitamins, such as vitamin E
derivatives, including vitamin E acetate and tocopherol nicotinate;
oil-soluble vitamin A derivatives, such as retinyl palmitate;
lanolin; ceramides; sterols and sterol esters; salicylic acid;
camphor; eucalyptol; essential oils; peppermint oil, Iso E Super
[(1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)ethanon-
e]; and mixtures there-of. Particularly preferred are lanolin,
essential oils, peppermint oil, coolants or senates and mixtures
thereof. Suitable synthetic coolants include derivatives of or
structurally related menthol compounds, i.e., containing the
cyclohexane moiety, and derivatized with functional groups
including carboxamide, ketal, ester, ether and alcohol.
Non-limiting examples include methyl emthylamido oxalate, (under
the tradename FRESCOLAT.RTM. X-cool available from Symrise),
menthyl lactate (such as FRESCOLAT.RTM. ML Natural available from
Symrise), and Menthyl Pyrrolidone Carboxylate also known as Menthyl
PCA (under the tradename QUESTICES.RTM. available from Givaudan).
Optional components which are liquids are included in determining
the total amount of liquid phase present
Method of Manufacture
[0140] Another aspect of the invention relates to a method of
manufacturing a lubricating member. The method comprises the steps
of: [0141] i) Providing a particulate of said water soluble
polymer, [0142] ii) Melting said lipophilic structurant, preferably
at a temperature of less than about 90.degree. C., more preferably
between about 45.degree. C. and about 60.degree. C. whilst mixing,
[0143] iii) Adding said liquid phase and optional ingredients,
[0144] iv) Optionally cooling the mixture, preferably to about
60.degree. C. or less and then adding said water soluble polymer
particles to said melted lipophilic structurant and liquid phase
mixture and mixing, [0145] v) Adding other optional ingredients and
mixing, [0146] vi) Transferring, for example pouring the resultant
mixture into a mould or container, [0147] vii) Optionally cooling
to about 25.degree. C.
Hair Removal Head
[0148] According to some embodiments of the invention, the
lubricating member finds particular application for hair removal
devices. Hair removal devices generally comprise a hair removal
head and a handle or grip portion, upon which the hair removal head
is mounted. The hair removal device can be manual or power driven
and can be used for wet and/or dry application. The hair removal
head can include a wide scraping surface such as where the hair
removal device is used with a depilatory, or be a razor cartridge
or foil where the device is a shaving razor. The hair removal head
may be replaceable and/or pivotally connected to a cartridge
connecting structure and in turn or independently (e.g. permanently
fixed) to a handle. In some embodiments, the cartridge connecting
structure includes at least one arm to releasably engage the hair
removal head.
[0149] The hair removal head typically comprises one or more
elongated edges usually positioned between a first and second end,
said one or more elongated edges comprising a tip extending towards
said first end. Where the hair removal head is a razor cartridge
the one or more elongated edges can include blades. For example,
U.S. Pat. No. 7,168,173 generally describes a FUSION.RTM. razor
that is commercially available from The Gillette Company and which
includes a razor cartridge with multiple blades. Additionally, the
razor cartridge may include a guard as well as a skin engaging
member. A variety of razor cartridges can be used in accordance
with the present invention. Non limiting examples of suitable razor
cartridges, with and without fins, guards, and/or shave aids,
include those marketed by The Gillette Company under the
FUSION.RTM., VENUS.RTM. product lines as well as those disclosed in
U.S. Pat. Nos. 7,197,825, 6,449,849, 6,442,839, 6,301,785,
6,298,558; 6,161,288, and U.S. Patent Publ. 2008/060201. Those of
skill in the art will understand that the lubricating member can be
used with any currently marketed system or disposable razor,
including those having 2, 3, 4 or 5 blades. In such a case, the
hair removal device is a razor, the hair removal head is a razor
cartridge and the one or more elongated edges are blades. Another
example of a hair removal device is a scraping tool for use with a
hair removal composition, i.e. a depilatory.
[0150] In some embodiments, said at least one lubricating member is
located on the portion of the cartridge that contacts skin during
the hair removal process, forward and/or aft of the blades. A
feature "forward" of the one or more elongated edges, for example,
is positioned so that the surface to be treated with by the hair
removal device encounters the feature before it encounters the
elongated edges. A feature "aft" of the elongated edge is
positioned so that the surface to be treated by the hair removal
device encounters the feature after it encounters the elongated
edges. Where more than one lubricating member is provided on the
hair removal device, they can be the same (identical) or different,
in terms of physical shape/structure and/or chemical composition,
and one or more of them may comprise the spray coated
particulate.
[0151] In some particular embodiments, a plurality (e.g. 2, a first
and second) of lubricating members may be provided on the hair
removal head, with the first skin engaging member comprising the
same composition or different. These lubricating members may be
placed collectively (for example adjacent to one another) ahead of
or behind the elongated edges (e.g. blades on a razor cartridge),
including side by side, or separately with one ahead of the
elongated edges and the other behind.
[0152] The lubricating member may be free standing utilizing a
suitable attachment means such as adhesive or may be contained at
least partially within a container.
[0153] The container typically has a base and at least one side
wall extending vertically preferably perpendicular from said base
and a skin contacting surface. In a preferred embodiment said
container comprises a base and at least 2 side walls, more
preferably at least 4 side walls, preferably said walls completely
enclosing the base. Typically, each pair of walls are substantially
parallel and preferably one pair of walls is substantially parallel
to the at least two blades. Alternatively, the base may be enclosed
by a one piece single wall. The container may form any shape
including substantially rectangular, or oval. The container
typically has a front wall adjacent the blades and a rear wall,
preferably substantially parallel thereto and furthest from said
blades.
[0154] The container is preferably further provided with at least
one dispensing orifice for dispensing the lubricating member onto
the skin during use. In one embodiment the container is provided
with a top extending substantially perpendicular from the side wall
(s). The container would in such an embodiment typically have a
receiving region for receiving the lubricating member. The top may
be substantially parallel to the base or it may be provided at an
angle such that the distance of the top from the blade plane
increases or decreases as the distance of the container from the
blades increases. In one embodiment the height of the top of the
container increases in distance from the blade plane as the
container distance from the blades increases. In an alternative
embodiment the height of the top of the container decreases in
distance from the blade plane as the container distance from the
blade increases.
[0155] The orifice may be of any shape and may, for example, have a
cross sectional area of from about 0.00324 to about 1.613 cm.sup.2.
Small orifices can also be provided with cross sectional area of
from about 0.0324 to about 0.324 cm.sup.2, or from about 0.0645 to
about 0.16135 cm.sup.2. Larger orifices can have cross sectional
areas of from about 0.324 to about 1.613 cm.sup.2, or from about
0.645 to about 1.29 cm.sup.2. The container may comprise a single
orifice or multiple orifices which may be large and or small. In
one embodiment the container comprises at least two orifices.
Combinations of small and large orifices can also be provided on
the same skin engaging member, or on separate members on the same
cartridge, depending on the desired dispense rate and amount of
exposure of the lubricating material to water. In one embodiment
the top of the container is provide with one preferably two
orifices, more preferably two substantially identical orifices
adjacent one another.
[0156] In some embodiments, at least a portion of said container is
not linear for example angled or curvilinear. Curvilinear as
defined herein means that at least a portion is curved such that it
does not form a straight line. Where at least two containers are
provided, they can also be positioned relative to one another such
that they do not form a straight line. Alternatively, the curved or
angled nature is such that it forms at least a partial ring. A
partial ring, as defined herein, means that the structure has at
least two curved or angled sections which are concave to form an
inner region. The partial ring can also include a curved or angled
portion which is positioned convex to said inner region. One or
more of said containers may also be positioned relative to one
another to form a full ring.
[0157] The container can be formed of a variety of materials. The
container may, preferably be for example, provided from a non-water
soluble material such that it does not degrade or dissolve during
normal use. The container typically has sufficient mechanical
strength and rigidity to provide adequate mechanical strength to
the entire skin engaging member, both as initially produced and
after a significant amount of lubricating material has leached out
of the container. Alternatively or in addition a further
reinforcing member may also be utilized. In some embodiments, the
container comprises a base and one or more side walls, forming a
receiving region, or channel, onto or into which the lubricating
material is placed.
[0158] The container may be made of a water-insoluble polymer,
particularly a thermoplastic resin. Thermoplastic resins are those
materials which can be extruded or molded into a shape and are
resilient under normal environmental conditions such as contact
with water, even up to normal household hot water temperatures (for
example up to 125.degree. C.); normal wear and tear by consumers
during use; device assembly and shipping, etc. Thermoplastic resins
suitable for use in the carrier include polystyrene, high impact
polystyrene (polystyrene-butadiene), polypropylene, filled
polypropylene, polyethylene, nylon ethylene vinyl acetate, and
blends such as 70% nylon/30% polyethylene oxide, 60%
polystyrene/40% polyethylene oxide butadiene styrene copolymer,
polyacetal, acrylonitrile-butadiene styrene copolymer, and mixtures
thereof. The preferred resins are high impact polystyrene,
polystyrene, ethylene vinyl acetate (EVA), and mixtures
thereof.
[0159] In some embodiments, the cartridge comprises a guard
comprising at least one elongated flexible protrusion to engage a
user's skin. The at least one flexible protrusion may comprise
flexible fins generally parallel to said one or more elongated
edges. Said at least one flexible protrusion may additionally or
alternatively comprise flexible fins comprising at least one
portion which is not generally parallel to said one or more
elongated edges. Non-limiting examples of suitable guards include
those used in current razor blades and include those disclosed in
U.S. Pat. Nos. 7,607,230 and 7,024,776; (disclosing
elastomeric/flexible fin bars); 2008/0034590 (disclosing curved
guard fins); 2009/0049695A1 (disclosing an elastomeric guard having
guard forming at least one passage extending between an upper
surface and a lower surface). In some embodiments, said lubricating
member is positioned on the cartridge aft of the guard and forward
of said elongated edge. In another embodiment, the lubricating
member is positioned on the cartridge forward of the guard. This
embodiment can be particularly useful to deliver the lubricating
member prior to contact with the guard.
Test Methods
Molecular Weight Distribution
[0160] The weight average molecular weight (Mw) is measured using
gel permeation chromatography (GPC) and multi-angle laser light
scattering (MALLS). The GPC/MALLS system used for the analysis is
comprised of a Waters Alliance e2695 Separations Module, a Waters
2414 interferometric refractometer, and a Wyatt Heleos II 18 angle
laser light scattering detector. The column set used for separation
is purchased from TOSOH Biosciences LLC, King of Prussia, Pa. and
included: Guard Column TSKgel G1000Hx-GMHxl-L (Cat #07113), TSKgel
G3000Hxl (Cat #0016136), TSKgel G2500Hxl (Cat #0016135), and TSKgel
G2000Hxl (Cat #0016134). Wyatt ASTRA 6 software was used for
instrument operation and data analysis. The 90 degree light
scattering detection angle is calibrated using filtered, anhydrous
toluene. The remaining detection angles are normalized using an
isotropic scatterer in THF. To verify instrument performance of the
MALLS and RI (refractive index) detectors, a poly(styrene) standard
with a known Mw and known dn/dc (in the mobile phase) is run.
Acceptable performance of the MALLS and RI detectors gives a
calculated Mw within 5% of the reported Mw of the poly(styrene)
standard and a mass recovery between 95 and 105%.
[0161] To complete the GPC/MALLS analysis, a value of dn/dc is
needed. The value of dn/dc is measured as follows. The RI detector
is thermostated to 35 degrees Celsius. A series of five
concentration standards of the metathesized unsaturated polyol
ester in THF is prepared in the range 0.5 mg/ml to 5.5 mg/ml. A THF
blank is injected directly into the refractive index detector,
followed by each of the metathesized unsaturated polyol ester
concentration standards, and ending with another THF blank. The
volume of each sample injected is large enough to obtain a flat
plateau region of constant differential refractive index versus
time; a value of 1.0 ml is typically used. In the ASTRA software, a
baseline is constructed from the initial and final THF injections.
For each sample, peak limits are defined and the concentrations
entered to calculate dn/dc in the ASTRA software. For the
metathesized canola oil of Example 2 in THF, a dn/dc value of 0.072
ml/g is obtained.
[0162] For the GPC/MALLS analysis of a metathesized unsaturated
polyol ester, a total of three samples are evaluated: the
metathesized unsaturated polyol ester, a non-metathesized
unsaturated polyol ester (glycerol trioleate [122-32-7],
Sigma-Aldrich, Milwaukee, Wis.), and a representative olefin
(1-octadecene, [112-88-9], Sigma-Aldrich, Milwaukee, Wis.). The GPC
samples are dissolved in tetrahydrofuran (THF). Concentrations for
the metathesized unsaturated polyol ester are approximately 20
mg/ml, and concentrations for the non-metathesized unsaturated
polyol ester and olefin are approximately 5 mg/ml. After all the
material is dissolved, each solution is filtered by a 0.45 micron
nylon filter disk into a GPC autosampler vial for analysis. The GPC
column temperature is at room temperature, approximately 25 degrees
Celsius. HPLC grade THF is used as the mobile phase and is
delivered at a constant flow rate of 1.0 ml/min. The injection
volume is 100 microliters and the run time is 40 minutes. Baselines
are constructed for all signals. Peak elution limits include
metathesized unsaturated polyol ester and non-metathesized
unsaturated polyol ester, but exclude later eluting residual
olefin. The retention times of the non-metathesized unsaturated
polyol ester and olefin were determined from the separate injection
runs of both the non-metathesized unsaturated polyol ester and
olefin. Baselines and scattering detectors are reviewed.
[0163] Oligomer Index
[0164] The oligomer index of the metathesized unsaturated polyol
ester is calculated from data that is determined by Supercritical
Fluid Chromatography-Fourier Transform Orbital Trapping Mass
Spectrometry (SFC-Orbitrap MS). The sample to be analyzed is
typically dissolved in methylene chloride or a methylene
chloride-hexane mixture at a concentration of 1000 ppm (1 mg/mL). A
further 25.times.-100.times. dilution is typically made into hexane
(for a final concentration of 10-40 ppm). A volume of 2-7.5 .mu.L
is typically injected on to a SFC column (for example, a
commercially available 3 mm i.d..times.150 mm Ethylpyridine column,
3 .mu.M particle size).
[0165] During the chromatography run, the mobile phase is typically
programmed from 100% carbon dioxide with a gradient of one percent
per minute methanol. The effluent from the column is directed to a
mixing tee where an ionization solution is added. The ionization
medium is typically 20 mM ammonium formate in methanol at a flow of
0.7 mL/min while the SFC flow is typically 1.6 mL/min into the tee.
The effluent from the mixing tee enters the ionization source of
the Orbitrap Mass Spectrometer, which is operated in the heated
electrospray ionization mode at 320.degree. C.
[0166] In one aspect, a hybrid linear ion trap--Orbitrap mass
spectrometer (i.e., the Orbitrap Elite from Thermoelectron Corp.)
is calibrated and tuned according to the manufacturer's guidelines.
A mass resolution (m/.DELTA.m peak width at half height) from
100,000 to 250,000 is typically used. C,H,O compositions of eluting
species (typically associated with various cations, e.g.,
NH.sub.4.sup.+, H.sup.+, Na.sup.+) are obtained by accurate mass
measurement (0.1-2 ppm) and are correlated to metathesis products.
Also, sub-structures may be probed by linear ion trap "MS"
experiments with subsequent accurate-mass analysis in the Orbitrap,
as practiced typically in the art.
[0167] The metathesis monomers, dimers, trimers, tetramers,
pentamers, and higher order oligomers are fully separated by SFC.
The chromatogram based on ion current from the Orbitrap MS may be
integrated, as typically practiced in the art, for each of the
particular oligomer groups including metathesis monomers,
metathesis dimers, metathesis trimers, metathesis pentamers, and
each of the higher order oligomers. These raw areas may then be
formulated into various relative expressions, based on
normalization to 100%. The sum of the areas of metathesis trimers
through the highest oligomer detected is divided by the sum of all
metathesis species detected (metathesis monomers to the highest
oligomer detected). This ratio is called the oligomer index. As
used herein, the "oligomer index" is a relative measure of the
fraction of the metathesized unsaturated polyol ester which is
comprised of trimers, tetramers, pentamers, and higher order
oligomers.
[0168] Iodine Value
[0169] Another aspect of the invention provides a method to measure
the iodine value of the metathesized unsaturated polyol ester. The
iodine value is determined using AOCS Official Method Cd 1-25 with
the following modifications: carbon tetrachloride solvent is
replaced with chloroform (25 ml), an accuracy check sample (oleic
acid 99%, Sigma-Aldrich; IV=89.86.+-.2.00 cg/g) is added to the
sample set, and the reported IV is corrected for minor contribution
from olefins identified when determining the free hydrocarbon
content of the metathesized unsaturated polyol ester.
[0170] Free Hydrocarbon Content
[0171] Another aspect of this invention provides a method to
determine the free hydrocarbon content of the metathesized
unsaturated polyol ester. The method combines gas
chromatography/mass spectroscopy (GC/MS) to confirm identity of the
free hydrocarbon homologs and gas chromatography with flame
ionization detection (GC/FID) to quantify the free hydrocarbon
present.
[0172] Sample Prep: The sample to be analyzed was typically
trans-esterified by diluting (e.g. 400:1) in methanolic KOH (e.g.
0.1N) and heating in a closed container until the reaction was
complete (i.e. 90.degree. C. for 30 min.) then cooled to room
temperature. The sample solution could then be treated with 15%
boron tri-fluoride in methanol and again heated in a closed vessel
until the reaction was complete (i.e. at 60.degree. C. for 30 min.)
both to acidify (methyl orange--red) and to methylate any free acid
present in the sample. After allowing to cool to room temperature,
the reaction was quenched by addition of saturated NaCl in water.
An organic extraction solvent such as cyclohexane containing a
known level internal standard (e.g. 150 ppm dimethyl adipate) was
then added to the vial and mixed well. After the layers separated,
a portion of the organic phase was transferred to a vial suitable
for injection to the gas chromatograph. This sample extraction
solution was analyzed by GC/MS to confirm identification of peaks
matching hydrocarbon retention times by comparing to reference
spectra and then by GC/FID to calculate concentration of
hydrocarbons by comparison to standard FID response factors.
[0173] A hydrocarbon standard of known concentrations, such as 50
ppm each, of typically observed hydrocarbon compounds (i.e.
1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
1-hexadecene, 1-heptadecene, 1-octadecene, dodecane, tridecane,
tetradecane, pentadecane, hexadecane, heptadecane and octadecane)
was prepared by dilution in the same solvent containing internal
standard as was used to extract the sample reaction mixture. This
hydrocarbon standard was analyzed by GC/MS to generate retention
times and reference spectra and then by GC/FID to generate
retention times and response factors.
[0174] GC/MS: An Agilent 7890 GC equipped with a split/splitless
injection port coupled with a Waters QuattroMicroGC mass
spectrometer set up in EI+ ionization mode was used to carry out
qualitative identification of peaks observed. A non-polar DB1-HT
column (15 m.times.0.25 mm.times.0.1 um df) was installed with 1.4
mL/min helium carrier gas. In separate runs, 1 uL of the
hydrocarbon standard and sample extract solution were injected to a
300.degree. injection port with a split ratio of 25:1. The oven was
held at 40.degree. C. for 1 minute then ramped 15 C..degree./minute
to a final temperature of 325.degree. C. which was held for 10
minutes resulting in a total run time of 30 minutes. The transfer
line was kept at 330.degree. C. and the temperature of the EI
source was 230.degree. C. The ionization energy was set at 70 eV
and the scan range was 35-550 m/z.
[0175] GC/FID: An Agilent 7890 GC equipped with a split/splitless
injection port and a flame ionization detector was used for
quantitative analyses. A non-polar DB1-HT column (5 m.times.0.25
mm.times.0.1 um df) was installed with 1.4 mL/min helium carrier
gas. In separate runs, 1 uL of the hydrocarbon standard and sample
extract solution was injected to a 330.degree. injection port with
a split ratio of 100:1. The oven was held at 40.degree. C. for 0.5
minutes then ramped at 40 C..degree./minute to a final temperature
of 380.degree. C. which was held for 3 minutes resulting in a total
run time of 12 minutes. The FID was kept at 380.degree. C. with 40
mL/minute hydrogen gas flow and 450 mL/min air flow. Make up gas
was helium at 25 mL/min. The hydrocarbon standard was used to
create a calibration table in the Chemstation Data Analysis
software including known concentrations to generate response
factors. These response factors were applied to the corresponding
peaks in the sample chromatogram to calculate total amount of free
hydrocarbon found in each sample.
EXAMPLES
[0176] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
[0177] Non-limiting examples of product formulations disclosed in
the present specification are summarized below.
Example 1: Synthesis of Metathesized Canola Oil
[0178] Prior to the metathesis reaction, the RBD (refined,
bleached, and deodorized) canola oil is pre-treated by mixing the
oil with 2% (by weight) bleaching clay (Filtrol F-160, BASF,
Florham Park, N.J.) and heating to 120.degree. C. with a nitrogen
sweep for 1.5 hours. The oil is cooled to room temperature,
filtered through a bed of CELITE.RTM. 545 diatomaceous earth (EMD,
Billerica, Mass.), and stored under inert gas until ready to
use.
[0179] To a round-bottomed flask, the oil is added and sub-surface
sparged with inert gas while mixing and heating to 55.degree. C.
The catalyst is dissolved in 1,2-dichloroethane ([107-06-2], EMD,
Billerica, Mass.) that is stored over 4 .ANG. molecular sieves and
sub-surface sparged with inert gas prior to use. After catalyst
addition to the reaction flask, a vacuum is applied to remove
volatile olefins that are generated. After .about.4 hours reaction
time, the vacuum is broken and the metathesized unsaturated polyol
ester is cooled to room temperature.
[0180] The metathesized canola oil is diluted in hexanes
([110-54-3], EMD, Billerica, Mass.). To the diluted material, 2%
bleaching clay (Filtrol F-160, BASF, Florham Park, N.J.) is added
and mixed for .about.6 hours. The oil is filtered through a bed of
CELITE.RTM. 545 diatomaceous earth. The oil is treated a second
time with 2% bleaching clay (Filtrol F-160, BASF, Florham Park,
N.J.) for .about.6 hours. The oil is filtered through a bed of
CELITE.RTM. 545 diatomaceous earth and then rotary evaporated to
concentrate.
[0181] The metathesized canola oil is then passed through a wipe
film evaporator at 180.degree. C. and <0.5 Torr vacuum to remove
olefins up to and including C-18 chain lengths. Representative
examples are summarized in the table below.
TABLE-US-00003 Pretreated Max Max Canola Oil Catalyst Temperature
Vacuum Example (g).sup.a Catalyst (g) (.degree. C.) (Torr) 1A 500
1.sup.b 0.25 61 7.9 1B 500 2.sup.c 0.25 62 0.6 .sup.aCanola oil
from J. Edwards, Braintree, MA. .sup.bTricyclohexylphosphine
[4,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene]
[2-thienylmethylene]ruthenium (II) dichloride [1190427-50-9]
available as CatMETium RF-3 from Evonik Corporation, Parsippany,
NJ.
.sup.cTricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylid-
ene][2-thienylmethylene] ruthenium(II) dichloride [1190427-49-6]
available as CatMETium RF-2 from Evonik Corporation, Parsippany,
NJ.
[0182] The samples 1A and 1B are analyzed for weight average
molecular weight, iodine value, free hydrocarbon content and
oligomer index, using methods described previously, and are found
to approximately have the following values:
TABLE-US-00004 Free Iodine Hydrocarbon Mw Value content Oligomer
Example (g/mol) (cg/g) (wt %) Index 1A 5,400 85 0.5 0.05 1B 3,900
85 0.5 0.04
Example 2: Remetathesis of Metathesized Unsaturated Polyol
Ester
[0183] Metathesized canola oil, sufficiently stripped of residual
olefins (176.28 g from Example 1A) is blended with pretreated
canola oil (350.96 g, pretreated as described in Example 1) in a
round-bottomed flask. The blend is sub-surface sparged with inert
gas while mixing and heating to 55.degree. C. The catalyst is
dissolved in 1,2-dichloroethane ([107-06-2], EMD, Billerica, Mass.)
that is stored over 4 .ANG. molecular sieves and sub-surface
sparged with inert gas prior to use. After catalyst addition to the
reaction flask, a vacuum is applied to remove volatile olefins that
are generated. After .about.4 hours reaction time, the vacuum is
broken and the metathesized unsaturated polyol ester is cooled to
room temperature.
[0184] The metathesized canola oil is diluted in hexanes
([110-54-3], EMD, Billerica, Mass.). To the diluted material, 2%
bleaching clay (Filtrol F-160, BASF, Florham Park, N.J.) is added
and mixed for .about.6 hours. The oil is filtered through a bed of
Celite.RTM. 545 diatomaceous earth. The oil is treated a second
time with 2% bleaching clay (Filtrol F-160, BASF, Florham Park,
N.J.) for .about.6 hours. The oil is filtered through a bed of
CELITE.RTM. 545 diatomaceous earth and then rotary evaporated to
concentrate.
[0185] The remetathesized canola oil is then passed through a wipe
film evaporator at 180.degree. C. and <0.5 Torr vacuum to remove
olefins up to and including C-18 chain lengths. A representative
example is summarized in the table below.
TABLE-US-00005 Oil Max Max Blend Catalyst.sup.a Temperature Vacuum
Example (g) (g) (.degree. C.) (Torr) 2 500 0.27 65 0.2
.sup.aTricyclohexylphosphine
[4,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene]
[2-thienylmethylene]ruthenium (II) dichloride [1190427-50-9]
available as CatMETium RF-3 from Evonik Corporation, Parsippany,
NJ.
[0186] The sample 2 is analyzed for weight average molecular
weight, iodine value, free hydrocarbon content and oligomer index,
using methods described previously, and is found to approximately
have the following values:
TABLE-US-00006 Free Iodine Hydrocarbon Mw Value content Oligomer
Example (g/mol) (cg/g) (wt %) Index 2 13,000 80 0.5 0.07
Example 3: Synthesis of Metathesized Unsaturated Polyol Esters
[0187] Prior to the metathesis reaction, the RBD (refined,
bleached, and deodorized) oil is pre-treated by mixing the oil with
2% (by weight) bleaching clay (Filtrol F-160, BASF, Florham Park,
N.J.) and heating to 120.degree. C. with a nitrogen sweep for 1.5
hours. The oil is cooled to room temperature, filtered through a
bed of CELITE.RTM. 545 diatomaceous earth (EMD, Billerica, Mass.),
and stored under inert gas until ready to use.
[0188] To a round-bottomed flask, the oil is added and sub-surface
sparged with inert gas while mixing and heating to 55.degree. C.
The catalyst is dissolved in 1,2-dichloroethane ([107-06-2], EMD,
Billerica, Mass.) that is stored over 4 .ANG. molecular sieves and
sub-surface sparged with inert gas prior to use. After catalyst
addition to the reaction flask, a vacuum is applied to remove
volatile olefins that are generated. After .about.4 hours reaction
time, the vacuum is broken and the metathesized unsaturated polyol
ester is cooled to room temperature.
[0189] The metathesized oil is diluted in hexanes ([110-54-3], EMD,
Billerica, Mass.). To the diluted material, 2% bleaching clay
(Filtrol F-160, BASF, Florham Park, N.J.) is added and mixed for
.about.6 hours. The metathesized oil is filtered through a bed of
CELITE.RTM. 545 diatomaceous earth. The metathesized oil is treated
a second time with 2% bleaching clay (Filtrol F-160, BASF, Florham
Park, N.J.) for .about.6 hours. The metathesized oil is filtered
through a bed of CELITE.RTM. 545 diatomaceous earth and then rotary
evaporated to concentrate.
[0190] The metathesized unsaturated polyol ester is then passed
through a wipe film evaporator at 180.degree. C. and <0.5 Torr
vacuum to remove olefins up to and including C-18 chain lengths.
Representative examples are summarized in the table below.
TABLE-US-00007 Max Starting Pretreated Temper- Max unsaturated Oil
Catalyst.sup.a ature Vacuum Example polyol ester (g) (g) (.degree.
C.) (Torr) 3A High erucic 500 0.25 61 7.9 acid rapeseed oil 3B
Blend of 500 (250 g 0.25 61 7.9 High erucic HEAR oil acid and 250 g
rapeseed oil canola oil) and canola oil, 50/50 by weight 3C High
oleic 500 0.25 61 7.9 soybean oil .sup.aTricyclohexylphosphine
[4,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene]
[2-thienylmethylene]ruthenium (II) dichloride [1190427-50-9]
available as CatMETium RF-3 from Evonik Corporation, Parsippany,
NJ.
Example 4
[0191] Hydrogenations are performed in a T316 stainless steel, 600
ml Parr reactor (Model Number 4563) containing internal cooling
coils and a stir shaft with 2 impellers comprised of 4 blades
each.
[0192] The metathesized unsaturated polyol ester (approximately 200
g) is dissolved in hexanes (120 ml, [110-54-3], EMD, Billerica Ma).
To this solution is added a slurry of Nickel on Silica (20 g,
[7440-02-0], Catalog #28-1900, Strem Chemicals, Inc., Newburyport,
Mass.). The slurried mixtures is transferred via vacuum to the Parr
reactor. The mixture is degassed with several vacuum/nitrogen fill
cycles. Then with stirring (800-900 rpm), hydrogen gas (550-650
psig, [1333-74-0], UHP grade, Wright Brothers, Inc., Montgomery,
Ohio) is charged to the reactor. The reaction is heated at
150.degree. C. and hydrogen gas pressure reduction monitored until
constant (.about.12 hours).
[0193] The reaction is cooled to 60.degree. C. and drained from the
reactor. The reactor is rinsed with methyl tert-butyl ether
([1634-04-4], EMD, Billerica, Mass.) and combined with the solid
hydrogenated metathesized polyol ester. A hot filtration is then
performed to remove the catalyst, followed by vacuum to remove all
residual solvent. Fully hydrogenated materials are obtained using
the method above. Lower hydrogenation levels are obtained by
decreasing the reaction temperature to 125 degrees Celsius using 5
grams of catalyst and reducing the reaction time and hydrogen
consumed. Iodine Value (IV) is measured, as described
elsewhere.
Example 5
[0194] The metathesis monomers, dimers, trimers, tetramers,
pentamers, and higher order oligomers from the product in Example 2
are fully separated by SFC using the method described above. The
individual SFC fractions are collected and trimers, tetramers, and
higher order oligomers are combined. The oligomer index of this
sample is about 1.
[0195] Example Lubricating Member Formulations
TABLE-US-00008 Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple
4 ple 5 Ingredient % w/w % w/w % w/w % w/w % w/w Polyox WSR coag --
10 20 10 -- Polyox N60k 30 -- -- -- -- Silwet L7210 * 20 40 -- --
10 Softcat SL5 ** -- -- 10 -- -- Nhance 3196 *** -- 10 -- -- --
Petrolatum -- -- 10 -- -- Methathesized 20 10- 30 35 35 unsaturated
polyol ester Cetyl alcohol 30 -- 25 55 55 Stearyl alcohol 25 -- --
Multiwax 180MH # -- 5 5 -- -- Total 100 100 100 Suppliers: *
Momentive, ** Dow Chemicals, *** Ashland, $ Dow Corning, #
Sonnenborn
[0196] Formulation Examples 1-5 were prepared as follows: [0197] 1.
Sanitize all equipment [0198] 2. Turn on water bath/vessel jacket
to 85.degree. C. [0199] 3. Add lipophilic structurants (cetyl
alcohol, stearyl alcohol, multiwax 180MH) and stir with overhead
stirrer until completely melted [0200] 4. Add oil phase ingredients
(Silwet, petrolatum, DC200, shea butter, methathesised polyol
esters) and mix until fully liquid [0201] 5. Reduce heat to
55.degree. C. and add powder ingredients (Polyox, Nhance 3196,
SoftCat) until fully dispersed. [0202] 6. Transfer mixture into a
mould [0203] 7. Assemble part onto razor cartridge.
[0204] Combinations:
[0205] An example is below:
A. A lubricating member comprising, [0206] a) a liquid phase
comprising a metathesized unsaturated polyol ester, said
metathesized unsaturated polyol ester having one or more of the
following properties: [0207] (i) a weight average molecular weight
of from about 5,000 Daltons to about 50,000 Daltons; [0208] (ii) an
oligomer index from greater than 0 to 1; [0209] (iii) an iodine
value of from about 30 to about 200; [0210] b) a lipophilic
structurant; and [0211] c) Optionally a water soluble polymer. B. A
lubricating member according to Paragraph A, wherein said
metathesized unsaturated polyol ester having a weight average
molecular weight of from about 5,000 Daltons to about 50,000
Daltons. C. A lubricating member according to Paragraph A, wherein
said metathesized unsaturated polyol ester has an iodine value of
from about 30 to about 200. D. A lubricating member comprising, a)
a liquid phase comprising a metathesized unsaturated polyol ester,
said metathesized unsaturated polyol ester having a weight average
molecular weight of from about 2,000 Daltons to about 50,000
Daltons; and one or more of the following properties: [0212] (i) a
free hydrocarbon content, based on total weight of metathesized
unsaturated polyol ester of from about 0% to about 5%; [0213] (ii)
an oligomer index from greater than 0 to 1; [0214] (iii) an iodine
value of from about 8 to about 200; b) a lipohilic structurant; and
c) optionally a water soluble polymer E. A lubricating member
according to Paragraph D, wherein said metathesized unsaturated
polyol ester has an iodine value of from about 10 to about 200. F.
A lubricating member according to Paragraph D, wherein said
metathesized unsaturated polyol ester has an oligomer index from
about 0.001 to 1. G. A lubricating member according to Paragraph A,
wherein said metathesized unsaturated polyol ester has a free
hydrocarbon content, based on total weight of metathesized
unsaturated polyol ester, of from about 0% to about 5%. H. A
lubricating member according to Paragraph A, said composition
comprising, based on total composition weight, from about 0.1% to
about 50% of said metathesized unsaturated polyol ester. I. A
lubricating member according to Paragraph A, wherein the
metathesized unsaturated polyol ester is metathesized at least
once. J. A lubricating member according to Paragraph A, wherein
said metathesized unsaturated polyol ester is derived from a
natural polyol ester and/or a synthetic polyol ester, preferably
said natural polyol ester is selected from the group consisting of
a vegetable oil, a animal fat, a algae oil and mixtures thereof;
and said synthetic polyol ester is derived from a material selected
from the group consisting of ethylene glycol, propylene glycol,
glycerol, polyglycerol, polyethylene glycol, polypropylene glycol,
poly (tetramethylene ether) glycol, pentaerythritol,
dipentaerythritol, tripentaerythritol, trimethylolpropane,
neopentyl glycol, a sugar, preferably, sucrose, and mixtures
thereof. K. A lubricating member according to Paragraph A, wherein
said metathesized unsaturated polyol ester is selected from the
group consisting of metathesized Abyssinian oil, metathesized
Almond Oil, metathesized Apricot Oil, metathesized Apricot Kernel
oil, metathesized Argan oil, metathesized Avocado Oil, metathesized
Babassu Oil, metathesized Baobab Oil, metathesized Black Cumin Oil,
metathesized Black Currant Oil, metathesized Borage Oil,
metathesized Camelina oil, metathesized Carinata oil, metathesized
Canola oil, metathesized Castor oil, metathesized Cherry Kernel
Oil, metathesized Coconut oil, metathesized Corn oil, metathesized
Cottonseed oil, metathesized Echium Oil, metathesized Evening
Primrose Oil, metathesized Flax Seed Oil, metathesized Grape Seed
Oil, metathesized Grapefruit Seed Oil, metathesized Hazelnut Oil,
metathesized Hemp Seed Oil, metathesized Jatropha oil, metathesized
Jojoba Oil, metathesized Kukui Nut Oil, metathesized Linseed Oil,
metathesized Macadamia Nut Oil, metathesized Meadowfoam Seed Oil,
metathesized Moringa Oil, metathesized Neem Oil, metathesized Olive
Oil, metathesized Palm Oil, metathesized Palm Kernel Oil,
metathesized Peach Kernel Oil, metathesized Peanut Oil,
metathesized Pecan Oil, metathesized Pennycress oil, metathesized
Perilla Seed Oil, metathesized Pistachio Oil, metathesized
Pomegranate Seed Oil, metathesized Pongamia oil, metathesized
Pumpkin Seed Oil, metathesized Raspberry Oil, metathesized Red Palm
Olein, metathesized Rice Bran Oil, metathesized Rosehip Oil,
metathesized Safflower Oil, metathesized Seabuckthorn Fruit Oil,
metathesized Sesame Seed Oil, metathesized Shea Olein, metathesized
Sunflower Oil, metathesized Soybean Oil, metathesized Tonka Bean
Oil, metathesized Tung Oil, metathesized Walnut Oil, metathesized
Wheat Germ Oil, metathesized High Oleoyl Soybean Oil, metathesized
High Oleoyl Sunflower Oil, metathesized High Oleoyl Safflower Oil,
metathesized High Erucic Acid Rapeseed Oil, and mixtures thereof.
L. A lubricating member for a razor cartridge according to
Paragraphs A or D comprising: from 20% to 90%, preferably from 20%
to 80% by weight of a lipid phase comprising a) from 10% to 70% by
weight of the lubricating member of a lipophilic structurant or
mixture thereof, b) from 10% to 70% by weight of the lubricating
member of a liquid phase, wherein said liquid phase has a melting
point below 45.degree. C., and wherein said lubricating member
further optionally comprises from 1% to 40% by weight of a water
soluble polymer or mixture thereof. M. A lubricating member
according to Paragraph L, wherein said lipophilic structurant has a
melting point of from 45.degree. C. to less than 60.degree. C. N. A
lubricating member according to Paragraph L, wherein said
lipophilic structurant has a melting point of from 45.degree. C. to
5.degree. C. less than the melting point of said water soluble
polymer. O. A lubricating member according to Paragraph L, wherein
said at least 90% of said water soluble polymer is in the form of
discrete particulates dispersed within said lipophilic structurant.
P. A lubricating member according to Paragraph L, wherein said
water soluble polymer has a melting point of 60.degree. C. or
greater. Q. A lubricating member for a razor cartridge according to
Paragraphs A or D, wherein said liquid phase comprises a component
selected from natural oil, synthetic oil, natural butters,
triglycerides, petrolatum, silicones and mixtures thereof. R. A
lubricating member for a razor cartridge according to Paragraphs A
or D, wherein said liquid phase comprises a material selected from
capric and or caprylic triglycerides, olive oil, shea butter, cocoa
butter, isopropyl isostearate, petrolatum, dimethicone, phenylated
silicones, silicone polyether block polymer and mixtures thereof.
S. A lubricating member for a razor cartridge according to
Paragraph R, wherein said liquid phase comprises a silicone
polyether block copolymer or mixtures thereof. T. A lubricating
member for a razor cartridge according to Paragraphs A or D,
wherein said liquid phase has a melting point of less than
40.degree. C., more preferably less than 30.degree. C., most
preferably 25.degree. C. or less. U. A lubricating member for a
razor cartridge according to Paragraphs A or D, wherein said
lipophilic structurant is selected from C14-C20 alcohols,
microcrystalline wax, stearyloxytrimethylsilane and mixtures
thereof, and is preferably selected from cetyl alcohol, stearyl
alcohol or mixtures thereof. V. A lubricating member for a razor
cartridge according to Paragraphs A or D, wherein said water
soluble polymer comprises a polyethylene oxide polymer. W. A
lubricating member for a razor cartridge according to Paragraphs A
or D, comprising from 25% to 35% of said lipophilic structurant,
from 10% to 40% of said liquid phase and from 20% to 30% of said
water soluble polymer. X. A lubricating member for a razor
cartridge according to any Paragraphs A or D, wherein said member
comprises less than 5% by weight, preferably less than 1% by
weight, more preferably is substantially free of a water insoluble
polymeric structurant. Y. A hair removal cartridge comprising a
lubricating member according to any one of Paragraphs A-X. Z. A
method of manufacturing a lubricating member according to Paragraph
A, comprising the steps of: [0215] i) providing a particulate of
said water soluble polymer, [0216] ii) melting said lipophilic
structurant, [0217] iii) adding said liquid phase and mixing,
[0218] iv) adding said water soluble polymer particles to said
melted lipophilic structurant and liquid phase mixture and mixing,
[0219] v) adding optional ingredients and mixing, [0220] vi)
transferring the resultant mixture into a mould or container, and
[0221] vii) optionally cooling to 25.degree. C.
[0222] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm."
[0223] Every document cited herein, including any cross referenced
or related patent or application and any patent application or
patent to which this application claims priority or benefit
thereof, is hereby incorporated herein by reference in its entirety
unless expressly excluded or otherwise limited. The citation of any
document is not an admission that it is prior art with respect to
any invention disclosed or claimed herein or that it alone, or in
any combination with any other reference or references, teaches,
suggests or discloses any such invention. Further, to the extent
that any meaning or definition of a term in this document conflicts
with any meaning or definition of the same term in a document
incorporated by reference, the meaning or definition assigned to
that term in this document shall govern.
[0224] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
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