U.S. patent application number 14/643338 was filed with the patent office on 2015-07-02 for compositions comrising solubilized essential oils.
The applicant listed for this patent is E I DU PONT DE NEMOURS AND COMPANY. Invention is credited to GYORGYI FENYVESI, RAJA HARI POLADI, HARI BABU SUNKARA.
Application Number | 20150182446 14/643338 |
Document ID | / |
Family ID | 43970716 |
Filed Date | 2015-07-02 |
United States Patent
Application |
20150182446 |
Kind Code |
A1 |
FENYVESI; GYORGYI ; et
al. |
July 2, 2015 |
COMPOSITIONS COMRISING SOLUBILIZED ESSENTIAL OILS
Abstract
Provided are methods for extracting flavor and fragrance
materials from natural plant materials, using poly(trimethylene
ether) glycol homopolymers and copolymers. The poly(trimethylene
ether) glycol homopolymers and copolymers act as solubilizers for
essential oils, and can be used to provide compositions having a
variety of uses in applications such as cosmetics, personal care
products, and industrial cleaning products.
Inventors: |
FENYVESI; GYORGYI;
(WILMINGTON, DE) ; POLADI; RAJA HARI; (BEAR,
DE) ; SUNKARA; HARI BABU; (HOCKESSIN, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
E I DU PONT DE NEMOURS AND COMPANY |
WILMINGTON |
DE |
US |
|
|
Family ID: |
43970716 |
Appl. No.: |
14/643338 |
Filed: |
March 10, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12938452 |
Nov 3, 2010 |
8486458 |
|
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14643338 |
|
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61257866 |
Nov 4, 2009 |
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Current U.S.
Class: |
424/745 ;
424/725; 424/748; 424/764 |
Current CPC
Class: |
A23L 27/13 20160801;
A61K 2800/10 20130101; A61P 17/00 20180101; A23L 27/11 20160801;
A61K 8/922 20130101; A23L 33/105 20160801; A61Q 19/00 20130101;
A61K 8/86 20130101; A23L 27/12 20160801; C11B 9/025 20130101; A61P
15/16 20180101 |
International
Class: |
A61K 8/97 20060101
A61K008/97; A61Q 19/00 20060101 A61Q019/00 |
Claims
1. A personal care or cosmetic formulation comprising an essential
oil, prepared by a method comprising: contacting the essential oil
with a composition comprising one or more esters of either a
poly(trimethylene ether) glycol homopolymer or copolymer, wherein
the one or more esters of the homopolymer or copolymer have a
number average molecular weight within the range of about 134 to
about 2000 to form a solution or microemulsion.
2. A personal care or cosmetic formulation comprising a solution or
microemulsion prepared by the method of claim 1.
3. A personal care or cosmetic formulation of claim 2, selected
from the group consisting of: skin care products, tooth pastes,
deodorants, anti-perspirants, insect repellants, anesthetics,
shampoos, hair conditioners, sun care products, shower gels, soaps,
cleansers, moisturizers, hair styling gels, hair anti-dandruff
compositions, hair growth promoter compositions, hair colorant
compositions, hair bleaching agent compositions, hair anti-frizzing
agent compositions, hair relaxer compositions, shaving product
compositions, lubricating gel compositions, spermicidal gel
compositions, and skin cleaning compositions.
4. A composition comprising at least one essential oil and one or
more esters of a poly(trimethylene ether) glycol homopolymer or
copolymer, wherein the one or more homopolymer or copolymer, or
esters thereof, have a number average molecular weight within the
range of about 250 to about 650, and wherein the composition has a
surface tension of at least 38.0 dynes/cm.
Description
RELATED APPLICATIONS
[0001] This application is a divisional application of U.S. Ser.
No. 12/938,452, filed on Nov. 3, 2010. This application is also
related to U.S. Ser. No. 13/917,025, filed Jun. 13, 2013.
TECHNICAL FIELD
[0002] The present invention is directed to methods using
polytrimethylene ether glycols for extracting flavor and fragrance
materials from natural plant materials and as solubilizers for
essential oils, and compositions made by the methods. The present
invention is also directed to methods of using polytrimethylene
ether glycols as a cleaning agent.
BACKGROUND
[0003] Solvents derived from petrochemicals are commonly used to
extract flavor and fragrance materials from botanical sources for
use in adding aroma to consumer products. Solvents are also used to
dissolve essential oils. Environmental, market, esthetic and other
factors have recently led to desire on the part of consumers and
producers for alternatives to petrochemicals as sources for
solvents and other components in a variety of products.
[0004] The "Common Fragrance and Flavor Materials" (Preparation,
Properties and Uses, 5.sup.th Ed. Horst Surburg and Johannes Panten
Copyright .COPYRGT. WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
discloses methods for the isolation of natural fragrance and flavor
concentrates. Major methods used to concentrate flavor and
fragrance materials include distillation, mechanical separation and
solvent extraction.
[0005] Essential oils can be obtained by distillation of plant
materials with water or steam. After condensation of the water
phase, the water separates from the essential oils. The essential
oils can be used directly as starting material for flavors and
fragrances or can be highly diluted with certain solvents.
Distillates can be obtained by the distillation of plant materials
with water-ethyl alcohol mixtures, and the products of the
distillation contain ethanol. Alcohol, however, is not desirable
for some products, and can cause skin irritants for some
individuals. While an aqueous solvent would be desirable, many
essential oils and other botanical materials are not water-soluble.
There are certain plant materials (e.g. jasmine) for which
distillation cannot be used successfully because the heat treatment
would deteriorate the aroma materials; therefore solvent extraction
is used to obtain flavor and fragrances from such plants.
[0006] It is generally desirable to avoid the use of volatile
organic compounds (VOC) in products such as personal care products.
Also other petrochemical solvents are broadly used for plant
extraction as hexane, toluene and petroleum ether. These solvents,
though are effective to extract flavor and fragrance materials from
plants, but can be difficult to remove completely, and. therefore
the final products can contain undesirable odor and harmful or
toxic ingredients, and may cause skin irritation or other health
related problems.
[0007] Water-based microemulsions containing perfumes or flavors,
have been developed, as disclosed, for example, in U.S. Pat. No.
6,403,109. However, microemulsions rely on the use of large amounts
of surfactants, which also may be undesirable for some consumer
products. Silicones, which are also present in the emulsions
disclosed in U.S. Pat. No. 6,403,109, may also be undesirable in
some products.
[0008] A need remains for materials that are non-petroleum based,
non-volatile, non-toxic, non-hazardous and biodegradable, and have
high efficacy to extract flavor and fragrance materials from plants
and to solubilize essential oils and other botanical extracts for
use in consumer and industrial products. It is also desirable to
have methods that are simple and safe, and eliminate the need for
removal of high VOC petroleum based solvents. It is further
desirable to be able to use renewably sourced and biodegradable
materials in consumer and industrial products containing botanical
extracts.
SUMMARY OF THE INVENTION
[0009] One aspect of the present invention is a method for
extracting essential oil from a plant comprising a) contacting
plant material with a composition comprising one or more of
poly(trimethylene ether) glycol homopolymer or copolymer, wherein
the homopolymer or copolymer has a molecular weight within the
range of about 134 to about 2000, to form an extract; and b)
isolating the extract from the plant material by filtration.
[0010] Another aspect of the present invention is method for
solubilizing an essential oil, comprising contacting the essential
oil with a composition comprising one or more of poly(trimethylene
ether) glycol homopolymer or copolymer, wherein the homopolymer or
copolymer has a molecular weight within the range of about 134 to
about 2000 to form a solution or microemulsion.
[0011] Another aspect of the present invention is an essential oil,
a solution or a microemulsion prepared by the above methods, and a
personal care or cosmetic formulation thereof.
[0012] Another aspect of the present invention is composition
comprising an essential oil and one or more of poly(trimethylene
ether) glycol homopolymer or copolymer, wherein the homopolymer or
copolymer has a molecular weight within the range of about 134 to
about 2000, and wherein the composition has a surface tension of at
least 38.0.
[0013] These and other aspects of the present invention will be
apparent to a person skilled in the art in view of the following
description and the appended claims.
DETAILED DESCRIPTION
[0014] Unless otherwise stated, the following terms as used herein
have the following meanings.
[0015] An "extractant" is an agent used to isolate or extract
desirable substances from natural plant materials
[0016] An "extract" is a composition obtained from a substance,
primarily by chemical or mechanical action. The extract can contain
non-volatile as well as volatile components.
[0017] A "concrete" is an extraction of fresh natural plant
materials obtained with non-polar organic solvents
[0018] A "tincture" is an ethanol or ethanol-water mixture
extraction in which the solvent is left as a diluent.
[0019] A "resinoid" is a solid or semi-solid material similar to
concrete but prepared from exudates by extraction and purification
with a solvent.
[0020] "Essential oils" are the volatile, lipophilic substances
obtained from plant materials (such as, for example, shrubs,
flowers, trees, roots, bark, and seeds) that are mainly
hydrocarbons or monofunctional compounds derived from mono- and
sesquiterpenes, phenylpropanoids, amino acids and from fatty
acids
[0021] A "solubilizer" is an agent used to dissolve essential oils
or other botanical extracts
[0022] "VOC" means the volatile organic compounds
[0023] A "microemulsion" is a thermodynamically stable colloidal
system, wherein the particles have average radii of about 10
nm.
[0024] The present invention provides methods and compositions for
extracting and solubilizing essential oils of plant sources, or
other botanical extracts, such as flavor and fragrance materials,
using a polytrimethylene ether glycol as an extractant or
solubilizer. In some embodiments, the polytrimethylene ether glycol
is renewably sourced.
[0025] Polytrimethylene ether glycol is typically prepared by
polycondensation of monomers comprising 1,3-propanediol, typically
in the presence of an acid catalyst, thus resulting in polymers or
copolymers containing a --(CH.sub.2CH.sub.2CH.sub.2O)-- linkage
(e.g., trimethylene ether repeating units). Typically, at least 50%
of the repeating units are trimethylene ether units.
[0026] One source of 1,3-propanediol is via a fermentation process
using a renewable biological source. As used herein, the term
"renewably sourced, when applied to poly(trimethylene ether) glycol
homopolymer or copolymer, refers to poly(trimethylene ether) glycol
homopolymer or copolymer made from 1,3-propanediol derived from a
renewable biological source. As an illustrative example,
biochemical routes to 1,3-propanediol (PDO) are known in the art
that utilize feedstocks produced from biological and renewable
resources such as corn feed stock. For example, bacterial strains
able to convert glycerol into 1,3-propanediol are found in the
species Klebsiella, Citrobacter, Clostridium, and Lactobacillus.
The technique is disclosed in several patents, including U.S. Pat.
No. 5,633,362, U.S. Pat. No. 5,686,276 and U.S. Pat. No. 5,821,092
(the disclosures of which are incorporated by reference herein for
all purposes as if fully set forth). For example, U.S. Pat. No.
5,821,092 discloses, inter alia, a process for the biological
production of 1,3-propanediol from glycerol using recombinant
organisms. The process incorporates E. coli bacteria, transformed
with a heterologous pdu diol dehydratase gene, having specificity
for 1,2-propanediol. The transformed E. coli is grown in the
presence of glycerol as a carbon source and 1,3-propanediol is
isolated from the growth media. Since both bacteria and yeasts can
convert glucose (e.g., corn sugar) or other carbohydrates to
glycerol, the processes disclosed in these publications provide a
rapid, inexpensive and environmentally responsible source of
1,3-propanediol monomer.
[0027] Essential oils useful as flavor and fragrance materials in
the methods and compositions disclosed herein can be obtained from
any plants, trees, algae, fungi or can be synthesized in a
laboratory. Various parts of the plant material can be extracted,
such as, for example, leaves, roots, stems, buds, twigs, rhizomes,
heartwood, bark, resin, flowers, seeds, fruits or, in some
embodiments, the entire plant. Examples of suitable plant families
can include: Anacardiaceae Araceae, Balanopaceae, Balsaminaceae,
Begoniaceae, Boraginaceae, Buxaceae, Caricaceae, Cucurbitaceae,
Clusiaceae, Daphniphyllaceae, Ericaceae, Euphorbiaceae, Fabaceae,
Fagaceae, Hippocastanaceae, Hostaceae, Hydrangeaceae, Labiateae,
Lilaeaceae, Magnoliaceae, Moringaceae, Myristicaceae, Myrtaceae,
Oleaceae, Orchidaceae, Peperomiaceae, Pinaceae, Primulaceae,
Rutaceae. Specific examples of plant and tree species include:
Achillea millefolium, Aesculus chinensis, Allium sativum, Artemisia
apiacea, Astrocaryum murumuru, Bactris gasipaes, Benincasa hispida,
Celastrus paniculatus, Cetraria islandica, Chenopodium quinoa,
Cinchona succirubra, Citrus bergamia, Citrus reticulata, Citrus
sinensis, Coriandrum sativum, Codium tomentosum, Commiphora molmol,
Crataegus cuneata, Cucumis sativus, Eucalyptus globulus, Gleditsia
sinensis, Gnetum amazonicum, Hibiscus rosa-sinensis, Jasminum
officinale, Lonicera caprifolium, Lonicera japonica, Lycopersicon
esculentum, Malus pumila, Matricaria recutita, Maximiliana maripa,
Melaleuca hypericifolia, Melaphis chinensis, Mentha piperita,
Mouriri apiranga, Nasturtium officinale, Nelumbo nucifera,
Oenothera biennis, Ophiopogon japonicus, Persea americana, Paffia
paniculata, Phellodendron amurense, Phyllanthus emblica, Pisum
sativum, Potentilla erecta, Pterocarpus santalinus, Rehmannia
chinensis, Ribes nigrum, Rosa centifolia, Rubus thunbergii,
Saccharomyces cerevisiae, Spondias amara, Styrax benzoin, and
Thymus vulgaris.
[0028] Families of algae from which aroma materials can be obtained
include: Acrochaeticaceae, Characeae, Codiaceae, Fucaceae,
Laminariaceae, Lemaneaceae, Ulvaceae, Pamariaceae. Specific
examples of algae species from which essential oils can be obtained
include: Lemanea fluviatilis (red algea), (L.), Ascophyllum nodosum
(brown alga), Lemanea fluviatilis, Lemanea fucina (red algea), Ulva
lactuca (green alga), Laminaria digitata, Laminaria ochroleuca.
[0029] Aroma materials can also be obtained from fungi, including
classes of
[0030] Homobasidiomycetes (true mushrooms). Mushroom families
suitable as sources for essential oils include Meripilaceae,
Tricholomataceae, Ganodermataceae (maitake, shiitake, reishi
mushrooms). Mushroom species for essential oils include Agaricus
bisporus, Agaricus campestris, Flammulina velutipes Hypsizygus
tessulatus, Lentinus edodes, Phellinus linteus, Pleurotus
cornucopiae, Pleurotus ostreatus, Tremella fuciformis, Sparassis
crispa, Tuber magnatum, Volvariella volvacea.
[0031] The essential oils are typically water insoluble. Essential
oils contain volatile and lipophilic substances and are mainly
derivatives of mono- and sesquiterpenes, phenylpropanoids, amino
acids and long chain fatty acids. Naturally-occurring essential
oils can be blended with synthetic fragrances and the term
"essential oils" is intended to encompass such blends.
[0032] The methods and compositions disclosed herein can be used
for making concretes and tinctures by extracting flavor and
fragrance materials from natural plant materials using a
polytrimethylene ether glycol as an extractant. The compositions
can be used following extraction without further treatment. In some
embodiments, the polytrimethylene ether glycol is renewably
sourced.
[0033] Examples of naturally-occurring essential oils include:
Basil, benzoin, bergamot, black pepper, cajuput, chamomile,
camphor, caraway, carrot seed, cassia, cedar wood, cinnamon,
citronella, clove, coriander, cypress, dill, eucalyptus, fennel,
geranium, ginger, grapefruit, jasmine, juniper, lavender, lemon,
lemongrass, lime, mandarin, marjoram, myrrh, nutmeg, orange,
peppermint, rose, sage, spearmint, sandalwood, tangerine, thyme,
tea tree, and ylang ylang.
[0034] The polytrimethylene ether glycols suitable for use in the
methods and compositions disclosed herein as an extractant or as a
solubilizer, have several advantages. For example, the
polytrimethylene ether glycols are non-volatile, generally
non-toxic, non-hazardous, materials which can be renewably sourced.
"Renewably sourced", as used herein with regard to the
polytrimethylene ether glycols, means that they are made using a
renewably sourced ingredient, 1,3-propanediol. The present
inventors surprisingly discovered the high efficacy of the
polytrimethylene ether glycols as extractants to remove flavor and
fragrance materials from natural plant based materials and also as
solubilizers for essential oils. Renewably sourced polytrimethylene
ether glycols thus can replace petroleum based materials in such
applications, which is desirable for many consumer and personal
care products.
[0035] The solubility of a substance (solute) in a solvent is
generally determined by the balance of intermolecular forces
between the solvent and solute. Solvents with relatively higher
intermolecular forces have relatively high surface tension and
relatively higher values of solubility parameter, and vice-versa.
The attractive interaction energy of the solvent molecules must
match the attractive intermolecular energy in the solute in order
to form a solution. The surface tension is a measure of the inward
force acting on the surface of a liquid due to the attraction of
molecules in the liquid. Polyethylene glycol (300 MW), with a
surface tension of 45.9 dynes/cm, is crystalline, viscous and polar
in nature due to higher intermolecular forces, whereas
polypropylene glycol (425 MW), with a surface tension of 32.9
dynes/cm, is a low viscosity liquid, amorphous and non-polar in
nature. Therefore, polyethylene glycol is used to solubilize polar
solutes and polypropylene glycol is used to solubilize non-polar
solutes. The surface tension value for polytrimethylene ether
glycol, on the other hand, is 42.7 dynes/cm for 250 MW polymer and
40.7 dynes/cm for 650 MW polymer, significantly higher than its
isomer, polypropylene glycol, 32.9 dynes/cm for 425 MW polymer, in
spite of having same number of carbon and oxygen atoms in the
backbone. The surface tension value for polytrimethylene ether
glycol is close to the hydrophilic polyethylene glycol suggesting
that it could be used in a same way as polyethylene glycol.
Surprisingly however, the solubilizing efficacy of polytrimethylene
ether glycol for essential oils is unpredictable, and shows greater
solubility than polyethylene glycol, 1,3-propanediol or
polypropylene glycol.
[0036] Suitable polytrimethylene ether glycols for use in the
methods disclosed herein are polytrimethylene ether glycol
homopolymers and copolymers of relatively low molecular weight, and
esters (mono-, diesters and mixtures thereof) of the
polytrimethylene ether glycols. In general, the non-polarity of the
polyether molecules increases with increase in molecular weight and
therefore, a desirable molecular weight can be selected based on
the materials to be extracted or solubilized. "Low molecular
weight" as used herein, means that typically the polymers have a
number average molecular weight within the range of 134 to 2000.
More typically the polymers have a number average molecular weight
less than 1000 or within the range of 250 to 1000, and in some
embodiments the polymers have a number average molecular weight
less than about 650, or within the range of 250 to 650. In another
embodiment the polymers have a number average molecular weight less
than about 250. Suitable polymers are commercially available, such
as, for example, Cerenol.RTM. H650 polytrimethylene ether glycol,
available from E. I. du Pont de Nemours and Company, Wilmington,
Del., or can be prepared as disclosed in U.S. Pat. No.
7,074,969.
[0037] Suitable copolymers include poly(trimethylene ether ester)
glycols such as those disclosed in U.S. Pat. Nos. 6,316,586 and
6,608,168, and poly (trimethylene-co-ethylene ether) glycol, such
as disclosed in U.S. Patent Publication No. 2005/0176921. Suitable
esters of polytrimethylene ether glycols are disclosed in U.S.
Patent Application No. 2009/108845.
[0038] In preparing concrete compositions according to the methods
disclosed herein, polytrimethylene ether glycol of desired number
average molecular weight is used to extract essential components of
the natural plant materials first by mixing both materials,
allowing sufficient time to dissolve, and by removing the
non-essential components that are not dissolved. The mixing of the
polyether glycol and plant material is done at room temperature or
at slightly elevated temperature and the separation of residual
materials from the extract is done by filtration. The extract
(tincture) rendered can be further diluted with polytrimethylene
ether glycol or any other desired solvent and can be used in
various formulations. If desired, the volatile flavor and fragrance
materials can be isolated from the extract by distillation at
atmospheric pressure or reduced pressure. The polytrimethylene
ether glycol polymers exhibit desirable solubility characteristics
for many natural plant materials and can used without further
purification in cosmetic, personal care, pharmaceutical or
industrial applications.
[0039] Generally, tinctures are prepared by treating the plant
materials with ethanol or ethanol-water mixtures. Polytrimethylene
ether glycols, typically having a number average molecular weight
in the range of 134 to 650, or mixtures of such polytrimethylene
ether glycols and water, are suitable to obtain tinctures of plant
materials.
[0040] Polytrimethylene ether glycols and esters (aliphatic,
aromatic or branched) of polytrimethylene ether glycols are also
very effective in dissolving the essential oil extracts of plant
sources, and can be used as solubilizers. Clear and homogeneous
solutions can be obtained by dissolving high concentrations of
essential oil in polytrimethylene ether glycol. In preparing
solutions, a polytrimethylene ether glycol having a desired number
average molecular weight is mixed with a desired essential oil or
other botanical extract at room temperature or slightly at elevated
temperature. The clarity of the solutions can be measured by
turbidity as a function of time and it is expressed in
nephelometric turbidity units (NTU). The NTU of the compositions is
100 or lower, typically 60 or lower, and desirably 40 or lower. In
some embodiments, the compositions are substantially free of
VOCs.
[0041] Compositions containing solubilized essential oils according
to the methods disclosed herein can be used include cosmetic and
personal care formulations such as decorative cosmetics (eye
creams, foundations, lipsticks, glosses), hair care (shampoos,
conditioners, hair gels, hair lotions and tonics), perfumes and
fragrances (colognes, toilet waters, perfumes), skin care (baby
care, body care, facial care, facial cleansing creams and lotions),
sun care (sun protection, after-sun and self tanning formulations)
and toiletries (antiperspirants and deodorants, depilators, hand
wash formulations, shower and bath formulations). The solubilized
essential oil compositions can be used for industrial applications,
such as cleansers, detergents (laundry detergents, dishwashing
detergents), fabric softeners, and also for textile treatments.
[0042] The method used for solubilizing an essential oil,
comprising contacting the essential oil with a composition
comprising one or more of poly(trimethylene ether) glycol
homopolymer or copolymer can also be used to prepare aqueous
solutions, emulsions or microemulsions by further adding water and
surfactant(s). Surfactants, which include emulsifiers, are
compounds that have hydrophobic and hydrophilic portions that act
to reduce the surface tension of the aqueous solutions in which
they are dissolved. Essential oils are in general water immiscible
and in order to make water based compositions, stable emulsions or
microemulsions can be used, but typically require large amounts of
surfactant(s). However, it has been found that solutions containing
essential oils dissolved in polytrimethylene ether glycol are
dispersible in water and therefore it is expected that clear and
transparent microemulsions from such solutions can be obtained with
reduced amounts of surfactant(s) as compared to conventional
emulsions and microemulsions. Solutions of ester (mono and diester
or mixture of esters) of polytrimethylene ether glycol and
essential oils can be used in oil-in-water, water-in-oil or
multiple emulsions or other types of cosmetic, pharmaceutical or
industrial formulations. Examples of suitable surfactants are
disclosed in US2003/0007939A1, U.S. Pat. No. 3,755,560 and U.S.
Pat. No. 4,421,769.
[0043] The amount of water added depends on the desired end use but
typically is up to about 80 percent by weight, or 50 percent, or 30
percent, or 10 percent based on the total weight of of the solution
or microemulsion.
[0044] In some embodiments, the compositions can contain less than
10 percent by weight of total surfactants, more typically less than
5 percent, less than 2 percent, less than 1 percent, or less than
0.5 percent. However, surfactants can be added to the solution
after solubilization, for use in certain formulations such as
moisturizing creams or other formulations containing ingredients
that are not readily soluble in the polyether glycols.
[0045] In some embodiments, the compositions are substantially
silicone free. Silicones, as used herein, refer broadly to linear
and cyclic silicones and siloxanes, including those referred to in
the art as dimethicone, cyclomethicone, etc. Although volatile
silicone fluids (i.e., silicone fluids having a vapor pressure at
room temperature equal to or greater than that of ethanol) can be
used in a variety of personal care and cosmetic formulations, and
such formulations are not intended to be excluded for making
products from the solutions disclosed herein, such products are not
required in making solutions having desired clarity.
[0046] Poly(trimethylene ether) glycol homopolymer or copolymer can
also be used by itself as a cleaning agent to remove polar
lipophilic soils such as adhesives, oils, or fats in industrial
applications where solvents with lower surface tension do not
function well. Poly(trimethylene ether) glycol homopolymer or
copolymer can also be used as a cosolvent with water, alcohol,
glycol ether and ketones, and as a component of cleansers,
detergents (laundry detergents, dishwashing detergents), fabric
softeners, and also for textile treatments.
[0047] In other embodiments, essential oils, solutions or
microemulsions can prepared by the methods disclosed herein, and
personal care or cosmetic formulations comprising the essential
oil, solution or microemulsion.
[0048] In some embodiments, a composition can be prepared
comprising essential oil and one or more of poly(trimethylene
ether) glycol homopolymer or copolymer, wherein the homopolymer or
copolymer has a number average molecular weight within the range of
about 134 to about 2000, and wherein the composition has a surface
tension of at least 38.0, or at least 40.0. The composition can
also have a turbidity of less than 60 nephelometric turbidity
units. The poly(trimethylene ether) glycol homopolymer or copolymer
are as described above. More typically the polymers have a number
average molecular weight less than 1000 or within the range of 250
to 1000, and most typically the polymers have a number average
molecular weight less than about 650 or within the range of 250 to
650. In another embodiment the polymers have a number average
molecular weight less than about 250.
[0049] The compositions can be used in personal care or cosmetic
formulations, or as disclosed hereinabove, as a component of
cleansers, detergents (laundry detergents, dishwashing detergents),
fabric softeners, and also for textile treatments. The compositions
can be in the form of a solution or microemulsion, which can be
neat or aqueous. They can also contain added water or surfactants.
The amount of water added depends on the desired end use but
typically be up to about 80 percent by weight, or 50 percent, or 30
percent, or 10 percent of the solution or microemulsion.
[0050] In some embodiments, the compositions can contain less than
10 percent by weight of total surfactants, more typically less than
5 percent, less than 2 percent, less than 1 percent, or less than
0.5 percent. However, surfactants can be added to the solution
after solubilization, for use in certain formulations such as
moisturizing creams or other formulations containing ingredients
that are not readily soluble in the polyether glycols. In some
embodiments, the compositions are substantially silicone free.
EXAMPLES
[0051] The meaning of the abbreviations used in the examples is as
follows: "s" means second(s), "min" means minute(s), "h" means
hour(s), "kg" means kilogram(s), "g" means gram(s), "mg" means
milligram(s), ".mu.g" means microgram(s), "oz" means ounce(s), "yd"
means yard(s), "mmol" means millimole(s), "m" means meter(s), "cm"
means centimeter(s), "mm" means millimeter(s), ".mu.m" means
micrometer(s), "mL" means milliliter(s), ".mu.L" means
microliter(s), "M" means molar, "N" means normal, "wt %" means
weight percent, "ppm" means parts per million, "MW" means molecular
weight, "M.sub.n" means number average molecular weight, "M.sub.w"
means weight average molecular weight. Unless otherwise specified,
any water used is distilled or deionized water.
[0052] Number average molecular weights (Mn) of the
polytrimethylene ether glycols were determined by end-group
analysis using NMR spectroscopic methods. Turbidity measurements on
the solubiized compositions were carried out using a nephelometric
turbidimeter (MicroTPW, Model 20000, Scientific Inc. FT. Myers,
Fla.) monitors light reflected off the suspended particles. The NTU
(Nephelometric Turbidity Unit) numbers represent the transparency
of a solution; the lower numbers represent higher transparency.
Surface tension was measured for neat glycols and glycols
containing essential oils by ring (DuNouy) method using Cahn
dynamic contact angle analyzer (model DCA-312).
[0053] Polytrimethylene ether glycol having Mn 250 and 500 were
prepared as disclosed in U.S. Pat. No. 7,074,969. Polytrimethylene
ether glycol having Mn 650 (Cerenol.RTM. H650) was obtained from E.
I. du Pont de Nemours and Company, Wilmington, Del. Plant materials
were obtained from Mountaine Rose Herbs, Eugene, Oreg.
[0054] The biodegradability of low molecular weight
polytrimethylene ether glycols were tested according to the
guidelines shown in Table 1 and the results are presented in Table
1.
TABLE-US-00001 TABLE 1 Molecular weight of polytrimethylene ether
glycol Test method Biodegradation 250 OECD 301 B 66% in 28 days 500
OECD 302 B 93% in 28 days
Examples 1-8 and Comparative Examples 1-3
[0055] The Examples 1-8 and Comparative examples 1-3 were all
prepared using the following procedure. The plant materials were
mixed with 50 g of polytrimethylene ether glycol in a glass jar and
placed on a shaking table, then the mixture was shaken for 72
hours. The plant material was filtered by gravity filtration and
the filtrate physical properties were recorded. The results are is
shown in Table 2.
TABLE-US-00002 TABLE 2 Physical properties of the extracts
Polytrimethylene ether glycol Physical appearance Plant (Mn) Color
Odor character Example 1 Jasmine (dried 250 Yellow, transparent
Mild flower), 10 g 5 Myrrh (gum), 10 g 650 Dark brown Strong, woody
6 Lavender (dried 650 Light brown, Pleasant, woody flower), 10 g
transparent 7 Chamomile 650 Yellow, transparent Mild (powder), 5 g
8 Jasmine (dried 650 Yellow Mild flower), 10 g 6 Myrrh (gum), 10 g
1 Jasmine (dried 650 Colorless, Mild, grass flower), 10 g
transparent 2 Chamomile 650 Yellow Mild (powder), 5 g Comparative
Example 1 Jasmine (dried Hexane Colorless, Mild, grass flower), 10
g transparent 2 Myrrh (resinoid), Hexane Colorless, Mild, grass 10
g transparent 3 Lavender (dried Ethanol Green, transparent
Pleasant, herbaceous flower), 10 g
[0056] As shown, the physical appearance (deep color), and the odor
character (strong herbaceous smell) of the products clearly
demonstrate that the renewably sourced polytrimethylene ether
glycol polymers can be successfully replace petrochemicals for
plant extraction and can provide safer, high purity materials,
which can be used in cosmetic, personal care, pharmaceutical or in
industrial applications even without further purification and
expensive and tedious removal of the solvent/s.
Example 9
Surface Tension of Liquids
[0057] 0.5 g of essential oil (lavender, Mountaine Rose Herbs,
Eugene, Oreg.) was mixed with 9.5 g of glycol. The surface tension
of the resulting solutions was compared with neat solvent. The
results are shown in Table 3.
TABLE-US-00003 TABLE 3 Surface Tension of Neat Solvents and the
Mixtures of Essential Oil and Solvent Surface tension (dynes/cm)
Solvent + 5% Sample Neat Solvent Lavender Lavender 28.1 --
1,3-Propanediol 48.3 33.8 Polyethylene glycol-300 MW 45.9 34.4
Polytrimethylene ether glycol-250 MW 42.7 38.9 Polytrimethylene
ether glycol-650 MW 40.7 40.0 Polypropylene glycol-425 MW 32.9
34.3
[0058] As shown in Table 3, the high surface tension of the liquid
solution containing polytrimethylene ether glycol and lavender
indicates stronger intermolecular attraction between these two
molecules when compared to other glycols. For example, lavender
essential oil has a surface tension of 28 dynes/cm and therefore
are expected to be less soluble in polar molecules such as,
polyethylene glycol and polytrimethylene ether glycol than in non
polar molecule such as polypropylene glycol. However, when the
lavender is added to the glycols, the surface tension values for
all of the resulting solutions are much lower than polytrimethylene
ether glycol solution, suggesting high degree of attraction between
lavender molecules and polytrimethylene ether glycols.
Examples 10-12
[0059] Essential oils of different plant materials were used for
testing as detailed below. The essential oils were mixed with 9.5 g
(95 wt %) of polytrimethylene ether glycol (Mn=250) and turbidity
was recorded periodically. Results are shown in Table 4.
TABLE-US-00004 TABLE 4 Turbidity of Essential Oils/Polytrimethylene
ether glycol mixtures Polytrimethylene Essential Oil ether glycol,
Turbidity Turbidity Turbidity Turbidity of Plant Mn = 250 @ 0 min @
5 min @120 min @ 300 min Example (g) (g) (NTU) (NTU) (NTU) (NTU) 10
Chamomile, 9.5 36.8 17.1 14.4 15.1 0.5 11 Lavender, 9.5 52.6 47.1
35.8 28.4 0.5 12 Jasmine, 9.5 32.9 20.4 21.0 20.3 0.5
[0060] Results in Table 4 demonstrate that polytrimethylene ether
glycols are excellent vehicles for the dissolution of essential
oils of different plant materials. Low turbidity was observed
within short period of time (in some cases after 5 minutes) after
gentle mixing of the materials, indicating fast dissolution of the
materials.
Example 13 and Comparative Examples 4-5
[0061] 0.5 g (5 wt %) of essential oils of different plant
materials were used for testing. The essential oils were mixed with
9.5 g (95 wt %) of polytrimethylene ether glycol (Mn=650), hexane
(Aldrich), and di-propylene glycol (DPG) (Aldrich), and turbidity
was recorded periodically as described above. Results are shown in
Table 5.
TABLE-US-00005 TABLE 5 Comparison of Turbidity of Essential
Oils/Polytrimethylene ether glycol mixtures with Turbidity of
Essential Oils/Petrochemical mixtures Essential Turbidity Turbidity
Turbidity Turbidity Turbidity Turbidity Oil of Plant Solvent @ 0
min @ 30 min @120 min @ 240 min @ 7 days @ 14 days (g) (g) (NTU)
(NTU) (NTU) (NTU) (NTU) (NTU) Example 13 Jasmine Polytrimethylene
7.2 5.4 4.5 4.2 4.2 3.9 0.5 ether glycol (Mn = 650) 9.5 Comp.
example 4 Jasmine Hexane 339.4 96.6 46.7 15.9 12.1* 7.7** 0.5 9.5 5
Jasmine Dipropylene 106 89 96.7 98 20* 8.5** 0.5 Glycol 9.5 *Phase
separation was observed, particles and dense bottom phase was seen
**Essential oil was dispersible, small drops were visually
observed
[0062] The results demonstrate that clear solution can be obtained
by mixing botanical essential oils with polytrimethylene ether
glycol homopolymers. The turbidity dramatically decreased rapidly
in case of jasmine and the solution was stable for at least 6
months at room temperature. In Comparative Example 4, phase
separation and small particles were visually observed.
Examples 14-16
[0063] 0.5 g (5 wt %) of essential oils were mixed with 9.5 g (95
wt %) of polytrimethylene ether glycol (Mn=250) and other
additives, and turbidity was recorded periodically and viscosity
was measured. Results are in Table 6.
TABLE-US-00006 TABLE 6 Turbidity of Essential Oils/Polytrimethylene
ether glycol/water mixtures Turbidity @ Turbidity Turbidity @ Plant
0 min @ 30 min 60 min Viscosity Example Essential Oil Solvent (NTU)
(NTU) (NTU) (cP) 14 Chamomile Polytrimethylene ether 36.8 14.5 14.7
88 @ sp 30 0.5 g glycol, 9.5 g 15 Chamomile Polytrimethylene ether
119 44.3 38 24 @ sp 60 0.5 g glycol, 6.5 g, + Water, 3 g 16
Chamomile Polytrimethylene ether 248 19.1 15.3 47.8 @ sp 0.5 g
glycol-250, 6.45 g + 60 Water, 3 g + sodium lauryl sulfate, 0.05
g
[0064] The results demonstrate that turbidity of mixture of
essential oils and polytrimethylene ether glycols were very low,
compared to the turbidity with the mixtures containing water.
Addition of a small amount of surfactant easily decreased turbidity
and a transparent microemulsion was obtained.
Examples 17-19 and Comparative Examples 6-7
[0065] 1 g of essential oils were mixed with 1 g of
polytrimethylene ether glycol (Mn=650). Solubility results are in
Table 7.
TABLE-US-00007 TABLE 7 Solubility of Essential Oils in Different
Solvents Essential Oil of Plant Solvent Solubility Example 17 50 wt
% Jasmine Polytrimethylene ether Miscible glycol 18 50 wt %
Chamomile Polytrimethylene ether Miscible glycol 19 50 wt %
Lavender Polytrimethylene ether Miscible glycol Comparative Example
6 15 wt % Jasmine 1,3-Propanediol Immiscible 7 5 wt % Jasmine Water
Immiscible
The results indicate that high concentrations of essential oils of
plant materials, compared to polar solvents like propylene glycol
and water, can be readily prepared in polytrimethylene ether glycol
polymers.
Examples 20-21
[0066] 0.5 g of essential oils were mixed with 9.5 g of
polytrimethylene ether glycol benzoate or laurate. The ester was
prepared as it is disclosed in patent U.S. Patent Number
2008/108845, and the molecular weight of the homopolymer was
Mn=440. The turbidity of the mixture of essential oil and ester was
periodically recorded. Results are in Table 8.
TABLE-US-00008 TABLE 8 Turbidity of Essential Oils and
Polytrimethylene ether glycol esters Turbidity Turbidity Turbidity
Turbidity @ 0 hr @ 1 hr @ 6 hr @ 24 hr Example Essential Oil
Solvent (NTU) (NTU) (NTU) (NTU) 20 5 wt % Chamomile
Polytrimethylene ether 37.4 2.2 2.2 2.3 glycol dibenzoate 21 5 wt %
Chamomile Polytrimethylene ether 34.5 0.8 0.8 0.8 glycol
laurate
[0067] The mixture of the essential oils and the esters of
polytrimethylene ether glycols had very low turbidity within a
short period of time after mixing.
* * * * *