WATER-INSOLUBLE CYCLODEXTRIN POLYCONDENSATE; USES AS A
CAPTURING AGENT
The subject of the present invention is a water-insoluble cyclodextrin
polycondensate which can be obtained by
esterification/polycondensation reaction :
A) of at least one cyclodextrin and
B) of at least one saturated or unsaturated or aromatic, linear or
branched or cyclic polycarboxylic acid and/or at least one ester or one
acid anhydride or one acid halide of said polycarboxylic acid and
C) of at least one thermoplastic polyol polymer and
D) optionally of at least one esterification catalyst and/or
E) optionally of at least one cyclic anhydride of a polycarboxylic acid
chosen to be other than the polycarboxylic acid anhydride of paragraph
B) and/or
F) optionally of at least one non-polymeric polyol comprising from 3 to 6
hydroxyl groups.
The invention also relates to the uses of these cyclodextrin
polycondensates as agents for capturing a large variety of substances in
many industrial fields.
The objective of the present invention is to search for new materials which
make it possible to trap, in their matrix, a very wide range of substances
or of mixtures of substances, for instance those capable of polluting the
environment, those capable of having a negative impact on a large
diversity of consumer products in many industrial fields or else in the
cosmetics field , and those capable of generating, for example,
uncomfortable reactions on a keratin material, in particular a human
keratin material.
Another objective of the present invention is also to search for new
materials which make it possible to trap at least one beneficial agent and
to delay its time for release to the exterior for the purpose of
(i) either protecting it, for example during its storage or during its
transportation, in order to prevent it from deteriorating, for example under
the influence of atmospheric agents such as heat or cold, variations in
temperature, ambient moisture, atmospheric oxygen or UV radiation ;
(ii) or else, owing to its sensitive chemical or physical nature, isolating it
and preventing or delaying its contact with one or more other ingredients
of a composition or of the site on which it must be applied , with which it is
incompatible;
(iii) or trapping it and prolonging the duration of its release out of the
capturing material in order to improve its effectiveness and/or its wear
property and/or its deposition on the area where it must be applied.
Among the beneficial agents used in particular in the cosmetics or
pharmaceutical industry, in perfumery, in the food-processing industry or
in products resulting from the textile or leather industry, in particular in
textile materials or else in cleaning products, mention may more
particularly be made of fragrances, fragranced essences, essential oils,
bleaching agents, insecticides, colorants, lipids, silicones, waxes,
flavourings, enzymes, oxidizing agents, microorganisms, phytosanitary
active agents, food additives such as flavour enhancers, textile softeners,
antibacterials, cooling agents, active ingredients of medicaments, and
cosmetic or dermatological active agents. Such beneficial agents are
generally expensive and/or volatile and/or physicochemically unstable
and/or effective over periods of time which are too short. There is
therefore a need to optimize their amount in order to limit costs, to
improve their stability, to protect them against their environment and/or to
improve their effectiveness over time.
One of the means known from the prior art for achieving these objectives
is the microencapsulation of these substances. In addition to the
advantages previously mentioned , this encapsulation can also make it
possible to render the material easier to use by diluting it and by
promoting its homogeneous distribution within the support.
Microencapsulation groups together all the technologies for coating or
trapping substances in solid, liquid or gas form within individualized
particles, the size of which ranges between a few microns and a few
millimetres. If these microparticles are hollow (vesicular) they are referred
to as microcapsules, and if they are solid (matricial) they are referred to
as microspheres. Their size ranges from 1 m to more than 1000 m.
These microparticles can be biodegradable or non-biodegradable and can
contain between 5% and 90% (by weight) of encapsulated substance.
The encapsulated substances are very varied in origin : pharmaceutical
active ingredients, cosmetic active ingredients, food additives,
phytosanitary products, fragranced essences, microorganisms, cells, or
else chemical reaction catalysts, etc.
The entire advantage of these known microcapsules lies in the presence
of a polymeric membrane, which isolates and protects the content from the
external environment. As required , the membrane will be destroyed during
use for the release of its content (for example: "scratch and sniff"
advertising inserts which release the fragrance when the microcapsules
are crushed), or else the membrane will remain present throughout the
release of the content, the rate of diffusion of which it will control
(example: encapsulation of medicaments for slow release).
The main methods of the prior art for carrying out the encapsulation of
substances in microparticles are interfacial polymerization , interfacial
crosslinking, emulsion followed by solvent evaporation or extraction ,
double emulsion solvent evaporation/extraction , spray drying, prilling,
coacervation, etc.
Microbeads consisting of hydrophobic polymeric materials which are
generally prepared by phase separation techniques (coacervation or
solvent extraction-evaporation) or by polymerization or polycondensation
are also known. The phase separation techniques generally use organic
solvents which have a certain number of drawbacks: elimination into the
atmosphere, persistence within galenical systems, denaturation of certain
microencapsulated molecules. The methods by polymerization or
polycondensation that are known to date have the drawback of using
highly reactive materials capable of reacting with the substances
encapsulated within the microbeads.
Microbeads formed from hydrophilic polymeric materials which are
generally prepared by gelling or coacervation techniques are also known
from the prior art. This technique which makes it possible to encapsulate
molecules in liquid or solid form is based on the desolvation of
macromolecules, resulting in phase separation within a solution .
As regards encapsulation in lipid materials, the technique of
microencapsulation by thermal gelling is known . This process, known as
hot melt, is based on melting the coating material. The substance to be
encapsulated is dissolved or dispersed in this molten material. The
mixture is emulsified in a dispersing phase, the temperature of which is
kept above the melting point of the coating. The solidification of the
dispersed globules is obtained by abruptly cooling the medium.
Alongside this type of particulate microencapsulation , molecular
encapsulation (cyclodextrins) is also known. The latter constitutes an
advantageous alternative to the conventional encapsulations described
above.
Cyclodextrins have in fact been increasingly used for this purpose since
the 1980s since they are cage molecules which can selectively and
reversibly complex a large diversity of organic molecules in the form of
"host-guest" inclusion complexes. Cyclodextrin inclusion complexes are
particularly useful for transporting, protecting and releasing chemically
and thermally sensitive ingredients. The release of the complexed
ingredients is generally brought about via water or temperature.
Cyclodextrins are a family of natural cyclic oligosaccharides obtained by
enzymatic degradation of starch . They consist of alpha-D-glucose units (6
to 12 units) linked to one another so as to form rings delimiting in their
centre a frustum-shaped cavity.
The most abundant are the hexamers (a-cyclodextrin), heptamers (b-
cyclodextrin) and octamers (g -cyclodextrin) which differ in terms of the
number of glucose units and consequently in terms of the size of the
conical cyclic cavity which results therefrom. All the hydroxyl (OH) polar
groups are located on the exterior, making the exterior hydrophilic and
explaining their solubility in water. Since the interior of the cavity
contains only the glycosidic oxygen atoms and the hydrogen atoms
directly bonded to the carbons, said cavity is hydrophobic and
considerably less polar. This amphiphilic nature enables cyclodextrins to
include in their cavity lipophilic (hydrophobic) molecules, provided that
the size and the geometric shape of the molecules lend themselves
thereto, so as to form inclusion complexes which are generally watersoluble.
Their non-toxic and biodegradable nature predisposes them to
important applications in the food-processing and pharmaceutical fields.
The encapsulation in cyclodextrins in fact makes it possible to protect
fragile molecules or to provide the slow and controlled release thereof.
Furthermore, the solubilization of water-insoluble medicaments in the
form of inclusion complexes in cyclodextrins makes it possible to have
injectable preparations.
Native cyclodextrins can be chemically modified , for example to give
ethers or esters, which will modify the solubility both of the modified
cyclodextrins and of the inclusion complexes. Many advantages follow
from this and allow cyclodextrins to be widely used in various industrial
fields.
Cyclodextrins are also commonly used as a formulation excipient in
medicaments. They make it possible in particular to convert liquid
compounds into solids (powders, tablets) by inclusion complex
precipitation . The complexation of the active ingredients makes it possible
to have better control of their passage into the bloodstream or the
progressivity of their diffusion . Another application is sublingual
treatment. The complexation of photosensitive or highly reactive active
ingredients often makes it possible to protect them or to stabilize them .
The food-processing industry also commonly uses cyclodextrins as taste
enhancers, allowing easy addition of taste compounds, or for fixing
molecules that are too volatile and prolonging, for example, the taste
duration of chewing gums. They are also used , on the contrary, for
removing certain undesirable molecules, in particular for reducing the
levels of cholesterol or of bitter compounds of ready meals or else as
masking agents against bad odours. Cyclodextrins are also used for
stabilizing emulsions such as mayonnaise or margarines.
In the cosmetics industry, they also make it possible to stabilize
emulsions and odorous or active molecules.
In the textile industry, they are used for attaching active compounds
(fragrances, antibacterials) to fabric.
However, the cyclodextrins commonly used have drawbacks.
From a geometric point of view, the inclusion will depend on the relative
size of the cavity of the cyclodextrin relative to the size of the guest
molecule; if said molecule is too large, it will not be able to penetrate
inside the cavity of the cyclodextrin and if, on the other hand , its size is
too small, it will have few interactions with the cyclodextrin . The steric
effect therefore plays an important role in the complexation phenomenon .
Furthermore, the cyclodextrin :guest molecule molar ratio of the inclusion
complexes is generally 1:1 or higher; in other words, at most one molecule
is transported per cyclodextrin molecule.
Finally, the chemical nature of the compounds which can form stable
inclusion complexes with cyclodextrins is restricted to lipophilic
(hydrophobic) compounds since they must displace the water molecules
present in the cavity.
The relatively low water-solubility of cyclodextrins, in particular of the
commercial cyclodextrins, and in particular of the one which is most
economically accessible, b-cyclodextrin ( 18 g/l, i.e. 15 mmol/l, at 25°C),
can constitute a limit in their use.
In order to remedy this situation , chemically modified cyclodextrins have
been proposed in the prior art. For example, primary alcohols have been
substituted with monosaccharide or oligosaccharide groups, on the one
hand so as to improve their water-solubility and , on the other hand , so as
to incorporate cell recognition signals into their structure (international
applications PCT WO 95/1 9994, WO 95/21 870 and WO 97/339 19).
However, the cyclodextrin derivatives of the prior art can have certain
limitations, in particular with respect to the substances that may be
transported , to the substance load capacity per unit weight of the
cyclodextrin derivative, to their capacity to complex certain families of
molecules, in particular hydrophilic molecules, to their cost, to their
toxicity, and to the ease with which they can be synthesized .
Also known in the prior art are cyclodextrin polymers which have polymersubstrate
complex stability constants that are often higher than those of
native cyclodextrin-substrate complexes, and for which the hydrophobic
and hydrophilic compounds and the supramolecules are more readily
complexed and less readily released by the cyclodextrin polymers than by
the native cyclodextrins.
Various types of cyclodextrin polymers and various preparation methods
are thus known in the prior art (see, for example, Comprehensive
Supramolecular Chemistry vol.3, J.L. Atwood et al. , Eds Pergamon Press
( 1 996)).
These cyclodextrin polymers can be categorized into two types depending
on whether the cyclodextrin constitutes the backbone of the polymer or
else is a side substituent of a polymer chain .
The methods for synthesizing these prior art cyclodextrin polymers, the
cyclodextrin of which constitutes the backbone, are based on the use of
generally bifunctional crosslinking agents, such as epichlorohydrin ,
dialdehydes, diacids, diesters, diisocyanates, dihalogenated derivatives,
polyisocyanates, bis-epoxides, acid dihalides in an organic solvent or else
phytic acid .
A process for producing copolymers of cyclodextrin(s) using
epichlorohydrin was proposed by Solms and Egi (Helv. Chim. Acta 48,
1225 ( 1 965); US 3 420 788). Likewise, several modifications of the
method of crosslinking with epichlorohydrin were later proposed in
documents Wiedenhof N. et al . , Die Starke 21(5), 119-1 23 ( 1 989),
Hoffman J.L. , J. Macromol. Sci.-Chem, A7(5), 1147-1 157 ( 1 973),
JP581 71404 and JP6 128360 1.
A process using a bifunctional agent, such as a dialdehyde, a diacid , a
diester, an acid dichloride, a diepoxide, a diisocyanate or a dihalogenated
derivative has been described in document US 3 472 835. This method
envisages the activation of cyclodextrins via the action of sodium metal in
liquid aqueous ammonia and then reaction with the bifunctional
crosslinking agent.
A process using polyisocyanates in aprotic organic solvents has been
described in documents US 4 917 956, Asanuma H. et al . Chem . Commun,
197 1- 1972 ( 1997) and W09822 197.
A process using ethylene glycol bis(epoxypropyl)ether has been described
by Fenyvesi E. et al. in document Ann. Univ. Sci. Budapest, Rolando
Eotvos Nominatae, Sect. Chim. 15 , 13-22 ( 1 979). A process using other
diepoxy compounds has also been described by Sugiura I. et al. in
document Bull . Chem. Soc. Jpn ., (62, 1643-1 651 ( 1 989)).
A process using dicarboxylic acid dihalides in an organic solvent has been
developed in documents US 4 958 015 and US 4 902 788.
A process based on phytic acid (which is a polyphosphoric acid) used for
crosslinking cyclodextrin via a heat treatment under vacuum has been
described in document US 5 734 03 1.
The main drawback of the processes for crosslinking cyclodextrins with
epichlorohydrin is the corrosive and toxic properties of this reagent. The
processes based on the use of diepoxy compounds prove to be toxic and
to have a high cost price. Crosslinkings with polyisocyanates and diacid
dihalides require the use of organic solvents which are harmful to the
environment and cannot therefore be used on a large scale.
The second type of polymer is that in which the cyclodextrin is a pendent
group of a polymer chain ; it is produced by grafting cyclodextrin(s) or
cyclodextrin derivative(s) onto a pre-existing polymer chain .
Thus, DE19520989 describes the grafting of cyclodextrins onto polymers.
Furthermore, cyclodextrins have also been functionalized with aldehyde
groups and then grafted onto chitosan via a reductive amination reaction ;
such a reaction is described by Tomoya T. et al. in J. Polym . Sci ., Part A:
Polym. Chem. 36 ( 1 1) , 1965-1 968 ( 1998).
These cyclodextrin-based polymers can also be synthesized by
functionalization of said cyclodextrin with polymerizable functional groups
such as acryloyl or methacryloyl. This functionalization is followed by
polymerization or copolymerization of these derivatives. Such processes
have been described in document DE4009825, by Wimmer T. et al. in
Minutes Int. Symp. Cyclodextrins 6th 106-1 09, ( 1992) Ed . Hedges A.R. Ed .
Sante Paris, and by Harada A. et al. in Macromolecules 9(5), 701-704
( 1976).
Finally, a process using acrylates, acrylic acid and styrene with
insolubilization of the cyclodextrin has been carried out by emulsion
polymerization in document EP78040 1.
In order to obtain cyclodextrin polymers under conditions which are nonpolluting,
non-toxic and less expensive than those of the processes
mentioned above, Martel et al. have described , in the patent
EP116562 1B1, the synthesis of polymers from a solid mixture of
cyclodextrin , of polycarboxylic acid or polycarboxylic acid anhydride and
of a crosslinking catalyst, at a temperature of 100 to 200°C without the
use of organic solvent. The mechanical properties and the molecular
weight of these polymers are not controllable, with low stability and a low
molecular weight. The work by B. Martel et al. (Journal of Applied Polymer
Science, Vol .97, 433-442 (2005)) describes a yield of 10% for obtaining
soluble polymers and of 70% for obtaining insoluble polymers. These
yields are low and require a very lengthy purification step (60 hours of
dialysis) followed by lyophilization .
Known in the application WO0 148025 (Kimberly Klarck) is a method of a
preparation of a composition which consists in reacting a cyclodextrin
with a polysaccharide for example cellulose fibers by crosslinking with a
reactive anionic polymer in forming esters bounds between them. The
reactive anionic polymer comprises functional anionic groups as a cyclic
acid anhydride like maleic acid anhydride and may react with a catalyst
in particular with sodium hypophosphite. The reactive anionic polymer
as used in the examples is a terpolymer of maleic acid
anhydride/vinylacetate/ethylacetate BELCLEN E DP80® (Durable Press
80). The cyclodextrin polycondensate as formed has a poor capacity in
the capture of malodorous compounds and has a weak encapsulation
capacity of a beneficial active ingredient like a perfume.
There remains therefore the need to provide novel cyclodextrin polymers
which can capture and/or encapsulate large amounts of substances
without the drawbacks previously mentioned and which can be easily
prepared without the use of toxic and/or expensive reagents.
In order to overcome the prior art drawbacks, the objective of the present
invention is to immobilize cyclodextrins in a crosslinked polymeric network
having absorbent properties and functioning like a sponge.
After considerable research , the applicant has discovered , surprisingly
and unexpectedly, that it is possible to efficiently, rapidly and
inexpensively immobilize cyclodextrins in a crosslinked polymeric network
by esterification/polycondensation reaction of polycarboxylic acid(s)
simultaneously with a thermoplastic polyol polymer and a cyclodextrin ,
and that these water-insoluble crosslinked cyclodextrin polycondensates
lead to improved performance levels in terms of encapsulation capacity
while at the same time being conveyable in numerous supports.
This discovery forms the basis of the present invention.
The subject of the present invention is therefore a water-insoluble
cyclodextrin polycondensate which can be obtained by
esterification/polycondensation reaction :
A) of at least one cyclodextrin and
B) of at least one saturated or unsaturated or aromatic, linear or
branched or cyclic polycarboxylic acid and/or at least one ester, one
acid anhydride or one acid halide of said polycarboxylic acid and
C) of at least one thermoplastic polyol polymer and
D) optionally of at least one esterification catalyst and
E) optionally of at least one cyclic anhydride of a polycarboxylic acid
chosen to be other than the polycarboxylic acid anhydride of paragraph
B) and/or
F) optionally of at least one non-polymeric polyol comprising from 3 to 6
hydroxyl groups.
Another subject of the invention consists of the use of a cyclodextrin
polycondensate as defined previously as a capturing agent.
Another subject of the invention relates in particular to the use of a
cyclodextrin polycondensate as defined previously as an agent for
capturing a substance or a mixture of substances capable of polluting
the environment or else a substance or mixture of substances capable of
having a negative impact on a consumer product.
Another subject of the invention relates in particular to the nontherapeutic
cosmetic use of a cyclodextrin polycondensate as defined
previously as an agent for capturing a substance or a mixture of
substances capable of generating, for example, uncomfortable reactions
on a keratin material , in particular a human keratin material .
Another subject of the invention relates in particular to the use of a
cyclodextrin polycondensate as defined previously as an agent for
capturing at least one beneficial active agent.
Another subject of the invention consists of a consumer product
comprising at least one cyclodextrin polycondensate as defined
previously, and more particularly the consumer product is a cosmetic or
dermatological composition comprising a physiologically acceptable
medium.
Definitions
For the purpose of the invention , the term "polycondensate" is intended to
mean any polymer obtained by polymerization in steps where each step is
a condensation reaction which is carried out with elimination of water or of
an alcohol or of a halogenated acid in the case of an esterification .
Monomers with two or more functional groups react so as to first form
dimers, then trimers and longer oligomers, then long-chain polymers.
The term "water-insoluble cyclodextrin polycondensate" is intended to
mean any cyclodextrin polycondensate which has a solubility in water at
25°C of less than 1% by weight, even less than 0.5% by weight, or even
less than 0 .1% by weight.
For the purpose of the invention , the term "capturing agent" is intended to
mean any chemical compound , in particular any polymer, capable of
trapping a substance or a mixture of substances in its structure, of
immobilizing it and/or of delaying its release to the exterior. The
cyclodextrin polycondensate polymers of the invention have a porous
network which combines sponge-type superabsorbent properties with the
capacity to form inclusion complexes in the cavities of cyclodextrins
immobilized within the polymeric network, thus making it possible to
capture substances which have an affinity with said polymeric network.
For the purpose of the present invention , the term "physiologically
acceptable medium" is intended to mean a medium that is suitable for the
topical administration of a composition .
A physiologically acceptable medium is preferably a cosmetically or
dermatologically acceptable medium, that is to say a medium which is
devoid of unpleasant odour or appearance and which is entirely
compatible with the topical administration route.
The term "keratin materials" is intended to mean the skin , hides, the
scalp, the lips, and/or the skin appendages such as the nails and keratin
fibres, such as, for example, animal furs, body hair, wool, the eyelashes,
the eyebrows and the hair.
The term "human keratin materials" is intended to mean the skin , the
scalp, the lips, and/or the skin appendages such as the nails and human
keratin fibres, such as, for example, body hair, the eyelashes, the
eyebrows and the hair.
For the purpose of the invention, the term "cosmetic composition" is
intended to mean any composition which has a non-therapeutic hygiene,
care, conditioning or makeup effect contributing to improving the wellbeing
and/or to making more attractive or modifying the appearance of the
human keratin material to which said composition is applied.
The term "consumer product" is intended to mean any manufactured
product intended to be used or consumed in the form in which it is sold
and which is not intended for subsequent manufacture or modification .
Without the examples being limiting, the consumer products according to
the invention may be cosmetic products including both cosmetic
formulations and application supports or articles comprising such
formulations, such as patches, wipes, nonwoven supports; intimate
hygiene products including care and hygiene formulations and also
articles intended for this purpose, such as sanitary tampons, wipes,
towels; products for oral hygiene, such as toothpastes, mouth care
products, deodorants such as sprays, breath lozenges, chewing gums,
sweets; cosmetic or dermatological products: creams, milks, lotions,
balms, sticks, talcs; makeup products; hair products; babycare products
including formulations and articles intended for this purpose, such as
wipes, nappies; pharmaceutical products and also medical and
paramedical articles such as dressings, patches, prostheses; products for
veterinary use, such as animal litters; animal hygiene and/or care
products; household products such as laundry care and/or cleaning
products (laundry detergents, softeners), washing-up products, products
for cleaning and/or maintaining household appliances, products for
cleaning and/or maintaining floors, tiles, wood , etc; sanitary products such
as deodorants, descaling products, unblocking products; textile materials,
clothing, fine leather goods such as shoes, soles and products for the
maintenance thereof; products resulting from the food-processing
industry; products resulting from agriculture; phytosanitary products;
products resulting from the wood and paper industry; paints; inks.
For the purpose of the invention, the term "beneficial agent" is intended to
mean any chemical compound present in a consumer product which
produces a beneficial effect noticed by the consumer during use thereof
and/or obtained on the consumer product itself, it being possible for said
beneficial effect to be a sensory improvement, in particular a visual and/or
olfactory and/or gustative and/or tactile improvement, an improvement or
modification of the comfort and/or ease of application , an aesthetic effect,
a hygiene effect, a feeling of cleanliness, a curative and/or prophylactic
effect.
CYCLODEXTRIN POLYCONDENSATES
The cyclodextrin polycondensates according to the invention can be easily
prepared , in a single synthesis step, and without producing waste, at low
cost, in particular by carrying out the reaction in an extruder.
Moreover, it is easily possible to modify the structure and/or the
properties of the cyclodextrin polycondensates according to the invention ,
by varying the chemical nature of the various constituents and/or the
proportions thereof.
The cyclodextrin polycondensates according to the invention make it
possible to generate a porous polymeric network which combines spongetype
superabsorbent properties with the capacity to form inclusion
complexes in the cavities of cyclodextrins immobilized within the
polymeric network.
The cyclodextrin polycondensates according to the invention can be
obtained by esterification/polycondensation , according to methods known
to those skilled in the art, of the constituents described hereinafter.
CYCLODEXTRINS
One of the constituents required for the preparation of the cyclodextrin
polycondensates according to the invention is a cyclodextrin.
For the purpose of the invention , the term "cyclodextrin" is intended to
mean any compound of general structure
or a derivative thereof, such as methylated , hydroxyalkylated ,
sulfoalkylated or sulfated derivatives, or cyclodextrins substituted with
sugars.
Among the preferred cyclodextrins, mention may be made of acyclodextrin
, b-cyclodextrin , g -cyclodextrin , and methylated derivatives
thereof such as TRI MEBs (heptakis(2,3,6-trimethyl)-3-CD), DIMEBs
(heptakis(2,6-dimethyl)-3-CD) or else RAMEBs (Randomly Methylated b-
Cyclodextrins); hydroxyalkylated derivatives thereof such as 2-
hydroxypropyl-3-cyclodextrin (H R b ; Kleptose® HPB), 3-hydroxypropyl-
b-cyclodextrin , 2,3-dihydroxypropyl-3-cyclodextrin , 2-hydroxyethyl-3-
cyclodextrin , 2-hydroxypropyl-Y-cyclodextrin and 2-hydroxyethyl-ycyclodextrin
; sulfobutylated derivatives thereof such as sulfobutyl ether b-
cyclodextrin sodium salt (SBE3CD; Captisol®); sulfated cyclodextrins such
as b-cyclodextrin sulfate; cyclodextrins substituted with sugars, such as
glucosyl-3-cyclodextrin , diglucosyl-3-cyclodextrin , maltosyl-3-cyclodextrin
or dimaltosyl-3-cyclodextrin .
A mixture of such cyclodextrins may obviously be used.
Preferably, the cyclodextrin is chosen from a-cyclodextrin , b-cyclodextrin ,
g -cyclodextrin and mixtures thereof, and even better still b-cyclodextrin .
The cyclodextrin(s) preferably represent(s) 10% to 70% by weight, in
particular 20% to 65% by weight and better still 30% to 60% by weight of
the total weight used in the synthesis of the cyclodextrin polycondensate.
POLYCARBOXYLIC ACIDS AND DERIVATIVES THEREOF
a) Polycarboxylic acids
Another constituent required for the preparation of the cyclodextrin
polymers according to the invention is a saturated or unsaturated or
aromatic, linear or branched or cyclic polycarboxylic acid comprising at
least 2 carboxylic COOH groups, preferably 2 to 4 COOH groups.
Said polycarboxylic acid may in particular be chosen from saturated or
unsaturated , or even aromatic, linear, branched and/or cyclic
polycarboxylic acids containing 2 to 50 carbon atoms, especially 2 to 40,
in particular 3 to 36 carbon atoms, or even 3 to 18 and even better still 4
to 12 carbon atoms, or even 4 to 10 carbon atoms; said acid comprises at
least two carboxylic COOH groups and preferably from 2 to 4 COOH
groups.
Among the polycarboxylic acids that may be used , mention may be made,
alone or as a mixture, of:
- dicarboxylic acids such as oxalic acid , malonic acid , succinic acid ,
glutaric acid , adipic acid , pimelic acid , suberic acid , azelaic acid , sebacic
acid , dodecanedioic acid , malic acid , tartaric acid , tartronic acid ,
citramalic acid , dioxymaleic acid , dioxymalonic acid , maleic acid , fumaric
acid , glutaconic acid , itaconic acid , fatty acid (in particular C3 6 fatty acid)
dimers, such as the products sold under the names Pripol 1006, 1009,
1013 and 10 17 by Uniqema, glutamic acid , aspartic acid , oxaloacetic acid ,
cyclopropanedicarboxylic acid , cyclohexanedicarboxylic acid ,
cyclobutanedicarboxylic acid , naphthalene-1 ,4-dicarboxylic acid ,
naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid ,
phthalic acid , terephthalic acid, isophthalic acid, tetrahydrophthalic acid or
hexahydrophthalic acid ;
- tricarboxylic acids such as citric acid , aconitic acid , isocitric acid ,
oxalosuccinic acid , 1,2,3-propanetricarboxylic acid , 1,2,5-
pentanetricarboxylic acid , 1,3,5-pentanetricarboxylic acid , transaconitic
acid , 3-butene-1 ,2,3-tricarboxylic acid , 3-butene-1 ,1,3-tricarboxylic acid ,
1,3,5-cyclohexanetricarboxylic acid, trimellitic acid , 1,2,3-
benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid ;
- tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid ,
pyromellitic acid , oxydisuccinic acid , thiodisuccinic acid , N-[1 ,2-
dicarboxyethyl]-L-aspartic acid , ethylenediaminetetraacetic acid ,
ethylenediaminetetrapropionic acid or N,N'-ethylenedi(L-aspartic) acid .
Preferably, said polycarboxylic acid , used alone or as a mixture, is
aliphatic, saturated and linear and contains 2 to 36 carbon atoms, in
particular 3 to 18 carbon atoms, or even 4 to 12 carbon atoms; or
alternatively is aromatic and contains 8 to 12 carbon atoms. It preferably
comprises 2 to 4 COOH groups.
Preferably, use may be made of citric acid , aconitic acid , tartaric acid ,
1,2,3-propanetricarboxylic acid and 1,2,3,4-butanetetracarboxylic acid ,
alone or as a mixture, preferably alone, and even better still citric acid
alone.
b) Polycarboxylic acid esters
Among the polycarboxylic acid ester derivatives, mention may be made of
the C 1- C 4 alkyl mono-, di-, tri- or tetraesters, in particular the methyl,
ethyl, isopropyl or n-butyl esters and more preferentially the methyl or
ethyl esters.
The preferred polycarboxylic acid esters are the methyl , ethyl, isopropyl or
n-butyl esters and more preferentially the methyl or ethyl esters of
aliphatic, saturated , linear polyacids (2 to 4 COOH groups) containing 2 to
36 carbon atoms, in particular 3 to 18 carbon atoms, or even 4 to 12
carbon atoms; or alternatively of an aromatic acid containing 8 to 12
carbon atoms. Preferably, use may be made of the methyl , ethyl , isopropyl
or n-butyl esters and more preferentially the ethyl or butyl esters of citric
acid , of aconitic acid , of tartaric acid , of 1,2,3-propanetricarboxylic acid
and of 1,2,3,4-butanetetracarboxylic acid , alone or as a mixture, and
even better still the ethyl or butyl esters of citric acid , such as triethyl
citrate, acetyltriethyl citrate, tributyl citrate and acetyltributyl citrate.
c) Polycarboxylic acid anhydrides
Among the polycarboxylic acid-derived acid anhydrides, mention may be
made of:
a) mixed anhydrides with a C2-C4 carboxylic acid , in particular acetic
acid , propionic acid or butyric acid , preferably acetic acid;
b) cyclic anhydrides of polycarboxylic acids, such as phthalic
anhydride, trimellitic anhydride, maleic anhydride, succinic
anhydride or N ,N ,N' ,N'-ethylenediaminetetraacetic acid dianhydride.
Preferably, the polycarboxylic acid anhydride, alone or as a mixture, is
chosen from maleic anhydride and succinic anhydride and more
preferentially is maleic anhydride alone.
d) Polycarboxylic acid halides
Among the acid halides derived from said polycarboxylic acids, mention
may be made of the acid chlorides or acid bromides of said polycarboxylic
acids, preferably the polycarboxylic acid chlorides.
Preferably, the acid halides, used alone or as a mixture, are the halides of
aconitic acid, of tartaric acid, of 1,2,3-propanetricarboxylic acid and of
1,2,3,4-butanetetracarboxylic acid, and preferably the chlorides of these
acids.
Said polycarboxylic acid(s) and/or ester, acid anhydride or acid halide
derivatives thereof, used alone or as a mixture, preferably represent(s)
5% to 40% by weight, more preferentially from 7% to 35% by weight and
better still 10% to 30% by weight, of the total weight used in the synthesis
of the cyclodextrin polycondensate.
THERMOPLASTIC POLYOL POLYMERS
Another constituent required for the preparation of the cyclodextrin
polycondensates according to the invention is a thermoplastic polyol
polymer.
The term "polyol polymer" is intended to mean a polymer having an
average molecular weight ranging from 1000 to 200 000 Daltons,
containing at least two hydroxyl functions.
The term "thermoplastic polyol polymer" is intended to mean a polyol
polymer which fluidifies (softens) in heat at a temperature between 100
and 250°C.
Various types of thermoplastic polyol polymers can be used according to
the invention. Mention will be made of polyether-polyols, polyesterpolyols,
polycarbonate-polyols, polyamide-polyols, polyurethane-polyols,
polyalkylene-polyols, polycaprolactone-polyols and polysaccharides.
Among the polyether-polyols, mention will be made of polyoxyethylene
glycols, polyoxypropylene glycols, block or random copolymers of ethylene
oxide and of propylene oxide, block or random copolymers of ethylene
oxide and/or propylene oxide with tetrahydrofuran , and more particularly
polytetramethylene glycols and polypropylene glycols.
Among the polyester-polyols, mention will in particular be made of those
obtained by polycondensation of dicarboxylic or tricarboxylic acids with
polyols (di-, tri- or tetraols), for instance poly(hexamethylene adipate),
and also those obtained by polycondensation of hydroxy acids, such as
polyhydroxyalkanoates and in particular polylactic acid ,
polyhydroxybutyrate (PH B) and polyhydroxybutyrate-valerate (PH BV).
Among the polycarbonate-polyols, mention will be made of those prepared
by reacting diols (propane-1 ,3-diol, butane-1 ,4-diol, hexane-1 ,6-diol, 1,9-
nonanediol, 2-methyloctane-1 ,8-diol, diethylene glycol, etc.) with diaryl
carbonates, such as diphenyl carbonate, or else with phosgene.
Among the polyamide-polyols, mention will be made more particularly of
those obtained by reacting a diamine and/or a polymeric diamine with a
dicarboxylic or polycarboxylic acid and a hydroxy acid , such as, for
example, 12-hydroxystearic acid .
Among the polyurethane-polyols, mention will be made of those obtained
by means of a polyaddition process consisting in reacting
polyisocyanates, preferably diisocyanates, with diols and/or polyols.
Among the polycaprolactone-polyols, mention will be made in particu lar of
the polycaprolactone-polyols obtained by polymerization of epsiloncaprolactone
with ring opening via polyols such as ethylene glycol, 1,2-
propanediol, 1,3-propanediol, glycerol or trimethylolpropane.
Among the polyalkylene-polyols, mention will be made of polyvinyl
alcohol, modified polyvinyl alcohol having a content of ethylene units of 4
mol% to 15 mol% and polybutadiene diols.
Among the polysaccharides, mention will be made quite particularly of
thermoplastic starches which are obtained by destructuring the native
granule in the presence of a plasticizer under thermomechanical stresses;
cellulose derivatives, such as cellulose acetate, cellulose acetobutyrate,
cellulose acetopropionate, methylcellulose, ethylcellulose,
hydroxypropylcellulose, hydroxyethyl cellulose,
hydroxypropylmethylcellulose, hydroxyethylmethylcellulose or
carboxymethylcellulose, alone or as a mixture with alginates, gums such
as guar gum, starches such as tapioca starch , modified starches such as
starch octenyl succinate (E. 1450), oxidized starches (E. 1404), crosslinked
starches (E. 1412 or 14 13), stabilized starches (E. 1420 or E.1440),
crosslinked/stabilized starches such as acetylated distarch adipate
(E. 1422) or hydroxypropylated distarch phosphate (E. 1442), sulfated
polysaccharides such as carrageenans, aminopolysaccharides such as
chitosan or chitin , oxidized polysaccharides such as those described in
application WO 2010/070235, patent FR 2 944 967 and application WO
201 1/ 161020, and more particularly starches, inulins, carrageenans,
alginates and glucomannans.
The polysaccharides are particularly preferred since they have a
renewable origin and are available at high tonnage and at low cost.
Preferably, among the polysaccharides, use may be made, alone or as a
mixture, of hydroxypropylcellulose and hydroxyethylcellulose, and even
better still hydroxypropylcellulose alone.
Said thermoplastic polyol polymer(s) preferably represent(s) 10% to 50%
by weight, in particular 15% to 45% by weight and better still 17% to 40%
by weight, of the total weight used in the synthesis of the cyclodextrin
polycondensate.
POLYCARBOXYLIC ACID CYCLIC ANHYDRIDES
According to one particular form of the invention , at least one
polycarboxylic acid cyclic anhydride chosen so as to be other than the
first polycarboxylic acid anhydride previously mentioned is also used for
the preparation of the cyclodextrin polycondensates according to the
invention .
The additional polycarboxylic acid cyclic anhydride may in particular
correspond to one of the following formulae:
in which the groups A and B are, independently of one another:
- a hydrogen atom ;
- a saturated or unsaturated , linear, branched and/or cyclic, or
alternatively aromatic, carbon-based radical containing 1 to 16 carbon
atoms, in particular 2 to 10 carbon atoms or even 4 to 8 carbon atoms, in
particular methyl or ethyl;
- or alternatively A and B, taken together, form a saturated or unsaturated,
or even aromatic, ring containing in total 5 to 7 and in particu lar 6 carbon
atoms.
Preferably, A and B represent a hydrogen atom or together form an
aromatic ring containing in total 6 carbon atoms.
Among the polycarboxylic acid cyclic anhydrides which may be used ,
mention may be made of, alone or as a mixture, phthalic anhydride,
trimellitic anhydride, maleic anhydride and succinic anhydride.
Preferably, use may be made of maleic anhydride and succinic anhydride
alone or as a mixture, and even better still maleic anhydride alone.
When said polycarboxylic acid cyclic anhydride is present among the
ingredients used , it preferably represents 0 .1% to 10% by weight, in
particular 0.5% to 5% by weight, or even 0.7% to 4% by weight, relative to
the total weight used in the synthesis of the cyclodextrin polycondensate.
ESTERIFICATION CATALYSTS
According to one particular form of the invention , at least one
esterification catalyst will be used for the preparation of the cyclodextrin
polycondensates according to the invention .
The esterification catalyst may in particular be chosen from dihydrogen
phosphates, hydrogen phosphates, phosphates, hypophosphites and
phosphites of alkali metals, alkali metal salts of polyphosphoric acids,
alkali metal or alkaline-earth metal carbonates, bicarbonates, acetates,
borates and hydroxides, aliphatic amines and aqueous ammonia,
optionally combined with an inorganic solid support such as alumina, silica
gels, Al silicates, zeolites, titanium oxides or zirconium oxides. The
esterification catalyst may also be chosen from sulfonic acids or titanates.
Use may preferably be made of sodium hydrogen phosphate, sodium
dihydrogen phosphate and sodium hypophosphite and even better still
sodium dihydrogen phosphate.
When said esterification catalyst is present among the ingredients used , it
preferably represents 0 .1% to 5% by weight, in particular 0.5% to 4% by
weight, or even 0.5% to 3% by weight, relative to the total weight used in
the synthesis of the cyclodextrin polycondensate.
NON-POLYMERIC POLYOLS
According to one particular form of the invention , at least one nonpolymeric
polyol comprising 3 to 6 hydroxyl groups will also be used for
the preparation of the cyclodextrin polycondensates according to the
invention . A mixture of such polyols may obviously be used.
Said polyol may in particular be a linear, branched and/or cyclic, saturated
or unsaturated carbon-based and in particular hydrocarbon-based
compound containing 3 to 18 carbon atoms, in particular 3 to 12 or even 4
to 10 carbon atoms, and 3 to 6 hydroxyl (OH) groups, and also possibly
comprising one or more oxygen atoms inserted in the chain (ether
function).
Said polyol is preferably a linear or branched saturated hydrocarbonbased
compound containing 3 to 18 carbon atoms, in particular 3 to 12 or
even 4 to 10 carbon atoms, and 3 to 6 hydroxyl (OH) groups.
It may be chosen , alone or as a mixture, from :
- triols such as 1,2,4-butanetriol, 1,2,6-hexanetriol, trimethylolethane,
trimethylolpropane or glycerol ;
- tetraols such as pentaerythritol (tetramethylolmethane), erythritol,
diglycerol or ditrimethylolpropane;
- pentols such as xylitol ;
- hexols such as sorbitol and mannitol; or alternatively dipentaerythritol or
triglycerol.
Preferably, the polyol is chosen from glycerol, pentaerythritol, diglycerol
and sorbitol, and mixtures thereof; and even better still the polyol is
glycerol alone.
When said polyol comprising 3 to 6 hydroxyl groups is present among the
ingredients used , it preferably represents 1% to 30% by weight, in
particular 2% to 25% by weight, or even 10% to 20% by weight, relative to
the total weight used in the synthesis of the cyclodextrin polycondensate .
In one preferred embodiment of the invention, the ratio between the
number of moles of polycarboxylic acid and the number of moles of the
cyclodextrin preferably ranges from 0.5 to 5 , especially from 0.6 to 4 and
in particular from 0.7 to 3 .
It has been noted that these proportions make it possible to obtain a
cyclodextrin polycondensate which is advantageously water-insoluble and
which , moreover, has at the same time an appropriate capacity for both
capturing and impregnating various ingredients.
Preferably, the cyclodextrin polycondensate according to the invention has
an acid number, expressed in mg of potassium hydroxide per g of
polycondensate, greater than or equal to 20, in particular ranging from 20
to 250 and even better still ranging from 40 to 180.
This acid number may be readily determined by those skilled in the art via
the conventional analytical methods. The amount of -COOH groups
present is evaluated according to the number of milligrams of potassium
hydroxide required to neutralize 1 g of cyclodextrin polycondensate, the
dispersion being carried out in a mixture of solvents ( 1 part of water and 1
part of absolute ethanol).
Preferably, the cyclodextrin polycondensate according to the invention
exhibits a degree of swelling in water, measured at 20°C, greater than or
equal to 100% , in particular ranging from 100% to 1000% and even better
still ranging from 300% to 900%. This degree of swelling is measured in
the manner described hereinafter.
Protocol for measuring the degree of swelling :
2 g of polycondensate are suspended in 20 g of demineralized water with
light stirring for 24 h at ambient temperature. The suspension is
centrifuged in order to separate the supernatant and then the solids
content is determined on the centrifugate using a thermobalance. The %
degree of swelling is obtained by calculating the evaporated weight/dry
weight ratio x 100.
The polycondensate according to the invention may be prepared via the
esterification/polycondensation processes usually used by those skilled in
the art.
By way of illustration, a general preparation process consists:
- in mixing together one or more cyclodextrins, a polycarboxylic acid
and/or a derivative thereof (esters, acid anhydrides or acid halides), at
least one thermoplastic polyol polymer and optionally at least one
polycarboxylic acid cyclic anhydride chosen so as to be other than the
previous polycarboxylic acid anhydride and/or at least one esterification
catalyst and/or at least one non-polymeric polyol comprising 3 to 6
hydroxyl groups,
- in heating the mixture, preferably under an inert atmosphere, to a
temperature ranging from 100 to 250°C, preferably while removing, during
the heating, the water, the alcohol or the acid formed , then
- in cooling the mixture to ambient temperature.
It is also possible to perform the reaction , totally or partly, in an inert
solvent such as xylene and/or under reduced pressure, to facilitate the
removal of the water, the alcohol or the acid formed .
Advantageously, no solvent is used .
Said preparation process may also comprise a step of adding at least one
antioxidant to the reaction medium , in particular in a weight concentration
preferably ranging from 0.01 % and 2% relative to the total weight used in
the synthesis of the cyclodextrin polycondensate, so as to limit the
possible degradation associated with prolonged heating.
The antioxidant may be chosen from hindered phenols, aromatic
secondary amines, organophosphorus compounds, sulfur compounds,
lactones and bisphenols, and mixtures thereof.
Among the antioxidants that are particularly preferred , mention may in
particular be made of BHT, BHA, TBHQ, ,3,5-trimethyl-2,4,6,tris(3,5-di-
(tert-butyl)-4-hydroxybenzyl)benzene, octadecyl 3,5,di-(tert-butyl)-4-
hydroxycinnamate, tetrakis[methylene-3-(3,5-di-(tert-butyl)-4-
hydroxyphenyl)propion ate] methane, octadecyl 3-(3,5-di-(tert-butyl)-4-
hydroxyphenyl)propionate, 2,5-di-(tert-butyl)hydroquinone, 2,2-
methylenebis(4-methyl-6-(tert-butyl)phenol), 2,2-methylenebis(4-ethyl-6-
(tert-butyl)phenol), 4,4-butylidenebis(6-(tert-butyl)-m-cresol), N,Nhexamethylenebis(
3,5-di-(tert-butyl)-4-hydroxyhydrocinnamamide),
pentaerythrityl tetrakis(3-(3,5-di-(tert-buty I)-4-hydroxy phenyl propionate),
in particular the product sold by Ciba under the name Irganox 10 10 ;
octadecyl 3-(3,5-di-(tert-butyl)-4-hydroxphenyl)propionate, in particular
the product sold by Ciba under the name Irganox 1076; 1,3,5-tris(3,5-di-
(tert-butyl)-4-hydroxybenzyl)-1 ,3,5-triazine-2, 4,6(1 H,3H ,5H)-trione, in
particular the product sold by Mayzo of Norcross, Ga under the name BNX
3114 ; di(stearyl)pentaerythritol diphosphite, tris(2,4-di-(tertbutyl)
phenyl)phosphite, in particular the product sold by Ciba under the
name Irgafos 168; dilauryl thiodipropionate, in particular the product sold
by Ciba under the name Irganox PS800; bis(2,4-di-(tertbutyl)
pentaerythritol diphosphite, in particular the product sold by Ciba
under the name Irgafos 126; bis(2,4-bis)[2-phenylpropan-2-
yl]phenyl)pentaerythritol diphosphite, triphenylphosphite, (2,4-di-(tertbutyl)
phenyl)pentaerythritol diphosphite, in particular the product sold by
GE Specialty Chemicals under the name Ultranox 626;
tris(nonylphenyl)phosphite, in particular the product sold by Ciba under
the name Irgafos TNPP; the 1:1 mixture of N,N-hexamethylenebis(3,5-di-
(tert-butyl)-4-hydroxyhydrocinnamamide) and of tris(2,4-di-(tertbutyl)
phenyl)phosphate, in particular the product sold by Ciba under the
name Irganox B 1171; tetrakis(2,4-di-(tert-butyl)phenyl)phosphite, in
particular the product sold by Ciba under the name Irgafos P-EPQ;
distearyl thiodipropionate, in particular the product sold by Ciba under the
name Irganox PS802; 2,4-bis(octylthiomethyl)-o-cresol, in particular the
product sold by Ciba under the name Irganox 1520; 4,6-
bis(dodecylthiomethyl)-o-cresol, in particular the product sold by Ciba
under the name Irganox 1726.
One particularly preferred mode of preparation of the cyclodextrin
polycondensates of the present invention consists in mixing at least one
cyclodextrin , at least one polycarboxylic acid and/or an ester, acid
anhydride or acid halide derivative thereof, at least one thermoplastic
polyol polymer and optionally at least one polycarboxylic acid cyclic
anhydride chosen to be other than the previous polycarboxylic acid
anhydride and/or optionally at least one esterification catalyst and/or
optionally at least one non-polymeric polyol, in an apparatus which makes
it possible to bring the mixture to a thermoplastic state by combining
sufficient temperature and shear force conditions, thus making the various
components compatible.
Preferably, use will be made of an extruder, for instance of the Clextral BC
21® twin-screw type or any other apparatus which can meet these criteria,
which operates at a temperature ranging from 100 to 250°C and
preferentially from 110 to 200°C.
The preferred mode of preparation of the materials of the invention
consists in incorporating, in a single step, all the ingredients in an
extruder at a temperature ranging from 110 to 200°C, preferably ranging
from 120 to 190°C and even better still from 150 to 180°C.
The residence time in an extruder preferably ranges from 1 to 10 minutes
and even better still from 1 to 5 minutes.
Depending on the purpose for which the cyclodextrin polycondensate of
the invention is intended , said polycondensate may subsequently be
ground if required .
Another subject of the invention consists of the use of a cyclodextrin
polycondensate as defined previously as an agent for capturing a
substance or a mixture of substances capable of polluting the
environment, such as gaseous pollutants (volatile organic compounds),
metal cations, oils and fats, polluting substances in drinking water,
industrial water and aqueous effluents and also in soils and surrounding
volatile odorous molecules.
Among the gaseous pollutants (VOCs), mention may in particular be made
of chlorinated compounds, for instance chlorobenzene, carbon
tetrachloride and monovinyl chloride.
Among the metal cations, mention may more particularly be made of lead ,
cadmium, mercury, iron and copper cations.
Among the oils and fats, they are of mineral , animal , vegetable, marine or
synthetic origin . Among them , mention may be made of the complex
mixtures of oil hydrocarbons constituting fuels, lubricants and brake
fluids, and also additives added in small amounts in order to improve
technical properties, for instance anti-detonating products, antioxidants,
antifreezes, lead substitutes and dyes.
Among the polluting substances contained in drinking water, industrial
water and aqueous effluents, mention may particularly be made of the
malodorous natural pollutants of drinking water, for instance (-)-geosmine
et (+)-2-methyl isoborneol.
Among the polluting substances contained in soils, mention will quite
particularly be made of chlorophenols (tri- and pentachlorophenol) and
polycyclic aromatic hydrocarbons (naphthalene, phenanthrene).
The cyclodextrin polycondensates of the invention , by virtue of their
chemical nature and their superabsorbent polymeric network, have in
particular a strong capacity to absorb fatty substances such as vegetable
oils, mineral oils, for instance hydrocarbons such as isohexadecane,
paraffin oil, terpenes, squalene, isoparaffins, ceresin , petroleum jelly,
hydrogenated oils, silicone oils, saturated or unsaturated fatty acids (such
as oleic acid), fatty acid esters, fatty alcohols (such as myristyl alcohol ,
cetyl alcohol, stearyl alcohol, myricyl alcohol), butters, ester waxes, or a
mixture thereof.
The cyclodextrin polycondensates make it possible in particular to capture
fats, dirt, fatty waste which may be produced during the manufacturer or
consumption of numerous consumer products, in particular foodprocessing
industry products, household products, for instance laundry
detergents, detergent products for textiles, for instance stain removers,
products for cleaning and/or maintaining floors, cosmetic cleansing
products, for instance makeup removers.
Another subject of the invention consists of the use of a cyclodextrin
polycondensate as defined previously as an agent for capturing and
protecting a substance or a mixture of substances which may deteriorate
under the influence of atmospheric agents (moisture, heat, oxygen , light,
etc.) or upon contact with one or more ingredients in a composition .
Among these substances termed particularly sensitive, fragile or unstable,
mention may in particular be made of fragrances (perfumery ingredients)
and flavourings, vitamins, hormones and dyes.
Another subject of the invention consists of the non-therapeutic cosmetic
use of a cyclodextrin polycondensate as defined previously as an agent
for capturing a substance or a mixture of substances capable of
generating, for example, uncomfortable reactions on a keratin material
and in particular a human keratin material .
The substances capable of generating uncomfortable reactions on a
keratin material, in particular a human keratin material, are chosen in
particular from:
(i) malodorous molecules, in particular malodorous bodily molecules;
(ii) the constituents of human sweat;
(iii) the constituents of sebum .
Among the substances capable of generating discomfort with regard to
keratin materials and in particular human keratin materials, mention may
be made of malodorous molecules and in particular malodorous bodily
molecules produced by sweat and the bacteria which grow therein during
its development.
Among the malodorous bodily molecules, mention may be made of:
a) linear or branched , saturated or unsaturated , and/or optionally
substituted C2-C2ofatty acids such as those of formula ( 1 ) below:
in which R represents i) a linear or branched (C1-C20) alkyl group which is
optionally substituted , preferably with at least one hydroxyl group,
ii) a linear or branched (C2-C2o)alkenyl group which is optionally
substituted , preferably with at least one hydroxyl group; in particular, the
alkyl or alkenyl group contains from 2 to 14 carbon atoms.
Among the malodorous bodily molecules, mention may in particular be
made of acetic acid , 2-propenoic acid, propanoic acid , propionic acid, 2-
methylpropanoic acid, 2-methylpropenoic acid , 2-butenoic acid , 2-methyl-
2-butenoic acid , 3-methyl-2-butenoic acid , butanoic acid , 2-methylbutanoic
acid , 3-methylbutanoic acid, 3-hydroxybutanoic acid, 3-hydroxy-3-
methylbutanoic acid , 2-methylbutyric acid , isovaleric acid , 2-pentenoic
acid , 2-methyl-2-pentenoic acid , 3-methyl-2-pentenoic acid , pentanoic
acid , 2-methylpentanoic acid , 3-methylpentanoic acid , 3-hydroxypentanoic
acid , 3-hydroxy-3-methylpentanoic acid, 3-methylhexanoic acid, 3-
hydroxy-3-methylhexanoic acid , hexanoic acid , (E)-3-methyl-2-hexenoic
acid , 2-heptenoic acid, 2-methyl-2-heptenoic acid, 3-methyl-2-heptenoic
acid , heptanoic acid, 2-methylheptanoic acid , 3-methylheptanoic acid, 3-
hydroxyheptanoic acid , 3-hydroxy-3-methylheptanoic acid , 2-octenoic
acid , 2-methyl-2-octenoic acid , 3-methyl-2-octenoic acid , octanoic acid,
2-methyloctanoic acid , 3-methyloctanoic acid , 3-hydroxyoctanoic acid , 3-
hydroxy-3-methyloctanoic acid , nonanoic acid , 2-nonenoic acid , 2-methyl-
2-nonenoic acid , 3-methyl-2-nonenoic acid , nonanoic acid , 2-
methylnonanoic acid , 3-methylnonanoic acid , 3-hydroxynonanoic acid , 3-
hydroxy-3-methylnonanoic acid , 2-decenoic acid, 2-methyl-2-decenoic
acid , 3-methyl-2-decenoic acid , decanoic acid , 2-methyldecanoic acid , 3-
methyldecanoic acid , 3-hydroxydecanoic acid , 3-hydroxy-3-
methyldecanoic acid , 10-hydroxydecanoic acid , 2-undecenoic acid , 2-
methyl-2-undecenoic acid , 3-methyl-2-undecenoic acid , undecanoic acid,
2-methylundecanoic acid , 3-methylundecanoic acid, 3-hydroxyundecanoic
acid , 3-hydroxy-3-methylundecanoic acid, dodecanoic acid , 2-
hydroxydodecanoic acid , tridecanoic acid , 2-hydroxydodecanoic acid and
tridecanoic acid .
In particular, the odorous fatty acids are chosen from propionic acid, 3-
methyl-2-hexenoic acid , isovaleric acid, 2-methylbutyric acid , hexanoic
acid , octanoic acid , nonanoic acid , decanoic acid and dodecanoic acid;
b) Mercaptoalkanols such as those of formula (2) below:
HS-R 2-OH (2)
in which R2 represents a linear or branched (C1-C10 ) and preferably (Ci-
C6) alkylene group.
In particular, the mercaptoalkanol odorous molecules are chosen from 3-
methyl-3-sulfanylhexan-1 -ol, 3-sulfanylhexan-1 -ol, 2-methyl-3-
sulfanylbutan-1 -ol , 3-sulfanylpentan-1 -ol, 3-sulfanylbutan-1 -ol , 3-methyl-3-
sulfanylpentan-1 -ol and 3-methyl-3-sulfanylbutan-1 -ol;
c) steroids such as those chosen from androst-1 6-ene steroids, in
particular 5a-androst-1 6-en-3-one and 5a-androst-1 6-en-3a-ol, androst-2-
en-1 7-one, androsta-4, 16-dien-3-one, androsta-5, 16-dien-3-ol, androst-4-
en-3, 17-dione, androstan-3-one, DHEA (dehydroepiandrosterone),
testosterone, DHT (dehydrotestosterone) and 3-hydroxy-5-androstan-1 7-
one;
d) sulfoconjugated steroids, in particular the sulfate derivatives of the
compounds defined in paragraph c) above.
In particular, the odorous sulfoconjugated steroid compounds are
preferentially chosen from the sulfates derived from
dehydroepiandrosterone (DH EA), from androsterone and from
testosterone, 5a-androst-1 6-en-3a-sulfate, androsta-5, 16-dien-33-sulfate,
dehydroepiandrosterone sulfate, testosterone sulfate, 5adehydrotestosterone
sulfate and 5a-androstan-1 7-on-3a-sulfate;
e) odorous-molecule precursors chosen from conjugated fatty amino acids,
such as the conjugated product of glutamine with (E)-3-methyl-2-hexenoic
acid (a) and the conjugated product of glutamine with 3-hydroxy-3-
methylhexanoic acid (b).
Mention may also be made of the following compounds:
N2-[3-methylhex-2-enoyl]glutamine, N2-[3-methyl-3-
hydroxyhexanoyljglutamine, N2-acetylglutamine, N2-[prop-2-
enoyljglutamine, N2-[2-methylprop-2-enoyl]glutamine, N2-
propanoylglutamine, N2-[2-methylpropanoyl]glutamine, N2-[but-2-
enoyljglutamine, N2-[2-methylbut-2-enoyl]glutamine, N2-
butanoylglutamine, N2-[2-methylbutanoyl]glutamine, N2-[3-
methylbutanoyljglutamine, N2-[3-hydroxybutanoyl]glutamine, N2-[3-
hydroxy-3-methylbutanoyl]glutamine, N2-[pent-2-enoyl]glutamine, N2-[2-
methylpent-2-enoyl]glutamine, N2-pentanoylglutamine, N2-[2-
methylpentanoyljglutamine, N2-[3-methylpentanoyl]glutamine, N2-[3-
hydroxypentanoyl]glutamine, N2-[3-hydroxy-3-methylpentanoyl]glutamine,
N2-[hex-2-enoyl]glutamine, N2-[2-methylhex-2-enoyl]glutamine, N2-
hexanoylglutamine, N2-[2-methylhexanoyl]glutamine, N2-[3-
methylhexanoyl]glutamine, N2-[3-hydroxyhexanoyl]glutamine, N2-[hept-2-
enoyl]glutamine, N2-[2-methylhept-2-enoyl]glutamine, N2-
heptanoylglutamine, N2-[2-methylheptanoyl]glutamine, N2-[3-
methylheptanoyl]glutamine, N2-[3-hydroxyheptanoyl]glutamine,
N2-[3-hydroxy-3-methylheptanoyl]glutamine, N2-[oct-2-enoyl]glutamine,
N2-[2-methyloct-2-enoyl]glutamine, N2-octanoylglutamine, N2-[2-
methyloctanoyl]glutamine, N2-[3-methyloctanoyl]glutamine, N2-[3-
hydroxyoctanoyl]glutamine, N2-[3-hydroxy-3-methyloctanoyl]glutamine,
N2-[non-2-enoyl]glutamine, N2-[2-methylnon-2-enoyl]glutamine, N2-
nonanoylglutamine, N2-[2-methylnonanoyl]glutamine, N2-[3-
methylnonanoyl]glutamine, N2-[3-hydroxynonanoyl]glutamine, N2-[3-
hydroxy-3-methylnonanoyl]glutamine, N2-[dec-2-enoyl]glutamine, N2-[2-
methyldec-2-enoyl]glutamine, N2-decanoylglutamine, N2-[2-
methyldecanoyl]glutamine, N2-[3-methyldecanoyl]glutamine, N2-[3-
hydroxydecanoyl]glutamine, N2-[3-hydroxy-3-methyldecanoyl]glutamine,
N2-[undec-2-enoyl]glutamine, N2-[2-methylundec-2-enoyl]glutamine, N2-
undecanoylglutamine, N2-[2-methylundecanoyl]glutamine, N2-[3-
methylundecanoyl]glutamine, N2-[3-hydroxyundecanoyl]glutamine, N2-[3-
hydroxy-3-methylundecanoyl]glutamine, N2-[dodec-2-enoyl]glutamine, N2-
[2-methyldodec-2-enoyl]glutamine, N2-dodecanoylglutamine, N2-[2-
methyldodecanoyl]glutamine, N2-[3-methyldodecanoyl]glutamine, N2-[3-
hydroxydodecanoyl]glutamine, N2-[3-hydroxy-3-
methyldodecanoyl]glutamine and Na-hexanoylglutamine;
f ) fatty acid esters such as the acid esters of formula ( 1 ) as defined
previously, preferentially the esters of formula (3) below:
in which :
R is as defined previously; and
R'i represents i) a linear or branched (Ci-C 2o)alkyl group which is
optionally substituted , preferably with at least one hydroxyl group, ii) a
linear or branched (C2-C2o)alkenyl group which is optionally substituted ,
preferably with at least one hydroxyl group.
According to one particular form , R contains from 1 to 14 carbon atoms,
and more particularly R'-i represents a linear or branched (Ci-C6)alkyl
group such as methyl.
In particular, mention may be made of the linear or branched (Ci-C6) alkyl
esters and in particular the methyl ester of 3-hydroxy-3-methylhexanoic
acid , 3-hydroxy-4-methyloctanoic acid, (E)-3-methyl-2-hexenoic acid , 3-
hydroxyhexanoic acid and 3-hydroxyoctanoic acid .
Mention may also be made of the linear or branched (Ci-C6) alkyl esters
and in particular the methyl esters of the following acids:
acetic acid , 2-propenoic acid , propanoic acid , 2-methylpropanoic acid , 2-
methylpropenoic acid , 2-butenoic acid, 2-methyl-2-butenoic acid , 3-
methyl-2-butenoic acid , butanoic acid , 2-methylbutanoic acid , 3-
methylbutanoic acid, 3-hydroxybutanoic acid , 3-hydroxy-3-methylbutanoic
acid , 2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic
acid , pentanoic acid, 2-methylpentanoic acid , 3-methylpentanoic acid, 3-
hydroxypentanoic acid , 3-hydroxy-3-methylpentanoic acid , 2-heptenoic
acid , 2-methyl-2-heptenoic acid , 3-methyl-2-heptenoic acid , heptanoic
acid , 2-methylheptanoic acid , 3-methylheptanoic acid , 3-hydroxyheptanoic
acid , 3-hydroxy-3-methylheptanoic acid, 2-octenoic acid , 2-methyl-2-
octenoic acid , 3-methyl-2-octenoic acid, octanoic acid , 2-methyloctanoic
acid , 3-methyloctanoic acid , 3-hydroxyoctanoic acid , 3-hydroxy-3-
methyloctanoic acid , 2-nonenoic acid, 2-methyl-2-nonenoic acid , 3-
methyl-2-nonenoic acid , nonanoic acid, 2-methylnonanoic acid , 3-
methylnonanoic acid, 3-hydroxynonanoic acid, 3-hydroxy-3-
methylnonanoic acid, 2-decenoic acid, 2-methyl-2-decenoic acid, 3-
methyl-2-decenoic acid , decanoic acid , 2-methyldecanoic acid , 3-
methyldecanoic acid , 3-hydroxydecanoic acid , 3-hydroxy-3-
methyldecanoic acid , 10-hydroxydecanoic acid , 2-undecenoic acid , 2-
methyl-2-undecenoic acid , 3-methyl-2-undecenoic acid , undecanoic acid,
2-methylundecanoic acid , 3-methylundecanoic acid, 3-hydroxyundecanoic
acid , 3-hydroxy-3-methylundecanoic acid , dodecanoic acid , 2-
hydroxydodecanoic acid , tridecanoic acid , 2-hydroxydodecanoic acid or
tridecanoic acid ;
g) conjugated products of 3-methyl-3-sulfanylhexan-1 -ol and in particular
the compounds of formula (4) below:
R4-X2-C(Xi )-ALK-X ,2-C(X , )-CH (X" 2H)- ALK'-S-R' 4 (4)
in which :
R4 and R'4, which may be identical or different, represent a hydrogen
atom , a linear or branched (Ci-C 8)alkyl or linear or branched (C2-
C8)alkenyl group, such as methyl, optionally substituted with a hydroxyl
group; preferably, R4 represents a hydrogen atom and R'4 represents a
(Ci-C 6)alkyl group optionally substituted with a hydroxyl group;
ALK and ALK', which may be identical or different, represent a linear or
branched (Ci-C 8)alkylene group optionally substituted with a group -X2-R4,
with R4;
X and X2, which may be identical or different, are as defined previously,
preferably X = X2 = O;
C and X'2, and X"2, which may be identical or different, are as defined
for and X2 respectively, preferably X'2 = X"2 = NH and/or C = O.
In particular, the odorous compounds of this class are chosen from the
following compounds:
S-(1 -hydroxy-3-methylhexan-3-yl)cysteinylglycine, S-(1 -hydroxy-2-
methylhexan-3-yl)cysteinylglycine, S-(1 -hydroxy-2-m ethyl butan-3-
yl)cysteinylglycine, S-(1 -hydroxy pentan-3-y I)cysteinylglycine, S-(1 -
hydroxybutan-3-yl)cysteinylglycine, S-(1 -hydroxy-3-m ethyl pen tan-3-
yl)cysteinylglycine, S-(1 -hydroxy-3-methylbutan-3-yl)cysteinylglycine, S-
( 1-hydroxyhexan-3-yl)cysteinylglycine and S-(1 -hydroxy-2-methylhexan-3-
yl)cysteinylglycine;
h) ketone compounds, such as 6 ,10-dimethyl-5,9-undecadien-2-one or
tridecanone;
i) alkanols such as isopentanol or 1-decanol.
More particularly, the odorous molecules capable of being efficiently
captured by the cyclodextrin polycondensates of the invention are chosen
from 3-methyl-2-hexenoic acid , octanoic acid , nonanoic acid , decanoic
acid , 6 ,10-dimethyl-5,9-undecadien-2-one, tridecanone, isopentanol and
1-decanol.
Among the substances capable of generating discomfort with regard to
keratin materials, mention may be made of sweat (eccrine or apocrine)
secreted by the sweat glands during perspiration . Sweat contains mainly
water. It also contains minerals, in addition to lactate which is an ionized
form of lactic acid , and urea.
The strong water-absorbing capacity of the cyclodextrin polycondensates
of the invention makes it possible to efficiently capture the constituents of
sweat when said polycondensates are applied to keratin materials.
A subject of the invention therefore consists of a process for cosmetic
treatment of human perspiration and/or of body odours, consisting in
applying, to the surface of a human keratin material, a composition
comprising, in a physiologically acceptable medium, at least one
cyclodextrin polycondensate as defined previously.
Among the substances capable of generating discomfort with regard to
keratin materials, mention may be made of the excess sebum produced by
the sebaceous glands in greasy skin or on individuals prone to greasy
hair. Human sebum generally comprises in its composition lipids
comprising squalene (approximately 15%), ester waxes (approximately
25%), cholesterol esters (approximately 2%), triglycerides (approximately
57%) and cholesterol (approximately 1%).
The strong lipid-adsorbing capacity of the cyclodextrin polycondensates of
the invention makes it possible to efficiently capture the excess sebum
when said polycondensates are applied to the surface of the skin , the hair
or the scalp, and to treat greasy skin and greasy hair against seborrhoea
and the appearance of oily dandruff and to prevent skin or hair disorders
resulting therefrom .
Another subject of the invention therefore consists of a non-therapeutic
cosmetic process for caring for and/or cleansing a human keratin material
which is greasy or prone to be greasy, comprising at least one step of
topical application , to said keratin material, of a composition comprising,
in a physiologically acceptable medium, at least one cyclodextrin
polycondensate as defined previously.
BENEFICIAL AGENTS
The cyclodextrin polycondensates according to the invention can also be
used for trapping at least one beneficial agent, as described previously.
These beneficial agents are chosen from :
a) Fatty substances
Fatty substances are commonly used in the formulation of pharmaceutical,
cosmetic and/or food-processing compositions. They may be chosen from
the group comprising:
(i) natural oils of vegetable, animal or marine origin , such as olive oil,
sesame oil, argan oil, palm oil, soya bean oil, woad oil, babassu oil, aloe
vera, avocado oil, allantoin , bisabol, grapeseed oil, apricot oil, wheat
germ oil, almond oil, groundnut oil, macadamia nut oil, buckthorn oil,
evening primrose oil, borage oil , ginger oil, geraniol , jujube oil , mink oil or
lanolin ,
(ii) synthetic oils,
(iii) mineral oils, such as isohexadecane, para-isoparaffin , ceresin or
petroleum jelly,
(iv) hydrogenated oils,
(v) silicone oils,
(vi) hydrocarbon-based compounds, such as paraffin oil ,
(vii) terpenes,
(viii) squalene,
(ix) saturated or unsaturated fatty acids, such as myristic acid ,
(x) fatty acid esters,
(xi) waxes, beeswax, jojoba oil which is in fact a liquid wax, ester waxes,
(xii) fatty alcohols, such as myristyl alcohol , cetyl alcohol, stearyl alcohol
or myricyl alcohol,
(xiii) butters, such as shea butter or cocoa butter,
(xiv) or a mixture thereof.
One of the possible applications according to the invention is the
conveying of fatty substances for cosmetic use or for food use or for
dietary cosmetic use, such as nutritive supplements.
b) Flavouring substances and taste enhancers
One of the possible applications according to the invention is the
conveying of flavouring substances and/or of taste enhancers for food use
or for dietary cosmetic use, such as nutritive supplements.
1) Flavouring substances
Among the flavouring substances, mention may be made of those chosen :
(i) from those indicated in the official list established by the
European Council in the publication Substances aromatisantes et
sources naturelles de matieres aromatisantes [Flavouring
substances and natural sources of flavouring materials], vol. 1,
4th edition , 1992, Maisonneuve;
(ii) from those indicated in the FEMA/GRAS official lists published
by the Food and Drug Administration (FDA).
2) Flavour enhancers
The European Union defines flavour enhancers in the list of food additives
via an E number. They are numbered from E620 (glutamic acid) to E641
(L-leucine).
Among the flavour enhancers, mention may be made of
i) glutamates such as glutamic acid (E620), monosodium glutamate
(E62 1) , monopotassium glutamate (E622), calcium diglutamate
(E623), ammonium glutamate (E624) or magnesium diglutamate
(E625);
(ii) guanylates such as guanylic acid or guanisine monophosphate
(E626), disodium guanylate (E627), dipotassium guanylate
(E628) or calcium guanylate (E629);
(iii) inosinates such as inosinic acid (E630), disodium inosinate
(E63 1) , dipotassium inosinate (E632) or calcium inosinate
(E633).
Mention may also be made of calcium 5'-ribonucleotide (E634), disodium
5'-ribonucleotide (E635), maltol (E636), ethylmaltol (E637), glycine (E640)
and L-leucine (E64 1) .
Mention may also be made of the following additives considered to be
enhancers: lactic acid (acidifier) (E270), sweeteners such as acesulfame-
K (E950), aspartame (E951 ) , thaumatin (E957), neohesperidin
dihydrochalcone (E959), neotame (E961 ) or erythritol (E968).
c) Fragrancing substances
The term "fragrancing substance" is intended to mean any fragrance or
aroma capable of giving off a pleasant odour.
Fragrances are compositions in particular containing the starting materials
described in S. Arctander, Perfume and Flavor Chemicals (Montclair, N.J .,
1969), in S. Arctander, Perfume and Flavor Materials of Natural Origin
(Elizabeth , N.J ., 1960) and in Flavor and Fragrance Materials - 1991,
Allured Publishing Co., Wheaton, III.
They may also be natural products, for instance essential oils, absolutes,
resinoids, resins, concretes, and/or synthetic products (terpene or
sesquiterpene hydrocarbons, alcohols, phenols, aldehydes, ketones,
ethers, acids, esters, nitriles or peroxides, which may be saturated or
unsaturated , and aliphatic or cyclic).
According to the definition given in international standard ISO 9235 and
adopted by the Commission of the European Pharmacopoeia, an essential
oil is an odorous product generally of complex composition , obtained from
a botanically defined plant starting material, either by steam distillation, or
by dry distillation , or via an appropriate mechanical method without
heating (cold pressing). The essential oil is generally separated from the
aqueous phase by a physical method which does not result in any
significant change in the composition .
Among the essential oils that may be used according to the invention ,
mention may be made of those obtained from plants belonging to the
following botanical families:
Abietaceae or Pinaceae: conifers; Amaryllidaceae; Anacardaceae;
Anonaceae: ylang ylang; Apiaceae (for example Umbelliferae): dill,
angelica, coriander, sea fennel, carrot, parsley; Araceae;
Aristolochiaceae; Asteraceae: yarrow, artemisia, camomile, helichrysum;
Betulaceae; Brassicaceae; Burseraceae: frankincense; Carophyllaceae;
Canellaceae; Cesalpiniaceae: copaifera (copaiba balsam);
Chenopodaceae; Cistaceae: rock rose; Cyperaceae; Dipterocarpaceae;
Ericaceae: gaultheria (wintergreen); Euphorbiaceae; Fabaceae;
Geraniaceae: geranium ; Guttiferae; Hamamelidaceae; Hernandiaceae;
Hypericaceae: St. John's wort; Iridaceae; Juglandaceae; Lamiaceae:
thyme, oregano, monarda, savory, basil, marjorams, mints, patchouli,
lavenders, sages, catnip, rosemary, hyssop, balm; Lauraceae: ravensara,
sweet bay, rosewood , cinnamon , litsea; Liliaceae: garlic; Magnoliaceae:
magnolia; Malvaceae; Meliaceae; Monimiaceae; Moraceae: hemp, hop;
Myricaceae; Myristicaceae: nutmeg; Myrtaceae: eucalyptus, tea tree,
paperbark tree, cajuput, backhousia, clove, myrtle; Oleaceae; Piperaceae:
pepper; Pittosporaceae; Poaceae: lemon balm, lemongrass, vetiver;
Polygonaceae; Renonculaceae; Rosaceae: roses; Rubiaceae; Rutaceae:
all citrus plants; Salicaceae; Santalaceae: sandalwood ; Saxifragaceae;
Schisandraceae; Styracaceae: benzoin ; Thymelaceae: agar wood;
Tilliaceae; Valerianaceae: valerian , spikenard ; Verbenaceae: lantana,
verbena; Violaceae; Zingiberaceae: galanga, turmeric, cardamom, ginger;
Zygophyllaceae.
Mention may also be made of the essential oils extracted from flowers
(lily, lavender, rose, jasmine, ylang ylang, neroli), from stems and leaves
(patchouli, geranium, petitgrain), from fruit (coriander, aniseed , cumin,
juniper), from fruit peel (bergamot, lemon, orange), from roots (angelica,
celery, cardamom, iris, rattan palm, ginger), from wood (pinewood,
sandalwood , gaiac wood, rose of cedar, camphor), from grasses and
gramineae (tarragon , rosemary, basil, lemongrass, sage, thyme), from
needles and branches (spruce, fir, pine, dwarf pine) and from resins and
balms (galbanum, elemi, benzoin , myrrh , olibanum , opopanax).
Examples of fragrancing substances are in particular: geraniol, geranyl
acetate, farnesol, borneol, bornyl acetate, linolool, linalyl acetate, linalyl
propionate, linalyl butyrate, tetrahydrolinolool, citronellol, citronellyl
acetate, citronellyl formate, citronellyl propionate, dihydromyrcenol,
dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, terpinyl acetate,
nopol , nopyl acetate, nerol, neryl acetate, 2-phenylethanol, 2-phenylethyl
acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl
acetate, benzyl benzoate, amyl salicylate, dimethylbenzylcarbinol,
trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyl acetate,
isononyl acetate, vetiveryl acetate, vetiverol, a-hexylcinnamaldehyde, 2-
methyl-3-(p-tert-butylphenyl)propanal, 2-methyl-3-(pisopropylphenyl)
propanal, 3-(p-tert-butylphenyl)propanal, 2,4-
dimethylcyclohex-3-enylcarboxaldehyde, tricyclodecenyl acetate,
tricyclodecenyl propionate, 4-(4-hydroxy-4-methylpentyl)-3-
cyclohexenecarboxaldehyde, 4-(4-methyl-3-pentenyl)-3-
cyclohexenecarboxaldehyde, 4-acetoxy-3-pentyltetrahydropyran , 3-
carboxymethyl-2-pentylcyclopentane, 2-n-4-heptylcyclopentanone, 3-
methyl-2-pentyl-2-cyclopentenone, menthone, carvone, tagetone,
geranylacetone, n-decanal, n-dodecanal, 9-decen-1 -ol, phenoxyethyl
isobutyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde
diethyl acetal, geranonitrile, citronellonitrile, cedryl acetate, 3-
isocamphylcyclohexanol, cedryl methyl ether, isolongifolanone,
aubepinonitrile, aubepine, heliotropin, coumarin , eugenol, vanillin ,
diphenyl ether, citral, citronellal, hydroxycitronellal, damascone, ionones,
methylionones, isomethylionones, solanone, irones, cis-3-hexenol and
esters thereof, musk-indans, musk-tetralins, musk-isochromans,
macrocyclic ketones, musk-macrolactones, aliphatic musks, ethylene
brassylate and rose essence, and mixtures thereof.
Another of the possible applications is, for example, the conveying of
fragrancing substances for the manufacture of perfumery products
(fragrances, eaux de toilette, eaux de parfum, aftershave lotions),
cosmetic products for caring for and/or cleansing keratin materials, in
particular human keratin materials, makeup products, laundry cleaning
and/or care products, household products, in the manufacture of clothing,
shoes, soles and products for the maintenance thereof, in products
intended for animal hygiene, such as litters, in inks, products resulting
from the paper industry, in products intended for babycare (wipes,
nappies), in products intended for intimate hygiene (tampons, wipes,
towels), in products for sanitary use, and in food-processing products and
products resulting from agriculture.
d) Pharmaceutical active ingredients
The term "pharmaceutical active ingredient" is intended to mean a
molecule which has a curative and/or prophylactic therapeutic effect.
For example, it may be any molecule with therapeutic properties which is
part of the composition of a medicament. Mention may be made, for
example, of non-steroidal anti-inflammatory drugs (NSAI Ds),
abortifacients, alpha-blockers, alpha2-agonists, aminosides, analgesics,
anaesthetics, local anaesthetics, anorexigenics, 5HT3 antagonists,
calcium antagonists, anti-angina agents, antiarrhythmics, antibiotics,
anticholinergics, anticholinesterases, antidiabetics, anti-diarrhoea agents,
antidepressants, antihistamines, antihypertensives, antimycotics,
antimalarials, antiparasitics, antipsychotics, antipyretics, antiretrovirals,
antiseptics, antispasmodics, antivirals, antiemetics, antiepileptics,
anxiolytics, barbiturates, benzodiazepines, bronchodilators, beta-blockers,
chemotherapy agents, corticosteroids, diuretics, loop diuretics, osmotic
diuretics, depressants, glucocorticoids, hallucinogenics, hypnotics,
immunosupressants, carbonic anhydrase inhibitors, neuraminidase
inhibitors, proton pump inhibitors, TNF inhibitors, selective serotonin
reuptake inhibitors, HMG-CoA reductase inhibitors (or statins),
keratolytics, laxatives, mineralocorticoids, muscle relaxants, neuroleptics,
psychotropics, spasmolytics, stimulants, sedatives, tocolytics or
vasodilators. This list is not exhaustive and extends to any therapeutic
active ingredient known to those skilled in the art.
e) Cosmetic active agents
The term "cosmetic active agent" is intended to mean any molecule which
has a hygiene, care, makeup or dyeing effect contributing to improving the
well-being and/or to making more attractive the appearance of the human
keratin material to which said composition is applied .
The cosmetic active agents can therefore be chosen from any of the
substances which meet this definition and which are present in products
such as
(i) hygiene products: makeup-removing products, toothpastes, deodorants,
antiperspirants, shower gels, bath preparations (bubble bath , bath oil ,
bath salts), intimate cleansing gels, soaps, shampoos,
(ii) care products: antiwrinkle cream , day cream, night cream , moisturizing
cream, floral water, scrubbing product, milk, beauty mask, lip balm , tonic,
(iii) hair care and/or treatment products, such as styling products, dyeing
products, permanent-waving products, conditioning products: conditioner,
hair relaxing product, hair straightening product; gel, oil, lacquer, mask,
(iv) makeup products: concealer, eyeliner, face powder, foundation , khol,
mascara, powder, skin whitening product, lipstick, nail varnish ,
(v) fragrances: eau de Cologne, eau de toilette, perfume,
(vi) suntan products: self-tanning products, aftersun and suntan creams,
milks, oils, sticks or solutions,
(vii) shaving products and hair removal products: aftershave, hair removal
cream, shaving foam and gels.
Among the active agents for caring for human keratin materials such as
the skin , the lips, the scalp, the hair, the eyelashes or the nails, examples
that may be mentioned include:
- vitamins and derivatives or precursors thereof, alone or as mixtures;
- antioxidants;
- cleansing agents;
- hair dyes;
- conditioning agents;
- hair relaxing and/or straightening and/or shaping agents;
- free-radical scavengers;
- agents for combating pollutants;
- photoprotective agents such as organic screening agents, inorganic UVscreening
agents;
- self-tanning agents;
- antiglycation agents;
- soothing agents;
- hair removal agents;
- deodorants;
- antiperspirants;
- essential oils;
- NO-synthase inhibitors;
- agents which stimulate the synthesis of dermal or epidermal
macromolecules and/or which prevent degradation thereof;
- agents which stimulate the proliferation of fibroblasts;
- agents which stimulate the proliferation of keratinocytes;
- dermo-relaxing agents;
- refreshing agents;
- tensioning agents;
- mattifying agents;
- depigmenting agents;
- propigmenting agents;
- keratolytic agents;
- desquamating agents;
- moisturizing agents;
- antimicrobial agents;
- slimming agents;
- agents which act on the energy metabolism of cells;
- insect repellents;
- substance-P or CGRP antagonists;
- agents for combating hair loss;
- antiwrinkle agents;
- anti-ageing agents.
The cyclodextrin polycondensates according to the invention can be used
very advantageously in a cosmetic or dermatological composition which
comprises, moreover, a physiologically acceptable medium .
The amount of cyclodextrin polycondensate present in the compositions
obviously depends on the type of composition and on the desired
properties and may vary within a very wide range, generally ranging from
0 .1% to 100% by weight, preferably from 0.5% to 95% by weight, in
particular from 1% to 70% by weight, or even from 1.5% to 50% by weight
and better still from 2% to 20% by weight, relative to the total weight of
the composition .
The composition may thus comprise, depending on the intended
application , constituents that are common for this type of composition .
The composition according to the invention may advantageously comprise
at least one fatty phase which may comprise at least one compound
chosen from volatile or non-volatile carbon-based , hydrocarbon-based ,
fluoro and/or silicone oils, waxes and/or solvents of mineral , animal, plant
or synthetic origin, alone or as a mixture, provided that they form a stable,
homogeneous mixture and are compatible with the intended use.
For the purpose of the invention , the term "volatile" is intended to mean
any compound that is capable of evaporating on contact with keratin
materials in less than one hour, at ambient temperature (25°C) and
atmospheric pressure ( 1 atm). In particular, this volatile compound has a
non-zero vapour pressure, at ambient temperature and atmospheric
pressure, ranging from 0 .13 Pa to 40 000 Pa ( 10 3 to 300 mmHg), in
particular ranging from 1.3 Pa to 13 000 Pa (0.0 1 to 100 mmHg), and more
particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
In contrast, the term "non-volatile" is intended to mean a compound that
remains on human keratin materials at ambient temperature and
atmospheric pressure for at least one hour and that in particular has a
vapour pressure of less than 10 3 mmHg (0. 13 Pa).
The fatty phase may represent from 1% to 99% by weight of the
composition , especially from 5% to 95% by weight, in particular from 10%
to 90% by weight, or even from 20% to 85% by weight, of the total weight
of the composition .
The composition may also comprise other ingredients commonly used in
cosmetic compositions. Such ingredients may be chosen from
antioxidants, fragrances, essential oils, preservatives, cosmetic active
agents, moisturizers, vitamins, ceramides, sunscreens, surfactants,
spreading agents, wetting agents, dispersants, antifoams, neutralizing
agents, stabilizers, polymers and in particular liposoluble film-forming
polymers, and mixtures thereof.
Needless to say, those skilled in the art will take care to select this or
these optional additional compound(s) and/or the amounts thereof so that
the advantageous properties of the composition for the use according to
the invention are not, or not substantially, adversely affected by the
envisaged addition .
The compositions according to the invention may be in any common
acceptable form for a cosmetic or dermatological composition .
Those skilled in the art may select the appropriate galenical form , and
also the method for preparing it, on the basis of their general knowledge,
taking into account both the nature of the constituents used , in particular
their solubility in the support, and also the intended use of the
composition .
The invention is illustrated in greater detail in the following examples.
Preparation examples
The information regarding the various starting materials used in the
examples that follow are summarized in the following table.
1) Synthesis of cyclodextrin polycondensates
Example 1a
The b-cyclodextrin polycondensate 1a was obtained after extrusion of the b-cyclodextrin
(CD) in the presence of hydroxypropylcellulose (HPC), citric acid and sodium dihydrogen
phosphate (DHPS). The proportions of each constituent are indicated as percentages by
weight below:
Polymer -CD HPC Citric Sodium dihydrogen
acid phosphate
1a 45.16 30 22.58 2.28
According to this preparation mode, all the ingredients which are part of the composition
for obtaining the polycondensate 1a were incorporated at the same time in the extrusion
tool (Clextral BC 2 1 twin-screw extruder) at a temperature of 170°C.
The extrusion conditions are summarized hereinafter:
After milling, the polycondensate 1a was obtained in the form of a cream-coloured
powder with an average particle size of 10 m h .
Protocol for measuring the degree of swelling in water:
2 g of milled cyclodextrin polycondensate 1a were suspended in 20 g of demineralized
water with light stirring for 24 h at ambient temperature. The suspension was centrifuged
in order to separate the supernatant and the solids content was determined on the
centrifugate using a thermobalance. The % degree of swelling was obtained by
calculating the evaporated weight/dry weight ratio x 100.
The cyclodextrin polycondensate 1a has an acid number of 150 mg of potassium
hydroxide per g of polycondensate and a degree of swelling in water of 805%.
Examples 1b, 2a, 2b and 2c
The following cyclodextrin polycondensates (composition and synthesis conditions) were
synthesized according to the same process: the proportions of each constituent are
indicated as percentages by weight hereinafter:
Cyclodextrin b -GD -CD Y-CD HPC Citric Maleic DHPS
polycondensates acid anhydride
1b 44.71 0 0 29.7 22.35 1 2.24
2a 40.63 0 4.51 30 22.58 0 2.28
2b 3 1.61 13.53 0 30 22.58 0 2.28
2c 3 1.61 9.02 4.51 30 22.58 0 2.28
The extrusion conditions, the acid number of the cyclodextrin polycondensates obtained
5 and also their degree of swelling in water, measured according to the same conditions as
Example 1a, are summarized hereinafter.
10 Comparative example A of cyclodextrin polycondensate synthesis according to
the process of patent EP1 165621 B1
1 litre of demineralized water, 50 g of sodium dihydrogen phosphate NaH2P0 4, 500 g of
citric acid monohydrate and 1 kg of b-cyclodextrin were placed in a 2-litre round-bottomed
15 flask. The reaction medium was stirred and heated to 60°C-70°C in order to completely
dissolve the starting compounds. The solution obtained was transferred into a
crystallizing dish, the size of which is chosen so as to obtain a liquid height of
approximately 6 cm. The crystallizing dish was placed in an oven heated at 100°C for 80
h (a soft gel was obtained). The temperature was then increased to 140°C for 4 h and
then allowed to return to ambient temperature. The solid obtained was detached from the
crystallizing dish and then finely milled using a knife mill of coffee mill type. It was
analyzed by 2D DOSY NMR which made it possible to demonstrate the covalent grafting
of the citric acid onto the b-cyclodextrin so as to form an oligomer, the diffusion coefficient
of which is 173 m 2/8, which corresponds to a molecular weight estimated at
approximately 3800 g/mol. Its acid number is 195 mg of potassium hydroxide per g of
polycondensate and its degree of swelling in water is 0% since it is entirely soluble at
ambient temperature (solubility greater than 30%).
2) Capturing of malodorous compounds
An analysis was carried out by two-dimensional gas chromatography (GCxGC/MS) for
the purpose of evaluating and mapping the capacity of the cyclodextrin polycondensates
according to the invention to capture/trap the malodorous compounds resulting from the
developing sweat.
Test protocol
500 m I of sweat were placed in a 6-ml Headspace® flask and 2, 5, 10 or 25 mg of
cyclodextrin polycondensate to be evaluated were added. The flask was crimped (with
Al/Si septum) and was placed in an oven at 37°C for 24 hours and then acidified by
adding 50 m I of 1N HCI.
A control sweat was used: same protocol but without the addition of cyclodextrin
polycondensate.
A solid-phase microextraction (SPME) was carried out on PDMS / DVB 65 m h fibre for 45
min at 37°C. The fibre was desorbed in the injector of the chromatograph GC1 for 5
minutes, and then conditioned for 30 minutes in another injector of a chromatograph
GC2.
The mapping of the odorous molecules produced by the developing sweat was evaluated
by mass spectography respectively on the control sweat and on the sweat incubated in
the presence of cyclodextrin polycondensate 1a.
GCxGC/MS instrumentation
Gas chromatograph 1
Autoinjector: GC-2010 and AOC-20i (Shimadzu)
Column: Rxi-5ms (Restek); 30 m x 0.25 mm ID x 0.1 m h df
Program temperature: 60°C ( 1 min) ® 270°C at 6°C/min
Constant linear speed: 27 cm/sec (initial helium pressure: 36.1 psi)
Injection mode: with divider (divider ratio: 10/1)
Injection temperature: 250°C
Injection mode: solid-phase microextraction
Transfer line temperature: 280°C
Gas chromatograph 2
Autoinjector: GC-2010 (Shimadzu)
Column: Rtx-200 (Restek); 1.5 m x 0.1 mm ID x 0.1 mhi df
Program temperature: 40°C (2 min) ® 245°C at 6°C/min
Mass spectrometer:
QP201 0 plus MS Detector (Shimadzu)
Mapper (Chrom Square)
Winder correction: 0.5 sec
Scale 20000 ® 1.0E6
Results obtained with polycondensate 1a
It was observed that, with the addition of 25 mg of polycondensate, the following
malodorous compounds produced by sweat: 3-methyl-2-hexenoic acid, octanoic acid,
6,10-dimethyl-5,9-undecadien-2-one, tridecanone, nonanoic acid, decanoic acid,
dodecanoic acid, isopentanol and 1-decanol, were totally captured.
3) Encapsulation of a fragrancing substance
The encapsulation properties of the b-cyclodextrin polymer 1a were measured and
compared with b-cyclodextrin alone, but also
- with the b-cyclodextrin polycondensate of Comparative Example A as described
above, and
- with the b-cyclodextrin polycondensate crosslinked with epichlorohydrin containing
54% of CD sold by Cyclolab under the reference CY-2009® (Comparative
Example B).
Protocol for measuring the encapsulation capacity
5 g of dihydromyrcenol (fragrance) were added to 1 g of each tested compound, and then
the mixture was left underlight stirring for 24 hours. After centrifugation to remove the
non-impregnated fragrance, and air-drying at ambient temperature in a dry atmosphere
for 24 h, the impregnated compound was heated at 150°C using a thermobalance, also
known as a halogen desiccator (Mettler Toledo model HG63), until the weight was
constant.
The amount of dihydromyrcenol encapsulated in the matrix of each tested compound was
thus measured.
An amount of between 0.5 g and 1 g of impregnated compound was deposited on the
dish and then the heating was begun, with the weight loss being recorded every 2
minutes. When the weight was constant, the apparatus automatically stopped the heating
and produced the following data: initial weight, final weight, % solids content at 2 minute
intervals, total duration of evaporation.
The results of dihydromyrcenol encapsulation according to the protocol described
previously are summarized in the table hereinafter:
It was observed that the b-cyclodextrin polycondensate of Example 1a according to the
invention exhibits a level of fragrance encapsulation which is 3.7 times greater than that
of b-cyclodextrin, than that of the comparative b-cyclodextrin polycondensate A and than
that of the comparative b-cyclodextrin polycondensate B.
Example 1: Deodorant and antiperspirant formulation
Examples 1c, 3a, 3b
The following cyclodextrin polycondensates (composition and synthesis conditions) were
synthesized according to the same process: the proportions of each constituent are
indicated as percentages by weight hereinafter:
Cyelodextrin P-CD HPC Citric Acid BELCLENE 283 ® DHPS
Polycondensate
1c (invention) 45,1 29,8 22,8 2,3
a (comparative) 65,9 29,8 2 2,3
b (comparative) 45,1 29,8 22,8 2,3
The extrusion conditions are summarized hereinafter.
Encapsulation of a fragrancing substance
The encapsulation properties of the b-cyclodextrin polymer 1c were measured and
compared to the b-cyclodextrin polycondensate 3a as described above, and
Protocol for measuring the encapsulation capacity
5 g of dihydromyrcenol (fragrance) were added to 1 g of each tested compound, and then
the mixture was left underlight stirring for 24 hours. After centrifugation to remove the
non-impregnated fragrance, and air-drying at ambient temperature in a dry atmosphere
for 24 h, the impregnated compound was heated at 150°C using a thermobalance, also
known as a halogen desiccator (Mettler Toledo model HG63), until the weight was
constant.
The amount of dihydromyrcenol encapsulated in the matrix of each tested compound was
thus measured.
An amount of between 0.5 g and 1 g of impregnated compound was deposited on the
dish and then the heating was begun, with the weight loss being recorded every 2
minutes. When the weight was constant, the apparatus automatically stopped the heating
and produced the following data: initial weight, final weight, % solids content at 2 minute
intervals, total duration of evaporation.
The results of dihydromyrcenol encapsulation according to the protocol described
previously are summarized in the table hereinafter:
It was observed that the b-cyclodextrin polycondensate of Example 1c according to the
invention exhibited a level of fragrance encapsulation which was 3.4 times greater than
that of the comparative b-cyclodextrin polycondensate 3a.
Reduction of malodor
Protocol of the test
A pool of sweat is extracted from a panel of 6 male volunteers having a more or less
pronounced malodour degree.
1ml of sweat were placed in a 10 ml Headspace® flask and 10 or 50 mg of cyclodextrin
polycondensate to be evaluated were added at a concentration respectively of 10mg/ml
(1% by weight) or 50 mg/ml (5% by weight).
The samples were placed in an oven at 35°C, in an orbital stirrer turning at 140 rpm and
were incubed during 24 hours.
The samples were evaluated after incubation and compared to two sweat controls on the
same time : a positive sweat control containing 0.1% by weight of Aluminium
Chlorhydrate and a negative sweat control with sweat alone.
3 separated experts evaluated the samples.
The deodorant efficacy was evaluated by a "sniff test" according to the following criteria :
- The intensity of the perspiration odour (scale of 0 : imperceptible smell intensity to 10 :
extremely strong smell intensity) ;
- Residual of the smell (scale of 0: imperceptible malodor to 10 : very important residual
malodor)
- The hedonic value (scale of 0: extremely unpleasant smell to 10: extremely pleasant
smell).
It was observed that the cyclodextrin polycondensate 1c according to the present
invention had a good deodorant efficacy which can reach the level of an aluminum salt
contrarily to the comparative cyclodextrin polycondensate 3a which had a low efficacy.

CLAIMS
1. Water-insoluble cyclodextrin polycondensate which can be obtained
by esterification/polycondensation reaction :
A) of at least one cyclodextrin and
B) of at least one saturated or unsaturated or aromatic, linear or
branched or cyclic polycarboxylic acid and/or at least one ester or one
acid anhydride or one acid halide of said polycarboxylic acid and
C) of at least one thermoplastic polyol polymer and
D) optionally of at least one esterification catalyst and/or
E) optionally of at least one cyclic anhydride of a polycarboxylic acid
chosen to be other than the polycarboxylic acid anhydride of paragraph
B) and/or
F) optionally of at least one non-polymeric polyol comprising from 3 to 6
hydroxyl groups.
2. Polycondensate according to Claim 1, in which the ratio between the
number of moles of polycarboxylic acid and the number of moles of the
cyclodextrin ranges from 0.5 to 5 , especially from 0.6 to 4 and in
particular from 0.7 to 3 .
3. Polycondensate according to Claim 1 or 2 , which has an acid number,
expressed in mg of potassium hydroxide per g of polycondensate,
greater than or equal to 20, preferably ranging from 20 to 250 and even
better still ranging from 40 to 180.
4. Polycondensate according to any one of Claims 1 to 3 , characterized
in that it exhibits a degree of swelling in water, measured at 20°C,
greater than or equal to 100%, in particular ranging from 100% to 1000%
and even better still ranging from 300% to 900%.
5. Polycondensate according to any one of Claims 1 to 4 , in which the
cyclodextrin is chosen from a-cyclodextrin , b-cyclodextrin , g -cyclodextrin
and mixtures thereof, and even better still is b-cyclodextrin .
6 . Polycondensate according to any one of Claims 1 to 5 , in which the
polycarboxylic acid is aliphatic, saturated and linear and contains 2 to
36 carbon atoms, in particular 3 to 18 carbon atoms or even 4 to 12
carbon atoms; or alternatively the polycarboxylic acid is aromatic and
contains 8 to 12 carbon atoms; more preferentially, it comprises from 2
to 4 COOH groups and is chosen more particularly from citric acid,
aconitic acid , tartaric acid , 1,2,3-propanetricarboxylic acid and 1,2,3,4-
butanetetracarboxylic acid , alone or as a mixture, preferably alone, and
even better still citric acid alone.
7. Polycondensate according to any one of Claims 1 to 6 , in which :
(i) the ester of said polycarboxylic acid is a C 1- C 4 alkyl mono-, di-, tri- or
tetraester and in particular the methyl, ethyl, isopropyl or n-butyl esters
and more preferentially the methyl or ethyl esters and more preferentially
the methyl or ethyl esters of aliphatic, saturated , linear polyacids
containing from 2 to 4 COOH groups and containing 2 to 36 carbon atoms,
in particular 3 to 18 carbon atoms, or even 4 to 12 carbon atoms; or
alternatively of an aromatic acid containing 8 to 12 carbon atoms;
(ii) the acid anhydride is chosen from a) mixed anhydrides with a C2-C4
carboxylic acid , in particular acetic acid , propionic acid or butyric acid ,
preferably acetic acid , or else b) cyclic anhydrides such as phthalic
anhydride, trimellitic anhydride, maleic anhydride, succinic anhydride or
N,N,N' ,N'-ethylenediaminetetraacetic acid dianhydride;
(iii) the acid halide is chosen from the acid chlorides and acid bromides of
said polycarboxylic acid , preferably the halides of aconitic acid , of tartaric
acid , of 1,2,3-propanetricarboxylic acid and of 1,2,3,4-
butanetetracarboxylic acid , and preferably the chlorides of these acids.
8 . Polycondensate according to any one of Claims 1 to 7 , in which the
thermoplastic polyol is chosen from polyether-polyols, polyester-polyols,
polycarbonate-polyols, polyamide-polyols, polyurethane-polyols,
polyalkylene-polyols, polycaprolactone-polyols and polysaccharides, and
preferably polysaccharides and more preferentially cellulose derivatives
and more particularly hydroxypropylcellulose and hydroxyethylcellulose
and even better still hydroxypropylcellulose alone.
9 . Polycondensate according to any one of Claims 1 to 8 , in which the
polycarboxylic acid cyclic anhydride, when present, corresponds to one of
the following formulae:
in which the groups A and B are, independently of each other:
- a hydrogen atom ;
- a saturated or unsaturated , linear, branched and/or cyclic aliphatic, or
alternatively aromatic, carbon-based radical containing 1 to 16 carbon
atoms, in particular 2 to 10 carbon atoms or even 4 to 8 carbon atoms, in
particular methyl or ethyl;
or alternatively A and B, taken together, form a saturated or
unsaturated , or even aromatic, ring containing in total 5 to 7 and in
particular 6 carbon atoms; more preferentially A and B represent a
hydrogen atom or together form an aromatic ring containing in total 6
carbon atoms, and more particularly, alone or as a mixture, phthalic
anhydride, trimellitic anhydride, maleic anhydride and succinic anhydride
and even better still maleic anhydride alone.
10 . Polycondensate according to any one of Claims 1 to 9 , in which the
esterification catalyst, when present, is chosen from dihydrogen
phosphates, hydrogen phosphates, phosphates, hypophosphites and
phosphites of alkali metals, alkali metal salts of polyphosphoric acids,
alkali metal or alkaline-earth metal carbonates, bicarbonates, acetates,
borates and hydroxides, aliphatic amines and aqueous ammonia,
optionally combined with an inorganic solid support such as alumina, silica
gels, aluminium silicates, zeolites, titanium oxides or zirconium oxides,
sulfonic acids or titanates and preferably is chosen from sodium hydrogen
phosphate, sodium dihydrogen phosphate and sodium hypophosphite and
even better still sodium dihydrogen phosphate.
1 1 . Polycondensate according to any one of Claims 1 to 10 , in which the
non-polymeric polyol containing 3 to 6 hydroxyl groups, when it is present,
is a linear, branched and/or cyclic, saturated or unsaturated carbon-based
and in particular hydrocarbon-based compound containing 3 to 18 carbon
atoms, in particular 3 to 12 or even 4 to 10 carbon atoms, and 3 to 6
hydroxyl (OH) groups, and also possibly comprising one or more oxygen
atoms inserted in the chain (ether function), and is preferably a linear or
branched saturated hydrocarbon-based compound containing 3 to 18
carbon atoms, in particular 3 to 12 or even 4 to 10 carbon atoms and even
more preferentially chosen from triols, tetraols, pentols and hexols and
more particularly chosen from glycerol, pentaerythritol, diglycerol and
sorbitol, and mixtures thereof; and even better still glycerol alone.
12 . Polycondensate according to any one of Claims 1 to 11, in which :
- the cyclodextrin(s) represent(s) from 10% to 70% by weight relative to
the total weight used in the synthesis of the polycondensate;
- the polycarboxylic acid(s) and/or ester, acid anhydride or acid halide
derivatives thereof represent from 5% to 40% by weight relative to the
total weight used in the synthesis of the polycondensate;
- the thermoplastic polyol polymer(s) represent(s) from 10% to 50% by
weight relative to the total weight used in the synthesis of the
polycondensate;
- the polycarboxylic acid cyclic anhydride(s) when present represent(s)
from 0 .1% to 10% by weight relative to the total weight used in the
synthesis of the polycondensate;
- the esterification catalyst(s), when it (they) is (are) present, represent(s)
from 0 .1% to 5% by weight relative to the total weight used in the
synthesis of the polycondensate;
- the non-polymeric polyol(s) comprising 3 to 6 hydroxyl groups
represent(s), when present, from 1% to 30% by weight relative to the total
weight used in the synthesis of the polycondensate.
13 . Process for preparing a cyclodextrin polycondensate as defined
according to any one of the preceding claims, characterized in that it
comprises at least the following steps:
i) at least one cyclodextrin , at least one polycarboxylic acid and/or an
ester, acid anhydride or acid halide derivative thereof, at least one
thermoplastic polyol polymer and optionally at least one polycarboxylic
acid cyclic anhydride other than the previous polycarboxylic acid
anhydride and/or at least one esterification catalyst and/or at least one
non-polymeric polyol comprising 3 to 6 hydroxyl groups are mixed
together,
ii) an antioxidant is optionally added to said mixture,
iii) the resulting mixture is heated to a temperature ranging from 100 to
250°C, preferably while removing, during the heating, the water, the
alcohol or the acid formed , then
iv) the resulting mixture is cooled to ambient temperature,
it being possible to perform the esterification/polycondensation reaction ,
totally or partly, in an inert solvent such as xylene and/or under reduced
pressure, to facilitate the removal of the water, said process preferably
being carried out without solvent.
14 . Process for preparing a cyclodextrin polycondensate as defined
according to any one of the preceding claims, characterized in that at
least one cyclodextrin , at least one polycarboxylic acid and/or an ester
derivative thereof, an acid anhydride derivative thereof or an acid halide
thereof, at least one thermoplastic polyol polymer and optionally at least
one polycarboxylic acid cyclic anhydride other than the previous
polycarboxylic acid anhydride and/or at least one esterification catalyst
and/or at least one non-polymeric polyol comprising 3 to 6 hydroxyl
groups are mixed together in an apparatus exerting shear forces sufficient
to bring said mixture to a thermoplastic state and preferably operating at a
temperature ranging from 100 to 250°C, preferentially from 110 to 200°C.
15 . Preparation process according to Claim 14 , characterized in that all
the ingredients are incorporated , in a single step, in an extruder at a
temperature ranging from 110 to 200°C, preferably ranging from 120 to
190°C and even better still from 150 to 180°C and with a residence time in
the extruder preferably ranging from 1 to 10 minutes and even better still
from 1 to 5 minutes.
16 . Use of a cyclodextrin polycondensate as defined in any one of the
claims, as a capturing agent.
17 . Use according to Claim 16 , as an agent for capturing a substance or
a mixture of substances chosen from :
(i) those capable of polluting the environment;
(ii) those capable of having a negative impact on a consumer product;
(iii) those capable of deteriorating under the influence of atmospheric
agents or upon contact with one or more ingredients in a composition;
(iv) those capable of generating uncomfortable reactions on a keratin
material, in particular a human keratin material ;
(v) beneficial agents.
18 . Use according to Claim 17 , in which the beneficial agents are chosen
from :
(i) fatty substances;
(ii) flavouring substances and/or taste enhancers;
(iii) fragrancing substances;
(iv) pharmaceutical active ingredients;
(v) cosmetic active agents.
19 . Use according to Claim 17 , in which the substance or the mixture of
substances capable of generating uncomfortable reactions on a keratin
material, in particular a human keratin material, are chosen from:
(i) malodorous molecules, in particular malodorous bodily molecules;
(ii) the constituents of human sweat;
(iii) the constituents of sebum .
20. Consumer product comprising at least one cyclodextrin
polycondensate as defined in any one of the preceding claims, said
consumer product being in particular a cosmetic or dermatological
composition comprising a physiologically acceptable medium.
2 1 . Process for cosmetic treatment of human perspiration and/or of body
odours, consisting in applying, to the surface of a human keratin
material, a composition comprising, in a physiologically acceptable
medium, at least one cyclodextrin polycondensate as defined in any one
of the preceding claims.
22. Non-therapeutic cosmetic process for caring for and/or cleansing a
human keratin material which is greasy or prone to be greasy,
comprising at least one step of topical application , to said keratin
material, of a composition comprising, in a physiologically acceptable
medium, at least one cyclodextrin polycondensate as defined in any one
of the preceding claims.