HYBRID COMPOUNDS BASED ON POLYOL(S) AND AT LEAST ONE OTHER MOLECULAR ENTITY, POLYMERIC OR NON-POLYMERIC, IN PARTICULAR OF THE POLYORGANOSILOXANE TYPE, PROCESS FOR THE PREPARATION THEREOF, AND APPLICATIONS THEREOF

• US 20100048738A1
• Filed: 05/15/2007
• Published: 02/25/2010
• Est. Priority Date: 05/15/2006
• Status: Abandoned Application

• Current Assignee: Centre National De La Recherche Scientifique, Rhodia Operations (Solvac SA)
• Original Assignee: Centre National De La Recherche Scientifique, Rhodia Operations (Solvac SA)
• Inventors: Fort, Sebastien, Cottaz, Sylvain, Hamaide, Thierry, Halila, Sami, Driguez, Hugues, Fleury, Etienne
• Application Number:
  US12/300,470
• Publication Number:
  US 20100048738A1
• Time in Patent Office: Days
• US Class Current: 514/772.700
• CPC Class Codes: A61K 8/891 saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
• CPC Class Codes: A61Q 19/10 Washing or bathing preparations
• CPC Class Codes: A61Q 5/02 Preparations for cleaning the hair
• CPC Class Codes: C07H 5/06 Aminosugars
• CPC Class Codes: C08G 77/42 Block-or graft-polymers containing polysiloxane sequences polymerising aliphatic unsaturated monomers on to a polysiloxane C08F283/12

Abstract

The invention relates to novel hybrid compounds comprising at least one polyon entity (Po)—for example oligomer or polymer—in which at least one of the hydroxyl functions of Po is substituted by at least one entity A that can be of a variable nature, for example polymer (e.g. polyorganosiloxane-POS), hydrocarbonated or mineral. The bond Ro between the entity Po and the entity A is obtained by means of “click chemistry” and corresponds to formula (II.1) or (II.2), Z representing —CH— or —N—. A is an entity selected from the group comprising the various polyols of Po, polyorganosiloxanes (POS), polyalkylene glycols, polyamides, polyesters, polystyrenes, alkyls, alkenyls, alkynyls, aryls, and combinations thereof, in addition to mineral materials such as silica and the combinations thereof. Said hybrid components can be used as emulsifiers, especially for cosmetics.

Claims

1. Hybrid compound Po-Ro-A containing at least one polyol entity (Po) and in which at least one of the atoms of Po is substituted with at least one group of the following general formula (I):

-Ro-A 

 

(I)

in which;

Ro is a linking hinge of the following formula (II.1) or (II.2);

with Z representing a carbon or a nitrogen atom;

the polyol entity Po is selected from the polymeric synthetic non-saccharide polyols, or from the saccharides (hydrogenated or not) containing at least two, preferably at least three monosaccharide units,

A is an inorganic or organic entity, optionally polymeric; and

if there is a plurality of entities A per molecule of hybrid compound, said entities A are mutually identical to or different, the organic entity A being selected or derived from a compound selected from the group comprising;

synthetic polymers, their copolymers or monomer units making it possible to obtain them

alkyls, alkenyls, alkynyls, aryls and combinations of the latter

and combinations thereof.

2. Compound according to claim 1, characterized in that at least one of the hydroxyl functions of the polyol entity (Po) is substituted with at least one grouping with the following general formula (I):

-Ro-A as defined in claim 1.

3. Hybrid compound according to claim 1, characterized in that the hinge Ro or at least one of the hinges Ro is linked to the entity Po and/or to the entity A by a divalent linkage -L-, L preferably being a hydrocarbon unit or an atom such as O or S.

4. Hybrid compound according to claim 1, characterized in that none of the hinges Ro is linked to the entity Po by a divalent linkage -L- and in that said hybrid compound has at least one entity A free from amino acid(s) and/or peptide(s) and/or their analogue(s) and/or derivative(s).

5. Hybrid compound according to claim 1, characterized in that the entity A is selected or derived from a compound selected from the group comprising:

synthetic polymeric non-saccharide polyols, their copolymers or the monomer units making it possible to obtain them;

polyorganosiloxanes (POS), their copolymers or the monomer units making it possible to obtain them;

polyalkylene glycols (or else alkylene polyoxides), preferably polyethylene glycols (or else ethylene polyoxides) and/or polypropylene glycols (or else propylene polyoxides), and/or polytetraethylene glycols, and/or copolymers or co-oligomers, in particular random or block copolymers or co-oligomers, thereof or of polypropylene glycols and of polypropylene glycols (or else random or block ethylene and propylene polyoxides), these polyalkylene glycols optionally being functionalised with or onto other groups, for example with or onto amine groups (Jeffamines), and/or optionally being terminated at least one end by a hydroxyl group or by an alkyl group, for example a C₁-C₃₀ alkyl;

polyamides, copolymers thereof or monomer units making it possible to obtain them;

polyesters, copolymers thereof or monomer units making it possible to obtain them;

polybutadienes, copolymers thereof or monomer units making it possible to obtain them;

polystyrenes, copolymers thereof or monomer units making it possible to obtain them;

optionally, alkyls, alkenyls, alkynyls, aryls and combinations of these;

inorganic substances other than silica;

and combinations thereof.

6. Hybrid compound according to claim 1, characterized in that the free valence bond of the nitrogen at the position 1 in formulae (II.1) and (II.2) links the hinge Ro to Po and the free valence bond of the carbon or of the atom Z at the 4 or 5 position in formulae (II.1) and (II.2) links the hinge Ro to A.

7. Hybrid compound according to claim 1, characterized in that the free valence bond of the nitrogen at the 1 position in formulae (II.1) and (II.2) links the hinge Ro to A and the free valence bond of the carbon or of the atom Z at the 4 or 5 position in formulae (II.1) and (II.2) links the hinge Ro to Po.

8. Hybrid compound according to claim 1, characterized in that the polyol entity Po or the polyols that can be contained in the entity A is (are) selected:

from the synthetic, polymeric, non-saccharide polyols,

and/or from the saccharides (hydrogenated or not) containing at least two, preferably at least three monosaccharide units.

9. Hybrid compound according to claim 1, characterized in that A contains at least one POS bearing siloxy units M, D, T and/or Q, preferably at least one POS bearing siloxy units M and D, optionally T and/or Q, and still more preferably at least one POS of type M(D)_dM, M(D)_d(T)_tM, MQ, with d,t being rational numbers greater than or equal to 0.

10. Hybrid compound according to claim 1, characterized in that it corresponds to at least one of the following formulae

in which:

R², identical or different, is a hydrocarbon group, preferably a methyl group,

R³, identical or different, is a group of formula -Ro-Po in which Ro and Po are as defined in any one of claims 1 to 7,

R¹, identical or different, is a group R² or R³,

R is a divalent group comprising an oxygen atom, preferably an —

O—

group,

m is an average number different from 0,

n is an average number greater than or equal to 0,

k and l are average numbers greater than or equal to 0, and

o and p, identical or different, are average numbers greater than or equal to 0.

11. Process for the preparation in particular of the hybrid compound according to claim 1, characterized in that

i. a synthon Po-X, containing at least one reactive unit X having at least one reactive end of formula (VII.1):

—

C≡

E;

with E=CH or N is used and/or is prepared;

ii. a synthon A-Y containing at least one reactive unit Y having at least one reactive end of formula (VII.2);

—

N₃;

the reactive end (VII.2) being capable of reacting with the reactive end (VII.1) is used and/or is prepared;

iii. the synthon Po-X is reacted with the synthon A-Y according to a cycloaddition mechanism, so as to obtain a hybrid compound Po-Ro-A containing at least one polyol entity (Po) in which at least one of the hydroxyl functions of Po is substituted with at least one grouping of the following general formula (I′

);

-Ro-A;

with Ro and A as defined in any one of claims 1 to 10;

iv. optionally, Po-Ro-A is separated from the reaction mixture so that it can be recovered.

12. Process according to claim 11, characterized in that the cycloaddition stage (iii) is carried out in an aqueous, aqueous alcoholic or organic medium capable of solubilising and/or swelling the synthon Po-X and/or the synthon A-Y, by means of at least one metallic catalyst in ionised form, preferably Cu⁺⁺, in the presence of at least one reducing agent of Cu⁺⁺ to Cu⁺, in situ, this reducing agent preferably being selected from the group comprising:

ascorbate, quinone, hydroquinone, vitamin K1, glutathione, cysteine, Fe²⁺, Co²⁺, applied electrical potential, metal of the group comprising Cu, Al, Be, Co, Cr, Fe, Mg, Mn, Ni, and Zn, and mixtures thereof.

13. Process according to claim 11, characterized in that the reaction medium contains at least one solvent selected from:

polar aprotic solvents, preferably dimethylformamide (DMF), dimethylacetamide (DMAc), acetone, methyl ethyl ketone or butanone

polar protic solvents, preferably methanol, isopropyl alcohol (IPA) or t-butanol (t-BuOH),

apolar solvents, preferably toluene, hexane or xylene,

water,

and mixtures thereof.

14. Process according to claim 11, characterized in that the optional separation (iv) of Po-Ro-A from the reaction mixture in particular consists of carrying out:

at least one chromatography, preferably at least one chromatography on silica gel, by means of an eluent containing a mixture of a first polar solvent and of at least one second less polar solvent, such as for example the mixture acetonitrile and water

and/or at least one evaporation to dry the product.

18. Mixed synthon Po-XY with Po as defined in claim 1, characterized in that it has at least one reactive unit X as defined in claim 15 and at least one reactive unit Y having at least one reactive end of formula (VII.2.1):

-[L₂]_a-N₃

with a=1;

said end being linked to the residue Po by a linkage L₂ which is a divalent hydrocarbon linkage.

19. Use of a hybrid compound according to claim 1, as ingredients in compositions selected from the group comprising:

detergent/surfactant compositions,

shampoo compositions,

soap compositions,

cleaning/washing compositions,

cosmetic compositions.

20. Compositions according to the use in claim 19.

21. Emulsion, preferably oil-in-water emulsion, containing a hybrid compound according to claim 1.

22. Use of a hybrid compound according to claim 11, as ingredients in compositions selected from the group comprising:

detergent/surfactant compositions,

shampoo compositions,

soap compositions,

cleaning/washing compositions,

cosmetic compositions.

23. Compositions according to the use in claim 22.

24. Emulsion, preferably oil-in-water emulsion, containing a hybrid compound obtained by the process according to claim 11.

15. Synthon Po-X characterized in that it comprises at least one reactive unit X having at least one reactive end of formula (VII.1.1):

-[L₁]_a-C≡

E

with E=CH or N, a=1, said end being linked to the residue Po by a L₁ which is a divalent hydrocarbon linkage.

16. Synthon Po-X according to claim 15, characterized in that:

1. according to a 1st possibility, Po contains at least one saccharide with;

L₁ containing at least one amine group (for example terminal) having reacted with the anomeric carbon of the Po,

and/or L₁ derived from a precursor having at least one halogeno group (for example bromo) having reacted with the OH group or groups of the Po;

2. according to a 2nd possibility, Po contains at least one residue (for example saccharide) functionalized with at least one functionalising group belonging to the group comprising the carboxylic, carboxylate, anhydride, thiol, isocyanate and epoxide functionalising groups with;

L₁ containing at least one amine group (for example terminal) having reacted with the functionalising group(s) of the Po,

and/or L₁ derived from a precursor having at least one halogeno group (for example bromo) having reacted with the functionalising group(s) of the Po;

3. according to a 3rd possibility, the first two possibilities are combined.

17. Synthon Po-X according to claim 15, characterized in that Po is a polymer.