Molecularly imprinted polymers and their use as antidandruff agents
AssigneeL'oreal
InventorsAndrew GREAVES, Christèle RIBAUD, Franco MANFRE, Karsten HAUPT
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Abstract
The invention relates to a molecularly imprinted polymer obtained by polymerization of a mixture comprising a basic ethylene monomer having an amine group, a crosslinking agent comprising at least 2 polymerizable ethylene unsaturations, a porogenic solvent and a C14-C20 fatty acid. A cosmetic composition comprising such a polymer. A cosmetic process to prevent and/or treat dandruff of the scalp using such a polymer.
Claims16
Process for preparing a molecularly imprinted polymer comprising a first step of polymerization of a mixture comprising:
- i) one or more basic ethylene monomer(s) having an amine group;
- ii) one or more crosslinking agent(s) comprising at least 2
- polymerizable ethylene unsaturations;
- iii) one or more porogenic solvent(s);
- iv) one or more C14-C20 fatty acid(s),
- followed by a second step of removing the C14-C20 fatty acid present in the polymer obtained from the first step.
Process according to the preceding claim, characterized in that the basic ethylene monomer comprising one amine group is chosen from:
- (meth)acrylates and (meth)acrylamides having an amine group having formula (I):
- in which R1 denotes H or methyl, X denotes O or NH, R denotes a divalent C1-C4 alkylene group,
- Z denotes an —NR2R3 or —N+R2R3R4 group, X−R2, R3 and R4 denoting independently of each other H or a C1-C4 alkyl,
- X− being an anion chosen from halides, (C2-C6)alkyl sulfates, phosphates, (C2-C6)alkyl- or (C2-C6)alkyl (C6-C10)aryl sulfonates, acetate anions, lactate anions;
- N-(meth)acryloyl-p-aminobenzamidine having formula (II):
- in which R′1 denotes H or methyl, and R′2, R′3, R′4 denote, independently of each other, H or a C1-C4 alkyl group;
- styryl amidines having formula (III):
- in which R5, R6, R7 denote, independently of each other, H or a C1-C4 alkyl group;
- amino styrenes having formula (IV):
- in which Z′ denotes an —NR8R9 or —N+R8R9R10X− group
- R8, R9 and R10 denote, independently of each other, H or a C1-C4 alkyl;
- X− being an anion chosen from halides or (C2-C6)alkyl sulfates, phosphates, (C2-C6)alkyl- or (C2-C6)alkyl (C6-C10)aryl sulfonates, acetate anions, lactate anions;
- W denotes a R′″ or OR′″ group, R′″ being a C1-C4 alkyl group;
- n being an integer equal to 0, 1 or 2;
- vinylpyridines having formula (V):
- in which Y denotes a R′″ or OR′″ group, R′″ being a C1-C4 alkyl group;
- mn being an integer equal to 0, 1 or 2.
Process according to one of the preceding claims, characterized in that the basic ethylene monomer having an amine group is N-acryloyl-p-aminobenzamidine or 2-aminoethyl methacrylate.
Process according to one of the preceding claims, characterized in that said mixture comprises one or more neutral additional ethylene monomers chosen from (meth)acrylamide, C1-C6 alkyl (meth)acrylates, C1-C6 hydroxyalkyl (meth)acrylates, acrylonitrile, styrene, (C1-C4)alkylstyrenes, 1-allyl-(thio)urea, vinylpyrrolidone.
Process according to any one of the preceding claims, characterized in that the crosslinking agent comprising at least 2 polymerizable ethylene unsaturations is chosen from monomers having the following formula (C3) or (C4):
- in which:
- A is a phenyl optionally substituted by —COOH;
- R8, the same or different, represents a hydrogen atom or a linear or branched (C1-C8)alkyl group, preferably C1-C6 such as methyl;
- X1 and X2, the same or different, are as defined previously;
- preferably X1=O or NH, and X2=O;
- and more particularly X1=X2=an oxygen atom, or else X1 forms a bond;
- W represents:
- i) either a 5- or 6-membered heteroaryl group such as pyridinyl or a 5- to 8-membered heterocycloalkyl group comprising at least one oxygen atom such as tetrahydrofuryl, piperazynyl or hexahydrofuro[3,2-b]furanyl, ii) or a *-A-(CR9R10)x-A* group when w is 2, with A as defined previously, R9 and R10, the same or different, representing a hydrogen atom or a (C1-C6)alkyl group such as methyl, x represents an integer comprised between 0 and 10 inclusive, preferably x=1 and * represents the attachment point to the —X1—C(X2)—C(═CH2)—R8 groups;
- iii) or a linear or branched polyvalent hydrocarbon-based chain, preferably di or trivalent, saturated or unsaturated, preferably saturated, comprising from 1 to 20 carbon atoms optionally substituted by a hydroxy group or by a phenyl group;
- n represents an integer comprised between 0 and 5 inclusive;
- more particularly between 0 and 3, such as n=0 or 1;
- u and w represent an integer comprised between 2 and 10 inclusive, more particularly between 2 and 5, such as u=2 and w=2 or 3.
Process according to one of the preceding claims, characterized in that the crosslinking agent comprising at least 2 polymerizable ethylene unsaturations is chosen from:
- Name
- Structure
- Styrene/divinyl benzene
- Diisopropyl benzene
- 1,3-phenylene diacrylamide;
- 1,4-phenylene diacrylamide
- N,N′-1,3-phenylenebis(2-methyl-2- propenamide);
- N,N′-1,4- phenylenebis(2-methyl-2- propenamide)
- 3,5-bisacrylamido-benzoic acid where R″ are identical and equal to H;
- and 3,5-bismethylacrylamido- benzoic acid where R″ are identical and equal to CH3
- 2,6-bisacryloylamidopyridine where R″ are identical and equal to H;
- 2,6- bismethylacryloylamidopyridine where R″ are identical and equal to CH3
- 1,4-diacryloylpiperazine where R″ are identical and equal to H;
- 1,4-dimethylacryloylpiperazine where R″ are identical and equal to CH3
- Ethylene glycol dimethacrylate where R″ are identical and equal to CH3 (EGDMA);
- Diacrylate ethylene glycol where R″ are identical and equal to H
- Tetramethylene dimethacrylate where R″ are identical and equal to CH3;
- Tetramethylene diacrylate where R″ are identical and equal to H
- Hexamethylene dimethacrylate where R″ are identical and equal to CH3 and Hexamethylene diacrylate where R″ are identical and equal to H
- Anhydroerythritoldimethacrylate where R″ are identical and equal to CH3 and Anhydroerythritoldiacrylate where R″ are identical and equal to H
- 1,4;3,6-dianhydro-p-sorbitol- 2,5-dimethacrylate where R″ are identical and equal to CH3;
- 1,4;3,6-dianhydro-p-sorbitol- 2,5-diacrylate where R″ are identical and equal to H
- Isopropylenebis(1,4- phenylene)-dimethacrylate where R″ are identical and equal to CH3;
- Isopropylenebis(1,4- phenylene)-diacrylate R″ are identical and equal to H
- 2,2-bis(Hydroxymethyl)butanol trimethacrylate where R″ are identical and equal to CH3 (TRIM);
- 2,2-bis(Hydroxymethyl) butanol triacrylate R″ are identical and equal to H
- Pentaerythritol triacrylate where R″ are identical and equal to H;
- Pentaerythritol trimethacrylate where R″ are identical and equal to CH3
- Pentaerythritol tetraacrylate where R″ are identical and equal to H (PETRA);
- Pentaerythritol tetramethacrylate where R″ are identical and equal to CH3
- N,O-bismethacryloyl- ethanolamine where Rc is equal to ethylene and R″ are identical and equal to CH3
- N,N′-methylene-bis-acrylamide where Rc = CH2 (MDAA);
- or N,N-1,2-ethanediylbis(2-methyl- 2-propenamide) N,N′-ethylene-bis- acrylamide where Rc =CH2—CH2;
- N,N′-butylene-bis-acrylamide where Rc = CH2—CH2—CH2—CH2;
- N,N′-hexylene-bis-acrylamide
- where Rc =
- CH2—CH2—CH2—CH2—CH2—CH2
Process according to one of the preceding claims, characterized in that the quantities of C14-C20 fatty acid (T), of basic ethylene monomer having an amine group and additional ethylene monomer if present (M) and of crosslinking agent (CL) added to the pre-polymerization mixture are found in a T/M/CL molar ratio comprised between 1:0.4:8 and 1:8:40 inclusive.
Process according to one of the preceding claims, characterized in that the porogenic solvent is chosen from water, C1-C8 alcohols, acetonitrile, tetrahydrofuran, dimethylformamide, diethylformamide, N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, N,N′-dimethylpropylene-urea, dimethylsulfoxide, and mixtures thereof.
Process according to one of the preceding claims, characterized in that the C14-C20 fatty acid is oleic acid.
Process according to one of the preceding claims, characterized in that the polymerization is a free-radical polymerization conducted in the presence of a free-radical initiator.
Process according to one of the preceding claims, characterized in that the polymerization is conducted at a temperature comprised between 0° C. and 80° C., more particularly between 25° C. and 70° C.
Process according to one of the preceding claims, characterized in that the step of removing the fatty acid is conducted by washing the polymer obtained at the first step with a washing solvent chosen from C1-C4 alcohols, water, acetonitrile, tetrahydrofuran (THF), dialkylformamide (dimethylformamide, diethylformamide), N-methyl-2-pyrrolidinone (NMP), N-ethyl-2-pyrrolidinone (NEP), N,N′-dimethylpropylene-urea (DMPU), dimethylsulfoxide (DMSO), chloroform, acetic acid, ammonia, diethylamine, and mixtures thereof.
Molecularly imprinted polymer that can be obtained according to the preparation process according to any one of the preceding claims.
Dependencies are inferred from the claim text.