Novel ethylenic copolymers, compositions and methods of the same

Abstract

The present disclosure relates to novel ethylenic copolymers comprising from 10% to 80% by weight, of at least one monomer of polyethylene glycol (meth)acrylate type, from 20% to 90% by weight, of at least one anionic monomer, and from 0% to 70% by weight, at least one additional nonionic hydrophilic monomer. The disclosure also relates to a composition, such as cosmetic or pharmaceutical compositions, comprising the copolymers and to a method of using the same.

1 . An ethylenic copolymer comprising: 
 a) from 10% to 80% by weight, relative to the total weight of the copolymer, of at least one monomer of formula (I):                          wherein:    R 1  is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C p H 2p+1  wherein p is an integer ranging from 1 to 12 inclusive;    Z is a divalent group chosen from —COO—, —CONH—, —CONCH 3 —, —OCO—, —O—, —SO 2 —, —CO—O—CO—, and —CO—CH 2 —CO—;    x is chosen from 0 and 1;    R 2  is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;    m is chosen from 0 and 1;    n is an integer ranging from 3 to 300 inclusive;    R 3  is chosen from a hydrogen atom and linear, branched and cyclic, saturated and unsaturated, optionally aromatic, hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 20 heteroatoms chosen from O, N, S, F, Si, and P; and salts thereof;    b) from 20% to 90% by weight, relative to the total weight of the copolymer, of at least one anionic monomer and salts thereof, chosen from maleic anhydride and monomers of formula (II):                          wherein:    R 1  is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C p H 2p+1  wherein p is an integer ranging from 1 to 12 inclusive;    Z′ is a divalent group chosen from —COO—, —OCO— and —O—, —SO 2 —, —CO—O—CO—, and —CO—CH 2 —CO—;    x′ is chosen from 0 and 1;    R 2 ′ is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;    m′ is chosen from 0 and 1; and    Y is a group chosen from —COOH, —SO 3 H, —OSO 3 H, —PO 3 H 2 , and —OPO 3 H 2 ; and    c) from 0% to 70% by weight, relative to the total weight of the copolymer, of at least one additional nonionic hydrophilic monomer.    
   
   
       2 . The copolymer according to  claim 1 , wherein, in formula (I), R 1  is chosen from hydrogen and from methyl, ethyl, propyl and butyl radicals.  
   
   
       3 . The copolymer according to  claim 1 , wherein, in formula (I), Z is chosen from —COO— and —CONH—.  
   
   
       4 . The copolymer according to  claim 1 , wherein, in formula (I), R 2  is or comprises a radical chosen from: 
 an alkylene radical;    a phenylene radical —C 6 H 4 — (ortho, meta or para) optionally substituted by a C 1 -C 2  alkyl radical optionally comprising from 1 to 25 heteroatoms chosen from O, N, S, F, Si, and P; and a benzylene radical —C 6 H 4 —CH 2 — optionally substituted by a C 1 -C 12  alkyl radical optionally comprising from 1 to 25 heteroatoms chosen from O, N, S, F, Si, and P;    a pyridinium radical of the formula:                          wherein R′ 1  to R′ 4 , which may be identical or different, are chosen from H and C 1 -C 12  alkyl radicals optionally comprising from 1 to 8 heteroatoms chosen from O, N, S, F, Si, and P;    a radical of formula —CH 2 —O—CO—O—, —CH 2 —CH 2 —O—CO—O—, —CH 2 —CO—O—, —CH 2 —CH 2 —CO—O—, —CH 2 —O—CO—NH—, —CH 2 —CH 2 —O—CO—NH—, —CH 2 —NH—CO—NH— and —CH 2 —CH 2 —NH—CO—NH—, —CH 2 —CHOH—, —CH 2 —CH 2 —CHOH—, —CH 2 —CH 2 —CH(NH 2 )—, —CH 2 —CH(NH 2 )—, —CH 2 —CH 2 —CH(NHR′)—, —CH 2 —CH(NHR′)—, —CH 2 —CH 2 —CH(NR′R″)—, —CH 2 —CH(NR′R″)—, —CH 2 —CH 2 —CH 2 —NR′—, —CH 2 —CH 2 —CH 2 —O—, and —CH 2 —CH 2 —CHR′—O— wherein R′ and R″ are chosen from linear and branched C 1 -C 22  alkyls optionally comprising from 1 to 12 heteroatoms chosen from O, N, S, F, Si, and P; and    mixtures thereof.    
   
   
       5 . The copolymer according to  claim 4 , wherein the alkylene radical is chosen from methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene, and n-docosenylene.  
   
   
       6 . The copolymer according to  claim 1 , wherein, in formula (I), n ranges from 5 to 200 inclusive.  
   
   
       7 . The copolymer according to  claim 6 , wherein, in formula (I), n ranges from 9 to 50 inclusive.  
   
   
       8 . The copolymer according to  claim 1 , wherein, in formula (I), R 3  is chosen from a hydrogen atom; from succinimido, maleimido, mesityl, tosyl, triethoxysilyl, phthalimido and —CH 2 —CH 2 CN radicals; from benzyl and phenyl radicals optionally substituted by a C 1 -C 12  alkyl radical optionally comprising from 1 to 25 heteroatoms chosen from O, N, S, F, Si, and P; and C 1 -C 30  alkyl radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P, wherein the the benzyl, phenyl and alkyl radicals may optionally comprise a functional group chosen from succinimido, glutarate-succinimido, glutarate, maleimido, mesityl, benzoate, tosyl, triethoxysilane, phthalimide, thioester, benzotriazole carbonate, butyraldehyde, acetaldehyde diethyl acetal, biotin, phospholipid, succinate N-hydroxysuccinimide, —SO 3 H, —COOH, —PO 4 , —NR 5 R 6 , and —N + R 5 R 6 R 7 , wherein R 5 , R 6  and R 7 , which may be identical or different, are chosen from H and linear, branched and cyclic C 1 -C 18  alkyls, optionally comprising at least one heteroatom and/or at least one protective group.  
   
   
       9 . The copolymer according to  claim 1 , wherein the at least one monomer of formula (I) is chosen from: 
 polyethylene glycol (meth)acrylate;    methylpolyethylene glycol (meth)acrylate;    alkylpolyethylene glycol (meth)acrylates;    phenylpolyethylene glycol (meth)acrylate;    a monomer of:                          wherein n ranges from 3 and 100 inclusive,    and mixtures thereof.    
   
   
       10 . The copolymer according to  claim 9 , wherein n ranges from 7 to 30 inclusive.  
   
   
       11 . The copolymer according to  claim 1 , wherein the at least one monomer of formula (I) is present in an amount ranging from 20% to 70% by weight, relative to the total weight of the copolymer.  
   
   
       12 . The copolymer according to  claim 11 , wherein the at least one monomer of formula (I) is present in an amount ranging from 30% to 60% by weight, relative to the total weight of the copolymer.  
   
   
       13 . The copolymer according to  claim 1 , wherein, in formula (II), R 1  is chosen from hydrogen and from methyl, ethyl, propyl and butyl radicals.  
   
   
       14 . The copolymer according to  claim 1 , wherein, in formula (II), Z′ is COO.  
   
   
       15 . The copolymer according to  claim 1 , wherein, in formula (II), R 2 ′ is or comprises a radical chosen from: 
 an alkylene radical;    a phenylene radical —C 6 H 4 — (ortho, meta or para) optionally substituted by a C 1 -C 12  alkyl radical optionally comprising from 1 to 5 heteroatoms chosen from N, O, S, F, Si, and/or P; and a benzylene radical —C 6 H 4 —CH 2 — optionally substituted by a C 1 -C 12  alkyl radical optionally comprising from 1 to 5 heteroatoms chosen from O, N, S, F, Si, and P;    a radical of formula —CH 2 —O—CO—O—, —CH 2 —CH 2 —O—CO—O—, —CH 2 —CO—O—, —CH 2 —CH 2 —CO—O—, —CH 2 —O—CO—NH—, —CH 2 —CH 2 —O—CO—NH—, —CH 2 —NH—CO—NH—, —CH 2 —CH 2 —NH—CO—NH—, —CH 2 —CHOH—, —CH 2 —CH 2 —CHOH—, —CH 2 —CH 2 —CH—O—, and —CH 2 —CH 2 —CHR′—O— wherein R′ is chosen from linear and branched C 1 -C 22  alkyl radicals optionally comprising from 1 to 12 heteroatoms chosen from O, N, S, F, Si, and P; and    mixtures thereof.    
   
   
       16 . The copolymer according to  claim 15 , wherein the alkylene radical is chosen from methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene, and n-docosenylene.  
   
   
       17 . The copolymer according to  claim 1 , wherein the at least one anionic monomer is chosen from maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, 2-carboxyethyl acrylate, styrenesulphonic acid, vinylbenzoic acid, vinylphosphonic acid, sulphopropyl (meth)acrylate, sulphatoethyl (meth)acrylate, and salts thereof.  
   
   
       18 . The copolymer according to  claim 17 , wherein the salts thereof comprise ammonium salts.  
   
   
       19 . The copolymer according to  claim 1 , wherein the at least one anionic monomer is present in an amount ranging from 30% to 80% by weight, relative to the total weight of the copolymer.  
   
   
       20 . The copolymer according to  claim 19 , wherein the at least one anionic monomer is present in an amount ranging from 40% to 70% by weight, relative to the total weight of the copolymer.  
   
   
       21 . The copolymer according to  claim 1 , wherein the at least one additional nonionic hydrophilic monomer exhibits a log P ranging from −8 to 2.  
   
   
       22 . The copolymer according to  claim 21 , wherein the at least one additional non-ionic hydrophilic monomer exhibits a log P ranging from −6 to 0.  
   
   
       23 . The copolymer according to  claim 1 , wherein the at least one additional nonionic hydrophilic monomer is chosen from those of formula (III), alone or as a mixture:  
     
       
         
         
             
             
         
       
     
     wherein: 
 R′ 1  is chosen from hydrogen and —CH 3 ;  
 Z″ is a divalent group chosen from —COO—, —CONH—, —CONCH 3 —, —OCO—, —SO 2 —, —CO—O—CO—, —CO—CH 2 —CO—, and —O—;  
 x″ is chosen from 0 and 1; and  
 R″ is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P.  
 
   
   
       24 . The copolymer according to  claim 23 , wherein the hydrocarbon radical of R″ is chosen from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, benzyl and furfuryl, and radicals of formula —CH 2 —CH 2 —CH 2 OH, —CH 2 —CH 2 —OH, and —CH 2 —CH 2 —CH 2 —OH.  
   
   
       25 . The copolymer according to  claim 1 , wherein the at least one additional nonionic hydrophilic monomer is chosen from: methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, ethoxyethyl methacrylate, ethoxyethyl acrylate, N-isopropylacrylamide, N-isopropylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, vinyl acetate, methyl vinyl ether, ethyl vinyl ether, vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, hydroxypropyl acrylate, N-vinyllactam, acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, and vinyl alcohol, copolymerized in the vinyl acetate form and then hydrolyzed.  
   
   
       26 . The copolymer according to  claim 1 , wherein the at least one additional nonionic hydrophilic monomer is present in an amount ranging from 0.1% to 35% by weight, relative to the total weight of the copolymer.  
   
   
       27 . The copolymer according to  claim 26 , wherein the at least one additional non-ionic hydrophilic monomer is present in an amount ranging from 5% to 9.5% by weight, relative to the total weight of the copolymer.  
   
   
       28 . The copolymer according to  claim 1 , wherein the copolymer exhibits a weight-average molecular mass (Mw) ranging from 500 to 5,000,000.  
   
   
       29 . The copolymer according to  claim 28 , wherein the copolymer exhibits a weight-average molecular mass (Mw) ranging from 8,000 to 100,000.  
   
   
       30 . The copolymer according to  claim 1 , wherein the copolymer is conveyed in an aqueous medium.  
   
   
       31 . The copolymer according to  claim 30 , wherein the aqueous medium is water-dispersible or water-soluble.  
   
   
       32 . The copolymer according to  claim 1 , wherein the copolymer exhibits a viscosity in water ranging from 1 mPa·s to 1000 mPa·s, measured at 25° C.  
   
   
       33 . The copolymer according to  claim 32 , wherein the copolymer exhibits a viscosity in water ranging from 2 mPa·s to 500 mPa·s, measured at 25° C.  
   
   
       34 . The copolymer according to  claim 1 , wherein the copolymer exhibits a glass transition temperature (Tg) ranging from −150° C. to 20° C.  
   
   
       35 . The copolymer according to  claim 34 , wherein the copolymer exhibits a glass transition temperature (Tg) ranging from −100° C. to 0° C.  
   
   
       36 . The copolymer according to  claim 1 , wherein the copolymer exhibits a water uptake ranging from 3% to 150% by weight, at 75% relative humidity (75% RH), and/or the copolymer exhibits a water uptake ranging from 5% to 90% by weight, at 85% relative humidity (85% RH).  
   
   
       37 . The copolymer according to  claim 36 , wherein the copolymer exhibits a water uptake ranging from 4.5% to 90% by weight, at 75% relative humidity (75% RH), and/or the copolymer exhibits a water uptake ranging from 15% to 60% by weight, at 85% relative humidity (85% RH).  
   
   
       38 . A composition comprising, in a physiologically acceptable medium, at least one copolymer comprising: 
 a) from 10% to 80% by weight, relative to the total weight of the copolymer, of at least one monomer of formula (I):                          wherein:    R 1  is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C p H 2p+1  wherein p is an integer ranging from 1 to 12 inclusive;    Z is a divalent group chosen from —COO—, —CONH—, —CONCH 3 —, —OCO—, —O—, —SO 2 —, —CO—O—CO—, and —CO—CH 2 —CO—;    x is chosen from 0 and 1;    R 2  is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;    m is chosen from 0 and 1;    n is an integer ranging from 3 to 300 inclusive;    R 3  is chosen from a hydrogen atom and linear, branched and cyclic, saturated and unsaturated, optionally aromatic, hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 20 heteroatoms chosen from O, N, S, F, Si, and P; and salts thereof;    b) from 20% to 90% by weight, relative to the total weight of the copolymer, of at least one anionic monomer and salts thereof, chosen from maleic anhydride and monomers of formula (II):                          wherein:    R 1  is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C p H 2p+1  wherein p is an integer ranging from 1 to 12 inclusive;    Z′ is a divalent group chosen from —COO—, —OCO— and —O—, —SO 2 —, —CO—O—CO—, and —CO—CH 2 —CO—;    x′ is chosen from 0 and 1;    R 2 ′ is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals with from 1 to 30 carbon atoms which optionally comprises from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;    m′ is chosen from 0 and 1; and    Y is a group chosen from —COOH, —SO 3 H, —OSO 3 H, —PO 3 H 2 , and —OPO 3 H 2 ; and    c) from 0% to 70% by weight, relative to the total weight of the copolymer, of at least one additional nonionic hydrophilic monomer.    
   
   
       39 . The composition according to  claim 38 , wherein the composition is in a form chosen from a cosmetic and pharmaceutical composition.  
   
   
       40 . The composition according to  claim 38 , wherein the copolymer is present in an amount ranging from 0.01% to 50% by weight on a dry basis, relative to the total weight of the composition.  
   
   
       41 . The composition according to  claim 40 , wherein the copolymer is present in an amount ranging from 3% to 20% by weight on a dry weight basis, relative to the total weight of the composition.  
   
   
       42 . The composition according to  claim 38 , wherein the physiologically acceptable medium comprises at least one constituent chosen from water; hydrophilic organic solvents; waxes, pasty fatty substances, gums and their mixtures of animal, vegetable, mineral and synthetic origin; lipophilic organic solvents; oils of animal, vegetable, mineral and synthetic origin; synthetic esters and ethers; pentaerythritol esters; fatty alcohols comprising from 12 to 26 carbon atoms; partially hydrocarbon-comprising and/or silicone-comprising fluorinated oils; volatile or nonvolatile and linear or cyclic silicone oils which are liquid or pasty at ambient temperature; pigments, pearlescent agents and fillers; water-soluble dyes and fat-soluble dyes; polymers; additional agents which are able to form a film; surfactants; vitamins, fragrances, pearlescent agents, thickeners, gelling agents, trace elements, softening agents, sequestering agents, basifying and acidifying agents, preservatives, sunscreens, antioxidants, agents for combating hair loss, antidandruff agents, propellants and ceramides; and mixtures thereof.  
   
   
       43 . The composition according to  claim 38 , wherein the composition is in the form of a suspension, a dispersion; an optionally thickened oily solution; an oil-in-water, water-in-oil or multiple emulsion; a gel or a foam; an oily or emulsified gel; a dispersion of vesicles; a two-phase or multiphase lotion; a spray; of a lotion, a cream, an ointment, a soft paste, a salve, a cast or molded solid, or a compacted solid.  
   
   
       44 . The composition according to  claim 38 , wherein the composition is a product for caring for and/or making up the skin of the body or face, the lips and the hair; an antisun or self-tanning product; or a hair product.  
   
   
       45 . The composition according to  claim 38 , wherein the composition is in the form of a hair composition; a rinse-out or leave-in conditioner; a perming, hair straightening, dyeing or bleaching composition; or a rinse-out composition, applied before or after a dyeing, bleaching, perming or a hair straightening or between the two stages of a perming or hair straightening composition.  
   
   
       46 . A method for treating keratinous substances comprising applying, to the keratinous substances, a cosmetic composition comprising, in a physiologically acceptable medium, at least one copolymer comprising: 
 a) from 10% to 80% by weight, relative to the total weight of the copolymer, of at least one monomer of formula (I):                          wherein:    R 1  is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C p H 2p+1  wherein p is an integer ranging from 1 to 12 inclusive;    Z is a divalent group chosen from —COO—, —CONH—, —CONCH 3 —, —OCO—, —O—, —SO 2 —, —CO—O—CO—, and —CO—CH 2 —CO—;    x is chosen from 0 and 1;    R 2  is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally comprising from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;    m is chosen from 0 and 1;    n is an integer ranging from 3 to 300 inclusive;    R 3  is chosen from a hydrogen atom and linear, branched and cyclic, saturated and unsaturated, optionally aromatic, hydrocarbon radicals having from 1 to 30 carbon atoms, said radicals optionally, comprising from 1 to 20 heteroatoms chosen from O, N, S, F, Si, and P; and salts thereof;    b) from 20% to 90% by weight, relative to the total weight of the copolymer, of at least one anionic monomer and salts thereof, chosen from maleic anhydride and monomers of formula (II):                          wherein:    R 1  is chosen from a hydrogen atom and linear and branched hydrocarbon radicals C p H 2p+1  wherein p is an integer ranging from 1 to 12 inclusive;    Z′ is a divalent group chosen from —COO—, —OCO— and —O—, —SO 2 —, —CO—O—CO—, and —CO—CH 2 —CO—;    x′ is chosen from 0 and 1;    R 2 ′ is chosen from linear, branched and cyclic, saturated and unsaturated, optionally aromatic, divalent hydrocarbon radicals with from 1 to 30 carbon atoms which optionally comprises from 1 to 18 heteroatoms chosen from O, N, S, F, Si, and P;    m′ is chosen from 0 and 1; and    Y is a group chosen from —COOH, —SO 3 H, —OSO 3 H, —PO 3 H 2 , and —OPO 3 H 2 ; and    c) from 0% to 70% by weight, relative to the total weight of the copolymer, of at least one additional nonionic hydrophilic monomer.    
   
   
       47 . The method according to  claim 46 , wherein said keratinous substances are chosen from the skin of the body or face, the nails, the hair, and the eyelashes.