Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

• the present invention relates to a process for the preparation of star-shaped copolymers comprising at least two types of polymeric arms of different chemical nature, said process comprising a step of radical polymerization of a composition comprising: - at least one crosslinking monomer, - a source of free radicals, and - at least two (co) polymers of first generation of different chemical nature and possibly of different molecular mass.
• the star-shaped polymers are polymers having a central portion and polymer-based arms extending radially from said central portion. These polymers are known to have multiple properties, possibly different from those of the polymeric arms constituting them. For example, the viscosity in dilute solution of star macromolecules, due to their compactness, is lower than that of a linear equivalent of the same molar mass (Fetters, LJ and coll. Advances in Chemical Physics; Wiley & Sons: Vol. XCIV Ed. I. Prigogine, SA Rice John Wiley & Sons, New York, (1996)).
• star polymers relate to their use as additives to reduce the viscosity of solvent-based formulations, or in a molten medium (processing aid), or even to improve the impact resistance of materials. Their use makes it possible to increase the dry extract rate of these formulations with the advantage of reducing solvent emissions and maintaining viscosity.
• the first category there are star-shaped polymers consisting of homopolymer arms generally based on polystyrene, poly (meth) acrylate, polydiene, polyether, polyester or polysiloxane.
• the second category includes star-shaped compounds made up of arms in the form of block copolymers, in which case they are star block copolymers most often having a structure of the heart / shell type.
• the third category concerns stars containing either polymer arms of the same type but of different lengths (asymmetric star polymers), or at least two different types of polymers emanating from the same core. In the latter case, the compounds are designated star copolymers of the “Mikto” type. A schematic representation of these different stars is given in FIG. 1.
• the processes for preparing star-shaped polymers can be essentially classified into two groups.
• the first corresponds to the formation of the polymer arms from a multifunctional compound constituting the center ("core-first” technique) (Kennedy, JP and coll. Macromolecules, 29, 8631 (1996), Deffieux, A. and coll Ibid, 25, 6744, (1992), Gnanou, Y. and coll. Ibid, 31, 6748 (1998)) and the second corresponds to a method where the polymer chains which will constitute the arms are first synthesized and then linked together on a core to form a star-shaped polymer ("arm-first” technique).
• the star polymers thus formed consist of a core based on microgel and arms of the pre-polymer radiating from this central portion (Rempp, P. Can. J. Chem. 1969, 47, 3379; Burchard, W. Makromol, Chem. 1973, 173, 235; Rempp, P. and coll., Polym. Sci. Part C, 22, 145 (1968), Fetters, LJ and coll. Macromolecules, 8, 90 (1975), Higashimura and coll Ibid, 24, 2309 (1991)).
• star copolymers of the “Mikto” type are generally obtained by deactivating polymer chains obtained by “living” anionic polymerization. on chlorosilane type compounds or using a coupling agent such as divinylbenzene or derivatives of 1,1-diphenylethylene (Hadjichristidis, NJ Polym.
• Controlled radical polymerization is a technique for synthesizing controlled or living polymers under much easier conditions than living ionic polymerizations as indicated in the following documents
• controlled radical polymerization techniques used for this purpose can involve control agents such as nitroxyls used as counter-radicals (T. Long, J Polym. Sci. Part A.: Polym. Chem. 2001, 39, 216) , transition metal complexes used in Atom Transfer Radical Polymerization (ATRP) technology (Matyjaszewski, K. Macromolecules, 1999, 32, 4482) or agents carrying thiocarbonyl thio groups such as dithioesters in a fragmentation addition process reversible (WO 00/02939 from BERGE et al.).
• control agents such as nitroxyls used as counter-radicals (T. Long, J Polym. Sci. Part A.: Polym. Chem. 2001, 39, 216) , transition metal complexes used in Atom Transfer Radical Polymerization (ATRP) technology (Matyjaszewski, K. Macromolecules, 1999, 32, 4482) or agents carrying thiocarbonyl thio groups
• the star-shaped polymers of this document can only be star-shaped homopolymers or else star-shaped block copolymers.
• the possibility of preparing star-shaped polymers by radical polymerization controlled by a “core first” method has also been described in document WO04 / 14535 from the company Rhodia Chimie.
• This step leads to a branched polymer designated “statistical microgel” endowed with re-activatable ends subjected, in a second step, to a chain extension by polymerization of a new charge of monomer. Star-shaped homopolymers or else star-shaped block copolymers are thus obtained.
• One of the aims of the present invention is therefore to propose a new process for the synthesis of star-shaped copolymers of the “mikto” type by controlled radical route which is easy to implement.
• Another object of the invention is to propose a process for synthesizing star-shaped copolymers of the Mikto type during which the length and / or the number of arms and therefore the average molar masses in number of the polymers can be varied. in Mikto type star.
• Another object of the invention is to propose a controlled radical polymerization process which makes it possible to achieve star-shaped copolymers of the “mikto” type having arms of very different average molar masses.
• Another object is to propose a controlled radical polymerization process which makes it possible to achieve star-shaped copolymers of the “mikto” type from a very wide range of monomers, compared to the techniques known from the prior art. .
• the present invention relates to a process for the preparation of star-shaped copolymers of the “mikto” type which comprises a step of radical polymerization of a composition comprising: - at least one crosslinking monomer, - a source of free radicals, and - at least two (co) polymers of first generation of different chemical nature and possibly of different molecular mass.
• the process of the invention relates to a process for the preparation of star-shaped copolymers comprising at least two types of polymeric arms of different chemical nature, said process comprising a stage of controlled radical polymerization carried out according to a process of type Atom Transfer Radical Polymerization (ATRP) or by a reversible transfer process by addition-fragmentation of thiocarbonylthio compounds, of a composition (1) comprising: - at least one crosslinking monomer, a source of free radicals, and at least two (co ) first generation polymers of different chemical nature and possibly of different molecular mass, obtained by a process which comprises a controlled radical polymerization step carried out according to a process of the Atom Transfer Radical Polymerization (ATRP) type or by a reversible transfer process by addition -fragmentation of thiocarbonylthio compounds of a composition (2) comprising: - at least one monoethylenically unsaturated monomer, a source of free radicals, and
• ATRP Atom Transfer Rad
• the process according to the invention has the advantage of being able to vary the number of arms and therefore the number-average molar masses of the star copolymers by adjusting a certain number of experimental parameters, including: the concentration of the reactants in the medium reaction, the proportion and the chemical nature of these reagents, such as the crosslinking agent or the first generation (co) polymers, and the molar mass of the first generation (co) polymer chains.
• the first generation (co) polymers can be obtained by radical polymerization controlled by transfer or reversible termination.
• the first generation (co) polymers can be homopolymers, random copolymers (of two or more monomers) or with a composition gradient, block copolymers (di, tri ....) or block copolymers where one, or even more than one, of the blocks is a random copolymer.
• first generation (co) polymers include: - any polymer carrying a thiocarbonylthio group (dithiocarbamate, dithiocarbonate, trithiocarbonate, dithioester, thioetherthione, dithiocarbazate) at the chain end, obtained by a reversible addition-fragmentation process; or - any polymer containing a halogen or pseudo-halogen group at the end of the chain obtained by ARTP.
• a thiocarbonylthio group dithiocarbamate, dithiocarbonate, trithiocarbonate, dithioester, thioetherthione, dithiocarbazate
• the first generation (co) polymers can be obtained separately and independently by a process which comprises a step of controlled radical polymerization of a composition comprising: - at least one monoethylenically unsaturated monomer - a source of free radicals , and - at least one control agent, it being understood that this process is carried out in the absence of multiethylenically unsaturated monomer.
• first generation polymers are all the monomers which polymerize in the presence of the control agent, to give active polymer chains.
• - X, X ', Y, Y' identical or different, represent H, a halogen or a group R 2 , OR 2 , O 2 COR 2 , NHCOH, OH, NH 2 , NHR 2 , N (R 2 ) 2 , (R 2 ) 2N + O ", NHCOR 2 , CO 2 H, CO 2 R 2 , CN, CONH 2 , CONHR 2 or CON (R 2 ) 2 , in which R 2 is chosen from alkyl, aryl, aralkyl groups , alkylaryl, alkene or organosilyl, optionally perfluorinated and optionally substituted by one or more carboxyl, epoxy, hydroxyl, alkoxy, amino, halogen or sulfonic groups.
• R 2 is chosen from alkyl, aryl, aralkyl groups , alkylaryl, alkene or organosilyl, optionally perfluorinated and optionally substituted by one
• styrene and styrene derivatives such as alphamethylstyrene or vinyltoluene - vinyl esters of carboxylic acid such as vinyl acetate, vinyl Versatate®, vinyl propionate, - vinyl and vinylidene halides,
• - ethylenic unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the mono-alkyl esters of the dicarboxylic acids of the type mentioned with the alkanols preferably having 1 to 4 carbon atoms and their N-substituted derivatives,
• - amides of unsaturated carboxylic acids such as acrylamide, methacrylamide, N-methylolacrylamide or methacrylamide, N-alkylacrylamides.
• ethylene monomers comprising a sulfonic acid group and its alkali or ammonium salts, for example vinyisulfonic acid, vinylbenzene sulfonic acid, alpha-acrylamido methylpropanesulfonic acid, 2-sulfoethylene-methacrylate,
• amides of vinylamine in particular vinylformamide, vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam,
• the unsaturated ethylenic monomers comprising a secondary, tertiary or quaternary amino group, or a heterocyclic group containing nitrogen such as for example vinylpyridines, vinylimidazole, aminoalkyl (meth) acrylates and (meth) acrylamides) aminoalkyl such as dimethylaminoethylacrylate or - methacrylate, ditertiobutylaminoethylacrylate or -methacrylate, dimethylaminomethyl-acrylamide or -methacrylamide, or zwitterionic monomers such as, for example, sulfopropyl (dimethyl) aminopropyl acrylate,
• the monomers comprising at least one boronate function or a precursor chosen, for example, from acryloylbenzene boronic acid, methacryloylbenzene boronic acid, 4-vinylbenzene boronic acid, 3-acrylamidophenylboronic acid, 3 acid -methacrylamidophenylboronic, alone or in mixtures, or in the form of salts,
• the monomers comprising phosphonates chosen for example from the N-methacrylamidomethylphosphonic acid esters derivatives, in particular the n-propyl ester (RN 31857-11-1), the methyl ester (RN 31857-12-2), l ethyl ester (RN 31857-13-3), n-butyl ester (RN 31857-14-4), isopropyl ester (RN 51239-00-0), as well as their monoacid and phosphonic acid derivatives, such N-methacrylamidomethylphosphonic diacid (RN 109421-20-7); N-methacrylamidoethylphosphonic acid esters derivatives, such as N-methacrylamidoethyl phosphonic acid dimethyl ester (RN 266356-40-5), N-methacrylamidoethyl phosphonic acid di (2- buty [-3,3-dimethyl) ester (RN 266356-45-0), as well as their monoacid and phosphonic acid
• Vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile.
• the amides of vinylamine for example vinylformamide or vinylacetamide, are preferably used as ethylenically unsaturated monomers. Then, the polymer obtained is hydrolyzed at acidic or basic pH.
• vinyl esters of carboxylic acid such as for example vinyl acetate
• vinyl acetate ethylenically unsaturated monomers.
• the polymer obtained is hydrolyzed at acidic or basic pH.
• the monoethylenically unsaturated monomers used in the preparation of first generation (co) polymers are chosen from styrenic monomers, vinyl esters, neutral or charged hydrophilic acrylates, hydrophobic acrylates, neutral or charged hydrophilic methacrylates, methacrylates hydrophobic, acrylamidohydrophilic, hydrophobic, neutral or charged, methacrylamidohydrophilic, hydrophobic, neutral or charged.
• the types and quantities of polymerizable monomers used for the preparation of first generation (co) polymers vary depending on the particular final application for which the Mikto star copolymer is intended. These variations are well known and can be easily determined by those skilled in the art. These monoethylenically unsaturated monomers can be used alone or in mixtures.
• the process of the invention is in all cases implemented in the presence of a source of free radicals.
• a source of free radicals for certain monomers, such as styrene, the free radicals making it possible to initiate the polymerization can be generated by the monoethylenically unsaturated monomer, at sufficiently high temperatures generally above 100 ° C. In this case, it is not necessary to add a source of additional free radicals.
• the nature of the source of free radicals and of the control agent depend on the method of synthesis of the first generation (co) polymers.
• the source of free radicals which is useful is generally an initiator of radical polymerization.
• the radical polymerization initiator can be chosen from the initiators conventionally used in radical polymerization.
• - hydrogen peroxides such as: tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl-peroxyacetate, t-butyl-peroxyben ⁇ oate, t-butylperoxyoctoate, t-butylperoxyneodecanoate, t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, 'ammonium, - azo compounds such as: 2-2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1 , 1'-azobis (cyclohexane-carbonitrile), 2- (t- hydrogen peroxides such as: tertiary
• the amount of initiator to be used is determined so that the amount of radicals generated is at most 50% by weight. mole, preferably at most 20 mol%, relative to the amount of control agent.
• control agents which can be used in radical polymerization by a process of the reversible transfer type by addition-fragmentation of thiocarbonylthio compounds, for preparing the first generation (co) polymers
• control agents which can be used in radical polymerization by a process of reversible transfer type by addition-fragmentation of thiocarbonylthio compounds are compounds which can be of the following formula (II): S R ⁇ -s- ⁇ z (il) in which : Z represents:. a hydrogen atom,. a chlorine atom,. an optionally substituted alkyl radical, optionally substituted aryl, . an optionally substituted heterocycle,. an optionally substituted alkylthio radical,. an optionally substituted arylthio radical,. an optionally substituted aikoxy radical,. an optionally substituted aryloxy radical,. an optionally substituted amino radical,. an optionally substituted hydrazine radical,.
• Z represents:. a hydrogen atom,. a chlorine atom,. an optionally substituted alkyl radical, optionally substituted aryl, . an optionally substituted heterocycle,. an optionally substituted alkylthio radical,. an optionally
• an optionally substituted alkoxycarbonyl radical represents:. an optionally substituted alkoxycarbonyl radical,. an optionally substituted aryloxycarbonyl radical,. a carboxy radical, optionally substituted acyloxy,. an optionally substituted aroyloxy radical,. an optionally substituted carbamoyl radical,. a cyano radical,. a dialkyl- or diaryl-phosphonato radical,. a dialkyl-phosphinato or diaryl-phosphinato radical, or. a polymer chain, - Ri represents:. an optionally substituted alkyl, acyl, aryl, aralkyl, alkene or alkyne group,. an optionally substituted aromatic carbon ring or heterocycle, saturated or unsaturated,. a polymer chain,
• the groups Ri or Z when they are substituted, may be substituted by optionally substituted phenyl groups, optionally substituted aromatic groups, saturated or unsaturated carbon rings, saturated or unsaturated heterocycles, or groups: alkoxycarbonyl or aryloxycarbonyl (- COOR), carboxy (-COOH), acyloxy
• R represents an alkyl or aryl group, or a polymer chain.
• R 1 is a substituted or unsubstituted alkyl group, preferably substituted.
• the compounds (A) useful in the present invention are, for example, the compounds in which Ri is chosen from:
• the optionally substituted alkyl, acyl, aryl, aralkyl or alkyne groups generally have 1 to 20 carbon atoms, preferably 1 to 12, and more preferably 1 to 9 carbon atoms. They can be linear or branched. They can also be substituted by oxygen atoms, in the form in particular of esters, sulfur or nitrogen atoms.
• alkyl radicals mention may in particular be made of the methyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, decyl or dodecyl radical.
• the alkyne groups are radicals generally of 2 to 10 carbon atoms, they exhibit at least one acetylenic unsaturation, such as the acetylenyl radical.
• the acyl group is a radical generally having from 1 to 20 carbon atoms with a carbonyl group.
• aryl radicals mention may in particular be made of the phenyl radical, optionally substituted in particular by a nitro or hydroxyl function.
• aralkyl radicals mention may in particular be made of the benzyl or phenethyl radical, optionally substituted in particular by a nitro or hydroxyl function.
• R 1 or Z is a polymer chain
• this polymer chain can result from radical or ionic polymerization or result from polycondensation.
• the following control agents are preferred: xanthates, dithiocarbamates, dithioesters, dithiocarbazates.
• xanthates are used as the control agent.
• the polymerization control agent is a transition metal associated with a ligand acting as a catalyst for polymerization.
• pyridylmethanimine CuX tris [2- (dimethylamino) ethyl] amine, CuX / N, N, N ', N ", N", - pentamethyldiethylenetriamine, CuX / tris [(2-pyridyl) methyl] amine, Mn (CO) 6 , RuXx (PPh3) 3, NiX [(o-o'-CH2NMe2) 2C6H3], RhX (PPh3) 3, NiX2 (PPh3) 2 and FeX2 / P (n-Bu) 3 where X is a halogen or a pseudo- halogen.
• An aluminum trialkylate AI (OR) 3 can be used as an additive to activate the polymerization.
• a detailed list of transition metals and associated ligands is described in document WO 96/30421, from page 22 line 6 to page 26, line 8.
• the metal complex (Mt n X) captures the halogen atom of the organic halide (RX) to form the radical R ' and the oxidized metallic species Mt ⁇ + 1 X 2 .
• R ' reacts with the monomer M to form a new radical active species RM * .
• the source of useful free radicals is generally an organic halide activated by redox route.
• the organic halides playing the role of source of free radicals in the ATRP process are for example: - an arenesulfonyl halide or an alkanesulfonyl halide of formula RSO2X, where X is a chlorine atom, a bromine atom or an iodine atom and R is an aryl, alkyl, substituted alkyl or substituted aryl group.
• RSO2X an arenesulfonyl halide or an alkanesulfonyl halide of formula RSO2X, where X is a chlorine atom, a bromine atom or an iodine atom and R is an aryl, alkyl, substituted alkyl or substituted aryl group.
• R'X A halide of formula R'X, where X is generally a chlorine atom, a bromine atom or an iodine atom and R 'an aryl, alkyl, substituted alkyl, substituted aryl or cycloalkyl group.
• R ′ A halide of formula R'X, where X is generally a chlorine atom, a bromine atom or an iodine atom and R 'an aryl, alkyl, substituted alkyl, substituted aryl or cycloalkyl group.
• the controlled radical polymerization used in the preparation of the first generation (co) polymers according to the invention is carried out according to a reversible transfer process by addition-fragmentation of thiocarbonylthio compounds.
• hard monomer is meant a monomer leading to a polymer with a glass transition temperature above 20 ° C.
• soft monomer is meant a monomer leading to a polymer with a glass transition temperature below 20 ° C.
• the subject of the invention is a process for the preparation of star-shaped copolymers of the “mikto” type which comprises a step of radical polymerization of a composition comprising: - at least one crosslinking monomer, - a source of free radicals, and - at least two (co) polymers of first generation of different chemical nature and possibly of different molecular mass.
• the crosslinking monomers can also be added to the first generation (co) polymers alone or with one or more monoethylenically unsaturated co-monomers or with another or more other crosslinking co-monomers.
• the crosslinking monomers can be introduced all at once, per portion, by continuous or semi-continuous addition.
• the crosslinking monomers useful in the process of the present invention are all the monomers which polymerize in the presence of the active polymer chains of the first generation polymer to give new active polymer chains whose controlled radical polymerization gives access to star-shaped polymers.
• the crosslinking monomers are chosen from organic compounds comprising at least two ethylenic unsaturations and at most 10 unsaturations and known to be radically reactive. Preferably, these monomers have two or three ethylenic unsaturations.
• acrylic, methacrylic, acrylamido, methacrylamido, vinyl ester, vinyl ether, diene, styrene, alpha-methyl styrene and allyl derivatives can also contain functional groups other than ethylenic unsaturations, for example hydroxyl, carboxyl, ester, amide, amino or substituted amino, mercapto, silane, epoxy or halo functions.
• the monomers belonging to these families are divinylbenzene and derivatives of divinylbenzene, vinyl methacrylate, methacrylic acid anhydride, allyl methacrylate, ethylene glycol dimethacrylate, phenylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, butanediol 1,3-dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-dimethacrylate hexanediol, dodecanediol 1,12-dimethacrylate, glycerol 1,3-dimethacrylate, diurethane dimethacrylate, trimethylolpropane trimethacrylate.
• vinyl acrylate bisphenol A epoxy diacrylate, diacrylate dipropylene glycol, tripropylene glycol diacrylate, polyethylene glycol 600 diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate diacrylate diacrylate diacrylate diacrylate glycol diacrylateacrylate diacrylate diacrylate glycol butanediol, hexanediol diacrylate, aliphatic urethane diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane propoxylated triacrylate, glycerol propoxylate triacrylate, triacrylate tearylacrylate dipentaerythitol pentaacrylate.
• vinyl ethers mention may in particular be made of vinyl crotonate, diethylene glycoldivinyl ether, divinyl ether of 1,4-butanediol, triethylene glycoldivinyl ether.
• allyl derivatives mention may in particular be made of diallylphthalate, diallyldimethylammoniumchloride, diallylmalleatate, sodium diallyloxyacetate, diallylphenylphosphine, diallylpyrocarbonate, diallylsuccinate, N, N'-diallyltartardiamide, N, N-2,2 2- trifluoroacetamide, the allyl ester of diallyloxy acetic acid, 1, 3-diallylurea, triallylamine, triallyltrimesate, triallylcyanurate, triallyltrimellitate, triallyl-1, 3,5-triazine-2,4,6 (1 H , 3H, 5H) -trione.
• acrylamido derivatives of N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, glyoxalbis acrylamide, diacrylamido acetic acid.
• styrenic derivatives mention may in particular be made of divinylbenzene and 1, 3-diisopropenylbenzene.
• dienic monomers mention may in particular be made of butadiene, chloroprene and isoprene.
• crosslinking monomers N, N'-methylenebisacrylamide, divinylbenzene, ethylene glycol diacrylate or trimethylolpropane triacrylate are preferred. These crosslinking monomers can be used alone or in mixtures.
• the types and quantities of crosslinking monomers used according to the present invention vary according to the particular final application for which the Mikto star copolymer is intended. These variations are easily determined by those skilled in the art.
• the molar ratio of crosslinking compounds relative to the first generation polymers is greater than or equal to 1. More preferably, this molar ratio is less than or equal to 100. More preferably, this ratio is between 5 and 70 , preferably between 5 and 20.
• crosslinking monomers can be used alone or in mixtures.
• the source of free radicals depends on the mode of controlled radical polymerization used to synthesize Mikto-type stars. It can be chosen from the list of free radical sources described in the synthesis of first (co) polymers generation for each controlled radical polymerization technique useful in the present invention.
• the source of free radicals is a source of free radicals as defined above for the preparation of (co) first generation polymers by a controlled radical polymerization process of reversible transfer type by addition-fragmentation of thiocarbonylthio compounds.
• the source of free radicals is an organic halide catalyst activated by redox route as described above.
• the controlled radical polymerization process used in the preparation of the Mikto-type star copolymer is of the reversible transfer type by addition-fragmentation of thiocarbonylthio compounds.
• the process according to the invention can be carried out in bulk, in solution, in emulsion, in dispersion or in suspension. Preferably, it is used in solution or in emulsion.
• the first generation (co) polymers can have a dry extract of between 1 and 99.9% by weight.
• the dry extract of the MIKTO star copolymer is advantageously between 1 and 30% by weight, even more advantageously from 5 to 20%.
• the temperature can vary between room temperature and 150 ° C depending on the nature of the crosslinking monomers used.
• the process for preparing Mikto type star copolymers is implemented in the absence of UV source, by thermal initiation in the case of a controlled radical polymerization process of reversible transfer type by addition-fragmentation of thiocarbonylthio compounds. , or by redox initiation in the case of a controlled radical polymerization process of the ATRP type.
• the Mikto star copolymers obtained by selecting specific monoethylenically unsaturated monomers, which enter into the composition of first generation (co) polymers and by choosing the order or the mode of introduction or the quantities. respective monomers introduced. It is advantageous to introduce the crosslinking monomer continuously. Likewise, in the case where a monoethylenically unsaturated monomer is added in addition to the crosslinking monomer as indicated above, it is preferred to add it continuously.
• (co) hard polymers is meant a (co) polymer with a glass transition temperature above 20 ° C.
• the term “soft (co) polymer” means a (co) polymer with a glass transition temperature of less than 20 ° C.
• the Mikto type star copolymers comprise at least two (co) polymers of first generation of different chemical nature and possibly of different molecular mass. These first generation (co) polymers can be used in equivalent proportions or, on the contrary, in very different proportions.
• the first generation (co) polymers of different chemical nature can be used in proportions ranging from 99.9% to 0.1%, the totality of the first generation (co) polymers being equal to 100%.
• the present invention also relates to the mikto star copolymers capable of being obtained by any of the methods previously described.
• These methods consist of a step of cleavage, such as in particular that described in Mori et al. in J. Org. Chem., 34, 12, 1969, 4170 (transformation of xanthate into thiol) or also that described by Udding et al. in J. Org. Chem. , 59, 1994, 6671 from Bu 3 SnH (transformation into halogen atom).
• This deactivation can also be carried out by an ozonolysis treatment by implementing a process as described for example in the document of the Applicant FR 03 12338.
• the ends of halogenated chains resulting from the ATRP process can also be chemically modified in various ways. Mention may be made, for example, of the dehydrohalogenation reaction in the presence of an unsaturated compound, described in patent WO99 / 54365, which generates unsaturation at the chain end.
• the halogenated end can also be transformed into other functionalities, for example by nucleophilic substitution or electrophilic addition, or even by radical addition. All of these techniques for transforming halogen chain ends are described in the document "Progress in Polymer Science (2001), 26 (3), 337".
• the subject of the invention is also a Mikto star copolymer resulting from a controlled radical polymerization of ATRP type in which the active part of the control agent has been at least partially deactivated at the end of the polymerization.
• the subject of the invention is in particular a copolymer characterized in that the (co) polymers constituting the arms are derived in particular from monoethylenically unsaturated monomers chosen from vinyl esters, hydrophobic, hydrophilic, neutral or charged acrylates, hydrophobic, hydrophilic methacrylates , neutral or charged, hydrophobic, hydrophilic, neutral or charged acrylamido and hydrophobic, hydrophilic, neutral or charged methacrylamido.
• the Mikto star-shaped copolymers according to the invention thus have the advantage of being able to comprise a large number of arms, this number being able to be controlled during their preparation.
• Mikto-type star copolymers can be used as additives for coating or adhesive compositions. They can also be used as additives for laundry care compositions (for example detergents or softeners), additives for cosmetic compositions (intended to be applied to the skin and / or the hair and / or the nails and / or eyelashes), additives for industrial compositions (emulsion polymerization, lubrication ...) or additives for fluids for the exploitation of oil and / or gas deposits.
• emulsifying agents can also be used as emulsifying agents, as rheological agents (agents modifying the rheological properties of a fluid, for example viscosity), as dispersants, as reinforcing agents for polymeric materials, as encapsulating agents, as sequestering agents or as nanoreactors , for example in the compositions mentioned above, or in other compositions.
• rheological agents agents modifying the rheological properties of a fluid, for example viscosity
• dispersants as reinforcing agents for polymeric materials
• encapsulating agents as sequestering agents or as nanoreactors
• the copolymers are used as emulsifying agents, for the preparation of a reverse water-in-oil emulsion, of a direct oil-in-water emulsion, and / or of a multiple water-in-oil-in-water emulsion, the copolymer star comprising first generation (co) polymers of different chemical natures chosen from hydrophilic (co) polymers combined with hydrophobic (co) polymers.
• the oil can also be called “hydrophobic phase”.
• Copolymers are thus versatile emulsifying agents (of high modularity) which can be used in many types of emulsions, which constitutes a surprising property.
• the copolymers are used for the preparation of a multiple water-in-oil-in-water emulsion, as a single emulsifying agent.
• This embodiment makes it possible in particular to simplify the preparation of multiple emulsions, for example by managing fewer raw materials.
• the emulsion comprises at least two immiscible liquid phases, an internal phase and an external phase, one of which is aqueous. It is not excluded that the emulsion comprises three immiscible phases, the emulsion then having an aqueous phase, a first group of droplets (first internal phase) dispersed in the external phase, and a second group of droplets (second phase internal) dispersed in the external phase.
• a phase (aqueous phase or not) immiscible with the internal phase are dispersed in the form of droplets inside the droplets of the internal phase.
• emulsions comprising an internal emulsion and an external emulsion.
• they can be water in oil in water emulsions, comprising an internal phase (water), an intermediate phase (oil) and an external phase.
• the dispersion of the internal phase in the intermediate phase constitutes an internal inverse emulsion
• the dispersion of the intermediate phase in the external phase constitutes a direct external emulsion.
• the notion of reverse emulsion covers both a simple reverse emulsion and an internal reverse emulsion of a multiple emulsion.
• the notion of direct emulsion covers both a simple direct emulsion and an external direct emulsion of a multiple emulsion.
• the aqueous phase can be an external phase, if necessary an external phase of a multiple emulsion. We are talking about direct emulsions.
• the aqueous phase is an internal phase, where appropriate the external phase of a multiple emulsion. We are talking about reverse emulsions.
• the aqueous phase naturally includes water, and if necessary other compounds.
• the other compounds can be solvents or co-solvents, dissolved or solid compounds dispersed in water, for example active materials.
• other compounds of the aqueous phase, we do not mean the internal liquid phase or the intermediate phase of a multiple emulsion.
• the mikto star copolymer is preferably dispersible or soluble in water.
• the aqueous phase may also contain compounds intended to give the solution a certain pH, and / or salts having no appreciable influence on the pH.
• the aqueous phase can also comprise compounds usually used in the fields of formulations in the form of emulsions or comprising emulsions, for example in the fields of laundry care, in the fields of cosmetics, in the industrial fields (emulsion polymerization , lubrication ..). It may, for example, be surfactants, anionic, cationic, amphoteric, zwitterionic, or nonionic, detergency builders (hydrators), hydrophilic active agents, salts, viscosifying agents.
• the emulsion comprises a phase immiscible with the aqueous phase. To put it simply, this phase will be designated by "non-aqueous phase" or by "oil phase", or by "hydrophobic phase".
• immiscible phases is meant that one phase is not more than 10% soluble in the other phase, at a temperature of 20 ° C.
• the non-aqueous phase can be the internal phase (direct emulsions), or the external phase (reverse emulsions). It may especially be an intermediate phase of a multiple emulsion. Examples of compounds constituting the nonaqueous phase, or included in the nonaqueous phase include:
• oils / waxes for example hydrocarbon paraffins
• - fatty acids saturated or not, comprising 10 to 40 carbon atoms; esters of such acids and of alcohol comprising 1 to 6 carbon atoms;
• water-insoluble monomers in particular used for the polymerizations of isocyanate with polyols or for the polymerizations of latex,
• organic oils / fats / waxes of animal origin there may be mentioned, among others, sperm whale oil, whale oil, seal oil, shark oil, cod liver oil, pork and mutton fats (tallow), perhydrosqualene, beeswax, alone or in a mixture.
• organic oils / fats / waxes of vegetable origin there may be mentioned, inter alia, rapeseed oil, sunflower oil, peanut oil, olive oil , walnut oil, corn oil, soybean oil, avocado oil, linseed oil, hemp oil, grape seed oil, copra, palm oil, cotton seed oil, babassu oil, jojoba oil, sesame oil, castor oil, macadamia oil, d oil sweet almond, carnauba wax, shea butter, cocoa butter, peanut butter, alone or in a mixture.
• rapeseed oil sunflower oil, peanut oil, olive oil , walnut oil, corn oil, soybean oil, avocado oil, linseed oil, hemp oil, grape seed oil, copra, palm oil, cotton seed oil, babassu oil, jojoba oil, sesame oil, castor oil, macadamia oil, d oil sweet almond, carnauba wax, shea butter, cocoa butter, peanut butter, alone or in a mixture.
• mineral oils / waxes there may be mentioned, inter alia, naphtenic, paraffinic (petrolatum), isoparaffinic oils, paraffinic waxes, alone or as a mixture.
• fatty acids the latter, saturated or unsaturated, contain 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can comprise one or more ethylenic unsaturations, conjugated or not. It should be noted that said acids may comprise one or more hydroxyl groups.
• saturated fatty acids mention may be made of palmitic, stearic and behenic acids.
• unsaturated fatty acids there may be mentioned myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic, ricinoleic acids, as well as their mixtures.
• esters of the acids listed above mention may be made of the esters of the acids listed above, for which the part deriving from the alcohol comprises 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, etc.
• the nonaqueous phase can comprise a silicone or a mixture of several of them. We often speak of silicone oils. Amino silicones are particularly useful in the areas of detergency. More details are given below as regards the silicones.
• It may in particular be an oil, a wax or a resin in a linear, cyclic, branched or crosslinked polyorganosiloxane.
• Said polyorganosiloxane preferably has a dynamic viscosity measured at
• it is a nonionic or amino polyorganosiloxane.
• the nonaqueous phase may comprise monomers which are insoluble in water, in particular usable for emulsion polymerization processes, for example for the manufacture of latex.
• the nonaqueous phase comprises an amount of water, or of monomers soluble in water, which does not exceed the limit of solubility of water or in monomers in said phase.
• monomers which can constitute or be included in the non-aqueous phase include, alone or in mixtures: - the esters of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation;
• esters of saturated carboxylic acids comprising 8 to 30 carbon atoms, optionally carrying a hydroxyl group; - ⁇ -ethylenically unsaturated nitriles, vinyl ethers, vinyl esters, vinyl aromatic monomers, vinyl or vinylidene halides;
• esters of (meth) acrylic acid with an alcohol comprising 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) n-butyl acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl acrylate, isodecyl acrylate; - vinyl acetate, vinyl Versatate®, vinyl propionate, vinyl chloride, vinylidene chloride, methyl vinyl ether, ethyl vinyl ether;
• the vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile; styrene, ⁇ -methylstyrene, vinyltoluene, butadiene, chloroprene.
• the non-aqueous internal phase can comprise a phase, aqueous or not, dispersed in the form of an emulsion within it. The emulsion is then a multiple emulsion.
• the weight ratio between the quantities of internal phase and external phase is preferably between 0.1 / 99.9 and 95/5, more preferably between 1/99 and 10/90.
• the weight ratio between the amounts of mikto star copolymer and of internal phase is preferably between 0.05 / 100 and 20/100, more preferably between 0.5 and 20/100, or even between 5/100 and 20 / 100. Furthermore, the proportion by weight of mikto star copolymer in the entire emulsion is preferably between 0.05% and 10%, even more preferably between 0.1% and 5%, for example of the order from 1%.
• the emulsions according to the invention are compositions which, in addition to the ingredients mentioned above, can comprise other ingredients.
• the nature and quantity of these other ingredients may depend on the destination or the use of the emulsion.
• these additional ingredients are known to those skilled in the art.
• the emulsion can comprise additional emulsifying agents, known, in association with mikto star copolymer, in particular surfactants, in particular nonionic or cationic surfactants, water-soluble amphiphilic polymers, comb polymers or block polymers.
• each of the aqueous phases can comprise agents intended to control the osmotic pressure.
• the emulsions can comprise nonionic, anionic, cationic or amphoteric surfactants (the zwitterionic surfactants being included in amphoterics).
• the emulsions can also include pH control agents, active ingredients, perfumes, etc.
• the polymerization reactions are carried out with a light sweep of argon in simple glass apparatus immersed in an oil bath preheated to 70 ° C.
• free radical generators 4'-azobis- 4-cyanopentanoic acid (ACP), 2'-2'-azobis- 2-methylbutylronitrile (AMBN) or ammonium peroxodisulfate are used.
• ACP 4'-azobis- 4-cyanopentanoic acid
• AMBN 2'-2'-azobis- 2-methylbutylronitrile
• ammonium peroxodisulfate are used.
• the crosslinker used in the following examples is N, N'-methylene- (bis) acrylamide (MBA).
• SEC steric exclusion chromatography
• GC gas chromatography
• HPLC high performance liquid chromatography
• the number-average molar masses M n (g. Mol "1 ) are expressed in poly (ethylene oxide) equivalents for hydrophilic polymers and in polystyrene for hydrophobic polymers.
• Example 2.1 Star copolymers based on poly (acrylic acid) and poly (butyl acrylate): [6]
• Example 2.2 Star copolymers based on poly (acrylamide) and poly (trimethyl acrylate, ammonium ethyl, methyl sulphate): [7]
• the analysis by light scattering shows a homogeneous population of polymer having an average diameter of 91 nm.
• the oil used is the rapeseed methyl ester (Phytorob 926-65 sold by Novance).
• This oily phase is mixed with an aqueous solution containing 0.1 M NaCl (internal aqueous phase), with a ratio between the aqueous phase and the oil of 50/50 by weight in order to obtain a reverse emulsion 50/50 w / o.
• the mixture is sheared using an ultra-turrax at 10,000 rpm for 10 minutes.
• Optical microscopy shows that the size of the droplets of this emulsion is of the order of 1 ⁇ m.
• Example 3.1 The reverse emulsion of Example 3.1 is poured dropwise into an aqueous solution (external aqueous phase) comprising 0.1 M NaCl, 1% by weight of gum
• the amounts of reverse emulsion and of aqueous solution are identical, in order to obtain a 50/50 emulsion by weight of the reverse emulsion in the external aqueous phase (that is to say w / o / w 25/25/50).
• Optical microscopy shows that the size of the droplets of this emulsion is of the order of 10-40 ⁇ m.
• This example illustrates the possibility of preparing multiple water in oil in water emulsions using a single emulsifying agent, identical for the preparation of the internal water in oil emulsion and for the preparation of the external emulsion (water in oil) in water.

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