Hybrid polymer and method for obtaining same

Abstract

The present invention pertains to the technical field of hybrid polymers. More specifically, the invention relates to a specific hybrid polymer. The hybrid polymer is obtained by a radical polymerization process between at least one ethylenically unsaturated monomer and at least one protein. The invention also relates to the use of said composition in various compositions. The invention also relates to the use of such compositions in various fields of application.

Description

[0001] HYBRID POLYMER AND PROCESS FOR OBTAINING SAME

[0002] FIELD OF THE INVENTION

[0003] The present invention belongs to the technical field of hybrid polymers. More specifically, the invention relates to a specific hybrid polymer. Said hybrid polymer is obtained by a radical polymerization process between at least one unsaturated ethylenic monomer and at least one protein. The invention also relates to the use of said hybrid polymer in various compositions. The invention also relates to the use of these compositions in various fields of application.

[0004] PREVIOUS ART

[0005] The development of hybrid polymers, that is, the development of a polymeric entity combining at least two polymers of different nature, has been the subject of enormous research work in recent years.

[0006] These hybrid polymers have the advantage of presenting unique functional properties and application potential, given the multitude of possible polymer combinations, which can lead to new synergies.

[0007] Among these hybrid polymers, there are hybrid polymers combining biopolymers from natural and / or renewable resources and synthetic polymers from fossil resources. This type of hybrid polymer is of significant interest in many industries due to their application performance, which is similar to that of synthetic polymers, and their sustainable development potential. These characteristics make them attractive polymers in many applications, offering opportunities for innovation and the development of ever more efficient and environmentally friendly products.

[0008] Many documents disclose hybrid polymers combining polysaccharides and synthetic polymers or polysaccharides and synthetic monomers. US Pat. Nos. 5,854,191; 5,223,171; 5,227,446 and 5,296,470 disclose the use of such hybrid copolymers in detergents. WO / 1810663, WO / 18108665 and WO / 18108667 disclose such hybrids used in cosmetic formulations.

[0009] The use of these polysaccharide hybrid polymers, however, remains very specific to given application areas, mainly in cosmetics. Such polysaccharide hybrids are not found in applications where hybrid polymers must withstand difficult conditions such as high temperatures or high pressure, such as petroleum applications or textiles, for example.

[0010] It has become more than necessary to develop hybrid polymers, meeting the expectations of different specifications, in various fields of application.

[0011] The Applicant has thus developed a hybrid polymer, combining a monomeric unit and a protein unit. Said hybrid polymer is included in a composition; itself used in various fields of application

[0012] STATEMENT OF THE INVENTION

[0013] The present invention relates to a hybrid polymer (HP).

[0014] According to a first aspect, the invention relates to a hybrid polymer (HP) comprising monomeric units of at least one monomer comprising at least one unsaturated ethylenic function, and protein units, characterized in that the monomeric units and the protein units are partially or totally linked by at least one covalent bond, in that the weight ratio between the monomeric units and the protein units is between 50 / 1 and 1 / 5

[0015] According to a second aspect, the invention relates to a hybrid polymer (PH) obtained by radical polymerization according to a process comprising the following successive steps:

[0016] (A) Prepare a mixture (Ml) comprising at least one monomer comprising at least one unsaturated ethylenic function; and between 0.1% and 50% by weight of at least one protein, optionally at least one solvent;

[0017] (B) Initiate polymerization in the mixture (Ml) to obtain a hybrid polymer (PH).

[0018] According to a third aspect, the invention relates to a hybrid polymer (PH) obtained by inverse radical emulsion polymerization according to a process comprising the following successive steps: (A1) Preparation of an aqueous phase comprising between 1% to 50% by weight of at least one protein, between 4% to 40% by weight of at least one monomer comprising at least one unsaturated ethylenic function and between 20 to 95% by weight of water;

[0019] (A2) Preparation of a lipophilic phase comprising between 70% to 99% by weight of an inert hydrophobic liquid and between 1 to 20% by weight of at least one surfactant;

[0020] (A3) Mixing said aqueous phase with said lipophilic phase in order to form an inverse emulsion;

[0021] (B) Polymerization of said inverse emulsion to obtain a hybrid polymer inverse emulsion (PH).

[0022] According to a fourth aspect, the invention relates to a hybrid polymer (PH) obtained by radical polymerization in the gel process according to a process comprising the following successive steps:

[0023] (A) Preparation of an aqueous solution) comprising between 10 and 40% by weight of at least one monomer comprising at least one unsaturated ethylenic function, and from 1 to 30% by weight of at least one protein, water, and optionally at least one pH regulator.

[0024] (B) Initiation of radical polymerization in the aqueous solution to obtain the hybrid polymer (PH) in the form of a gel;

[0025] (C) Grinding and drying of the obtained gel to obtain the hybrid polymer (PH) in powder form.

[0026] According to a fifth aspect, the invention relates to the use of the hybrid polymer (PH) according to the invention, in particular as a viscosifying agent.

[0027] This aspect of the invention also relates to the use of the hybrid polymer (PH) according to the invention in various compositions, and to compositions comprising at least one hybrid polymer (PH) according to the invention.

[0028] The invention also relates to the use of such compositions in a field chosen from hydrocarbon recovery; in well drilling and cementing; in the stimulation of hydrocarbon wells; in water treatment; in the treatment of fermentation musts; in the treatment of sludge; in papermaking; in construction; in wood treatment; in the treatment of hydraulic composition; in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in textile manufacturing; in the manufacture of battery components; in geothermal energy; in the manufacture of hygienic diapers; or in agriculture.

[0029] DETAILED DESCRIPTION OF THE INVENTION

[0030] Definitions and generalities

[0031] Throughout this application, the following definitions apply unless specifically indicated otherwise.

[0032] “Hydrophilic monomer” means a monomer which has an octanol / water partition coefficient, Kow, less than or equal to 1, in which the Kow partition coefficient is determined at 25°C in an octanol / water mixture having a volume ratio of 1 / 1, at a pH between 6 and 8.

[0033] By "hydrophobic monomer" is meant a monomer which has an octanol / water partition coefficient, Kow, greater than 1, in which the Kow partition coefficient is determined at 25°C in an octanol / water mixture having a volume ratio of 1 / 1, at a pH between 6 and 8.

[0034] The octanol / water partition coefficient, Kow, represents the ratio of concentrations (g / L) of a monomer between the octanol phase and the aqueous phase. It is defined as follows:

[0035] [Math 1]

[0036] With

[0037] [monomer] octanol = equilibrium concentration of monomer solubility in g / L in n-octanol

[0038] [monomer] water = equilibrium monomer concentration in g / L in water.

[0039] According to the invention, “X and / or Y” means “X”, or “Y”, or “X and Y”.

[0040] Also part of the invention are all possible combinations between the different embodiments disclosed, whether preferred embodiments or given by way of example. Furthermore, when ranges of values ​​are indicated, the limits are part of these ranges. The disclosure also includes all combinations between the limits of these ranges of values. For example, the ranges of values ​​"1-20, preferably 5-15", imply the disclosure of the ranges "1-5", "1-15", "5-20" and "15-20" and the values ​​1, 5, 15 and 20.

[0041] According to the present invention, the weight average molecular weight of the synthetic polymers according to the invention is determined by measuring the intrinsic viscosity. The intrinsic viscosity can be measured by methods known to those skilled in the art and can in particular be calculated from the reduced viscosity values ​​for different concentrations by a graphical method consisting of plotting the reduced viscosity values ​​(on the y-axis) as a function of the concentrations (on the x-axis) and extrapolating the curve to a zero concentration. The intrinsic viscosity value is read on the y-axis or using the least squares method. Then, the weight average molecular weight can be determined by the well-known Mark-Houwink equation:

[0042] [r|] = KM“

[0043] [r] represents the intrinsic viscosity of the polymer determined by the solution viscosity measurement method,

[0044] K represents an empirical constant,

[0045] M represents the molecular weight of the polymer, a represents the Mark-Houwink coefficient, a and K depend on the particular polymer-solvent system. Tables known to those skilled in the art give the values ​​of a and K depending on the polymer-solvent system.

[0046] By "monomer unit" we mean the chemical unit relative to the corresponding monomer when it is found polymerized in the polymer chain of the polymer.

[0047] The term "protein unit" refers to the chemical unit relative to a corresponding protein, when it is grafted into the polymer chain of the polymer.

[0048] Hybrid polymer (PH)

[0049] According to a first aspect, the invention relates to a hybrid polymer (HP) comprising monomeric units of at least one monomer comprising at least one unsaturated ethylenic function, and protein units, characterized in that the monomeric units and the protein units are partially or totally linked by at least one covalent bond, in that the weight ratio between the monomeric units and the protein units is between 50 / 1 and 1 / 5.

[0050] The weight ratio between the monomeric units and the protein units is between 50 / 1 and 1 / 5, preferably between 25 / 1 and 1 / 3, more preferably between 10 / 1 and 1 / 2, more preferably between 6 / 1 and 1 / 1.

[0051] The hybrid polymer (HP) has a weight average molecular weight advantageously between 20,000 and 20,000,000 daltons, preferably between 100,000 and 15,000,000 daltons.

[0052] The hybrid polymer (HP) has a Brookfield viscosity preferably between 1,000 and 100,000 cps, more preferably between 2,500 and 75,000 cps, more preferably between 5,000 and 50,000 cps. The Brookfield viscosity is measured on a 1% by weight polymer solution in water with a Brookfield viscometer RVT module with a rotation speed of 20 rpm.

[0053] The hybrid polymer (HP) comprises less than 40% by mass of protein, preferably 10 to 50% by mass of protein, even more preferably 15 to 45% by mass of protein.

[0054] The hybrid polymer (HP) can be in the form of a solution, powder, inverse emulsion, water-in-water dispersion, suspension, or in the form of "clear", that is to say a dispersion of solid polymer particles in an aqueous or oily fluid. When the hybrid polymer (HP) is in the form of a powder, it can be in the form of particles or beads.

[0055] According to the invention, the hybrid polymer (HP) can be linear or structured. A structured polymer refers to a non-linear polymer which has side chains so as to obtain, when this polymer is dissolved in water, a strong state of entanglement leading to very high low gradient viscosities. This is also referred to as a crosslinked polymer.

[0056] Monomers and monomeric units:

[0057] As a reminder, a monomeric unit designates the chemical unit relating to a corresponding monomer when it is polymerized in the hybrid polymer (PH). The monomers constituting the monomeric units of the hybrid polymer (PH) are chosen from monomers comprising at least one unsaturated ethylenic function. In the present application, the expressions “monomer unit” and monomer are used appropriately. With regard to the hybrid polymer (PH) according to the first aspect of the invention, the expression “monomer unit” is appropriate and used because the monomer has reacted during the polymerization and is part of the polymer chain. With regard to the polymer (PH) obtained according to a process (by radical polymerization, or by inverse emulsion, or by gel route), the expression “monomer” is appropriate and used because the monomer is described in its form before polymerization.

[0058] Both expressions may be used in the same sentence, for example a claim, if said claim refers on the one hand to at least one claim of the type "hybrid polymer (PH comprising. . . " and on the other hand at least one claim of the type "hybrid polymer (PH) obtained according to a process (by radical polymerization, or by inverse emulsion, or by gel route). And the monomers and preferences set out below are applicable for both expressions.

[0059] Said monomers may be of a synthetic and / or bio-sourced nature, this includes monomers from patents: FR3125048, FR3125045, FR3125044, FR3125043, FR3125046, WO2023 / 281233, EP4175939, WO2023 / 281088, WO2023 / 281077, WO2023 / 281076, WO2023 / 281078, WO2023 / 281084, WO2023 / 281081.

[0060] Preferably, these monomers are hydrophilic monomers, chosen from non-ionic, anionic, cationic and / or zwitterionic hydrophilic monomers. Preferably, these monomers have a single ethylenic unsaturation (double bond between two carbon atoms).

[0061] The non-ionic hydrophilic monomers are preferably chosen from the group comprising water-soluble vinyl monomers, such as acrylamide, methacrylamide, N-alkylacrylamides, N-alkylmethacrylamides, N,N-dialkyl acrylamides (e.g., N,N-dimethylacrylamide or N,N-diethylacrylamide), N,N-dialkylmethacrylamides, alkoxylated esters of acrylic acid, alkoxylated esters of methacrylic acid, N-vinylpyrrolidone, N-methylol(meth)acrylamide, N-vinyl caprolactam, N-vinylformamide (NVF), N-vinyl acetamide, N-vinyl imidazole, N-vinyl succinimide, acryloyl morpholine (ACMO), methacrylate, glycidyl, glyceryl methacrylate, diacetone acrylamide, methacrylic anhydride, acrylonitrile, maleic anhydride, itaconic anhydride, fitaconamide, vinylpyridine, hydroxyalkyl (meth)acrylate, thioalkyl (meth)acrylate, isoprenol and its alkoxylated derivatives,hydroxy ethyl(meth)acrylates and their alkoxylated derivatives, hydroxypropylacrylate and its alkoxylated derivatives, vinyl acetate, and mixtures thereof. Among these non-ionic monomers, the alkyl groups are advantageously C1-C5, more advantageously C1-C3. They are preferably linear alkyls.,

[0062] The non-ionic monomeric units represent between 1 and 99 mol% of the monomeric units of the hybrid polymer (PH), preferably between 2 and 70 mol%.

[0063] The anionic hydrophilic monomers are preferably chosen from acrylic acid; methacrylic acid; dimethylacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; acrylamido undecanoic acid; 3-acrylamido 3-methylbutanoic acid; maleic anhydride; strong acid monomers having for example a sulfonic acid or phosphonic acid function such as vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, 2-methylidenepropane-1,3-disulfonic acid, 2-sulfoethylmethacrylate, sulfopropylmethacrylate, sulfopropylacrylate, allylphosphonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), 2-acrylamido-2-methylpropane disulfonic acid;water-soluble salts of these monomers such as their alkali metal salts (as distinct from the crystalline form of the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid), alkaline earth metal salts, or ammonium salts; and mixtures thereof.;

[0064] The anionic monomeric units represent between 1 and 99 mol% of the monomeric units of the hybrid polymer (PH), preferably between 2 and 70 mol%, more preferably between 3 and 50 mol%.

[0065] Salified means the substitution of a proton of at least one acid function of the type -R(=O)- OH (with R= P, S or C) of the anionic monomer by a metal or ammonium cation to form a salt of the type -R(=O)-OX (X being a metal or ammonium cation). In other words, the non-salified form corresponds to the acid form of the monomer, for example RC(=O)-OH in the case of the carboxylic acid function, while the salified form of the monomer corresponds to the form RC(=O)-O- X+, X+ corresponding to a metal cation, preferably alkaline or ammonium. The salification of the acid functions of the polymer can be partial or total. The salified form advantageously corresponds to the salts of alkali metals (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium (for example the ammonium ion or a tertiary ammonium). The preferred salts are sodium salts.

[0066] Salification can be done before or after polymerization.

[0067] The cationic hydrophilic monomers are preferably chosen from monomers derived from vinyl-type units (advantageously acrylamide, acrylic, allyl or maleic), these monomers having a phosphonium function, an ammonium salt or quaternary ammonium.

[0068] Mention may be made, in particular and without limitation, of diallyldialkyl ammonium salts such as diallyl dimethyl ammonium chloride (DADMAC); acidified or quaternized salts of dialkylaminoalkylacrylamides; acidified or quaternized salts of dialkylaminoalkylmethacrylamides, such as for example methacrylamidopropyl trimethyl ammonium chloride (MAPTAC), acrylamidopropyl trimethyl ammonium chloride (APTAC), acidified or quaternized salts of dialkyl aminoalkyl acrylate such as quaternized or salified dimethylaminoethyl acrylate (ADAME), acidified or quaternized salts of dialkyl aminoalkyl methacrylate such as quaternized or salified dimethylaminoethyl methacrylate (MADAME) and mixtures thereof. Advantageously, the alkyl groups are C1-C3.

[0069] The cationic monomeric units represent between 1 and 99 mol% of the monomeric units of the hybrid polymer (PH), preferably between 2 and 70 mol%, more preferably between 3 and 60 mol%.

[0070] Furthermore, the present invention also covers DADMAC, APTAC and MAPTAC type monomers whose counterion is a sulfate, fluoride, bromide or iodide instead of chloride.

[0071] Preferably, the cationic hydrophilic monomer is dimethylaminoethyl methacrylate in its quaternized form.

[0072] A person skilled in the art will know how to prepare the quaternized monomers, for example using a quaternizing agent of type RX, R being an alkyl group and X being a halogen or a sulfate.

[0073] The term "quaternizing agent" means a molecule capable of alkylating a tertiary amine. The quaternizing agent may be chosen from dialkyl sulfates comprising from 1 to 6 carbon atoms or alkyl halides comprising from 1 to 6 carbon atoms. Preferably, the quaternizing agent is chosen from methyl chloride, benzyl chloride, dimethyl sulfate or diethyl sulfate.

[0074] The zwitterionic monomers are preferably chosen from derivatives having a vinyl-type unit, in particular acrylamide, acrylic, allylic or maleic. Preferably, this monomer comprises an amine or quaternary ammonium function and an acid function of carboxylic (or carboxylate), sulfonic (or sulfonate) or phosphoric (or phosphate) type. Mention may be made in particular and in a non-limiting manner of dimethylaminoethyl acrylate derivatives, such as 2-((2-9-(acryloyloxy)ethyl)dimethylammonio)ethane-1-sulfonate, 3-((2-(acryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate, 4-((2-(acryloyloxy)ethyl)dimethylammonio)butane-1-sulfonate, [2-(acryloyloxy)ethyl]

[0075] (dimethylammonio) acetate, dimethylaminoethyl methacrylate derivatives such as 2- ((2-(methacryloyloxy)ethyl)dimethylammonio)ethane-l -sulfonate, 3 -((2-

[0076] (methacryloyloxy)ethyl)dimethylammonio)propane-l -sulfonate, 4-(2-(methacryloyloxy)ethyl)dimethylammonio)butane-l -sulfonate, [2(methacryloyloxy)ethyl](dimethylammonio) acetate, propyl acrylamide dimethylamino derivatives such as 2-((3-acrylamidopropyl)dimethylammonio)ethane-l -sulfonate, 3-((3-acrylamidopropyl)dimethylammonio)propane-l -sulfonate, 4-((3-acrylamidopropyl)dimethylammonio)butane-l -sulfonate, [3-(acryloyl)oxy)propyl](dimethylammonio) acetate, dimethylaminopropylmethylacrylamide, 2-((3-methacrylamidopropyl)dimethylammonio)ethane-1 -sulfonate, 3-(dimethylammonio)propane-l-sulfonate-4-((3- methacrylamidopropyl)dimethylammonio)butane-l -sulfonate, propyl [3-(methacryloyloxy)] (dimethylammonio) acetate; and mixtures thereof.

[0077] Other zwitterionic monomers are described by the Applicant in document WO21123599.

[0078] Preferably, the preferred hydrophilic monomers are acrylamide, acrylic acid, an oligomer of acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS) and / or its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyldiallyammonium chloride (DADMAC), quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME). According to one aspect of the invention, the monomers having an ethylenic function in addition to being chosen from the hydrophilic monomers as described above may also be chosen from hydrophobic monomers.

[0079] Hydrophobic monomers, whose partition coefficient Kow is greater than 1, can also be used in the preparation of the hybrid polymer (HP). They are advantageously chosen, in particular, from:

[0080] - (meth)acrylic acid esters with an alkyl, arylalkyl and / or ethoxylated and / or propoxylated chain; (meth)acrylamide derivatives with an alkyl, arylalkyl or dialkyl and / or ethoxylated and / or propoxylated chain; cationic allylic derivatives with an alkyl, arylalkyl or dialkyl and / or ethoxylated and / or propoxylated chain; anionic or cationic hydrophobic derivatives of (meth)acryloyl; and anionic or cationic monomeric derivatives of (meth)acrylamide bearing a hydrophobic chain. The alkyl groups of these hydrophobic monomers are preferably C6 to C24 alkyl groups. The most preferred monomers are bromoalkyl derivatives of methacrylamido dimethyl amino propyl with a C8-C16 alkyl chain and ethoxylated behenyl methacrylate.

[0081] - n-hexyl (meth)acrylate, n-octyl (meth)acrylate, octyl (meth)acrylamide, lauryl (meth)acrylate, lauryl meth)acrylamide, myristyl (meth)acrylate, myristyl (meth)acrylamide, pentadecyl (meth)acrylate, pentadecyl (meth)acrylamide, cetyl (meth)acrylate, cetyl (meth)acrylamide, oleyl (meth)acrylate, oleyl (meth)acrylamide, erucyl (meth)acrylate, erucyl (meth)acrylamide, and combinations thereof.

[0082] - LCST (Lower Critical Solution Temperature) and / or UCST (Upper Critical Solution Temperature) monomers or macromonomers. In other words, the hydrophobic character can come from the LCST and / or the properties of the monomers or macromonomers. Patent application WO2020 / 094960 A1 refers to such macromonomers having the LCST property.

[0083] Among these hydrophobic monomers:

[0084] - the alkyl groups are preferably C3-C20, more preferably C3-C8. The C6-C20 alkyls are preferably linear alkyls while the C3-C5 alkyls are preferably branched,

[0085] - the arylalkyl groups are preferably C7-C25, more preferably C7-C15, - the ethoxylated chains preferably comprise 6 to 100 -CH2-CH2-O- groups, more preferably 10 to 40,

[0086] - the propoxylated chains preferably comprise 1 to 50 -CH2-CH2-CH2-O- groups, more preferably 1 to 20.

[0087] According to this aspect of the invention, the preferred hydrophobic monomers are selected from N-isopropyl acrylamide; N,N-dimethylacrylamide; N,N-diethyl acrylamide; N-tert butyl acrylamide; N-vinyl caprolactam; and diacetone acrylamide.

[0088] Still according to this aspect of the invention, the concentration of hydrophobic monomers is preferably between 0.0001% and 10% mol, more preferably between 0.001% and 5% mol, even more preferably between 0.01% and 3% mol, even more preferably between 0.1 and 2% mol, even more preferably between 0.2 and 1.5% mol, even more preferably between 0.3 and 1.3% mol, the molar percentage being expressed relative to the total number of moles of monomers in the mixture (Ml).

[0089] The quantities of the different monomer(s) will be adjusted by those skilled in the art so as not to exceed 100 mol% during the preparation of the water-soluble polymers according to the invention.

[0090] Proteins and protein units

[0091] As a reminder, a protein unit designates the unit relative to a corresponding protein, when it is grafted into the hybrid polymer (PH).

[0092] In the present application, the expressions "protein unit" and protein are appropriately used. With regard to the hybrid polymer (HP) according to the first aspect of the invention, the expression "protein unit" is appropriate and used because at least one protein reacts during the polymerization and is part of the polymer chain. With regard to the polymer (HP) obtained by a process (by radical polymerization, or by inverse emulsion, or by gel route), the expression "protein" is appropriate and used because the protein is described in its form before polymerization.

[0093] Both expressions may be used in the same sentence, for example in a claim if said claim refers on the one hand to at least one claim of the type "hybrid polymer (PH comprising. . . " and on the other hand to at least one claim of the type "hybrid polymer (PH) obtained according to a process (by radical polymerization, or by inverse emulsion, or by gel route). And the proteins and preferences set out below are applicable for both expressions.

[0094] The term "protein" is used herein to include both native (or chemically unmodified) proteins and modified proteins. By "modified proteins" is meant a protein that has undergone one or more pre-treatments. These pre-treatments may be physical by shearing, chemical by acid, alkaline, and / or enzymatic hydrolysis by a protease.

[0095] The proteins are obtained by conventional methods known to those skilled in the art, for example by dissolving, grinding, screening and classification. The protein(s) may be added in solid or liquid form to the mixture (Ml). Advantageously, the proteins are added in powder form.

[0096] Advantageously, native proteins are preferred.

[0097] The protein(s) constituting the protein unit(s) of the hybrid polymer (HP) may be of animal origin; among the animal proteins that may be cited as examples: milk proteins such as P-lactoglobulin, casein, whey; serum proteins such as horse serum; placental proteins; fibrous dermal proteins such as collagen, elastin, silk proteins.

[0098] The protein(s) according to the invention may be of plant origin, such as corn, wheat, barley and oats, soybeans, peas, for example glutelin, prolamin, zein and gluten. Preferably, the plant proteins are chosen from soy proteins, wheat proteins, oat proteins, pea proteins. The proteins may be obtained from seeds, for example soybeans, cotton seeds, peanuts, sunflower, rapeseed, coconut, flax seeds, sesame, saflour, peas, beans and lentils.

[0099] There are also proteins of bacterial, fungal, algae and yeast origin.

[0100] Proteins can be soluble or insoluble in water. The choice of protein solubility plays a real role in the desired final application aspect.

[0101] To convert proteins into a soluble form, digestion by physical, chemical, or enzymatic treatment is often necessary, such as hydrolysis with acid or alkali, fermentation with yeasts, bacteria, or enzymes, extraction methods to remove minor constituents, coagulation from extracts by heating, addition of an electrolyte, adjustment of pH, or addition of precipitants.

[0102] Preferably, the selected protein(s) are water-soluble.

[0103] Preferably, the protein chosen will be casein, whey protein or wheat protein.

[0104] Alternatively, the proteins may be present as a mixture. This means a mixture containing several proteins originating from the same or different living kingdoms. For example, a mixture containing several proteins of animal origin, or a mixture containing at least one protein of animal origin and at least one protein of plant origin and / or one protein of bacterial origin.

[0105] Proteins used in graft copolymerization can be chemically modified in various ways before or after graft polymerization.

[0106] Hybrid polymer (PH) obtained by root polymerization

[0107] According to a second aspect, the invention relates to a hybrid polymer (PH) obtained by radical polymerization according to a process comprising the following successive steps:

[0108] (A) Prepare a mixture (Ml) comprising at least one monomer comprising at least one unsaturated ethylenic function; and between 0.1% and 50% by weight of at least one protein, optionally at least one solvent;

[0109] (B) Initiate polymerization in the mixture (Ml) to obtain a hybrid polymer (PH).

[0110] The mixture (Ml) preferably comprises between 5% and 90% by weight of at least one monomer comprising at least one unsaturated ethylenic function, more preferably between 10 and 80%, more preferably between 15 and 80%, more preferably between 20 and 80%, more preferably between 25 and 80%, more preferably between 30 and 80%, more preferably between 35 and 75%, more preferably between 40 and 75%, more preferably between 45 and 75%, more preferably between 50 and 70%, more preferably between 55 and 65%. The mixture (Ml) preferably comprises between 0.1% and 50% by weight of at least one protein, more preferably between 1 and 40%, more preferably between 3 and 35%, more preferably between 5 and 30%, more preferably between 10 and 25%.

[0111] The mixture (Ml) preferably comprises between 1% and 90% by weight of at least one solvent, more preferably between 5 and 80%, more preferably between 10 and 70%, more preferably between 15 and 60%, more preferably between 20 and 50%.

[0112] The invention particularly relates to a hybrid polymer (PH) obtained by a radical polymerization process comprising the following successive steps:

[0113] (A) Prepare a mixture (Ml) comprising between 5% and 90% by weight of at least one monomer comprising at least one unsaturated ethylenic function, and between 0.1% and 50% by weight of at least one protein, and at least 1% by weight of a solvent,

[0114] (B) Initiate polymerization in the mixture (Ml) to obtain at least one hybrid polymer (PH).

[0115] Suitable solvents can be polar and non-polar.

[0116] Non-polar solvents include cyclohexane, heptane, benzene, toluene, xylene, ethylbenzene and linear, branched or cyclic alkanes having 2 to 20 carbon atoms, dichloromethane, ethyl acetate.

[0117] Preferably, the hybrid polymer is polymerized by radical polymerization in a polar solvent. The polar solvent then comprises water, an alcohol and / or a ketone. It is possible to use a polar solvent or a mixture of polar solvents.

[0118] The alcohol or ketone is preferably chosen from methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2 propanol, 1-butanol, 2-butanol, dimethyl ketone, diethyl ketone, pentan-2-one, butanone, tetrahydropyran, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 1,4-dioxane. The mixture of polar solvents is preferably a mixture of protic solvents (proton donors).

[0119] The solvent is preferably water.

[0120] The protein(s) are added to the polymerization feedstock, in the mixture (Ml) in step (A) of the process described in this second aspect of the present application.

[0121] Preferably, a single protein is added to the polymerization feedstock to form the hybrid polymer (HP). The polymerization is a radical polymerization. By radical polymerization, we include polymerization using photochemical (UV or radiation), azo, thermal, or redox salt initiators, as well as controlled radical polymerization (CRP) or template polymerization techniques.

[0122] As controlled radical polymerization techniques, we can cite, without limitation, techniques such as iodine transfer polymerization (ITP), nitroxide-mediated polymerization (NMP), atom transfer (ATRP), reversible addition-fragmentation chain transfer (RAFT), which includes the MADIX technology (MAcromolecular Design by Interchange of Xanthates), various variations of polymerizations with organometallic compounds (OMRP), and heteroatomic-mediated radical polymerization (OHRP).

[0123] Advantageously used polymerization initiators may be selected from compounds that dissociate into radicals under polymerization conditions, for example: organic peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds and redox catalysts. The use of water-soluble initiators is preferred. In some cases, it is advantageous to use mixtures of various polymerization initiators, for example mixtures of redox salts and azo compounds.

[0124] Advantageously, the quantity of initiator is between 5 and 1,000 ppm, preferably between 10 and 500 ppm, more preferably between 20 and 100 ppm, relative to the total weight of the polymerization charge.

[0125] Said initiator can be added all at once to the mixture (Ml), by pouring, or discontinuously to the medium.

[0126] Preferably, the polymerization is carried out in a temperature range from 20° to 160° C, preferably from 30° to 100° C. It is preferably carried out at atmospheric pressure.

[0127] According to the invention, the hybrid polymer (HP) can be linear or structured. A structured polymer refers to a non-linear polymer which has side chains so as to obtain, when this polymer is dissolved in water, a strong state of entanglement leading to very high low gradient viscosities. This is also referred to as a crosslinked polymer.

[0128] The polymer according to the invention can be structured:

[0129] - by at least one structural agent, which may be chosen from the group comprising monomers with polyethylene unsaturation (having at least two unsaturated functions), such as for example vinyl functions, in particular allylic, acrylic and epoxy and we can cite for example methylene bis acrylamide (MBA), triallyamine, or tetraallylammonium chloride or 1,2 dihydroxyethylene bis- (N-acrylamide), and / or

[0130] - by macroinitiators such as polyperoxides, polyazos and polytransfer agents such as polymercaptant (co)polymers, and polyols, and / or

[0131] - by functionalized polysaccharides.

[0132] The amount of branching / crosslinking agent in the monomer mixture is advantageously less than 4% by weight relative to the monomer content (weight), more advantageously less than 1%, and even more advantageously less than 0.5%. According to a particular embodiment, it may be at least equal to 0.00001% by weight relative to the monomer content.

[0133] The polymerization is preferably carried out in an inert gas atmosphere in the absence of atmospheric oxygen, for example using nitrogen, argon, or carbon dioxide as the inert gas or using enzymatic deoxygenation.

[0134] Advantageously, the monomers comprising at least one unsaturated ethylenic function to be polymerized and the protein are introduced into the reaction vessel at the beginning with at least one polymerization initiator and polymerized by heating to the optimum polymerization temperature. It may be advantageous to use two or more proteins. The terms "polymerization initiator" and "polymerization initiator" correspond to the same product having the same function, that of starting the polymerization reaction.

[0135] The order in which the reactants are dosed into the polymerization reactor can be freely changed. If several monomers are used in the graft copolymerization, the individual monomers can be dosed into the polymerization zone successively, or as a mixture, or simultaneously from separate dosing means. For example, it is possible to heat a solution or dispersion of the protein in the reactor to the required polymerization temperature and add the monomers and initiators continuously or in batches.

[0136] Likewise, the pH of the reaction medium can influence the hybrid polymer (PH). Acidic or basic monomers can be used in the form of the corresponding salts. For example, acrylic acid is used in the form of a free acid or in the form of an alkali salt. The polymerization can be carried out in a pH range from 1 to 14, preferably from 6 to 12. By changing the pH, it is possible, for example, to precipitate the graft copolymers from solutions. This possibility can be used during the processing, purification and isolation of the graft copolymers.

[0137] According to the invention, the hybrid polymer (HP) may have a linear, branched, ramified, star-shaped or comb-shaped structure. This structure may be obtained, according to the general knowledge of a person skilled in the art, for example by selection of the initiator, the transfer agent, the polymerization technique such as reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP) or atom transfer radical polymerization (ATRP), the incorporation of structural monomers, or the concentration.

[0138] The hybrid polymer (PH) obtained by radical polymerization may be in the forms described in the section "Hybrid Polymer (PH)" set out above. The elements concerning the weight average molecular weight and the Brookfield viscosity of the polymer previously described are applicable to the hybrid polymer (PH) obtained according to this aspect of the invention.

[0139] Hybrid polymer (HP) obtained by radical inverse emulsion polymerization

[0140] According to a third aspect, the invention relates to a hybrid polymer (PH) obtained by radical polymerization, said radical polymerization being an inverse emulsion polymerization. The polymer (PH) is then in the form of an inverse emulsion or a powder obtained by drying the inverse emulsion.

[0141] The expression "inverse emulsion" refers in the present application to both inverse emulsions and inverse microemulsions. Inverse emulsion polymerization, i.e. a water-in-oil emulsion, consists of emulsifying an aqueous phase comprising the monomer(s) and the protein, in an organic phase. This emulsification is carried out using a water-in-oil reversing agent.

[0142] In the present invention, the term "inverting agent" refers to an agent capable of emulsifying oil in water. More specifically, an inverting agent is considered to be a surfactant having an HLB greater than or equal to 10, and a "surfactant" is considered to be a surfactant having an HLB strictly less than 10. A surfactant having an HLB between 8 and 10 is considered to be a wetting agent. Those skilled in the art may refer to the document "Handbook of Applied Surface and Colloid Chemistry" by K. Holmberg, Chapter 11, if necessary.

[0143] The hydrophilic-lipophilic balance (HLB) of a chemical compound is a measure of its hydrophilic and / or lipophilic properties, determined by calculating the values ​​for different regions of the molecule, as described by Griffin in 1949 (Griffin WC, Classification of Surface Active Agents by HLB, Journal of the Society of Cosmetic Chemists, 1949, 1, pages 311-326).

[0144] In the present invention, we have adopted Griffin's method based on calculating a value based on the chemical groups of the molecule. Griffin assigned a dimensionless number between 0 and 20 to give information about the solubility in water and oil. Substances with an HLB value of 10 are distributed between the two phases so that the hydrophilic group (molecular mass Mh) projects completely into the water while the hydrophobic group (molecular mass Mp) is adsorbed in the non-aqueous phase.

[0145] The HLB value of a substance having a total molecular mass M, a hydrophilic part of molecular mass Mh and a hydrophobic part of molecular mass Mp is given by:

[0146] HLB = 20 (Mh / Mp)

[0147] According to this third aspect, the invention relates to a hybrid polymer (PH) obtained by inverse radical emulsion polymerization according to a process comprising the following successive steps: (A1) Preparation of an aqueous phase comprising between 1% to 50% by weight of at least one protein, between 4% to 40% by weight of at least one monomer comprising at least one unsaturated ethylenic function and between 20 to 95% by weight of water;

[0148] (A2) Preparation of a lipophilic phase comprising between 70% to 99% by weight of an inert hydrophobic liquid and between 1 to 20% by weight of at least one surfactant;

[0149] (A3) Mixing said aqueous phase with said lipophilic phase in order to form an inverse emulsion;

[0150] (B) Polymerization of said inverse emulsion to obtain a hybrid polymer inverse emulsion (PH).

[0151] Steps (A1), (A2) and (A3) correspond to sub-steps of step (A) in the radical polymerization process for obtaining the hybrid polymer (PH) according to the second aspect of the invention. The inverse emulsion obtained in step (A3) corresponds to the mixture (M1) of step (A) in the radical polymerization process for obtaining the hybrid polymer (PH) according to the second aspect of the invention.

[0152] The weight ratio of the aqueous phase to the lipophilic phase is preferably from 20 / 80 to 80 / 20, more preferably from 70 / 30 to 30 / 70.

[0153] An inverting agent is preferentially added to the inverse emulsion after the polymerization step.

[0154] In step (A1), the aqueous phase is prepared by mixing at least one protein, at least one ethylenically unsaturated hydrophilic monomer, and water. The mixture may include other compounds, such as a crosslinking agent.

[0155] The aqueous phase of step (A1) comprises from 1 to 50% by weight of at least one protein, preferably between 1 and 40%, more preferably between 1 and 40% by weight. The protein(s) are chosen from those mentioned above, with the same preferences.

[0156] The aqueous phase of step (A1) comprises between 4% and 40% by weight of at least one hydrophilic monomer with ethylenic unsaturation, preferably between 10 and 35%, more preferably between 20 and 35% by weight. The monomer(s) comprising at least one unsaturated ethylenic function are chosen from the monomers comprising at least one unsaturated ethylenic function cited above with the same preferences. The aqueous phase of step (A1) comprises between 20 and 95% by weight of water, preferably between 25 and 80%, more preferably between 35 and 75% by weight.

[0157] Said aqueous phase is preferably prepared at a solid matter concentration of 20% to 45% by weight. Those skilled in the art will be able to adjust the monomer and protein ratios according to the desired properties.

[0158] In step (A2), the lipophilic phase is prepared by mixing at least one inert hydrophobic liquid and at least one surfactant.

[0159] The lipophilic phase of step (A2) comprises between 70% and 99% by weight of an inert hydrophobic liquid, preferably between 75 and 96%, more preferably between 80 and 93% by weight.

[0160] The lipophilic phase also comprises an inert hydrophobic liquid or a mixture of inert hydrophobic liquids. The inert hydrophobic liquid advantageously refers to an oil or a solvent immiscible with water. The oil used to prepare the water-in-oil emulsion of the invention may be a mineral oil, a vegetable oil, a synthetic oil or a mixture of several of these oils. Examples of mineral oil are mineral oils containing saturated hydrocarbons of the aliphatic, naphthenic, paraffinic, isoparaffinic, cycloparaffinic or naphthyl type. Examples of synthetic oil are hydrogenated polydecene or hydrogenated polyisobutene; an ester such as octyl stearate or butyl oleate. ExxonMobil's Exxsol® products are suitable oils.

[0161] More precisely, the lipophilic phase consists of a heavy oil, a light oil and a surfactant. Those skilled in the art will know how to adjust the ratios between these three compounds, allowing them to obtain a stable system capable of withstanding distillation under reduced pressure.

[0162] The lipophilic phase of step (A2) comprises between 1 and 20% by weight of at least one surfactant, preferably between 1 and 15%, more preferably between 3 and 12% by weight.

[0163] The lipophilic phase includes at least one "surfactant", otherwise known as an emulsifying agent. It corresponds to an agent capable of emulsifying water in oil, more precisely the aqueous phase in the lipophilic phase.

[0164] Examples of such a surfactant include surfactant polymers such as polyesters having a molecular weight of between 1000 and 3000, condensation products between a poly(isobutenyl)succinic acid or its anhydride and a polyethylene glycol, block copolymers having a molecular weight of between 2500 and 3500, for example those sold under the names Hypermer®, sorbitan extracts, for example sorbitan monooleate, sorbitan isostearate or sorbitan sesquioleate, polyethoxylated sorbitan esters, or diethoxylated oleocetyl alcohol or tetraethoxylated lauryl acrylate, condensation products of higher fatty alcohols with ethylene oxide, such as the reaction product of oleyl alcohol with 2 ethylene oxide units; condensation products of alkylphenols and ethylene oxide, such as the reaction product of nonylphenol with 4 ethylene oxide units.Products such as Witcamide® 511, betaine products and ethoxylated amines are also good candidates as emulsifying agents.

[0165] In a preferred embodiment, the surfactant is sorbitan monoleate, polyethoxylated sorbitan esters or tall oil fatty acid diethanolamine.

[0166] The surfactant can also be of a bio-sourced nature chosen from sucroesters, alkylpolyglucosides (APG), diglycerol esters or even phospholipids.

[0167] The inverse emulsion may contain at least two surfactants, preferably at least three agents, even more preferably at least four surfactants in the lipophilic phase.

[0168] The inverse emulsion obtained according to the process preferably contains between 0.8 and 20% by weight of emulsifying agent, more advantageously 1 to 10% by weight.

[0169] In step (A3), the aqueous phase obtained in step (A1) and the lipophilic phase obtained in step (A2) are mixed so as to obtain an inverse emulsion. Generally, a step of emulsification of the two phases is carried out with means known to those skilled in the art.

[0170] For example, in a reactor equipped with a temperature probe, an inert gas supply, preferably nitrogen, and mechanical stirring, the lipophilic phase and then the aqueous phase are added before proceeding with the emulsification and thus obtaining an inverse emulsion, preferably stable. The medium obtained is then degassed with nitrogen before proceeding with the initiation of the polymerization, the subject of step (B), and thus obtaining the inverse emulsion of hybrid polymer (PH). The polymerization is a radical polymerization.

[0171] In a particular mode, once the maximum temperature is reached, the system is placed in aging mode.

[0172] After polymerization, an inverting agent is added to the inverse emulsion.

[0173] The reversing agent is a surfactant having an HLB value greater than or equal to 10. As an example of such a reversing agent, reference may be made to ethoxylated sorbitan esters such as ethoxylated sorbitan oleate with 20 equivalents of ethylene oxide (EO 20), polyethoxylated sorbitan laurate with 20 mol of ethylene oxide, polyethoxylated castor oil with 40 mol of ethylene oxide, decaethoxylated oleodecyl alcohol, heptaethoxylated lauryl alcohol or polyethoxylated sorbitan monostearate with 20 mol of ethylene oxide.The inversion agent may also be a polyoxyethylene alkylphenol; a polyoxyethylene cetyl ether (10 moles); a polyoxyethylene alkylaryl ether; quaternary ammonium derivatives; potassium oleate; N-cetyl-N-ethylmorpholinium ethosulfate; sodium lauryl sulfate; condensation products of higher fatty alcohols with ethylene oxide, such as the reaction product of oleyl alcohol with 10 ethylene oxide units; condensation products of alkylphenols and ethylene oxide, such as the reaction products of isooctylphenol with 12 ethylene oxide units; condensation products of higher fatty acid amines with five or more ethylene oxide units; ethylene oxide of tristerylphenol; ethylene oxide condensation products of higher partial fatty esters of polyhydric alcohols and their internal anhydrides (e.g. g., mannitol anhydride and sorbitol anhydride); amine oxide; an alkyl polyglucoside; a glucamide; a phosphate ester or salt of alkylbenzene sulfonic acid; a water-soluble polymeric surfactant.

[0174] In a preferred embodiment, the reversing agent is an ethoxylated nonylphenol, preferably having a 4 to 10 ethoxylation, an ethoxy / propoxy alcohol, preferably having a C12 to C25 ethoxy / propoxylation, or an ethoxylated tridecyl alcohol, or an ethoxy / propoxy fatty alcohol.

[0175] The inverse emulsion may contain at least two inverting agents, preferably at least three inverting agents, even more preferably at least four inverting agents.

[0176] The polymer (PH) obtained by inverse emulsion polymerization is in the form of an inverse emulsion or a powder obtained by drying the inverse emulsion.

[0177] It is also possible for the resulting inverse emulsion to be diluted or concentrated. Dilution is usually achieved by adding water and / or oil to the inverse emulsion. It is possible to concentrate the resulting emulsion, for example by distillation. This results in a partially dehydrated inverse emulsion.

[0178] Generally, distillation under reduced pressure allows the product to be concentrated by removing all or part of the water and ingredients from the lipophilic phase, such as light oil.

[0179] An inverting agent, or a mixture of inverting agents, can be added post-distillation, i.e. at the very end of the process.

[0180] According to this third aspect of the invention, the polymer (PH) is in the form of an inverse emulsion. When the polymer (PH) found in the emulsified water droplets in the lipophilic phase is structured or crosslinked, then the polymer (PH) is in the form of microgels dispersed in the lipophilic phase. This includes hybrid polymers dispersed in the lipophilic main phase. When the inverse emulsion is implemented in an aqueous phase, the hybrid polymers are then dispersed in the main aqueous phase.

[0181] The inverse polymer emulsion (PH) obtained by inverse emulsion polymerization according to the invention preferably comprises between 10% and 70% by weight of hybrid polymer (PH), relative to the total weight of the inverse emulsion, preferably between 30% by weight and 60% by weight.

[0182] Advantageously, the inverse emulsion comprises at least one hybrid polymer (HP), water (generally between 10 and 50% by weight), an inert hydrophobic liquid (generally between 5 and 50% by weight), at least one surfactant (generally between 1 and 10% by weight), and at least one inverting agent (generally between 1 and 10% by weight). The polymer inverse emulsion (HP) obtained by inverse emulsion polymerization according to the invention can be dried to obtain a powder. A particularly advantageous drying method is spray drying.

[0183] In this third aspect according to the invention, the same elements are taken up, including their preferences, as those cited previously, namely: the nature of the polymerization initiators, the quantity of said initiators, the nature of the structuring and / or crosslinking agents, the quantity of said structuring and / or crosslinking agents, the molecular weight of the polymer (PH) obtained, the radical polymerization, the structure of the hybrid polymer (PH) (linear, structured, etc.).

[0184] Hybrid polymer (PH} obtained by radical polymerization by gel route

[0185] According to a fourth aspect of the present invention, the hybrid polymer (PH) is obtained by a radical gel polymerization process comprising the following successive steps:

[0186] (A) Preparation of an aqueous solution comprising between 10 and 40% by weight of at least one monomer comprising at least one unsaturated ethylenic function, and from 1 to 30% by weight of at least one protein, water, and optionally at least one pH regulator.

[0187] (B) Initiation of radical polymerization in the aqueous solution to obtain the hybrid polymer (PH) in the form of a gel;

[0188] (C) Grinding and drying of the obtained gel to obtain the hybrid polymer (PH) in powder form.

[0189] The protein(s) are chosen from those mentioned above, with the same preferences. The monomer(s) comprising at least one unsaturated ethylenic function are chosen from the monomers comprising at least one unsaturated ethylenic function mentioned above with the same preferences.

[0190] Before step (B), the aqueous solution is generally degassed, for example with nitrogen to minimize the presence of dioxygen in the aqueous solution. During step (B) one or more polymerization initiators are added. The same polymerization initiators as those previously mentioned can be used, in the same quantities.

[0191] Steps (A) and (B) are preferably carried out in the same reactor, called the polymerization reactor.

[0192] In a preferred embodiment, the gel obtained in step (B) is aged at a final polymerization temperature of between 80°C and 150°C for at least 60 minutes without heating.

[0193] According to this aspect, the gel obtained in step (B), and before being ground and dried, comprises between 10% and 70% by weight of hybrid polymer (HP), preferably between 20% and 60% by weight, even more preferably between 30% and 55% by weight. The gel thus obtained is generally transported into a granulator to be cut. Then the gel thus cut is dried, ground and sieved to obtain the hybrid polymer (HP) in powder form.

[0194] The pH regulator is advantageously chosen from the following elements: hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, formic acid, acetic acid, adipic acid, propionic acid, oxalic acid, benzoic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate. A person skilled in the art will be able to define the pH to be reached at the end of step b) as well as the quantity and choice of pH regulators depending on the chemistry of the polymer to be synthesized, in particular depending on the nature of the monomers (cationic, anionic, etc.).

[0195] As soon as the polymerization begins, the aqueous solution is heated or heats up (exothermic reaction) depending on the starting conditions chosen. Advantageously, due to the released heat of polymerization, the temperature of the reaction mixture generally rises from 80 to 150°C, preferably from 80°C to 100°C. The polymerization is advantageously carried out at atmospheric pressure.

[0196] The reactor used is in most cases jacketed so that the reaction mixture can be cooled or heated as required. Once the polymerization reaction is complete, the resulting gel can be quickly cooled, for example by cooling the reactor wall.

[0197] At the end of the polymerization reaction, after allowing the gel to age for at least 60 minutes, the product resulting from the polymerization is a viscous gel which is “self-supporting”.

[0198] Granulation involves cutting the gel into small pieces. Advantageously, the average size of these gel pieces is less than 1 cm, more advantageously it is between 4 and 8 mm. Those skilled in the art will know how to choose the appropriate method for optimal granulation. Granulation is also described in the section relating to the presentation of the state of the art.

[0199] The drying method and its conditions (time + temperature) are routine choices for those skilled in the art. Industrially, drying is advantageously carried out by a fluidized bed or rotor dryer, advantageously using air heated to a temperature between 70°C and 200°C, the air temperature depending on the nature of the product and the drying time applied.

[0200] A Tissue drying process physically transforms the composition into powder form and then grinds and sifts.

[0201] The grinding step consists of breaking the large polymer particles into smaller particles. This can be done by shearing or by mechanically crushing the particle between two hard surfaces. Different types of equipment known to those skilled in the art can be used for this purpose. Examples include rotor mills, where the rotating part crushes the particle against a compression blade, or roller mills, where the particle is crushed between two rotating rollers. The screening then aims to eliminate, depending on the specifications, medium-sized particles that are too small or too large.

[0202] The hybrid polymer (HP) obtained by gel polymerization can be a hydroswelling polymer, a superabsorbent. This is the case when the hybrid polymer (HP) is structured or crosslinked with one or more structuring and / or crosslinking agents.

[0203] In this fourth aspect according to the invention, the same elements are taken up, including their preferences, as those cited previously, namely: the nature of the polymerization initiators, the quantity of said initiators, the nature of the structuring and / or crosslinking agents, the quantity of said structuring and / or crosslinking agents, the molecular weight of the polymer (PH) obtained, the radical polymerization, the structure of the hybrid polymer (PH) (linear, structured, etc.).

[0204] Use of hybrid polymer (HP) in various applications

[0205] In a fifth aspect, the invention relates to the use of the hybrid polymer (PH), in particular as a viscosifying agent. This aspect of the invention also relates to the use of the hybrid polymer (PH) according to the invention in various compositions, the use of the hybrid polymer (PH) as a viscosifying agent, the compositions comprising at least one hybrid polymer (PH) according to the invention, as well as the methods using said compositions.

[0206] -Tl- Said use relates to the hybrid polymer (PH) according to the first aspect of the invention, or obtained according to the second aspect of the invention (by radical polymerization), or obtained according to the third aspect of the invention (by inverse emulsion polymerization), or obtained according to the fourth aspect of the invention (by gel polymerization).

[0207] The invention therefore relates to the use of said hybrid polymer (HP) as a viscosifying agent in the recovery of hydrocarbons (oil and / or gas); in the drilling and cementing of wells; in the treatment of water in open, closed or semi-closed circuits; in the treatment of fermentation musts in the treatment of sludge; in paper manufacturing; in construction; in wood processing; in the treatment of hydraulic compositions (concrete, cement, mortar and aggregates); in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in the manufacture of textile printing paste; in the manufacture of battery components; in geothermal energy; in the manufacture of hygienic diapers; or in agriculture.

[0208] Advantageously, the invention relates to the use of the hybrid polymer (PH) according to the invention in the manufacture of cosmetic compositions as a thickening (agent), conditioning (agent), stabilizing (agent), emulsifying (agent), fixing (agent) or film-forming (agent).

[0209] The invention also relates to the use of the hybrid polymer (PH) as a viscosifying agent for a pigment composition used in textile printing, said agent comprising at least one hybrid polymer according to the invention. The invention also relates to the use of the polymer (PH) according to the invention as a superabsorbent.

[0210] The hybrid polymer (HP) according to the invention can be used as a flocculating agent, coagulating agent, binding agent, fixing agent, viscosity reducing agent, thickening agent, absorbent agent, friction reducing agent, dewatering agent, drainage agent, charge retention agent, dehydrating agent, conditioning agent, stabilizing agent, fixing agent, film-forming agent, sizing agent, superplasticizing agent, clay inhibitor or dispersant. The invention also relates to a viscosifying agent, comprising at least one hybrid polymer (HP) according to the invention in a field chosen from hydrocarbon recovery; in well drilling and cementing; in the stimulation of hydrocarbon wells; in papermaking; in construction; in mining industry; in the formulation of cosmetic products; in the formulation of detergents; in textile manufacturing.Due to the various possible uses of the present composition, the latter is used in various compositions. The invention also relates to an aqueous composition comprising at least one hybrid polymer (PH) according to the invention, preferably for thickening said composition.

[0211] The hybrid polymer (PH) according to the invention is capable of thickening aqueous compositions, coagulating, binding, fixing, reducing viscosity, having absorbent power, reducing friction, draining, draining, retaining, dehydrating, conditioning, stabilizing, fixing, filming, gluing depending on the intended field of application.

[0212] The implementation of the composition according to the invention in compositions may be carried out according to the knowledge and practices of the formulators depending on the field of applications targeted.

[0213] Advantageously, the composition according to the invention comprises between 0.001% and 5% by weight of the composition, relative to the total weight of the formulation.

[0214] More specifically, the use of the composition may be made in a field chosen from hydrocarbon recovery; in well drilling and cementing; in hydrocarbon well stimulation; in water treatment; in fermentation must treatment; in sludge treatment; in paper manufacturing; in construction; in wood treatment; in hydraulic composition treatment; in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in textile manufacturing; in the manufacture of battery components; in geothermal energy; in the manufacture of hygienic diapers; or in agriculture.

[0215] The invention also relates to the use of such compositions in a field chosen from hydrocarbon recovery; in well drilling and cementing; in the stimulation of hydrocarbon wells; in water treatment; in the treatment of fermentation musts; in the treatment of sludge; in papermaking; in construction; in wood treatment; in the treatment of hydraulic composition; in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in textile manufacturing; in the manufacture of battery components; in geothermal energy; in the manufacture of hygienic diapers; or in agriculture. The invention also relates to a method for enhanced oil or gas recovery by sweeping an underground formation comprising the use of at least one hybrid polymer (HP) according to the invention.

[0216] EXAMPLES

[0217] The following examples best illustrate the advantages of the invention in a clear and non-limiting manner.

[0218] I- Preparation of polymers in inverse emulsion

[0219] Example 1 (invention): Synthesis of hybrid polymer PHi, in inverse emulsion

[0220] An aqueous phase is prepared with 24.16% by weight of sodium acrylate, 2.68% by weight of milk whey protein powder, 73.11% by weight of deionized water and 0.04% by weight of Versenex 80, and 0.006% by weight of an azo initiator. The pH is adjusted to 7.0 ± 0.1.

[0221] A lipophilic phase is prepared from 40.52% by weight of heavy oil (MYRISTATE octyldodecyl), 44.78% by weight of light oil (Isopar J) and the following surfactants: 4.90% by weight of Witcamide®511 (diethanolamine of tall oil fatty acids), 1.96% by weight of sorbitan monooleate VG and 7.84% by weight of HYPERMER 6212

[0222] The aqueous phase is added to the lipophilic phase while mixing to form an emulsion. The resulting dispersion is bubbled with nitrogen for 30 minutes while the temperature is stabilized at 25 °C, at which time a 10 mL solution containing 0.002% by weight of the tert-butyl hydroperoxide emulsion and a 10 mL solution containing 0.04% by weight of the sodium metabisulfite (MBS) emulsion are introduced into the dispersion at a rate of 0.1 milliliters per minute. The polymerization temperature is controlled between 38 °C and 42 °C for approximately 90 minutes. Residual monomers are trapped by introducing a 0.03% by weight sodium metabisulfite (MBS) solution at a rate of 1.0 milliliters per minute.

[0223] The water-in-oil emulsion is then filtered through a 300 pm filter before being distilled under reduced pressure for 1 hour 30 minutes at 95°C between 250 mbar and 80 mbar.

[0224] A water-in-oil hybrid polymer emulsion is then obtained. 4.5% by weight of an inverting agent (ethoxylated fatty alcohol: TO 06) is added to the water-in-oil polymer emulsion.

[0225] Example 2 (invention): Synthesis of hybrid polymer PH2, in inverse emulsion.

[0226] An aqueous phase is prepared with 4.21% by weight of acrylamide, 45.79% by weight of an acrylamido 2-(acryloyloxy)ethyl trimethylammonium chloride solution, 5.55% by weight of a milk whey protein powder, 44.42% by weight of deionized water, and 0.03% by weight of an azo initiator.

[0227] The pH is adjusted to 6.5 ± 0.1.

[0228] A lipophilic phase is prepared from 58.95% by weight of heavy oil (octyldodecyl myristate), 28.10% by weight of light oil (Isopar J) and the following surfactants: 4.02% by weight of Witcamide®511 (diethanolamine of tall oil fatty acids), 1.79% by weight of sorbitan monooleate VG and 7.14% by weight of HYPERMER 6212

[0229] The aqueous phase is added to the lipophilic phase while mixing to form an emulsion.

[0230] The resulting dispersion is bubbled with nitrogen for 30 minutes while the temperature is stabilized at 25 0 C, at which point 0.004% by weight of peroxide is added to the emulsion and 10 mL of a 0.04% by weight solution of the sodium bisulfite emulsion is introduced into the dispersion at a rate of 10 milliliters per hour.

[0231] The polymerization temperature is controlled between 38 0 C and 42 0 C for about 90 minutes.

[0232] The water-in-oil emulsion is then filtered through a 300 pm filter before being distilled under reduced pressure for 1 hour 30 minutes at 90°C between 250 mbar and 80 mbar.

[0233] We then obtain a water-in-oil hybrid polymer emulsion.

[0234] 4.5% by weight of a high HUB surfactant (TO 06) is added to the water-in-oil polymer emulsion.

[0235] (Counterexample): Synthesis of polymer P3, in inverse emulsion. The same protocol as example 2 was applied by removing the protein from the formulation.

[0236] Example 3: Viscosity measurement

[0237] Brookfield viscosity was measured on a 1.5% by weight hybrid polymer solution in water using a Brookfield RVT module viscometer with a rotation speed of 20 rpm at 25°C. Table 1 summarizes the results.

[0238] Table 1 - Viscosity measurement results

[0239] The PH2 hybrid polymer develops a viscosity in water at 1.5% much higher than that of the P3 polymer.

[0240] In this case, the Applicant observes that the integration of the serum protein into this type of emulsion therefore has a real interest in improving the viscosifying performance of the hybrid polymer according to the invention.

[0241] II- Synthesis of hybrid polymer according to the invention in gel process

[0242] Example 4 (invention): Synthesis of the hybrid polymer PH4, in gel process

[0243] In an aqueous solution containing 550 g of deionized water, 310 g of acrylamido 2- (acryloyloxy)ethyl trimethylamm onium chloride (ADC) and 95 g of acrylamide, 45 g of serum protein are gradually added.

[0244] This aqueous solution is placed in a 2 L beaker then cooled to 0°C before being placed in a Dewar.

[0245] This aqueous solution is then homogenized using a hand mixer at a speed of 500 rpm for 15 seconds before being degassed under nitrogen bubbling for 15 minutes. The following are then added to the aqueous solution: 0.5 g of azo initiator (V50) and 0.003 g of transfer agent (sodium hypophosphite) and the reaction is initiated by successive additions of 2.6 x 10' 4 g of / c / V-butyl hydroperoxide then 1g sodium bisulfite. The reaction time is 60 minutes, for a final temperature of 94°C. The resulting PH4 hybrid polymer is in the form of a gel. Therefore, it is possible to granulate it, then dry it in an air flow at 70°C overnight. The dry grains of PH4 polymer are then ground.

[0246] The obtained PH4 polymer is 100% water-soluble and has a UL viscosity of 5 g / L = 2.96 cps, LVT-60 TPM modulus at 25°C?

[0247] Example 5 (invention): PH4 application tests

[0248] • Flocculation test on sludge from the Andrézieux treatment plant with a dry matter content of 12.2 g / L:

[0249] In order to compare the effectiveness of the PH4 polymer, flocculation tests were carried out with a reference polymer.

[0250] Polymers are tested at a concentration of 3 g / L in deionized water.

[0251] Flocculation tests are carried out in a beaker to assess the quality of flocculation as well as the quantity of water drained at 10 seconds. Table 2 summarizes the results.

[0252] Table 2 - Application test results

[0253] The Applicant observes that the PH4 polymer achieves application performances similar to the reference polymer at a similar dosage.

[0254] • Drainage test:

[0255] In a 400mL beaker, containing 200 mL of sludge, 5mL of a 3 g / L solution of the polymers to be tested (PH4 polymer, reference 1 polymer, reference 2 polymer) are added. The solutions are then mixed by transfer until flocculation. A filter cloth is placed in a 90 mm diameter Buchner, the whole is wetted.

[0256] The Buchner is placed under a graduated cylinder.

[0257] The flocculated sludge solution is poured into the Buchner, and the stopwatch is started.

[0258] The volumes elapsed after 5 and 10 seconds are recorded.

[0259] For a sampled volume of 5 mL of a 3 g / L polymer solution. Table 3 summarizes the results.

[0260] Table 3 - Drainage results

[0261] Drainage corresponds to the volume of water recovered at a given time, the higher the value, the better the performance of the polymer.

[0262] The applicant observes that the PH4 polymer is a better flocculant than the reference polymers.

[0263] Example 6 (invention): Synthesis of the hybrid polymer PH5, in gel process

[0264] In an aqueous solution containing 670 g of deionized water, 125 g of potassium acrylate and 200 g of acrylamide, 140 g of serum protein and 10 g of crosslinking agent (methylene bis acrylamide) are gradually added.

[0265] This aqueous solution is placed in a 2 L beaker then cooled to 0°C before being placed in a Dewar.

[0266] This aqueous solution is then homogenized using a hand mixer at a speed of 500 rpm for 15 seconds before being degassed under nitrogen bubbling for 10 minutes.

[0267] Then added to the aqueous solution: 0.21 g of sodium persulfate, 0.15 g of sodium metabisulfite (MBS) and 0.01 g of Mohr's salt. The reaction time is 60 minutes, for a final temperature of 94°C. The PHs hybrid polymer obtained is in the form of a gel, this formed gel is left to age for 2 hours. Therefore, it is possible to granulate it, then dry it in an air flow at 70°C overnight. The dry grains of PHs polymer are then ground.

[0268] Example 7 (invention): Application tests of PHs

[0269] • Hydro-swelling application of PHs

[0270] Case 1) 0.5 g of PHs powder are added to 750 mL of deionized water.

[0271] The mixture is made in a Sorbonne, in a rotating stainless steel drum with a diameter of 20 cm for 3 hours.

[0272] Case 2) 0.5 g of PHs powder are added to 750 mL of tap water.

[0273] The mixture is made in a Sorbonne, in a rotating stainless steel drum with a diameter of 20 cm for 3 hours.

[0274] In each case, the entire mixture obtained is placed on a 100pm mesh sieve, subjected to a vibration of amplitude 1.5 mm / "g" (lg=9.81m / s 2 ) for 1 minute (AS 200 control sieve from Retsch).

[0275] The product retained by the filter is weighed to obtain the absorption rate.

[0276] Table 4 summarizes the results.

[0277] Table 4 - Retention test results

[0278] The PH5 polymer has a retention rate similar to the reference polymer.

Claims

CLAIMS 1- Hybrid polymer (HP) comprising monomeric units of at least one monomer comprising at least one unsaturated ethylenic function, and protein units, characterized in that the monomeric units and the protein units are partially or totally linked by at least one covalent bond, in that the weight ratio between the monomeric units and the protein units is between 50 / 1 and 1 / 5. 2- Hybrid polymer (PH) obtained by a radical polymerization process comprising the following successive stages: (A)Prepare a mixture (Ml) comprising at least one monomer comprising at least one unsaturated ethylenic function, and between 0.1% and 50% by weight of at least one protein, optionally at least one solvent, (B) Initiate polymerization in the mixture (Ml) to obtain at least one hybrid polymer (PH). 3- Hybrid polymer (PH) according to claim 2, obtained by radical inverse emulsion polymerization according to a process comprising the following successive steps: (Al) Preparation of an aqueous phase comprising between 1% to 50% by weight of at least one protein, between 4% to 40% by weight of at least one monomer comprising at least one unsaturated ethylenic function and between 20 to 95% by weight of water; (A2) Preparation of a lipophilic phase comprising between 70% to 99% by weight of an inert hydrophobic liquid and between 1 to 20% by weight of at least one surfactant; (A3) Mixing said aqueous phase with said lipophilic phase in order to form an inverse emulsion; (B) Polymerization of said inverse emulsion to obtain a hybrid polymer inverse emulsion (PH). 4- Hybrid polymer (PH) according to any one of claims 1 to 3, characterized in that the monomeric units of at least one monomer comprising at least one unsaturated ethylenic function, or the at least one monomer comprising at least one unsaturated ethylenic function are hydrophilic, and non-ionic and / or anionic and / or cationic. 5- Hybrid polymer (PH) according to any one of the preceding claims, characterized in that the monomeric units of at least one monomer comprising at least one unsaturated ethylenic function, or the at least one monomer comprising at least one unsaturated ethylenic function are chosen from acrylamide, acrylic acid, an oligomer of acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS) and / or its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyldiallyammonium chloride (DADMAC), quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME). 6- Hybrid polymer (PH) according to any one of the preceding claims, characterized in that the protein units, or the at least one protein are plant and / or animal. 7- Hybrid polymer (PH) according to any one of the preceding claims, characterized in that the protein units, or the at least one protein are a casein, a serum protein or wheat protein. 8- Hybrid polymer (PH) according to any one of the preceding claims, characterized in that the weight average molecular weight is between 20,000 and 20,000,000 daltons. 9- Hybrid polymer (PH) according to any one of the preceding claims, characterized in that the polymer is in the form of an inverse emulsion. 10- Use of the hybrid polymer (PH) according to any one of claims 1 to 9 as a flocculating agent, coagulating agent, binding agent, fixing agent, viscosity reducing agent, thickening agent, absorbent agent, friction reducing agent, draining agent, drainage agent, charge retention agent, dehydrating agent, conditioning agent, stabilizing agent, fixing agent, film-forming agent, sizing agent, superplasticizing agent, clay inhibitor or dispersant. 11- Use of the hybrid polymer (PH) according to any one of claims 1 to 9 in a field chosen from hydrocarbon recovery; in well drilling and cementing; in the stimulation of hydrocarbon wells; in water treatment; in the treatment of fermentation musts; in the treatment of sludge; in paper manufacturing; in construction; in wood treatment; in the treatment of hydraulic composition; in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in textile manufacturing; in the manufacture of battery components; in geothermal energy; in the manufacture of hygienic diapers; or in agriculture. 12- Aqueous composition comprising at least one hybrid polymer (PH) according to any one of claims 1 to 9, said composition comprising between 0.001% and 5% by weight of said hybrid polymer (PH). 13- Use of the composition according to claim 12 in a field chosen from hydrocarbon recovery; in well drilling and cementing; in the stimulation of hydrocarbon wells; in water treatment; in the treatment of fermentation musts; in the treatment of sludge; in paper manufacturing; in construction; in wood treatment; in the treatment of hydraulic composition; in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in textile manufacturing; in the manufacture of battery components; in geothermal energy; in the manufacture of hygienic diapers; or in agriculture. -SS

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