Hybrid polymers and uses thereof

Abstract

The present invention relates to hybrid polymers obtained from at least one monomer comprising at least one unsaturated ethylenic functional group by a free radical precipitation polymerization process in the presence of at least one protein. The invention also relates to the use of said hybrid polymer as a tackifier in various formulations or compositions.

Description

Technical Field

[0001] The present invention belongs to the technical field of hybrid polymers. More specifically, it relates to hybrid polymers obtained from at least one monomer containing at least one ethylenically unsaturated functional group by free radical precipitation polymerization in the presence of at least one protein. The invention also relates to the use of these hybrid polymers as viscosity-increasing agents in various formulations or compositions. Background Art

[0002] For many years, synthetic polymers have been used as viscosifiers in many applications to increase the viscosity of various aqueous formulations.

[0003] These polymers offer unparalleled application properties, but they are derived 100% from fossil resources. Due to increasing demand and insufficient crude oil reserves, the monomers used to produce these synthetic polymers are experiencing a shortage in the near future. Consequently, there is a need to replace these synthetic polymers with hybrid polymers derived at least partially from renewable natural sources. These hybrid polymers retain their optimal application properties.

[0004] The grafting of natural materials (such as sugars and starches) with monomers has been described in the literature. For example, U.S. Patents 5,854,191, 5,223,171, 5,227,446, and 5,296,470 disclose the use of graft copolymers in cleaning applications. Patents WO / 18108663-65-67 describe the use of such mixtures in cosmetic compositions.

[0005] These hybrid thickening polymers are good alternatives, however their use is still limited to specific applications. They are not compatible with more challenging applications, such as petroleum applications, which require the polymer to withstand high temperatures.

[0006] Therefore, there is an increasing need to develop universal tackifiers that meet the expected application properties in various application fields.

[0007] Surprisingly, the Applicant Company has developed hybrid polymers obtained by free-radical precipitation polymerization that remedy the above-mentioned drawbacks. Summary of the Invention

[0008] The present application relates to hybrid polymers obtained from at least one monomer comprising at least one ethylenically unsaturated functional group by a free radical precipitation polymerization method in the presence of at least one protein.

[0009] More specifically, the present invention relates to a hybrid polymer (HP) in particulate form obtained by a free radical precipitation polymerization process according to the following successive steps:

[0010] (A) preparing a solution (S1) comprising:

[0011] - 50% to 95% by weight of at least one polar solvent,

[0012] - 4% to 40% by weight of at least one monomer comprising at least one ethylenically unsaturated functional group, and

[0013] - 0.1% to 40% by weight of at least one protein; the percentages are given relative to the total weight of (S1), totaling 100%;

[0014] (B) initiating polymerization in the solution (S1) to obtain a dispersion (D1) comprising at least one hybrid polymer (HP), said polymer (HP) being precipitated in a polymerization solvent;

[0015] (C) Isolating the hybrid polymer (HP) in the form of particles from the dispersion (D1).

[0016] The present invention also relates to the use of said hybrid polymer (HP) as a viscosity enhancer.The present invention also relates to a viscosity modifier comprising at least one hybrid polymer (HP) according to the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1

[0018] [ Figure 1 ] shows the NMR / DOSY spectra of individual serum proteins.

[0019] Figure 2

[0020] [ Figure 2 ] shows the NMR / DOSY spectrum of the hybrid polymer (HP). DETAILED DESCRIPTION

[0021] Definitions and concepts

[0022] Throughout this application, the following definitions apply unless expressly stated otherwise.

[0023] All intervals are inclusive and combinable. Numerical ranges include lower and upper limits. Thus, the numerical ranges of "0.1-1.0" and "0.1-1" include 0.1 and 1.0. The number of significant figures does not constitute a limitation on the accuracy of the quantity or data shown.

[0024] As used herein, the term "hydrophilic monomer" refers to a monomer having an octanol / water partition coefficient, Kow, less than 1, measured at a temperature of 25°C and a pH of 6-8.

[0025] As used herein, the term "hydrophobic monomer" refers to a monomer having an octanol / water partition coefficient, Kow, greater than 1, measured at a temperature of 25°C and a pH of 6-8.

[0026] The partition coefficient Kow is defined as follows:

[0027] [Mathematical formula 1]

[0028]

[0029] Wherein, [monomer] octanol = the equilibrium solubility concentration of the monomer in n-octanol (g / L), and [monomer] water = the equilibrium concentration of the monomer in water (g / L).

[0030] According to the present invention, the weight average molecular weight of the synthetic polymer according to the present 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 be calculated in particular by a graphical method based on the reduced viscosity values ​​of different concentrations, wherein the reduced viscosity value (y-axis) is plotted as a function of the concentration (x-axis) and the curve is extrapolated to zero concentration. The intrinsic viscosity value is read on the y-axis or using the least squares method. The weight average molecular weight can then be determined by the well-known Mark-Houwink equation:

[0031] [η] = KM α

[0032] [η] represents the intrinsic viscosity of the polymer determined by the method of measuring solution viscosity,

[0033] K represents the empirical constant,

[0034] M represents the molecular weight of the polymer,

[0035] α represents the Mark-Houwink coefficient,

[0036] α and K depend on the specific polymer-solvent system. Tables known to those skilled in the art give the values ​​of α and K as a function of the polymer-solvent system.

[0037] According to the present invention, the monomers containing at least one ethylenically unsaturated functional group can be polymerized with each other to form a polymer. The term "polymer" refers to a product formed by the polymerization of two or more monomers. A polymer prepared from a single monomer type is called a homopolymer. A polymer composed of two or more different monomer types is called a copolymer.

[0038] As used herein, the term "water-soluble polymer" means a polymer that is soluble in water at 25°C in 2g.L -1 The polymer was dissolved in deionized water with stirring for 4 hours to obtain an aqueous solution free of insoluble particles.

[0039] "Anionic polymer" refers to a polymer containing anionic monomers and optionally nonionic monomers. "Nonionic polymer" refers to a polymer containing only nonionic monomers.

[0040] Amphoteric polymers are polymers comprising cationic and anionic charges, preferably the anionic charges being as numerous as the cationic charges; they may also contain nonionic monomers.

[0041] The term "particle size" denotes the average size (in number) of the water-soluble polymer particles. It corresponds to the largest dimension, for example the diameter of spherical particles, and is preferably measured using a laser measuring device using conventional techniques familiar to those skilled in the art. Mastersizer-type devices from Malvern, such as the MS2000 device, can be used for this purpose. Such devices allow the particle size distribution of particles in a liquid medium or in solid form to be measured by laser diffraction.

[0042] The term "monomeric unit" refers to a chemical unit that is associated with a corresponding monomer when the corresponding monomer is polymerized in a polymer chain of a polymer.

[0043] The term "protein unit" denotes a chemical unit that is associated with the corresponding protein when the protein is grafted into the polymer chain of a polymer.

[0044] The present invention therefore relates to a hybrid polymer (HP) in particulate form obtained by a free-radical precipitation polymerization process according to the following consecutive steps:

[0045] (A) preparing a solution (S1) comprising:

[0046] - 50% to 95% by weight of at least one polar solvent,

[0047] - 4% to 40% by weight of at least one monomer comprising at least one ethylenically unsaturated functional group, and

[0048] - 0.1% to 40% by weight of at least one protein; the percentages are given relative to the total weight of (S1), totaling 100%;

[0049] (B) initiating polymerization in the solution (S1) to obtain a dispersion (D1) comprising at least one hybrid polymer (HP), said polymer (HP) being precipitated in a polymerization solvent;

[0050] (C) Isolating the hybrid polymer (HP) in the form of particles from the dispersion (D1).

[0051] The solution (S1) is preferably produced by first mixing a monomer having at least one ethylenically unsaturated functional group with at least one polar solvent and subsequently adding the protein to this mixture.

[0052] The monomer comprising at least one ethylenically unsaturated functional group of step (A) is preferably a hydrophilic monomer.

[0053] The hydrophilic monomer is preferably nonionic and / or anionic. When it is nonionic, it is selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyridine, N-vinylpyrrolidone, acryloylmorpholine (ACMO), diacetoneacrylamide or a mixture of these monomers, and when it is anionic, it is selected from the following group: monomers having carboxylic acid functional groups and salts thereof, monomers having sulfonic acid functional groups and salts thereof, or monomers having phosphonic acid functional groups and salts thereof or a mixture of these monomers.

[0054] The solution (S1) preferably comprises from 10% to 30% by weight of at least one hydrophilic monomer, the percentages being given relative to the total weight of the solution (S1).

[0055] In step (A), the solution (S1) is preferably prepared from a mixture of polar solvents and at least one monomer containing at least one unsaturated ethylenic functional group, wherein the mixture of polar solvents comprises 0.5% to 10% by weight of water and at least 90% by weight of an alcohol containing 1 to 4 carbon atoms. The alcohol containing 1 to 4 carbon atoms is preferably tert-butyl alcohol. The mixture of polar solvents preferably comprises 1% to 5% by weight of water and 95% to 99% by weight of tert-butyl alcohol.

[0056] The protein is preferably selected from proteins of animal origin, plant origin and / or mixtures thereof. The protein is preferably casein, serum albumin, wheat protein or mixtures thereof.

[0057] The hybrid polymer (HP) preferably comprises monomeric units of at least one monomer comprising at least one ethylenically unsaturated functional group and protein units, said monomeric units and said protein units being partially or completely linked via at least one covalent bond.

[0058] Preferably, the weight average molecular weight of the hybrid polymer (HP) is 200,000-2,000,000 Daltons.

[0059] The invention also relates to the use of the hybrid polymer (HP) according to the invention as a tackifier in hydrocarbon recovery, drilling and cementing, stimulation of hydrocarbon wells, papermaking, construction, mining, cosmetic formulations, detergent formulations or textile production.

[0060] The invention also relates to a tackifier comprising at least one hybrid polymer (HP) according to the invention for use in hydrocarbon recovery, drilling and cementing, stimulation of hydrocarbon wells, papermaking, construction, mining, cosmetic formulations, detergent formulations or textile production.

[0061] The present invention also relates to aqueous compositions thickened with the hybrid polymers (HP) according to the invention. Contains at least one Monomers with ethylenically unsaturated groups

[0062] The hybrid polymer (HP) according to the invention is obtained by precipitation polymerization of monomers comprising at least one ethylenically unsaturated functional group in the presence of at least one protein.

[0063] Preferably, the solution (S1) comprises 4-40 wt. % of monomers comprising at least one ethylenically unsaturated functional group, more preferably 10-30 wt. %, the weight percentages being given relative to the total weight of the solution (S1).

[0064] The monomers may be synthetic and / or bio-based.

[0065] Advantageously, these monomers are preferably hydrophilic monomers. Said hydrophilic monomers are nonionic, anionic, cationic or zwitterionic monomers. Preferably, these monomers have a single ethylenically unsaturated bond (a double bond between two carbon atoms).

[0066] Advantageously, the nonionic monomers that can be used in the present invention are in particular chosen from the group consisting of water-soluble vinyl monomers such as acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethacrylamide, N,N-dialkylacrylamide (for example N,N-dimethylacrylamide or N,N-diethylacrylamide), N,N-dialkylmethacrylamide, alkoxylated esters of acrylic acid, alkoxylated esters of methacrylic acid, N-vinylpyrrolidone, N-hydroxymethyl(meth)acrylamide, N-vinylcaprolactam, N-vinylformamide (NVF), N-vinyl The nonionic monomers include acetamide, N-vinylimidazole, N-vinylsuccinimide, acryloylmorpholine (ACMO), glycidyl methacrylate, glyceryl methacrylate, diacetoneacrylamide, methacrylic anhydride, acrylonitrile, maleic anhydride, itaconic anhydride, itaconamide, hydroxyalkyl (meth)acrylates, thioalkyl (meth)acrylates, isoprenol and its alkoxylated derivatives, hydroxyethyl (meth)acrylate and its alkoxylated derivatives, hydroxyethyl (meth)acrylate and its alkoxylated derivatives, hydroxypropyl acrylate and its alkoxylated derivatives, vinyl acetate and mixtures thereof. In these nonionic monomers, the alkyl group is advantageously a C1-C5, more advantageously a C1-C3 alkyl group. They are preferably straight-chain alkyl groups. Preferably, the nonionic monomer is acrylamide.

[0067] Said solution (S1) advantageously comprises 1 mol% to 99 mol% of nonionic monomers, preferably 2 mol% to 70 mol%, said molar percentage being expressed relative to the total moles of monomers in said solution (S1).

[0068] Advantageously, the anionic monomers can be selected from a wide group. These monomers can have vinyl, acrylic, maleic, fumaric, malonic, itaconic or allyl functional groups and contain carboxylate, phosphonate, phosphate, sulfate or sulfonate groups, or other anionic charged groups. Examples of suitable monomers include acrylic acid; methacrylic acid; dimethacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; acrylamidoundecanoic acid; 3-acrylamido-3-methylbutanoic acid; maleic anhydride; strong acid monomers having, for example, sulfonic acid or phosphonic acid type functional groups, such as vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, 2-methylenepropane-1,3-disulfonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allylphosphonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), 2-acrylamido-2-methylpropanesulfonic acid; water-soluble salts of these monomers, such as their alkali metal salts (other than the sodium salt crystalline form of 2-acrylamido-2-methylpropanesulfonic acid), alkaline earth metal salts or ammonium salts; and mixtures thereof. Preferably, the anionic monomer is acrylic acid and / or its salts.

[0069] The solution (S1) advantageously comprises 1 mol% to 99 mol% of anionic monomers, preferably 2 mol% to 70 mol%, more preferably 3 mol% to 50 mol%, the molar percentages being expressed relative to the total moles of monomers in the solution (S1).

[0070] According to one aspect of the present invention, the carboxylic acid functional group of the anionic monomer is salified with a salifying agent, also known as a neutralizing agent. The term "salting" should be understood to mean that at least one acid functional group of the anionic monomer is replaced by a salt capable of neutralizing the negative charge of the acid functional group. In other words, the non-salted form corresponds to the acid form of the monomer, for example, the carboxylic acid functional group corresponds to RC(=O)-OH, while the neutralized form of the monomer corresponds to the RC(=O)O-X+ form, where X+ corresponds to the positively charged ion. Neutralization of the acid functional group can be partial or complete.

[0071] Typically, salt formation is carried out prior to polymerization.

[0072] In a particular embodiment of the present invention, 30 to 100 mol % of the acid functions are salified, more advantageously 60 to 100 mol % of the acid functions are salified.

[0073] The salt-forming agent is advantageously a Bronsted base. It is preferably selected from ammonia, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and mixtures thereof. Ammonia is most particularly preferred.

[0074] Advantageously, the cationic monomers useful in the present invention are selected from monomers derived from vinyl units, in particular units of acrylamide, acrylic acid, allyl or maleic acid, which monomers have phosphonium or quaternary ammonium functional groups. In particular, there may be mentioned (but not limited to) aminoalkyl (meth)acrylates, quaternized dimethylaminoethyl acrylate (DMAEA), quaternized dimethylaminoethyl methacrylate (DMAEMA), dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) and methacrylamidopropyltrimethylammonium chloride (MAPTAC). The quaternizing agent may be selected from alkyl chlorides, dialkyl sulfates or alkyl halides. Preferably, the quaternizing agent is selected from methyl chloride and diethyl sulfate.

[0075] Said solution (S1) advantageously comprises 5-35 mol% of cationic monomers, said molar percentage being expressed relative to the total number of moles of monomers in said solution (S1).

[0076] Those skilled in the art know how to prepare quaternized monomers, for example, by means of alkyl halides of the type R*-X, where R* is an alkyl group and X is a halogen group (particularly methyl chloride). Furthermore, the present invention also encompasses monomers of the DADMAC, APTAC and MAPTAC types, where the halide anion is fluoride, bromide or iodide instead of chloride.

[0077] Advantageously, the zwitterionic monomers may be derivatives of vinyl units, in particular acrylamide, acrylic acid, allyl or maleic, having an amine or quaternary ammonium function and an acid function of the carboxylic acid (or carboxylate), sulfonic acid (or sulfonate) or phosphoric acid (or phosphate) type. In particular, there may be mentioned, but are not limited to, derivatives of dimethylaminoethyl acrylate, such as 2-((2-(acryloyloxy)ethyl)dimethylamino)ethane-1-sulfonate, 3-((2-(acryloyloxy)ethyl)dimethylamino)propane-1-sulfonate, 4-((2-(acryloyloxy)ethyl)dimethylamino)butane-1-sulfonate, [2-(acryloyloxy)ethyl](dimethylamino)acetate; derivatives of dimethylaminoethyl methacrylate, such as 2-((2-(methacryloyloxy)ethyl)dimethylamino)ethane-1-sulfonate, 3-((2-(methacryloyloxy)ethyl)dimethylamino)propane-1-sulfonate, 4-((2-(methacryloyloxy)ethyl)dimethylamino)butane-1-sulfonate, [2-(methacryloyloxy)ethyl](dimethylamino)acetate; derivatives of dimethylaminopropyl acrylamide, such as 2-((3-acrylamidopropyl)dimethylamino)ethane-1-sulfonate, 3-((3-acrylamidopropyl)dimethylamino)propane-1-sulfonate, 4-((3-acrylamidopropyl)dimethylamino)butane-1-sulfonate, [3-(acryloyloxy)propyl](dimethylamino)acetate; derivatives of dimethylaminopropyl methacrylamide, such as 2-((3-methacrylamidopropyl)dimethylamino)ethane-1-sulfonate, 3-((3-methacrylamidopropyl)dimethylamino)propane-1-sulfonate, 4-((3-methacrylamidopropyl)dimethylamino)butane-1-sulfonate and [3-(methacryloyloxy)propyl](dimethylamino)acetate, and mixtures thereof.

[0078] Preferred hydrophilic monomers are acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS) or mixtures thereof, N-vinylpyrrolidone (NVP), MADC, ADC and acrylamide.

[0079] According to one aspect of the present invention, the monomer having an ethylenic functional group may be selected from hydrophobic monomers in addition to the hydrophilic monomers described above.

[0080] The hydrophobic monomers having a partition coefficient Kow greater than 1 are preferably selected from the following list.

[0081] (Meth)acrylates with alkyl, aralkyl, and / or ethoxylated and / or propoxylated chains; (meth)acrylamide derivatives with alkyl, aralkyl, or dialkyl, and / or ethoxylated and / or propoxylated chains; cationic allyl derivatives with alkyl, aralkyl, or dialkyl, and / or ethoxylated and / or propoxylated chains; hydrophobic anionic or cationic (meth)acryloyl derivatives; and anionic or cationic monomeric derivatives of (meth)acrylamide with hydrophobic chains. The alkyl groups of these hydrophobic monomers are preferably C6-C24 alkyl groups. The most preferred monomers are alkylated derivatives of dimethylaminopropyl bromide of methacrylamide with C8-C16 alkyl chains and ethoxylated behenyl methacrylate.

[0082] - 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.

[0083] - LCST (lower critical solution temperature) and / or UCST (upper critical solution temperature) monomers or macromers. In other words, the hydrophobicity can be derived from the LCST and / or from the properties of the monomer or macromer. Patent application WO 2020 / 094960 A1 relates to such macromers with LCST properties.

[0084] Other zwitterionic monomers are described by the applicant in document WO21123599.

[0085] Among these hydrophobic monomers:

[0086] -alkyl is preferably C3-C20, more preferably C3-C8 alkyl. C6-C20 alkyl is preferably linear alkyl, while C3-C5 alkyl is preferably branched.

[0087] - aralkyl is preferably C7-C25, more preferably C7-C15 aralkyl,

[0088] - the ethoxylated chain preferably contains 6 to 100 -CH2-CH2-O- groups, more preferably 10 to 40,

[0089] The -propoxylated chain preferably contains 1 to 50 -CH2-CH2-CH2-O- groups, more preferably 1 to 20.

[0090] Preferred hydrophobic monomers are selected from the group consisting of N-isopropylacrylamide; N,N-dimethylacrylamide; N,N-diethylacrylamide; N-tert-butylacrylamide; N-vinylcaprolactam; and diacetoneacrylamide.

[0091] According to this aspect of the invention, the concentration of the hydrophobic monomer is preferably 0.0001 mol%-10 mol%, more preferably 0.001 mol%-5 mol%, even more preferably 0.01 mol%-3 mol%, even more preferably 0.1 mol%-2 mol%, even more preferably 0.2 mol%-1.5 mol%, even more preferably 0.3 mol%-1.3 mol%, the molar percentage being expressed relative to the total moles of the monomers in the solution (S1).

[0092] If hydrophobic monomers are added during the precipitation polymerization, the hydrophilic monomers will preferably be selected from anionic and / or nonionic hydrophilic monomers.

[0093] During the preparation of the water-soluble polymer according to the present invention, those skilled in the art can adjust the amount of various monomers so that it does not exceed 100 mol%.

[0094] protein

[0095] The hybrid polymer (HP) according to the invention is obtained from at least one protein. It can also be obtained from a plurality of proteins of different nature.

[0096] In step (A) of the method described herein, a protein is added to the polymeric feed in solution (S1).

[0097] The protein is obtained by conventional methods known to those skilled in the art, for example by dissolving, grinding, screening and sorting. The protein can be added to the solution in solid or liquid form (S1). Advantageously, the protein is added in powder form.

[0098] According to the present invention, the solution (S1) contains 0.1-40 wt% protein, preferably 1-20 wt%, more preferably 2-15 wt%, still more preferably 5-10 wt% protein.

[0099] As used herein, the term "protein" includes both native (or chemically unmodified) proteins and modified proteins. The term "modified protein" refers to a protein that has been subjected to one or more pretreatments. These pretreatments can be physical shearing, chemical acid or alkaline hydrolysis, and / or enzymatic proteases.

[0100] Advantageously, native proteins are preferred.

[0101] The proteins according to the invention may be of animal origin and examples of animal proteins that may be mentioned include: milk proteins such as β-lactoglobulin, casein, whey; serum proteins such as horse serum; placental proteins; fibrous skin proteins such as collagen, elastin, silk.

[0102] The protein according to the present invention may be of plant origin, such as corn, wheat, barley and oats, soy, peas, for example gluten, prolamin, zein and gluten. Advantageously, the plant protein is selected from soy protein, wheat protein, oat protein and pea protein. The protein may be obtained from seeds, such as soy, cottonseed, peanut, sunflower, rapeseed, coconut, linseed, sesame, safflower, pea, bean and lentil.

[0103] Other sources of protein are bacteria, fungi, algae and yeasts, such as Pseudomonas, Lactobacillus, Penicillium, Escherichia coli, cyanobacteria, green algae, Chlorella, Spirulina and spent yeast.

[0104] Preferably, the protein of choice is casein, serum albumin or wheat protein.

[0105] To convert proteins into soluble forms, digestion by physical, chemical or enzymatic treatment is usually required, such as hydrolysis with acid or alkali, fermentation with yeast, bacteria or enzymes, extraction methods to remove trace components, coagulation from extracts by heating, addition of electrolytes, pH adjustment or addition of precipitants. Pure products can be prepared, for example, by fractional dissolution and precipitation or by dialysis.

[0106] The proteins used according to the present invention can be water-soluble or water-insoluble. This has no effect on the viscosity-increasing efficacy of the final hybrid polymer (HP). However, the choice of protein solubility is a real goal in terms of application. If the goal is to obtain a viscous gel, especially for cosmetic applications, a translucent gel is preferred, and in this case, a soluble protein is preferred. If the transparency of the application gel is not important, an insoluble protein can be selected.

[0107] The protein may be present in the form of a mixture. This means a mixture containing multiple proteins originating from the same biological kingdom or different biological kingdoms. For example, a mixture containing multiple animal-derived proteins, or a mixture containing at least one animal-derived protein and at least one plant-derived protein and / or one bacterial-derived protein.

[0108] Preferably, a single protein is added to the polymerisation feed of step (A).

[0109] polymerization

[0110] Precipitation polymerization in a solvent medium involves polymerizing monomers soluble in a solvent, while the resulting polymer itself is insoluble and therefore precipitates in the solvent. Upon completion of polymerization, the polymer appears as a precipitate in the reaction medium. The hybrid polymer (HP) precipitates in the polymerization solvent. The hybrid polymer (HP) precipitates during the polymerization step. It does not occur after the polymerization step. More precisely, precipitation of the hybrid polymer (HP) occurs when the hybrid polymer (HP) reaches a certain degree of polymerization. At the beginning of polymerization, the hybrid polymer (HP) is soluble in the reaction solvent, and its degree of polymerization (such as the length of the polymer chain) increases. During polymerization, above a certain degree of polymerization, the hybrid polymer (HP) becomes insoluble in the polymerization solvent and precipitates. Polymerization continues until completion.

[0111] The hybrid polymer (HP) results from the polymerization of at least one monomer comprising at least one ethylenically unsaturated functional group and at least one protein. According to the invention, the hybrid polymer (HP) is polymerized by free radical precipitation polymerization in a polar solvent medium.

[0112] For step (A) of the method, a solution (S1) is prepared comprising 4% to 40% by weight of at least one monomer having an ethylenically unsaturated functional group as described above, 60% to 95% by weight of at least one polar solvent and 0.1% to 40% by weight of at least one protein; the percentages are given relative to the total weight of (S1) and amount to 100%.

[0113] According to a preferred embodiment, the solution (S1) is prepared by first mixing a monomer having an ethylenically unsaturated functional group and at least one polar solvent, and subsequently adding the protein to the mixture.

[0114] According to the invention, a polar solvent or a mixture of polar solvents can be used. The mixture of polar solvents preferably comprises water and an alcohol or a ketone.

[0115] The alcohol or ketone is preferably selected 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).

[0116] In a particular embodiment of the present invention, the solvent used for precipitation polymerization is preferably an alcohol containing 1 to 4 carbon atoms. It is advantageously selected from methanol, ethanol, propan-1-ol, isopropanol, tert-butanol, or a mixture thereof. Preferably, the solvent used is only tert-butanol.

[0117] The mixture of polar solvents preferably contains up to 10% by weight of water, preferably from 1% to 6% by weight of water, more preferably from 2% to 4% by weight of water.

[0118] The mixture of polar solvents preferably contains at least 90% by weight of alcohol, more preferably at least 95% by weight, still more preferably at least 97% by weight of alcohol.

[0119] Therefore, preferably, the mixture of polar solvents used for the precipitation polymerization contains less than 10% by weight of water and at least 90% by weight of tert-butanol, preferably 1% to 5% by weight of water and 99% to 95% by weight of tert-butanol, more preferably 2.5% by weight of water and 97.5% by weight of tert-butanol.

[0120] According to the present invention, the polymerization is preferably carried out under oxygen-free conditions. Degassing comprises removing residual oxygen from the solution (S1) obtained at the end of step (A). To this end, an inert gas is introduced to degas the solution (S1). The inert gas is generally passed through the solution. Suitable inert gases for this purpose are, for example, nitrogen or carbon dioxide.

[0121] According to one aspect of the present invention, a surfactant is added to stabilize the medium to achieve optimal polymerization conditions. Solution (S1) may contain at least one surfactant having an HLB (hydrophile-lipophile balance) of less than 15, preferably 9-13, to stabilize solution (S1) and improve polymerization. Typically, the amount of the surfactant in solution (S1) is 0.2% to 20% by weight, preferably 1% to 10%.

[0122] The hydrophilic-lipophilic balance (HLB) of a compound is a measure of its hydrophilic and / or lipophilic nature and is determined by calculating the values ​​for different regions of the molecule as described by Griffin in 1949.

[0123] The surfactant may be a nonionic, anionic, cationic, amphoteric or zwitterionic surfactant, preferably a nonionic surfactant. The surfactant is preferably selected from ethoxylated surfactants, PEG diacrylates, ethoxylated fatty alcohol ethers, sugar or polyol esters or betaines, esters based on glycerol, diglycerol or triglycerol or other alcohols (such as sugars, such as maltitol or sorbitol) and mixtures thereof. Advantageously, alkyl polyglycosides are used.

[0124] According to one aspect of the present invention, solution (S1) may include a cross-linking agent. The cross-linking agent is advantageously selected from multifunctional reagents, such as methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, cyano methacrylate, ethylene oxide ethyl acrylate, vinyloxy methacrylate, triallylamine, trimethylolpropane triacrylate (TMPTA), tetraallyl ammonium chloride (TAAC), formaldehyde, glyoxal, glycidyl ethers such as ethylene glycol diglycidyl ether, epoxides and mixtures thereof. Preferably, the cross-linking agent is trimethylolpropane triacrylate (TMPTA).

[0125] The solution (S1) preferably comprises 500 ppm to 5000 ppm by weight, more preferably 1600 ppm to 3700 ppm by weight, still more preferably 2500 ppm to 3200 ppm by weight of the crosslinking agent relative to the total weight of the solution (S1).

[0126] According to the method of the present invention, polymerization is initiated using a free radical initiator with one or more of the above-mentioned hydrophilic and / or hydrophobic monomers and a protein. Examples of free radical initiators include redox pairs in which the oxidizing agent comprises cumene hydroperoxide or tert-butyl peroxide, and the reducing agent comprises persulfates such as sodium metabisulfite and Mohr's salt. Azo compounds (such as 2,2'-azobis(isovaleronitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2-amidinopropane) hydrochloride) can also be used in the same manner as peroxide compounds, such as benzoyl peroxide, tert-butyl hydroperoxide, or lauroyl peroxide.

[0127] Degassing is stopped at reflux for several hours, preferably at least 2 hours, before starting polymerization.

[0128] According to the present invention, the free radical precipitation polymerization is carried out at a temperature of 60-85° C. under atmospheric pressure.

[0129] Step (B) of the method is to initiate polymerization of the solution (S1) to obtain a dispersion (D1) comprising the hybrid polymer (HP). The polymer (HP) is present in the form of a precipitate. Step (C) of the method is to isolate the hybrid polymer (HP) in particulate form. The hybrid polymer (HP) can be readily isolated using conventional separation, evaporation, and drying methods known to those skilled in the art. The solvent can be extracted by filtration or distillation, advantageously by distillation.

[0130] The hybrid polymer (HP) is then recovered in the form of particles. Typically, the size of the particles of the hybrid polymer (HP) is advantageously 5 nm to 5 mm, more advantageously 50 nm to 5 mm, preferably 100 nm to 2 mm, and more preferably 200 μm to 1 mm. In particular, it may be 50 nm to 1 mm, or 500 μm to 5 mm, or 5 μm to 1 mm, or 100 μm to 1 mm.

[0131] Hybrid polymers

[0132] The weight average molecular weight of the hybrid polymer (HP) is advantageously between 200,000 and 2,000,000 Daltons, preferably between 300,000 and 1,500,000 Daltons.

[0133] The Brookfield viscosity of the hybrid polymer (HP) is preferably 1000-100000 cP, more preferably 2500-75000 cP, more preferably 5000-50000 cP. The Brookfield viscosity is measured using a Brookfield RVT unit viscometer at a rotation speed of 20 rpm in a 1 wt% aqueous polymer solution.

[0134] The hybrid polymer (HP) may be linear, structured or branched. Preferably, (HP) is structured, ie star-branched or in comb-like form.

[0135] The hybrid polymer (HP) comprises less than 40 wt% protein, preferably 10-40 wt% protein, more preferably 15-35 wt% protein.

[0136] In the hybrid polymer (HP), the weight ratio of monomer units to protein units is preferably 50 / 1 to 1 / 5, preferably 25 / 1 to 1 / 3, more preferably 10 / 1 to 1 / 2, still more preferably 6 / 1 to 1 / 1.

[0137] Figure 1 From the NMR / DOSY analysis it can be observed that the hybrid polymer (HP) according to the present invention has at least partial covalent bonds between the protein and the monomer comprising at least one ethylenic functional group.

[0138] This analysis makes it possible to conclude that the hybrid polymer (HP) according to the invention is present in a mixture comprising at least: a hybrid polymer (HP) having at least partial covalent bonds between a protein and a monomer comprising at least one ethylenic functional group, a monomer comprising at least one ethylenic functional group which reacts with one another to form a water-soluble polymer, and a separate protein.

[0139] D2O and TSP-d4 are deuterated NMR solvents. They can dissolve the product being analyzed without generating a signal. This is because the solvents are usually present in large excess, and their peaks would obstruct the reading of the NMR spectrum.

[0140] Uses of hybrid polymers in various applications

[0141] The invention also relates to the use of the hybrid polymer (HP) as a viscosifier for the recovery of hydrocarbons (oil and / or natural gas); drilling and cementing of wells; treating water in open, closed or semi-closed circuits; treating fermentation slurries in sludge treatment; papermaking; construction; wood treatment; treating hydraulic compositions (concrete, cement, mortar and aggregates); mining; cosmetic preparations; detergent preparations; manufacturing of textile printing and dyeing pastes; manufacturing of battery components; geothermal applications; manufacturing of sanitary layers; or agriculture.

[0142] Advantageously, the present invention relates to the use of the hybrid polymer (HP) according to the invention for the preparation of cosmetic compositions as thickener (thickener), conditioner (conditioner), stabilizer (stabilizer), emulsifier (emulsifier), fixative (fixative) or film former (film former).

[0143] The present invention also relates to the use of a hybrid polymer (HP) as a tackifier for pigment compositions used in textile printing, said tackifier comprising at least one hybrid polymer according to the invention.

[0144] The present invention also relates to a method for enhanced oil or gas recovery by flushing a subterranean formation, comprising the use of at least one hybrid polymer (HP) according to the invention.

[0145] The present invention also relates to a tackifier comprising at least one hybrid polymer (HP) according to the invention for use in a field selected from the group consisting of: hydrocarbon recovery; drilling and cementing; stimulation of hydrocarbon wells; papermaking; construction; mining; cosmetic preparations; detergent preparations; and the manufacture of textiles.

[0146] The present invention also relates to aqueous compositions thickened with the hybrid polymers (HP) according to the invention.

[0147] Other subjects according to the invention

[0148] The present invention also relates to a hybrid polymer (HP) comprising monomer units of at least one monomer containing at least one ethylenically unsaturated functional group and protein units, characterized in that the monomer units and the protein units are partially or completely connected by at least one covalent bond, wherein the weight ratio of the monomer units to the protein units is 50 / 1 to 1 / 5, preferably 25 / 1 to 1 / 3, more preferably 10 / 1 to 1 / 2, more preferably 6 / 1 to 1 / 1.

[0149] The present invention also relates to a hybrid polymer (HP) obtained by free radical polymerization according to a process comprising the following consecutive steps:

[0150] (A) preparing a mixture (M1) comprising at least one monomer comprising at least one ethylenically unsaturated functional group; and 0.1% to 50% by weight of at least one protein, and optionally at least one solvent;

[0151] (B) Initiating polymerization in the mixture (M1) to obtain a hybrid polymer (HP).

[0152] The mixture (M1) preferably contains 5% to 90% by weight, more preferably 10% to 80% by weight, more preferably 15% to 80% by weight, more preferably 20% to 80% by weight, more preferably 25% to 80% by weight, more preferably 30% to 80% by weight, more preferably 35% to 75% by weight, more preferably 40% to 75% by weight, more preferably 45% to 75% by weight, more preferably 50% to 70% by weight, more preferably 55% to 65% by weight of at least one monomer containing at least one ethylenically unsaturated functional group.

[0153] The mixture (M1) preferably comprises 0.1 wt% to 50 wt%, more preferably 1 wt% to 40 wt%, more preferably 3 wt% to 35 wt%, more preferably 5 wt% to 30 wt%, more preferably 10 wt% to 25 wt% of at least one protein.

[0154] The mixture (M1) preferably comprises 1 wt% to 90 wt%, more preferably 5 wt% to 80 wt%, more preferably 10 wt% to 70 wt%, more preferably 15 wt% to 60 wt%, more preferably 20 wt% to 50 wt% of at least one solvent.

[0155] The present invention according to this further subject matter also relates to the use of the above-mentioned hybrid polymer (HP) as a viscosity enhancer. The present invention also relates to a viscosity modifier comprising at least said hybrid polymer (HP).

[0156] Typically, the polymerization is initiated by free-radical initiators in the present application; it can also be initiated by the action of UV radiation.

[0157] The polymerization is preferably carried out at a temperature in the range of 20°C to 160°C, preferably 30°C to 100°C.

[0158] The polymerization is preferably carried out in an inert gas atmosphere free of atmospheric oxygen, for example using nitrogen or carbon dioxide as inert gas.

[0159] The reaction temperature and the amount of initiator generally have a significant influence on the polymerization of the hybrid polymer (HP).

[0160] Advantageously, the monomers containing at least one ethylenically unsaturated functional group to be polymerized and the protein and at least one polymerization initiator are initially introduced into a reaction vessel and the polymerization is carried out by heating to the optimal polymerization temperature. It may be advantageous to use two or more proteins.

[0161] The order in which the reactants are added to the polymerization reactor can be freely adjusted. If multiple monomers are used in the graft copolymerization, each monomer can be added to the polymerization zone sequentially, as a mixture, or simultaneously via separate feeding devices. For example, a protein solution or dispersion can be heated to the desired polymerization temperature in the reactor, and the monomers and initiator can be added continuously or in batches.

[0162] Similarly, the pH of the reaction medium also has an impact on the hybrid polymer (HP). Acidic or basic monomers can be used in the form of the corresponding salts. For example, acrylic acid can be used in the form of a free acid or an alkali metal salt. Polymerization can be carried out in a pH range of 1-14, preferably 6-12. For example, by varying the pH, the graft copolymer can be precipitated from the solution. This possibility can be used in the processing, purification, and isolation of the graft copolymer.

[0163] The proteins used for graft copolymerization can be chemically modified in various ways before or after graft polymerization.

[0164] The DOSY experiment, an NMR method, allows the separation of substances based on their diffusion coefficients in a solvent, the analysis of complex mixtures, and the detection of trace amounts. The purpose of this experiment is to demonstrate the presence of at least one covalent bond between a monomer containing at least one olefinic functional group and a protein. A DOSY experiment involves recording a proton spectrum while simultaneously varying the applied gradient force G, and thus the diffusion force. A linear increase in the gradient strength results in an exponential decrease in the NMR signal intensity. A DOSY experiment produces a two-dimensional image.

[0165] After Fourier transform processing, the second dimension F2 of a DOSY experiment corresponds to the first dimension 1H. The first dimension F1 corresponds to the decrease in the NMR signal as a function of the applied gradient force. After processing the F2 dimension, the diffusion coefficient is extracted and the DOSY map is obtained. If two substrates have the same diffusion coefficient, this means that they have the same hydrodynamic radius and can therefore be grafted. On the other hand, if two substrates have different diffusion coefficients, this means that one substrate is not affected by the other.

[0166] exist Figure 1 and 2 NMR analysis was performed on a Bruker 400 MHz ASCEND equipped with a 10 mm BBO 400 MHz ZG radiation probe. TMThe results were carried out on an Avance IIIHD apparatus. TSP-d4 is deuterated sodium trimethylsilyl propionate.

[0167] in conclusion:

[0168] The diffusion coefficient of the signal associated with the protein in the hybrid polymer is different from that of the individual (isolated) proteins.

[0169] NMR / DOSY (Diffusion Ordered Spectroscopy) analysis of a sample of the pure product (product obtained after polymerization and without further treatment) made it possible to show the grafting of the protein onto the ATBS and subsequently also the grafting of the unsaturated monomer onto the oligomer.

[0170] Example

[0171] The advantages of the present invention are best illustrated in a clear, non-limiting manner by the following examples.

[0172] I-Synthesis of the Hybrid Polymer According to the Invention

[0173] Example 1: HPA = ATBS homopolymer + casein

[0174] 450g of tert-butyl alcohol containing 2.5% by mass of water is introduced into a jacketed reactor equipped with a stirrer blade. 2-Acrylamido-2-methylpropanesulfonic acid (ATBS) is added under stirring. Gaseous ammonia is bubbled in the medium for 30 minutes while checking that the pH does not exceed 7. The preparation is degassed in the reactor for 30 minutes by injecting nitrogen. During this period, the medium is gradually heated to 55°C. Then, trimethylolpropane triacrylate (TMPTA, crosslinking / branching agent) is added, followed by casein (milk protein), and the temperature of the medium is adjusted to 70°C using a thermostatically controlled bath. The polymerization reaction is initiated by adding 0.6g of dilauroyl peroxide. Polymerization starts quickly and reaches an exothermic maximum. After reaching the maximum temperature, the medium is refluxed for 2 hours.

[0175] A white precipitate was observed in the solvent (tert-butanol + 2.5% by mass of water). This white precipitate corresponds to the hybrid copolymer of the present invention. The oil was then heated to 90°C using a rotary evaporator and the solvent removed under a reduced pressure of 100 mbar. The resulting copolymer was then dried at 70°C overnight.

[0176] Table 1 below summarizes the composition of the polymer HPA and its viscosity.

[0177] Brookfield viscosity was measured in a 1 wt% aqueous solution of the polymer using a Brookfield RVT unit viscometer at a rotation speed of 20 rpm.

[0178] [Table 1]

[0179]

[0180]

[0181] Example 2: HPB = ATBS + acrylic acid copolymer + casein

[0182] The procedure was identical to that used in Example 1, Hybrid Polymer 1, except that the monomers used were 2-acrylamido-2-methylpropanesulfonic acid (ATBS) and acrylic acid (30 / 70 mol%). Polymerization was initiated by adding 0.4 g of 2,2'-azobis(2-methylpropionamidine) dihydrochloride. Polymerization began rapidly and reached an exothermic maximum. After reaching the maximum temperature, the medium was refluxed for 2 hours.

[0183] Hybrid polymer 2 was recovered in the same manner as above.

[0184] The amount of protein and cross-linker can be adjusted to achieve the desired viscosity and native / biodegradability targets.

[0185] Table 2 below summarizes the composition of polymer HPB and its viscosity.

[0186] [Table 2]

[0187]

[0188] Example 3: HP C = HP without crosslinking agent A

[0189] 450 g of tert-butyl alcohol containing 2.5% by mass of water are introduced into a jacketed reactor equipped with a stirrer blade. 2-Acrylamido-2-methylpropanesulfonic acid (ATBS) is added under stirring. Gaseous ammonia is bubbled in the medium for 30 minutes while checking that the pH does not exceed 7. The preparation is degassed in the reactor by injecting nitrogen for 30 minutes. During this period, the medium is gradually heated to 55°C. Then, micellar casein (milk protein) is added and the medium temperature is raised to 70°C using a thermostatically controlled bath. The polymerization reaction is initiated by adding 0.6 g of dilauroyl peroxide. Polymerization starts quickly and reaches an exothermic maximum. After reaching the maximum temperature, the medium is refluxed for 2 hours.

[0190] A white precipitate was observed in the solvent (tert-butanol + 2.5% by mass of water). This white precipitate corresponds to the hybrid copolymer of the present invention. The oil was then heated to 90°C using a rotary evaporator and the solvent removed under a reduced pressure of 100 mbar. The resulting copolymer was then dried at 70°C overnight.

[0191] Table 3 below summarizes the polymer HP C composition and viscosity.

[0192] [Table 3]

[0193]

[0194] Example 4: Hybrid Polymer HP D to HP O Synthesis

[0195] The hybrid copolymer HP was prepared according to the protocol of Example 1. D to HP O The polymerization was carried out under the condition that the mass fraction of the active material was 15% (relative to the reaction medium). The amounts of the various monomers were adjusted to obtain the proportions of the various examples shown in Table 4 below.

[0196]

[0197] [Table 4]

[0198] II-Application Examples

[0199] Example 5: Textile Application:

[0200] Pigment printing pastes are prepared in aqueous solution.

[0201] The prepared pigment printing paste had a viscosity of 6500 cP, measured at 25°C using a Brookfield RV unit viscometer at 20 rpm. The printing paste included 12% Helizarin 83Liq C binder (styrene / acrylic acid copolymer) from Archroma or an equivalent, and 1.5% PIGMACOLOR BLUE blue pigment dispersion from KEMITEKS. The mixture was mixed, and then Hybrid Polymer D from Example 1 was added as a thickener, with stirring to thicken the printing paste. The amounts of Hybrid Polymer D and other components were adjusted to achieve a target viscosity of 6500 cP.

[0202] Hybrid polymer D according to Example 1 and two comparative examples outside the invention are shown in Table 5 below: thickened acrylic inverse emulsion and thickened acrylic polymer obtained by precipitation polymerization (PA-PPP).

[0203] [Table 5]

[0204]

[0205] The produced pastes were evaluated for their application properties, coloring rate, fixation and penetration, which are the main control parameters for screen printing.

[0206] The printing system was a FAM-R type printing table from the company Stork; the magnetic transfer doctor blade was of the type with a diameter of 10 mm and a length of 30 cm, and the printing frame was of the type with a 125 mesh opening.

[0207] Three types of fabrics were used to characterize various parameters:

[0208] -100% cotton canvas;

[0209] -100% polyester satin and

[0210] -97 / 3 cotton stretch satin.

[0211] After printing, the pattern was fixed by drying in a dryer at 160°C for 3 minutes.

[0212] The results were compared according to the judgment of those skilled in the art. These results are recorded in Table 6 below.

[0213] [Table 6]

[0214] Hybrid polymer D Inverse Emulsion Benchmark PA-PPP Benchmark Coloring rate ＝ Reference -- Permeability ＝ Reference - fixation ＝ Reference --

[0215] =: Performance is the same as the reference "inverse emulsion benchmark"

[0216] Reference: Reference performance of "Inverse Emulsion Benchmark"

[0217] -: Performance is lower than the reference "Inverse Emulsion Benchmark"

[0218] --: Performance is much lower than the reference "inverse emulsion benchmark"

[0219] The application performance quality of acrylic polymers obtained by precipitation polymerization is inferior to the benchmark obtained by inverse emulsion. Therefore, in the field of screen printing, inverse emulsion thickeners are usually preferred.

[0220] Surprisingly, it was observed that the hybrid polymer D obtained according to the invention by precipitation polymerization has significantly better printing and dyeing performance qualities than the "benchmark" acrylic (PA-PPP) obtained by a similar polymerization process. In addition, the hybrid polymer D meets the benchmark obtained by inverse emulsion, while having lower consumption, which represents a clear advantage.

[0221] Example 6: Petroleum Application:

[0222] Hybrid polymer HPp was prepared according to the method of Example 1. Its composition and characteristics are described in Table 7 below.

[0223]

[0224] [Table 7]

[0225] Tests for drilling applications:

[0226] 600g of 4.5g G-grade cement, 4.5g of hybrid polymer HPp, 1.8g of retarder (CR104), 1.2g of dispersant (CD-1B), and 264g of deionized water were added to a mixer. The entire mixture was mixed at 4000rpm for 15 seconds, then at 12000rpm for 35 seconds, and then placed in a consistency meter at 85°C for 20 minutes.

[0227] Fluid loss was then studied using an HTHP filter press at 85°C and 1000 psi over a 30-minute period. In the baseline test, the fluid loss was 32 mL. In the case of the hybrid polymer, it was 38 mL, which is well in line with the desired performance.

[0228] Example 7: Cosmetic Application:

[0229] The following compositions comprise hybrid polymer C or I, which is a hybrid polymer obtained according to Example 1.

[0230] Table 8 below details examples of cosmetic formulations comprising 1% by weight of hybrid polymers C and I.

[0231] [Table 8]

[0232]

[0233] Cosmetic compositions comprising the hybrid polymers according to the present invention meet cosmetic technical requirements while achieving a target viscosity.

Claims

1. A hybrid polymer (HP) in the form of particles obtained by a free radical precipitation polymerization process according to the following successive steps: (A) preparing a solution (S1) comprising: - 50% to 95% by weight of at least one polar solvent, - 4% to 40% by weight of at least one monomer comprising at least one ethylenically unsaturated functional group, and - 0.1% to 40% by weight of at least one protein; the percentages are given relative to the total weight of (S1), totaling 100%; (B) initiating polymerization in the solution (S1) to obtain a dispersion (D1) comprising at least one hybrid polymer (HP), said polymer (HP) being precipitated in a polymerization solvent; (C) isolating the hybrid polymer (HP) in particle form from the dispersion (D1).

2. The hybrid polymer (HP) according to claim 1, characterized in that The solution (S1) is prepared by first mixing a monomer having at least one ethylenically unsaturated functional group and at least one polar solvent, and then adding the protein to the mixture.

3. Hybrid polymer (HP) according to one of the preceding claims, characterized in that The monomer comprising at least one ethylenically unsaturated functional group of step (A) is a hydrophilic monomer.

4. The hybrid polymer (HP) according to claim 3, characterized in that The hydrophilic monomer is nonionic and / or anionic. When it is nonionic, it is selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyridine, N-vinylpyrrolidone, acryloylmorpholine (ACMO), diacetoneacrylamide or a mixture of these monomers. When it is anionic, it is selected from the following group: monomers having carboxylic acid functional groups and salts thereof, monomers having sulfonic acid functional groups and salts thereof, or monomers having phosphonic acid functional groups and salts thereof or a mixture of these monomers.

5. Hybrid polymer (HP) according to one of the preceding claims, characterized in that The solution (S1) comprises 10% to 30% by weight of at least one hydrophilic monomer, the percentages being given relative to the total weight of the solution (S1).

6. Hybrid polymer (HP) according to one of the preceding claims, characterized in that In step (A), the solution (S1) is prepared from a mixture of polar solvents and at least one monomer comprising at least one unsaturated ethylenic functional group, wherein the mixture of polar solvents comprises 0.5 wt % to 10 wt % of water and at least 90 wt % of an alcohol comprising 1 to 4 carbons.

7. The hybrid polymer (HP) according to claim 6, characterized in that The alcohol containing 1 to 4 carbon atoms is tert-butanol.

8. Hybrid polymer (HP) according to one of claims 6 or 7, characterized in that The mixture of polar solvents comprises 1 wt% to 5 wt% of water and 95 wt% to 99 wt% of tert-butanol.

9. Hybrid polymer (HP) according to one of the preceding claims, characterized in that The protein is selected from proteins of animal origin, proteins of plant origin and / or mixtures thereof.

10. Hybrid polymer (HP) according to one of the preceding claims, characterized in that The protein is casein, serum albumin, wheat protein or a mixture thereof.

11. Hybrid polymer (HP) according to one of the preceding claims, characterized in that The hybrid polymer (HP) comprises monomeric units of at least one monomer comprising at least one ethylenically unsaturated functional group and protein units, the monomeric units and the protein units being partially or completely linked by at least one covalent bond.

12. Hybrid polymer (HP) according to one of the preceding claims, characterized in that The weight average molecular weight of the hybrid polymer (HP) is 200,000-2,000,000 Daltons.

13. Use of the hybrid polymer (HP) according to any one of claims 1 to 12 as a viscosity enhancer in hydrocarbon recovery, drilling and cementing, stimulation of hydrocarbon wells, papermaking, construction, mining, cosmetic preparations, detergent preparations or textile production.

14. Tackifier comprising at least one hybrid polymer (HP) according to any one of claims 1 to 12, for use in hydrocarbon recovery, drilling and cementing, stimulation of hydrocarbon wells, papermaking, construction, mining, cosmetic preparations, detergent preparations or textile production.

15. Aqueous composition thickened with a hybrid polymer (HP) according to any one of claims 1 to 12.

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