[go: up one dir, main page]

WO2025040784A1 - Polymère soluble dans l'eau en tant que matériau liant pour batterie - Google Patents

Polymère soluble dans l'eau en tant que matériau liant pour batterie Download PDF

Info

Publication number
WO2025040784A1
WO2025040784A1 PCT/EP2024/073677 EP2024073677W WO2025040784A1 WO 2025040784 A1 WO2025040784 A1 WO 2025040784A1 EP 2024073677 W EP2024073677 W EP 2024073677W WO 2025040784 A1 WO2025040784 A1 WO 2025040784A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
acid
soluble polymer
cationic
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/073677
Other languages
English (en)
Inventor
Cédrick FAVERO
Johann Kieffer
Thomas BOURSIER
Frédéric BLONDEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SNF Group
Original Assignee
SNF Group
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SNF Group filed Critical SNF Group
Publication of WO2025040784A1 publication Critical patent/WO2025040784A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloyl morpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to a method for preparing a binder for an electrode ink, said binder consisting of a water-soluble polymer, a binder composition and a battery comprising said binder.
  • Lithium-ion batteries are used in a wide range of products, including medical devices, electric cars, aircraft and, above all, consumer products such as laptops, cell phones and cameras. Due to their high energy density, high operating voltage, and low self-discharge, lithium-ion batteries have invaded the secondary battery market and continue to find novel uses in developing industries and products.
  • lithium-ion batteries comprise an anode, a cathode and an electrolyte material such as an organic solvent containing a lithium salt. More specifically, the anode and cathode (collectively, the “electrodes”) are formed by mixing one or more active electrode materials, such as lithium oxides (cathode) or graphite (anode) with a polymer (called and used as a binder) and a solvent to form a paste or ink, which is then applied and dried on a current collector, such as aluminum or copper, to form a film. The anode and cathode are then stacked and wound before being housed in a pressurized case containing electrolyte material, which together form a lithium- ion cell.
  • active electrode materials such as lithium oxides (cathode) or graphite (anode)
  • a polymer called and used as a binder
  • a solvent to form a paste or ink
  • the binder plays several important roles in both mechanical and electrochemical performance. Firstly, it helps to disperse the other components in the solvent during the manufacturing process (some also acting as thickeners), enabling homogeneous distribution. Secondly, it holds the other components together, including the active components, conductive additives, and current collector, ensuring that all these parts remain in contact. Through chemical or physical interactions, the binder connects these separate components, holding them together and ensuring the mechanical integrity of the electrode without significantly impacting electronic or ionic conductivity. Thirdly, it must contribute to the formation of a stable solid electrolyte interface (SEI), thus preventing continuous depletion of the electrolyte's lithium reservoir and protecting the electrode from corrosion.
  • SEI solid electrolyte interface
  • binders must have a certain degree of elasticity if they are not to crack or develop defects. Brittleness can lead to problems during battery manufacture or assembly.
  • Amphoteric diblock copolymers composed of anionic (poly(sodium p-styrenesulfonate) and cationic poly(vinylbenzyl trimethylammonium chloride) blocks, prepared via a controlled radical polymerization method, have been reported (Fukumoto et al., “Polystyrene-based amphoteric diblock copolymers with upper critical solution temperature (UCST) in aqueous solutions”, Chemistry Letters, vol. 50, no. 6, 2021, pages 1114-1117).
  • UST critical solution temperature
  • Ampholytic diblock copolymers of poly(2-(dimethylamino)ethyl methacrylate)-b- poly(methacrylic acid) have been described (Gohy et al., “Aggregates formed by amphoteric diblock copolymers in water”, Macromolecules, vol. 33, no. 17, 2000, pages 6378-6387).
  • Amphoteric diblock copolymers composed of poly(2-acrylamido-2-methylpropanesulfonic acid sodium salt) with poly(3-(acrylamido)propyl trimethylammonium chloride) blocks, synthesized via reversible addition-fragmentation chain transfer radical polymerization, have been reported (Kawata et al., “Thermo-responsive behavior of amphoteric diblock copolymers bearing sulfonate and quaternary amino pendant groups”, Langmuir, vol. 35, no. 5, 2018, pages 1458-1464).
  • EP 4 130 077 describes multiblock copolymers of 2-acrylamido-2-methylpropanesulfonic acid and cationic monomers such as N-vinylpyrrolidone, N-vinylformamide or diallyldimethylammonium chloride obtained by addition-fragmentation chain transfer radical polymerization.
  • CN 109 935 476 describes an amphoteric gel polymer electrolyte.
  • the polymer according to the invention offers good performance, giving the ink better properties in terms of dispersion, adhesion, stability, flexibility, and capacity retention, thus meeting the needs of industrialists without any inconvenience to them. Even more surprisingly, there appears to be a synergistic effect between the use of the polymer according to the invention and flexibility agents such as CMC, SBR or combinations thereof.
  • the resulting polymers and their use are part of a general principle of improving product performance, and more specifically the properties of binders in batteries.
  • the improved performance of the polymers obtained by the method according to the invention makes it possible to reduce the quantity of product required for the application, which therefore implies a reduction in the release of greenhouse gases such as CO2 associated with the manufacture and use of synthetic polymers.
  • This invention relates to a method for preparing a binder for an electrode ink, said binder consisting of a water-soluble polymer.
  • this invention relates to a method for preparing a binder for an electrode ink, said binder consisting of a water-soluble polymer comprising:
  • At least 30 mol% of the cationic hydrophilic monomers A of this water-soluble polymer are in form of cationic blocks, the cationic blocks having a molecular weight of between 500 and 50,000 g/mol.
  • This invention also relates to a composition for an electrode ink comprising:
  • this invention also relates to a battery, preferably a lithium-ion battery, comprising an electrode comprising:
  • At least one binder consisting of a water-soluble polymer comprising:
  • the cationic hydrophilic monomers A are in form of cationic blocks, the cationic blocks having a molecular weight of between 500 and 50,000 g/mol;
  • polymer we mean a polymer obtained from at least one cationic monomer A and at least one anionic monomer B. It may also comprise other monomers chosen from non-ionic hydrophilic monomers, zwitterionic hydrophilic monomers and hydrophobic monomers.
  • water-soluble polymer we mean a polymer which gives an aqueous solution without insoluble particles when dissolved with stirring at 25°C and a concentration of 10 g.L' 1 in deionized water.
  • molecular weight and “weight average molecular weight”, also noted M w , are synonyms and are used indiscriminately.
  • hydrophilic monomer is meant a monomer which has an octanol/water partition coefficient, Kow, less than or equal to 1, wherein the partition coefficient K ow is determined at 25°C in an octanol/water mixture having a volume ratio of 1/1, at a pH of between 6 and 8.
  • hydrophobic monomer is meant a monomer which has an octanol/water partition coefficient, Kow, greater than 1, wherein the partition coefficient K ow is determined at 25°C in an octanol/water mixture having a volume ratio of 1/1, at a pH of between 6 and 8.
  • the octanol/water partition coefficient, K ow represents the ratio of concentrations (g/L) of a monomer between the octanol phase and the aqueous phase. It is defined as follows: [ monomer] octanol [monomer] water
  • X and/or Y means "X” or "Y", or "X and Y”.
  • the invention also includes all possible combinations of the other than disclosed embodiments, whether they are preferred embodiments or given by way of example.
  • ranges of values are indicated, the terminals are part of these ranges.
  • the disclosure also includes all combinations between the bounds of these value ranges. For example, the value ranges "1-20, preferably 5-15", imply disclosure of the ranges “ 1-5", “ 1-15", “5-20” and “ 15-20” and the values 1, 5, 15 and 20.
  • macromer we mean a macromolecule with at least one end group that enables it to behave as a monomer and to be incorporated into a polymer chain in such a way that each macromolecule contributes only one monomer unit to the polymer formed.
  • macromolecule we mean a molecule with a weight-average molecular weight advantageously of at least 300 g/mol, preferably between 300 and 5,000 g/mol, even more preferably between 500 and 3,000 g/mol.
  • macro-transfer agents and macro-initiators we mean a macromolecule possessing at least one functional group enabling it to ensure its function as transfer agent or initiator respectively.
  • these molecules have a number of functions capable of ensuring their respective function of at least 2, preferably at least 5, more preferably at least 10 and advantageously less than 100, preferably less than 50, more preferably less than 20.
  • crosslinking macro-agents we mean a macromolecule possessing at least two groups enabling it to ensure its crosslinking function.
  • these molecules have a number of functions able to ensure their respective function of at least 5, preferably at least 10 and advantageously less than 100, preferably less than 50, more preferably less than 20.
  • the water-soluble polymer represents 100% by weight of the binder.
  • the water-soluble polymer according to the invention is a synthetic polymer.
  • block polymer we mean di-block, tri-block or multi-block, grafted block polymers, branched block polymers (also known as linear star polymers).
  • Block-by-block polymers are polymers composed of at least two blocks of other than the same monomer.
  • Di-block polymers have two distinct blocks; tri-block polymers have three, etc... They are advantageously obtained by successively polymerizing different monomer species.
  • the polymer has an X-Y structure when composed of two different monomers.
  • a first block comprises only monomers X
  • a second block comprises only monomers Y.
  • the first fraction comprises X monomers only. These are first polymerized, and when all the monomers X have reacted, the second fraction comprising monomers Y is added.
  • the polymer has an X-Y-Z structure when composed of three different monomers.
  • the first fraction comprises only monomers X. These are first polymerized, and when all the monomers X have reacted, the second fraction comprising monomers Y is added. When all monomers Y have reacted, the third fraction comprising monomers Z is added.
  • This polymerization system may be extended to obtain so-called multi-block polymers with the structure Xi-Yi-...-Xn-i-Y n -i-Xn-Y n , n being an integer greater than or equal to 2 representing the number of blocks.
  • the water-soluble polymer is a comb polymer wherein the blocks are on the backbone and/or on the side chains of the water-soluble polymer.
  • the water-soluble polymer is obtained by polymerization of at least one macromonomer, in addition to monomers.
  • the water-soluble polymer according to the invention comprises at least:
  • a monomer C chosen from non-ionic hydrophilic monomers, zwitterionic hydrophilic monomers, hydrophobic monomers, macromonomers, and mixtures thereof.
  • the cationic hydrophilic monomers A constitute the cationic blocks of the water-soluble polymer.
  • the number of cationic blocks in the water-soluble polymer is at least 2, preferably at least 3, more preferably at least 5, most preferably at least 8.
  • the number of cationic blocks in the water-soluble polymer is less than 30, preferably less than 25, more preferably less than 15 and most preferably less than 12.
  • the water-soluble polymer comprises a number of cationic blocks of between 2 and 10.
  • the number of cationic blocks can be adjusted by one skilled in the art, as it depends on the weightaverage molecular weight of the polymer, to achieve the desired properties.
  • the number of blocks in the water-soluble polymer can be determined by methods widely known by those skilled in the art, in particular Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared spectroscopy (FTIR) or Mass Spectrometry (MS).
  • NMR Nuclear Magnetic Resonance
  • FTIR Fourier Transform Infrared spectroscopy
  • MS Mass Spectrometry
  • the water-soluble polymer has a ratio between the number of anionic charges and the number of cationic charges of between 1.01 and 24, preferably between 1.01 and 20, more preferably between 1.1 and 12.5, more preferably between 1.5 and 8, even more preferably between 2 and 5 and even more preferably between 2.5 and 3.2.
  • the water-soluble polymer according to the invention may comprise one or more cationic hydrophilic monomers designated as "monomer A”.
  • hydrophilic cationic monomer(s) which can be used in the context of the invention are chosen, in particular, from monomers of the vinyl type, in particular acrylamide, acrylic, allylic or maleic monomers possessing a protonable amine or ammonium function, advantageously quaternary ammonium.
  • diallyldialkyl ammonium salts such as diallyldimethyl ammonium chloride (DADMAC); acidified or quatemized salts of dialkyl-aminoalkyl(meth)acrylamides such as methacrylamido propyltrimethyl ammonium chloride (MAPTAC), acrylamido propyltrimethyl ammonium chloride (APTAC); acidified or quatemized salts of dialkylaminoalkyl acrylate, such as quatemized or salified dimethylaminoethyl acrylate (DMAEA); acidified or quatemized salts of dialkylaminoalkyl methacrylate, such as quatemized or salified dimethylaminoethyl methacrylate (DMAEMA); acidified or quatemized salts of N,N-dimethylallylamine; acidified or quatemized salts of diallylmethylamine; acidified or quatemized salts of diallylamine;
  • the alkyl groups are Ci-C 7 , preferably Ci-C 3 and can be linear, cyclic, saturated or unsaturated chains.
  • the hydrophilic cationic monomer A is preferably selected from the group consisting of quatemized or salified dimethylaminoethyl acrylate, quatemized or salified dimethylaminoethyl methacrylate, diallyldimethyl ammonium chloride, acrylamido propyltrimethyl ammonium chloride, methacrylamido propyltrimethyl ammonium chloride, quatemized or salified N,N- dimethylallylamine, quatemized or salified diallylmethylamine, quatemized or salified diallylamine, vinylamine derived from vinylformamide hydrolysis or Hofmann degradation, and mixtures thereof.
  • the water-soluble polymer advantageously comprises between 4 and 49 mol% of cationic hydrophilic monomer(s) A, preferably between 10 and 49 mol%, more preferably between 10 and 40 mol%, most preferably between 10 and 25 mol%.
  • quaternized monomers for example using a quatemizing agent of the R-X type, where R is an alkyl group and X is a halogen or sulfate.
  • quatemizing agent we refers to a molecule capable of alkylating a tertiary amine.
  • the quatemizing agent may be selected from dialkyl sulfates containing 1 to 6 carbon atoms or alkyl halides containing 1 to 6 carbon atoms.
  • the quatemizing agent is chosen from methyl chloride, benzyl chloride, dimethyl sulfate or diethyl sulfate.
  • this invention also covers DADMAC, APTAC and MAPTAC monomers whose counterion is a sulfate, fluoride, bromide, or iodide instead of chloride.
  • the water-soluble polymer according to the invention may comprise one or more anionic hydrophilic monomers designated as "monomer B".
  • the anionic hydrophilic monomer(s) B which can be used in the context of the invention can be selected from a wide group.
  • the monomers may have vinyl functions (advantageously acrylic, maleic, fumaric, malonic, itaconic, or allylic) and contain a carboxylate, phosphonate, phosphate, sulfate, sulfonate, or other anionically charged group.
  • the hydrophilic anionic monomer(s) B are selected from the group consisting of acrylic acid; methacrylic acid; dimethylacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; 3-acrylamido 3 -methylbutanoic acid; C1-C3 itaconic acid hemi-esters; acryloyl chloride; strong acid monomers with, for example, a sulfonic acid or phosphonic acid function, such as vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, 2- methylidenepropane-l,3-disulfonic acid, 2-sulfoethylmethacrylate, sulfopropylmethacrylate, sulfopropylacrylate, allylphosphonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS)
  • the anionic hydrophilic monomer(s) are acrylic acid and/or 2-acrylamido-2- methylpropane sulfonic acid and/or the water-soluble salts of these monomers, more preferably acrylic acid and/or its water-soluble salts.
  • the anionic hydrophilic monomer(s) can be partially or fully salified.
  • the acid functions of the polymer may be partially or fully salified.
  • the salified form advantageously corresponds to salts of alkali metals (Li, Na, K%), alkaline earth metals (Ca, Mg%) or ammonium (e.g., ammonium ion or tertiary ammonium), or mixtures thereof.
  • Preferred salts are sodium and lithium salts.
  • Salification can be carried out, either fully or partially, before, during, or after polymerization.
  • the anionic hydrophilic monomers of the water-soluble polymer are in salified form, preferably between 10 and 90 mol%, more preferably between 30 and 80 mol%.
  • the water-soluble polymer according to the invention advantageously comprises between 5 and 96 mol% of anionic hydrophilic monomers B, preferably between 10 and 80 mol%, more preferably between more than 25 and 50 mol%.
  • the water-soluble polymer has a greater number of anionic charges than cationic charges.
  • the water-soluble polymer according to the invention may comprise one or more non-ionic hydrophilic monomers and/or zwitterionic hydrophilic monomers and/or hydrophobic monomers and/or macromonomers and mixtures thereof designated as "monomer C".
  • non-ionic hydrophilic monomer or monomers which can be used in the context of the invention are 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), glycidyl methacrylate, glyceryl methacrylate,
  • the water-soluble polymer according to the invention advantageously comprises between 0 and less than 91 mol% non-ionic hydrophilic monomers, preferably between 20 and 75 mol%, and more preferably between 25 and 65 mol%.
  • the zwitterionic hydrophilic monomer or monomers which can be used in the context of the invention are chosen, in particular, from derivatives of a vinyl-type unit (advantageously acrylamide, acrylic, allylic or maleic), this monomer having an amine or quaternary ammonium function and an acid function of the carboxylic (or carboxylate), sulfonic (or sulfonate) or phosphoric (or phosphate) type.
  • this monomer comprises an amine or quaternary ammonium function and an acid function of the carboxylic (or carboxylate), sulfonic (or sulfonate) or phosphoric (or phosphate) type.
  • Dimethylaminoethyl acrylate derivatives such as 2-((2-9(acryloyloxy)ethyl)dimethylammonio) ethane- 1 -sulfonate
  • examples of zwitterionic monomers are for example: 3-((2-(acryloyloxy)ethyl)dimethylammonio)propane-l-sulfonate; 4- ((2-(acryloyloxy)ethyl)dimethylammonio)butane- 1 -sulfonate; [2-(acryloyloxy)ethyl]
  • dimethylammonio)acetate dimethylaminoethyl methacrylate derivatives such as 2-((2- (methacryloyloxy)ethyl)dimethylammonio)ethane-l -sulfonate, 3-((2-(methacryloyloxy)ethyl) dimethylammonio)propane- 1 -sulfonate, 4-((2-(methacryloyloxy)ethyl)dimethylammonio)butane- 1 -sulfonate, [2-(methacryloyloxy)ethyl] (dimethylammonio)acetate; dimethylamino propylacrylamide derivatives such as 2-((3-acrylamidopropyl)dimethylammonio)ethane-l- sulfonate, 3 -((3 -acrylamidopropyl)dimethylammonio)propane-l -sulfonate, 4-((3-acryl
  • hydrophilic zwitterionic monomers can be used, in particular those described by the Applicant in document WO2021/123599.
  • the water-soluble polymer according to the invention advantageously comprises between 0 and 30 mol% zwitterionic hydrophilic monomers, preferably between 0.01 and 20 mol% and more preferably between 0.1 and 15 mol%.
  • the water-soluble polymer according to the invention may comprise one or more hydrophobic monomers.
  • the monomer or monomers with a hydrophobic character which can be used in the context of the invention can be chosen, in particular, from esters of (meth)acrylic acid with a (i) C4-C30 alkyl chain, or (ii) arylalkyl (C4-C30 alkyl, C4-C30 aryl), or (iii) propoxylated, or (iv) ethoxylated, or (v) ethoxylated and propoxylated; alkyl aryl sulfonates (C4-C30 alkyl, C4-C30 aryl); mono- or di-substituted amides of (meth)acrylamide with a (i) C4-C30 alkyl chain, or (ii) arylalkyl chain (alkyl C 4 -C 3 o, aryl C4-C30 ), or (iii) propoxylated, or (iv) ethoxylated, or
  • - alkyl groups are preferably C4-C20, more preferably C4-C8.
  • the C6-C20 alkyls are preferably linear alkyls, while the C4-C5 alkyls are preferably branched,
  • the arylalkyl groups are advantageously C7-C25, preferably C7-C15,
  • the ethoxylated chains advantageously comprise from 1 to 2OO-CH2-CH2-O- groups, more preferably from 10 to 40,
  • the propoxylated chains advantageously comprise from 1 to 50 -CH2-CH2-CH2-O- groups, preferably from 1 to 20.
  • Preferred monomers belonging to these classes are, for example:
  • R independently an alkyl chain containing 1 to 4 carbons
  • Ri an alkyl or arylalkyl chain containing 8 to 30 carbons
  • X a halide selected from the group consisting of bromides, chlorides, iodides, fluorides and any negatively charged counterion; and, preferably, hydrophobic cationic derivatives of the methacryloyl type corresponding to formula (III):
  • - A represents O or N-R5 (preferably A represents N-R5)
  • R2 independently a hydrogen atom or an alkyl chain containing 1 to 4 carbons,
  • - X a halide selected from the group consisting of bromides, chlorides, iodides, fluorides and any negatively charged counterion.
  • the water-soluble polymer according to the invention generally comprises less than 3 mol% hydrophobic monomers.
  • water-soluble polymer according to this invention comprises hydrophobic monomers, they are present in such quantities that the polymer remains soluble in water.
  • the polymer comprises no hydrophobic monomer.
  • the water-soluble polymer may be obtained by polymerizing the hydrophilic cationic A and anionic B monomers and at least one macromonomer bearing an unsaturated function.
  • the hydrophilic cationic A and anionic B monomer(s) and the macromonomer(s) are polymerized simultaneously in a reactor.
  • the polymer chain is gradually formed in the presence of the hydrophilic monomers and macromonomers.
  • the water-soluble polymer according to the invention advantageously comprises between 0 and 20 mol% macromonomer, preferably between 0.1 and 15 mol%, more preferably between 1 and 10 mol%.
  • the macromonomer is a macromonomer of formula (IV):
  • - R9 is hydrogen or methyl
  • - n is a number between 1 and 200, preferably between 6 and 100, and more preferably between 10 and 40;
  • - m is a number between 0 and 50, preferably between 0 and 20;
  • - EO is an ethylene oxide group (-CH2-CH2-O-);
  • - PO is a propylene oxide group (-CH2-CH(CH3)-O-);
  • - Rio is a hydrogen atom or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic carbon radical comprising 1 to 30 carbon atoms, comprising 0 to 4 heteroatoms, selected from the group comprising O, N, and S.
  • n is greater than or equal to m.
  • the sum n+m is between 6 and 100, preferably between 10 and 40.
  • hydrophilic monomer(s) that can be used to prepare the macromonomer are advantageously chosen from the anionic hydrophilic and/or non-ionic hydrophilic and/or cationic hydrophilic and/or zwitterionic hydrophilic and/or hydrophobic monomers described preceding.
  • the macromonomer is a thermosensitive macromonomer.
  • thermosensitive macromonomer we mean a macromolecule composed of monomers that change the physical properties of the polymer as a function of temperature.
  • Examples include Lower Critical Solution Temperature (LCST) groups and Upper Critical Solution Temperature (UCST) groups.
  • LCST Lower Critical Solution Temperature
  • UST Upper Critical Solution Temperature
  • the heat-sensitive macromonomer has a molecular weight of between 500 g/mol and 200,000 g/mol, preferably between 1,000 g/mol and 100,000 g/mol, more preferably between 1,500 g/mol and 100,000 g/mol.
  • Molecular weight refers to weight-average molecular weight.
  • the molar percentage of units derived from heat-sensitive macromonomers in the water-soluble polymer is greater than 10' 4 mol% relative to the total number of moles of heatsensitive monomers and macromonomers, preferably greater than 10' 3 mol%, even more preferably greater than 5.1 O' 3 mol%.
  • the molar percentage of units derived from heat-sensitive macromonomers in the water-soluble polymer is preferably less than 9.1 O' 2 mol% relative to the total number of moles of heat-sensitive monomers and macromonomers, preferably less than 8.10" 2 mol%, more preferably less than 6.10' 2 mol%, even more preferably less than 5.10' 2 mol%, even more preferably less than 4.10' 2 mol%.
  • the heat-sensitive macromonomer is a monomer. Thus, unless otherwise indicated, when the weight of monomers is mentioned, it includes the weight of any heat-sensitive macromonomer(s).
  • the polymer may also be structured with a branching agent.
  • a structured polymer is a non-linear polymer with side chains.
  • - structural agents which may be chosen from the group comprising polyethylenically unsaturated compounds (having at least two unsaturated functions) different from monomer A, such as vinyl functions, in particular allyl or acrylic functions, and may include, for example, methylene bis acrylamide (MBA), triallylamine, or tetraallylammonium chloride or 1,2 dihydroxy ethylene bis- (N-acrylamide),
  • - macroinitiators such as polyperoxides, polyazoids and transfer polyagents such as polymercaptant polymers, and polyols,
  • the amount of branching agent in the water-soluble polymer is advantageously between 5 and 10,000 ppm relative to the total weight of the monomers of the water-soluble polymer, preferably between 10 and 5,000 ppm, more preferably between 15 and 1,000 ppm.
  • the branching agent is a macro-branching agent, for example polyethylene oxide diacrylate.
  • branching macro-agents enables the polymer to be structured, for example in a star or comb-like, dendritic fashion.
  • the water-soluble polymer according to the invention includes a branching agent
  • the polymer remains water-soluble.
  • One skilled in the art will know how to adjust the amount of crosslinking agent, and possibly the amount of transfer agent, to achieve this result.
  • the water-soluble polymer does not comprise a branching agent.
  • the water-soluble polymer comprises at least one transfer agent.
  • the transfer agent is advantageously selected from methanol; isopropyl alcohol; sodium hypophosphite; calcium hypophosphite; magnesium hypophosphite; potassium hypophosphite; ammonium hypophosphite; formic acid; sodium formate; calcium formate; magnesium formate; potassium formate; ammonium formate; 2-mercaptoethanol; 3 -mercaptopropanol; dithiopropylene di thiopropanol; dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene dithiopropylene magnesium formate; potassium formate; ammonium formate; 2-mercaptoethanol; 3- mercaptopropanol; dithiopropylene glycol; thioglycerol; thioglycolic acid;
  • the quantity of transfer agent in the water-soluble polymer according to the invention is advantageously between 100 and 50,000 ppm relative to the total weight of the monomers of the water- soluble polymer, preferably between 200 and 10,000 ppm, more preferably between 300 and 5,000 ppm.
  • the water-soluble polymer does not comprise a specific transfer agent, and this role may be ensured by the polymerization solvent (such as isopropanol).
  • the polymerization solvent such as isopropanol
  • the water-soluble polymer does not comprise a transfer agent.
  • the transfer agent is a macro -transfer agent chosen from polymercaptants and polyols.
  • macro -transfer agents enables the polymer to be structured in a dendritic manner, for example in the form of a star or comb.
  • the water-soluble polymer according to the invention has a weight average molecular weight advantageously between 50,000 and 5 million g/mol, preferably between 100,000 and 3,000,000 g/mol, more preferably between 300,000 and 800,000 g/mol, even more preferably between 400,000 and 600,000 g/mol.
  • the weight average molecular weight is advantageously determined by the intrinsic viscosity of the polymer.
  • Intrinsic viscosity may be measured by methods known to one skilled in the art and can be calculated from the reduced viscosity values for different polymer concentrations, using a graphical method consisting of plotting the reduced viscosity values (y-axis) against the concentration (x-axis) and extrapolating the curve to zero concentration.
  • the intrinsic viscosity value is plotted on the y-axis or using the least-squares method.
  • the molecular weight may then be determined by the Mark-Houwink equation:
  • [q] represents the intrinsic viscosity of the polymer as determined by the solution viscosity method.
  • K is an empirical constant.
  • M represents the molecular weight of the polymer.
  • a represents the Mark-Houwink coefficient.
  • K and a depend on the particular polymer-solvent system.
  • This water-soluble polymer has at least 30 mol% of its cationic hydrophilic monomers A in the form of cationic blocks.
  • the cationic blocks have a molecular weight of between 500 and 50,000 g/mol, preferably between 1,000 and 40,000 g/mol, more preferably between 5,000 and 30,000 g/mol.
  • the molecular weight of the blocks in the water-soluble polymer can be determined by methods widely known by those skilled in the art, in particular nuclear magnetic resonance (NMR), Fourier Transform Infrared spectroscopy (FTIR) or Mass Spectrometry (MS).
  • NMR nuclear magnetic resonance
  • FTIR Fourier Transform Infrared spectroscopy
  • MS Mass Spectrometry
  • the water-soluble polymer is obtained by polymerization in the presence of at least one anionic template.
  • polymer formation takes place in the presence of another low- molecular-weight polymer template.
  • some of the monomers are spatially distributed around these templates by electrostatic interactions, Van der Waals forces or hydrogen bonds, so that, once polymerization has begun, blocks with a well-defined structure in terms of size, polarity and functionality are formed.
  • the simultaneous or delayed addition of a comonomer produces a polymer with block inclusions whose properties are other than those of a polymer obtained by conventional polymerization. Interactions/bonds with the template are reversible, enabling them to be recycled once polymerization is complete.
  • the template(s) are prepared from anionic monomers, in particular and without limitation vinylfunctional monomers such as acrylic, maleic, fumaric, itaconic or allylic monomers. Monomers with a carboxylate, phosphonate, phosphate, sulfonate, sulfate or other anionically charged group.
  • Preferred monomers belonging to this class are, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acrylamido undecanoic acid, 3-acrylamido 3 -methylbutanoic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS), vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, 2-sulfoethylmethacrylate, sulfopropylmethacrylate, sulfopropylacrylate, allylphosphonic acid, styrene sulfonic acid, 2- acrylamido-2-methylpropane disulfonic acid, and mixtures thereof.
  • the molecular weight of the anionic template is between 500 and 50,000 g/mol. Molecular weight is defined as weight-average molecular weight.
  • the water-soluble polymer is obtained by radical polymerization controlled by reversible deactivation (RDRP).
  • RDRP reversible deactivation
  • the polymerization is advantageously a reversible deactivation controlled radical polymerization (RDRP).
  • RDRP reversible deactivation controlled radical polymerization
  • Polymerization can take place in solution, by precipitation, in emulsion (aqueous or inverse), in suspension, or water-in-water, preferably in solution.
  • Radical polymerization includes free-radical polymerization using UV, azo, redox or thermal initiators, as well as controlled radical polymerization (CRP) or matrix polymerization techniques.
  • RDRP includes techniques such as Iodine Transfer Polymerization (ITP), Nitroxide Mediated Polymerization (NMP), Atom Transfer Radical Polymerization (ATRP), Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT), which includes MADIX technology (Macromolecular Design by Interchange of Xanthates), various variations of Organometallic Mediated Radical Polymerization (OMRP), and OrganoHeteroatom-mediated Radical Polymerization (OHRP).
  • IIP Iodine Transfer Polymerization
  • NMP Nitroxide Mediated Polymerization
  • ATRP Atom Transfer Radical Polymerization
  • RAFT Reversible Addition Fragmentation Chain Transfer Polymerization
  • MADIX technology Macromolecular Design by Interchange of Xanthates
  • OMRP Organometallic Mediated Radical Polymerization
  • OHRP OrganoHeteroatom-mediated Radical Polymerization
  • Controlled radical polymerization may therefore have the following distinctive aspects: 1. the number of polymer chains is fixed throughout the reaction,
  • the average molecular weight is controlled by the monomer/precursor molar ratio.
  • the controlled character is all the more pronounced when the rate of chain radical reactivation is so much greater than the rate of chain growth. However, in some cases, the rate of chain radical reactivation is greater than or equal to the rate of chain propagation. In these cases, conditions 1 and 2 are not observed and, consequently, molecular weight control is not possible.
  • a first fraction of cationic monomer constituting the water-soluble polymer sufficient to achieve a molecular weight of between 500 and 50,000 g/mol, is polymerized.
  • a second fraction of the water-soluble polymer monomers is added and polymerized. And so on, alternating fractions constituting the blocks and the remainder of the monomers constituting the water-soluble polymer, until the desired molecular weight is achieved.
  • the reversible deactivation-controlled radical polymerization technique is selected from reversible addition-fragmentation chain transfer (RAFT), nitroxide- controlled polymerization (NMP) and atom transfer radical polymerization (ATRP).
  • RAFT reversible addition-fragmentation chain transfer
  • NMP nitroxide- controlled polymerization
  • ATRP atom transfer radical polymerization
  • the polymerization initiator(s) used are advantageously chosen from compounds which dissociate into radicals under polymerization conditions, for example: organic peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds and redox catalysts.
  • organic peroxides for example: organic peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds and redox catalysts.
  • water-soluble initiators is preferred.
  • it is advantageous to use mixtures of various polymerization initiators for example mixtures of redox catalysts and azo compounds.
  • the quantity of initiator is advantageously between 2,000 and 20,000 ppm relative to the total weight of monomer, preferably between 4,000 and 10,000 ppm.
  • the initiator is a macroinitiator.
  • macroinitiators enables the polymer to be structured, resulting in star-shaped, combshaped or dendritic structures.
  • the macroinitiator(s) that can be used in the context of the invention can be chosen from polyperoxides and polyazoics.
  • the initiator may be 2,2'-Azobis[2-(2-imidazolin- 2-yl)propane]dihydrochloride.
  • the technique for controlled radical polymerization by reversible deactivation is reversible addition-fragmentation chain transfer (RAFT) polymerization.
  • RAFT addition-fragmentation chain transfer
  • RAFT is based on a reversible chain transfer mechanism consisting of two addition-fragmentation equilibria involving a control agent. Initiation and termination between radicals are the same as in conventional radical polymerization. After decomposition of the initiator into radicals, the first radical species produced adds to the monomer to form a carbon radical, which then reacts rapidly with the control agent to form the corresponding radical entity. The latter will fragment into an initiator and a novel radical capable of re-initiating polymerization.
  • Reversible addition-fragmentation chain transfer polymerization requires the presence of at least one control agent, advantageously of formula (V): in which
  • - Z represents O, S, NR3 or is a direct bond to Ri;
  • R2 and R3 which may be identical or different, represent:
  • an optionally substituted or aromatic, saturated or unsaturated heterocycle (iii), these groups and rings (i), (ii) and (iii) may be substituted by substituted aromatic groups or by alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxy (-COOH), acyloxy (-O2CR), carbamoyl (- C0N(R)2), cyano (-CN) groups, alkylcarbonyl, alkyl aryl carbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-N(R)2), halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups of hydrophilic or ionic character such as alkali salts of carboxylic acids, alkali salts of sulfonic acid, polyalkylene oxide chains
  • R is an alkyl or aryl group C1-C20;
  • R3 may also represent a hydrogen atom
  • - Q is a linear or structured polymer chain comprising n identical or different monomers comprising at least one ethylenic function
  • - n is an integer between 0 and 500, advantageously between 1 and 500, more advantageously between 1 and 100.
  • Q is a single bond between the sulfur atom and the R2 group.
  • the monomer or monomers used to form Q are advantageously chosen from the same monomers as those described for forming the branched water-soluble polymer (monomers A and/or B and/or C). Examples include acrylamide, acrylic acid and mixtures thereof.
  • the two R groups may be identical or different from each other.
  • control agent is of formula V in which Z represents O.
  • control agent is of formula V in which:
  • - Q is a linear or structured polymer chain obtained from 1 to 100 monomers comprising at least one non-ionic hydrophilic monomer and/or at least one anionic hydrophilic monomer and/or at least one cationic hydrophilic monomer described preceding.
  • control agent is of formula (VI): in which Q is a linear or structured polymeric chain obtained from 1 to 100 monomers chosen from acrylamide, acrylic acid or quatemized or salified dimethylaminoethyl acrylate, preferably between 1 and 50.
  • control agent is of formula V in which Z represents S.
  • control agent is of formula (VII): in which the groups R3, which are identical or different, independently represent a hydrogen atom or a CH3 or a cation, the cation being advantageously chosen from alkali metal cations (Li, Na, K%), alkaline earth metal cations (Ca, Mg%) or ammonium cations (e.g., ammonium ion or tertiary ammonium), preferably sodium.
  • control agent is of formula (VIII): in which:
  • the groups R3 are identical or different and independently represent a hydrogen atom or a CH3 or a cation, the cation advantageously being chosen from alkali metal cations (Li, Na, K%), alkaline earth metal cations (Ca, Mg%) or ammonium cations (e.g., ammonium ion or tertiary ammonium), preferably sodium;
  • - Q is a linear or structured polymeric chain obtained from 1 to 100 monomers chosen from acrylamide, acrylic acid or quatemized or salified dimethylaminoethyl acrylate, preferably between 1 and 50.
  • control agent is of formula (IX): in which the R3 are identical or other than, independently represent a hydrogen atom or a CH or a cation, the cation being advantageously chosen from alkali metal cations (Li, Na, K%), alkaline earth metal cations (Ca, Mg%) or ammonium cations (e.g., ammonium ion or tertiary ammonium), preferably sodium.
  • alkali metal cations Li, Na, K
  • alkaline earth metal cations Ca, Mg
  • ammonium cations e.g., ammonium ion or tertiary ammonium
  • control agent is of formula (X): in which
  • - Q is a linear or structured polymeric chain obtained from 1 to 100 monomers chosen from acrylamide, acrylic acid or quatemized or salified dimethylaminoethyl acrylate, preferably between 1 and 50.
  • the molar ratio between monomers and control agent is advantageously between 700: 1 and 42,000:1, preferably between 1,400: 1 and 14,000: 1, more preferably between 2,800: 1 and 11,500:1, even more preferably between 5,600: 1 and 11,500: 1.
  • the reversible deactivation-controlled radical polymerization technique is nitroxide polymerization (NMP).
  • An alkoxyamine is a compound of formula (XI): in which:
  • R4 and R5 are identical or different, independently represent an H or an alkyl group which may be linear, branched, cyclic, saturated or unsaturated, and may comprise one or more heteroatoms, advantageously C1-C30, preferably C1-C20, more preferably Ci-Cs;
  • - Re represents an alkyl group which may be linear, branched, cyclic, saturated or unsaturated and may comprise one or more heteroatoms, advantageously from C1-C30, preferably from C1-C20, more preferably from Ci-Cs.
  • This functional group is that under certain conditions, homolysis of the C-0 bond may occur, yielding a stable radical in the form of a 2-center, 3 -electron N-0 system and a carbon radical that serves as an initiator for radical polymerization.
  • nitrogen-bonded R groups are always bulky, sterically troublesome groups, and oxygen-bonded R groups must allow mesomerization of the radical to form a stable radical (e.g., a benzyl, t-butyl, ester-type group) for successful polymerization to occur.
  • a stable radical e.g., a benzyl, t-butyl, ester-type group
  • NMP provides excellent control of chain length and structure, as well as a relative absence of true termination, allowing polymerization to continue as long as monomer is available.
  • Alkoxyamines suitable for NMP are listed in documents W02002/48109, WO99/46261 or W02010/015599.
  • the molar ratio between monomers and alkoxyamine is advantageously between 700: 1 and 42,000:1, preferably between 1,400: 1 and 14,000: 1, more preferably between 2,800: 1 and 11,500:1, even more preferably between 5,600: 1 and 11,500: 1.
  • the reversible deactivation controlled radical polymerization technique is atom transfer polymerization (ATRP).
  • ATRP uses a transition metal complex as catalyst with an alkyl halide as initiator (R-X).
  • Various transition metal complexes including those of Cu, Fe, Ru, Ni and Os, can be used.
  • the dormant species is activated by the transition metal complex to generate radicals via an electron transfer process.
  • the transition metal is oxidized to a higher oxidation state. This reversible process rapidly establishes an equilibrium, with each growing chain having the same probability of propagating with monomers to form living or dormant polymer chains (R-Pn-X).
  • R-Pn-X dormant polymer chains
  • the number of polymer chains is determined by the amount of initiator.
  • the initiator(s) are advantageously chosen from alkyl halides whose structures are similar to that of the radical being propagated.
  • Alkyl halides such as alkyl bromides are more reactive than alkyl chlorides, the alkyl being advantageously Ci-Cs, preferably C1-C4.
  • Suitable primers for ATRP are listed in documents W02002/48109, WO99/46261 or W02010/0015599.
  • the molar ratio between monomers and initiator is advantageously between 700: 1 and 42,000: 1, preferably between 1,400: 1 and 14,000: 1, more preferably between 2,800: 1 and 11,500: 1, most preferably between 5,600: 1 and 11,500: 1.
  • the water-soluble polymer is obtained by polymerization with a macromonomer.
  • the water-soluble polymer of the invention may be obtained by polymerizing at least one type of anionic hydrophilic monomer B and at least one macromonomer.
  • the water-soluble polymer is obtained by polymerization of at least one anionic hydrophilic monomer B and at least one macromonomer, the macromonomer comprising the cationic hydrophilic monomer A and constituting the blocks of the water-soluble polymer.
  • telomerization is a method for synthesizing oligomers with low molecular weights (known as telomers).
  • Telomerization agents can be selected from thiols, alcohols, disulfides, phosphorus, boron and halogen derivatives. In particular, they can be used to introduce specific functions at the end of telomer chains, such as silane, trialkoxysilane, amine, epoxy, hydroxyl, phosphonate or acid functions.
  • a water-soluble polymer (the backbone) is first obtained by polymerizing the water-soluble monomers, then oligomers are grafted onto said water- soluble polymer.
  • the oligomers are cationic blocks.
  • the Applicant discovered that the structure of the polymer according to the invention enabled it to offer good performance by giving the ink better properties, whether in terms of dispersion, adhesion, stability or flexibility, and thus meet the needs of industrialists without any disadvantages for them.
  • the performance provided by the polymer according to the invention is enhanced when used in combination with a flexibility agent such as carboxymethylcellulose CMC, styrene-butadiene rubber SBR, or combinations thereof.
  • a flexibility agent such as carboxymethylcellulose CMC, styrene-butadiene rubber SBR, or combinations thereof.
  • This invention also relates to a composition for an electrode ink comprising:
  • At least one binder consisting of a water-soluble polymer comprising:
  • the cationic hydrophilic monomers A are in form of cationic blocks, the cationic blocks having a molecular weight of between 500 and 50,000 g/mol;
  • At least one flexibility agent chosen from polysaccharides, styrene-butadiene rubber and mixtures thereof.
  • the solvent is water.
  • This composition comprises a quantity of water-soluble polymer advantageously between 0.5 and 15% by weight relative to the total weight of the composition, preferably between 0.7 and 10% by weight, more preferably between 0.9 and 7% by weight and even more preferably between 1 and 5% by weight.
  • the flexibility agent is a polysaccharide, advantageously chosen from the group comprising carboxymethylcellulose, alginates, xanthan gums, diutan gum, welan gum, their salts and mixtures thereof.
  • the flexibility agent is carboxymethylcellulose.
  • This composition has a quantity of flexibility agent advantageously between 0.5 and 10% by weight relative to the total weight of the composition, preferably between 0.5 and 5% by weight, more preferably between 1 and 3% by weight.
  • the composition has a weight ratio between the at least one water-soluble polymer and the at least one flexibility agent of between 0.1 and 30, preferably between 0.1 and 14, and more preferably between 0.33 and 5.
  • This invention also relates to a battery, preferably a lithium-ion battery, comprising an electrode comprising:
  • At least one binder consisting of a water-soluble polymer comprising:
  • the cationic hydrophilic monomers A are in form of cationic blocks, the cationic blocks having a molecular weight of between 500 and 50,000 g/mol;
  • ADC Dimethylaminoethyl acrylate quaternized with methyl chloride
  • SBR Styrene Butadiene Rubber (from Zeon BM 400)
  • 190.0 g of deionized water are added to a one-liter jacketed reactor equipped with a refrigerant and mechanical stirrer with a half-moon module and nitrogen inlet, and heated to 80°C under a nitrogen atmosphere (nitrogen flow).
  • a sodium persulfate solution is prepared in a dropping funnel, by dissolving 17.0 g of sodium persulfate in 100.0 g of deionized water.
  • a second ampoule is filled with 690.0 g of 2-acrylamido- 2-methylpropane sulfonic acid sodium salt solution 50% by weight in water).
  • the sodium persulfate solution is added to the reactor over 20 minutes, keeping the reactor at 80°C.
  • the sodium salt solution of 2-acrylamido-2-methylpropane sulfonic acid is added over 90 minutes. Once the sodium persulfate solution has been added, the solution is kept stirring at 80°C for 60 minutes.
  • a G1 polymer with a weight-average molecular weight equal to 41,000 g/mol, determined from the intrinsic viscosity, is thus obtained.
  • the resulting solution is heated to 45°C. Nitrogen bubbles are then applied for 30 minutes to remove all traces of dissolved oxygen.
  • a solution of propanic acid 2-[(ethoxythioxomethyl)thio]-methyl ester is prepared by mixing 2.0 g of propanic acid 2-[(ethoxythioxomethyl)thio]-methyl ester in 30 mL of deionized water and 70 mL of acetone. 1 mL of this solution is added to the reactor.
  • the medium is degassed for 20 minutes and heated to 60°C.
  • telomer T1 The medium containing telomer T1 is cooled to 10°C and the pH maintained between 7 and 9. Sodium hydroxide solution and methacrylic anhydride are then added.
  • Syringe pump flow rates are adjusted to control the exothermicity of the reaction and maintain a pH between 7 and 9.
  • the result is a macromonomer Ml .
  • the medium is degassed for 20 minutes and heated to 60°C.
  • VA- 044® from the Wako company
  • Example 4- Synthesis of a comb polymer (P4) with a NaA backbone (85 mol%) and 10,000 g/mol ADC side chains (15 mol%) and incorporating a hydrophobic link.
  • the medium is degassed for 20 minutes and heated to 60°C.
  • VA- 044® from the Wako company
  • the medium is degassed for 20 minutes and heated to 60°C.
  • VA- 044® from the Wako company
  • the medium is left to stir for a further 1 hour.
  • 1.2g of 40% sodium metabisulfite solution (by weight) in water is then added to the medium, and the medium is left to stir for 30 min.
  • the pH of the solution is then adjusted to 6.5.
  • the PCI polymer is then obtained.
  • Example 3 The method described in Example 3 is repeated, adjusting the quantities so that the M2 macromonomer has side chains of 90,000 g/mol, to obtain the PC3 polymer.
  • the medium is degassed for 20 minutes and heated to 60°C.
  • Amonomer solution A comprising 10.1 g of80% ADC (by weight in water) is prepared.
  • a monomer solution B comprising 18.4 g AA and 40.4 g 80% ADC (by weight in water) is prepared.
  • the initiator solution and a third of solution A are added to the reactor and left to react for 45 min.
  • One third of solution B is then added and the medium is left to react for 80 min.
  • solution A followed by solution B is repeated a further 2 times.
  • An initiator solution may be re-injected if polymerization slows down.
  • the medium is left to stir for a further 1 hour.
  • 1.20 g of a 40% sodium metabisulfite solution (by weight in water) is added to the medium and left to stir for 30 min.
  • the pH of the solution is then adjusted to 6.5.
  • the PC4 polymer is then obtained.
  • % block cationicity percentage of cationic monomers in block form.
  • Molecular weights are determined by steric exclusion chromatography. They are measured by an Agilent 1260 Infinity system equipped with a Dawn HELOS, OPtilab T-Rex multi-angle light scattering detector and 3 columns in series: Shodex SB 807-G, Shodex SB 807-HQ and Shodex 805-HQ.
  • the percentage of block-by-block cationicity corresponds to the percentage of cationic charges involved in cationic triads. This percentage is determined by proton NMR. It is measured by a Bruker 400 MHz ASCEND (TM) Avance III HD equipped with a 10 mm BBO 400 MHz Z-G radiating probe.
  • MWBC corresponds to the molecular weight by weight of the cationic blocks. It is measured in different ways depending on the one particular embodiment employed:
  • the molecular weight M W BC is obtained by applying the poly dispersity index of the copolymer.
  • the molecular weight of the macromonomer Ml corresponds to M W BC. This is determined directly by steric exclusion chromatography.
  • the polymers obtained are then used as anode binders.
  • Ink preparation Inks composed of 83.5% GHDR 15-4 graphite from Imerys, 3% C-Energy Super C65 carbon black from Imerys, 10% SiQC 99 from Nanomakers and 3.5% active polymer are produced.
  • the powders are first introduced into a 150 mL flask adapted to the Thinky ARM 310 stirrer. They are shaken for 1 minute at 1,100 rpm to homogenize the powder mixture.
  • the polymer is diluted in the appropriate amount of deionized water. The latter is adjusted to obtain a viscosity at 10 s' 1 of between 5,000 and 10,000 cP.
  • the proportion of ink solids with a viscosity within this range is denoted TS.
  • the powders and polymer solution are mixed at 1,100 rpm for 2 min, then at 2,000 rpm for 5 min.
  • the inks thus prepared are deposited on a 20 pm-thick copper foil using an RK Print K303 lab coater.
  • the thickness of the layer is adjusted using the other than bars supplied to achieve between 3.8 and 4.3 mAh/cm 2 (5.2- 6.0 mg/cm 2 ).
  • the electrode is then dried for 12 hours at 60°C in a vacuum oven.
  • the electrode is then calendered to achieve a porosity of 30% +/- 3%.
  • CR 2032 button cells are used.
  • the cathode is NMC 622 from Customcells (3.5 mAh/cm 2 )
  • the separator is a 16.5 mm Celgard 2,500 disk
  • the electrolyte is LP 57 from E-Lyte ( IM LiPFe in EC:EMC (30:70% by weight + 10% FEC)) added at 20 pL to the anode and cathode.
  • Button cell capacity retention is assessed using BCS 805 galvanostatic cyclers from the Biologic company. Batteries are cycled at 25°C between 2.5 and 4.2 V at C/10 for 100 cycles, with a 5- minute rest period between each charge/discharge cycle.
  • Solids content represents the amount of dry matter in the ink. The higher the value, the better the ink, as less energy is required to evaporate the solvent.
  • the quality of mineral particle dispersion is assessed using a fineness gauge. 2 mL of ink are placed on the gauge and the ink is squeegeed off. Any agglomerates present leave streaks from a certain depth, which we note as P. This depth determines the size of the powder agglomerates and should therefore be as small as possible, or even zero.
  • One of the roles of the polymer is to guarantee ink stability. 30 mL of ink is stored at 25°C in a transparent tube 10 cm high and 1.5 cm in diameter for 12 hours. The amount of water recovered from the surface is weighed and noted as E. The lower the water content, the greater the stability of the mixture. If the mixture remains homogeneous, no water is removed.
  • a 1 cm wide strip of dry electrode is cut and wound around a 2 mm diameter cylinder and held for 5 min.
  • the strip is then unfolded, and if any cracks are present, the polymer is assigned a value of 1. If no cracks are present, a value of 0 is assigned. Flexibility is rated C.
  • a pull-off measurement is performed on 5 cm strips of dry electrode using a Testometric M250 tensile tester equipped with a 2.5 kN cell. The measurement is performed at 180°C at a speed of 10 mm/s and repeated 3 times. The average pull-out force is denoted F. The higher the average pull-out force, the greater the electrode's ability to withstand the mechanical stresses experienced during charging and discharging cycles.
  • the percentage retention capacity after 100 cycles is calculated as follows ((Qioo- Qo )/Qo ) x 100, where Qioo: capacity after 100 cycles; and Qo: capacity before the cycles. The higher the latter, the more efficient the binder. Retention capacity is given by RCioo.
  • the binders of this invention lead to inks with fewer defects and greater stability than the proposed counter-examples. Once dried, the electrodes are easy to handle, and no cracking was observed in our test. The composite layer adheres better than the CMC and SBR reference and the counter-examples. Capacity retention is also significantly improved when the polymers of the invention are used. Furthermore, the binders of the invention combined with CMC and/or SBR see their application performance significantly improved, which is not the case with the counter-examples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un liant pour une encre d'électrode, une composition de liant et une batterie comprenant ledit liant.
PCT/EP2024/073677 2023-08-24 2024-08-23 Polymère soluble dans l'eau en tant que matériau liant pour batterie Pending WO2025040784A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2308927A FR3152279A1 (fr) 2023-08-24 2023-08-24 Polymere hydrosoluble comme liant pour batterie
FRFR2308927 2023-08-24

Publications (1)

Publication Number Publication Date
WO2025040784A1 true WO2025040784A1 (fr) 2025-02-27

Family

ID=88689456

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/073677 Pending WO2025040784A1 (fr) 2023-08-24 2024-08-23 Polymère soluble dans l'eau en tant que matériau liant pour batterie

Country Status (2)

Country Link
FR (1) FR3152279A1 (fr)
WO (1) WO2025040784A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999046261A1 (fr) 1998-03-09 1999-09-16 Ciba Specialty Chemicals Holding Inc. Derives nitroxyliques a groupes glycidyle ou alkylcarbonyle convenant comme amorceurs de polymerisation des radicaux
WO2002048109A3 (fr) 2000-12-14 2002-08-29 Ciba Specialty Chemiclas Holdi Composes a base de n-alkoxy-4,4-dioxy-polyalkyl-piperidine presentant des groupes glycidyle ou alkylcarbonyle qui servent d'initiateurs fonctionnels de polymerisation radicalaire controlee
WO2010015599A1 (fr) 2008-08-05 2010-02-11 Polymers Crc Limited Membranes de polyamide à film mince fonctionnalisées
US20100280169A1 (en) 2007-01-24 2010-11-04 Mathias Destarac Ampholytic copolymer with controlled architecture
WO2016162532A1 (fr) 2015-04-10 2016-10-13 S.P.C.M. Sa Procede de deviation d'une formation souterraine
CN109935476A (zh) 2019-03-08 2019-06-25 齐鲁工业大学 具有良好性能的两性凝胶聚合物电解质及其制备、应用
US20210147604A1 (en) * 2017-07-06 2021-05-20 HYDRO-QUéBEC Polymers comprising imidazole derivatives and their use in electrochemical cells
WO2021123599A1 (fr) 2019-12-16 2021-06-24 Spcm Sa Nouveaux monomeres sulfobetaine, procede de preparation et leurs utilisations
EP4130077A1 (fr) 2021-08-06 2023-02-08 Clariant International Ltd Agent raft symétrique pour polymérisation radicalaire contrôlée de copolymères à plusieurs blocs pour monomères avec différentes activités

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999046261A1 (fr) 1998-03-09 1999-09-16 Ciba Specialty Chemicals Holding Inc. Derives nitroxyliques a groupes glycidyle ou alkylcarbonyle convenant comme amorceurs de polymerisation des radicaux
WO2002048109A3 (fr) 2000-12-14 2002-08-29 Ciba Specialty Chemiclas Holdi Composes a base de n-alkoxy-4,4-dioxy-polyalkyl-piperidine presentant des groupes glycidyle ou alkylcarbonyle qui servent d'initiateurs fonctionnels de polymerisation radicalaire controlee
US20100280169A1 (en) 2007-01-24 2010-11-04 Mathias Destarac Ampholytic copolymer with controlled architecture
WO2010015599A1 (fr) 2008-08-05 2010-02-11 Polymers Crc Limited Membranes de polyamide à film mince fonctionnalisées
WO2016162532A1 (fr) 2015-04-10 2016-10-13 S.P.C.M. Sa Procede de deviation d'une formation souterraine
US20210147604A1 (en) * 2017-07-06 2021-05-20 HYDRO-QUéBEC Polymers comprising imidazole derivatives and their use in electrochemical cells
CN109935476A (zh) 2019-03-08 2019-06-25 齐鲁工业大学 具有良好性能的两性凝胶聚合物电解质及其制备、应用
WO2021123599A1 (fr) 2019-12-16 2021-06-24 Spcm Sa Nouveaux monomeres sulfobetaine, procede de preparation et leurs utilisations
EP4130077A1 (fr) 2021-08-06 2023-02-08 Clariant International Ltd Agent raft symétrique pour polymérisation radicalaire contrôlée de copolymères à plusieurs blocs pour monomères avec différentes activités

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
C. J. HAWKER ET AL.: "New Polymer Synthesis by Nitroxide Mediated Living Radical Polymerizations", CHEMICAL REVIEWS, pages 3661 - 3688
FUKUMOTO ET AL.: "Polystyrene-based amphoteric diblock copolymers with upper critical solution temperature (UCST) in aqueous solutions", CHEMISTRY LETTERS, vol. 50, no. 6, 2021, pages 1114 - 1117, XP093130387, DOI: 10.1246/cl.210135
GOHY ET AL.: "Aggregates formed by amphoteric diblock copolymers in water", MACROMOLECULES, vol. 33, no. 17, 2000, pages 6378 - 6387, XP093130385, DOI: 10.1021/ma992016j
J.NISKANENH.TENHU: "How to manipulate the upper critical solution temperature (UCST)?", POLYMER CHEMISTRY, vol. 8, 2017, pages 220
KAORU ADACHIYASUHISA TSUKAHARA: "Encyclopedia of Polymeric Nanomaterials, if required", article "Macroinitiator and Macromonomer: Preparation and Application"
KAWATA ET AL.: "Thermo-responsive behavior of amphoteric diblock copolymers bearing sulfonate and quaternary amino pendant groups", LANGMUIR, vol. 35, no. 5, 2018, pages 1458 - 1464, XP093130381, DOI: 10.1021/acs.langmuir.8b01684
STEFAN POLOWINSKI: "emplate polymerisation and co-polymerisation", PROG. POLYM. SCI., vol. 27, 2002, pages 537 - 577
ZHIYING ET AL.: "Dual-stimuli responsive behaviors of diblock polyampholyte PDMAEMA-b-PAA in aqueous solution", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 356, no. 2, 2011, pages 557 - 565, XP028172411, DOI: 10.1016/j.jcis.2011.01.067

Also Published As

Publication number Publication date
FR3152279A1 (fr) 2025-02-28

Similar Documents

Publication Publication Date Title
JP7476801B2 (ja) 二次電池電極用バインダー及びその利用
JP5970183B2 (ja) 電極用バインダー
EP3370288A1 (fr) Liant pour électrode de batterie rechargeable à électrolyte non aqueux, procédé de production de liant et son utilisation
CN108292741A (zh) 具有人造sei层的阳极活性材料颗粒
JP7530052B2 (ja) 二次電池電極用バインダー、二次電池電極合剤層用組成物、二次電池電極及び二次電池
PT1419181E (pt) Processo para a preparação de látices utilizando copolímeros em blocos como surfactantes
CN108292753A (zh) 非水系二次电池粘接层用组合物、非水系二次电池用粘接层以及非水系二次电池
JP7428181B2 (ja) 二次電池電極用バインダー及びその利用
JP7680209B2 (ja) 二次電池電極用バインダー、二次電池電極合剤層用組成物及び二次電池電極
US11870076B2 (en) Binder for nonaqueous electrolyte secondary battery electrode
US20250023048A1 (en) Acrylate binder
JP2018170218A (ja) 電池用正極ペースト
US20200335791A1 (en) Binder for secondary battery electrode, and use thereof
CN114175383A (zh) 非水系二次电池耐热层用浆料组合物、非水系二次电池用耐热层和非水系二次电池
US12040491B2 (en) Binder for a secondary battery electrode and use thereof
JP7160222B2 (ja) 非水電解質二次電池電極用バインダーの製造方法
CN102304206B (zh) 制备水性介质中pH不敏感的无表面活性剂的聚合物颗粒分散体的方法
WO2025040784A1 (fr) Polymère soluble dans l'eau en tant que matériau liant pour batterie
KR102746405B1 (ko) 축전 디바이스용 조성물, 축전 디바이스 전극용 슬러리, 축전 디바이스 전극 및 축전 디바이스
WO2025040801A1 (fr) Procédé de préparation d'un liant pour électrode constituée d'un polymère hydrosoluble ramifié
CN107534152A (zh) 非水系电池电极用粘合剂用组合物、非水系电池电极用粘合剂、非水系电池电极用组合物、非水系电池电极以及非水系电池
JP2025518116A (ja) 二次電池の負極用の電極スラリー組成物中のポリマーバインダーとしてのポリマーｐの水性分散体の使用
CN118369360A (zh) 硅阳极粘合剂
JP2004161873A (ja) 多分岐高分子、その製造方法、固体電解質及び電気化学素子並びに分離膜
CN118324994B (zh) 树脂聚合物、树脂组合物及其制备方法、改性粘结剂、电极浆料、极片和电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24758527

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)