Sonopolymerization of unsaturated carboxylic acid

Abstract

The invention relates to the preparation of a water-soluble polycarboxylic polymer by carrying out a radical sonopolymerization reaction on an unsaturated carboxylic acid at a frequency ranging from 20 kHz to 5 MHz. The polymer prepared according to the invention has a well controlled molecular weight and can be used in an aqueous grinding aid, anti-scale or dispersing agent, in particular for treating a mineral or organic material.

Description

[0001] SONOPOL YMERIZATION OF UNSATURATED CARBOXYLIC ACID

[0002] The invention relates to the preparation of a water-soluble polycarboxylic polymer by a radical sonopolymerization reaction at a frequency ranging from 20 kHz to 5 MHz of an unsaturated carboxylic acid. The polymer prepared according to the invention has a well-controlled molecular weight and can be used in an aqueous grinding aid or anti-scaling or dispersing agent, in particular for the treatment of a mineral or organic material.

[0003] Frequently, the treatment of mineral materials, particularly using grinding aids, anti-scaling agents or dispersing agents, requires the development of polymers with improved properties. These agents are often essential for controlling the rheology of mineral suspensions, in particular for controlling their viscosity or flow threshold or for controlling their stability. They also make it possible to control the particle size of mineral suspensions, as well as the good dispersion of particles for both concentrated mineral suspensions and more dilute media. The properties of these mineral treatment agents can be significantly disrupted in the event of variations in their own characteristics but also due to the presence of impurities or by-products, in particular impurities or by-products resulting from their preparation such as certain inorganic compounds or certain mineral salts.

[0004] Improving the efficiency of the methods for preparing the polymers used in these agents must be sought. This includes reducing direct or indirect energy consumption linked to polymerization reactions, improving the yield of these reactions, reducing the number and quantities of reagents and solvents used, as well as reducing or eliminating by-products formed during these polymerization reactions.

[0005] In particular, limiting or banning the use of initiator compounds or chain transfer agents during polymerization reactions is an important objective during the preparation of polymers. Indeed, mineral salts and in particular sulfur salts or phosphorus salts, metals and in particular iron or copper, or certain chemical elements such as sulfur or phosphorus, which are regularly derived from these initiator compounds and these chain transfer agents, can be detrimental during the use of these polymers, in particular when using these polymers as mineral treatment agents. Obtaining polymers whose average molecular weight Mw and whose polydispersity index Ip are well controlled is also an important goal during the preparation of these polymers.

[0006] Furthermore, from an environmental or toxicological point of view, it is important to have available mineral treatment agents, and therefore suitable polymers, which are prepared using reagents or solvents which are not harmful either at the time of their preparation or during the use of the polymers obtained.

[0007] EP 3620075 describes a non-water-soluble polymeric absorbent foam which is prepared after ultrasonic treatment of the monomer composition. WO 2019217985 describes the preparation of very high molecular weight polymers by controlled sonopolymerization reaction. KR 20210028903 describes the preparation of a copolymeric emulsion used as a coagulating agent to prepare diene copolymers. WO 2014049252 relates to the preparation of poly(meth)acrylic acids by radical polymerization in the presence of a particular RAFT agent.

[0008] The method for preparing a water-soluble polycarboxylic polymer according to the invention makes it possible to provide a solution to all or part of the problems of the preparation methods of the state of the art. Thus, the invention provides a method for preparing a composition C comprising a water-soluble polymer P of molecular mass Mw, measured by CES, ranging from 1,000 g / mol to 1,500,000 g / mol and prepared by a radical sonopolymerization reaction in aqueous medium, at a frequency ranging from 20 kHz to 5 MHz, of at least one anionic compound Ml comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts. Essentially, the preparation method according to the invention implements a radical sonopolymerization reaction. The polymerization reaction according to the invention is therefore carried out under ultrasonic irradiation.According to the invention, the polymerization reaction can be carried out partially or completely under ultrasonic irradiation. Also, the irradiation can be permanent or sequenced.

[0009] Preferably according to the invention, the sonopolymerization reaction is carried out under irradiation at an intensity ranging from 5 W / cm 2 at 500 W / cm 2 ; preferably ranging from 5 W / cm 2 at 200 W / cm 2 or 10 W / cm 2 at 150 W / cm 2 .

[0010] Preferably according to the invention, the sonopolymerization reaction is carried out under irradiation at a power ranging from 10 W to 50,000 W; more preferably ranging from 20 W to 20,000 W or from 30 W to 15,000 W. Advantageously according to the invention, the sonopolymerization reaction is carried out under irradiation by means of at least one ultrasonic wave generator whose power can be adapted to the different conditions encountered. In particular, the power of the generator can be chosen specifically. Thus, the generator can have a power of a few tens or hundreds of watts to several thousand watts. For example, it is possible to use one or more generators having a power ranging from 10 W to 50,000 W, preferably ranging from 20 W to 20,000 W or from 30 W to 15,000 W.On an industrial scale, it is possible to use one or more generators with a power ranging from 200 W to 50,000 W, preferably from 500 W to 20,000 W or from 1,000 W to 15,000 W.

[0011] Particularly advantageously according to the invention, the use of ultrasonic waves during the polymerization reaction makes it possible to improve the reaction conditions. In particular, the polymerization temperature can be adapted. Preferably, the sonopolymerization reaction is carried out at a temperature below 100°C. More preferably, the temperature ranges from 20°C to 95°C.

[0012] According to the invention, the sonopolymerization reaction is carried out in water, alone or combined with at least one polar solvent. Where appropriate, the polar solvent is a protic solvent, preferably an alcohol, more preferably isopropanol.

[0013] Preferably, the sonopolymerization reaction is carried out in water alone.

[0014] During the sonopolymerization reaction, the concentration of monomer M1 in the reaction medium can vary quite widely. Preferably, the concentration of monomer M1 during the sonopolymerization reaction is greater than 10% by weight relative to the total amount of the reaction medium. More preferably, the concentration of monomers, preferably monomer M1, during the sonopolymerization reaction is greater than 5% by weight, preferably greater than 10% by weight, relative to the total amount of the reaction medium. Generally, the concentration of monomers, preferably monomer M1, during the sonopolymerization reaction is less than 25% by weight, preferably less than 20% by weight or less than 15% by weight, more preferably less than 13% by weight, relative to the total amount of the reaction medium.

[0015] When implementing the preparation method according to the invention, the reaction medium comprises the various reagents and catalysts, initiator compounds or chain transfer agents, in particular the monomer M1, as well as the optional solvent. Thus, for the preparation method according to the invention, the sonopolymerization reaction can be carried out in the presence of at least one initiator compound. Preferably, the initiator compound can be used in a concentration ranging from 0.1% by weight to 10% by weight, preferably from 0.5% by weight to 8% by weight or from 1% by weight to 6% by weight, relative to the quantity by weight of monomers.

[0016] Also preferably, the initiator compound is selected from 4,4'-azobis-4-cyanopentanoic acid (ACP A), hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, an alkali metal persulfate (especially sodium persulfate, potassium persulfate, ammonium persulfate), an azo compound and their respective combinations or associations with an ion selected from Fe 11 , Fe 111 , Cu 1 , Cu 11 .

[0017] However, for the method according to the invention, the sonopolymerization reaction can also be carried out in the absence of an initiator compound. Then, the sonopolymerization reaction is preferably carried out in the absence of a compound chosen from 4,4'-azobis-4-cyanopentanoic acid (ACP A), hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, an alkali metal persulfate (in particular sodium persulfate, potassium persulfate, ammonium persulfate), an azo compound and their respective combinations or associations with an ion chosen from Fe 11 , Fe 111 , Cu 1 , Cu 11 .

[0018] For the preparation method according to the invention, the sonopolymerization reaction can be carried out in the presence of at least one chain transfer agent. Preferably, the chain transfer agent can be used in a concentration ranging from 0.1% by weight to 10% by weight, preferably from 0.5% by weight to 8% by weight or from 1% by weight to 6% by weight, relative to the quantity by weight of monomers.

[0019] Also preferably, the chain transfer agent may be chosen from a compound comprising P 1 , a compound comprising P 111 , a compound comprising S IV. Preferably, the chain transfer agent is chosen from a compound comprising phosphite, a compound comprising hypophosphite, a compound comprising hydrogen sulfite; more preferably a chain transfer agent chosen from phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, sodium hydrogen sulfite.

[0020] However, for the method according to the invention, the sonopolymerization reaction can also be carried out in the absence of a chain transfer agent. Then, the sonopolymerization reaction is preferably carried out in the absence of a compound comprising P 1 , of compound comprising P 111 , of compound comprising S IV; preferably in the absence of a compound comprising phosphite, a compound comprising hypophosphite, a compound comprising hydrogen sulfite; more preferably in the absence of phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, sodium hydrogen sulfite.

[0021] Preferably according to the invention, the sonopolymerization reaction is carried out in the presence of hydrogen peroxide in combination with an Fe ion. 11 or Fe 111 or in the presence of hydrogen peroxide in combination with an Fe ion 11 or Fe 111 and with a Cu ion 1 or Cu 11 .

[0022] Essentially according to the invention, the preparation method uses at least one monomer Ml. Preferably for the method according to the invention, the compound Ml is chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt, an acrylic acid oligomer, a methacrylic acid oligomer, a salt of an acrylic acid oligomer, a salt of a methacrylic acid oligomer and combinations thereof. Preferably, the monomer Ml is chosen from acrylic acid, an acrylic acid salt, an acrylic acid oligomer, a salt of an acrylic acid oligomer and combinations thereof. Acrylic acid is the preferred monomer Ml.

[0023] The preparation method according to the invention may also use one or more other monomers different from the monomer M1, preferably in a minority weight quantity relative to the quantity of monomer M1 used. Preferably, the polymerization reaction may also use at least one other compound chosen from:

[0024] • another anionic compound M2 different from M1, preferably a compound M2 chosen from itaconic acid, maleic acid, maleic anhydride and their combinations;

[0025] • a sulfur compound M3, preferably a compound M3 chosen from 2-acrylamido-2-methylpropane sulfonic acid, a salt of 2-acrylamido-2-methylpropane sulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, a salt of 2-(methacryloyloxy)ethanesulfonic acid, sodium methallyl sulfonate, sodium vinyl sulfonate, styrene sulfonate and combinations thereof; • a non-ionic compound M4 comprising at least one polymerizable olefinic unsaturation, preferably at least one polymerizable ethylenic unsaturation and in particular a polymerizable vinyl function, more preferably a non-ionic compound M4 chosen from styrene, vinylcaprolactam, esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid chosen from acrylic acid, methacrylic acid, and combinations thereof, for example hydroxyethylacrylate, hydroxypropylacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, alkyl acrylate,in particular Ci-Cio-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, w-propyl acrylate, isopropyl acrylate, isobutyl acrylate, / / -butyl acrylate, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, w-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, / / -butyl methacrylate, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxyethylacrylate, aryl methacrylate, preferably phenylmethacrylate, benzylmethacrylate, phenoxyethylmethacrylate;,

[0026] • a compound M5 of formula I: in which:

[0027] - R 1 and R 2 , identical or different, independently represent H or CH3,

[0028] - L 1independently represents a group chosen from C(O), CH2, CH2- CH2 and O-CH2-CH2-CH2-CH2,

[0029] - L 2 independently represents a group chosen from (CH2-CH2O) X , (CH2CH(CHA)O)y, (CH(CH3)CH2O) Z and their combinations and

[0030] - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 150 and the sum x+y+z is between 10 and 150;

[0031] • a crosslinking compound M6 or a compound M6 comprising at least two olefinic unsaturations; preferably in an amount of less than 5% by weight, also preferably from 0.01% by weight to 4% by weight, in particular from 0.02% by weight to 4% by weight or from 0.02% by weight to 2% by weight, in particular from 0.02% by weight to 1% by weight, of compound M6 relative to the total amount by weight of monomers.

[0032] According to the invention, the water-soluble polycarboxylic polymer may not be crosslinked. It is then prepared in the absence of compound (b6). Preferably, the water-soluble polycarboxylic polymer prepared according to the invention is not in the form of an emulsion.

[0033] The preparation method according to the invention makes it possible to obtain a polymer P whose weight-average molecular mass Mw and polymolecularity index Ip can be well controlled in ranges which can vary quite widely, in particular depending on the reaction conditions chosen. Thus, according to the invention, the polymer P has a molecular mass Mw, measured by CES, ranging from 1,000 g / mol to 1,200,000 g / mol. Preferably, the molecular mass Mw of the polymer P ranges from 1,000 g / mol to 1,000,000 g / mol or from 2,000 g / mol to 1,200,000 g / mol; preferably from 1,000 g / mol to 800,000 g / mol or from 2,000 g / mol to 800,000 g / mol; more preferably from 1,000 g / mol to 500,000 g / mol or from 2,000 g / mol to 500,000 g / mol.

[0034] According to the invention, the polymer P has a polymolecularity index Ip, measured by CES, of less than 4 or ranging from 1.2 to 40 or from 1.5 to 40. Preferably, the polymolecularity index Ip of the polymer P ranges from 1.2 to 35 or from 1.5 to 30; preferably from 1.2 to 25 or even from 1.5 to 20. Also preferably, the polymolecularity index Ip of the polymer P, having a molecular mass Mw measured by CES, of less than 100,000 g / mol, is less than 8 or less than 6; preferably ranges from 1.2 to 4 or from 1.5 to 4; preferably from 1.2 to 3.5 or even from 1.5 to 3.5; more preferably from 1.2 to 2.5 or even from 1.5 to 2.5.

[0035] According to the invention, the molecular weight or mass of the polymer P up to 100,000 g / mol and its polymolecularity index Ip are determined by Size Exclusion Chromatography (SEC). A test portion of the polymer dispersion corresponding to 90 mg of dry matter is introduced into a 10 mL flask. Mobile phase, containing 0.04% dimethylformamide (DMF), is added up to a total mass of 10 g. The composition of this mobile phase is as follows: NaHCOs: 0.05 mol / L, NaNOs: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaNs: 0.03% by mass.The CES chain is composed of a "Waters" 510 isocratic pump, whose flow rate is set at 0.8 mL / min, a "Waters" 717+ sample changer, an oven containing a "Guard Column Ultrahydrogel Waters" precolumn of 6 cm length and 40 mm inner diameter, followed by a linear column of "Ultrahydrogel Waters" of 30 cm length and 7.8 mm inner diameter. Detection is ensured by means of a differential refractometer of "RI Waters" 410 type. The oven is brought to the temperature of 60 ° C and the refractometer is brought to the temperature of 45 ° C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by "Polymer Standard Service" with peak molecular weights between 900 and 2,250,000 g / mol and polydispersity index between 1.4 and 1.7.The calibration curve is linear and takes into account the correction obtained using the flow marker: dimethylformamide (DMF). The acquisition and processing of the chromatogram are carried out using the software “PSS WinGPC Scientific” v 4.02. The chromatogram obtained is integrated into the area corresponding to molecular weights greater than 250 g / mol.

[0036] According to the invention, the molecular weight or mass of the polymer P above 100,000 g / mol and its polymolecularity index Ip are determined by Size Exclusion Chromatography (SEC). A test portion of the polymer solution corresponding to 20 mg of dry matter is introduced into a 10 mL flask. Mobile phase, containing 0.04% dimethylformamide (DMF), is added up to a total mass of 10 g. The composition of this mobile phase is as follows: NaHCOv 0.05 mol / L, NaNOv 0.1 mol / L, triethanolamine: 0.02 mol / L, NaNs 0.03% by mass. The CES chain consists of a “Waters” 510 isocratic pump, with a flow rate set at 1 mL / min, a “Waters” 717+ autosampler, an oven containing a “PSS Suprema” guard column of 5 cm length and 8 mm inner diameter, followed by a “PSS Suprema” 30,000 Å column of 30 cm length and 8 mm inner diameter.Detection is ensured by means of a differential refractometer type "RI Waters" 410. The oven is brought to the temperature of 60°C and the refractometer is brought to the temperature of 45°C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by "Polymer Standards Service" with a molecular weight at the peak between 1,200 g / mol and 1,390,000 g / mol and a polydispersity index Ip between 1.09 and 2. The calibration curve is of the linear type and takes into account the correction obtained thanks to the flow marker: dimethylformamide (DMF). The acquisition and processing of the chromatogram are carried out using the software "ConSenxus hs NTeqGPC" V 5.1.5. The chromatogram obtained is integrated in the zone corresponding to molecular weights greater than 180 g / mol. The invention provides a particularly effective method for the preparation of a composition C comprising a water-soluble polymer P.Composition C constitutes another aspect of the invention. Thus, the invention also provides a composition C prepared according to the preparation method according to the invention.

[0037] Preferably, composition C according to the invention comprises an amount of residual monomer, measured by high performance liquid chromatography (HPLC), which is less than 5% by weight, preferably less than 1% by weight, relative to the amount by weight of monomers.

[0038] More preferably according to the invention, composition C comprises a quantity of sulfur-containing polymer or phosphorus-containing polymer or residual monomer which is zero.

[0039] Composition C according to the invention has properties which are particularly useful in many technical fields, in particular for the treatment of mineral or organic materials. The invention then provides an aqueous grinding aid or anti-scale or dispersing agent comprising at least one composition C according to the invention.

[0040] Preferably according to the invention, the composition C according to the invention can be used for the treatment of a mineral or organic material, synthetic or of natural origin. Thus, the invention provides a method for treating a mineral or organic material, synthetic or of natural origin, comprising bringing this material into contact with at least one composition C according to the invention.

[0041] Preferably for the treatment method according to the invention, the material is chosen from alkaline earth metal carbonate, more preferably calcium carbonate (natural calcium carbonate or precipitated calcium carbonate), strontium carbonate, magnesium carbonate, barium carbonate, dolomite, kaolin, titanium dioxide, talc, lime, calcium sulfate, barium sulfate, magnesium carbonate, magnesium silicate, calcium silicate, calcium phosphate, hydraulic binder, carbon particles, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene, hardened carbon, graphite carbon fibers, graphite carbon particles, metal fibers, metal particles, silicon particles, an electroactive material, for example an electroactive material chosen from lithium, iron, nickel, manganese, cobalt and combinations thereof, preferably chosen from iron, nickel, manganese,cobalt and their combinations, preferably chosen from LiFePCU (LFP), Li(Ni,Mn,Co)O2(NMC).,

[0042] The advantageous, particular or preferred characteristics of the method of preparation of the composition C or of the polymer P according to the invention define compositions C according to the invention and aqueous agents as well as treatment methods which are also advantageous, particular or preferred.

[0043] EXAMPLES

[0044] The following examples provide an illustration of the various aspects of the invention. IP era according to the invention

[0045] In a 1 L glass reactor, introduce 200 g of acrylic acid, add 20 g of ammonium persulfate and 1000 g of bipermuted water. Then, introduce a “Hielscher Ultrasonics” UP200St / Sonotrode S26dl4 ultrasonic probe into the reactor maintained at room temperature, adjust the probe frequency (26 kHz) and its power (40 W). After 1 hour of continuous irradiation, stop the reaction to obtain the PI polymer according to the invention at 17% by weight of dry extract, the characteristics of which are presented in Table 1.

[0046] Preparation of a polymer P2 according to the invention

[0047] In a 1 L glass reactor, introduce 200 g of acrylic acid, add 10 g of ammonium persulfate and 1000 g of bipermuted water. Then, introduce a “Hielscher Ultrasonics” UP200St / Sonotrode S26dl4 ultrasonic probe into the reactor maintained at room temperature, adjust the frequency of the probe (26 kHz) and its power (40 W). After 1 hour of continuous irradiation, stop the reaction to obtain the polymer P2 according to the invention at 16.8% by weight of dry extract whose characteristics are presented in Table 1.

[0048] Preparation of a polymer P3 according to the invention

[0049] In a 1 L glass reactor, introduce 200 g of acrylic acid, add 1000 g of bipermuted water. Then, introduce a “Hielscher Ultrasonics” UP200St / Sonotrode S26dl4 ultrasonic probe into the reactor maintained at room temperature, adjust the frequency of the probe (26 kHz) and its power (40 W). After 1 hour of continuous irradiation, stop the reaction to obtain the polymer P3 according to the invention at 16.7% by weight of dry extract whose characteristics are presented in Table 1.

[0050] Preparation of a polymer P4 according to the invention

[0051] In a 1 L glass reactor, introduce 200 g of acrylic acid, add 0.2 g of iron sulfate heptahydrate, 0.5 g of copper sulfate pentahydrate, 28 g of hydrogen peroxide in aqueous solution at 35% by mass and 1000 g of bipermuted water. Then, introduce a “Hielscher Ultrasonics” UP200St / Sonotrode S26dl4 ultrasonic probe into the reactor maintained at room temperature, adjust the frequency of the probe (26 kHz) and its power (40 W). After 1 hour of continuous irradiation, stop the reaction to obtain the polymer P4 according to the invention at 16.7% by weight of dry extract whose characteristics are presented in Table 1.

[0052] Table 1

Claims

CLAIMS 1. Method for preparing a composition C comprising a water-soluble polymer P with a molecular mass Mw, measured by CES, ranging from 1,000 g / mol to 1,500,000 g / mol and prepared by a radical sonopolymerization reaction in an aqueous medium, at a frequency ranging from 20 kHz to 5 MHz, of at least one anionic compound Ml comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts.

2. Method according to claim 1 for which the compound Ml is chosen from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid, an oligomer of acrylic acid, an oligomer of methacrylic acid, a salt of an oligomer of acrylic acid, a salt of an oligomer of methacrylic acid and combinations thereof; preferentially chosen from acrylic acid, a salt of acrylic acid, an oligomer of acrylic acid, a salt of an oligomer of acrylic acid and combinations thereof; more preferentially acrylic acid.

3. Method according to one of claims 1 or 2 for which: - the sonopolymerization reaction is carried out under irradiation at an intensity ranging from 5 W / cm 2 at 500 W / cm 2 ; preferably ranging from 5 W / cm 2 at 200 W / cm 2 or 10 W / cm 2 at 150 W / cm 2 ; Or - the sonopolymerization reaction is carried out under irradiation at a power ranging from 10 W to 50,000 W; more preferably ranging from 20 W to 20,000 W or from 30 W to 15,000 W; or - the sonopolymerization reaction is carried out under irradiation by means of one or more generators having a power ranging from 200 W to 50,000 W, preferably ranging from 500 W to 20,000 W or from 1,000 W to 15,000 W; or - the sonopolymerization reaction is carried out at a temperature below 100°C; preferably at a temperature ranging from 20°C to 95°C; or - the sonopolymerization reaction is carried out in water, alone or combined with at least one polar, protic solvent, preferably an alcohol, more preferably isopropanol; or - the concentration of monomers, preferably monomer M1, during the sonopolymerization reaction is greater than 5% by weight, preferably greater than 10% by weight, relative to the total quantity of the reaction medium; or - the concentration of monomers, preferably monomer Ml, during the sonopolymerization reaction is less than 25% by weight, preferably less than 20% by weight or less than 15% by weight, more preferably less than 13% by weight, relative to the total quantity of the reaction medium.

4. Method according to one of claims 1 to 3 for which: - the sonopolymerization reaction is carried out in the presence of at least one initiator compound; preferably an initiator compound used in a concentration ranging from 0.1% by weight to 10% by weight, preferably from 0.5% by weight to 8% by weight or from 1% by weight to 6% by weight, relative to the quantity by weight of monomers; also preferably an initiator compound chosen from 4,4'-azobis-4-cyanopentanoic acid (ACP A), hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, an alkali metal persulfate (in particular sodium persulfate, potassium persulfate, ammonium persulfate), an azo compound and their respective combinations or associations with an ion chosen from Fe 11 , Fe 111 , Cu 1 , Cu 11 ; Or - the sonopolymerization reaction is carried out in the presence of at least one chain transfer agent; preferably a chain transfer agent used in a concentration ranging from 0.1% by weight to 10% by weight, preferably from 0.5% by weight to 8% by weight or from 1% by weight to 6% by weight, relative to the quantity by weight of monomers; also preferably a chain transfer agent chosen from a compound comprising P 1 , a compound comprising P 111 , a compound comprising S IV ; preferably a chain transfer agent chosen from a compound comprising phosphite, a compound comprising hypophosphite, a compound comprising hydrogen sulfite; more preferably a chain transfer agent chosen from phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, sodium hydrogen sulfite.

5. Method according to one of claims 1 to 4 for which: - the sonopolymerization reaction is carried out in the absence of an initiator compound; preferably in the absence of a compound chosen from 4,4'-azobis-4-cyanopentanoic acid (ACP A), hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, an alkali metal persulfate (especially sodium persulfate, potassium persulfate, ammonium persulfate), an azo compound and their respective combinations or associations with an ion selected from Fe 11 , Fe 111 , Cu 1 , Cu 11 ; Or - the sonopolymerization reaction is carried out in the absence of a chain transfer agent; preferably in the absence of a compound comprising P 1 , of compound comprising P 111 , of compound comprising S IV; preferably in the absence of a compound comprising phosphite, a compound comprising hypophosphite, a compound comprising hydrogen sulfite; more preferably in the absence of phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, sodium hydrogen sulfite.

6. Method according to one of claims 1 to 5 for which the polymerization reaction also uses at least one other compound chosen from: • another anionic compound M2 different from M1, preferably a compound M2 chosen from itaconic acid, maleic acid, maleic anhydride and their combinations; • a sulfur compound M3, preferably a compound M3 chosen from 2-acrylamido-2-methylpropane sulfonic acid, a salt of 2-acrylamido-2-methylpropane sulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, a salt of 2-(methacryloyloxy)ethanesulfonic acid, sodium methallyl sulfonate, sodium vinyl sulfonate, styrene sulfonate and combinations thereof; • a non-ionic compound M4 comprising at least one polymerizable olefinic unsaturation, preferably at least one polymerizable ethylenic unsaturation and in particular a polymerizable vinyl function, more preferably a non-ionic compound M4 chosen from styrene, vinylcaprolactam, esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid chosen from acrylic acid, methacrylic acid, and combinations thereof, for example hydroxyethylacrylate, hydroxypropylacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, alkyl acrylate, in particular C1-C10-alkyl acrylate, preferably C1-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, w-propyl acrylate, isopropyl acrylate, isobutyl acrylate, / / -butyl acrylate, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, / / -propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, / / -butyl methacrylate, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxyethylacrylate, aryl methacrylate, preferably phenylmethacrylate, benzylmethacrylate, phenoxyethylmethacrylate; • a compound M5 of formula I: in which: - R 1 and R 2 , identical or different, independently represent H or CH3, - L 1 independently represents a group chosen from C(O), CH2, CH2- CH2 and O-CH2-CH2-CH2-CH2, - L 2 independently represents a group chosen from (CH2-CH2O) X, (CH2CH(CHA)0)y, (CH(CH3)CH2O) Z and their combinations and - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 150 and the sum x+y+z is between 10 and 150; • a crosslinking compound M6 or a compound M6 comprising at least two olefinic unsaturations; preferably in an amount of less than 5% by weight, also preferably from 0.01% by weight to 4% by weight, in particular from 0.02% by weight to 4% by weight or from 0.02% by weight to 2% by weight, in particular from 0.02% by weight to 1% by weight, of compound M6 relative to the total amount by weight of monomers.

7. Method according to one of claims 1 to 6 for which: - the polymer P has a molecular mass Mw, measured by CES, ranging from 1,000 g / mol to 1,200,000 g / mol; preferably from 1,000 g / mol to 1,000,000 g / mol or from 2,000 g / mol to 1,200,000 g / mol; more preferably from 1,000 g / mol to 800,000 g / mol or 2,000 g / mol to 800,000 g / mol; more preferably 1,000 g / mol to 500,000 g / mol or 2,000 g / mol to 500,000 g / mol; or - the polymer P has a polymolecularity index Ip, measured by CES, of less than 4 or ranging from 1.2 to 40 or from 1.5 to 40; preferably from 1.2 to 35 or from 1.5 to 30; preferably from 1.2 to 25 or even from 1.5 to 20.

8. Composition C prepared according to the method according to one of claims 1 to 7.

9. Composition C according to claim 8 comprising an amount, measured by high performance liquid chromatography (HPLC), of sulfur-containing polymer or phosphorus-containing polymer or residual monomer which is zero or comprising an amount of residual monomer which is less than 5% by weight, preferably less than 1% by weight, relative to the amount by weight of monomers.

10. Aqueous grinding aid or anti-scale or dispersant agent, in particular for the treatment of a mineral or organic material, synthetic or of natural origin, comprising at least one composition C according to one of claims 8 or 9.

11. Method for treating a mineral or organic material, synthetic or of natural origin, comprising bringing this material into contact with at least one composition C according to one of claims 8 or 9.

12. Method according to claim 11 for which the material is chosen from alkaline earth metal carbonate, more preferably calcium carbonate (natural calcium carbonate or precipitated calcium carbonate), strontium carbonate, magnesium carbonate, barium carbonate, dolomite, kaolin, titanium dioxide, talc, lime, calcium sulfate, barium sulfate, magnesium carbonate, magnesium silicate, calcium silicate, calcium phosphate, hydraulic binder, carbon particles, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene, hardened carbon, graphite carbon fibers, graphite carbon particles, metal fibers, metal particles, silicon particles, an electroactive material, for example an electroactive material chosen from lithium, iron, nickel, manganese, cobalt and combinations thereof, preferably chosen from iron, nickel, manganese,cobalt and their combinations, preferably chosen from LiFePCU (LFP), Li(Ni,Mn,Co)O2(NMC).,

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