Composition for water treatment

Abstract

Composition for water treatment. The present invention relates to a composition, a process for obtaining said composition, and the use of said composition, in particular as a coagulant in water treatment. (no figures)

Description

Title of the invention: Composition for water treatment Technical field of the invention

[0001] The present invention relates to a composition, a method for obtaining said composition and the use of said composition, in particular as a coagulant in water treatment. Prior state of the art

[0002] Water stress is a growing problem worldwide. It results from the increasing demand for water from human, industrial, and agricultural needs, combined with limited water availability, particularly in certain regions of the world. The preservation and sustainable management of water are therefore crucial ecological imperatives for the future of humankind. Faced with this situation, wastewater recycling and treatment are becoming essential to meet growing water needs while preserving available resources. It is estimated that approximately 359 billion cubic meters of wastewater are produced globally each year, equivalent to 144 million Olympic-sized swimming pools.

[0003] A key step in the wastewater treatment process is the separation of solid particles, sometimes microscopic, suspended in the water. To enable this separation, it is necessary to artificially increase the size of these particles, in order to form flocs large enough to be easily separated from the water, and at the same time to increase the cohesive strength of these particle flocs so that they do not redisperse.

[0004] To facilitate this separation, it is common practice to treat this wastewater using coagulants and flocculants, which can be inorganic or organic. These compounds most often consist of charged polymers that interact with the solid particles and allow them to clump together into flocs.

[0005] Inorganic coagulants have the advantage of high resilience to overdosing, but require high dosages, which leads to an increase in the amount of sludge generated. Furthermore, their production process poses environmental problems and risks to operator safety. Indeed, they are obtained from metals, primarily aluminum or iron, which, in addition to being limited resources, require energy-intensive extraction processes involving the use of hazardous chemicals.

[0006] Organic coagulants, on the other hand, exhibit low resilience to overdosing but require much lower dosages. They can be synthetic, i.e., derived from petrochemicals, or natural, i.e., derived from biomass. Synthetic coagulants offer better application performance. While natural coagulants have the advantage of being bio-based and biodegradable, they possess few or no coagulating properties. They therefore require functionalization to improve their effectiveness, which consequently reduces their biodegradability.

[0007] This is why so-called hybrid coagulants, that is, those comprising a synthetic component and a component of natural origin, have been developed in recent years in an attempt to obtain products offering the advantages of both families. However, these coagulants have limited application performance, particularly in wastewater treatment.

[0008] Indeed, one of the main problems lies in the fluctuating composition of wastewater. Wastewater originates from a multitude of sources and is generally collected and treated in the same location. Variations in pH, temperature, or chemical composition make it difficult to maintain optimal dosage. Thus, depending on the wastewater source, the time of day, climatic conditions, or the season, the composition of this water varies, and consequently impacts the performance of the coagulants used to treat it, particularly in the case of hybrid coagulants. These fluctuations necessitate continuous monitoring and adjustment of the coagulant dosage to guarantee the effectiveness of wastewater treatment.

[0009] The Applicant has discovered a new composition comprising a combination of a water-soluble polymer, preferably a coagulant, and a saccharide having a specific degree of polymerization. This combination offers increased efficiency at low dosages and greater resilience to variations in treatment conditions, particularly with regard to overdosing, thus reducing the quantities of polymers used and the amount of sludge generated. Furthermore, the composition according to the invention has the advantage of being stable over time, especially compared to compositions comprising a hybrid polymer, which ensures better efficiency after prolonged storage while limiting waste related to its degradation during excessively long storage.

[0010] The invention is based on a principle of environmental awareness and an understanding of the impact of industry and humankind on the planet. Indeed, the composition according to the invention allows for greater adaptability to changes in the nature and composition of wastewater. The composition is at least partially, preferably entirely, bio-based, resulting in a lower environmental impact than purely synthetic polymers and also exhibiting greater long-term stability than natural or hybrid polymers, thus limiting the loss of efficiency associated with storage and the need for overdosing caused by this loss of efficiency. The reduced quantity of sludge generated decreases the overall amount of greenhouse gases, such as CO2, produced during incineration. Furthermore, this sludge contains less aluminum or iron salts, thus reducing non-recoverable and environmentally damaging residues.

[0011] Furthermore, in the present invention, the monomer(s) used to prepare the water-soluble polymer are advantageously of biological origin, for example, extracted from renewable raw material(s) such as biomass, preferably second-generation biomass, or recycled; or derived from biological synthesis, for example, enzymatic catalysis. The energy used to carry out the polymerization process according to the invention is advantageously derived from a heat pump, a waste heat network, or from renewable sources, for example, wind, photovoltaic, fuel cells, lithium batteries, or nuclear power. Description of the invention

[0012] The present invention relates to a composition C2 comprising: (i) at least one water-soluble polymer PI, representing between 30 and 95% by weight relative to the dry matter of composition C2; ii) at least one saccharide having a degree of polymerization between 1 and 5, representing between 5 and 70% by weight relative to the dry matter of composition C2.

[0013] The present invention also relates to a method for preparing composition C2 comprising at least the following steps: a) Polymerization of at least one hydrophilic monomer, optionally in the presence of saccharide SA1, to obtain a composition Cl comprising a water-soluble polymer PI and optionally at least one saccharide SA1, b) Addition of at least one SA2 saccharide to composition Cl in order to obtain a composition C2, said addition being optional if at least one SA1 saccharide is present during step a) the saccharide SA1 and the saccharide SA2 having, independently of each other, a degree of polymerization between 1 and 5, the total quantity of saccharides (SA1 + SA2) representing between 5 and 70% by weight relative to the dry matter of composition C2; the amount of water-soluble polymer PI representing between 30 and 95% by weight relative to the dry matter of composition C2.

[0014] The invention also relates to a water treatment process comprising bringing solid particles into contact with composition C2.

[0015] The present invention also relates to the use of composition C2 in: hydrocarbon recovery (oil or gas); well drilling; the well cementing#; hydrocarbon (oil or gas) well stimulation such as hydraulic fracturing, conformance and diversion#; construction#; paper or cardboard manufacturing#; battery industry#; wood processing#; construction#; mining industry#; cosmetic formulation#; detergent formulation#; textile manufacturing#; geothermal energy#; sanitary diaper manufacturing#; or agriculture. Description of the invention

[0016] The term "polymer" refers to a homopolymer or a copolymer. A homopolymer is a polymer composed of a single identical repeating unit, and a copolymer is composed of at least two repeating units. The repeating unit(s) are selected from anionic hydrophilic monomers, cationic hydrophilic monomers, nonionic hydrophilic monomers, zwitterionic hydrophilic monomers, hydrophobic monomers, and mixtures thereof.

[0017] The expression hydrophilic monomer is used for the hydrophilic monomer as such, as well as for the monomeric unit present in the water-soluble polymer.

[0018] The term “saccharide” means monosaccharides, modified monosaccharides, oligosaccharides and modified oligosaccharides.

[0019] “Modified monosaccharides and modified oligosaccharides” means a monosaccharide or oligosaccharide that has undergone one or more chemical or enzymatic treatments. Examples of chemical and enzymatic treatments include: - cationization, for example by reaction with 3-chloro-2-hydroxypropyltrimethylammonium chloride or 2,3-epoxypropyltrimethylammonium chloride, or by Michael reaction with an acidified or quaternized dialkylaminoalkyl(meth)acrylamide salt, such as methacrylamidopropyl trimethylammonium chloride (MAPTAC) or acrylamidopropyl trimethylammonium chloride (APTAC), or an acidified or quaternized dialkylaminoalkyl(meth)acrylate salt, such as dimethylaminoethyl acrylate (ADAME) or dimethylaminoethyl methacrylate (MADAME) or enzymatic; - oxidation (chemical or enzymatic) to form an aldehyde function.

[0020] Not "degree of polymerization," but rather the number of sugar units present in the saccharide. A degree of polymerization of 1 corresponds to a simple sugar such as glucose, while a saccharide with a degree of polymerization of 2 corresponds to a chain of 2 sugar units, such as 2 units of glucose or fructose, for example. The monosaccharides included in the composition according to the invention have a degree of polymerization of 1, and the oligosaccharides and modified oligosaccharides included in the composition according to the invention have a degree of polymerization between 2 and 5.

[0021] By "hydrophilic monomer" is meant a monomer which has an octanol / water partition coefficient, log (Kow), less than or equal to 1. This coefficient is determined at 25 °C in an octanol / water mixture having a volume ratio of 1 / 1, at a pH between 6 and 8.

[0022] By "hydrophobic monomer" is meant a monomer which has an octanol / water partition coefficient, log (Kow), greater than 1. This coefficient is determined at 25 °C in an octanol / water mixture having a volume ratio of 1 / 1, at a pH between 6 and 8.

[0023] The octanol / water partition coefficient represents the ratio of the concentrations (g / L) of a monomer between the octanol phase and the aqueous phase. It is defined as follows:

[0024] [Math.l] [monomer], irr __ L yxtanol Row ~ \monomer]water

[0025] By "water-soluble polymer" is meant a polymer which gives an aqueous solution without insoluble particles when dissolved under stirring at 25°C and with a concentration of 10 g.l1 in deionized water.

[0026] According to the invention, "X and / or Y" means "X", or "Y", or "X and Y".

[0027] Also part of the invention are all possible combinations between the The disclosure includes various embodiments, whether preferred or given by way of example. Furthermore, when ranges of values ​​are specified, the bounds are included within those ranges. The disclosure also encompasses all combinations of the bounds within those ranges. For example, the value ranges "1-20, preferably 5-15" imply the disclosure of the ranges "1-5", "1-15", "5-20", and "15-20", as well as the values ​​1, 5, 15, and 20.

[0028] All the particular and / or preferred modes described in the invention can be combined provided that they are not incompatible. Composition C2

[0029] Composition C2 comprises: (i) at least one water-soluble polymer PI, representing between 30 and 95% by weight relative to the dry matter of composition C2; ii) at least one saccharide having a degree of polymerization between 1 and 5, representing between 5 and 70% by weight relative to the dry matter of composition C2.

[0030] The water-soluble polymer PI preferably represents between 40 and 90% by weight relative to the dry matter of composition C2, more preferably between 45 and 85% by weight, and more preferably 55 and 85% by weight.

[0031] The water-soluble polymer PI is obtained by polymerization of at least one hydrophilic monomer selected from cationic hydrophilic monomers, non-ionic hydrophilic monomers, anionic hydrophilic monomers, zwitterionic hydrophilic monomers and mixtures thereof.

[0032] In a preferred mode, the water-soluble polymer PI comprises at least one cationic hydrophilic monomer.

[0033] The hydrophilic cationic monomer(s) used in the context of the invention are advantageously chosen from vinyl-type monomers, in particular acrylamide, acrylic, allylic, or maleic monomers having a protonable amine or ammonium function, advantageously a quaternary ammonium. Preferably, the cationic hydrophilic monomer(s) are chosen from: diallyldialkyl ammonium salts such as dimethyldiallylammonium chloride (DADMAC); acidified or quaternized dialkyl-aminoalkyl(meth)acrylamide salts, such as (3-methacrylamidopropyl)trimethylammonium chloride (MAPTAC) or (3-acrylamidopropyl)trimethylammonium chloride (APTAC); acidified or quaternized dialkyl-aminoalkyl acrylate salts such as quaternized or salified dimethylaminoethyl acrylate (ADAME); acidified or quaternized salts of dialkyl aminoalkyl methacrylate such as quaternized or salified dimethylaminoethyl methacrylate (MADAME);Acidified or quaternized salts of N,N-dimethylallylamin; acidified or quaternized salts of diallylmethylamine; acidified or quaternized salts of diallylamine; acidified or quaternized salts of vinylamine obtained by the (basic or acidic) hydrolysis of an amide group -N(R2)-CO-R', where R1 and R2 are, independently, a hydrogen atom or an alkyl chain of 1 to 6 carbons, for example, acidified or quaternized salts of vinylamine from the hydrolysis of vinylformamide; acidified or quaternized salts of vinylamine obtained by Hofmann degradation; and mixtures thereof. Advantageously, the alkyl groups are in the C1-C5 configuration, preferably C1-C3, and may be linear, cyclic, saturated, or unsaturated chains. Preferably, it is dimethyldialylammonium chloride.

[0034] A person skilled in the art will know how to prepare the quaternized monomers, for example by means of quaternizing agent of type RX, R being an alkyl group and X being a halogen or a sulfate.

[0035] By “quaternizing agent” is meant a molecule capable of alkylating a tertiary amine.

[0036] The quaternizing agent can be chosen from dialkyl sulfates comprising 1 to 6 carbon atoms or alkyl halides comprising 1 to 6 carbon atoms. Preferably, the quaternizing agent is chosen from chloride methyl, benzyl chloride, dimethyl sulfate, or diethyl sulfate. Furthermore, the present invention also covers DADMAC, APTAC, and MAPTAC type monomers in which the counterion is a sulfate, fluoride, bromide, or iodide instead of chloride.

[0037] The cationic hydrophilic monomer advantageously represents at least 50 mol% of the water-soluble polymer PI, preferably at least 60 mol%, more preferably at least 70 mol%, more preferably at least 80 mol%, more preferably at least 90 mol%.

[0038] In a preferred mode, the cationic hydrophilic monomer represents 100 mol% of the water-soluble polymer PI.

[0039] Advantageously, the non-ionic hydrophilic monomer(s) used in the context of the invention are selected from acrylamide, methacrylamide, N-alkylacrylamides, N-alkylmethacrylamides, N,N-dialkyl acrylamides (for example, 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 chloride, and acryloyl morpholine. (ACMO), glycidyl methacrylate, vinyl acetate, glyceryl methacrylate, diacetone acrylamide, methacrylic anhydride, acrylonitrile, maleic anhydride, itaconic anhydride, itaconamide, hydroxyalkyl (meth)acrylate, thioalkyl (meth)acrylate, isoprenol and its alkoxylated derivatives,Hydroxyethyl(meth)acrylates and their alkoxylated derivatives, hydroxypropyl(meth)acrylate and its alkoxylated derivatives, and mixtures thereof. Among these nonionic monomers, the alkyl groups are advantageously C1-C5, more advantageously C1-C3. The C3-C5 alkyl groups are advantageously branched. Preferably, the hydrophilic nonionic monomer is acrylamide.

[0040] The non-ionic hydrophilic monomer advantageously represents less than 50 mol% of the water-soluble polymer PI, preferably less than 40 mol%, more preferably less than 30 mol%, more preferably less than 20 mol%, more preferably less than 10 mol%.

[0041] In a preferred mode, the water-soluble polymer PI is devoid of non-ionic hydrophilic monomer.

[0042] The hydrophilic anionic monomer(s) used in the context of the invention are advantageously chosen from monomers having a vinyl function, in particular acrylic, maleic, sulfonic, fumaric, malonic, itaconic, or allylic. They may also contain a carboxylate, phosphonate, phosphate, sulfonate, sulfate, or other anionically charged group. Preferably the hydrophilic monomer(s) are chosen from: acrylic acid; methacrylic acid; dimethylacrylic acid; crotonic acid; maleic acid; fumaric acid; 3-acrylamido 3-methylbutanoic acid; strong acid type monomers having for example a sulfonic acid or phosphonic acid type function such as vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, 2-methylidenepropane-1,3-disulfonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allylphosphonic acid, ethylene glycol methacrylate phosphate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS), 2-acrylamido-2-methylpropane disulfonic acid, 3-allyloxy-2-hydroxypropane sulfonic acid, diethylallylphosphonate, carboxyethyl acrylate;water-soluble salts of these monomers such as their alkali metal, alkaline earth metal, or ammonium salts; and mixtures thereof. Preferably, the hydrophilic anionic monomer is acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid (ATBS).

[0043] The anionic hydrophilic monomer advantageously represents less than 50 mol% of the water-soluble polymer PI, preferably less than 40 mol%, more preferably less than 30 mol%, more preferably less than 20 mol%, more preferably less than 10 mol%.

[0044] In a preferred mode, the water-soluble polymer PI is devoid of anionic hydrophilic monomer.

[0045] In a particular mode, when the anionic hydrophilic monomer is 2-acrylamido-2-methylpropanesulfonic acid (ATBS), it is in its hydrated form. The hydrated form of ATBS is a particular form of ATBS that can be obtained by controlled crystallization of the ATBS monomer. US Patent 10,759,746 describes this hydrated form of ATBS.

[0046] In a particular mode, the anionic monomer(s) may be salified. It may also be a mixture of acidic and salified forms, for example a mixture of acrylic acid and acrylate.

[0047] By "salified," we mean the substitution of a proton of at least one acidic function of the type -Ra(=O)-OH (with Ra representing P, S, or C) of the anionic monomer by a metal or organic cation in order to form a salt of the type -Ra(=O)-OA (A being a metal or organic cation). In other words, the unsalified form corresponds to the acidic form of the monomer, for example Rb-C(=O)-OH in the case of the carboxylic acid function, while the salified form of the monomer corresponds to the form Rb-C(=0)-0 A+, where A+ corresponds to a metallic or organic cation. Salification of acidic groups can be partial or total.

[0048] The metal cation is advantageously an alkali metal cation (Li, Na, K...) or an alkaline earth metal cation (Ca, Mg...), and the organic cation is advantageously the ammonium ion or a tertiary ammonium compound. Preferred salts are sodium salts.

[0049] Salification can take place before or after polymerization.

[0050] The hydrophilic zwitterionic monomer(s) used in the context of the invention are chosen from derivatives of a vinyl type motif (advantageously acrylamide, acrylic, allyl or maleic), this monomer having a quaternary amine or ammonium function and an acid function of the carboxylic (or carboxylate), sulfonic (or sulfonate) or phosphoric (or phosphate) type.

[0051] Preferably, the hydrophilic zwitterionic monomer comprises a quaternary amine or ammonium function and an acid function of the carboxylic (or carboxylate), sulfonic (or sulfonate) type or phosphoric (or phosphate).

[0052] Advantageously, the hydrophilic zwitterionic monomer(s) are selected from: dimethylaminoethyl acrylate derivatives, such as 2-((2-9(acryloyloxy)ethyl)dimethylammonio)ethane-1-sulfonate, may be mentioned in particular and in a non-limiting manner, 3-((2-(acryloyloxy)ethyl)dimethylammonio)propane-1-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-1-sulfonate, 3-((2-(methacryloyloxy)ethyl) dimethylammonio) propane-1-sulfonate, 4-((2-(methacryloyloxy)ethyl) dimethylammonio) butane-1-sulfonate, [2-(methacryloyloxy)ethyl](dimethylammonio) acetate, propylacrylamide dimethylamino derivatives such as 2-((3-acrylamidopropyl) dimethylammonio) ethane-1-sulfonate,3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate, 4-((3-acrylamidopropyl)dimethylammonio)butane-1-sulfonate, [3-(acryloyl)oxy)propyl](dimethylammonio)acetate, dimethylaminopropyl methylacrylamide, or derivatives such as 2-((3-methacrylamidopropyl)dimethylammonio)ethane-1-sulfonate, 3-((3-me dimethylammonio)propane-1-sulfonate, 4-((3-methacrylamidopropyl)dimethylammonio)butane-1-sulfonate and propyl [3-(methacryloyloxy)](dimethylammonio)acetate and mixtures thereof.

[0053] Other hydrophilic zwitterionic monomers are described by the Applicant in document WO2021 / 123599 AL

[0054] The water-soluble polymer PI may further comprise at least one hydrophobic monomer.

[0055] The hydrophobic monomer(s) are advantageously chosen from (meth)acrylic acid esters having a (i) C4-C30 alkyl chain, or (ii) arylalkyl (the alkyl being in C4-C30 and the aryl in C4-C30), or (iii) propoxylated, or (iv) ethoxylated, or (v) ethoxylated and propoxylated; alkyl aryl sulfonates (the alkyl being in C4-C30 and the aryl in C4-C30); mono-substituted (meth)acrylamide amides having a (i) C4-C30 alkyl chain, or (ii) arylalkyl (alkyl being C4-C30 and aryl being C4-C30), or (iii) propoxylated, or (iv) ethoxylated, or (v) ethoxylated and propoxylated; alkyl aryl sulfonates (alkyl being C4-C30 and aryl being C4-C30); di-substituted (meth)acrylamide amides having two chains selected from (i) C4-C30 alkyl, or (ii) arylalkyl (alkyl being C4-C30 and aryl being C4-C30), or (iii) propoxylated, or (iv) ethoxylated, or (v) ethoxylated and propoxylated;Anionic or cationic monomeric derivatives of (meth)acrylamide bearing a hydrophobic chain; anionic or cationic monomeric derivatives of (meth)acrylic acid bearing a hydrophobic chain; vinylpyridine; and mixtures thereof.

[0056] Among these hydrophobic monomers: - Alkyl groups are preferentially located at C4-C2O, and more preferentially at C4-C8. Alkyls at C6-C2O are preferentially linear alkyls, while alkyls at C4-C5 are preferentially branched. - arylalkyl groups are preferentially located at C7-C25, more preferentially at C7-C15, - ethoxylated chains advantageously comprise between 1 and 200 -CH2-CH2-O- groups, preferably between 6 and 100, more preferably between 10 and 40, - propoxylated chains advantageously comprise between 1 and 50 -CH2-(CH3)CH-O- groups, preferably between 1 and 20.

[0057] The preferred hydrophobic monomers are: - n-hexyl (meth)acrylate, n-octyl (meth)acrylate, octyl (meth)acrylamide, lauryl (meth)acrylate, lauryl (meth)acrylamide, myristyle (meth)acrylate, myristyle (meth)acrylamide, pentadecyl (meth)acrylate, pentadecyl (meth)acrylamide, cetyl (meth)acrylate, cetyl (meth)acrylamide, oleyl (meth)acrylate, oleyl (meth)acrylamide, erucyl (meth)acrylate, erucyl (meth)acrylamide, N-tert-butyl(meth)acrylamide, vinylpyridine, 2-ethylhexyl acrylate, C4-C22 itaconic acid hemi-esters, acidified or quaternized salts of C4-C22 dialkyl aminoalkyl (meth)acrylate, acidified or quaternized salts of C4-C22 dialkyl-aminoalkyl (meth)acrylamides, acrylamidoundecanoic acid, and mixtures thereof,

[0058] - cationic allyl derivatives of formula (I) or (II): [Chem.l] (H)

[0059]

[0060]

[0061] in which: R independently represents an alkyl chain containing 1 to 4 carbons; Ri represents an alkyl or arylalkyl chain comprising 7 to 30 carbons; X: - represents: - a halide chosen from: bromide, chloride, iodide, fluoride; or - an organic anion of the carboxylate type, for example an acetate, a citrate, a lactate or a formate; or - an inorganic anion, for example, a sulfate, a nitrate or a phosphate. - cationic derivatives of the (meth)acryloyl type corresponding to formula (III): [Chem.2]

[0062] (III) in which: * A represents O or N-R5 (preferably A represents N-R5), * R2, R3, R4, R5, R6, R? independently represent a hydrogen atom or an alkyl chain containing 1 to 4 carbons, * Q represents an alkyl chain comprising 1 to 20 carbons, * R8 represents an alkyl or arylalkyl chain comprising 7 to 30 carbons, * X represents: - a halide chosen from: bromide, chloride, iodide, fluoride; or - an organic anion of the carboxylate type, for example an acetate, a citrate, a lactate or a formate; or - an inorganic anion, for example, a sulfate, a nitrate or a phosphate.

[0063] The water-soluble polymer PI advantageously comprises less than 5 mol% of hydrophobic monomers and their quantity is adjusted so that the water-soluble polymer PI is soluble in water.

[0064] In a preferred mode, the water-soluble polymer PI is devoid of hydrophobic monomer.

[0065] The quantities of the different monomers will be adjusted by a person skilled in the art to represent 100% molar during the preparation of the water-soluble polymer PL

[0066] In a preferred mode, the water-soluble polymer PI comprises, preferably is made up of, at least one cationic hydrophilic monomer and at least one non-ionic hydrophilic monomer.

[0067] The water-soluble PI polymer can have a linear, branched, ramified, star-shaped or comb-shaped structure, preferably it is linear. This structure can be obtained, according to the general knowledge of a person skilled in the art, for example by selection of the initiator, the transfer agent, the polymerization technique such as reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP) or atom transfer radical polymerization (ATRP), the incorporation of structural monomers, or the concentration.

[0068] The water-soluble polymer PI can be structured by a branching agent. A structured polymer is defined as a non-linear polymer that has side chains.

[0069] The branching agent is advantageously chosen from: - structural agents, which may be chosen from the group comprising polyethylenic unsaturation compounds (having at least two unsaturated functions) and different from the monomers described previously, such as vinyl functions, in particular (meth)allylic, (meth)acrylamide or (meth)acrylic, and examples include: diacrylamide, di(meth)acrylate esters, tri(meth)acrylate esters such as ethoxylated trimethylol triacrylate (9-20 EO), tetra(meth)acrylate esters, ethylene glycol diacrylates, diacrylates polyethylene glycol, trimethylopropane trimethacrylates, ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, vinyl or allylic esters of di- or trifunctional acids, polyfunctional vinyl derivatives of a polyalcohol, methylene bisacrylamide (MBA), triallyamine, or tetraallylammonium chloride or 1,2-dihydroxyethylene bis-(N-acrylamide), - compounds having at least two epoxy groups, - compounds having at least one unsaturated group and one epoxy group, - macroinitiators such as polyperoxides, polyazo compounds, and polyols, - functionalized polysaccharides, - water-soluble metal complexes composed of: * of a metal with a valence greater than 3 such as, by way of example and without limitation, aluminium, boron, zirconium or titanium, and * of a ligand bearing a hydroxyl function.

[0070] Examples of diacrylate esters are polyethylene glycol diacrylate (PEG diacrylate): PEG diacrylate 200, PEG diacrylate 400, PEG diacrylate 600, PEG diacrylate 1000; ethylene glycol diacrylate; diethylene glycol diacrylate; treethylene glycol diacrylate; tetraethylene glycol diacrylate.

[0071] The amount of branching agent in the water-soluble polymer PI is advantageously between 0 and 10,000 ppm relative to the total weight of monomers of the water-soluble polymer PI, preferably between 0 and 5,000 ppm, more preferably between 0 and 2,500 ppm.

[0072] In a preferred mode, the water-soluble polymer PI is devoid of a branching agent.

[0073] When the water-soluble polymer PI comprises at least one branching agent, it remains soluble in water. A person skilled in the art will know how to adjust the amount of branching agent, and possibly the amount of transfer agent, to achieve this result.

[0074] In a particular mode, the water-soluble polymer PI can be prepared in the presence of a transfer agent.

[0075] 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 glycol; thioglycerol; thioglycolic acid; thiohydracrylic acid; thiolactic acid; thiomalic acid; cysteine; aminoethanethiol; thioglycolates; allyl phosphites; allyl mercaptans; sodium methallysulfonate; methallysulfonate calcium; magnesium methallysulfonate; potassium methallysulfonate; ammonium methallysulfonate; polythiols and mixtures thereof. Preferably, sodium hypophosphite or sodium formate.

[0076] In a particular mode, the transfer agent is a polytransfer agent, such as polymercaptans.

[0077] The amount of transfer agent in the water-soluble polymer PI is advantageously between 0 and 20,000 ppm relative to the total weight of monomers of the water-soluble polymer PI, preferably between 100 and 10,000 ppm, more preferably between 500 and 5,000 ppm.

[0078] The water-soluble polymer PI advantageously has a weight average molecular weight between 1,000 and 1,500,000 g / mol, preferably between 2,000 and 1,000,000 g / mol, more preferably between 20,000 and 700,000 g / mol.

[0079] The molecular weight can be determined by size exclusion chromatography using calibrated measuring standards of pullulan, poly(dimethyldiallylammonium chloride) or poly(acrylic acid).

[0080] As an example, it is possible to use an Agilent 1260 Infinity system with calibration by average molecular weight standards.

[0081] In a preferred mode, the various monomers, branching agents and transfer agents used in the context of the invention are of renewable and non-fossil origin.

[0082] In the context of the invention, the term "of renewable and non-fossil origin" refers to the origin of a chemical compound derived from biomass or syngas, that is, the result of one or more chemical transformations carried out on one or more raw materials of natural, non-fossil origin. The terms "bio-based" or "bio-resourced" may also be used to characterize the renewable and non-fossil origin of a chemical compound. The renewable and non-fossil origin of a compound includes renewable and non-fossil raw materials from the circular economy that have been previously recycled, one or more times, in a biomass-derived material recycling process, such as materials from polymer depolymerization or pyrolysis oil processing.

[0083] According to the invention, the quality of "at least partly of renewable and non-fossil origin" of a compound means a bio-sourced carbon content preferably between 5% by weight and 100% by weight relative to the total weight of carbon of said compound.

[0084] In the context of the invention, ASTM D6866-21, Method B is used to characterize the bio-based nature of a chemical compound and to determine the bio-based carbon content of said compound. The value is expressed as a percentage by weight of bio-based carbon relative to the total weight of carbon in said compound.

[0085] ASTM D6866-21 is a test method that teaches how to experimentally measure the bio-based carbon content of solids, liquids and gaseous samples by radiocarbon analysis.

[0086] In a preferred mode, the water-soluble polymer PI has a renewable and non-fossil carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon of the water-soluble polymer PI, preferably between 30% by weight and 100% by weight, more preferably between 50% by weight and 100% by weight, more preferably between 70% by weight and 100% by weight, more preferably between 90% by weight and 100% by weight and even more preferably 100% by weight of the carbon of the water-soluble polymer PI is of renewable and non-fossil origin, the bio-based carbon content is measured in accordance with ASTM D6866-21, Method B.

[0087] The saccharide having a degree of polymerization between 1 and 5 represents preferably between 10 and 60% by weight relative to the dry matter of composition C2, preferably between 15 and 55% by weight, and more preferably between 15 and 45% by weight.

[0088] The saccharide having a degree of polymerization between 1 and 5 can be extracted from plants, animals or produced by microorganisms such as bacteria, fungi, prokaryotes and eukaryotes.

[0089] Advantageously, the saccharide(s) having a degree of polymerization between 1 and 5 are chosen from: glucose, fructose, galactose, ribose, deoxyribose, mannose, xylose, arabinose, maltose, lactose, sucrose, trehalose, cellobiose, isomaltose, gentiobiose, laminaribiose, maltodextrins, insulin, fructooligosides, galastooligosides, xylooligosides and mixtures thereof.

[0090] Examples of mixtures of saccharides are, for example, glucose syrup, corn syrup, fructose syrup, rice syrup, wheat syrup.

[0091] The present invention also relates to a method of preparing composition C2. Method for preparing composition C2

[0092] The present invention also relates to a method for preparing composition C2 comprising at least the following steps: a) Polymerization of at least one hydrophilic monomer, optionally in the presence of saccharide SA1, to obtain a composition Cl comprising a water-soluble polymer PI and optionally at least one saccharide SA1, b) Addition of at least one SA2 saccharide to composition Cl in order to obtain a composition C2, said addition being optional if at least one SA1 saccharide is present during step a) the saccharide SA1 and the saccharide SA2 having, independently of each other, a degree of polymerization between 1 and 5, the total quantity of saccharides (SA1 + SA2) representing between 5 and 70% by weight relative to the dry matter of composition C2; the amount of water-soluble polymer PI representing between 30 and 95% by weight relative to the dry matter of composition C2.

[0093] Step a)

[0094] Step a) corresponds to the radical polymerization of the at least hydrophilic monomer in order to form the composition Cl.

[0095] Said radical polymerization is carried out in the presence of a radical polymerization initiator.

[0096] Step a) of polymerization is in particular carried out in an aqueous solvent.

[0097] An SA1 saccharide is optionally present during step a).

[0098] Step a) thus includes in particular a step a-1) of mixing in an aqueous solvent: i) of at least one hydrophilic monomer; ii) of at least one radical polymerization initiator; iii) optionally of at least one SA1 saccharide.

[0099] The aqueous solvent advantageously comprises: - more than 50% by weight of water, relative to the total weight of solvents constituting the aqueous solvent, and; - less than 50% by weight of at least one alcohol having 1 to 4 carbon atoms, relative to the total weight of solvents constituting the aqueous solvent.

[0100] In a preferred mode, the aqueous solvent comprises: - more than 60% by weight of water relative to the total weight of solvents constituting the aqueous solvent, preferably more than 70% by weight, more preferably at least 80% by weight, more preferably more than 90% by weight, and - less than 40% by weight of alcohol(s) having 1 to 4 carbon atoms, relative to the total weight of solvents constituting the aqueous solvent, preferably less than 30% by weight, more preferably less than 20% by weight, more preferably less than 10%.

[0101] Among alcohols having 1 to 4 carbon atoms, ethanol, isopropanol and tert-butanol can be mentioned in particular.

[0102] In a particularly preferred mode, the aqueous solvent consists of water.

[0103] The mixing in step a-1) can be done by any means known to a person skilled in the art.

[0104] The quantity of hydrophilic monomers in the aqueous solvent represents advantageously between 1 and 90% by weight relative to the weight of the aqueous solvent, preferably between 10 and 80% by weight, more preferably between 20 and 75% by weight.

[0105] Radical polymerization initiators are advantageously chosen from among compounds that generate radicals under the polymerization conditions, for example: organic peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds, redox salts, and enzymes such as glucose oxidase. The use of water-soluble initiators is preferred. In some cases, it is advantageous to use mixtures of various polymerization initiators, for example, mixtures of redox salts and azo compounds or persulfates.

[0106] In a particular mode, the radical polymerization initiator is an enzyme, preferably glucose oxidase.

[0107] The use of enzymes as polymerization initiators, and in particular glucose oxidase, is particularly interesting because it has the advantage of using a bio-based catalyst under mild conditions and making it possible to do without the degassing step and therefore to reduce greenhouse gas emissions such as CO2 associated with these steps.

[0108] In a particular mode, the radical polymerization initiator is a pair of redox salts.

[0109] The reducing agent of the redox salt couple is advantageously chosen from among the sulfites of alkali metal salts (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium (for example the ammonium ion or a tertiary ammonium), sulfur dioxide, metabisulfites of alkali metal salts (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium (for example the ammonium ion or a tertiary ammonium), bisulfites of alkali metal salts (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium (for example the ammonium ion or a tertiary ammonium), sulfur dioxide, sodium formaldehyde sulfoxylate, sodium fluorosulfate.

[0110] The oxidant of the redox salt couple is advantageously chosen from among peroxides such as tert-butyl hydroperoxide, persulfates of alkali metals (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium (for example the ammonium ion or a tertiary ammonium), hydrogen peroxide.

[0111] In a preferred mode, the radical polymerization initiator is a Fenton or derivative system. By "Fenton or derivative" is meant a system comprising at least one peroxide and at least one oxidant.

[0112] The Fenton or derivative system has the advantage of initiation at room temperature and therefore a reduction in the energy required to obtain the hybrid polymer, thus reducing greenhouse gas emissions such as CO2.

[0113] Advantageously, the Fenton system comprises (1) at least one peroxide and (2) at least one inorganic compound comprising at least one metal salt. The metal salt comprising at least one metal ion and at least one ligand.

[0114] The metal ion or ions are advantageously chosen from: aluminium, lanthanum, iron, chromium, manganese, gallium, copper, indium, thallium, bismuth, cerium, titanium, ruthenium, vanadium and mixtures thereof, preferably from cerium, chromium, iron, vanadium and mixtures thereof, more preferably from iron and vanadium and even more preferably from iron.

[0115] The ligand is advantageously chosen from among halides (such as chloride or bromide), sulfates, chlorosulfates, citrates, nitrates, cations (such as sodium, potassium or ammonium), acetates, water, hydroxide ions, acetyacetonates, the oxide anion O2- and mixtures thereof. Preferably, it is a halide.

[0116] Metal salts can be used in any form, as long as they can be ionized in the polymerization system.

[0117] In a preferred mode, the metallic salt is advantageously selected from ferric chloride, ferric chlorosulfate, ferric sulfate, ferric ammonium citrate, sodium ferredetate (ethylenediaminetetraacetic acid, iron(III) and sodium salt), ferric ammonium sulfate, ferric nitrate, vanadyl sulfate, vanadyl acetylacetonate, chromium sulfate, sodium chromate, potassium dichromate, cerium sulfate, cerium ammonium nitrate, ferrous chloride, ferrous chlorosulfate, ferrous sulfate, ferrous ammonium citrate, sodium ferredetate (ethylenediaminetetraacetic acid, iron(II) and sodium salt), ferrous ammonium sulfate, ferrous nitrate, copper chloride, copper chlorosulfate, copper sulfate, copper ammonium citrate, the sodium feredetate (ethylenediaminetetraacetic acid, copper and sodium salt), copper ammonium sulfate, copper nitrate,vanadium oxychloride, vanadium trichloride, vanadyl oxalate, vanadyl sulfate, vanadic anhydride, ammonium metavanadate, ammonium hypovanadyl sulfate (NH₄SO₄VSO₄O₄), ammoniacal vanadium sulfate (NH₄)V(SO₄)₂H₂O, copper(II) acetate, copper(II) bromide, copper(II) acetoacetate, cupric ammonium chloride, copper carbonate, copper(II) chloride, copper(II) citrate, copper(II) formate, copper(II) hydroxide, copper(II) nitrate, copper naphthenate, copper oleate, copper maleate, copper phosphate, copper(II) sulfate, copper(I) chloride, copper(I) cyanide, copper iodide, copper(I) oxide, copper(I) thiocyanate, iron acetylacetonate, ferric ammonium citrate, ammonium oxalate, ferric, ferrous ammonium sulfate, ferric ammonium sulfate, iron citrate, iron fumarate, iron maleate, ferrous lactate, ferric nitrate, iron pentacarbonyl, ferric phosphate, and ferric pyrophosphate, metal oxides such as vanadium pentaoxide, copper(II) oxide, ferrous oxide, ferric oxide, metal sulfides such as copper sulfide, iron sulfide, as well as copper powder and iron powder.

[0118] The peroxide(s) are advantageously chosen from hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, organic hydroperoxides (such as cumene hydroperoxide and t-butyl hydroperoxide), persulfates and mixtures thereof. Preferably, it is hydrogen peroxide.

[0119] The metallic salt and the peroxide can be added together or separately, in parallel or one after the other, they can be added all at once, in several stages or by pouring.

[0120] In a preferred mode, the metal salt is added to the polymerization feedstock and the peroxide is poured throughout step a) of polymerization.

[0121] In a particular mode, Fenton catalysis can be activated by ultraviolet rays, ultrasound, electrochemically, or with the aid of ascorbic acid.

[0122] In a particular mode, polymerization can be initiated with a system combining ultraviolet (UV) rays and ozone.

[0123] Advantageously, the amount of initiator is between 0.01 and 100,000 ppm relative to the total weight of hydrophilic monomers, preferably between 0.1 and 70,000 ppm, more preferably between 1 and 50,000 ppm, and even more preferably between 5,000 and 25,000 ppm.

[0124] The initiator(s) can be added in one go, in several goes or continuously, i.e. in continuous pouring throughout step a) of polymerization.

[0125] In the case of redox salts, the reducing agent and the oxidizing agent can be added continuously, i.e., by pouring, in parallel or one after the other. Advantageously, at least the reducing agent or the oxidizing agent is used to load the polymerization, and the other component of the redox couple is added continuously, i.e., by continuous pouring throughout step a) of polymerization.

[0126] In a preferred mode, at least one SA1 saccharide having a degree of polymerization between 1 and 5 is used in step a).

[0127] The quantity of SA1 saccharides added in step a) is between 0 and 100% by weight relative to the total weight of saccharide (SA1 + SA2) of composition C2, preferably between 0 and 70% by weight, more preferably between 5 and 50% by weight, and more preferably between 10 and 30% by weight.

[0128] The SA1 saccharide can be added all at once, in several stages or continuously, i.e. by pouring throughout step b). Preferably the SA1 saccharide is added all at once.

[0129] In general, radical polymerization can be carried out using all polymerization techniques known to those skilled in the art. These may include, in particular, solution polymerization; gel polymerization; precipitation polymerization; emulsion polymerization (direct or reverse); suspension polymerization; and water-in-water polymerization. Preferably, solution polymerization is used.

[0130] By radical polymerization, we include free radical polymerization using UV, azo, redox or thermal initiators as well as controlled radical polymerization (CRP) techniques or matrix polymerization techniques.

[0131] As examples of controlled radical polymerization techniques, one may mention, without limitation, 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 organometallic-mediated radical polymerization (OMRP), and organoheteroatom-mediated radical polymerization (OHRP).

[0132] In a preferred mode, the polymerization is carried out by reversible addition-fragmentation chain transfer polymerization (RAFT).

[0133] RAFT is a reversible deactivation radical polymerization (RDRP) technique that combines both the ease of implementation of conventional radical polymerization and the liveness of ionic polymerization.

[0134] It is based on a reversible activation-deactivation equilibrium between a dormant species and an active species (growing macroradical). This activation-deactivation process allows the chains to grow at the same rate until the monomer is completely consumed, making it possible to control the molecular weights of the polymers and obtain narrow molecular weight distributions. This also minimizes compositional heterogeneity. The reversible deactivation of the growing chains is the basis of The minimization of irreversible termination reactions means that the vast majority of polymer chains remain in a dormant state and are therefore reactivatable. This allows for the functionalization of chain ends to initiate other polymerization modes or to create chain extensions. This is key to achieving high molecular weights, controlled compositions, and architectures.

[0135] Controlled radical polymerization therefore has the following distinctive aspects: 1. the number of polymer chains is fixed throughout the duration of the reaction, 2. the polymer chains all grow at the same rate, which results in: * a linear increase in molecular weights, * a tight distribution of molecular weights, 3. the average molecular weight is controlled by the monomer / precursor molar ratio.

[0136] The controlled nature of the chain is all the more pronounced when the rate of reactivation of the chains into radicals is much greater than the rate of chain growth (propagation). However, in some cases, the rate of reactivation of the chains into radicals is greater than or equal to the rate of propagation. In these cases, conditions 1 and 2 are not observed and, consequently, control of the molecular weights is not possible.

[0137] Reversible addition-fragmentation chain transfer polymerization requires the use of a control agent.

[0138] In the context of the invention, the control agent is water-soluble of formula (IV):

[0139] [Chem.3] (IV)

[0140] in which - W= Ri, or Z-R3 with Z= an oxygen atom (O), a sulfur atom (S) or an amine (NR4); - Rb R2, R3 and R4, whether identical or different, represent: * a group (i), alkyl, acyl, alkenyl or alkynyl, possibly substituted, or * a carbon ring (ii), saturated or unsaturated, possibly substituted or aromatic, or * a heterocycle (iii), saturated or unsaturated, possibly substituted or aromatic, these groups and rings (i), (ü) and (iii) can be substituted by substituted aromatic groups or by alkoxycarbonyl or aryloxycarbonyl groups (-COOR), carboxy (-COOH), acyloxy (-O2CR), carbamoyl (-CON(R)2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-N(R)2), halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups exhibiting hydrophilic or ionic character such as alkali salts of carboxylic acids, alkali salts of sulfonic acid, polyalkylene oxide chains (POE, POP), cationic substituents (quaternary ammonium salts); - R represents an alkyl or aryl group in CrC2O; - R4 can also represent a hydrogen atom; - Q is a linear or structured polymer chain comprising n identical or different hydrophilic monomers; - n is an integer between 0 and 500, advantageously between 2 and 500, more advantageously between 2 and 100. When n is equal to 0, Q is a single bond between the sulfur atom and the R2 group.

[0141] The hydrophilic monomer(s) used to form Q are advantageously chosen from the same hydrophilic monomers as those described to form the water-soluble polymer PL

[0142] In functions N(R)2, the two groups R can be identical or different from each other.

[0143] According to a preferred mode, the water-soluble control agent of formula (IV) is a dithiocarbonate or xanthate derivative in which Z represents an oxygen atom (O).

[0144] According to another preferred embodiment, the water-soluble controlling agent has formula (IV) in which: - Z represents an oxygen atom (O); - Q is a linear or structured polymer chain obtained from 0 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 and / or at least one monomer containing an LCST group.

[0145] According to another preferred embodiment, the water-soluble controlling agent has the formula (V):

[0146] [Chem.4] (V)

[0147] wherein Q is a linear or structured polymeric chain obtained from 2 to 100 hydrophilic monomers, preferably between 2 and 50 monomers.

[0148] According to another preferred embodiment, the water-soluble controlling agent has formula (V) in which Q is a linear or structured polymeric chain obtained from 2 to 100 hydrophilic monomers selected from quaternized or salified acrylamide, acrylic acid, or dimethylaminoethyl acrylate, preferably from 2 to 50 monomers. In another preferred embodiment, the controlling agent has formula (IV) in which Z represents a sulfur atom (S).

[0149] In another preferred mode, the control agent is of formula (VI):

[0150] [Chem.5] (VI)

[0151] wherein: the R3s are identical or different, independently represent an H or a CH3 or a salt, advantageously chosen from the salts of alkali metals (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium ions (for example the ammonium ion or a tertiary ammonium), preferably a sodium salt.

[0152] In another preferred mode, the controlling agent is a trithiocarbonate of formula (VII):

[0153] [Chem.6] (VII)

[0154] in which: - the R3s are identical or different, independently represent an H or a CH3 or a monovalent or divalent cation, advantageously chosen from the cations of alkali metals (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium ion (for example the ammonium ion or a tertiary ammonium), preferably it is sodium; - Q is a linear or structured polymer chain obtained from 2 to 100 hydrophilic monomers, preferably between 2 and 50 monomers.

[0155] In another preferred embodiment, the controlling agent is a trithiocarbonate of formula (VII) in which: - the R3s are identical or different, independently represent an H or a CH3 or a monovalent or divalent cation, advantageously chosen from the cations of alkali metals (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium ion (for example the ammonium ion or a tertiary ammonium), preferably it is sodium; - Q is a linear or structured polymer chain obtained from 2 to 100 monomers chosen from acrylamide, acrylic acid or quaternized or salified dimethylaminoethyl acrylate, preferably between 2 and 50 monomers.

[0156] In another preferred mode, the control agent is of the following formula (VIII):

[0157] [Chem.7] (VIII)

[0158] wherein the R3s are identical or different, independently represent an H, a CH3 or a salt, advantageously chosen from the salts of alkali metals (Li, Na, K...), alkaline earth metals (Ca, Mg...) or ammonium ions (for example the ammonium ion or a tertiary ammonium). Preferably it is a sodium salt.

[0159] In another preferred mode, the control agent is of formula (IX):

[0160] [Chem.8] (IX)

[0161] in which: - the R3s are identical or different, independently representing an H, a CH3 or a monovalent or divalent cation, advantageously chosen from alkali metal cations (Li, Na, K...), alkaline earth metal cations (Ca, Mg...) or ammonium ion (for example the ammonium ion or a tertiary ammonium), preferably sodium; and - Q is a linear or structured polymer chain obtained from 2 to 100 hydrophilic monomers, preferably between 2 and 50 monomers.

[0162] In another preferred embodiment, the controlling agent is of formula (IX) in which: - the R3s are identical or different, independently represent an H, a CH3 or a monovalent or divalent cation, advantageously chosen from alkali metal cations (Li, Na, K...), alkaline earth metal cations (Ca, Mg...) or ammonium ion (for example the ammonium ion or a tertiary ammonium), preferably sodium; and - Q is a linear or structured polymer chain obtained from 2 to 100 monomers chosen from acrylamide, acrylic acid or quaternized or salified dimethylaminoethyl acrylate, preferably between 2 and 50 monomers.

[0163] During polymerization, it is possible to cast the different components constituting the water-soluble polymer PI; for example, it is possible to cast at least the hydrophilic monomer and / or at least the saccharide SA1, or one or more hydrophobic monomers constituting the water-soluble polymer PI; it is also possible to cast the branching agent(s) and / or the agent(s) transfer occurs when at least one of them is present. It is also possible to partially pour the different compounds constituting the water-soluble PI polymer.

[0164] Once polymerization has begun, the temperature is controlled to be advantageously between 5°C and 115°C, preferably between 25°C and 115°C.

[0165] The pressure during polymerization can be adjusted by a person skilled in the art to achieve the desired temperature.

[0166] The pressure during polymerization can be controlled, it is advantageously between 800 mbar and 10 bars, preferably between 900 mbar and 5 bars, more preferably the polymerization is carried out at atmospheric pressure.

[0167] During polymerization, the pH is advantageously controlled at a value between 1 and 14, preferably between 5 and 7.

[0168] The polymerization time is advantageously between 1 minute and 900 minutes, preferably between 30 minutes and 180 minutes.

[0169] In a particular embodiment, the process of the invention comprises, following polymerization, a step for removing residual monomers. The removal of residual monomers can be carried out, for example, by adding an excess of initiator and / or water.

[0170] At the end of step a) a composition Cl is obtained comprising a water-soluble polymer PI and optionally a saccharide SA1.

[0171] Step b)

[0172] In a step b), at least one SA2 saccharide can be added to composition Cl in order to obtain composition C2.

[0173] The addition of the SA2 saccharide can be done in one step, in several steps or by pouring.

[0174] The SA2 saccharide is chosen from the same saccharides as those previously described for SA1.

[0175] The SA2 saccharide may be the same as the SA1 saccharide or it may be different, preferably it is the same.

[0176] The amount of saccharide SA2 added in step b) is between 0 and 100% by weight relative to the total weight of saccharide (SA1 + SA2) of composition C2, between 30 and 100% by weight, more preferably between 50 and 95% by weight and even more preferably between 70 and 90% by weight.

[0177] Step b) is advantageously carried out at a temperature between 5 and 115°C, preferably between 20 and 90°C, more preferably between 50 and 80°C.

[0178] The pressure during polymerization can be controlled, it is advantageously between 800 mbar and 10 bars, preferably between 900 mbar and 5 bars, more preferably the polymerization is carried out at atmospheric pressure.

[0179] Step b) advantageously lasts between 1 minute and 180 minutes, preferably between 10 minutes and 120 minutes, more preferably between 20 minutes and 60 minutes.

[0180] During step b), the pH is advantageously controlled at a value between 1 and 14, preferably between 4 and 7.

[0181] At the end of step b) we obtain composition C2.

[0182] When step b) is not present, the composition Cl corresponds to the composition C2.

[0183] The process for preparing composition C2 can be carried out in batch, semi-batch or continuous.

[0184] In a preferred mode, at least one SA1 saccharide and at least one SA2 saccharide are added during the process of preparing composition C2.

[0185] The invention also relates to a water treatment process comprising bringing a suspension of solid particles into contact with the composition C2 described above, as well as the composition C2 obtained according to the process of the invention.

[0186] The treated water may come from mining, oil sands extraction, urban, industrial or agricultural sources.

[0187] When the treated water originates from mining operations or oil sands extraction, the process can be carried out in a thickener, which is a retention zone, generally in the form of a section of pipe several meters in diameter with a conical bottom in which particles can settle. According to a specific embodiment, the aqueous suspension is conveyed by means of a pipe to a thickener, and the polymer is added to said pipe.

[0188] According to another embodiment, composition C2 is added to a thickener that already contains the suspension to be treated. In a typical mineral processing operation, suspensions are often concentrated in a thickener. This results in a higher density slurry exiting the bottom of the thickener, and an aqueous fluid released from the treated suspension (called liquor) exiting by overflow from the top of the thickener. In general, the addition of composition C2 increases the concentration of the slurry and increases the clarity of the liquor.

[0189] According to another embodiment, composition C2 is added to the particle suspension during the transport of said suspension to a settling zone. Preferably, composition C2 is added in the pipe that transports said suspension to a settling zone. It is on this settling zone that the treated suspension is spread for dehydration and solidification. The settling zones may be open, such as an undefined area of ​​soil, or closed, such as a basin or a cell.

[0190] An example of such treatments during the transport of the suspension is the spreading of the suspension treated with composition C2 onto the ground for dehydration and solidification, followed by the spreading of a second layer of the treated suspension over the first solidified layer. Another example is the continuous spreading of the suspension treated with composition C2 such that the treated suspension falls continuously onto the suspension previously unloaded in the deposition area, thus forming a mass of treated material from which the water is extracted.

[0191] According to another embodiment, composition C2 is added to the suspension, and then mechanical treatment is carried out, such as centrifugation, pressing or filtration.

[0192] Composition C2 can be added simultaneously in different stages of the suspension treatment, i.e. for example in the pipe transporting the suspension to a thickener and in the slurry exiting the thickener which will be conveyed either to a settling area or to a mechanical treatment device.

[0193] When treated water comes from municipal or industrial sources, composition C2 is generally added to the water stream upstream of the separation unit, such as flotation or sedimentation.

[0194] Effective water treatment requires the removal of dissolved compounds and dispersed and suspended solids from the water. This treatment is generally enhanced by chemicals such as coagulants and flocculants.

[0195] Composition C2 is advantageously used in combination with inorganic coagulants such as aluminium salts.

[0196] Composition C2 can also be used to treat sludge from the treatment of this wastewater. Sewage sludge (urban or industrial) is the main waste product of a wastewater treatment plant from liquid effluents. Sludge treatment generally consists of dewatering it. This dewatering can be carried out by centrifugation, filter press, belt filter press, electrodewatering, reed bed drying, or solar drying. Dewatering reduces the water concentration of the sludge.

[0197] In this water treatment process, composition C2 can be added in powder form or as a solution.

[0198] The amount of C2 composition added during the water treatment process depends on the nature of the water being treated; a person skilled in the art will be able to adjust the amount according to the parameters usually considered in such a process. Generally, the amount of C2 composition added is between 10 ppm and 100,000 ppm relative to the amount of water to be treated.

[0199] The present invention also relates to the use of composition C2 described above, as well as composition C2 obtained according to the process of the invention in#: hydrocarbon recovery (oil or gas)#; well drilling#; well cementing#; hydrocarbon (oil or gas) well stimulation such as hydraulic fracturing, conformance and diversion#; construction#; paper or cardboard manufacturing#; battery industry#; wood processing#; mining#; cosmetic formulation#; detergent formulation#; textile manufacturing#; geothermal energy#; sanitary diaper manufacturing#; or agriculture. Examples

[0200] Example: Preparation of compositions C2-1 to C2-10 Step a)

[0201] 431.1 g of dimethyldialylammonium chloride (64% by weight in water) and 69 g glucose syrup (SA1) (80% by weight in water) are introduced into an IL reactor under stirring at room temperature. Separately, a solution comprising 55 mg of ethylenediaminetetraacetic acid, 236 mg of tert-butyl hydroperoxide, 166 mg of sodium formaldehyde sulfoxylate and 14 mg of Mohr's salt in 5 mL of water is prepared and then added to the reactor.

[0202] Once the maximum temperature peak is reached, a sodium persulfate solution (7.1 g in 186 g of water) is added to the reactor over a period of 120 minutes. 20.7 g of sodium bisulfite (40 wt% in water) are added at the end of the 120 minutes. The reaction is left for one hour at boiling temperature in order to obtain the composition Cl comprising the water-soluble polymer PI and glucose SA1. Step b)

[0203] The temperature of the reaction medium is lowered to stop boiling, then a solution composed of 200 g of water and 46 g of glucose syrup (SA2) (80% by weight in water) is added over 20 minutes. The pH is adjusted to 6. Finally, the reaction medium is cooled to room temperature to obtain the C2-1 composition.

[0204] The same experimental protocol is reproduced by modifying the proportions and nature of the saccharides used in order to prepare compositions C2-1 to C2-5, their compositions are presented in Table 1.

[0205] Composition C2-6 is obtained according to the preparation protocol of compositions C2-1 to C2-5 without the addition of saccharide.

[0206] Composition C2-7 corresponds to a single saccharide, without water-soluble polymer.

[0207] Composition C2-8 is obtained according to the preparation protocol of compositions C2-1 to C2-5 but with a saccharide having a degree of polymerization outside the claimed range.

[0208] Compositions C2-9 and C2-10 are obtained according to the preparation protocol of compositions C2-1 to C2-5 but with an amount of saccharide outside the claimed range.

[0209] [Tables 1] Composition Saccharid Degree of Polymerization Quantity of saccharide (% by weight) / (saccharide + pDADMAC) SA1 / SA2 Ratio (% by weight) C2-1 Invention Glucose Syrup 2-5 25 15 / 10 C2-2 Invention Glucose 1 35 0 / 35 C2-3 Invention Maltodextrin 5 15 15 / 0 C2-4 Invention Fructose / Glucose 1 20 0 / 20 C2-5 Invention Fructose 1 30 0 / 30 C2-6 Counter-example - - - - C2-7 Counter-example Glucose Syrup 2-5 - - C2-8 Counter-example Maltodextrin 6 25 15 / 10 C2-9 Counter-example Glucose 1 3 0 / 3 C2-10 Glucose 1 75 15 / 60 Counter-example pie

[0210] Table 1 - Composition and nature of compositions C2-1 to C2-10

[0211] Example 1b Time stability test of C2-1 to C2-10 compositions

[0212] The stability of the C2-1 to C2-10 compositions is studied by leaving the compositions at room temperature for 3 and 6 months. The composition is considered stable when it is transparent and unstable when it is cloudy; the evaluation is done visually.

[0213] [Tables2] Composition Stability at 3 months Stability at 6 months C2-1 Invention Yes Yes C2-2 Invention Yes Yes C2-3 Invention Yes Yes C2-4 Invention Yes Yes C2-5 Invention Yes Yes C2-6 Counterexample Yes Yes C2-7 Counterexample Yes Yes C2-8 Counterexample No No C2-9 Counterexample Yes Yes C2-10 Counterexample Yes Yes

[0214] Table 2 - Stability test of compositions C2-1 to C2-10

[0215] It can be seen from Table 2 that the compositions according to the invention are stable over time, unlike the counterexamples for which a cloudiness forms after 6 months of storage, only the counterexample C2-6 which corresponds to a synthetic polymer is stable over this period.

[0216] Example: The coagulation test of compositions C2-1 to C2-10

[0217] The coagulation efficiency of compositions C2-1 to C2-10 is measured according to the jar test according to the following protocol: In a beaker containing 500 mL of the solution to be treated, a quantity of compositions C2-1 to C2-10 is added. Agitation using a magnetic stirrer is carried out at 300 rpm (revolutions per minute) for 1 minute. Then the agitation is reduced to 50 rpm for 5 minutes. The resulting solution is left to stand for 5 minutes to allow sedimentation, then the turbidity is measured using a Hach® 2100Q turbidimeter.

[0218] The results of the turbidity measurements are shown in Table 3.

[0219] [Tables3] Dosage ( C2-1 C2-1 C2-3 C2-4 C2-5 C2-6 C2-7% C2-8 C2-9 C2-10 PPM ac %NVS %NVS %NVS %NVS %NVS %NVS NVSC %NVS %NVS %NVS tif) Inv Inv Inv Inv Inv CEx Ex CEx CEx CEx 0.2 19 18.5 22.5 16.5 17 25 540 55 28 30 0.4 15 13 17 12.5 12.1 23 510 45 25 28 1 6.5 5.2 5.5 5.2 5.2 15 450 38 16 17 2 8.8 7.5 9 7.9 6.9 10 520 32 13 15 4 11.8 10.5 13 10.5 11 20 490 35 22 23 8 19.5 16 20 18.8 16.8 49 530 57 43 56

[0220] Table 3 - Results of coagulation tests of compositions C2-1 to C2-10 (Inv: Invention; CEx: Counterexample) (%NVS: non-volatile substances in solution).

[0221] As can be seen in Table 3, the compositions according to the invention exhibit better resilience to overdose.

Claims

Demands

1. Composition C2 comprising: i) at least one water-soluble polymer PI, representing between 30 and 95% by weight relative to the dry matter of composition C2; ii) at least one saccharide having a degree of polymerization between 1 and 5, representing between 5 and 70% by weight relative to the dry matter of composition C2.

2. Composition according to claim 1, characterized in that at least the water-soluble polymer PI comprises at least one cationic hydrophilic monomer.

3. Composition according to claim 2, characterized in that the cationic hydrophilic monomer is dimethyldialylammonium chloride.

4. Composition according to claim 1, characterized in that the water-soluble polymer PI comprises at least one cationic hydrophilic monomer and at least one non-ionic water-soluble monomer.

5. Composition according to any one of claims 1 to 4, characterized in that the water-soluble polymer PI has a weight-average molecular weight between 1,000 and 1,500,000 g / mol.

6. Composition according to any one of claims 1 to 5, characterized in that the water-soluble polymer PI has a renewable and non-fossil carbon content of between 5% by weight and 100% by weight, relative to the total carbon weight of the water-soluble polymer PI, the bio-based carbon content is measured in accordance with ASTM D6866-21, Method B.

7. A method for preparing composition C2 according to any one of claims 1 to 6, comprising at least the following steps: a) Polymerization of at least one hydrophilic monomer, optionally in the presence of saccharide SA1, to obtain a composition Cl comprising a water-soluble polymer PI and optionally at least one saccharide SA1, b) Addition of at least one saccharide SA2 to composition Cl to obtain composition C2, said addition being optional if at least one saccharide SA1 is present at step a), saccharide SA1 and saccharide SA2 having, independently of each other, a degree of polymerization between 1 and 5, the total quantity of saccharides (SA1 + SA2) representing between 5 and 70% by weight relative to the dry matter of composition C2; the quantity of water-soluble polymer PI representing between 30 and 95% by weight relative to the dry matter of composition C2.

8. A method according to claim 7, characterized in that step a) is carried out in the presence of a radical polymerization initiator, said initiator being a Fenton system or derivative.

9. A method according to any one of claims 7 or 8, characterized in that at least one SA1 saccharide and at least one SA2 saccharide are added.

10. A process according to any one of claims 7 to 9, characterized in that the monomer(s) used is / are extracted from renewable raw material(s) or obtained from enzymatic catalysis.

11. A method according to any one of claims 7 to 10, characterized in that the energy used to carry out the method comes from a heat pump, a waste heat network, renewable energy, a fuel cell, a lithium battery or a nuclear battery.

12. A water treatment process comprising contacting solid particles with the composition according to any one of claims 1 to 6 or with the composition C2 obtained by the process according to any one of claims 7 to 11.