Method for manufacturing pulp

Abstract

This invention relates to a method for manufacturing dried commercial pulp sheets, which includes adding a polymer composition.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a dried commercial pulp, comprising adding a polymer composition having a cellulose fiber suspension. Background Technology

[0002] Dry market pulp is manufactured in pulp mills, where wood and / or other cellulosic materials are milled to form a suspension of cellulose fibers, also known as pulp. The pulp is then subjected to physical and chemical treatments to form dried pulp boards, known as "dry market pulp." This dry market pulp forms the basis of most paper, paperboard, and similar manufacturing methods, in which it is fed into an aqueous medium for decomposition and dilution to form a whole or partial thick pulp. Dry market pulp exists in the form of dried pulp boards. These boards are typically packaged in ball bundles.

[0003] Typically, the main steps that enable the formation of paper, cardboard, or the like can be as follows: - A cellulose fiber suspension is formed from the original cellulose material. - A fiber mat is formed by draining a suspension of cellulose fibers onto a wire. - The fiber mat is pressed (dehydrated) to form a pulp board. - Dry the pulp board to form a dried commercial pulp. - After the dried commercial pulp is broken down and diluted, a concentrated pulp is formed by dispersing cellulose fibers in an aqueous medium. - By diluting the concentrated slurry, a diluted slurry is formed. - Paper, paperboard or the like is formed from the diluted pulp.

[0004] The problems encountered by manufacturers producing this dried commercial pulp differ from those encountered in the formation of paper, paperboard, and the like. The treatment of the cellulose raw material to obtain this dried commercial pulp leads to limitations and problems that are not present in the formation of paper, paperboard, and the like.

[0005] One of the biggest problems involves water removal during the formation of dry market pulp. In fact, the fiber mat formed during the preparation of dry market pulp is much thicker than the fiber mat formed during the drainage step in the papermaking process. As a result, water removal is undoubtedly more complex. Without being bound by any theory, it seems that the different treatments that cellulose fibers undergo during their transformation (from wood and / or other cellulose materials) into dry market pulp induce an increase in water retention in the fibers at two levels (free water and bound water).

[0006] Free water refers to the water that naturally flows out of the pulp during the formation of the fiber pad. The removal of free water can be accelerated through physical treatments such as mechanical pressing to obtain the pulp board. In fact, free water typically accounts for 95 to 99% of the water present in the pulp fiber pad.

[0007] Bound water corresponds to the water captured and retained by the cellulose fibers in the pulp fiber pad after the drainage step, and is present in the pulp board after the pressing step. This water cannot be removed by mechanical processing; it requires an additional drying step at high temperatures to be significantly removed. It typically accounts for 30 to 70% of the weight of the pulp board.

[0008] Conventional drainage agents used in the papermaking process may not be able to remove bound water, especially at pH 6 or higher.

[0009] Various additives have been developed to improve water removal in the pulp manufacturing process. For example, documents EP 335576 and US8916026 disclose combinations of cationic polymers with bentonite. However, these solutions primarily improve the removal of free water, without significantly improving the removal of bound water.

[0010] The necessity of additional drying means consuming more energy to prepare the commercial pulp.

[0011] This problem does not occur in the formation of paper, paperboard and the like, because the drying step of paper actually takes place immediately after drying on the rollers, while thicker pulp boards require more energy to dry, which results in higher costs for manufacturers and also produces significant negative ecological impacts.

[0012] To facilitate the removal of this bound water, the wastewater treatment process in commercial pulp is carried out under acidic conditions. However, acidic conditions cause environmental problems because they require large amounts of harmful chemicals and necessitate subsequent wastewater treatment before the water can be released back into nature.

[0013] This invention aims to replace the use of these harmful chemicals during the drainage step in the drying process of commercial pulp manufacturing. At the same time, this invention does not increase the energy required during the drying step.

[0014] The applicant has prepared a specific polymer composition that can solve these problems when added to pulp board.

[0015] This reduces the environmental impact of drying commodity pulp production and increases productivity because pulpboard requires less drying time. Furthermore, the addition of the polymer composition allows for a reduction in the amount of adhesives. The polymer composition also enables a reduction, or even elimination, of yellowing of the cellulose fibers within the board.

[0016] The method according to the invention aligns with environmental awareness and the principles of industrial and human impact on the planet. The method reduces the demand for harmful products and the amount of drying energy required to produce or dry commercial pulp, thereby reducing greenhouse gas emissions, such as carbon dioxide typically associated with papermaking.

[0017] This invention is advantageously implemented using biologically derived materials (e.g., biomass) or recycled materials. The synthesis of the monomers used in this invention is advantageously biosynthetic, for example, by enzymatic catalysis or extraction from renewable feedstocks. The energy used to implement the method according to the invention is advantageously derived from heat pumps or renewable sources, such as wind power, photovoltaic power, or from fuel cells or lithium-ion battery types. Summary of the Invention

[0018] The present invention aims at a method for manufacturing dried commercial pulp boards, comprising adding a polymer composition prior to the step of draining an aqueous suspension of cellulose fibers, wherein the polymer composition is obtained by polymerization of at least one cationic hydrophilic monomer in the presence of at least one water-soluble polymer selected from the group consisting of: poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof.

[0019] More specifically, the present invention relates to a method for manufacturing dried commercial pulp boards, comprising the following steps: - A cellulose fiber aqueous suspension SA1 was prepared by pulping raw cellulose material in the presence of water. - A polymer composition is added to the cellulose fiber aqueous suspension SA1 to form an aqueous suspension SA2, said polymer composition being obtained by polymerizing at least one cationic hydrophilic monomer in the presence of at least one water-soluble polymer selected from the group consisting of: poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof. - By draining the aqueous suspension SA2 onto a web at a pH of 6 to 8, a fiber mat with a thickness of 1 mm to 100 mm is formed. - By pressing the fiber pad to form pulp board, and - Dry the pulp board to obtain dried commercial pulp.

[0020] The present invention also relates to a dried commercial pulp comprising: - 0.001 to 1% by weight of a polymer composition obtained by polymerizing at least one cationic hydrophilic monomer in the presence of at least one water-soluble polymer selected from the group consisting of: poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof; - 79.999 to 99.999% by weight of cellulose fibers; - Optional 0.01 to 20% by weight of inorganic particles.

[0021] The dried commercial pulp according to the present invention is generally available in the form of plates. Detailed Implementation

[0022] "Polymer" refers to a homopolymer prepared from a cationic hydrophilic monomer or a copolymer prepared from at least two different monomers, namely, a cationic hydrophilic monomer and monomers selected from the group consisting of: anionic hydrophilic monomers, nonionic hydrophilic monomers, zwitterionic hydrophilic monomers, hydrophobic monomers, and mixtures thereof. Preferably, these monomers have one CH2=C- functional group, and more preferably only one.

[0023] The term "paper" also includes cardboard.

[0024] "Hydrophilic monomer" refers to the octanol / water partition coefficient K. ow Monomers less than or equal to 1, where the partition coefficient K ow It was determined at 25°C in a 1 / 1 volume ratio octanol / water mixture at pH 6 to 8.

[0025] "Hydrophobic monomer" refers to the octanol / water partition coefficient K. ow Monomers with a partition coefficient greater than 1, where the partition coefficient K ow It was determined at 25°C in a 1 / 1 volume ratio octanol / water mixture at pH 6 to 8.

[0026] Octyl alcohol / partition coefficient K ow This represents the monomer concentration (g / L) ratio between the octanol phase and the aqueous phase. Its definition is as follows: "Water-soluble polymer" refers to a polymer that, when stirred at 25°C, dissolves in 10g of water. -1 When the concentration is dissolved in deionized water, an aqueous solution free of insoluble particles is obtained.

[0027] Throughout the instruction manual, Brookfield viscosity is measured using a Brookfield viscometer in an aqueous solution at 25°C with an LV module.

[0028] Those skilled in the art can determine the module and speed of the Brookfield viscometer based on the range of viscosity to be measured. These types of measurements are actually part of common knowledge to those skilled in the art.

[0029] According to the present invention, "X and / or Y" means "X", or "Y", or "X and Y".

[0030] All possible combinations between the different disclosed embodiments also form part of this invention, whether these embodiments are preferred embodiments or embodiments given as examples. Furthermore, when numerical ranges are specified, the limit values ​​form part of these ranges. This disclosure also includes all combinations between the endpoints of these numerical ranges. For example, the numerical range “1-20, preferably 5-15” means the disclosure of ranges “1-20”, “1-5”, “1-15”, “5-20”, and “15-20”, as well as the values ​​1, 5, 15, and 20.

[0031] "Pure cellulose material" refers to cellulose fibers derived from cellulose material that has never undergone a drainage process. In other words, this invention is limited to the manufacture of dried commercial pulp and does not relate to the manufacture of paper or the manufacture of dried commercial pulp from recycled cellulose fibers. In other words, the pure cellulose material has never been dried.

[0032] Method for manufacturing dried commercial pulp Methods for producing dried commercial pulp are known to those skilled in the art. For further details regarding the steps involved in producing dried commercial pulp, please refer, if necessary, to Ek. Monica's literature "Pulping Chemistry and Technology" Volume 2 (2009).

[0033] A method for producing a dried commercial pulp typically includes the following steps: a) Prepare cellulose fiber aqueous suspension by pulping raw cellulose material; a') Optionally bleaching the aqueous suspension of the cellulose fibers; a'') Optionally beat the cellulose fiber aqueous suspension; b) Forming a fiber pad by draining the cellulose fiber aqueous suspension of one of steps a), a'), or a''); c) Forming a pulp board by pressing the fiber pad; d) Dry the pulp board to obtain dried commercial pulp in board form.

[0034] The polymer composition according to the invention can be added to any step of the method prior to the formation of the fiber mat (step b) or to one or more steps. Preferably, it is added after a step prior to the formation of the fiber mat (step b), for example, after pulping, bleaching, or beating.

[0035] Aqueous suspension SA1 refers to an aqueous suspension of cellulose fibers before the addition of the polymer composition.

[0036] Aqueous suspension SA2 refers to an aqueous suspension of cellulose fibers used to form fiber mats (i.e., after the addition of a polymer composition).

[0037] The amount of polymer composition added to the aqueous suspension SA1 is advantageously 0.001 to 10 kg / t of dried cellulose fibers, preferably 0.002 to 5 kg / t, more preferably 0.005 to 1 kg / t.

[0038] In a preferred embodiment, the aqueous suspension SA2 is mixed after the addition of the polymer composition and before the formation of the fiber mat in order to homogenize the cellulose fiber suspension with the polymer composition.

[0039] In a preferred embodiment, the method according to the invention includes adding inorganic particles prior to the formation of the fiber mat, i.e., adding them to the aqueous suspension SA1 and / or SA2 between pulping and the formation of the fiber mat. As inorganic particles, bentonite particles, silica particles, talc particles, aluminum salt particles, and mixtures thereof may be mentioned in a non-limiting manner. Preferably, these inorganic particles are bentonite or silica particles, more preferably bentonite.

[0040] The amount of inorganic particles is advantageously 0.01 to 20 kg / t of cellulose fiber, preferably 0.05 to 15 kg / t, and more preferably 1 to 5 kg / t.

[0041] Bentonite is typically used advantageously in powder, slurry (advantageously 4 to 5% by weight), or thick slurry (advantageously 13 to 17% by weight). Bentonite slurry is a mixture of water and bentonite.

[0042] The addition of inorganic particles can occur at any step of the process, but may be done once or multiple times before the step of draining the cellulose fiber suspension. Advantageously, they are added all at once in the same step as the addition of the polymer composition.

[0043] The inorganic particles and polymer composition can be added sequentially (i.e., one after another (adding the inorganic particles first, followed by the polymer composition, or vice versa), simultaneously, or in the form of a pre-prepared mixture. Preferably, the inorganic particles and polymer composition are added sequentially, with the inorganic particles added before the polymer composition.

[0044] The raw cellulose material is pulped to form a cellulose fiber suspension. The primary cellulose material can be derived from any type of cellulose raw material that has not undergone a drainage process. Examples, and in a non-limiting manner, include wood (hardwood and softwood), bamboo, straw, bagasse, or jute. Preferably, the cellulose raw material is derived from wood.

[0045] Pulping can be carried out by any known method. This can be mechanical pulping, thermomechanical pulping, chemo-thermomechanical pulping, chemical pulping, organic solvent pulping, or a biological pulping process using fungi or enzymes. Preferably, it is chemo-thermomechanical pulping or chemical pulping, more preferably chemical pulping.

[0046] Pulping occurs in the presence of water.

[0047] As a chemical pulping process, the Kraft method, the sulfite method, or alkali metal carbonate (especially sodium) or alkaline earth metal treatment can be mentioned. Preferably, it is the sulfite method.

[0048] Based on the total weight of the suspension, the concentration of cellulose fibers from the pulped cellulose fiber aqueous suspension is typically at least 1% by weight, preferably at least 2% by weight, and more preferably at least 3% by weight. Typically, the concentration of the cellulose fiber aqueous suspension is at most 20% by weight, preferably at most 15% by weight, and more preferably at most 10% by weight.

[0049] Bleached cellulose fiber aqueous suspension According to one implementation plan, cellulose fiber aqueous suspensions can be bleached through chemical treatment.

[0050] Bleaching typically consists of several consecutive, distinct steps, including the addition of compounds. These steps are part of the general knowledge known to those skilled in the art, who can consult the literature "Pulping Chemistry and Technology" if needed.

[0051] After the bleaching step, the cellulose fiber suspension can form the object of the washing step in order to remove undissolved impurities and / or remove the products used during the bleaching step, as well as any residues that may be present in those products.

[0052] Pulping cellulose fiber suspension The terms "beating" and "refining" are used interchangeably. They refer to the mechanical treatment of cellulose fiber suspensions to make them suitable for subsequent papermaking. Cellulose fiber suspensions, without prior beating, are never actually converted into dry market pulp after chemo-thermomechanical pulping or chemopreservation. Beating is a crucial step in this process because the pulp, without mechanical modification, does not possess paper properties. The effects of beating on the fibers can be broadly categorized into five parts: cell wall movement and deformation, primary and secondary cell wall rupture, water absorption and swelling, fibrillation, and transverse cutting. Depending on the beating conditions, the physical properties of the pulp can be altered, allowing for the production of papers with different physical properties for various applications.

[0053] A significant effect of beating is a reduction in the drainage capacity of the cellulose fiber suspension, as this tends to make the fibers more difficult to dewater. The use of the polymer compositions of this invention is of particular interest for cellulose fiber suspensions that have undergone a beating step. Therefore, in a preferred embodiment, a method for producing dry commercial pulp includes the step of beating a cellulose fiber suspension.

[0054] Forming a dry commercial pulp The thickness of the fiber pad is 1 mm to 100 mm, preferably 2 mm to 50 mm, and more preferably 3 mm to 30 mm.

[0055] The formation of the fiber mat is carried out at a pH of 6 to 8, preferably 6.5 to 7.5, more preferably 6.7 to 7.3.

[0056] The steps of draining, pressing, and drying pulp boards are routine and are part of common knowledge to those skilled in the art.

[0057] Advantageously, the weight of cellulose fibers in the dried commercial pulp board is 250 to 5000 g / m³. 2 Preferred concentration: 280 to 4000 g / m 2 More preferably 300 to 3000 g / m 2 .

[0058] polymer composition The polymer composition is obtained by polymerizing at least one cationic hydrophilic monomer in the presence of at least one water-soluble polymer selected from the group consisting of poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof.

[0059] In the remainder of the specification, the water-soluble polymer is referred to as the "host polymer".

[0060] Polymer composition - host polymer The main polymer is a polyamine with ammonium and hydroxyl (-OH) groups at pH 7.

[0061] The main polymer can be obtained using any polymerization technique. Preferably, it is obtained by solution polymerization.

[0062] The main polymer is a polyamine selected from the group consisting of: poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof.

[0063] In a preferred embodiment, the host polymer is poly(dimethylamine-epoxychloropropane-ethylenediamine). This polymer is obtained through a reaction between dimethylamine, ethylenediamine, and epichlorohydrin.

[0064] In one implementation, the host polymer may be structured by a branching agent.

[0065] When the host polymer contains a branching agent, the polymer remains soluble in water. The host polymer can also be prepared in the presence of a transfer agent. Those skilled in the art know how to adjust the amount of branching agent, and optionally, the amount of transfer agent, to achieve this result.

[0066] In a preferred embodiment, the main polymer is free of branching agents.

[0067] In one embodiment, the host polymer comprises a transfer agent.

[0068] In one embodiment, the host polymer does not contain a transfer agent.

[0069] The molecular weight of the host polymer is advantageously at least 1000 g / mol, preferably at least 2000 g / mol, and even more preferably at least 5000 g / mol. Typically, the molecular weight of the host polymer is advantageously less than 2 million g / mol, and more advantageously less than 1 million g / mol.

[0070] Weight-average molecular weight is preferably measured by gel permeation chromatography connected to a Malles detector. This is the weight-average molecular weight.

[0071] Composition of polymer composition The polymer composition is obtained by polymerizing at least one cationic hydrophilic monomer in the presence of a host polymer selected from the group consisting of poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof.

[0072] The at least one cationic hydrophilic monomer is advantageously selected from vinyl monomers, particularly acrylamide derivatives, acrylic acid derivatives, allyl derivatives or maleic acid derivatives having a protonable amine functional group or an ammonium group (advantageously a quaternary ammonium group). Preferably, the at least one cationic hydrophilic monomer is selected from the group consisting of: diallyl dialkylammonium salts, such as dimethyl diallyl ammonium chloride (DADMAC); acidified or quaternized salts of dialkyl-aminoalkyl (meth)acrylamides, such as (3-methacrylamidopropyl)trimethylammonium chloride (MAPTAC) and (3-acrylamidopropyl)trimethylammonium chloride (APTAC); acidified or quaternized salts of dialkyl-aminoalkyl acrylates, such as quaternized or salted dimethylaminoethyl acrylate (DMAEA); acidified or quaternized salts of dialkyl-aminoalkyl methacrylates, such as quaternized or salted dimethylaminoethyl methacrylate (DMAEMA); acidified or quaternized salts of N,N-dimethylallylamine; acidified or quaternized salts of diallyl methylamine; acidified or quaternized salts of diallylamine; and salts containing an amide group -N(R 2 )-CO-R 1 Vinylamine is obtained by hydrolysis (basic or acidic), wherein R 1 and R 2 The monomer is independently a hydrogen atom or an alkyl chain with 1 to 6 carbon atoms, such as vinylamines derived from the hydrolysis of vinylformamide; vinylamines obtained by Hoffmann degradation; and mixtures thereof. Advantageously, the alkyl group is C1-C7, preferably C1-C3, and can be a straight-chain, cyclic, saturated, or unsaturated chain. Preferably, the cationic hydrophilic monomer is selected from the group consisting of: quaternized or salt-forming dimethylaminoethyl acrylate (DMAEA), quaternized or salt-forming dimethylaminoethyl methacrylate (DMAEMA), and mixtures thereof. More preferably, it is quaternized or salt-forming dimethylaminoethyl acrylate (DMAEA).

[0073] Based on the total molar amount of the polymerized monomers, the amount of the polymerized cationic hydrophilic monomers is advantageously 1 to 80 mol%, preferably 2 to 60 mol%, more preferably 5 to 40 mol%.

[0074] Those skilled in the art will know how to prepare quaternized monomers, for example, by means of RX-type quaternizing agents, where R is an alkyl group and X is a halogen or sulfate group.

[0075] "Quaternary ammonium alkylating agent" refers to a molecule that can alkylate tertiary amines.

[0076] The quaternizing agent may be selected from dialkyl sulfate containing 1 to 6 carbon atoms or alkyl halides containing 1 to 6 carbon atoms. Preferably, the quaternizing agent is selected from the group consisting of chloromethane, benzyl chloride, dimethyl sulfate, diethyl sulfate, and mixtures thereof.

[0077] In addition, the present invention also includes DADMAC-type monomers, APTAC-type monomers and MAPTAC-type monomers, wherein the counterion is sulfate, fluoride, bromide or iodide instead of chloride.

[0078] The at least one cationic hydrophilic monomer can be polymerized in the presence of one or more hydrophilic monomers, wherein the hydrophilic monomer is selected from the group consisting of: nonionic hydrophilic monomers, anionic hydrophilic monomers, zwitterionic hydrophilic monomers and mixtures thereof.

[0079] In addition to at least one cationic hydrophilic monomer, the preparation of a polymer composition may include polymerizing at least one monomer selected from the group consisting of: nonionic hydrophilic monomers, anionic hydrophilic monomers, zwitterionic hydrophilic monomers, and mixtures thereof.

[0080] Advantageously, the nonionic hydrophilic monomers used in this invention are selected from the group consisting of: acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethylacrylamide, N,N-dialkylacrylamide (e.g., N,N-dimethylacrylamide or N,N-diethylacrylamide), N,N-dialkylmethylacrylamide, alkoxyacrylate, alkoxymethacrylate, N-vinylpyrrolidone, N-hydroxymethyl (meth)acrylamide, N-vinylcaprolactam, N-vinylformamide (NVF), N-vinylacetamide, N-vinylimidazolium, N-vinylsuccinimide, acrylmorpholine (ACMO), glycidyl methacrylate, vinyl acetate, glyceryl methacrylate, diketone acrylamide, methacrylic anhydride, acrylonitrile, maleic anhydride, itaconic anhydride, itacamide, hydroxyalkyl (meth)acrylate, thioalkyl (meth)acrylate, isoprene alcohol and its alkoxy derivatives, hydroxyethyl (meth)acrylate and its alkoxy derivatives, hydroxypropyl (meth)acrylate and its alkoxy derivatives, and mixtures thereof. Among these nonionic monomers, the alkyl group is advantageously C1-C5, and more advantageously C1-C3. Preferably, the nonionic hydrophilic monomer is acrylamide.

[0081] Based on the total molar amount of the polymerized monomers, the amount of the polymerized nonionic hydrophilic monomers is advantageously 20 to 99 mol%, preferably 40 to 98 mol%, more preferably 60 to 95 mol%.

[0082] Advantageously, the anionic hydrophilic monomers used in this invention are selected from monomers having vinyl functional groups (especially acrylic acid, sulfonic acid, maleic acid, fumaric acid, itaconic acid, or allyl functional groups). They may also contain carboxyl, phosphonate, phosphate, sulfonate, sulfate groups, or another group with an anionic charge. Preferred monomers belonging to this class are, for example, acrylic acid; methacrylic acid; dimethacrylic acid; itaconic acid; C1-C3 itaconic acid half ester; acryloyl chloride; crotonic acid; maleic acid; fumaric acid; 3-acrylamido-3-methylbutyric acid; strong acid monomers having, for example, sulfonic or phosphonic functional groups, such as vinyl sulfonic acid, vinyl phosphonic acid, allyl sulfonic acid, methyl allyl sulfonic acid, 2-methylene propane-1,3-disulfonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allyl phosphonic 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, allyl phosphonate diethyl ester, carboxyethyl acrylate; water-soluble salts of these monomers, such as their alkali metal salts, alkaline earth metal salts or ammonium salts; and mixtures thereof. Preferably, the anionic hydrophilic monomer is acrylic acid or a salt thereof.

[0083] Based on the total molar amount of the polymerized monomers, the amount of polymerized anionic hydrophilic monomers is advantageously 0 to 80 mol%, preferably 1 to 60 mol%, more preferably 2 to 40 mol%.

[0084] In one implementation, the anionic hydrophilic monomer can be partially or completely salted.

[0085] "Salt formation" refers to the formation of salts by the -R group of anionic monomers. a (=O)-OH type (where R) a A proton representing at least one acidic functional group (P, S, or C) is substituted by a metal cation or an ammonium cation to form -R. a (=O)-OX type (X is a metal cation or an organic cation) salt. In other words, the non-salt-forming form corresponds to the acid form of the monomer, for example, R in the case of a carboxylic acid functional group. b -C(=O)-OH, while the salt-forming form of the monomer corresponds to R. b -C(=O)-O- X + Form, X + Corresponding to basic cations or organic cations. Acidic functional groups can partially or completely form salts.

[0086] Salt formation advantageously corresponds to alkali metal salts (Li, Na, K, etc.), alkaline earth metal salts (Ca, Mg, etc.), or ammonium salts (e.g., ammonium ions or tertiary ammonium) or mixtures thereof. Preferred salts are sodium salts.

[0087] Salt formation can occur partially or entirely before, during, or after polymerization.

[0088] In one embodiment, 1 to 100 mol%, preferably 10 to 90 mol%, of the anionic hydrophilic monomer is in salt-forming form.

[0089] Advantageously, the zwitterionic hydrophilic monomer used is selected from vinyl derivatives (advantageously acrylamide, acrylic, allyl or maleic acid derivatives).

[0090] Preferably, the monomer contains an amine or ammonium functional group (e.g., quaternary ammonium) and a carboxylic acid (or carboxylate) type acid functional group, a sulfonic acid (or sulfonate) type acid functional group, or a phosphoric acid (or phosphate) type acid functional group.

[0091] The zwitterionic hydrophilic monomer is advantageously selected from the group consisting of: dimethylaminoethyl acrylate derivatives, such as 2-((2-(acryloyloxy)ethyl)dimethylammonium)ethane-1-sulfonate, 3-((2-(acryloyloxy)ethyl)dimethylammonium)propane-1-sulfonate, 4-((2-(acryloyloxy)ethyl)dimethylammonium)butane-1-sulfonate, [2-(acryloyloxy)ethyl](dimethylammonium)acetate, dimethylaminoethyl methacrylate derivatives, such as 2-((2-(methacryloyloxy)ethyl)dimethylammonium)ethane-1-sulfonate, 3-((2-(methacryloyloxy)ethyl)dimethylammonium)propane-1-sulfonate, 4-((2-(methacryloyloxy)ethyl)dimethylammonium)butane-1-sulfonate, [2 [3-(methacryloyloxy)ethyl](dimethylammonium)acetate, dimethylammonium propylacrylamide derivatives, such as 2-((3-acryloamidopropyl)dimethylammonium)ethane-1-sulfonate, 3-((3-acryloamidopropyl)dimethylammonium)propane-1-sulfonate, 4-((3-acryloamidopropyl)dimethylammonium)butane-1-sulfonate, [3-(acryloyloxy)propyl](dimethylammonium)acetate, dimethylammonium propylmethacrylamide or its derivatives, such as 2-((3-methacryloamidopropyl)dimethylammonium)ethane-1-sulfonate, 3-(dimethylammonium)propane-1-sulfonate, 4-((3-methacryloamidopropyl)dimethylammonium)butane-1-sulfonate and propyl[3-(methacryloyloxy)](dimethylammonium)acetate and mixtures thereof.

[0092] Other zwitterionic hydrophilic monomers may be used, particularly those described by the applicant in document WO2021 / 123599.

[0093] Based on the total molar amount of the polymerized monomers, the amount of the polymerized zwitterionic hydrophilic monomers is advantageously less than 30 mol%, preferably less than 10 mol%.

[0094] In a preferred embodiment, the polymer composition is free of zwitterionic hydrophilic monomers.

[0095] In one embodiment, the polymerization of the polymer composition may include one or more hydrophobic monomers.

[0096] Advantageously, the hydrophobic monomers used are selected from the group consisting of (i)C4-C 30 Alkyl chain or (ii) aryl alkyl (C4-C) 30 Alkyl, C4-C 30 (iii) aryl acrylates, or (iv) propoxylated, or (v) ethoxylated, or (v) ethoxylated and propoxylated; alkyl aryl sulfonates (C4-C 30 Alkyl, C4-C 30 aryl); having (i)C4-C 30 Alkyl chain, or (ii) arylalkyl (C4-C 30 Alkyl, C4-C 30 (iii) aryl, or (iv) propoxylated, or (v) ethoxylated, or (v) ethoxylated and propoxylated monosubstituted or disubstituted (meth)acrylamides; anionic or cationic (meth)acrylamide or (meth)acrylic acid monomer derivatives with hydrophobic chains; and mixtures thereof. Hydrophobic monomers may include halogen atoms, for example, chlorine.

[0097] Among these hydrophobic monomers: - Alkyl groups are preferably C4-C 20 More preferably, C4-C8. C6-C 20 The alkyl group is preferably a straight-chain alkyl group, while C4-C5 alkyl groups are preferably branched. - Arylalkyl groups are preferably C7-C 25 More preferably C7-C 15 , - The ethoxylated chain advantageously comprises 1 to 200, preferably 6 to 100, more preferably 10 to 40 -CH2-CH2-O- groups. - The propoxylated chain advantageously comprises 1 to 50, more preferably 1 to 20 -CH2-CH2-CH2-O- groups.

[0098] Preferred hydrophobic monomers belonging to these categories are, for example: - (Meth)hexyl acrylate, (Meth)octyl acrylate, octyl(meth)acrylamide, (Meth)acrylate lauryl acrylate, lauryl(meth)acrylamide, (Meth)acrylate myristyl acrylate, myristyl(meth)acrylamide, (Meth)acrylate pentadecyl acrylate, pentadecyl(meth)acrylamide, (Meth)acrylate hexadecyl acrylate, hexadecyl(meth)acrylamide, (Meth)acrylate oleyl ester, oleyl(meth)acrylamide, (Meth)acrylate mustard ester, erucic acid (meth)acrylamide, N-tert-butyl(meth)acrylamide, vinylpyridine, 2-ethylhexyl acrylate, C4-C 22 Itaconic acid half ester, C4-C 22 Acidified or quaternized salts of dialkylaminoalkyl (meth)acrylates, C4-C 22 Acidified or quaternized salts of dialkylaminoalkyl(methyl)acrylamide, acrylamide undecanoic acid, and mixtures thereof. - Allyl cationic derivatives of formula (I) or (II): in: R: Independently an alkyl chain containing 1 to 4 carbons; R1: An alkyl or aralkyl chain containing 8 to 30 carbon atoms; X: Halogen ions selected from the following groups: bromide ions, chloride ions, iodide ions, fluoride ions, and any negatively charged counterions; And preferably, the (meth)acryloyl type hydrophobic cationic derivative corresponding to formula (III): in: - A represents O or N-R5 (preferably A represents N-R5). - R2, R3, R4, R5, R6, R7: independently hydrogen atoms or alkyl chains containing 1 to 4 carbon atoms (R2 and R3 are preferably hydrogen atoms). - Q: Alkyl chains containing 1 to 20 carbons, - R8: An alkyl or aralkyl chain containing 8 to 30 carbons. - X: Selected from the following groups of halide ions: bromide ions, chloride ions, iodide ions, fluoride ions, and any negatively charged counterion.

[0099] The polymer composition advantageously contains less than 3 mol% of hydrophobic monomers.

[0100] When a polymer composition contains hydrophobic monomers, they are present in an amount that makes the polymer composition soluble in water.

[0101] In a preferred embodiment, the polymer composition does not contain hydrophobic monomers.

[0102] In the process of preparing the polymer composition, those skilled in the art will adjust the amount of different monomers so as not to exceed 100 mol.

[0103] In a preferred embodiment, the polymer composition is obtained by polymerizing at least two different types of hydrophilic monomers, at least one cationic hydrophilic monomer, and advantageously at least one nonionic hydrophilic monomer in the presence of at least one water-soluble polymer selected from poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof. Preferably, the polymer composition is obtained by polymerizing a cationic hydrophilic monomer (e.g., DMAEA quaternized with chloromethane) and acrylamide.

[0104] The mass ratio between the hydrophilic monomer (optionally hydrophobic) and the host polymer is advantageously between 99 / 1 and 1 / 99, preferably between 95 / 5 and 40 / 60.

[0105] Obtaining polymer compositions The polymer composition is obtained by polymerizing at least one cationic hydrophilic monomer in the presence of at least one water-soluble polymer selected from poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof. Optionally, the polymerization is carried out in the presence of at least one branching agent and / or at least one transfer agent.

[0106] The optional branching agent and optional transfer agent are different from the host polymer. They are also different from the monomers that are polymerized in the presence of the host polymer to prepare the polymer composition.

[0107] The branching agent is advantageously selected from the group consisting of: - Structural agents selected from the group consisting of: polyene-bonded unsaturated compounds (having at least two unsaturated functional groups) that are different from cationic hydrophilic monomers, such as vinyl functional groups, especially allyl or acrylic functional groups, and such as methylenebisacrylamide (MBA), triallylamine, tetraallyl ammonium chloride, or 1,2-dihydroxyethylenebis-(N-acrylamide). - Compounds having at least two epoxy functional groups, - A compound having at least one unsaturated functional group and one epoxy functional group. - Macromolecular initiators, such as polyperoxides, polyazo compounds, and polyols. - Functionalized polysaccharides, - Water-soluble metal complexes, which consist of the following: *Metals with a valence greater than or equal to 3, such as, but not limited to, aluminum, boron, zirconium, or titanium, and *Ligands with hydroxyl functional groups can be mentioned.

[0108] Based on the total weight of the monomers used in the preparation of the polymer composition, the amount of branching agent is advantageously 0 to 1000 ppm, more preferably 1 to 500 ppm.

[0109] When a polymer composition contains a branching agent, the polymer composition remains soluble in water. Those skilled in the art know how to adjust the amount of the branching agent, and optionally the amount of the transfer agent, to achieve this result.

[0110] In one embodiment, the polymerization composition does not contain the use of a branching agent during the polymerization process.

[0111] The transfer agent is advantageously selected from the group consisting of: methanol; isopropanol; 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; mercaptoacetic acid; mercaptopropionic acid; thiolactic acid; thiomalic acid; cysteine; aminoethanethiol; mercaptoacetate; allyl phosphites; allyl thiols, such as n-dodecyl thiols; sodium methylallyl sulfonate; calcium methylallyl sulfonate; magnesium methylallyl sulfonate; potassium methylallyl sulfonate; ammonium methylallyl sulfonate; alkyl phosphites, such as trialkyl phosphites (C 12 -C 15 ) esters, dioleyl hydrogen phosphite, dibutyl phosphite; dialkyl dithiophosphates, such as dioctyl phosphonate; tert-nonyl thiols; 2-ethylhexyl mercaptoacetate; n-octyl thiols; n-dodecyl thiols; tert-dodecyl thiols; isooctyl mercaptoacetate; 2-ethylhexyl mercaptoacetate; 2-ethylhexyl mercaptoacetate; polythiols; and mixtures thereof. Preferably, this is sodium hypophosphite or sodium formate.

[0112] In one embodiment, the transfer agent is a polytransfer agent, such as a polythiol polymer.

[0113] The amount of transfer agent is advantageously 0 to 1000 ppm, more preferably 1 to 500 ppm, based on the total weight of the monomers used in the preparation of the polymer composition.

[0114] In a preferred embodiment, the water-soluble polymer acts as a transfer agent. Therefore, the polymerization of at least one cationic hydrophilic monomer can be carried out in the absence of a non-polymer transfer agent. Advantageously, the non-polymer transfer agent has a molecular weight of less than 200 g / mol.

[0115] In one embodiment, the polymer composition is prepared without the use of a transfer agent.

[0116] In a preferred embodiment, the at least one cationic hydrophilic monomer or the monomer constituting the water-soluble polymer is derived from a raw material containing at least a portion of renewable and non-fossil sources.

[0117] In the context of this invention, the term "renewable and non-fossil-derived" refers to a source of compounds derived from biomass or syngas (syngas), i.e., the result of one or more chemical transformations of one or more natural and non-fossil-derived feedstocks. The terms "bio-derived" or "bioresource-based" can also be used to describe compounds that are renewable and non-fossil-derived. Renewable and non-fossil-derived compounds include renewable and non-fossil feedstocks from the circular economy that have been pre-recycled once or multiple times during the recycling process of materials derived from biomass, such as materials from polymer depolymerization or from pyrolysis oil conversion.

[0118] According to the present invention, "at least partially renewable and non-fossil-derived" means that, based on the total carbon weight of the compound, the content of bio-derived carbon is from 5% to 100% by weight, preferably at least 30%, more preferably at least 50%, even more preferably at least 70%, more preferably at least 90%, and even more preferably 100% bio-derived carbon.

[0119] In the context of this invention, the bio-source properties of the compounds are characterized using standard ASTM D6866-21 Method B, and the bio-source content of the compounds is determined. This value is expressed as a weight percentage of bio-source carbon based on the total weight of carbon in the compound.

[0120] ASTM D6866-21 is a test method that teaches how to measure the biogenic carbon content of solid, liquid, and gaseous samples using radiocarbon analysis experiments.

[0121] This standard primarily utilizes accelerator mass spectrometry (AMS). This technique is used to naturally measure the presence of radionuclides in a sample, where atoms are ionized, accelerated to high energies, separated, and counted individually in a Faraday cup. This high-energy separation is highly effective at shielding against isotopic interference, allowing AMS to accurately measure the abundance of carbon-14 relative to carbon-12 (14C / 12C) with an accuracy of 1.10. -15 .

[0122] ASTM D6866-21 Standard Method B uses AMS and IRMS (isotope ratio mass spectrometry). This testing method allows for the direct differentiation between contemporary carbon-based carbon atoms and fossil-based carbon atoms. The measurement of the carbon-14 versus carbon-12 or carbon-14 versus carbon-13 content of a product is determined based on modern carbon-based reference materials accepted in the field of radiocarbon dating (e.g., NIST Standard Reference Material (SRM) 4990C (oxalic acid)).

[0123] The standard describes the sample preparation method and requires no special instructions, as it is a commonly used procedure.

[0124] The analysis, interpretation, and reporting of the results are described below. The isotopic ratios of carbon-14 to carbon-12 or carbon-14 to carbon-13 content were measured using AMS. These isotopic ratios were determined relative to a standard traceable to the modern reference standard NIST SRM 4990C. The “modern carbon fraction” (fM) represents the ratio of the carbon-14 content in the tested product to a modern standard. It is often referred to as the modern carbon percentage (pMC), which is equivalent to fM (e.g., fM1 = 100 pMC).

[0125] All pMC values ​​obtained from radiocarbon analysis must be corrected for isotopic fractionation using a given stable isotope. Where possible, correction should be made using the carbon-14 to carbon-13 ratio determined directly using AMS. If this is not possible, correction should be made using δ¹³C (δ¹³C) measured by IRMS, CRDS (cavity ring-down spectroscopy), or any other equivalent technique that can provide an accuracy within ±0.3‰.

[0126] "Zero pMC" means that there is absolutely no measurable 14C in the material above the background signal, thus indicating a fossil (e.g., petroleum-based) carbon source. A pMC value of 100 indicates a completely "modern" carbon source. pMC values ​​from 0 to 100 represent the proportion of carbon derived from a fossil source relative to a "modern" source.

[0127] The pMC may be higher than 100% due to the ongoing but gradually diminishing effects of 14C injection into the atmosphere resulting from the atmospheric nuclear testing program. The pMC value needs to be adjusted using an atmospheric correction factor (REF) to obtain the actual biogenic content of the sample.

[0128] The correction factor is based on the excess 14C activity in the atmosphere at the time of testing. The REF value for 2015 was 102 pMC based on measurements of CO2 in the air of rural Lutjewad, Groningen. The first edition of this standard (ASTM D6866-04) had a reference value of 107.5 pMC in 2004, while subsequent editions of ASTM D6866-10 (2010) had a reference value of 105 pMC. These data points represent a decrease of 0.5 pMC per year. Therefore, prior to 2019, the values ​​in Table 1 below were used as REF values ​​on January 2nd of each year, reflecting the same decrease of 0.5 pMC per year. The REF values ​​(pMC) for 2020 and 2021 were determined to be 100.0 based on continuous measurements in the Netherlands (Lutjewad, Groningen) up to 2019. The following are references reporting carbon isotope ratio data for 14C and 13C, respectively: Roessler, N., Valenta, RJ, and van Cauter, S., “Time-resolved Liquid Scintillation Counting”, LiquidScintillation Counting and Organic Scintillators, Ross, H., Noakes, JE, and Spaulding, JD, Eds., Lewis Publishers, Chelsea, MI, 1991, pp. 501-511; and Allison, CE, Francy, RJ, and Meijer, HAJ, “Reference and Intercomparison Materials for Stable Isotopes of Light Elements”, International Atomic Energy Agency, Vienna, Austria, IAEATECHDOC-825, 1995.

[0129] The percentage of bio-derived carbon content is calculated by dividing pMC by REF and multiplying the result by 100. For example, [10²(pMC) / 10²(REF)] × 100 = 100% bio-derived carbon. The result is expressed as a weight percentage (wt%) of bio-derived carbon relative to the total carbon weight in the compound. Table 1: Modern Carbon Percentage Reference Values ​​(pMC) In a particularly preferred embodiment, 100 wt% of the carbon in the polymer composition is derived from a raw material containing recycled or bio-based materials, with the bio-based carbon content measured according to ASTM D6866-21 Method B.

[0130] Preparation of polymer compositions Typically, the polymeric composition can be obtained using any polymerization technique well known to those skilled in the art. In particular, this can be achieved through: solution polymerization; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous or reverse phase); suspension polymerization; reactive extrusion polymerization; water-in-water polymerization; or micellar polymerization. Preferably, the polymerization is reverse emulsion polymerization or water-in-water polymerization. More preferably, it is reverse emulsion polymerization.

[0131] The polymerization is typically a radical-controlled free radical polymerization. Free radical polymerization includes free radical polymerization via UV, azo, redox, or thermal initiators, as well as controlled radical polymerization (CRP) or matrix polymerization techniques.

[0132] Preparation of polymer composition-reverse emulsion The term "reverse emulsion" refers to reverse emulsions and reverse microemulsions. These emulsions are water-in-oil emulsions, in which an aqueous phase is dispersed in the form of microdroplets or droplets in a lipophilic phase.

[0133] Reverse emulsions consist of a two-phase medium. They can be unstable in the absence of surfactants (the surfactant group includes water-in-oil and oil-in-water emulsifiers). Under stirring, hydrophilic particles dispersed in the lipophilic phase are observed, exhibiting a wide size distribution with an average size of approximately 1 micrometer. During reverse emulsion polymerization, monomers are dispersed in large droplets (diameter: approximately 50 nm to 10 µm) and small emulsion micelles (diameter: approximately 5 to 10 nm).

[0134] This polymerization technique is well known to those skilled in the art. It involves placing a hydrophilic phase into an emulsion containing one or more monomers in a lipophilic phase. This emulsification is accomplished using a water-in-oil emulsifier.

[0135] Inverse emulsions typically contain at least: - A hydrophilic phase containing at least one hydrophilic monomer; - Lipophilic phase; - At least one water-in-oil emulsifier; - Optional oil-in-water emulsifier.

[0136] "Water-in-oil emulsifiers" refer to compounds that can emulsify water in oil, and "oil-in-water emulsifiers" are compounds that can emulsify oil in water. Generally, water-in-oil emulsifiers are considered surfactants with an HLB strictly less than 8, and oil-in-water emulsifiers are surfactants with an HLB greater than or equal to 10. Surfactants with an HLB of 8 to 10 are considered wetting agents. Those skilled in the art may refer to Chapter 11 of K. Holmberg's "Handbook of Applied Surface and Colloid Chemistry" if needed.

[0137] The hydrophilic-lipophilic balance (HLB) of a compound is a measurement of its hydrophilicity and / or lipophilicity, determined by calculating the values ​​in different regions of the molecule, as described by Griffin in 1949.

[0138] In this invention, the Griffin method is employed, which calculates values ​​based on the chemical groups of molecules. Griffin proposes a dimensionless number from 0 to 20 to provide solubility information for water and oil.

[0139] The HLB value of a substance with a total molecular mass of M and a hydrophilic molecular mass of Mh is obtained by the following formula: HLB = 20 (Mh / M).

[0140] Water is the hydrophilic phase of an emulsion.

[0141] The lipophilic phase of an emulsion can be mineral oil, vegetable oil, synthetic oil, or a mixture of several of these oils.

[0142] Examples of mineral oils are those containing aliphatic, cycloalkanes, paraffins, isoparaffins, cycloparaffins, or naphthyl saturated or unsaturated hydrocarbons.

[0143] Examples of vegetable oils include squalene, ester-type or triglyceride-type oils such as cocoyl octanoate / caprylate, octyl dodecyl myristate, ethoxylated vegetable oils, jojoba oil, and macadamia oil.

[0144] Examples of synthetic oils are hydrogenated polydecene or hydrogenated polyisobutylene, and esters (such as octyl stearate or butyl oleate). ExxonMobil's Exxsol® product line is well-suited for this purpose.

[0145] Water-in-oil emulsifiers are advantageously selected from the group consisting of: polyesters with a molecular weight of 1000 to 3000 g / mol; condensation products of poly(isobutylene) succinic acid or its anhydrides with polyethylene glycol; sequential block polymers with a molecular weight of 2500 to 3500 g / mol, such as those sold under the name Hypermer®; sorbitan extracts, such as monooleate or polyoleate, polyethoxylated sorbitan esters; diethoxylated cetyl alcohol; tetraethoxylated lauryl acrylate; condensation products of fatty alcohols larger than ethylene, such as oleyl alcohol reaction products having two ethylene oxide units; condensation products of alkylphenols and ethylene oxide, such as nonylphenol reaction products having four ethylene oxide units. Ethoxylated fatty amines such as Witcamide® 511, alkyl phosphates, betaine-based products, and ethoxylated amines are also good candidates for water-in-oil emulsifiers.

[0146] Based on the total weight of the reverse emulsion, the amount of water-in-oil emulsifier in the reverse emulsion is advantageously 0.5 to 10% by weight, preferably 1 to 6% by weight, and more preferably 2 to 4% by weight.

[0147] The method of the present invention may include adding at least one oil-in-water emulsifier.

[0148] Oil-in-water emulsifiers are advantageously selected from the group consisting of: ethoxylated nonylphenol, preferably having 4 to 10 ethoxy groups (i.e., preferably having a degree of ethoxylation of 4 to 10); ethoxylated / propoxylated alcohols, preferably having ethoxy / propoxy groups comprising 12 to 25 carbon atoms; ethoxylated tridecyl alcohol; ethoxylated / propoxylated fatty alcohols; ethoxylated sorbitan esters (advantageously having 20 molar equivalents of ethylene oxide); polyethoxylated sorbitan laurate (advantageously having 20 molar equivalents of ethylene oxide); polyethoxylated castor oil (advantageously having 40 molar equivalents of ethylene oxide); and decaethoxylated oleodecyclic alcohol. alcohol); heptaoxyethylated lauryl alcohol; polyethoxylated sorbitan monostearate (advantageously having 20 molar equivalents of ethylene oxide); cetyl ether polyethoxylated alkylphenol (advantageously having 10 molar equivalents of ethylene oxide); aryl ether alkyl polyethylene oxide ethylenepolyoxides); N-cetyl-N-ethylmorpholinium ethyl sulfate; sodium lauryl sulfate; condensation products of fatty alcohols with ethylene oxide (advantageously having 10 molar equivalents of ethylene oxide); condensation products of alkylphenols with ethylene oxide (advantageously having 12 molar equivalents of ethylene oxide); condensation products of fatty amines with 5 molar equivalents or more (advantageously 5 to 50 molar equivalents) of ethylene oxide; condensates of ethoxylated tristyrylphenol, ethylene oxide and partially esterified polyols with aliphatic chains, and their anhydrous forms; amine oxides advantageously having alkyl polyglucosides; glucamides; phosphate esters; alkylbenzene sulfonic acids and their salts; and surfactant block polymers and mixtures thereof. The alkyl groups in these oil-in-water emulsifiers refer to straight-chain or branched groups, advantageously having 1 to 20 carbon atoms, more advantageously having 3 to 15 carbon atoms. Furthermore, the aryl groups of these oil-in-water emulsifiers advantageously contain 6 to 20 carbon atoms, and more advantageously 6 to 12 carbon atoms.

[0149] Typically, based on the total weight of the reverse emulsion, the reverse emulsion contains 1 to 4% by weight of an oil-in-water emulsifier.

[0150] The oil-in-water emulsifier can be added before, during, or after polymerization. Preferably, the oil-in-water emulsifier is added after polymerization.

[0151] The weight ratio of the hydrophilic phase to the lipophilic phase in the reverse emulsion is advantageously 50 / 50 to 90 / 10, preferably 60 / 40 to 85 / 15, and more preferably 70 / 30 to 80 / 20.

[0152] Based on the total weight of the reverse emulsion, the reverse emulsion advantageously contains 20 to 55% by weight, preferably 30 to 45% by weight, of a polymer composition.

[0153] Preparation of polymer composition - water-in-water polymerization Water-in-water polymerization involves polymerizing at least one hydrophilic monomer in an aqueous phase saturated with salt or charged substances. As polymer chains extend, the polymer precipitates as droplets. Thus, a polymer dispersion (discontinuous phase) in the form of dispersed droplets is obtained in the salt-saturated aqueous phase (continuous phase). In this system, the two phases are in thermodynamic equilibrium due to the immiscibility of the polymer in the salt-saturated or charged substance-saturated aqueous phase.

[0154] Water-in-water polymerization is based on stabilizing the reaction medium by forcing the formation of a polymer precipitate. This polymerization is advantageously achieved according to one of three methods: - Water saturation through additives prevents polymer particles from forming and hydrating upon contact with the continuous phase. These additives are primarily salts or ionic substances that inhibit the dissolution of the compound by shielding surface charges and the ionic forces they generate in solution.

[0155] - By saturating water with additives, the expansion of the polymer produced by polymerization can be restricted through steric hindrance mechanisms. This primarily stabilizes the polymer; - A combination of the two methods mentioned above.

[0156] These additives (salts or ionic substances that prevent the dissolution of compounds) allow compounds present in discontinuous phases to be kept in a well-dispersed state, thus avoiding decantation, creaming, or agglomeration. All of these additives affect the variables of Stokes' law (density and viscosity of the continuous phase).

[0157] These salts are not limited by their properties. These salts can advantageously be alkali metal salts, alkaline earth metal salts, organic cation salts (such as ammonium), and mixtures thereof.

[0158] In the case of this invention, the stabilized polymer corresponds to the host polymer.

[0159] Based on the total weight of the dispersion, the dispersion advantageously contains 5 to 45% by weight, preferably 10 to 40% by weight, and more preferably 15 to 35% by weight of a polymer composition.

[0160] In the process of water-in-water polymerization, the dispersion may also contain fluidizing additives, such as polyfunctional alcohols, such as glycerol, polyethylene glycol and polypropylene glycol; polyalkylene glycols or water-in-oil emulsifiers.

[0161] Those skilled in the art will know how to select and adjust operating conditions to optimize water-in-water polymerization based on the polymer composition they are trying to obtain, as this remains a routine adjustment.

[0162] Physical characteristics of polymer compositions The Brookfield viscosity of the polymer composition is advantageously 100 to 10,000 cps, preferably 200 to 5,000 cps.

[0163] The present invention also relates to a method for manufacturing paper, comprising the following steps: a / Prepare the dried commercial pulp board as described above, b / Prepare the paper, which includes the following steps: - Decompose and dry commercial pulp boards in an aqueous medium to form a concentrated pulp. - Dilute the concentrated pulp to form a diluted pulp. - Paper is formed from diluted pulp. - Dry the paper.

[0164] The present invention also relates to a dried commercial pulp comprising: - 0.001 to 1% by weight of a polymer composition obtained by polymerizing at least one cationic hydrophilic monomer in the presence of at least one water-soluble polymer selected from the group consisting of: poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof; - 79.999 to 99.999% by weight of cellulose fibers; - Optional 0.01 to 20% by weight of inorganic particles.

[0165] Example List of abbreviations: AM: Acrylamide DMAEA.MeCl: Chloromethyl dimethylaminoethyl acrylate DMAEMA.BnCl: Benzyl chloride dimethylaminoethyl methacrylate V-50: 2,2'-Azobis(2-methylpropanedinium) dihydrochloride DMA: Dimethylamine Epi: Epichlorohydrin EDA: Ethylenediamine PVAm: Polyvinylamine Material Bentonite: The bentonite used corresponds to the product sold by Clariant under the name Opazil AOG.

[0166] Silicone: The silica used corresponds to the product sold by CWK under the name KOSTROSOL 0515.

[0167] Polyamine (PA): Polyamine (PA) corresponds to the product sold by SNF SA under the name FL 2949 SEP and corresponds to structured poly(DMA-Epi-EDA) (Mw = 225000g / mol).

[0168] Example 1: Preparation of polymer compositions CP1 and CP2 according to the present invention Example 1a: Preparation of polymer composition CP1 consisting of AM / DMAEA.MeCl (70 mol% / 30 mol%) by reverse emulsion polymerization In a 1 L reactor equipped with a mechanical stirrer, thermometer, coolant, and gaseous nitrogen impregnation rod, an oleophilic phase was prepared by introducing 214.2 g of Exxsol D100S oil, 26 g of dehydrated sorbitan monooleate, and 3.8 g of surfactant polymer (Rhodibloc RS).

[0169] An aqueous phase was prepared by mixing 287.8 g of acrylamide (50 wt% aqueous solution), 210.1 g of DMAEA.MeCl (80 wt% aqueous solution), 0.7 g of water, and 237.5 g of PA. The pH of the solution was adjusted to 4 to 5 using H2SO4 (96 wt% aqueous solution). Then, 150 ppm (based on monomer + polymer weight) of potassium bromate and 1000 ppm (based on monomer + polymer weight) of pentasodium diethylenetriaminepentaacetate were added as a polymerization inhibitor (damper).

[0170] Then, the aqueous phase was transferred to the lipophilic phase and subjected to Ultra-Turax at 8000 rpm. -1 Emulsify for 1 minute to obtain a uniform reverse emulsion.

[0171] The reverse emulsion was deoxidized by nitrogen sputtering for 30 minutes. Polymerization was inhibited by adding sodium bisulfite using a syringe pump until exothermic termination was achieved. The reaction medium was then maintained at 55°C for 1 hour and 30 minutes. The reaction medium was treated with excess sodium bisulfite to reduce the amount of free monomer in the reaction medium.

[0172] The resulting reverse emulsion corresponds to polymer composition CP1.

[0173] The Brookfield viscosity of the obtained reverse emulsion was measured (module UL, NaCl 1 M, 60 rpm). -1 (23°C). For 43% active material, a UL viscosity of 3.61 cps was obtained.

[0174] Example 1b: Preparation of polymer composition CP2 consisting of AM / DMAEA.MeCl (70 mol% / 30 mol%) by water-in-water polymerization. In a 1 L reactor equipped with a mechanical stirrer, thermometer, coolant, and gaseous nitrogen impregnation rod, 195.4 g AM (50 wt% aqueous solution), 135.7 g DMAEA.MeCl (80 wt% aqueous solution), 365 g saturated water containing 240 g PA, 20 g polyethylene glycol, 5 g ammonium sulfate, and 5 g citric acid were mixed. The solution was deoxidized by nitrogen spraying for 30 minutes, and then heated at 42–45 °C. Polymerization was inhibited by adding V-50 using a syringe pump until exothermic termination was achieved. The temperature of the reaction medium was then controlled and maintained at 45 °C for 6 hours.

[0175] The Brookfield viscosity of the obtained water-in-water dispersion was measured (module UL, NaCl 1 M, 60 rpm). -1 (23°C). For 33.7% active material, a UL viscosity of 3.41 cps was obtained.

[0176] Example 1c: Preparation of polymer compositions CP3 and CP-CE1 to CE8 Another polymer composition CP3 was prepared according to Example 1a, and comparative polymer compositions CP-CE1 to CP-CE8 were also prepared.

[0177] Details of all polymer compositions are shown in Table 1 below. Table 1 - Tests conducted. E = Invention, CE = Comparative Example a Corresponding to polymer D described in US8916026B2 b Polymer 1 corresponding to that described in EP0335576 c A mixture of AM / DMAEA.MeCl polymer and PA Example 2: Evaluation of the properties of polymer compositions in a method for preparing dried commercial slurry Eucalyptus Fiber Pulp: The wet pulp is passed through a refiner for 60 minutes at a dry matter concentration of 2% to obtain a shopper degree of 22 to 26. After passing through the refiner, water is added to obtain a cellulose fiber concentration of 1.5% by mass.

[0178] Example 2a: Evaluation of the water retention capacity (WRV) of the polymer composition WRV (Water Retention Value) allows for the quantification of the amount of water bound to the fiber, and this water requires an additional drying step to remove after drainage.

[0179] To measure this value, free water must first be removed using a DDA (Dynamic Drainage Analyzer). The polymer is added to the wet slurry (0.8 L of 1.5% cellulose fiber slurry) in the DDA cylinder while stirring at 1000 rpm. T=0s: Agitator T=10s: Add the polymer composition described in Example 1 (0.2 kg / t) T=20s: Add inorganic particles (1.5 kg / t) if necessary. T=30s: Stop stirring and drain water, continue for 60 s at pH 7 and 200 mbar vacuum.

[0180] The resulting fiber pad was 10 mm thick and then pressed at a pressure of 4 bars to remove any trace amounts of free water, and then weighed (W1).

[0181] The fiber pad was then dried in a heating chamber at 105°C for 4 hours and then weighed again (W2) to measure the remaining amount of bound water.

[0182] Calculate the %WRV value using the following formula: The %WRV values ​​for different tests are summarized in Table 2. The higher the value, the more bound water has been removed. These values ​​are expressed as a percentage improvement based on the blank test (i.e., no polymer). Table 2 - Effect of adding the polymer composition according to the invention on the water-bound value on cellulose fibers compared to the comparative polymer composition examples. These results demonstrate that, compared with existing technologies, the polymer composition of the present invention exhibits superior performance in removing bound water from pulp.

[0183] Especially in the case of the comparative polymer composition CE1, which consists only of polyamine, an increase in the amount of bound water can be observed compared to the blank test. Conversely, when the polyamine is present during monomer polymerization, the resulting complex allows this effect to be offset, and a synergistic effect is observed.

[0184] Example 2b: Effect of fiber pad thickness on bound water retention value (WRV).

[0185] Compared with the comparative polymer composition, the WRV of various fiber pads with different thicknesses (according to or not according to the invention) was measured after adding the polymer composition according to the invention.

[0186] The pH of the drainage was also assessed. Table 3 - Effect of adding or not adding the polymer composition according to the invention and pH on the bound water retention value (WRV) on cellulose fibers on fiber mats of different thicknesses (0.1-50 mm).

[0187] *Pad thickness not specified in this invention ** Water retention achieved at pH 4 These results indicate that the compositions according to the invention improve the drainage of bound water (larger WRV) when the thickness of the fiber mat is at least 1 mm. However, the comparative examples (fiber mats less than 1 mm thick and / or different polymer compositions) did not show any significant improvement.

[0188] As can be seen, contrary to all expectations, when the thickness of the fiber mat is less than 1 mm, especially when the fiber mat has the thickness of paper, the composition according to the invention does not provide any improvement under acidic conditions.

[0189] These results also indicate that, when the thickness is less than 1 mm and depends on the pH used for drainage, additives used to improve drainage during the papermaking process do not improve drainage in the manufacture of dry commercial pulpboard.

[0190] Example 2c: Evaluation of the effect of polymer composition on white water turbidity Turbidity refers to the amount of substances in a suspension that affect the fluid (white water). These suspended substances partially correspond to colloids. Turbidity is measured using a HANNA spectrophotometer, which measures the decrease in light intensity at a wavelength of 860 nm at a 90° angle and is expressed as %NTU.

[0191] Table 4 summarizes the %NTU values ​​for different tests. A higher %NTU value indicates a lower amount of suspended matter affecting the medium. These values ​​are expressed as improvements based on the blank test (i.e., without polymers). Table 4 - Results of white water turbidity after adding the polymer composition according to the invention and the comparative example These results demonstrate that, compared with existing technologies, the polymer composition of the present invention exhibits superior performance in reducing the amount of adhesives present in pulp.

Claims

1. A method for manufacturing dried commercial pulp boards, comprising the following steps: - A cellulose fiber aqueous suspension SA1 was prepared by pulping the original cellulose material in the presence of water. - A polymer composition is added to the cellulose fiber aqueous suspension SA1 to form an aqueous suspension SA2, said polymer composition being obtained by polymerizing at least one cationic hydrophilic monomer in the presence of at least one water-soluble polymer selected from the group consisting of: poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof. - By draining the aqueous suspension SA2 onto a web at a pH of 6 to 8, a fiber mat with a thickness of 1 mm to 100 mm is formed. - The fiber pad is pressed to form a pulp board. - Dry the pulp board to obtain dried commercial pulp.

2. The method according to claim 1, characterized in that... The method includes adding inorganic particles to the aqueous suspension SA1 or SA2 before forming the fiber pad.

3. The method according to claim 2, characterized in that... The inorganic particles are bentonite particles.

4. The method according to any one of claims 2 or 3, characterized in that... The inorganic particles and the polymer composition are added sequentially, with the inorganic particles added before the polymer composition.

5. The method according to any one of claims 1 to 4, characterized in that... The cellulose fiber weight of the dried commercial pulp board is 250 to 5000 g / m³. 2 .

6. The method according to any one of claims 1 to 5, characterized in that... The polymer composition is obtained by polymerizing at least one cationic hydrophilic monomer in the presence of at least one monomer selected from nonionic hydrophilic monomers, anionic hydrophilic monomers, zwitterionic hydrophilic monomers and mixtures thereof, preferably by polymerizing at least one nonionic hydrophilic monomer in the presence of at least one water-soluble polymer.

7. The method according to any one of claims 1 to 6, characterized in that... 100 wt% of the carbon atoms in the polymer composition are derived from raw materials containing recycled or bio-based materials, wherein the carbon atoms preferably have a 100% bio-based carbon content as measured according to ASTM D6866-21 Method B.

8. The method according to any one of claims 1 to 7, characterized in that... The polymer composition is obtained by reverse emulsion polymerization or water-in-water polymerization.

9. The method according to any one of claims 1 to 8, characterized in that... The polymer composition is obtained by reverse emulsion polymerization.

10. A dried commodity pulp, comprising: - 0.001 to 1% by weight of a polymer composition obtained by polymerizing at least one cationic hydrophilic monomer in the presence of at least one water-soluble polymer selected from the group consisting of: poly(dimethylamine-epoxychloropropane), poly(dimethylamine-epoxychloropropane-ethylenediamine), and mixtures thereof; - 79.999 to 99.999% by weight of cellulose fibers; - Optional 0.01 to 20% by weight of inorganic particles.

11. The method according to any one of claims 1 to 9, characterized in that... The monomers used in this invention are prepared by enzyme catalysis or extracted from renewable raw materials.

12. The method according to any one of claims 1 to 9 or 11, characterized in that... The energy used to implement the method is derived from a heat pump or a renewable source, such as wind power, photovoltaic power, or from fuel cells or lithium batteries.

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