Novel polymers and methods for producing the same

Abstract

The present invention relates to a novel water-soluble dialdehyde-functionalized polymer, a process for its preparation and its use, in particular for applications in the field of the manufacture of paper or cardboard.

Description

[Technical Field]

[0001] The present invention relates to novel water-soluble dialdehyde-functionalized (preferably glyoxal-functionalized) polymers, methods for producing the same, and uses, particularly for applications in the field of paper or cardboard manufacturing. [Background technology]

[0002] The paper industry is constantly seeking improvements in the manufacturing methods of paper or cardboard, particularly in terms of cost reduction, yield, productivity, and the characteristics of the final product.

[0003] Water-soluble dialdehyde-functionalized polyacrylamides are widely used in paper manufacturing processes, particularly to improve the dry strength of these papers. These water-soluble polyacrylamides are mainly made from nonionic, cationic, anionic, or amphoteric polymers called base polymers, to which dialdehydes are reacted.

[0004] Reference US20110056640 describes a method for producing paper that yields a compound obtained by the reaction of a dialdehyde-functionalized material with an acrylamide / diallyldimethylammonium chloride copolymer. This method improves drainage only.

[0005] The applicant's document FR2987375 describes an improved method for producing paper, which includes a base copolymer containing a polyfunctional compound incorporated during the polymerization of a base copolymer monomer, and its reaction with a dialdehyde, wherein the incorporation of the polyfunctional compound enables improvements in the drying strength and drainage performance of the paper.

[0006] Reference US20170247489 describes a method for producing paper using a terpolymer obtained by copolymerizing a base polymer with glyoxal, wherein the base polymer is obtained by copolymerizing a primary amide-containing monomer with a cationic monomer.

[0007] Reference US10,730,989 relates to a method for producing (meth)acrylamide copolymer-based papermaking additives. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] US20110056640 [Patent Document 2] FR2987375 [Patent Document 3] US20170247489 [Patent Document 4] US10,730,989 [Patent Document 5] US10,759,746 [Patent Document 6] WO2021123599 [Non-patent literature]

[0009] [Non-Patent Document 1] Handbook for Pulp & Paper Technologists, 4th Edition, GA Smook [Overview of the project] [Problems that the invention aims to solve]

[0010] Currently, there are two main problems with the dialdehyde process (especially glyoxalization).

[0011] The first problem is that commercially available dialdehyde-functionalized (especially glyoxal-functionalized) polyacrylamide products contain a large number of unreacted amide groups, which may react with dialdehyde (especially glyoxal) during storage, leading to continuous crosslinking of the base polyacrylamide molecules and reducing the product's shelf life. In addition, in practice, polyacrylamide contains a relatively small amount, generally less than about 5 mol percent, of ionic monomers, which limits the contribution of the ionic charge of these polymers.

[0012] The second problem relates to the acid treatment used to stop the reaction between the dialdehyde and the base polymer, which is associated with a significant decrease in the viscosity of the aqueous polymer solution. The polymer thus obtained exhibits reduced application performance.

Means for Solving the Problems

[0013] The applicant has surprisingly discovered that the synthesis of a polymer according to a specific method makes it possible to increase its molecular weight without affecting its viscosity. This increase in the base polymer molecular weight gives the paper improved application performance from the perspective of dry strength compared to existing prior art solutions, improves drainage, and thus enables an increase in the speed of the paper machine, and therefore, productivity also seems to improve.

[0014] The use of the polymer obtained from the present invention is part of the general principle of improving product performance, more specifically, dry strength and drainage characteristics. The better performance of the polymer according to the present invention makes it possible to reduce the amount of the product required for application, and therefore, this includes reducing greenhouse gas emissions such as carbon dioxide associated with the production and use of synthetic polymers.

[0015] The present invention relates to a water-soluble dialdehyde-functionalized polymer, - at least one cationic or anionic monomer A, and - at least one non-ionic monomer B, - It is at least one type of structured system, (i) at least one compound I, which is different from at least one monomer A, and is selected from allyl sulfonic acid, methallyl sulfonic acid, allyl disulfonic acid, methallyl disulfonic acid, salts thereof, and mixtures thereof, (ii) At least one monomer different from monomer B, formula (1)

[0016] [ka]

[0017] [In the formula, R1 and R2 are independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a CH2-OH group.] In the formula, R1 and R2 cannot both be hydrogen atoms (if R2=H, then R1≠H; if R1=H, then R2≠H). at least one compound II A structured system including at least one type of structure, - Optionally, at least one zwitterionic or hydrophobic monomer C, - Optionally, at least one crosslinking agent, - Optionally, at least one type of transport agent and This relates to a water-soluble dialdehyde-functionalized polymer containing [the specified compound].

[0018] This water-soluble dialdehyde-functionalized polymer is produced by the following process: a) A step of forming a solution (S1) comprising at least a first fraction (F1) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, b) Polymerization step 1 (PO1) of fraction F1 to form a solution of the first gradient polymer (PG1), c) A step of adding a second fraction (F2) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, to a solution containing PG1, d) A step of polymerization 2 (PO2) of fraction F2 to PG1 to form a solution of the second gradient polymer (PG2), e) A step of adding a third fraction (F3) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, to a solution containing PG2, f) A step of polymerization 3 (PO3) of fraction F3 into PG2 to form a solution containing the base polymer, g) A step of diluting a solution containing a base polymer and reacting at least one dialdehyde (preferably glyoxal) with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized). Obtained according to, At least one of fractions F1, F2, or F3 contains at least one monomer A, At least one of fractions F1, F2, or F3 contains at least one monomer B, At least one of fractions F1, F2, or F3 contains at least one compound I, At least one of fractions F1, F2, or F3 contains at least one compound II.

[0019] Monomer A is either cationic or anionic. It is not a mixture of cationic and anionic monomers.

[0020] If monomer A is anionic, the water-soluble dialdehyde-functionalized polymer does not contain cationic monomers.

[0021] If monomer A is cationic, the water-soluble dialdehyde-functionalized polymer does not contain anionic monomers except for compound I.

[0022] The present invention also relates to a method for producing this water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0023] The present invention also relates to a method for producing paper or cardboard, wherein the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) is realized.

[0024] The present invention also relates to the use of this water-soluble dialdehyde-functionalized polymer (preferably glyoxal-functionalized) in the recovery of hydrocarbons (oil and / or gas); in the drilling or cementing of wells (particularly hydrocarbon wells); in the stimulation of hydrocarbon wells (oil and / or gas), e.g., in hydraulic fracturing, fitting, and conversion; in the treatment of open, closed, or semi-closed circulating water; in the treatment of fermentation masts; in sludge treatment; in construction; in timber treatment; in the treatment of hydraulic compositions (concrete, cement, mortar, and aggregates); in mining; in the formulation of cosmetics; in the formulation of detergents; in textile manufacturing; in the geothermal sector; in the manufacture of sanitary napkins; or in agriculture.

[0025] The present invention also relates to the use of polymers according to the present invention as flocculants, coagulants, binders, fixatives, viscosity reducers, viscosity enhancers, absorbents, friction reducers, drainage agents, charge retainers, dehydrators, conditioning agents, stabilizers, fixatives, film-forming agents, sizing agents, superplasticizer agents, clay inhibitors, or dispersants. [Modes for carrying out the invention]

[0026] "Polymer" is used to specify a copolymer produced using a structured system comprising at least two different monomers, at least one monomer A (cationic or anionic) and at least one nonionic monomer B, and at least one compound I and at least one compound II, which optionally also comprises at least one zwitterionic monomer and / or one hydrophobic monomer and / or a crosslinking agent and / or a transfer agent.

[0027] The water-soluble polymer is dissolved in 10 g / l of deionized water. -1 This refers to a polymer that, when dissolved at a certain concentration under stirring at 25°C, yields an aqueous solution free of insoluble particles.

[0028] In the present invention, the first and second gradient polymers are prepolymers.

[0029] Throughout this specification, viscosity is measured in aqueous solution at 25°C using a Brookfield viscometer.

[0030] In this specification, it is assumed that those skilled in the art can determine a suitable speed according to the Brookfield viscometer module and the viscosity range to be measured. In practice, this type of measurement is part of the general knowledge of those skilled in the art.

[0031] In this invention, "X and / or Y" specifies "X" or "Y", or "X and Y".

[0032] All possible combinations between the various embodiments disclosed, whether they are preferred embodiments or embodiments given as examples, are equally part of the present invention. In addition, where ranges of values ​​are given, these ranges include endpoint values. This disclosure also includes all combinations between endpoint values ​​and these ranges of values. For example, the value range "1 to 20, preferably 5 to 15" includes the ranges "1 to 5", "1 to 15", "5 to 20", and "15 to 20", and the disclosure of values ​​1, 5, 15, and 20.

[0033] The water-soluble base polymer obtained by the method of the present invention is referred to as the base polymer before undergoing the reaction with a dialdehyde (preferably glyoxal) according to step g) below.

[0034] Water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) The present invention relates to a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) characterized by a method for obtaining it.

[0035] The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) according to the present invention is - At least one monomer A that is cationic or anionic, - At least one nonionic monomer B, - (i) at least one compound I, which is different from at least one monomer A, and is selected from allyl sulfonic acid, methallyl sulfonic acid, allyl disulfonic acid, methallyl disulfonic acid, salts thereof, and mixtures thereof, and (ii) At least one monomer different from monomer B, formula (1)

[0036] [ka]

[0037] [R1 and R2 are independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a CH2-OH group.] In the formula, R1 and R2 cannot both be hydrogen atoms (if R2=H, then R1≠H; if R1=H, then R2≠H). at least one compound II A structured system including at least one type of structure, - At least one type of dialdehyde, preferably glyoxal, - Optionally, at least one zwitterionic or hydrophobic monomer C, - Optionally, at least one crosslinking agent, - Optionally, at least one type of transport agent and It includes (or, more favorably, is composed of them).

[0038] Monomer A is either cationic or anionic. It is not a mixture of cationic and anionic monomers.

[0039] If monomer A is anionic, the water-soluble dialdehyde-functionalized polymer does not contain cationic monomers.

[0040] If monomer A is cationic, the water-soluble dialdehyde-functionalized polymer does not contain anionic monomers except for compound I.

[0041] Monomer composition Monomer A The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) according to the present invention is a synthetic polymer. It may contain one or more cationic monomers or one or more anionic monomers (designated "monomer A").

[0042] Advantageously, the cationic monomer A may be selected from vinyl-type monomers, preferably acrylamide, acrylic, allyl, or malee, having an ammonium functional group, and preferably quaternary ammonium. Particularly, non-limiting examples include quaternary dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), diallyldimethylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC), and methacrylamidopropyltrimethylammonium chloride (MAPTAC), and mixtures thereof. Preferably, it is diallyldimethylammonium chloride (DADMAC).

[0043] The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) preferably contains cationic monomer A in an amount between 1 and 60 mol%, preferably between 3 and 40 mol%, more preferably between 4 and 30 mol%, and the remaining monomers constituting the water-soluble dialdehyde-functionalized polymer to reach 100 mol% are selected from monomer B and / or monomer C, preferably from monomer B.

[0044] Those skilled in the art know, for example, how to produce quaternized monomers by RX-type alkyl halides (where R is an alkyl group (preferably C1-C3) and X is a halogen (RX may be methyl chloride in particular)). In addition, the present invention also includes DADMAC, APTAC, and MAPTAC-type monomers in which the halide counterion is fluoride, bromide, or iodide instead of chloride.

[0045] Advantageously, the anionic monomer A may be selected from a larger group. These monomers may have vinyl-type functional groups, particularly acrylic, malee, fuma, malon, itacone, or allyl functional groups. They may also contain carboxylic acid groups, phosphonic acid groups, phosphoric acid groups, sulfonic acid groups, or other groups having an anionic charge. Preferred monomers belonging to this class are, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acrylamide undecanoic acid, 3-acrylamide 3-methylbutanoic acid, maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid (ATBS), vinyl sulfonic acid, vinyl phosphonic acid, 2-sulfoethyl methacrylic acid, sulfopropyl methacrylic acid, sulfopropyl acrylic acid, allylphosphonic acid, styrene sulfonic acid, 2-acrylamide-2-methylpropanedisulfonic acid, their salts, and mixtures thereof. Preferably, it is acrylic acid or itaconic acid, and more preferably acrylic acid.

[0046] Therefore, in certain embodiments of the present invention, the anionic monomer may be chlorinated.

[0047] Chlorinated means that the proton substitution of at least one acidic functional group of the -R(O)-OH type (R=P, S, or C) of anionic monomer A is replaced by a metal cation to form a -R(O)-OX type (X is a metal cation) salt. In other words, the unchlorinated form corresponds to the acidic form of the monomer, for example, RC(=O)-OH in the case of a carboxylic acid functional group, while the chlorinated form of the monomer corresponds to the RC(=O)-O-X+ form, where X+ corresponds to an alkali cation. Chlorination of the acidic functional group of a water-soluble dialdehyde-functionalized polymer can be partial or total.

[0048] The chlorinated form is advantageously an alkali metal salt (Li, Na, K…), an alkaline earth metal salt (Ca, Mg…), or an ammonium salt (e.g., ammonium ion or tertiary ammonium). The preferred salt is a sodium salt.

[0049] Chloridation can be carried out before or after polymerization.

[0050] A water-soluble dialdehyde-functionalized anionic polymer (preferably glyoxalized) preferably contains an anionic monomer A in an amount between 1 and 99 mol%, preferably between 2 and 70 mol%, more preferably between 3 and 50 mol%, and even more preferably between 5 and 35 mol%. The remaining monomers constituting the water-soluble dialdehyde-functionalized polymer to reach 100 mol% are selected from monomer B and / or monomer C, preferably from monomer B.

[0051] In a particular embodiment of the present invention, if the anionic monomer A is 2-acrylamido-2-methylpropanesulfonic acid (ATBS), then it is a hydrated form. The hydrated form is a particular form of ATBS that can be obtained by controlled crystallization of the ATBS monomer. References US10,759,746 describe this hydrated form of ATBS.

[0052] In a preferred embodiment of the present invention, monomer A is preferably a cationic monomer.

[0053] Monomer B The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) may contain one or more nonionic monomers (referred to as "monomer B").

[0054] Advantageously, the nonionic monomer B may be selected from a group that includes water-soluble vinyl monomers in particular. Preferred monomers belonging to this class are, for example, acrylamide, acrylonitrile, methacrylamide, and mixtures thereof. Preferably, this is acrylamide.

[0055] The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) preferably contains nonionic monomer B in an amount between 40 and 99 mol%, preferably between 30 and 98 mol%, more preferably between 60 and 97 mol%, and even more preferably between 70 and 96 mol%.

[0056] Monomer C The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) may contain one or more zwitterionic monomers or hydrophobic monomers (referred to as "monomer C").

[0057] Zwitterionic monomers are ionic monomers with a total charge of zero. In practice, zwitterionic monomers have the same number of cation charges and anion charges.

[0058] Advantageously, zwitterionic monomers that can be used in the context of the present invention can be selected from vinyl-type motifs in particular, especially derivatives of acrylamide, acrylic, allyl, or malee. Preferably, this monomer comprises an amine or quaternary ammonium functional group and a carboxylate, sulfonate, or phosphoric acid-type functional group. The zwitterionic monomer is a dimethylaminoethyl acrylate derivative, for example, 2-((2-9(acryloyloxy)ethyl)dimethylammonio)ethane-1-sulfonate, 3-((2-(acryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate, 4-((2-(acryloyloxy)ethyl)dimethylammonio)butane-1-sulfonate, [2-(acryloyloxy)ethyl [2-(methacryloyloxy)ethyl](dimethylaminoethyl)acetate; derivatives of dimethylaminoethyl methacrylate, e.g., 2-((2-(methacryloyloxy)ethyl)dimethylaminoethyl)ethane-1-sulfonate, 3-((2-(methacryloyloxy)ethyl)dimethylaminoethyl)propane-1-sulfonate, 4-((2-(methacryloyloxy)ethyl)dimethylaminoethyl)butane-1-sulfonate, [2-(methacryloyloxy)ethyl](dimethylaminoethyl) Derivatives of dimethylaminopropylacrylamide, 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, dimethylaminopropylmethylacrylamide; or further, derivatives such as 2-((3-methacrylamidopropyl)dimethylammonio)ethane-1-sulfonate, 3-((3-medimethylammonio)propane-1-sulfonate, 4-((3-methacrylamidopropyl)dimethylammonio)butane-1-sulfonate, and propyl[3-(methacryloyloxy)](dimethylammonio)acetate, as well as mixtures thereof, may be selected.

[0059] Other zwitterionic monomers are described by the applicant in the document WO2021123599.

[0060] The water-soluble dialdehyde-functionalized polymer according to the invention advantageously comprises between 0.001 and 30 mol%, preferably between 0.01 and 20 mol%, more preferably between 0.1 and 15 mol% of zwitterionic monomer.

[0061] Advantageously, the hydrophobic monomer C is an ester of (meth)acrylic acid having an alkyl chain of C4-C 30 alkyl, propoxylated, ethoxylated, or arylalkyl (C4-C 30 alkyl, C4-C 30 aryl) which is ethoxylated and propoxylated; a derivative of (meth)acrylamide presenting an alkyl chain of C1-C3, propoxylated, ethoxylated, or arylalkyl (C4-C 30 alkyl, C4-C 30 aryl), or dialkyl (C4-C 30 alkyl); a derivative of alkylaryl sulfonate (C4-C 30 alkyl, C4-C 30 alkyl, C4-C 30 aryl) presenting an alkyl chain of C4-C 30 alkyl, C4-C 30 aryl), or a mono- or di-substituted amide of (meth)acrylamide; a derivative of (meth)acrylamide presenting an alkyl chain of C4-C 30 alkyl, propoxylated, ethoxylated, or arylalkyl (C4-C 30 alkyl, C4-C 30 aryl), or C4-C 30 dialkyl; alkylaryl sulfonate (C4-C 30alkyl, C4~C 30 The group may be selected from the aryls, and mixtures thereof.

[0062] Water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) generally contain less than 1 mol% hydrophobic monomer C. They may also be hydrophobic monomer C-free.

[0063] If the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) according to the present invention contains one or more hydrophobic monomers C, they are present in amounts such that the polymer remains water-soluble.

[0064] The amounts of each different monomer will be adjusted by those skilled in the art so as not to exceed 100 mol% during the production of the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized). Preferably, monomers A and B represent monomers of 100 mol% of the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0065] structured system The structured systems of water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) are: (i) at least one compound I, (ii) at least one compound II and Includes.

[0066] Compound I is selected from allyl sulfonic acid, methallyl sulfonic acid, allyl disulfonic acid, methallyl disulfonic acid, their salts, and mixtures thereof. Preferably, this is methallyl sulfonic acid, for example, sodium methallyl sulfonate.

[0067] The chlorinated form is advantageously an alkali metal salt (Li, Na, K…), an alkaline earth metal salt (Ca, Mg…), or an ammonium salt (e.g., ammonium ion or tertiary ammonium). The preferred salt is a sodium salt.

[0068] The water-soluble dialdehyde-functionalized polymer is advantageous in that it contains compound I in an amount between 500 and 50,000 ppm, preferably between 1,000 and 20,000 ppm, and more preferably between 2,000 and 10,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of the water-soluble dialdehyde-functionalized polymer.

[0069] Compound II used in the context of the present invention is of formula (1)

[0070] [ka]

[0071] [R1 and R2 are independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a CH2-OH group.] R1 and R2 cannot both be hydrogen atoms (if R2=H, then R1≠H; if R1=H, then R2≠H). It belongs to them.

[0072] Compound II is advantageously selected from N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-isopropylacrylamide, N-methylolacrylamide, and mixtures thereof. Preferably, it is N,N-dimethylacrylamide.

[0073] The water-soluble dialdehyde-functionalized polymer according to the present invention is advantageous in that it contains compound II in an amount between 500 and 50,000 ppm, preferably between 1,000 and 20,000 ppm, and more preferably between 2,000 and 10,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of the water-soluble dialdehyde-functionalized polymer.

[0074] In a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized), the mass ratio of compound I to compound II is preferably between 0.01 and 100, more preferably between 0.1 and 10.

[0075] In a preferred embodiment of the present invention, the amount of compound I is greater than the amount of compound II. Therefore, the mass ratio of compound I to compound II is advantageously greater than 1 and 100 or less, and preferably greater than 1 and 10 or less.

[0076] Optional The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) may further contain at least one crosslinking agent. This crosslinking agent can be selected from, for example, polyethylene unsaturated monomers (having at least two unsaturated functional groups) such as vinyl functional groups, particularly allyl and acrylic, or monomers having at least two epoxy functional groups. Examples include methylenebisacrylamide (MBA), triallylamine, tetraallylammonium chloride, 1,2-dihydroxyethylene bis-(N-acrylamide), and mixtures thereof. Preferably, it is methylenebisacrylamide (MBA).

[0077] The amount of crosslinking agent in the water-soluble dialdehyde-functionalized polymer is advantageously between 5 and 5,000 ppm, more preferably between 50 and 3,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of the water-soluble dialdehyde-functionalized polymer.

[0078] In certain embodiments of the present invention, the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) does not contain a crosslinking agent.

[0079] The water-soluble dialdehyde-functionalized polymer according to the present invention (preferably glyoxalized) may also contain at least one transfer agent selected from, for example, methanol, isopropyl alcohol, sodium hypophosphate, 2-mercaptoethanol, and mixtures thereof. Other transfer agents include xanthogenic salts, dithiocarbonates, dithiocarbamates, and trithiocarbonates, and mixtures thereof, preferably sodium hypophosphate.

[0080] The amount of the transfer agent in the water-soluble dialdehyde-functionalized polymer is advantageously between 10 and 10,000 ppm, more preferably between 50 and 5,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of the water-soluble dialdehyde-functionalized polymer.

[0081] In certain embodiments of the present invention, the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) does not contain a transport agent.

[0082] Physical characteristics of the base polymer The base polymer advantageously has a mass-average molecular weight between 1,000,000 and 25,000,000 daltons, preferably between 2,000,000 and 15,000,000 daltons, more preferably between 2,000,000 and 10,000,000 daltons, for example, between 3,000,000 and 10,000,000 daltons. This is the mass-average molecular weight.

[0083] The mass-average molecular weight is preferably measured by gel permeation chromatography connected to a Malls detector.

[0084] The base polymer is advantageously obtained and used in liquid form.

[0085] The viscosity of the solution containing the base polymer is advantageously between 1,000 and 50,000 cps, preferably between 2,000 and 20,000 cps, for example between 5,000 and 20,000 cps.

[0086] Renewable origins In a preferred embodiment of the present invention, a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) is produced using monomers that are at least partially renewable and of non-fossil origin.

[0087] In the context of the present invention, the term “renewable and non-fossil origin” specifies the origin of a compound that arises from biomass or synthesis gas (syngas), i.e., the result of one or more chemical transformations performed on one or more raw materials of natural and non-fossil origin. The terms “bio-derived” or “bioresource” can also be used to characterize the renewable and non-fossil origin of a compound. The renewable and non-fossil origin of a compound comes from a circular economy and includes renewable and non-fossil raw materials that have been recycled once or more times before in a recycling process of biomass-derived materials, such as materials resulting from polymer depolymerization or the conversion of pyrolysis oils.

[0088] According to the present invention, "at least partially renewable and non-fossil origin" means a bio-derived carbon content that is between 5% and 100% by mass relative to the total carbon mass of the compound, preferably at least 30%, more preferably at least 50%, even more preferably at least 70%, more preferably at least 90%, and even more preferably at least 100%.

[0089] In the context of the present invention, standard ASTM D6866-21, method B is used to characterize the bio-derived nature of a compound and to determine the bio-derived content of the compound. The value is expressed as the mass percentage of bio-derived carbon relative to the total mass of carbon in the compound.

[0090] gradient The base polymer and the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) according to the present invention are gradient polymers.

[0091] A polymer having a gradient structure is composed of at least two monomers, and the change in monomer composition is gradual. Unlike block polymers, which undergo abrupt changes in composition, and random polymers, which do not have continuous changes in composition, gradient polymers are different. Due to the gradual change in composition along the length of the polymer chain, inter-chain and intra-chain repulsive forces are not observed to a great extent.

[0092] Gradient polymerization can be formed by spontaneous or forced gradients. Spontaneous gradient polymerization results from differences in monomer reactivity. Forced gradient polymerization involves varying the monomer composition introduced throughout the polymerization time.

[0093] The forced method includes (1) introducing a first fraction of monomers into the reactor, (2) preferably adding at least one additional monomer fraction different from the first, and (3) polymerization of the monomers introduced into the reactor. Polymerization of the monomers is initiated by the introduction of the first fraction.

[0094] The addition of additional monomer fractions may occur in parallel with the introduction of the first monomer fraction into the reactor (so that the introduction of the fractions can begin and end simultaneously). Alternatively, the start of the supply of the first monomer (first fraction) to the reactor may precede the start of the addition of the second monomer fraction. Alternatively, the first and second fractions may be introduced simultaneously, but the time required to add the second fraction may be longer than the time required to add the first fraction to the reactor. This embodiment is also applicable to methods using at least three monomer fractions.

[0095] According to the method of the present invention, the resulting water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) is formed by the sequential addition of monomers, i.e., it is preferably a forced gradient.

[0096] The method according to the present invention comprises a first fraction (F1) and at least two additional fractions (F2 and F3). At least one of the fractions F1, F2, and F3 of the method is different from the other fractions. Preferably, fractions F1, F2, and F3 are different. Different fractions mean fractions composed of different monomers (ratio of monomers and / or properties), and / or compounds I and II (ratio of compounds I and II and / or properties).

[0097] Polymerization method A stepwise polymerization method for water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) involves the following steps: a) A step of forming a solution (S1) comprising at least a first fraction (F1) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, b) A polymerization step 1 (PO1) of fraction F1 to form a solution of the first gradient polymer (PG1), c) A step of adding a second fraction (F2) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, to a solution containing PG1, d) A step of polymerization 2 (PO2) of fraction F2 to PG1 to form a solution of the second gradient polymer (PG2), e) A step of adding a third fraction (F3) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, to a solution containing PG2, f) Polymerization step 3 (PO3) of fraction F3 to PG2 to form a solution containing the base polymer, g) A step of diluting a solution containing a base polymer and reacting at least one dialdehyde (preferably glyoxal) with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized). Includes, At least one of fractions F1, F2, or F3 contains at least one monomer A, At least one of fractions F1, F2, or F3 contains at least one monomer B, At least one of fractions F1, F2, or F3 contains at least one compound I, At least one of fractions F1, F2, or F3 contains at least one compound II.

[0098] This method may include the addition of additional fractions, but not after step g) of the dialdehyde reaction.

[0099] The improved performance of polymers obtained by the method of the present invention may be due to the fact that polymerization is carried out sequentially and continuously, i.e., without interruption.

[0100] "Sequentially" means that the polymerization of the base polymer monomers takes place in multiple fractions and without interruption; that is, the fractions are added continuously and the polymerization does not stop. Each of the different steps a) to f) is performed sequentially. In other words, in order to obtain the base polymer at the end of polymerization, the first fraction of monomers may be poured in (in a fluid form), polymerize to form the first gradient polymer PG1, which continues to polymerize with fraction F2 to form gradient polymer PG2, which itself continues to polymerize with fraction F3. At least one of fractions F1, F2, and F3 is different from the other fractions. Preferably, fractions F1, F2, and F3 are different. The addition of different fractions in the polymerization method makes it possible to obtain a gradient in the base polymer composition.

[0101] In certain embodiments, polymerization can be stopped after PO1 and / or PO2 and continued at different localizations. In this embodiment, the gradient polymer PG formed during the preceding steps is used. X Fraction F added to X+1 (X=1 or 2) is PG X It polymerizes and interacts with PGX+1 The process forms, and the process continues in subsequent steps to finally obtain the base polymer. Once polymerization is complete, step g) is performed on the base polymer immediately following the end of polymerization or at another time (later). Preferably, it is performed immediately following. In other words, the base polymer used for step g) no longer continues to polymerize. However, it undergoes post-treatment to modify its chemical structure. Step g) is advantageously performed in a different reactor from the polymerization reactor because it requires dilution of the solution containing the base polymer. The dilution of the base polymer is advantageously performed in water.

[0102] In the polymerization method according to the present invention, the sum of the molar percentages of monomers from different fractions is equal to the sum of the molar percentages of monomers in a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0103] Step a) Formation of solution (S1) containing the first fraction (F1) Solution (S1) Solution S1 is typically - Solvent and, - Initiator, - First fraction F1 and It is composed of.

[0104] The solvent is advantageously water, or a solvent in which the monomer and base polymer are soluble. Preferably, the solvent is water.

[0105] The polymerization initiators used can be any compounds that dissociate into radicals under polymerization conditions, such as organic peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds, and redox pairs. The use of water-soluble initiators is preferred. In some cases, it is advantageous to use mixtures of various polymerization initiators, such as mixtures of redox catalysts and azo compounds. Preferably, these are persulfates.

[0106] In one particular embodiment, solution S1 is formed by mixing a solvent, an initiator, and a fraction F1 in a polymerization vessel.

[0107] In this particular embodiment, fraction F1 may be added to the solvent / initiator mixture all at once, in several portions, or by pouring (in a fluid state), i.e., progressively and continuously (e.g., dropwise). Preferably, fraction F1 is added to the polymerization vessel all at once.

[0108] In certain embodiments of the present invention, the initiator and fraction F1 are poured (in a fluid state) into a polymerization vessel containing a solvent. They may be added separately or pre-mixed. Preferably, they are added separately.

[0109] In a preferred embodiment of the present invention, the initiator is added continuously throughout the polymerization process. In this case, the initiator is advantageously added in parallel with different fractions during different polymerization steps and during possible aging steps of different gradient polymers (PG1 and PG2) and base polymers.

[0110] In this preferred embodiment of the present invention, the duration of initiator pouring is between 50 and 560 minutes, preferably between 130 and 430 minutes.

[0111] First fraction (F1) Advantageously, fraction F1 contains monomers (A and / or B, and optionally C) in an amount between 10 and 45% by mass, preferably 15 and 40% by mass, relative to the total mass of monomers (A and B, and optionally C) of the water-soluble dialdehyde-functionalized polymer.

[0112] Fraction F1 preferably contains monomer A (preferably cationic) in an amount between 0 and 65 mol%, preferably between 5 and 55 mol%, relative to the total number of moles of monomers in fraction F1.

[0113] Fraction F1 is advantageous in that it contains nonionic monomer B in an amount between 35 and 100 mol%, preferably between 45 and 95 mol%, relative to the total number of moles of monomers in fraction F1.

[0114] Fraction F1 preferably contains compound I in an amount between 250 and 30,000 ppm, preferably between 500 and 10,000 ppm, and more preferably between 1,000 and 7,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0115] Fraction F1 preferably contains compound II in an amount between 250 and 30,000 ppm, preferably between 500 and 10,000 ppm, and more preferably between 1,000 and 5,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0116] The different monomers and compounds contained in fraction F1 are advantageously added in solution form. These solutions can be added to the polymer tank separately or as a mixture, all at once, in several portions, or by pouring (in a fluid form), i.e., dropwise, to form solution S1. Preferably, the addition is made as a mixture and all at once.

[0117] When fraction F1 is poured in (in a fluid form), the pouring is advantageously to continue for 10 to 80 minutes, preferably 40 to 70 minutes.

[0118] In a preferred embodiment, fraction F1 is prepared in a reactor (polymerization tank) before the addition of the initiator.

[0119] In a preferred embodiment, fraction F1 contains at least one monomer A, at least one monomer B, at least one compound I, and at least one compound II.

[0120] Step b) Polymerization of fraction F1 to form the first gradient polymer (PG1) Polymerization 1 (PO1) Prior to polymerization of PO1, the atmosphere in the polymerization vessel can be replaced with an inert gas such as nitrogen or argon.

[0121] Polymerization of PO1 is generally radical polymerization. Polymerization initiators, particularly those that dissociate into radicals under polymerization conditions, can be used.

[0122] Polymerization of PO1 is generally initiated at a temperature between 70 and 90°C, preferably between 75 and 85°C, and the polymerization temperature is then controlled using cooling means so as not to exceed 95°C.

[0123] Polymerization of PO1 typically lasts for 10 to 80 minutes, preferably 40 to 70 minutes.

[0124] Advantageously, when the first monomer, solvent, and initiator are in contact, polymerization advantageously starts, in other words, the duration of polymerization PO1 advantageously corresponds to the duration of pouring of fraction F1.

[0125] Gradient polymer (PG1) At the end of polymerization PO1, a gradient polymer (PG1) is obtained.

[0126] In a particular embodiment of the present invention, the gradient polymer PG1 is aged for 5 to 60 minutes, preferably for 10 to 30 minutes.

[0127] "Aging" means that after polymerization is complete, the temperature of the medium is maintained between 80 and 90°C to allow for an increase in viscosity through the branching phenomenon within the polymer. This definition of aging applies to all steps of the polymerization method.

[0128] Step c) Addition of the second fraction (F2) to the solution containing PG1. Second fraction F2 Advantageously, fraction F2 contains monomers (A and / or B, and optionally C) in an amount between 30 and 80% by mass, preferably 40 and 70% by mass, relative to the total mass of monomers (A and B and optionally C) of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0129] Fraction F2 preferably contains monomer A (preferably cationic) in an amount between 0 and 50 mol%, preferably between 0 and 40 mol%, relative to the total number of moles of monomers in fraction F2.

[0130] Fraction F2 is advantageous in that it contains nonionic monomer B in an amount between 0 and 100 mol%, preferably between 60 and 100 mol%, relative to the total number of moles of monomers in fraction F2.

[0131] Fraction F2 preferably contains compound I in an amount between 250 and 30,000 ppm, preferably between 500 and 10,000 ppm, and more preferably between 1,000 and 5,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0132] Fraction F2 preferably contains compound II in an amount between 250 and 30,000 ppm, preferably between 500 and 10,000 ppm, and more preferably between 1,000 and 5,000 ppm, with respect to the total mass of A and B monomers (and optionally C monomer) of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0133] The different monomers and compounds contained in fraction F2 are advantageously added in solution form. These solutions can be added to the polymer tank separately or as a mixture, all at once, in several portions, or by pouring (in a fluid state). Preferably, the addition is carried out as a mixture and poured (in a fluid state).

[0134] When fraction F2 is poured in (in a fluid form), the pouring is advantageously to last between 10 and 100 minutes, preferably between 30 and 90 minutes.

[0135] By adding fraction F2 in a fluid form (for example, dropwise), it becomes possible to control the exothermic reaction, which may become excessively high even when using a condenser.

[0136] In a preferred embodiment, fraction F2 contains at least one monomer A, at least one monomer B, at least one compound I, and at least one compound II.

[0137] Step d) Polymerization of fraction F2 to PG1 to form a second gradient polymer (PG2) Polymerization (PO2) Polymerization of PO2 is carried out as a continuation of polymerization of PO1, and it is carried out under the same time and temperature conditions (favorably 70-90°C).

[0138] The polymerization of PO2 is advantageously carried out for 10 to 100 minutes, preferably 30 to 90 minutes.

[0139] Polymerization of PO2 begins with the addition of the first monomer of fraction F2.

[0140] Advantageously, the duration of polymerization PO2 corresponds to the duration of pouring fraction F2.

[0141] Gradient polymer (PG2) At the end of the polymerization of PO2, a gradient polymer (PG2) is obtained.

[0142] In a particular embodiment of the present invention, the gradient polymer PG2 is aged for 5 to 6 minutes, preferably for 10 to 30 minutes.

[0143] Step e) Addition of the third fraction (F3) to the solution containing PG2. Fraction F3 Advantageously, fraction F3 contains monomers (A and / or B, and optionally C) in an amount between 5 and 40% by mass, preferably 10 and 30% by mass, relative to the total mass of monomers (A and B and optionally C) of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0144] Fraction F3 preferably contains monomer A (preferably cationic) in an amount between 0 and 50 mol%, preferably between 0 and 35 mol%, relative to the total number of moles of monomers in fraction F3.

[0145] Fraction F3 is advantageous in that it contains nonionic monomer B in an amount between 50 and 100 mol%, preferably between 65 and 100 mol%, relative to the total number of moles of monomers in fraction F3.

[0146] Fraction F3 preferably contains compound I in an amount between 0 and 10,000 ppm, preferably between 10 and 5,000 ppm, and more preferably between 20 and 1,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0147] Fraction F3 preferably contains compound II in an amount between 0 and 10,000 ppm, more preferably between 0 and 1,000 ppm, relative to the total mass of monomers A and B (and optionally monomer C) of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0148] The different monomers and compounds contained in fraction F3 are advantageously added in solution form. These solutions can be added to the polymer tank separately or as a mixture, all at once, in several portions, or by pouring (in a fluid state), i.e., dropwise. Preferably, the addition is carried out as a mixture and poured (in a fluid state).

[0149] When fraction F3 is poured in (in a fluid form), the pouring is advantageously to last between 10 and 100 minutes, preferably between 30 and 90 minutes.

[0150] By adding fraction F3 in a fluid form (for example, dropwise), it becomes possible to control the exothermic reaction, which may become excessively high even when using a condenser.

[0151] In a preferred embodiment, fraction F3 contains at least one monomer B and at least one compound I.

[0152] In one embodiment, the amount of compound I in fraction F3 is less than 500 ppm, preferably less than 300 ppm, preferably less than 200 ppm, and more preferably less than 100 ppm.

[0153] Such small amounts enable the desired physical and characteristic properties of the base polymer, and subsequently the final water-soluble dialdehyde-functionalized polymer.

[0154] Step f) Polymerization of fraction F3 to PG2 to form a water-soluble dialdehyde-functionalized polymer. Polymerization (PO3) Polymerization of PO3 is carried out as a continuation of polymerization of PO2, and it is carried out under the same time and temperature conditions as PO2 (favorably, 10 to 100 minutes, preferably 30 to 90 minutes, at 70 to 90°C).

[0155] Polymerization of PO3 begins with the addition of the first monomer of fraction F3.

[0156] Advantageously, the duration of polymerization PO3 corresponds to the duration of pouring fraction F3.

[0157] At the end of the polymerization of PO3, the base polymer is obtained.

[0158] In a particular embodiment of the present invention, prior to the removal of residual monomers, the base polymer is aged for 5 to 60 minutes, preferably for 10 to 30 minutes.

[0159] The reaction is stopped by the addition of excess initiator and / or water, a step used to remove any residual monomers that may be present in the solution containing the base polymer.

[0160] Optional process The method according to the present invention may also include additional steps, and is not limited to the steps described above.

[0161] In certain embodiments of the present invention, the polymerization method according to the present invention may include the addition of additional fractions constituting the base polymer.

[0162] In a preferred embodiment of the present invention, the base polymer is aged for 10 to 100 minutes, preferably 30 to 90 minutes, after step f) of polymerization of PO3 and prior to step g). If supplemental fractions are added, aging is performed after the final polymerization step and prior to step g).

[0163] In certain embodiments of the present invention, a crosslinking agent and / or a mobile agent is added in at least one of the steps described above.

[0164] In a particular embodiment of the present invention, the crosslinking agent is added to fraction F1 and / or fraction F2.

[0165] If a crosslinking agent is added, it is advantageous to select one from the crosslinking agents listed above.

[0166] If a crosslinking agent is added, the amount is preferably between 5 and 5,000 ppm, more preferably between 50 and 3,000 ppm, relative to the total mass of the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) (monomers A, B, and optionally C).

[0167] In a particular embodiment of the present invention, the transfer agent is added to fraction F1 and / or fraction F2.

[0168] If a transport agent is to be added, it is advantageous to select it from the transport agents listed above.

[0169] If a transfer agent is added, its amount is preferably between 10 and 10,000 ppm, more preferably between 50 and 5,000 ppm, relative to the total mass of the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) (monomers A, B, and optionally C).

[0170] Step g) Dialdehyde conversion of the base polymer (preferably, glyoxal conversion) Advantageously, the dialdehyde functionalization reaction (advantageously, glyoxalization) involves at least the following sequential steps: g1) A step of diluting (preferably in water) a solution containing the base polymer to form a diluted base polymer solution (SD1), g2) Optional step of adjusting the pH of SD1 to at least 10, g3) A step of adding at least one dialdehyde to the solution obtained in step g1) or g2) in order to form a diluted solution (SD2), g4) A step of acidifying the solution obtained in step g3) to an optional pH between 2 and 4, preferably between 2.5 and 3.5, in order to form a diluted solution (SD3) Includes.

[0171] Advantageously, in step g1), the amount of base polymer in the diluted solution (SD1) is between 1 and 15% by mass, preferably between 2 and 13% by mass. Dilution is advantageously carried out in water.

[0172] Advantageously, the dialdehyde added in step g3) is selected from the group comprising glyoxal, glutaraldehyde, furan-dialdehyde, adipoaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyacetaldehyde, diexo compounds, and mixtures thereof. Preferably, this is glyoxal.

[0173] Advantageously, the mass concentration of the dialdehyde is between 5 and 30%, preferably between 10 and 25%, and more preferably between 15 and 20%, relative to the total mass of monomers A and B (and optionally C).

[0174] Advantageously, step g3) is carried out in a reactor under stirring at a temperature between 19 and 26°C. Preferably, and after g2), the pH at the start of the addition of the dialdehyde is maintained between 10 and 11, for example, with a 10% by mass sodium solution in water. Following the reaction of the dialdehyde with the base polymer in step g3), the viscosity of the aqueous solution increases.

[0175] In a particular embodiment of the present invention, if g2) is not performed, at the end of step g3), the pH is adjusted to at least 8 with, for example, a 10% by mass sodium solution in water, and the pH is maintained throughout step g3).

[0176] In certain embodiments of the present invention, the diluted solution (SD2) is used directly and added to the paper pulp.

[0177] Step g3) preferably lasts for 2 to 90 minutes, more preferably for 5 to 75 minutes.

[0178] Once the desired viscosity is reached, step g4) may be performed.

[0179] Step g4) is preferably carried out in a reactor, preferably with stirring, at a temperature between 19 and 26°C, by adding an acid, such as concentrated sulfuric acid.

[0180] Preferably, the dialdehyde (or glyoxal) reaction is monitored by measuring viscosity, turbidity, delta P, etc.

[0181] At the end of step g4) or g3), a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) is obtained.

[0182] In a particular embodiment of the present invention, step g) includes step g5), which involves adding at least one dialdehyde to the solution obtained in step g4).

[0183] Advantageously, the dialdehyde is selected from the group described earlier, and preferably it is the same as in step g3).

[0184] In certain embodiments, and advantageously, the mass concentration of the dialdehyde added in steps g3) and g5) is between 5 and 30%, preferably between 10 and 25%, and more preferably between 15 and 20%, relative to the total mass of monomers A and B (and optionally C).

[0185] Advantageously, the mass concentration added in step g3) is the same as the mass concentration added in step g5).

[0186] In certain embodiments of the present invention, a fine cellulose compound is reacted with a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0187] Subsequently, in all of the specific embodiments described above, a mixture of fine cellulose / water-soluble dialdehyde-functionalized polymer can be added to the paper pulp as an additive instead of the water-soluble dialdehyde-functionalized polymer (alone) according to the present invention.

[0188] Advantageously, the fine cellulose compound is selected from nanofibrillated cellulose, fine fibrillated cellulose, nanocrystalline cellulose, and nanocellulose.

[0189] Advantageously, a fine cellulose compound is added to the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) in an amount between 10% and 100% by mass, preferably between 10% and 50% by mass, relative to the mass of the water-soluble dialdehyde-functionalized polymer (preferably glyoxalized).

[0190] The water-soluble dialdehyde-functionalized polymer of the present invention is manufactured in solution, but can be used in solid form. In practice, the solid form is obtained by a method consisting of drying the solution in step g) above all else. The technical principles of solid / liquid separation are drying by atomization or spraying (consisting of creating a cloud of fine droplets in a hot gas stream for a controlled period of time), drum drying, or fluidized bed drying.

[0191] paper making method The present invention also relates to a method for producing paper or cardboard, comprising the steps of (1) adding a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) according to the present invention to an aqueous suspension of fibers, and (2) forming a sheet of paper or cardboard. Accordingly, the present invention relates to the use of a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) in papermaking.

[0192] The various processes in papermaking, cardboard, etc., are publicly known and adhere to techniques that are part of the knowledge of those skilled in the art. Since these are publicly known and remain classic examples of the knowledge of those skilled in the art, further detailed explanation is unnecessary. If necessary, refer to the literature Handbook for Pulp & Paper Technologists, 4 th You can refer to the Edition and GA Smook.

[0193] According to the present invention, a water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) is added in a papermaking process before or after the formation of a sheet such as paper or cardboard. Therefore, contacting a cellulose material with the polymer of the present invention can be carried out in various ways, particularly according to typical methods known to those skilled in the art.

[0194] Water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) can be added to cellulose materials in the form of diluted or undiluted aqueous solutions. They can be applied by impregnation techniques or added directly to fibrous suspensions at any point in a papermaking process where drying strength agents are typically introduced.

[0195] Therefore, the polymer according to the present invention can be introduced into both dense and dilute paper stocks. It can be added in a mixing pump before the headbox or filter sieve. Preferably, the polymer is introduced before the headbox.

[0196] Preferably, the polymer according to the present invention is industrially added to a fibrous suspension, i.e., before its dilution with pulp water (concentrated paper stock). The viscosity of the pulp is approximately 1-5% by mass of cellulose fibers.

[0197] The papermaking method according to the present invention can be carried out using any type of paper pulp, such as virgin fiber pulp (kraft, bisulfite), recycled fiber, deinked pulp, mechanical and thermomechanical pulp.

[0198] Water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) are advantageously added directly to the fibrous suspension before sheet formation.

[0199] It can be added at a single input point or at two input points.

[0200] The papermaking method according to the present invention may also include the addition of other additives and / or polymers as necessary, including, but not limited to, biocides, coagulants, yield enhancers, flocculants, and starches.

[0201] use The present invention also relates to the use of this water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) in the recovery of hydrocarbons (oil and / or gas); in well drilling or cementing; in stimulating hydrocarbon wells (oil and / or gas), for example, in hydraulic fracturing, fitting, and conversion; in open, closed, or semi-closed circulating water treatment; in fermentation mast treatment; in sludge treatment; in construction; in timber treatment; in the treatment of hydraulic compositions (concrete, cement, mortar, and aggregates); in mining; in cosmetic formulation; in detergent formulation; in textile manufacturing; in the geothermal sector; in sanitary napkin production; or in agriculture.

[0202] The present invention also relates to the use of water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) as flocculants, coagulants, binders, fixatives, viscosity reducers, viscosity enhancers, absorbents, friction reducers, drainage agents, charge retainers, dehydrators, conditioning agents, stabilizers, fixatives, film-forming agents, sizing agents, high-performance water-reducing agents, clay inhibitors, or dispersants.

[0203] The present invention and the advantages derived therefrom become clearer in the following examples, which are provided to illustrate and not limit the present invention. [Examples]

[0204] List of abbreviations DADMAC: Diallyldimethylammonium chloride (monomer A) AMD: Acrylamide (Monomer B) DMAM: Dimethylacrylamide (Compound II) SMS: Sodium methallyl sulfonate (compound I) SPS: Sodium persulfate (polymerization initiator) MBA: Methylenebisacrylamide (crosslinking agent) PEI: Polyethyleneimine

[0205] Explanation of the molecular weight characterization of GPC-Malls Gel permeation chromatography is a method that allows for the separation of polymers according to their hydrodynamic volume, and it is coupled to a Malls detector, which allows for the measurement of light scattering at multiple angles.

[0206] The synthesized polymer is analyzed under the following conditions. - Equipment: GPC-2 - Column: Shodex SB-807-HQ & SB-805 Custom - method Temperature: 30℃ Mobile phase: 0.5M NaNO3, HEPES (pH=8), 100ppm NaN3 Input: 100μL Flow rate: 0.3mL / min detection: (i) Light scattering detector (MALS): Absolute molar mass (ii) Refractive index measurement (RI): concentration

[0207] Viscosity is measured using a Brookfield viscometer at 60 rpm, with a Brookfield LVI module, and at 25°C.

[0208] Production of polymers 1-3 (INV) according to the present invention Base polymer 1 (P1) First order: Gradient polymer PG1 In a 1-liter reactor equipped with a mechanical stirrer, thermometer, condenser, and nitrogen gas immersion rod, a first fraction F1 containing 140 g of water, 89.3 g of acrylamide (50% by mass in water), 16.7 g of diallyldimethylammonium chloride (64% by mass in water), 1 g of citric acid, 0.5 g of dimethylacrylamide, and 0.87 g of sodium methallyl sulfonate is introduced into the reactor. The medium is heated and maintained at a temperature between 79 and 81°C using a water bath. The addition of 0.05 g of sodium persulfate allows this starter to begin, initiating the polymerization of monomers (PO1) to form the first gradient polymer PG1.

[0209] Second order: Gradient polymer PG2 Once the exothermic reaction is complete, the pouring process is initiated: an initiator (44 g of SPS at 0.33% by mass in water) is added over 130 minutes, while simultaneously, a second fraction F2 consisting of 24.3 g of water, 178.6 g of acrylamide (50% by mass in water), 16.7 g of DADMAC (64% by mass in water), 0.5 g of dimethylacrylamide, and 0.41 g of sodium methallyl sulfonate is added over 50 minutes. After pouring in fraction F2, the gradient polymer PG2 is aged for 10 minutes (polymerization PO2 to form gradient polymer PG2 occurs during the pouring of fraction F2 and during aging).

[0210] Third order: Base polymer 1 (P1) Next, a third fraction, F3, consisting of 115.6 g of water, 89.3 g of acrylamide (50% by mass in the water), and 0.01 g of sodium methallyl sulfonate, is poured in over 60 minutes. At the end of the addition of fraction F3, the polymer is aged for 10 minutes (polymerization PO3 for polymer formation occurs during the pouring of fraction F3 and during aging).

[0211] After aging is complete, 140 g of water and 0.15 g of sodium persulfate are added. When the desired viscosity is reached, the reaction is stopped by adding 0.6 g of sodium bisulfite (40% by mass in water) and 140 g of water. A new aging period of 60 minutes is applied before cooling. The solution containing base polymer 1 (P1) has a pH of 3.5, 20% by mass of active material, a viscosity of 4,100 cps, and a molecular weight of 4,300,000 Da obtained by GPC-Malls.

[0212] Glyoxalization of base polymer 1 (P1) according to the present invention (P1-A / B(INV)) Polymer 1-A (P1-A) 64 g of base polymer 1(P1) and 728 g of water are introduced into a 1-liter reactor equipped with a mechanical stirrer. The reactor is equipped with a pH probe. After stirring for 10 minutes, the pH is adjusted to 10.3 with a 10% by mass sodium solution in water. The temperature is maintained between 20 and 22°C. 8 g of glyoxal (40% by mass in water) is added. By checking the pH and monitoring the viscosity, it is possible to obtain 39 cps of product after a reaction time of 58 minutes. When the desired viscosity is reached, the reaction is stopped by lowering the pH to less than 3.5 by adding H2SO4 (92% by mass in water) to obtain polymer 1-A(P1-A) according to the present invention.

[0213] Polymer 1-B (P1-B) The protocol for producing polymer 1-A was reproduced by changing the amount of glyoxal added to obtain polymer 1-B (P1-B) according to the present invention. The composition is summarized in Table 2 (Table 3).

[0214] Base polymers 2 and 3 (P2 and P3) To produce base polymers 2 (P2) and 3 (P3) according to the present invention, the protocol for producing polymer 1 is reproduced by changing the composition of different fractions. The compositions of the different fractions used to obtain these base polymers are summarized in Table 1a.

[0215] Glyoxalization of base polymers 2 and 3 (INV) according to the present invention (P2-A / B and P3-A / B) To obtain polymers 2-A, 2-B, 3-A, and 3-B, the protocol for the production of polymer 1-A / B is reproduced by changing the amount of glyoxal added. Their compositions are summarized in Table 2 (Table 3).

[0216] Manufacturing of comparative polymers 4-7 (CE1-CE4) Polymer 4 (CE1) This polymer is manufactured in a single sequence.

[0217] 526 g of water and 33.1 g of DADMAC (64% by mass in water) are introduced into a 1-liter reactor equipped with a mechanical stirrer, thermometer, condenser, and nitrogen gas immersion rod. The pH is adjusted to 2.5 using H2SO4. The medium is heated and maintained at a temperature between 79 and 81°C using a water bath. 357.8 g of acrylamide (50% by mass in water) is incorporated by continuous pouring over 90 minutes, and a solution of sodium persulfate is incorporated by pouring over 90 minutes. After aging for 10 minutes, 0.6 g of sodium bisulfite (40% by mass in water) is added to react any remaining monomers that may be present. A new aging period of 60 minutes is applied before cooling. The resulting solution containing base polymer 4 (CE1) has a pH of 5.0, 20.1% by mass of active material, a viscosity of 4,100 cps, and a molecular weight of 429,000 Da as determined by GPC-Malls.

[0218] Glyoxalization of polymer 4 (CE1-A / B) The protocol for producing polymer 1-A is reproduced while varying the amount of glyoxal added. Comparative examples of glyoxalized polymers 4-A (CE1-A) and 4-B (CE1-B) are obtained, and their compositions are summarized in Table 2 (Table 3).

[0219] Polymer 5 (CE2) Polymer 5(CE2) is obtained according to Example 4 of reference FR2987375.

[0220] Glyoxalization of polymer 5 (CE2-A / B) The protocol for producing polymer 1-A is reproduced, while varying the amount of glyoxal added. Polymers 5-A (CE2-A) and 5-B (CE2-B) are obtained, and their compositions are summarized in Table 2 (Table 3).

[0221] Polymer 6 (CE3) Polymer 6 is obtained according to Example 12 of reference FR2987375.

[0222] Glyoxalization of polymer 6 (CE3-A / B) The protocol for producing polymer 1-A is reproduced, while varying the amount of glyoxal added. Polymers 6-A (CE3-A) and 6-B (CE3-B) are obtained, and their compositions are summarized in Table 2 (Table 3).

[0223] Polymer 7 (CE4-A / B) Polymer 7 (CE4) is prepared according to a protocol that is the same as that for polymer 1 in only two order. The compositions of different fractions of the polymerization process for preparing base polymers 1-3 (P1-P3) and comparative base polymers (CE1-CE4) according to the present invention are summarized in Table 1a.

[0224] In Table 1a, the monomer content described for each fraction represents the molar mass percentage of the AMD (or DADMAC) monomer relative to the total molar mass of the corresponding monomer in all fractions. Therefore, for example, the sum of the percentages of AMD monomer in three fractions is equal to 100%.

[0225] The content of compounds I (SMS) and II (DMAM) is expressed in mass ppm relative to the total mass of monomers in the three fractions.

[0226] [Table 1]

[0227] The physicochemical properties of these obtained base polymers are described in Table 1b (Table 2) below.

[0228] [Table 2]

[0229] Table 2 (Table 3) describes the viscosity and composition of the glyoxalized polymers 1-3 (P1-A-P3-B) and comparative example glyoxalized polymers CE1-A-CE4-B according to the present invention.

[0230]

Table 3

[0231] Applicability test The wet pulp used in all of the applicability examples is obtained by the disintegration of dry pulp to obtain a final aqueous mass concentration of 1%. This is pH-neutral pulp using 100% recycled newsprint fibers.

[0232] Evaluation of drainage performance (DDA) under reduced pressure The DDA (Dynamic Drainage Analyzer) makes it possible to automatically determine the time (in seconds) required to vacuum-dewater the fibrous suspension on the cloth. The polymer is added to the wet pulp (0.6 liters of pulp to 1.0% mass) in the cylinder of the DDA under agitation at 1000 revolutions per minute. T = 0 s: Agitation of the pulp T = 10 s: Addition of the polymer T = 30 s: Stopping of the agitation and vacuum drainage at 200 mBar for 60 s.

[0233] The pressure under the cloth is recorded as a function of time. As water is discharged from the fibrous mat, air passes through it, which causes a break in the slope on the curve representing the pressure under the cloth as a function of time. The time represented in seconds related to this break in slope on the curve corresponds to the drainage time. The shorter the time, the better the vacuum drainage.

[0234] Performance in dry-resistant applications, 80 g / m -2 basis weight 80 g / m -2 To finally obtain a sheet corresponding to a basis weight of 80 g / m, the necessary amount of pulp is taken as a sample.

[0235] The wet pulp is introduced into a dynamic hand sheet former tank and held under agitation. Different compounds are added to this pulp according to the previously defined order. Generally, there is a contact time of 30-45 seconds between polymer additions.

[0236] Paper hand sheets are manufactured using an automatic dynamic hand sheet forming machine. The blotting paper and forming cloth are placed in the tank of the dynamic hand sheet forming machine, and then rotated at 1000 revolutions per minute. -1 The tank is then started to rotate, creating a wall of water. The processed pulp is distributed on the water wall, forming a fibrous mat on the forming cloth.

[0237] After draining the water, the fibrous mat is collected, pressed under a press with four bars, and then dried at 117°C. The resulting sheets are packed and left overnight in a room with controlled humidity and temperature (50% relative humidity and 23°C). The drying resistance of all sheets obtained by this procedure is then measured.

[0238] The bursting strength will be measured using a Messmer Buchel M 405 bursting tester in accordance with the TAPPI T403 om-02 standard.

[0239] The amount of polymer added is expressed in kilograms of active polymer per ton of dry fiber. A trial was conducted with 1.5 kg / t, and the results are summarized in Table 3 (Table 4). The results are expressed as a percentage increase compared to no polymer.

[0240] [Table 4]

[0241] It is worth noting that the polymers of the present invention (P1-A to P3-B) exhibit improved drainage performance (DDA) and mechanical characteristics (rupture; DBL; rupture in a dry state) compared to polymers produced according to conventional methods (CE1-A and CE1-B) or prior art polymers (CE2-A to CE4-B).

Claims

1. A method for sequentially producing water-soluble dialdehyde-functionalized polymers, comprising the following steps: a) A step of forming a solution (S1) comprising at least a first fraction (F1) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, At least one monomer A is a cationic monomer or anionic monomer, At least one monomer B is a nonionic monomer, At least one compound I is selected from allyl sulfonic acid, methallyl sulfonic acid, allyl disulfonic acid, methallyl disulfonic acid, salts thereof, and mixtures thereof. At least one compound II is different from at least one monomer B, formula (1) 【Chemistry 1】 [In the formula, R 1 and R 2 These are independent of each other: a hydrogen atom, or a methyl group, ethyl group, isopropyl group, or CH 2 -OH group, R 1 and R 2 [It is impossible for both to be hydrogen atoms.] It belongs to The process, b) A step of polymerization 1 (PO1) of fraction F1 to form a solution of the first gradient polymer (PG1), c) A step of adding a second fraction (F2) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, to a solution containing PG1, d) A step of polymerization 2 (PO2) of fraction F2 to PG1 to form a solution of the second gradient polymer (PG2), e) A step of adding a third fraction (F3) containing (1) at least one monomer selected from monomers A and B, and (2) at least one compound selected from compounds I and II, to a solution containing PG2, f) A step of polymerization 3 (PO3) of fraction F3 into PG2 to form a solution containing the base polymer, g) A step of diluting a solution containing a base polymer and reacting at least one dialdehyde with the base polymer to obtain a water-soluble dialdehyde polymer. Includes, At least one of fractions F1, F2, or F3 contains at least one monomer A, At least one of fractions F1, F2, or F3 contains at least one monomer B, At least one of fractions F1, F2, or F3 contains at least one compound I, At least one of fractions F1, F2, or F3 contains at least one compound II, Unlike a mixture of cationic and anionic monomers, Monomer A is When monomer A is anionic, the water-soluble dialdehyde-functionalized polymer does not contain cationic monomers. If monomer A is cationic, the water-soluble dialdehyde-functionalized polymer does not contain anionic monomers except for compound I. The water-soluble dialdehyde-functionalized polymer contains compound I in an amount between 500 and 50,000 ppm relative to the total mass of monomers A and B, and compound II in an amount between 500 and 50,000 ppm relative to the total mass of monomers A and B. method.

2. The method according to claim 1, characterized in that at least one monomer A is cationic.

3. The method according to claim 1, characterized in that at least one monomer A is selected from quaternary dimethylaminoethyl acrylate, quaternary dimethylaminoethyl methacrylate, diallyldimethylammonium chloride, propyltrimethylammonium acrylamide chloride, propyltrimethylmethacrylamide ammonium chloride, and mixtures thereof, and the dialdehyde is selected from the group consisting of glyoxal, glutaraldehyde, furan dialdehyde, adipoaldehyde, succinaldehyde, dialdehyde starch, and mixtures thereof.

4. The method according to claim 1, characterized in that at least one nonionic monomer B is selected from acrylamide, acrylonitrile, and methacrylamide, and the dialdehyde is glyoxal.

5. The method according to claim 1, characterized in that compound II is selected from N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-isopropylacrylamide, N-methylolacrylamide, and mixtures thereof.

6. The method according to claim 1, characterized in that at least one of the fractions F1, F2, or F3 is different from the others.

7. The method according to claim 1, characterized in that the initiator is added continuously throughout the polymerization process, and the dialdehyde is glyoxal.

8. The method according to claim 1, characterized in that it includes an aging step of 10 to 100 minutes after step f) polymerization (PO3).

9. The dialdehyde reaction involves at least the following steps: g1) A step of diluting a solution containing the base polymer to form a diluted solution (SD1) of the base polymer, g2) Optional step of adjusting the pH of SD1 to at least 10, g3) A step of adding at least one dialdehyde to the solution obtained in step g1) or g2) in order to form a diluted solution (SD2), g4) an optional step of acidifying the solution obtained in step g3) to a pH between 2 and 4 in order to form a diluted solution (SD3) and The method according to claim 1, characterized by including

10. A method for producing paper or cardboard, comprising the steps of adding a water-soluble dialdehyde-functionalized polymer produced by the method of any one of claims 1 to 9 to an aqueous solution of fibers, and forming a sheet of paper or cardboard.

11. Use of a water-soluble dialdehyde-functionalized polymer produced by the method of any one of claims 1 to 9 in: hydrocarbon recovery; well drilling or cementing; hydrocarbon well stimulation; water treatment in open circulation; fermentation mast treatment; sludge treatment; construction; timber processing; treatment of hydraulic compositions; mining; cosmetic formulation; detergent formulation; textile manufacturing; geothermal sector; sanitary napkin production; or agriculture.

12. Use of a water-soluble dialdehyde-functionalized polymer produced by any one of claims 1 to 9 as a flocculant, coagulant, binder, fixative, viscosity reducer, viscosity thickener, absorbent, friction reducer, drainage agent, charge retainer, dehydrating agent, conditioning agent, stabilizer, fixative, film-forming agent, sizing agent, high-performance water-reducing agent, clay inhibitor, or dispersant.

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