Polymers and methods for their preparation

Abstract

The invention relates to a novel water-soluble dialdehyde-functionalized polymer, a method for its preparation and its use, in particular in the field of paper or paperboard manufacturing.

Description

Technical Field

[0001] This invention relates to a novel water-soluble dialdehyde-functionalized (advantageously glyoxal-functionalized) polymer, its preparation method and its uses, particularly in the field of paper or paperboard manufacturing. Background Technology

[0002] The paper industry has been seeking improvements in its methods of manufacturing paper, paperboard, or the like, particularly in terms of cost reduction, yield, productivity, and even the properties of the final product.

[0003] Water-soluble dialdehyde-functionalized polyacrylamides are widely used in papermaking processes, especially to improve the dry strength of these papers. These water-soluble polyacrylamides are mainly made of nonionic polymers, cationic polymers, anionic polymers, or zwitterionic polymers, called base polymers, on which the dialdehyde reacts.

[0004] Document US20110056640 describes a papermaking method using a compound produced by the reaction between a dialdehyde-functionalized compound and an acrylamide / diallyldimethylammonium chloride copolymer. This method only improves drainage.

[0005] The applicant’s document FR2987375 describes an improved papermaking method involving a base copolymer and its reaction with dialdehyde, the base copolymer containing a polyfunctional compound introduced during the polymerization of the base copolymer monomer, the introduction of the polyfunctional compound improving the dry strength and drainage properties of the paper.

[0006] Document US20170247489 describes a papermaking method using terpolymers obtained by copolymerizing a base polymer with glyoxal, which is obtained by copolymerizing a primary amide-containing monomer and a cationic monomer.

[0007] Document US10,730,989 relates to a method for preparing an additive for papermaking based on (meth)acrylamide copolymers.

[0008] Currently, there are two main problems with dialdehyde conversion methods (especially glyoxal conversion).

[0009] The first problem is that commercially available dialdehyde-functionalized polyacrylamide products (especially glyoxal-functionalized ones) contain a large number of unreacted amide groups. These amide groups may react with dialdehyde (especially glyoxal) during storage, leading to continuous cross-linking of the base polyacrylamide molecules and reducing the product's shelf life. Furthermore, in practice, polyacrylamides contain relatively small amounts of ionic monomers, typically less than about 5 mol%, which limits the contribution of ionic charge to these polymers.

[0010] The second problem involves 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 resulting polymer exhibits reduced application performance.

[0011] The applicant was surprised to discover that, by synthesizing polymers using a specific method, their molecular weight could be increased without affecting their viscosity. Compared to solutions using existing technologies, it appears that the increase in the molecular weight of the base polymer imparts improved application properties to the paper in terms of dry strength, while also improving drainage, thus enabling increased paper machine speed and thereby increasing productivity.

[0012] The polymers obtained by this invention are used to improve product performance, and more specifically, as part of the general principles of improved dry strength and drainage properties. The improved properties of the polymers according to the invention allow for a reduction in the amount of product required for applications, thus relating to a reduction in greenhouse gas emissions, such as carbon dioxide, associated with the manufacture and use of synthetic polymers. Summary of the Invention

[0013] This invention relates to water-soluble dialdehyde functionalized polymers, comprising:

[0014] -At least one monomer A: a cationic monomer or an anionic monomer;

[0015] -At least one monomer B: a nonionic monomer;

[0016] - At least one structured system comprising:

[0017] (i) at least one compound I, which is different from at least one monomer A, wherein compound I is selected from: allyl sulfonic acid, methyl allyl sulfonic acid, allyl disulfonic acid, methyl allyl disulfonic acid, salts thereof, and mixtures thereof;

[0018] (ii) at least one compound II of formula (1), which is different from at least one monomer B:

[0019]

[0020] R1 and R2 are independently hydrogen atoms, methyl, ethyl, isopropyl or CH2-OH groups;

[0021] R1 and R2 are not both hydrogen atoms (when R2 = H, R1 ≠ H; when R1 = H, R2 ≠ H);

[0022] -Optionally, at least one monomer C: an amphoteric monomer or a hydrophobic monomer.

[0023] -Optionally, at least one crosslinking agent

[0024] -Optionally, at least one transfer agent.

[0025] The water-soluble dialdehyde functionalized polymer is obtained according to the following steps:

[0026] a) forming a solution (S1) comprising at least a first portion (F1), wherein the first portion (F1) contains (1) at least one monomer selected from monomers A and B and (2) at least one compound selected from compounds I and II;

[0027] b) A portion of F1 is polymerized to form a solution of the first gradient polymer (PG1);

[0028] c) Add a second part (F2) to a solution containing PG1, the second part (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;

[0029] d) A portion of F2 is polymerized on PG1 to form a solution of a second-gradient polymer (PG2);

[0030] e) Add a third part (F3) to a solution containing PG2, the third part (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;

[0031] f) A portion of F3 is polymerized on PG2 to form a solution containing the base polymer;

[0032] g) Dilute the solution containing the base polymer and react at least one dialdehyde (advantageously glyoxal) with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer (advantageously glyoxalized), and

[0033] At least one of F1, F2, or F3 contains at least one monomer A.

[0034] At least one of F1, F2, or F3 contains at least one monomer B.

[0035] At least one of F1, F2, or F3 contains at least one compound I, and

[0036] At least one of F1, F2 or F3 contains at least one compound II.

[0037] Monomer A is either a cationic monomer or anionic monomer only. Monomer A is not a mixture of cationic and anionic monomers.

[0038] When monomer A is an anionic monomer, the water-soluble dialdehyde functionalized polymer does not contain cationic monomers.

[0039] When monomer A is a cationic monomer, the water-soluble dialdehyde functionalized polymer does not contain anionic monomers other than compound I.

[0040] The present invention also relates to a method for preparing such a water-soluble dialdehyde functionalized polymer (advantageously glyoxalized).

[0041] The present invention also relates to a method for manufacturing paper or paperboard using the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized).

[0042] The present invention also relates to the use of this water-soluble dialdehyde functionalized polymer (advantageously glyoxal functionalized) in: hydrocarbon (oil and / or natural gas) recovery; drilling or cementing (especially hydrocarbon wells); stimulation of hydrocarbon wells (oil and / or natural gas), for example, in hydraulic fracturing, conformance, and diversion; water treatment in open, closed, or semi-closed circulation systems; treatment of fermentation mash; treatment of sludge; in construction; in timber treatment; in the treatment of hydraulic compositions (concrete, cement, mortar, and aggregates); in the mining industry; in cosmetic formulations; in detergent formulations; in textile production; in the geothermal field; in the manufacture of sanitary napkins; or in agriculture.

[0043] The present invention also relates to the use of polymers according to the invention as flocculants, coagulants, adhesives, fixatives, viscosity reducers, thickeners, absorbents, friction reducers, drainage agents, charge retention agents, dehydrating agents, regulators, stabilizers, fixatives, film-forming agents, sizing agents, superplasticizers, clay inhibitors, or dispersants. Detailed Implementation

[0044] The term "polymer" is used to refer to a copolymer prepared using at least two different monomers, having at least one monomer A (cationic or anionic monomer) and at least one nonionic monomer B, and a structured system comprising at least one compound I and at least one compound II. Optionally, the polymer may contain at least one zwitterionic monomer and / or at least one hydrophobic monomer and / or a crosslinking agent and / or a transfer agent.

[0045] Water-soluble polymers refer to polymers that, when dissolved in water at 25°C at a concentration of 10 g·L⁻¹, can be dissolved in water.-1 When the concentration is stirred and dissolved in deionized water, a polymer is produced in an aqueous solution without insoluble particles.

[0046] In this invention, the first gradient polymer and the second gradient polymer are prepolymers.

[0047] Throughout the instructions, viscosity is measured in aqueous solution at 25°C using a Brookfield viscometer.

[0048] This specification assumes that those skilled in the art can determine the appropriate Brookfield viscometer module and speed based on the viscosity range to be measured. In fact, such measurement is part of common knowledge to those skilled in the art.

[0049] According to the present invention, "X and / or Y" means "X", or "Y", or "X and Y".

[0050] All possible combinations between different disclosed embodiments, whether these are preferred embodiments or embodiments given as examples, are part of this invention. Furthermore, when numerical ranges are given, endpoint values ​​are included within those ranges. This disclosure also includes endpoint values ​​and all combinations between these numerical ranges. For example, the numerical range "1-20, preferably 5-15" includes the ranges "1-5", "1-15", "5-20", and "15-20", as well as the disclosed values ​​1, 5, 15, and 20.

[0051] In the following text, the water-soluble base polymer obtained according to the method of the invention is referred to as the base polymer prior to its reaction with dialdehyde (advantageously glyoxal) according to step g).

[0052] Water-soluble dialdehyde-functionalized polymers (advantageously, glyoxalization).

[0053] This invention relates to water-soluble dialdehyde functionalized polymers (advantageously glyoxalized), characterized by a method for obtaining them.

[0054] The water-soluble dialdehyde-functionalized polymer (advantageously glyoxalized) according to the invention comprises (advantageously consisting of):

[0055] -At least one monomer A: a cationic monomer or an anionic monomer;

[0056] -At least one monomer B: a nonionic monomer;

[0057] - At least one structured system comprising:

[0058] (i) at least one compound I, which is different from at least one monomer A, wherein compound I is selected from: allyl sulfonic acid, methyl allyl sulfonic acid, allyl disulfonic acid, methyl allyl disulfonic acid, salts thereof, and mixtures thereof;

[0059] (ii) at least one compound II of formula (1), which is different from at least one monomer B:

[0060]

[0061] R1 and R2 are independently hydrogen atoms, methyl, ethyl, isopropyl, or CH2-OH groups; wherein R1 and R2 are not both hydrogen atoms (when R2 = H, R1 ≠ H; when R1 = H, R2 ≠ H);

[0062] - At least one dialdehyde, preferably glyoxal,

[0063] -Optionally, at least one monomer C: an amphoteric monomer or a hydrophobic monomer.

[0064] -Optionally, at least one crosslinking agent

[0065] -Optionally, at least one transfer agent.

[0066] Monomer A is either a cationic monomer or anionic monomer only. Monomer A is not a mixture of cationic and anionic monomers.

[0067] When monomer A is an anionic monomer, the water-soluble dialdehyde functionalized polymer does not contain cationic monomers.

[0068] When monomer A is a cationic monomer, the water-soluble dialdehyde functionalized polymer does not contain anionic monomers other than compound I.

[0069] Monomer composition

[0070] Monomer A

[0071] The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) according to the invention is a synthetic polymer. This water-soluble dialdehyde-functionalized polymer may contain one or more cationic monomers, or one or more anionic monomers (referred to as "one or more monomers A").

[0072] Advantageously, one or more cationic monomers A may be specifically selected from vinyl monomers, preferably from acrylamide, acrylic acid, allyl, or maleic acid monomers having an ammonium functional group (advantageously quaternary ammonium). Specifically, in a non-limiting manner, the following may be referenced: quaternized dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), diallyl dimethyl ammonium chloride (DADMAC), acrylamide propyltrimethylammonium chloride (APTAC), and methacrylamide propyltrimethylammonium chloride (MAPTAC), and mixtures thereof. Preferably, cationic monomer A is diallyl dimethyl ammonium chloride (DADMAC).

[0073] The water-soluble dialdehyde-functionalized polymer (advantageously glyoxalized) advantageously comprises 1 to 60 mol%, preferably 3 to 40 mol%, more preferably 4 to 30 mol% of one or more cationic monomers A; the remaining monomers constituting the water-soluble dialdehyde-functionalized polymer up to 100 mol% are selected from monomers B and / or C, preferably selected from monomer B.

[0074] Those skilled in the art know how to prepare quaternized monomers, for example, by means of RX-type haloalkanes, where R is an alkyl group (advantageously C1-C3) and X is a halogen (RX can specifically be chloromethane). Furthermore, the invention also includes DADMAC, APTAC, and MAPTAC-type monomers, whose counterion halide is a fluoride, bromide, or iodide rather than a chloride.

[0075] Advantageously, one or more anionic monomers A can be selected from a large group. These monomers can have vinyl functional groups, particularly acrylic acid, maleic acid, fumaric acid, malonic acid, itaconic acid, or allyl. These monomers may also contain carboxyl, phosphonate, phosphate, sulfonate, or another anionicly charged group. Preferred monomers belonging to this class are, for example: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acrylamidodecanoic acid, 3-acrylamido-3-methylbutyric acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), vinyl sulfonic acid, vinyl phosphonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allyl phosphonic acid, styrene sulfonic acid, 2-acrylamido-2-disulfonic methylpropane acid, their salts, and mixtures thereof. Preferably, the anionic monomer A is acrylic acid or itaconic acid, and even more preferably acrylic acid.

[0076] Therefore, in a particular embodiment of the present invention, one or more anionic monomers can be salted.

[0077] Salt formation refers to the substitution process in which the proton of at least one acidic functional group of the anionic monomer A (of the type -R(O)-OH, where R = P, S, or C) is replaced by a metal cation to form a salt of the type -R(O)-OX (where X is a metal cation). In other words, the non-salt-forming form corresponds to the acidic form of the monomer, such as RC(=O)-OH in the case of a carboxylic acid functional group, while the salt-forming form of the monomer corresponds to RC(=O)-OX. + Form, X + Corresponding to alkali metal cations. The acid functional groups of water-soluble dialdehyde functionalized polymers can partially or completely form salts.

[0078] The salt formation forms advantageously correspond to alkali metal salts (Li, Na, K…), alkaline earth metal salts (Ca, Mg…), or ammonium salts (e.g., ammonium ions or tertiary ammonium). The preferred salt is a sodium salt.

[0079] Salt formation can occur before or after polymerization.

[0080] The water-soluble dialdehyde-functionalized anionic polymer (advantageously glyoxalized) advantageously comprises 1 to 99 mol%, preferably 2 to 70 mol%, more preferably 3 to 50 mol%, and even more preferably 5 to 35 mol% of one or more anionic monomers A. One or more remaining monomers constituting up to 100 mol% of the water-soluble dialdehyde-functionalized polymer are selected from monomers B and / or C, preferably from monomer B.

[0081] In a specific embodiment of the invention, when the anionic monomer A is 2-acrylamido-2-methylpropanesulfonic acid (ATBS), the anionic monomer is in its hydrated form. The hydrated form is a special form of ATBS that can be obtained through controlled crystallization of the ATBS monomer. This hydrated form of ATBS is described in US 10,759,746.

[0082] In a preferred embodiment of the invention, monomer A is preferably a cationic monomer.

[0083] Monomer B

[0084] Water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) may contain one or more nonionic monomers (referred to as "one or more monomers B").

[0085] Advantageously, the nonionic monomer B can be specifically selected from the group comprising water-soluble vinyl monomers. Preferred monomers belonging to this class are, for example, acrylamide, acrylonitrile, methacrylamide, and mixtures thereof. Preferably, the monomer is acrylamide.

[0086] The water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) advantageously contains 40 to 99 mol%, preferably 30 to 98 mol%, more preferably 60 to 97 mol%, and even more preferably 70 to 96 mol% of nonionic monomer B.

[0087] Monomer C

[0088] Water-soluble dialdehyde-functionalized polymers (advantageously glyoxalized) may contain one or more zwitterionic or hydrophobic monomers (referred to as "one or more monomers C").

[0089] Amphoteric monomers are ionic monomers with a total charge of zero. In fact, zwitterionic monomers have the same cation and anion charge numbers.

[0090] Advantageously, one or more zwitterionic monomers may be used in the context of this invention, particularly selected from vinyl motif derivatives, especially acrylamide, acrylic acid, allyl, or maleic acid. Preferably, the monomer comprises an amine or quaternary ammonium functional group and a carboxylic acid (or carboxyl group), sulfonic acid (or sulfonate group), or phosphoric acid (or phosphate group) functional group. The one or more zwitterionic monomers may be selected from the following: dimethylaminoethyl acrylate derivatives, such as 2-((2-9-(acryloyloxy)ethyl)dimethylammonium)ethane-1-sulfonate, and may be particularly mentioned but not limited to 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-(methacryloyloxy)ethyl](dimethylammonium)acetate; and dimethylaminoethylpropylacrylamide. Derivatives of dimethylamino(dimethylamino) such as 2-((3-acryloyl)propyl)dimethylammonium)ethane-1-sulfonate, 3-((3-acryloyl)propyl)dimethylammonium)propane-1-sulfonate, 4-((3-acryloyl)propyl)dimethylammonium)butane-1-sulfonate, [3-(acryloyl)oxy)propyl](dimethylammonio)acetate, dimethylaminopropylmethacrylamide, or even its derivatives such as 2-((3-methacryloyl)propyl)dimethylammonium)ethane-1-sulfonate, 3-((3-methyldimethylammonium)propane-1-sulfonate (3-((3-me dimethylammonio)propane-1-sulfonate, 4-((3-methylacrylamidopropyl)dimethylammonium)butane-1-sulfonate and [3-(methacryloyloxy)](dimethylammonium)propyl acetate and mixtures thereof.

[0091] The applicant described other zwitterionic monomers in document WO2021123599.

[0092] The water-soluble dialdehyde functionalized polymer according to the invention advantageously contains 0.001 to 30 mol%, preferably 0.01 to 20 mol%, more preferably 0.1 to 15 mol% of zwitterionic monomer.

[0093] Advantageously, one or more hydrophobic monomers C can be selected from the group consisting of: having C4-C 30 Alkyl chain, arylalkyl (C4-C) 30 Alkyl, C4-C 30 Aryl) propoxylated, ethoxylated, or ethoxylated and propoxylated (meth)acrylates; having C1-C3 alkyl chains, arylalkyl (C4-C) 30 Alkyl, C4-C 30 aryl), or dialkyl (C4-C) 30 Alkyl) propoxylated, ethoxylated, ethoxylated, and propoxylated (meth)acrylamide derivatives; alkyl aryl sulfonates (C4-C 30 Alkyl, C4-C 30 Aryl), or having C4-C 30 Alkyl chain, arylalkyl (C4-C) 30 Alkyl, C4-C 30 Mono- or disubstituted amides of (meth)acrylamides that are propoxylated, ethoxylated, or ethoxylated and propoxylated; having a C4-C4 ratio. 30 Alkyl chain, arylalkyl (C4-C) 30 Alkyl, C4-C 30 Aryl), or C4-C 30 Dialkyl propoxylated, ethoxylated, ethoxylated, and propoxylated (meth)acrylamide derivatives; alkyl aryl sulfonates (C4-C 30 Alkyl, C4-C 30 Aryl groups and their mixtures.

[0094] Water-soluble dialdehyde-functionalized polymers (advantageously glyoxalized) typically contain less than 1 mol% of the hydrophobic monomer C. Water-soluble dialdehyde-functionalized polymers may not contain the hydrophobic monomer C.

[0095] When the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) according to the invention contains one or more hydrophobic monomers C, they are present in an amount that makes the polymer water-soluble.

[0096] Those skilled in the art will adjust the amounts of different monomers so that they do not exceed 100 mol% in the preparation of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized). Preferably, monomers A and B represent 100 mol% of the monomers in the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized).

[0097] Structured system

[0098] The structural systems of water-soluble dialdehyde-functionalized polymers (preferably glyoxalized) include:

[0099] (i) at least one compound I;

[0100] (ii) at least one compound II.

[0101] Compound I is selected from the following: allyl sulfonic acid, methyl allyl sulfonic acid, disulfonically acid, disulfonic methyl allyl acid, salts thereof, and mixtures thereof. Preferably, compound I is methyl allyl sulfonic acid, such as sodium methyl allyl sulfonate.

[0102] The salt formation forms advantageously correspond to alkali metal salts (Li, Na, K…), alkaline earth metal salts (Ca, Mg…), or ammonium salts (e.g., ammonium ions or tertiary ammonium). The preferred salt is a sodium salt.

[0103] Based on the total weight of monomers A and B (+optional monomer C) of the water-soluble dialdehyde functionalized polymer, the water-soluble dialdehyde functionalized polymer advantageously contains 500 to 50,000 ppm, preferably 1,000 to 20,000 ppm, more preferably 2,000 to 10,000 ppm of compound I.

[0104] Compound II, as used in the context of this invention, has formula (1):

[0105]

[0106] R1 and R2 are independently hydrogen atoms, methyl, ethyl, isopropyl, or CH2-OH groups; R1 and R2 are not both hydrogen atoms (when R2 = H, R1 ≠ H; when R1 = H, R2 ≠ H).

[0107] Compound II is advantageously selected from the group consisting of N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-isopropylacrylamide, N-hydroxymethylacrylamide, and mixtures thereof. Preferably, compound II is N,N-dimethylacrylamide.

[0108] Based on the total weight of monomers A and B (+optional monomer C) of the water-soluble dialdehyde functionalized polymer, the water-soluble dialdehyde functionalized polymer according to the invention advantageously contains 500 to 50,000 ppm, preferably 1,000 to 20,000 ppm, more preferably 2,000 to 10,000 ppm of compound II.

[0109] In the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), the mass ratio between compound I and compound II is advantageously from 0.01 to 100, preferably from 0.1 to 10.

[0110] In a preferred embodiment of the invention, the amount of compound I is greater than the amount of compound II. Therefore, the mass ratio between compound I and compound II is advantageously greater than 1 and less than or equal to 100, preferably greater than 1 and less than or equal to 10.

[0111] Optional

[0112] The water-soluble dialdehyde-functionalized polymer (preferably glyoxalized) may further comprise at least one crosslinking agent. This crosslinking agent may be selected from unsaturated polyethylene monomers (having at least two unsaturated functional groups), such as vinyl functional groups, particularly allyl functional groups, acrylic functional groups, or monomers having at least two epoxy functional groups. For example, methylenebisacrylamide (MBA), triallylamine, tetraallyl ammonium chloride, 1,2-dihydroxyethylenebis(N-acrylamide), and mixtures thereof may be used. Preferably, the crosslinking agent is methylenebisacrylamide (MBA).

[0113] Based on the total weight of monomers A and B (+optionally, monomer C) in the water-soluble dialdehyde functionalized polymer, the amount of crosslinking agent in the water-soluble dialdehyde functionalized polymer is advantageously 5 to 5,000 ppm, more preferably 50 to 3,000 ppm.

[0114] In a particular embodiment of the invention, the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalized) does not contain a crosslinking agent.

[0115] The water-soluble dialdehyde functionalized polymer (preferably glyoxalized) according to the invention may further comprise at least one transfer agent selected from, for example, methanol, isopropanol, sodium hypophosphite, 2-mercaptoethanol, and mixtures thereof. Other transfer agents include xanthates, dithiocarbonates, dithiocarbamates, and trithiocarbonates, and mixtures thereof, preferably sodium hypophosphite.

[0116] Based on the total weight of monomers A and B (+optionally, monomer C) in the water-soluble dialdehyde functionalized polymer, the amount of transfer agent in the water-soluble dialdehyde functionalized polymer is advantageously 10 to 10,000 ppm, more preferably 50 to 5,000 ppm.

[0117] In a particular embodiment of the invention, the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) does not contain a transfer agent.

[0118] Physical properties of basic polymers

[0119] The weight-average molecular weight of the base polymer is advantageously from 1,000,000 to 25,000,000 Daltons, preferably from 2,000,000 to 15,000,000 Daltons, more preferably from 2,000,000 to 10,000,000 Daltons, for example from 3,000,000 to 10,000,000 Daltons. This is the weight-average molecular weight.

[0120] Weight-average molecular weight is preferably measured by a combination of gel permeation chromatography and a Malls detector.

[0121] The basic polymers are advantageously available and used in liquid form.

[0122] 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.

[0123] renewable sources

[0124] In a preferred embodiment of the invention, water-soluble dialdehyde functionalized polymers (advantageously glyoxalized) are prepared using monomers that are at least partially renewable and of non-fossil origin.

[0125] In the context of this invention, the term "renewable non-fossil source" refers to a source of compounds derived from biomass or syngas, i.e., the result of one or more chemical transformations of one or more natural non-fossil source raw materials. The terms "bio-sourced" or "bio-resourced" can also be used to indicate a renewable non-fossil source of the compound. Renewable non-fossil sources of compounds include renewable non-fossil feedstocks from the circular economy, which have been preselected to be recycled once or multiple times in the recycling of materials from biomass (e.g., materials from polymer depolymerization or from pyrolysis oil conversion).

[0126] According to the present invention, "at least partially renewable non-fossil source" means that the content of bio-based carbon is 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 at least 100% bio-based carbon, based on the total carbon weight of the compound.

[0127] In the context of this invention, standard ASTM D6866-21, Method B, is used to characterize the bio-origin properties of compounds and to determine the bio-origin content of said compounds. This value is expressed as a weight percentage of bio-origin carbon based on the total weight of carbon in said compound.

[0128] gradient

[0129] The basic polymer and the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) according to the invention are gradient polymers.

[0130] Polymers with gradient structures are polymers composed of at least two monomers, where the composition changes gradually, unlike block polymers which experience abrupt compositional changes, and random polymers which do not exhibit continuous compositional changes. In gradient polymers, inter-chain and intra-chain repulsion is less observed because the composition changes gradually along the length of the polymer chain.

[0131] This gradient can be formed spontaneously or by a forced gradient. Spontaneous gradient polymerization is due to differences in monomer reactivity. Forced gradient polymerization involves changing the composition of the introduced monomers throughout the polymerization process.

[0132] The forced method includes (1) introducing a first monomer fraction into the reactor, (2) adding at least one additional monomer fraction that is advantageously different from the first fraction, and (3) polymerizing the monomer introduced into the reactor. The monomer begins polymerization upon introduction of the first fraction.

[0133] The addition of additional monomer fractions can be carried out in parallel with the introduction of the first monomer fraction into the reactor (therefore, the introduction of fractions can begin and end simultaneously). Alternatively, the feeding of the first monomer (first fraction) into the reactor can begin before the addition of the second monomer fraction. Alternatively, the first and second fractions can be introduced simultaneously, but the time taken to add the second fraction can be longer than the time taken to add the first fraction into the reactor. This embodiment also applies to methods with at least three monomer fractions.

[0134] According to the method of the invention, the obtained water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) is formed by the stepwise addition of monomers, that is, preferably by a forced gradient.

[0135] The method according to the invention comprises a first part (F1) and at least two additional parts (F2 and F3). At least one of parts F1, F2, and F3 differs from the other parts. Preferably, parts F1, F2, and F3 are different. Different parts refer to parts composed of different monomers (the ratio and / or properties of monomers) and / or compounds I and II (the ratio and / or properties of compounds I and II).

[0136] Aggregation methods

[0137] A stepwise polymerization method for water-soluble dialdehyde-functionalized polymers (advantageously glyoxalized) includes the following steps:

[0138] a) forming a solution (S1) comprising at least a first portion (F1), the first portion (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;

[0139] b) A portion of F1 is polymerized to form a solution of the first gradient polymer (PG1);

[0140] c) Add a second part (F2) to a solution containing PG1, the second part (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;

[0141] d) A portion of F2 is polymerized on PG1 to form a solution of a second-gradient polymer (PG2);

[0142] e) Add a third part (F3) to a solution containing PG2, the third part (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;

[0143] f) A portion of F3 is polymerized on PG2 to form a solution containing the base polymer;

[0144] g) Dilute the solution containing the base polymer and react at least one dialdehyde (advantageously glyoxal) with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer (advantageously glyoxalized), wherein at least one of F1, F2 or F3 contains at least one monomer A.

[0145] At least one of F1, F2, or F3 contains at least one monomer B.

[0146] At least one of F1, F2 or F3 contains at least one compound I, and at least one of F1, F2 or F3 contains at least one compound II.

[0147] This method may include adding an additional component, but no additional component is added after step g) of the dialdehyde reaction.

[0148] It is possible that the improved properties of the polymer obtained by the method according to the invention may be due to the fact that the polymerization is carried out stepwise and continuously, i.e. without interruption.

[0149] "Stepwise" means that the monomers of the base polymer are polymerized in multiple portions without interruption; that is, portions are added continuously and polymerization does not stop. The different steps a) through f) are performed stepwise. In other words, a first portion of monomers can be poured (in flowing form) and polymerized to form a first gradient polymer PG1, which continues to polymerize with portion F2 to form a gradient polymer PG2, which itself continues to polymerize with portion F3 to obtain the base polymer at the end of polymerization. At least one of portions F1, F2, and F3 is different from the others. Preferably, portions F1, F2, and F3 are different. Adding different portions in the polymerization method allows for a gradient in the composition of the base polymer.

[0150] In a particular embodiment, polymerization may be stopped after PO1 and / or PO2 and continued at different locations. In this embodiment, the gradient polymer PG formed in one or more preceding steps will be added. X Part F in X+1 (X=1 or 2) are aggregated and combined with PG X Interactions to form PG X+1 The process continues in the following steps to finally obtain the base polymer. After polymerization is complete, step g) is continuously performed on the base polymer until the polymerization ends or at another time (later). Preferably, the process is continuous. In other words, the base polymer used in step g) is no longer polymerized. However, the base polymer used in step g) undergoes a post-treatment to change its chemical structure. Step g) is advantageously carried out in a different reactor than polymerization because it requires dilution of the solution containing the base polymer. Advantageously, the dilution of the base polymer is carried out in water.

[0151] In the polymerization method according to the invention, the sum of the molar percentages of the monomers in the different portions is equal to the sum of the molar percentages of the monomers in the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalized). Step a), forming a solution (S1) comprising the first portion (F1).

[0152] Solution (S1)

[0153] Solution (S1) typically consists of the following:

[0154] - Solvent;

[0155] -Initiator;

[0156] - Part 1 F1.

[0157] The solvent is advantageously water, or a solvent in which the monomer and the raw material polymer are soluble. Preferably, the solvent is water.

[0158] The polymerization initiator used can be any compound that dissociates into free radicals under polymerization conditions, such as organic peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds, and redox pairs. Water-soluble initiators are preferred. In some cases, it is advantageous to use a mixture of various polymerization initiators, for example, a mixture of a redox catalyst and an azo compound. Preferably, the polymerization initiator is a persulfate.

[0159] In one particular embodiment, solution S1 is formed by mixing solvent, initiator and a portion of F1 in a polymerization tank.

[0160] In this particular embodiment, a portion of F1 may be added to the solvent / initiator mixture all at once, in multiple portions, or poured (in a flowing form) (i.e., gradually and continuously (e.g., dropwise)). Preferably, a portion of F1 is added to the polymerization tank all at once.

[0161] In a particular embodiment of the invention, the initiator and a portion of F1 are poured (in flowing form) into a polymerization tank containing a solvent. They can be added separately or pre-mixed. Preferably, they are added separately.

[0162] In a preferred embodiment of the invention, the initiator is added continuously throughout the polymerization process. In this case, the initiator is advantageously added in parallel with different portions during different polymerization steps and during possible aging steps with different gradient polymers (PG1 and PG2) and the base polymer.

[0163] In this preferred embodiment of the invention, the duration of the pouring initiator is 50 to 560 minutes, preferably 130 to 430 minutes.

[0164] Part 1 (F1)

[0165] Advantageously, based on the total weight of the monomers (A+B+optional C) of the water-soluble dialdehyde functionalized polymer, part F1 contains 10 to 45% by weight, preferably 15 to 40% by weight, of the monomers (A and / or B, +optional C).

[0166] Based on the total number of moles of monomers in the fraction F1, the fraction F1 advantageously contains 0 to 65 mol%, preferably 5 to 55 mol%, of monomer A (advantageously a cationic monomer).

[0167] Based on the total number of moles of monomers in the fraction of F1, the fraction of F1 advantageously contains 35 to 100 mol%, preferably 45 to 95% of nonionic monomer B.

[0168] Based on the total weight of monomers A and B (+optional monomer C) of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), a portion of F1 advantageously contains 250 to 30,000 ppm, preferably 500 to 10,000 ppm, more preferably 1,000 to 7,000 ppm of compound I.

[0169] Based on the total weight of monomers A and B (+optionally monomer C) of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), a portion of F1 advantageously contains 250 to 30,000 ppm, preferably 500 to 10,000 ppm, more preferably 1,000 to 5,000 ppm of compound II.

[0170] The different monomers and compounds contained in part F1 are advantageously added in solution form. These solutions may be added individually or in mixtures, all at once, in multiple portions, or poured (in flow form) (i.e., dropwise) into the polymer tank to form solution S1. Preferably, they are added in mixture form and all at once.

[0171] When pouring (in flowing form) portion F1, the pouring advantageously lasts for 10 to 80 minutes, preferably 40 to 70 minutes.

[0172] In a preferred embodiment, a portion of F1 is prepared in a reactor (polymerization tank) before the initiator is added.

[0173] In a preferred embodiment, part F1 contains at least one monomer A, at least one monomer B, at least one compound I, and at least one compound II.

[0174] Step b) involves polymerizing a portion of F1 to form a first-gradient polymer (PG1).

[0175] Polymer 1 (PO1)

[0176] Before polymerizing PO1, the air in the polymerization tank can be replaced with an inert gas (such as nitrogen or argon).

[0177] Polymerization of PO1 is typically a free radical polymerization. Polymerization initiators can be used, especially initiators that dissociate into free radicals under polymerization conditions.

[0178] The polymerization of PO1 is typically started at a temperature of 70 to 90°C, preferably 75 to 85°C, and then a cooling device is used to control the polymerization temperature so that it does not exceed 95°C.

[0179] Polymerization of PO1 typically lasts 10 to 80 minutes, preferably 40 to 70 minutes.

[0180] Advantageously, polymerization begins when the first monomer, solvent, and initiator come into contact; in other words, the duration of polymerization of PO1 advantageously corresponds to the duration of partial pouring of F1.

[0181] Gradient polymer (PG1)

[0182] At the end of the polymerization of PO1, a gradient polymer (PG1) is obtained.

[0183] In a specific embodiment of the invention, the gradient polymer PG1 is aged for 5 to 60 minutes, preferably 10 to 30 minutes.

[0184] "Aging" refers to maintaining the temperature of the medium at 80 to 90°C after polymerization to allow for increased viscosity through internal branching of the polymer. The definition of aging applies to all steps of the polymerization process.

[0185] Step c) Add the second part (F2) to the solution containing PG1.

[0186] Part 2 F2

[0187] Advantageously, based on the total weight of the monomers (A+B, + optional C) of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), part of F2 contains 30 to 80% by weight, preferably 40 to 70% by weight, of the monomers (A and / or B, + optional C).

[0188] Based on the total number of moles of monomers in the fraction of F2, the fraction of F2 advantageously contains 0 to 50 mol%, preferably 0 to 40 mol%, of monomer A (advantageously a cationic monomer).

[0189] Based on the total number of moles of monomers in the fraction of F2, the fraction of F2 advantageously contains 0 to 100 mol%, preferably 60 to 100 mol%, of nonionic monomer B.

[0190] Based on the total weight of monomers A and B (+optional monomer C) of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), a portion of F2 advantageously contains 250 to 30,000 ppm, preferably 500 to 10,000 ppm, more preferably 1,000 to 5,000 ppm of compound I.

[0191] The portion of F2 advantageously contains 250 to 30,000 ppm, preferably 500 to 10,000 ppm, more preferably 1,000 to 5,000 ppm of compound II relative to the total weight of monomers A and B (optionally, monomer C) of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized).

[0192] The different monomers and compounds contained in part F2 are advantageously added in solution form. These solutions may be added individually or in mixtures, either all at once, in multiple portions, or poured (in flow form) into the polymer tank. Preferably, they are added in mixture form and poured (in flow form).

[0193] When pouring (in flowing form) portion F2, the pouring advantageously lasts from 10 to 100 minutes, preferably from 30 to 90 minutes.

[0194] Adding a portion of F2 in a flowing form (e.g., dropwise) allows control over the exothermic nature of the reaction, which could otherwise be excessive even when using a cooler.

[0195] In a preferred embodiment, part of F2 contains at least one monomer A, at least one monomer B, at least one compound I, and at least one compound II.

[0196] Step d) involves polymerizing a portion of F2 on PG1 to form a second-gradient polymer (PG2) polymer (PO2).

[0197] The polymerization of PO2 proceeds as a continuation of the polymerization of PO1; the polymerization of PO2 is carried out under the same time and temperature conditions (advantageously 70 to 90 °C).

[0198] The polymerization of PO2 is advantageously sustained for 10 to 100 minutes, preferably 30 to 90 minutes.

[0199] The polymerization of PO2 begins when the first monomer of F2 is added.

[0200] Advantageously, the duration of PO2 polymerization corresponds to the duration of partial F2 dumping.

[0201] Gradient polymer (PG2)

[0202] At the end of the polymerization of PO2, a gradient polymer (PG2) is obtained.

[0203] In a particular embodiment of the invention, the gradient polymer PG2 is aged for 5 to 60 minutes, preferably 10 to 30 minutes.

[0204] Step e) Add the third part (F3) to the solution containing PG2.

[0205] Partial F3

[0206] Advantageously, based on the total weight of the monomers (A+B+optionally C) of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), part of F3 contains 5 to 40% by weight, preferably 10 to 30% by weight, of the monomers (A and / or B+optionally C).

[0207] Based on the total number of moles of monomers in the fraction of F3, the fraction of F3 advantageously contains 0 to 50 mol%, preferably 0 to 35 mol%, of monomer A (advantageously a cationic monomer).

[0208] Based on the total number of moles of monomers in the fraction of F3, the fraction of F3 advantageously contains 50 to 100 mol%, preferably 65 to 100 mol%, of nonionic monomer B.

[0209] Based on the total weight of monomers A and B (+optional monomer C) of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), a portion of F3 advantageously contains 0 to 10,000 ppm, preferably 10 to 5,000 ppm, more preferably 20 to 1,000 ppm of compound I.

[0210] Based on the total weight of monomers A and B (+optionally monomer C) of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), a portion of F3 advantageously contains 0 to 10,000 ppm, preferably 0 to 1,000 ppm, of compound II.

[0211] The different monomers and compounds contained in part F3 are advantageously added in solution form. These solutions may be added individually or in mixtures, either all at once, in multiple portions, or by pouring (in a flow form) (i.e., dropwise) into the polymer tank. Preferably, they are added in mixture form and by pouring (in a flow form).

[0212] When a portion of F3 is poured (in flowing form), the pouring advantageously continues for 10 to 100 minutes, preferably 30 to 90 minutes.

[0213] Adding a portion of F3 in a flowing form (e.g., dropwise) allows control over the exothermic nature of the reaction, which could otherwise be excessive even when using a cooler.

[0214] In a preferred embodiment, part of F3 contains at least one monomer B and at least one compound I.

[0215] In the embodiments, the amount of compound I in a portion of F3 is less than 500 ppm, preferably less than 300 ppm, more preferably less than 200 ppm, and even more preferably less than 100 ppm.

[0216] This small amount allows for the achievement of the desired physical and unique properties of the base polymer and the subsequent final water-soluble dialdehyde functionalized polymer.

[0217] Step f) involves polymerizing a portion of F3 on PG2 to form a water-soluble dialdehyde functionalized polymer polymer (PO3).

[0218] The polymerization of PO3 is carried out as a continuation of the polymerization of PO2; the polymerization of PO3 is carried out under the same time and temperature conditions as that of PO2 (advantageously at 70 to 90°C for 10 to 100 minutes, preferably 30 to 90 minutes).

[0219] The polymerization of PO3 begins with the addition of a portion of the first monomer, F3.

[0220] Advantageously, the duration of PO3 polymerization corresponds to the duration of partial F3 dumping.

[0221] At the end of the polymerization of PO3, the basic polymer is obtained.

[0222] In a particular embodiment of the invention, the base polymer is allowed to age for 5 to 60 minutes, preferably 10 to 30 minutes, before removing residual monomers.

[0223] The reaction is stopped by adding an excess of initiator and / or water; this step is used to eliminate any residual monomers that may be present in the solution containing the base polymer.

[0224] Optional steps

[0225] The method according to the invention may also include additional steps, and is not limited to the steps described above.

[0226] In a particular embodiment of the invention, the polymerization method according to the invention may include the addition of additional components constituting the base polymer.

[0227] In a preferred embodiment of the invention, after step f) of polymerizing PO3 and before step g), the base polymer is allowed to age for 10 to 100 minutes, preferably 30 to 90 minutes. In the case of the addition of a supplementary component, aging is performed after the final polymerization step and before step g).

[0228] In a particular embodiment of the present invention, a crosslinking agent and / or a transfer agent are added during at least one of the above steps.

[0229] In a particular embodiment of the invention, the crosslinking agent is added to a portion of F1 and / or a portion of F2.

[0230] When a crosslinking agent is added, it is advantageously selected from the crosslinking agents described above.

[0231] When a crosslinking agent is added, the amount of crosslinking agent is advantageously from 5 to 5,000 ppm, preferably from 50 to 3,000 ppm, based on the total weight of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) (monomers A, B and optional C).

[0232] In a particular embodiment of the invention, the transfer agent is added to portions F1 and / or F2.

[0233] When a transfer agent is added, it is advantageously selected from the transfer agents described above.

[0234] When the transfer agent is added, the amount of the transfer agent is advantageously 10 to 10,000 ppm, preferably 50 to 5,000 ppm, based on the total weight of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) (monomers A, B and optional C).

[0235] Step g), dialdehydeization of the base polymer (advantageously glyoxalization).

[0236] Advantageously, the dialdehyde functionalization reaction (advantageously glyoxalization) includes at least the following sequential steps:

[0237] g1) Dilute (advantageously in water) the solution containing the base polymer to form a diluted solution of the base polymer (SD1);

[0238] g2) Optionally adjust the pH of SD1 to at least 10;

[0239] g3) Add at least one dialdehyde to the solution obtained in step g1) or g2) to form a diluted solution (SD2);

[0240] g4) Optionally, the solution obtained in step g3) is acidified to a pH of 2 to 4, preferably 2.5 to 3.5, in order to form a diluted solution (SD3).

[0241] Advantageously, in step g1), the amount of the base polymer in the diluted solution (SD1) is 1 to 15% by weight, preferably 2 to 13% by weight. The dilution is advantageously carried out in water.

[0242] Advantageously, the dialdehyde added in step g3) is selected from the group consisting of: glyoxal, glutaraldehyde, furanyl dialdehyde, adipaldehyde, succinyl dialdehyde, dialdehyde starch, 2,2-dimethoxyacetaldehyde, diepoxides, and mixtures thereof. Preferably, the dialdehyde is glyoxal.

[0243] Advantageously, based on the total weight of monomers A and B (optionally C), the mass concentration of the dialdehyde is 5 to 30%, preferably 10 to 25%, and more preferably 15 to 20%.

[0244] Advantageously, step g3) is carried out in a reactor at a temperature of 19 to 26°C with stirring. Preferably, after g2), the pH at which the dialdehyde is first added is maintained at 10 to 11, for example, with a 10% by weight aqueous solution of sodium bicarbonate. Following the reaction between the dialdehyde and the base polymer in step g3), the viscosity of the aqueous solution increases.

[0245] In a particular embodiment of the invention, when g2) is not performed, at the end of step g3), for example, the pH is adjusted to at least 8 with a 10% by weight sodium bicarbonate solution and maintained at that pH throughout step g3).

[0246] In a particular embodiment of the invention, the diluted solution (SD2) is used directly and injected into the pulp.

[0247] Step g3) advantageously lasts from 2 to 90 minutes, preferably from 5 to 75 minutes.

[0248] After the desired viscosity is reached, step g4 can be performed.

[0249] Step g4) is preferably carried out in a reactor at a temperature of 19 to 26°C by adding an acid (e.g., concentrated sulfuric acid) with stirring.

[0250] Advantageously, the dialdehyde reaction (preferably glyoxalization) is monitored by measuring viscosity, turbidity, δP, etc.

[0251] At the end of step g4) or g3), a water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) is obtained.

[0252] In a particular embodiment of the invention, step g) includes step g5), which includes adding at least one dialdehyde to the solution obtained in step g4).

[0253] Advantageously, the dialdehyde is selected from the group mentioned above, and preferably, the dialdehyde is the same as that in step g3).

[0254] In a particular embodiment, advantageously, based on the total weight of monomers A and B (optionally C), the mass concentration of the dialdehyde added in steps g3) and g5) is 5% to 30%, preferably 10% to 25%, more preferably 15% to 20%.

[0255] Advantageously, the mass concentration of the dialdehyde added in step g3) is the same as the mass concentration added in step g5).

[0256] In a particular embodiment of the invention, the microcellulose compound reacts with a water-soluble dialdehyde-functionalized polymer (advantageously glyoxalized).

[0257] The microcellulose / water-soluble dialdehyde functionalized polymer mixture can then be added to the pulp as an additive, in place of the water-soluble dialdehyde functionalized polymer (alone) according to the invention in all the aforementioned specific embodiments.

[0258] Advantageously, the microcellulose compound is selected from nanofibrillated cellulose, microfibrillated cellulose, nanocrystalline cellulose, and nanocellulose.

[0259] Advantageously, based on the weight of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized), 10% to 100% by weight, preferably 10% to 50% of the microcellulose compound is added to the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized).

[0260] Even though it is prepared in solution, the water-soluble dialdehyde functionalized polymer of the present invention can also be used in solid form. In practice, the solid form is obtained in other ways (by a solution method including a drying step g). The technical principle of solid / liquid separation is through atomization or spray drying (which involves generating a fine droplet in a hot gas stream for a controlled period of time), drum drying, fluidized bed dryer...

[0261] Papermaking methods

[0262] The present invention also relates to a method of manufacturing paper or paperboard, comprising (1) adding a water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) according to the invention to an aqueous suspension of fibers, and (2) forming paper or paperboard. Therefore, the present invention relates to the use of a water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) in a papermaking process.

[0263] The various steps in the production methods of paper, paperboard, or the like are known and constitute part of the knowledge of those skilled in the art; therefore, it is unnecessary to describe them in further detail, as they remain known and classic to those skilled in the art. If necessary, these steps can be referenced in the following literature: Handbook for Pulp & Paper Technologists, 4th Edition, GASmook.

[0264] According to the present invention, the water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) is added during the papermaking process, either before or after the formation of paper, paperboard, etc. Therefore, contact between the cellulose material and 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.

[0265] Water-soluble dialdehyde-functionalized polymers (advantageously glyoxalized) can be added to cellulose materials in diluted or undiluted aqueous solutions. They can be applied via impregnation techniques or added directly to the fiber suspension at any point in the papermaking process where dry strength agents are typically introduced.

[0266] Therefore, the polymer according to the invention can be introduced into thick or thin slurries. It can be added at the mixing pump, before the headbox, or before the filter. Preferably, the polymer is introduced before the headbox.

[0267] Preferably, the polymer according to the invention is industrially injected into a fiber suspension, i.e., before it is diluted by pulp water (thick pulp). The pulp consistency is about 1 to 5% by weight of cellulose fibers.

[0268] The papermaking method according to the invention can be implemented with any type of pulp, such as virgin fiber pulp (kraft paper, bisulfite), recycled fiber, deinking pulp, mechanical pulp and thermomechanical pulp.

[0269] Water-soluble dialdehyde-functionalized polymers (advantageously glyoxalized) are advantageously added directly to the fiber suspension before paper formation.

[0270] It can be added at a single injection point or at two injection points.

[0271] As needed, the papermaking method according to the present invention may further include the addition of other additives and / or polymers; by way of example and not limitation, we may cite: biocides, coagulants, retention aids, flocculants, starch...

[0272] use

[0273] The present invention also relates to the use of this water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) in: hydrocarbon (oil and / or natural gas) recovery; drilling or cementing; production enhancement of hydrocarbon wells (oil and / or natural gas), for example, in hydraulic fracturing, homogenization, diversion; water treatment in open, closed or semi-closed circulation systems; treatment of fermentation mash; treatment of sludge; in construction; in timber treatment; in the treatment of hydraulic compositions (concrete, cement, mortar and aggregate); in the mining industry; in cosmetic formulations; in detergent formulations; in textile production; in the geothermal field; in the manufacture of sanitary napkins; or in agriculture.

[0274] The present invention also relates to the use of water-soluble dialdehyde functionalized polymers (advantageously glyoxalized) as flocculants, coagulants, adhesives, fixatives, viscosity reducers, thickeners, absorbents, friction reducers, drainage agents, charge retention agents, dehydrating agents, regulators, stabilizers, fixatives, film-forming agents, sizing agents, superplasticizers, clay inhibitors, or dispersants.

[0275] In order to illustrate the invention in a non-limiting manner, the invention and its advantages will become more apparent in the embodiments given below.

[0276] Example

[0277] List of abbreviations:

[0278] DADMAC: Diallyl dimethylammonium chloride (monomer A)

[0279] AMD: Acrylamide (monomer B)

[0280] DMAM: Dimethylacrylamide (Compound II)

[0281] SMS: Sodium methyl allyl sulfonate (Compound I)

[0282] SPS: Sodium persulfate (polymerization initiator)

[0283] MBA: Methylenebisacrylamide (crosslinking agent)

[0284] PEI: Polyethyleneimine

[0285] Characterization description of GPC-Malls by molecular weight

[0286] Gel permeation chromatography is a method that allows the separation of macromolecules based on their hydrodynamic volume; when combined with a Malls detector, gel permeation chromatography enables the measurement of light diffusion from multiple angles.

[0287] The synthesized polymers were analyzed under the following conditions:

[0288] -Instrument: GPC-2

[0289] - Columns: Shodex SB-807-HQ and SB-805custom

[0290] -method:

[0291] *Temperature: 30℃

[0292] *Mobile phase: 0.5M NaNO3, HEPES (pH=8), 100ppm NaN3

[0293] *Injection: 100μL

[0294] *Flow rate: 0.3 mL / min

[0295] *Detection:

[0296] (i) Light scattering detector (MALS): absolute molar mass

[0297] (ii) Refractometer (RI): Concentration

[0298] Viscosity was measured at 25°C and 60 rpm using a Brookfield viscometer with a Brookfield LVI module.

[0299] Preparation of polymers 1 to 3 (INV) according to the present invention

[0300] Basic polymer 1 (P1)

[0301] Step 1: Gradient polymer PG1

[0302] In a 1-liter reactor equipped with a mechanical stirrer, thermometer, condenser, and nitrogen-impregnated rod, a first fraction F1 containing 140 g water, 89.3 g acrylamide (50 wt% aqueous solution), 16.7 g diallyldimethylammonium chloride (64 wt% aqueous solution), 1 g citric acid, 0.5 g dimethacrylamide, and 0.87 g sodium methylallyl sulfonate was introduced. The medium was heated using a water bath and maintained at a temperature of 79–81 °C. The addition of 0.05 g sodium persulfate initiated the polymerization of the starter and monomer (PO1) to form the first gradient polymer PG1.

[0303] Step 2: Gradient polymer PG2

[0304] When the exothermic reaction is complete, begin pouring: Add the initiator (44 g SPS, 0.33 wt% aqueous solution) over 130 minutes, simultaneously adding the second portion F2 over 50 minutes, which consists of: 24.3 g water, 178.6 g acrylamide (50 wt% aqueous solution), 16.7 g DADMAC (64 wt% aqueous solution), 0.5 g dimethacrylamide, and 0.41 g sodium methyl allyl sulfonate. After pouring portion F2, allow the gradient polymer PG2 to age for 10 minutes (polymerization of PO2 to form gradient polymer PG2 occurs during the pouring of portion F2 and during aging).

[0305] Step 3: Basic Polymer 1 (P1)

[0306] Then, pour out the third portion, F3, which consists of: 115.6 g water, 89.3 g acrylamide (50% by weight aqueous solution), and 0.01 g sodium methyl allyl sulfonate within 60 minutes. At the end of the addition of portion F3, allow the polymer to age for 10 minutes (polymerization of PO3 to form the polymer occurs during the pouring of portion F3 and during aging).

[0307] After aging, 140 g of water and 0.15 g of sodium persulfate were added. When the desired viscosity was reached, the reaction was stopped by adding 0.6 g of sodium bisulfite (40 wt% aqueous solution) and 140 g of water. A new aging process was carried out for 60 minutes before cooling. The solution containing base polymer 1 (P1) had a pH of 3.5, 20 wt% active material, a viscosity of 4,100 cps, and a molecular weight of 4,300,000 Da obtained by GPC-Malls.

[0308] Glyoxalization of the basic polymer 1 (P1) according to the present invention (P1-A / B(INV))

[0309] Polymer 1-A (P1-A)

[0310] 64 g of base polymer 1 (P1) and 728 g of water were introduced into a 1-liter reactor equipped with a mechanical stirrer and a pH probe. After stirring for 10 minutes, the pH was adjusted to 10.3 with a 10 wt% sodium bicarbonate solution. The temperature was maintained at 20 to 22°C. 8 g of glyoxal (40 wt% aqueous solution) was added. pH monitoring and viscosity control allowed a product of 39 cps to be obtained after a reaction time of 58 minutes. When the desired viscosity was reached, the reaction was stopped by adding H2SO4 (92 wt% aqueous solution) to lower the pH to less than 3.5, and polymer 1-A (P1-A) according to the invention was obtained.

[0311] Polymer 1-B (P1-B)

[0312] By varying the amount of glyoxal added, the same method for preparing polymer 1-A was repeated to obtain polymer 1-B (P1-B) according to the present invention. The composition is summarized in Table 2.

[0313] Basic polymers 2 and 3 (P2 and P3)

[0314] The method of preparing polymer 1 was repeated by changing the composition of different parts in order to prepare the basic polymers 2 (P2) and 3 (P3) of the present invention. The composition of the different parts used to obtain these basic polymers is summarized in Table 1a.

[0315] Glyoxalization of the basic polymers 2 and 3 according to the present invention (P2-A / B and P3-A / B) (INV)

[0316] The method for preparing polymer 1-A / B was repeated by varying the amount of glyoxal added to obtain polymers 2-A, 2-B, 3-A, and 3-B. Their compositions are summarized in Table 2.

[0317] Preparation of comparative polymers 4 to 7 (CE1 to CE4)

[0318] Polymer 4 (CE1)

[0319] The polymer was prepared in one step.

[0320] In a 1-liter reactor equipped with a mechanical stirrer, thermometer, condenser, and nitrogen-impregnated rod, 526 g of water and 33.1 g of DADMAC (64 wt% aqueous solution) were introduced. The pH was adjusted to 2.5 with H₂SO₄. The medium was heated using a water bath and maintained at a temperature of 79–81 °C. 357.8 g of acrylamide (50 wt% aqueous solution) was added by continuous pouring over 90 minutes, followed by the addition of sodium persulfate solution by pouring over 90 minutes. After aging for 10 minutes, 0.6 g of sodium bisulfite (40 wt% aqueous solution) was added to allow any remaining monomers to react. A new 60-minute aging phase was carried out before cooling. The resulting solution containing base polymer 4 (CE1) had a pH of 5.0, 20.1 wt% active material, a viscosity of 4,100 cps, and a molecular weight of 429,000 Da obtained by GPC-Malls.

[0321] Glyoxalization of polymer 4 (CE1-A / B)

[0322] The preparation of polymer 1-A was repeated, while varying the amount of glyoxal added. Comparative glyoxalized polymers 4-A (CE1-A) and 4-B (CE1-B) were obtained, and their compositions are summarized in Table 2.

[0323] Polymer 5 (CE2)

[0324] Polymer 5 (CE2) was obtained according to Example 4 of document FR2987375.

[0325] Glyoxalization of polymer 5 (CE2-A / B)

[0326] The preparation of polymer 1-A was repeated, while varying the amount of glyoxal added. Polymers 5-(CE2-A) and 5-B(CE2-B) were obtained, and their compositions are summarized in Table 2.

[0327] Polymer 6 (CE3)

[0328] Polymer 6 was obtained according to Example 12 of document FR2987375.

[0329] Glyoxalization of polymer 6 (CE3-A / B)

[0330] The preparation of polymer 1-A was repeated, while varying the amount of glyoxal added. Polymers 6-(CE3-A) and 6-B(CE3-B) were obtained, and their compositions are summarized in Table 2.

[0331] Polymer 7 (CE4-A / B)

[0332] Polymer 7 (CE4) was prepared according to the same scheme as polymer 1, but with only two steps. The compositions of the different parts of the polymerization process for preparing the basic polymers 1-3 (P1 to P3) according to the invention and the comparative basic polymer examples (CE1 to CE4) are summarized in Table 1a.

[0333] In Table 1a, the monomer content described in each section represents the molar weight percentage of the AMD (or DADMAC) monomer relative to the total molar amount of the corresponding monomer in the total section. Therefore, for example, the sum of the percentages of the AMD monomer in the three sections equals 100%.

[0334] The contents of compounds I (SMS) and II (DMAM) are expressed in ppm by weight, based on the total weight of one or more monomers in the three parts.

[0335] Table 1a: Composition of one or more polymerization methods for obtaining the basic polymers P1 to P3 (P1-P3(INV)) and comparative examples P4 to P7 (CE1 to CE4) according to the present invention.

[0336] The physicochemical properties of these obtained basic polymers are described in Table 1b below:

[0337] Table 1b: Physicochemical properties of the basic polymers P1 to P3 and comparative examples CE1 to CE4 according to the present invention.

[0338] Table 2 describes the viscosity and composition of glyoxalized polymers 1 to 3 (P1-A to P3-B) according to the present invention and comparative glyoxalized polymers CE1-A to CE4-B. Table 2: Viscosity results of the glyoxalized polymers P1-A to P3-B and comparative examples CE1-A to CE4-B of the present invention.

[0339] Application testing

[0340] The wet pulp used in all application examples was obtained by breaking down dry pulp to achieve a final water mass concentration of 1%. This is a pH-neutral pulp with 100% recycled paperboard fibers.

[0341] Evaluation of vacuum drainage (DDA) performance

[0342] The DDA (Dynamic Drainage Analyzer) allows for the automatic determination of the time (in seconds) required for vacuum dehydration of the fiber suspension on the fabric. The polymer is added to the wet pulp (0.6 liters of pulp, reaching 1.0% by mass) in the DDA drum while agitated at 1000 rpm:

[0343] T=0s: Stirring the pulp

[0344] T = 10s: Add one or more polymers

[0345] T=30s: Stop stirring and vacuum drain the water for 60s at 200mBar.

[0346] The pressure beneath the fabric is recorded as a function of time. As water is expelled from the fiber pad, air passes through it, causing a sudden change in the slope of the curve representing the pressure beneath the fabric as a function of time. The time (in seconds) associated with this sudden change in slope on the curve corresponds to the drainage time.

[0347] The shorter the time, the better the vacuum drainage performance.

[0348] Performance in dry applications, based on a weight of 80 g·m -2

[0349] Take a sample of the necessary amount of pulp to ultimately obtain a pulp with a particle size of 80 g·m³. -2 The base weight of the paper.

[0350] The wet pulp is introduced into a dynamic hand-made paper forming tank that is kept agitated. Different compounds are injected into the pulp in a predetermined sequence. Typically, there is a contact time of 30 to 45 seconds between the addition of polymers.

[0351] Paper hand sheets are manufactured using an automated dynamic paper hand sheet forming machine: Absorbent paper and forming fabric are placed into the canister of the dynamic paper hand sheet forming machine before the canister begins rotating at 1000 revolutions per minute and a water wall is built. The treated pulp is distributed on the water wall to form a fibrous mat on the forming fabric.

[0352] After the water was drained, the fiber pads were recycled, pressed under a pressure of 4 bar, and then dried at 117°C. The resulting paper was packaged overnight in a room with controlled humidity and temperature (50% relative humidity and 23°C). The dryness resistance of all the paper obtained through this step was then measured.

[0353] Bursting strength was measured using a Messmer Buchel M 405 bursting strength tester according to the TAPPI T403 om-02 standard.

[0354] The amount of polymer added is expressed in kilograms of active polymer per ton of dry fiber. Tests were conducted at 1.5 kg / t, and the results are summarized in Table 3. Results are expressed as a percentage increase compared to the control group (no polymer).

[0355] Table 3: Comparison of drainage and dry strength properties of glyoxalized polymers 1 to 3 (P1-A to P3-B) and comparative polymers 4 to 6 (CE1-A to CE4-B) according to the present invention.

[0356] Interestingly, it is noted that the polymers of the present invention (P1-A to P3-B) exhibit improved drainage performance (DDA) and mechanical properties (bursting resistance; DBL; fracture in the dry state) compared to polymers prepared according to conventional methods (CE1-A and CE1-B) or prior art polymers (CE2-A to CE4-B).

Claims

1. A water-soluble dialdehyde functionalized polymer, comprising... - At least one monomer A: a cationic monomer or anionic monomer, When monomer A is a cationic monomer, it is selected from quaternized dimethylaminoethyl acrylate, quaternized dimethylaminoethyl methacrylate, diallyl dimethyl ammonium chloride, acrylamide propyltrimethylammonium chloride, methacrylamide propyltrimethylammonium chloride, and mixtures thereof. When monomer A is an anionic monomer, it is selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acrylamide undecanoic acid, 3-acrylamido-3-methylbutyric acid, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allyl phosphonic acid, styrene sulfonic acid, 2-acrylamido-2-disulfonic methylpropane acid, their salts, and mixtures thereof; - At least one monomer B: a nonionic monomer selected from acrylamide, acrylonitrile, methacrylamide and mixtures thereof; - At least one structured system comprising: (i) at least one compound I, selected from: allyl sulfonic acid, methyl allyl sulfonic acid, allyl disulfonic acid, methyl allyl disulfonic acid, salts thereof, and mixtures thereof; (ii) at least one compound II selected from: N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-isopropylacrylamide, N-hydroxymethylacrylamide, and mixtures thereof. The polymer is obtained according to the following steps: a) forming a solution (S1) comprising at least a first portion (F1), wherein the first portion (F1) contains (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 portion of F1 is polymerized to form a solution of the first gradient polymer (PG1); c) Add a second part (F2) to a solution containing PG1, the second part (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; d) A portion of F2 is polymerized on PG1 to form a solution of a second-gradient polymer (PG2); e) Add a third part (F3) to a solution containing PG2, said third part (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; f) A portion of F3 is polymerized on PG2 to form a solution containing the base polymer; g) Dilute the solution containing the base polymer and react at least one dialdehyde with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer. At least one of F1, F2, or F3 contains at least one monomer A. At least one of F1, F2, or F3 contains at least one monomer B. At least one of F1, F2, or F3 contains at least one compound I, and At least one of F1, F2 or F3 contains at least one compound II; Monomer A is different from a mixture of cationic and anionic monomers. When monomer A is an anionic monomer, the water-soluble dialdehyde functionalized polymer does not contain any cationic monomers. When monomer A is a cationic monomer, the water-soluble dialdehyde functionalized polymer does not contain any anionic monomers other than compound I.

2. The water-soluble dialdehyde functionalized polymer according to claim 1, characterized in that... At least one of the parts F1, F2 or F3 is different from the other parts.

3. The water-soluble dialdehyde functionalized polymer according to claim 1 or 2, characterized in that... At least one monomer A is a cationic monomer.

4. The water-soluble dialdehyde functionalized polymer according to claim 1 or 2, characterized in that... At least one monomer A is selected from quaternized dimethylaminoethyl acrylate, quaternized dimethylaminoethyl methacrylate, diallyl dimethyl ammonium chloride, acrylamide propyltrimethyl ammonium chloride, methacrylamide propyltrimethyl ammonium chloride and mixtures thereof, and the dialdehyde is selected from the group consisting of glyoxal, glutaraldehyde, furanyl dialdehyde, adipaldehyde, succinaldehyde, dialdehyde starch and mixtures thereof.

5. The water-soluble dialdehyde functionalized polymer according to claim 1 or 2, characterized in that... The at least one nonionic monomer B is selected from acrylamide, acrylonitrile, and methacrylamide, and the dialdehyde is glyoxal.

6. The water-soluble dialdehyde functionalized polymer according to claim 1 or 2, characterized in that, Based on the total weight of monomers A and B, the water-soluble dialdehyde functionalized polymer contains 500 to 50,000 ppm of compound I and wherein, based on the total weight of monomers A and B, the water-soluble dialdehyde functionalized polymer contains 500 to 50,000 ppm of compound II.

7. A method for stepwise preparation of water-soluble dialdehyde functionalized polymers, comprising the following steps: a) forming a solution (S1) comprising at least a first portion (F1), wherein the first portion (F1) contains (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. When monomer A is a cationic monomer, it is selected from quaternized dimethylaminoethyl acrylate, quaternized dimethylaminoethyl methacrylate, diallyl dimethyl ammonium chloride, acrylamide propyltrimethylammonium chloride, methacrylamide propyltrimethylammonium chloride, and mixtures thereof. When monomer A is an anionic monomer, it is selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acrylamide undecanoic acid, 3-acrylamido-3-methylbutyric acid, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allyl phosphonic acid, styrene sulfonic acid, 2-acrylamido-2-disulfonic methylpropane acid, their salts, and mixtures thereof; At least one monomer B is a nonionic monomer selected from acrylamide, acrylonitrile, methacrylamide and mixtures thereof; At least one compound I is selected from the following: allyl sulfonic acid, methyl allyl sulfonic acid, Allyl disulfonic acid, methyl allyl disulfonic acid, their salts and mixtures thereof; At least one compound II, selected from: N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-isopropylacrylamide, N-hydroxymethylacrylamide, and mixtures thereof. b) A portion of F1 is polymerized to form a solution of the first gradient polymer (PG1); c) Add a second part (F2) to a solution containing PG1, the second part (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; d) A portion of F2 is polymerized on PG1 to form a solution of a second-gradient polymer (PG2); e) Add a third part (F3) to a solution containing PG2, said third part (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; f) A portion of F3 is polymerized on PG2 to form a solution containing the base polymer; g) Dilute the solution containing the base polymer and react at least one dialdehyde with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer. At least one of F1, F2, or F3 contains at least one monomer A. At least one of F1, F2, or F3 contains at least one monomer B. At least one of F1, F2, or F3 contains at least one compound I, and At least one of F1, F2 or F3 contains at least one compound II; Monomer A is different from a mixture of cationic and anionic monomers. When monomer A is an anionic monomer, the water-soluble dialdehyde functionalized polymer does not contain any cationic monomers. When monomer A is a cationic monomer, the water-soluble dialdehyde functionalized polymer does not contain any anionic monomers other than compound I.

8. The method according to claim 7, characterized in that, At least one of the parts F1, F2 or F3 is different from the other parts.

9. The method according to claim 7 or 8, characterized in that, The initiator is added continuously throughout the polymerization process, and the dialdehyde is glyoxal.

10. The method according to claim 7 or 8, characterized in that, Following step f) of polymerization (PO3), the method includes an aging step of 10 to 100 minutes.

11. The method according to claim 7 or 8, characterized in that, Step g) The dialdehyde reaction is carried out by at least the following steps: g1) Dilute the solution containing the base polymer to form a diluted solution of the base polymer (SD1). g2) Optionally, adjust the pH of SD1 to at least 10; g3) Add at least one dialdehyde to the solution obtained in step g1) or g2) to form a diluted solution (SD2). g4) Optionally, the solution obtained in step g3) is acidified to a pH of 2 to 4 in order to form a diluted solution (SD3).

12. A method of manufacturing paper or paperboard, comprising adding the water-soluble dialdehyde functionalized polymer according to any one of claims 1 to 6 to an aqueous solution of fibers, and forming paper or paperboard.

13. The use of the water-soluble dialdehyde functionalized polymer according to any one of claims 1 to 6 in: hydrocarbon harvesting; open circulating water treatment; fermentation mash treatment; sludge treatment; construction; wood processing; mining; cosmetic formulation; detergent formulation; textile production; geothermal field; sanitary napkin manufacturing; or agriculture.

14. Use of the water-soluble dialdehyde functionalized polymer according to any one of claims 1 to 6 in drilling or cementing.

15. Use of the water-soluble dialdehyde functionalized polymer according to any one of claims 1 to 6 in enhancing the production of hydrocarbon wells.

16. Use of the water-soluble dialdehyde functionalized polymer according to any one of claims 1 to 6 in the treatment of a hydrodynamic composition.

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