Novel polymer and preparation method thereof

Abstract

The invention relates to a novel water-soluble dialdehyde functionalized polymer as well as a preparation method and application thereof, in particular to application in the field of paper or paperboard manufacturing.

Description

Technical Field

[0001] The present invention relates to a novel water-soluble dialdehyde-functionalized (advantageously glyoxal-functionalized) polymer, a process for its preparation and its use, in particular in the field of paper or paperboard production. Background Art

[0002] The paper industry is constantly seeking improvements in its methods of manufacturing paper, paperboard or the like, particularly with regard to 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 for improving the dry strength of these papers. These water-soluble polyacrylamides are mainly made of nonionic, cationic, anionic or zwitterionic polymers, called base polymers, on which the dialdehyde is reacted.

[0004] Document US20110056640 describes a papermaking method using a compound resulting from a reaction between a dialdehyde-functionalized compound and an acrylamide / diallyldimethylammonium chloride copolymer. This method can only improve drainage.

[0005] Document FR 2 987 375 of the applicant describes an improved papermaking process involving a base copolymer and its reaction with a dialdehyde, the base copolymer containing a polyfunctional compound introduced during the polymerization of the base copolymer monomers, the introduction of which improves the dry strength and drainage properties of the paper.

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

[0007] Document US Pat. No. 10,730,989 relates to a method for preparing an additive for papermaking based on a (meth)acrylamide copolymer.

[0008] Currently, dialdehyde processes, especially glyoxalation, suffer from two major problems.

[0009] The first problem is that commercially available dialdehyde functionalized polyacrylamide products (especially glyoxal functionalized) contain a large number of unreacted amide groups, which may react with dialdehydes (especially glyoxal) during storage, resulting in continuous crosslinking of the base polyacrylamide molecules and reducing the shelf life of the product. In addition, in practice, polyacrylamides contain relatively small amounts of ionic monomers, usually less than about 5 mol%, which limits the contribution of the ionic charge of these polymers.

[0010] The second problem is related to the acid treatment used to stop the reaction between the dialdehyde and the base polymer, which is associated with a significant drop in the viscosity of the aqueous polymer solution. The polymers thus obtained exhibit reduced application properties.

[0011] The Applicant has surprisingly found that synthesizing a polymer according to a specific method allows its molecular weight to be increased without affecting its viscosity. Compared to the prior art solutions, 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 improving drainage, thus making it possible to increase the paper machine speed and thus productivity.

[0012] The use of the polymers obtained by the invention is part of a general principle of improved product properties, more particularly improved dry strength and drainage characteristics. The better properties of the polymers according to the invention make it possible to reduce the amount of product required for an application, which therefore involves reducing greenhouse gas emissions, such as carbon dioxide, associated with the manufacture and use of synthetic polymers. Summary of the invention

[0013] The present invention relates to a water-soluble dialdehyde-functionalized polymer 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, which compound I is selected from the group consisting of allylsulfonic acid, methallylsulfonic acid, allyldisulfonic acid, methallyldisulfonic acid, salts thereof and mixtures thereof;

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

[0019]

[0020] Where R 1 and R 2 are independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a CH2 -OH group;

[0021] Where R 1 and R 2 Not all hydrogen atoms (when R 2 =H, R 1 ≠H; when R 1 =H, R 2 ≠H);

[0022] - Optionally, at least one monomer C: a zwitterionic monomer or a hydrophobic monomer,

[0023] - optionally, at least one cross-linking 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 part (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;

[0027] b) subjecting part F1 to polymerization 1 (PO1) to form a solution of a first gradient polymer (PG1);

[0028] c) adding a 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 to the solution comprising PG1;

[0029] d) polymerizing part F2 on PG1 (PO2) to form a solution of a second gradient polymer (PG2);

[0030] e) adding a 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 to the solution comprising PG2;

[0031] f) polymerizing 3(PO3) part F3 on PG2 to form a solution comprising the base polymer;

[0032] g) diluting the solution comprising the base polymer and reacting at least one dialdehyde, advantageously glyoxal, with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated, and

[0033] at least one of the fractions F1, F2 or F3 contains at least one monomer A,

[0034] at least one of the fractions F1, F2 or F3 contains at least one monomer B,

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

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

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

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

[0039] When monomer A is a cationic monomer, the water-soluble dialdehyde-functionalized polymer contains no anionic monomers other than compound I.

[0040] The present invention also relates to a process for the preparation of such water-soluble dialdehyde-functionalized polymers, advantageously glyoxalized.

[0041] The invention also relates to a process for the manufacture of paper or paperboard using the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated.

[0042] The invention also relates to the use of the water-soluble dialdehyde-functionalized polymers (advantageously glyoxal-functionalized) in the recovery of hydrocarbons (oil and / or gas); in drilling or cementing wells (in particular hydrocarbon wells); in the stimulation of hydrocarbon wells (oil and / or gas), for example, in hydraulic fracturing, conformance, diversion; in the treatment of water in open, closed or semi-closed cycles; in the treatment of fermentation mash; in the treatment of sewage sludge; in construction; in wood treatment; in the treatment of hydraulic compositions (concrete, cement, mortar and aggregates); in the mining industry; in the formulation of cosmetics; in the formulation of detergents; in textile production; in the geothermal field; in the manufacture of sanitary napkins; or in agriculture.

[0043] The invention also relates to the use of the polymers according to the invention as flocculants, coagulants, adhesives, fixatives, viscosity reducers, thickeners, absorbents, friction reducers, drainage agents, charge retention agents, dehydrating agents, conditioners, stabilizers, fixatives, film formers, sizing agents, superplasticizers, clay inhibitors or dispersants. DETAILED DESCRIPTION

[0044] "Polymer" is used to denote a copolymer prepared using at least two different monomers, having at least one monomer A (cationic or anionic) and at least one nonionic monomer B, and a structuring 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 crosslinker and / or a transfer agent.

[0045] A water-soluble polymer is a polymer that can be dissolved in water at 25°C at 10 g·l -1 A polymer that, when dissolved in deionized water with stirring, produces an aqueous solution free of insoluble particles.

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

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

[0048] In this specification, it is considered that the skilled person is able to determine the appropriate Brookfield viscometer module and speed according to the viscosity range to be measured. In fact, such measurements are part of the common knowledge of the skilled person.

[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 provided as examples, are all parts of the present invention. In addition, when numerical ranges are given, endpoint values ​​are included within these ranges. The disclosure also includes all combinations between endpoint values ​​and these numerical ranges. For example, the numerical range "1-20, preferably 5-15" includes the scope of "1-5", "1-15", "5-20" and "15-20", and the disclosure of numerical values ​​1, 5, 15 and 20.

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

[0052] Water-soluble dialdehyde functionalized polymer (advantageously, glyoxalated)

[0053] The present invention relates to water-soluble dialdehyde-functionalized polymers, advantageously glyoxalated, and is characterized by a process for obtaining them.

[0054] The water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) according to the invention comprises (advantageously consists 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, which compound I is selected from the group consisting of allylsulfonic acid, methallylsulfonic acid, allyldisulfonic acid, methallyldisulfonic acid, salts thereof and mixtures thereof;

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

[0060]

[0061] R 1 and R 2 are independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a CH 2 -OH group;

[0062] Where R 1 and R 2 Not all hydrogen atoms (when R 2 =H, R 1 ≠H; when R 1 =H, R 2 ≠H);

[0063] - at least one dialdehyde, advantageously glyoxal,

[0064] - Optionally, at least one monomer C: a zwitterionic monomer or a hydrophobic monomer,

[0065] - optionally, at least one cross-linking agent,

[0066] - Optionally, at least one transfer agent.

[0067] Monomer A is only a cationic monomer or only an anionic monomer. Monomer A is not a mixture of a cationic monomer and an anionic monomer.

[0068] When monomer A is an anionic monomer, the water-soluble dialdehyde-functionalized polymer does not contain a cationic monomer.

[0069] When monomer A is a cationic monomer, the water-soluble dialdehyde-functionalized polymer contains no anionic monomers other than compound I.

[0070] Monomer composition

[0071] Monomer A

[0072] The water-soluble dialdehyde-functionalized polymers (advantageously glyoxalated) according to the invention are synthetic polymers. The water-soluble dialdehyde-functionalized polymers may comprise one or more cationic monomers, or one or more anionic monomers (referred to as "monomer(s) A").

[0073] Advantageously, the one or more cationic monomers A can be specifically chosen from vinyl monomers, preferably from acrylamide, acrylic acid, allyl or maleic acid monomers with ammonium functional groups (advantageously quaternary ammonium). Specifically, in a non-limiting manner, the following can be cited: quaternized dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), diallyldimethylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) and methacrylamidopropyltrimethylammonium chloride (MAPTAC) and mixtures thereof. Preferably, the cationic monomer A is diallyldimethylammonium chloride (DADMAC).

[0074] The water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) advantageously comprises from 1 to 60 mol %, preferably from 3 to 40 mol %, more preferably from 4 to 30 mol % of one or more cationic monomers A; the remaining one or more monomers constituting up to 100 mol % of the water-soluble dialdehyde-functionalized polymer are selected from monomers B and / or monomers C, preferably from monomers B.

[0075] A person skilled in the art knows how to prepare quaternary ammonium monomers, for example by alkyl halides of the type RX, R being an alkyl group (advantageously C 1 -C 3 ) and X is a halogen (RX may specifically be methyl chloride). In addition, the present invention also includes DADMAC, APTAC and MAPTAC type monomers whose counter ion halide is fluoride, bromide or iodide instead of chloride.

[0076] 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 can also contain carboxylate, phosphonate, phosphate, sulfonate or another group with anionic charge. Preferred monomers belonging to this class are for example: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acrylamido undecanoic acid, 3-acrylamido 3-methylbutyric acid, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid (ATBS), vinyl sulfonic acid, vinylphosphonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allylphosphonic acid, styrene sulfonic acid, 2-acrylamido-2-disulfonic methylpropane acid, its salt and mixture thereof. Preferably, the anionic monomer A is acrylic acid or itaconic acid, even more preferably acrylic acid.

[0077] Thus, in certain embodiments of the present invention, one or more anionic monomers may be salted.

[0078] Salt formation refers to the substitution process in which the proton of at least one acid functional group of the anionic monomer A of the -R(O)-OH type (where R=P, S or C) is replaced by a metal cation to form a salt of the -R(O)-OX type (X is a metal cation). In other words, the non-salt-forming form corresponds to the acid form of the monomer, for example 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 + The acid functional groups of the water-soluble dialdehyde-functionalized polymer may be partially or completely salted.

[0079] The salted form advantageously corresponds to an alkali metal salt (Li, Na, K...), an alkaline earth metal salt (Ca, Mg...) or an ammonium salt (eg ammonium ion or tertiary ammonium). The preferred salt is the sodium salt.

[0080] The salt formation can be carried out before or after the polymerization.

[0081] The water-soluble dialdehyde-functionalized anionic polymer (advantageously glyoxalated) advantageously comprises from 1 to 99 mol%, preferably from 2 to 70 mol%, more preferably from 3 to 50 mol%, even more preferably from 5 to 35 mol% of one or more anionic monomers A. The remaining monomer or monomers constituting up to 100 mol% of the water-soluble dialdehyde-functionalized polymer are selected from monomers B and / or monomers C, preferably from monomers B.

[0082] In a particular embodiment of the present 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 by controlled crystallization of the ATBS monomer. Document US10,759,746 describes this hydrated form of ATBS.

[0083] In a preferred embodiment according to the present invention, monomer A is preferably a cationic monomer.

[0084] Monomer B

[0085] The water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) may comprise one or more nonionic monomers (referred to as "monomer(s) B").

[0086] Advantageously, the nonionic monomer B may be selected in particular 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.

[0087] The water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated, advantageously comprises from 40 to 99 mol % of nonionic monomer B, preferably from 30 to 98 mol %, more preferably from 60 to 97 mol %, even more preferably from 70 to 96 mol %.

[0088] Monomer C

[0089] The water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) may comprise one or more zwitterionic monomers or hydrophobic monomers (referred to as "monomer(s) C").

[0090] Zwitterionic monomers are ionic monomers that have an overall charge of zero. In fact, zwitterionic monomers have the same number of cationic charges and anionic charges.

[0091] Advantageously, the one or more zwitterionic monomers that can be used in the context of the present invention can be chosen in particular from derivatives of vinyl motifs, especially acrylamide, acrylic acid, allyl or maleic acid. Preferably, the monomers contain an amine or quaternary ammonium functional group and a carboxylic acid (or carboxylate), sulfonic acid (or sulfonate) or phosphoric acid (or phosphate) type functional group. The one or more zwitterionic monomers may be selected from the following: derivatives of dimethylaminoethyl acrylate, for example, 2-((2-9(acryloyloxy)ethyl)dimethylammonium)ethane-1-sulfonate, and in particular, 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, derivatives of dimethylaminoethyl methacrylate, for example, 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, dimethylaminoethylpropylacrylamide dimethylammonio)acetate, dimethylaminopropyl methacrylamide, or even derivatives thereof such as 2-((3-acrylamidopropyl)dimethylammonio)ethane-1-sulfonate, 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate, 4-((3-acrylamidopropyl)dimethylammonio)butane-1-sulfonate, [3-(acryloyl)oxy)propyl](dimethylammonio)acetate, dimethylaminopropyl methacrylamide, or even derivatives thereof such as 2-((3-methylacrylamidopropyl)dimethylammonio)ethane-1-sulfonate, 3-((3-methyldimethylammonio)propane-1-sulfonate, 4-((3-acrylamidopropyl)dimethylammonio)butane-1-sulfonate, [3-(acryloyl)oxy)propyl](dimethylammonio)acetate, dimethylaminopropyl methacrylamide, or even derivatives thereof such as 2-((3-methylacrylamidopropyl)dimethylammonio)ethane-1-sulfonate, 3-((3-methyldimethylammonio)propane-1-sulfonate dimethylammonio)propane-1-sulfonate), 4-((3-methacrylamidopropyl)dimethylammonium)butane-1-sulfonate and [3-(methacryloyloxy)](dimethylammonio)propyl acetate and mixtures thereof.

[0092] The applicant describes other zwitterionic monomers in document WO2021123599.

[0093] The water-soluble dialdehyde-functionalized polymer according to the invention advantageously comprises from 0.001 to 30 mol %, preferably from 0.01 to 20 mol %, more preferably from 0.1 to 15 mol % of zwitterionic monomer.

[0094] Advantageously, the one or more hydrophobic monomers C may be selected from the group consisting of: 4 -C 30 Alkyl chain, arylalkyl (C 4 -C 30 Alkyl, C 4 -C 30 (meth)acrylates having a propoxylated, ethoxylated, or ethoxylated and propoxylated group; having C 1 -C 3 Alkyl chain, arylalkyl (C 4 -C 30 Alkyl, C 4 -C 30 Aryl), or dialkyl (C 4 -C 30 alkyl) propoxylated, ethoxylated, ethoxylated and propoxylated (meth)acrylamide derivatives; alkylaryl sulfonates (C 4 -C 30 Alkyl, C 4 -C 30 Aryl), or having C 4 -C 30 Alkyl chain, arylalkyl (C 4 -C 30 Alkyl, C 4 -C 30 aryl) propoxylated, ethoxylated, or ethoxylated and propoxylated (meth)acrylamide mono- or di-substituted amides; having C 4 -C 30 Alkyl chain, arylalkyl (C 4 -C 30 Alkyl, C 4 -C 30 Aryl), or C 4 -C 30 Dialkyl propoxylated, ethoxylated, ethoxylated and propoxylated (meth)acrylamide derivatives; alkyl aryl sulfonates (C 4 -C 30 Alkyl, C 4 -C 30 aryl) and mixtures thereof.

[0095] The water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated, generally comprises less than 1 mol % of hydrophobic monomers C. The water-soluble dialdehyde-functionalized polymer may be free of hydrophobic monomers C.

[0096] When the water-soluble dialdehyde-functionalized polymer according to the invention, advantageously glyoxalated, comprises one or more hydrophobic monomers C, they are present in such an amount that the polymer remains water-soluble.

[0097] The skilled person will adjust the amount of the different monomers so that it does not exceed 100 mol % during the preparation of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalated). Preferably, monomers A and B represent 100 mol % of the monomers of the water-soluble dialdehyde functionalized polymer (advantageously glyoxalated).

[0098] Structured system

[0099] The structuring system of a water-soluble dialdehyde functionalized polymer (advantageously glyoxalated) comprises:

[0100] (i) at least one compound I;

[0101] (ii) at least one compound II.

[0102] Compound I is selected from the group consisting of allylsulfonic acid, methallylsulfonic acid, disulfonically acid, disulfonic methallyl acid, salts thereof and mixtures thereof. Preferably, compound I is methallylsulfonic acid, such as sodium methallylsulfonate.

[0103] The salified form advantageously corresponds to an alkali metal salt (Li, Na, K . . . ), an alkaline earth metal salt (Ca, Mg . . . ) or to an ammonium salt (eg ammonium ion or tertiary ammonium). The preferred salt is the sodium salt.

[0104] The water-soluble dialdehyde-functional polymer advantageously comprises 500 to 50,000 ppm, preferably 1,000 to 20,000 ppm, more preferably 2,000 to 10,000 ppm of compound I, based on the total weight of monomers A and B (+ optional monomers C) of the water-soluble dialdehyde-functional polymer.

[0105] The compound II used in the context of the present invention has the formula (1):

[0106]

[0107] R 1 and R 2 are independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a CH 2 -OH group;

[0108] R 1 and R 2 Not all hydrogen atoms (when R 2 =H, R 1 ≠H; when R 1 =H, R 2 ≠H).

[0109] Compound II is advantageously chosen from the group consisting of N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-isopropylacrylamide, N-methylolacrylamide and mixtures thereof. Preferably, compound II is N,N-dimethylacrylamide.

[0110] The water-soluble dialdehyde-functional polymer according to the invention advantageously comprises from 500 to 50,000 ppm, preferably from 1,000 to 20,000 ppm, more preferably from 2,000 to 10,000 ppm of compound II, based on the total weight of monomers A and B (+ optional monomers C) of the water-soluble dialdehyde-functional polymer.

[0111] The mass ratio between compound I and compound II in the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated, is advantageously between 0.01 and 100, preferably between 0.1 and 10.

[0112] In a preferred embodiment according to the present 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.

[0113] Optional

[0114] The water-soluble dialdehyde functionalized polymer (advantageously glyoxalized) may further comprise at least one crosslinking agent. The crosslinking agent may be selected from polyethylenically unsaturated monomers (having at least two unsaturated functional groups), for example, vinyl functional groups, in particular allyl functional groups, acrylic functional groups, or selected from 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 cited. Preferably, the crosslinking agent is methylenebisacrylamide (MBA).

[0115] The amount of crosslinker in the water-soluble dialdehyde-functional polymer is advantageously from 5 to 5,000 ppm, more preferably from 50 to 3,000 ppm, based on the total weight of monomers A and B (+ optionally monomer C) of the water-soluble dialdehyde-functional polymer.

[0116] In a particular embodiment according to the invention, the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated, does not comprise a crosslinking agent.

[0117] The water-soluble dialdehyde functionalized polymer according to the present invention (advantageously glyoxalized) may also contain at least one transfer agent selected, for example, from the group consisting of methanol, isopropanol, sodium hypophosphite, 2-mercaptoethanol and mixtures thereof. Other transfer agents include xanthates, dithiocarbonates, dithiocarbamates and trithiocarbonates and mixtures thereof, preferably sodium hypophosphite.

[0118] The amount of transfer agent in the water-soluble dialdehyde-functionalized polymer is advantageously from 10 to 10,000 ppm, more preferably from 50 to 5,000 ppm, based on the total weight of monomers A and B (+ optionally monomer C) of the water-soluble dialdehyde-functionalized polymer.

[0119] In a particular embodiment according to the invention, the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated, does not comprise a transfer agent.

[0120] Physical properties of base polymers

[0121] 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.

[0122] The weight average molecular weight is preferably measured by gel permeation chromatography coupled with a Malls detector.

[0123] The base polymer is advantageously obtained and used in liquid form.

[0124] The viscosity of the solution containing the base polymer is advantageously from 1,000 to 50,000 cps, preferably from 2,000 to 20,000 cps, for example from 5,000 to 20,000 cps.

[0125] Renewable sources

[0126] In a preferred embodiment according to the invention, monomers of at least partly renewable, non-fossil origin are used to prepare the water-soluble dialdehyde-functionalized polymers (advantageously glyoxalated).

[0127] In the context of the present invention, the term "renewable non-fossil origin" means a source of a compound derived from biomass or syngas, i.e. the result of one or more chemical transformations of one or more raw materials of natural non-fossil origin. The terms "bio-sourced" or "bio-resourced" may also be used to denote a renewable non-fossil source of a compound. A renewable non-fossil source of a compound comprises renewable non-fossil raw materials from a circular economy and which have been preselected to be recycled one or more times in a recycling process of materials from biomass (e.g., materials from polymer depolymerization or from pyrolysis oil conversion).

[0128] According to the present invention, "at least partially renewable non-fossil origin" means that the content of biogenic carbon is from 5% to 100% by weight, preferably at least 30%, more preferably at least 50%, even more preferably at least 70%, more preferably at least 90%, even more preferably at least 100% biogenic carbon, based on the total carbon weight of the compound.

[0129] In the context of the present invention, standard ASTM D6866-21, method B, is used to characterize the biogenic nature of a compound and to determine the biogenic content of said compound. This value is expressed as a weight percentage of biogenic carbon based on the total weight of carbon in said compound.

[0130] gradient

[0131] The base polymer and the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) according to the invention are gradient polymers.

[0132] A polymer with a gradient structure is a polymer composed of at least two monomers in which the change in monomer composition is gradual, unlike block polymers which undergo abrupt changes in composition, and random polymers which do not have a continuous change in composition. In gradient polymers, inter-chain and intra-chain repulsions are less observed because the composition changes gradually over the length of the polymer chain.

[0133] The gradient can be formed by spontaneous or forced gradients. Spontaneous gradient polymerization is due to differences in monomer reactivity. Forced gradient polymerization involves changing the composition of the introduced monomers throughout the polymerization time.

[0134] The forced process comprises (1) introducing a first portion of monomers into a reactor, (2) adding at least one additional portion of monomers advantageously different from the first portion, and (3) polymerizing the monomers introduced into the reactor. The monomers begin to polymerize upon introduction of the first portion.

[0135] The addition of the additional monomer portion can be carried out in parallel with the introduction of the first portion of monomer into the reactor (therefore, the introduction of the portion can start and end simultaneously). Alternatively, the first monomer (first portion) can be fed into the reactor before the second monomer portion is added. Alternatively, the first portion and the second portion can be introduced simultaneously, but the time used to add the second portion can be longer than the time used to add the first portion into the reactor. This embodiment is also applicable to methods with at least 3 monomer portions.

[0136] According to the process of the invention, the water-soluble dialdehyde-functionalized polymer obtained, advantageously glyoxalated, is formed by stepwise addition of the monomers, that is to say, preferably by forced gradient.

[0137] The method according to the invention comprises a first part (F1) and at least two additional parts (F2 and F3). At least one of the parts F1, F2 and F3 of the method is different from the other parts. Preferably, the parts F1, F2 and F3 are different. Different parts refer to parts consisting of different monomers (ratios and / or properties of monomers) and / or compounds I and II (ratios and / or properties of compounds I and II).

[0138] Aggregation methods

[0139] The stepwise polymerization process of a water-soluble dialdehyde functionalized polymer (advantageously glyoxalated) comprises the following steps:

[0140] a) forming a solution (S1) comprising at least a first part (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;

[0141] b) subjecting part F1 to polymerization 1 (PO1) to form a solution of a first gradient polymer (PG1);

[0142] c) adding a 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 to the solution comprising PG1;

[0143] d) polymerizing part F2 on PG1 (PO2) to form a solution of a second gradient polymer (PG2);

[0144] e) adding a 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 to the solution comprising PG2;

[0145] f) polymerizing part F3 on PG2 (PO3) to form a solution comprising the base polymer;

[0146] g) diluting the solution comprising the base polymer and reacting at least one dialdehyde, advantageously glyoxal, with the base polymer to obtain a water-soluble dialdehyde functionalized polymer, advantageously glyoxal

[0147] and at least one of the fractions F1, F2 or F3 contains at least one monomer A,

[0148] at least one of the fractions F1, F2 or F3 contains at least one monomer B,

[0149] At least one of the fractions F1, F2 or F3 contains at least one compound I, and

[0150] At least one of the fractions F1, F2 or F3 contains at least one compound II.

[0151] The process may include adding an additional portion, but no additional portion is added after step g) of reacting the dialdehyde.

[0152] It is possible that the improved properties of the polymers obtained by the process according to the invention may be due to the fact that the polymerization is carried out stepwise and continuously, ie without interruptions.

[0153] "Stepwise" means that the monomers of the base polymer are polymerized in multiple parts, without interruption, i.e. the parts are added continuously and the polymerization is not stopped. The different steps a) to f) are carried out stepwise. In other words, the first part of the monomers can be poured (in a flowing form) and polymerized to form a first gradient polymer PG1, which continues to be polymerized with part F2 to form a gradient polymer PG2, which itself continues to be polymerized with part F3 so as to obtain the base polymer at the end of the polymerization. At least one of parts F1, F2 and F3 is different from the other parts. Preferably, parts F1, F2 and F3 are different. The addition of different parts in the polymerization process allows to obtain a gradient in the base polymer composition.

[0154] In certain embodiments, the polymerization may be stopped after PO1 and / or PO2 and continued at a different location. In this embodiment, the polymer is added to the gradient polymer PG formed in one or more of the previous steps. X Part F X+1 (X=1 or 2) and PG X interact to form PG X+1, the process continues in the following steps to finally obtain the base polymer. After the polymerization is completed, step g) is continuously performed on the base polymer until the polymerization ends or another time (later). Preferably, the process is performed continuously. In other words, the base polymer used for step g) is no longer polymerized. However, the base polymer used for step g) is subjected to a post-treatment to change its chemical structure. Step g) is advantageously performed in a reactor different from the polymerization because it requires diluting the solution containing the base polymer. The dilution of the base polymer is advantageously performed in water.

[0155] In the polymerization process according to the invention, the sum of the molar percentages of the monomers of the different fractions is equal to the sum of the molar percentages of the monomers of the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated.

[0156] Step a), forming a solution (S1) comprising a first part (F1)

[0157] Solution (S1)

[0158] The solution (S1) usually consists of:

[0159] - solvents;

[0160] - initiator;

[0161] -Part I F1.

[0162] The solvent is advantageously water, or a solvent in which the monomers and base polymer are soluble. Preferably, the solvent is water.

[0163] The polymerization initiator used can be any compound that dissociates into free radicals under the polymerization conditions, for example: organic peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds and redox pairs. Preferably, water-soluble initiators are used. 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.

[0164] In a particular embodiment, solution S1 is formed by mixing solvent, initiator, and part F1 in a polymerization tank.

[0165] In this particular embodiment, part F1 can be added to the solvent / initiator mixture all at once, in portions or poured (in flowing form), ie gradually and continuously (eg dropwise). Preferably, part F1 is added all at once to the polymerization tank.

[0166] In a particular embodiment of the invention, the initiator and part F1 are poured (in flowing form) into the polymerization tank containing the solvent. They can be added separately, or premixed. Preferably, they are added separately.

[0167] 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 the different parts during the different polymerization steps and in the possible aging steps of the different gradient polymers (PG1 and PG2) and the base polymer.

[0168] In this preferred embodiment of the invention, the duration of pouring the initiator is from 50 minutes to 560 minutes, preferably from 130 minutes to 430 minutes.

[0169] Part 1 (F1)

[0170] Advantageously, fraction F1 comprises from 10 to 45% by weight, preferably from 15 to 40% by weight, of monomers (A and / or B, + optional C), based on the total weight of monomers (A+B+optionally C) of the water-soluble dialdehyde-functionalized polymer.

[0171] Fraction F1 advantageously comprises from 0 to 65 mol %, preferably from 5 to 55 mol %, of monomers A, advantageously cationic monomers, based on the total number of moles of monomers in fraction F1.

[0172] Fraction F1 advantageously comprises from 35 to 100 mol %, preferably from 45 to 95 mol %, of nonionic monomers B, based on the total number of moles of monomers in fraction F1.

[0173] Fraction F1 advantageously comprises from 250 to 30,000 ppm, preferably from 500 to 10,000 ppm, more preferably from 1,000 to 7,000 ppm of compound I, based on the total weight of monomers A and B (+ optional monomers C) of the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated.

[0174] Fraction F1 advantageously comprises from 250 to 30,000 ppm, preferably from 500 to 10,000 ppm, more preferably from 1,000 to 5,000 ppm of compound II, based on the total weight of monomers A and B (+ optional monomers C) of the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated.

[0175] The different monomers and compounds contained in part F1 are advantageously added in the form of solutions. These solutions can be added individually or in the form of a mixture all at once, in multiple portions or poured (in a flowing form) (i.e. dropwise) into the polymer tank to form solution S1. Preferably, they are added in the form of a mixture and all at once.

[0176] When pouring (in flowing form) fraction F1 , this pouring advantageously lasts from 10 minutes to 80 minutes, preferably from 40 minutes to 70 minutes.

[0177] In a preferred embodiment, fraction F1 is prepared in the reactor (polymerization tank) before the initiator is added.

[0178] 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.

[0179] Step b), polymerizing part F1 to form a first gradient polymer (PG1)

[0180] Polymer 1 (PO1)

[0181] Prior to polymerizing PO1, the air in the polymerization tank may be replaced with an inert gas (eg, nitrogen or argon).

[0182] The polymerization PO1 is usually a free radical polymerization. A polymerization initiator may be used, in particular an initiator which dissociates into free radicals under the polymerization conditions.

[0183] The polymerization PO1 is usually started at a temperature of 70 to 90°C, preferably 75 to 85°C, and then the polymerization temperature is controlled using a cooling device so as not to exceed 95°C.

[0184] The polymerization PO1 generally lasts from 10 to 80 minutes, preferably from 40 to 70 minutes.

[0185] Advantageously, the polymerization advantageously starts when the first monomer, the solvent and the initiator are brought into contact, in other words, the duration of the polymerization PO1 advantageously corresponds to the duration of the pouring of the fraction F1 .

[0186] Gradient polymer (PG1)

[0187] At the end of the polymerization of PO1, a gradient polymer (PG1) is obtained.

[0188] In a particular embodiment according to the present invention, the gradient polymer PG1 is left to age for 5 to 60 minutes, preferably 10 to 30 minutes.

[0189] "Standing and aging" means that after the polymerization is completed, the temperature of the medium is maintained at 80 to 90°C in order to increase the viscosity through the internal branching phenomenon of the polymer. The definition of aging applies to all steps of the polymerization process. Step c) Adding the second part (F2) to the solution containing PG1

[0190] Part 2 F2

[0191] Advantageously, fraction F2 comprises from 30 to 80 wt.-%, preferably from 40 to 70 wt.-% of monomers (A and / or B, + optional C), based on the total weight of monomers (A+B, + optional C) of the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated.

[0192] Fraction F2 advantageously comprises from 0 to 50 mol %, preferably from 0 to 40 mol %, of monomers A, advantageously cationic monomers, based on the total number of moles of monomers in fraction F2.

[0193] Fraction F2 advantageously comprises from 0 to 100 mol %, preferably from 60 to 100 mol %, of nonionic monomers B, based on the total moles of monomers in fraction F2.

[0194] Fraction F2 advantageously comprises from 250 to 30,000 ppm, preferably from 500 to 10,000 ppm, more preferably from 1,000 to 5,000 ppm of compound I, based on the total weight of monomers A and B (+ optional monomers C) of the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated).

[0195] Fraction F2 advantageously comprises from 250 to 30,000 ppm, preferably from 500 to 10,000 ppm, more preferably from 1,000 to 5,000 ppm of compound II relative to the total weight of A and B monomers (+ optionally C monomers) of the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated).

[0196] The different monomers and compounds contained in part F2 are advantageously added in the form of solutions. These solutions can be added all at once, in multiple portions or poured (in a flowing form) into the polymer tank, either individually or in the form of a mixture. Preferably, they are added in the form of a mixture and poured (in a flowing form).

[0197] When pouring (in flowing form) fraction F2, this pouring advantageously lasts from 10 minutes to 100 minutes, preferably from 30 minutes to 90 minutes.

[0198] Adding part F2 in flowing form (eg dropwise) allows controlling the exotherm of the reaction which may otherwise be too high even when a cooler is used.

[0199] 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.

[0200] Step d), polymerizing part F2 on PG1 to form a second gradient polymer (PG2)

[0201] Polymerization (PO2)

[0202] The polymerization PO2 is carried out as a continuation of the polymerization PO1; the polymerization PO2 is carried out under the same time and temperature conditions (advantageously between 70 and 90° C.).

[0203] The polymerization PO2 advantageously lasts from 10 to 100 minutes, preferably from 30 to 90 minutes.

[0204] Polymerization PO2 starts with the addition of the first monomer of fraction F2.

[0205] Advantageously, the duration of polymerizing PO2 corresponds to the duration of pouring of fraction F2.

[0206] Gradient Polymer (PG2)

[0207] At the end of the polymerization of PO2, a gradient polymer (PG2) is obtained.

[0208] In a specific embodiment of the present invention, the gradient polymer PG2 is left to age for 5 minutes to 60 minutes, preferably 10 minutes to 30 minutes.

[0209] Step e) adding the third part (F3) to the solution containing PG2

[0210] Section F3

[0211] Advantageously, fraction F3 comprises from 5 to 40 wt. %, preferably from 10 to 30 wt. %, of monomers (A and / or B + optional C), based on the total weight of monomers (A + B + optional C) of the water-soluble dialdehyde functionalized polymer, advantageously glyoxalated.

[0212] Fraction F3 advantageously comprises from 0 to 50 mol %, preferably from 0 to 35 mol %, of monomers A, advantageously cationic monomers, based on the total number of moles of monomers in fraction F3.

[0213] Fraction F3 advantageously comprises from 50 to 100 mol %, preferably from 65 to 100 mol %, of nonionic monomers B, based on the total moles of monomers in fraction F3.

[0214] Fraction F3 advantageously comprises from 0 to 10,000 ppm, preferably from 10 to 5000 ppm, more preferably from 20 to 1,000 ppm of compound I, based on the total weight of monomers A and B (+ optional monomers C) of the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated).

[0215] Fraction F3 advantageously comprises from 0 to 10,000 ppm, preferably from 0 to 1,000 ppm, of compound II, based on the total weight of monomers A and B (+ optional monomers C) of the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated.

[0216] The different monomers and compounds contained in part F3 are advantageously added in the form of solutions. These solutions can be added all at once, in multiple portions or poured (in flowing form) (i.e. dropwise) into the polymer tank, either individually or in the form of a mixture. Preferably, they are added in the form of a mixture and poured (in flowing form).

[0217] When portion F3 is poured (in flowing form), this pouring advantageously lasts from 10 minutes to 100 minutes, preferably from 30 minutes to 90 minutes.

[0218] Adding part F3 in a flowing form (eg dropwise) allows controlling the exotherm of the reaction which may otherwise be too high even when a cooler is used.

[0219] In a preferred embodiment, fraction F3 contains at least one monomer B and at least one compound I.

[0220] In an embodiment, the amount of compound I in fraction F3 is less than 500 ppm, preferably less than 300 ppm, preferably less than 200 ppm, even more preferably less than 100 ppm.

[0221] Such small amounts enable desired physical and unique properties to be achieved in the base polymer and subsequently in the final water-soluble dialdehyde functionalized polymer.

[0222] Step f), polymerizing part F3 on PG2 to form a water-soluble dialdehyde functionalized polymer (PO3)

[0223] 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 PO2 (advantageously at 70 to 90° C. for 10 to 100 minutes, preferably 30 to 90 minutes).

[0224] Polymerization PO3 starts with the addition of the first monomer of fraction F3.

[0225] Advantageously, the duration of polymerizing PO3 corresponds to the duration of pouring of fraction F3.

[0226] At the end of the polymerization of PO3, the base polymer is obtained.

[0227] In a particular embodiment according to the invention, the base polymer is left to age for 5 to 60 minutes, preferably 10 to 30 minutes, before the residual monomers are removed.

[0228] The reaction is stopped by adding excess initiator and / or water; this step serves to eliminate any residual monomers that may be present in the solution comprising the base polymer.

[0229] Optional Steps

[0230] The method according to the present invention may also include additional steps and is not limited to the above steps.

[0231] In a particular embodiment of the present invention, the polymerization process according to the invention may comprise the addition of additional moieties constituting the base polymer.

[0232] In a preferred embodiment of the invention, after step f) of polymerizing PO3 and before step g), the base polymer is left to age for 10 to 100 minutes, preferably 30 to 90 minutes. In the case of adding a supplementary part, the ageing is carried out after the last polymerization step and before step g).

[0233] In a particular embodiment of the invention, a crosslinking agent and / or a transfer agent is added during at least one of the above steps.

[0234] In a particular embodiment of the invention, the crosslinking agent is added in part F1 and / or part F2.

[0235] When a crosslinking agent is added, it is advantageously selected from the crosslinking agents described above.

[0236] When a crosslinking agent is added, the amount 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 glyoxalated) (monomers A, B and optionally C).

[0237] In a particular embodiment of the invention, the transfer agent is added in part F1 and / or part F2.

[0238] When a transfer agent is added, it is advantageously selected from the transfer agents described above.

[0239] When a transfer agent is added, the amount of transfer agent is advantageously from 10 to 10,000 ppm, preferably from 50 to 5,000 ppm, based on the total weight of the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) (monomers A, B and optionally C).

[0240] Step g), diformylation (advantageously glyoxalation) of the base polymer

[0241] Advantageously, the dialdehyde functionalization reaction (advantageously glyoxalation) comprises at least the following consecutive steps:

[0242] g1) diluting (advantageously in water) a solution comprising the base polymer so as to form a diluted solution of the base polymer (SD1);

[0243] g2) optionally adjusting the pH of SD1 to at least 10;

[0244] g3) adding at least one dialdehyde to the solution obtained in step g1) or g2) to form a diluted solution (SD2);

[0245] g4) Optionally acidifying the solution obtained in step g3) to a pH of 2 to 4, preferably 2.5 to 3.5, so as to form a diluted solution (SD3).

[0246] Advantageously, in step g1), the amount of base polymer in the diluted solution (SD1) is between 1 and 15% by weight, preferably between 2 and 13% by weight. The dilution is advantageously carried out in water.

[0247] Advantageously, the dialdehyde added in step g3) is selected from the group comprising glyoxal, glutaraldehyde, furan dialdehyde, adipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyacetaldehyde, diepoxides and mixtures thereof. Preferably, the dialdehyde is glyoxal.

[0248] Advantageously, the mass concentration of the dialdehyde is from 5 to 30%, preferably from 10 to 25%, more preferably from 15 to 20%, based on the total weight of monomers A and B (optionally C).

[0249] Advantageously, step g3) is carried out in a reactor with stirring at a temperature of 19 to 26° C. Preferably, after g2), the pH at the start of the addition of the dialdehyde is maintained at 10 to 11, for example, with a 10% by weight soda solution in water. After the reaction between the dialdehyde and the base polymer in step g3), the viscosity of the aqueous solution increases.

[0250] In a particular embodiment according to the invention, when g2) is not carried out, at the end of step g3), the pH is adjusted to at least 8, for example with a 10% by weight aqueous soda solution, which pH is maintained throughout step g3).

[0251] In a particular embodiment of the invention, the diluted solution (SD2) is used directly and injected into the pulp.

[0252] Step g3) advantageously lasts from 2 minutes to 90 minutes, preferably from 5 to 75 minutes.

[0253] After the desired viscosity has been reached, step g4) can be carried out.

[0254] Step g4) is preferably carried out at a temperature of 19 to 26° C. in a reactor, preferably with stirring, by adding an acid, such as concentrated sulfuric acid.

[0255] Advantageously, the dialdehyde reaction, advantageously glyoxalation, is monitored by measuring viscosity, turbidity, delta P, . . . or the like.

[0256] At the end of step g4) or g3), a water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) is obtained.

[0257] In a particular embodiment of the present invention, step g) comprises a step g5) which comprises adding at least one dialdehyde to the solution obtained in step g4).

[0258] Advantageously, the dialdehyde is selected from the aforementioned group, preferably, the dialdehyde is the same as in step g3).

[0259] In a particular embodiment, advantageously, 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%, based on the total weight of monomers A and B (optionally C).

[0260] Advantageously, the mass concentration of the dialdehyde added in step g3) is the same as that added in step g5).

[0261] In a particular embodiment of the invention, the microcellulose compound is reacted with a water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated.

[0262] The microcellulose / water-soluble dialdehyde-functionalized polymer mixture can then be added to the paper pulp as an additive, replacing the water-soluble dialdehyde-functionalized polymer (alone) according to the invention in all the aforementioned specific embodiments.

[0263] Advantageously, the microcellulose compound is selected from nanofibrillated cellulose, microfibrillated cellulose, nanocrystalline cellulose, nanocellulose.

[0264] Advantageously, 10 to 100 wt%, preferably 10 to 50 wt%, of the microcellulose compound is added to the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated), based on the weight of the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated).

[0265] Even if it is prepared in solution, the water-soluble dialdehyde-functionalized polymer of the invention can also be used in solid form. In practice, the solid form is obtained in other ways (by a process comprising drying the solution in step g)). The technical principle of solid / liquid separation is by atomization or spray drying (which consists in producing a cloud of fine droplets in a hot gas stream for a controlled period of time), drum drying, fluidized bed dryer ... Papermaking method

[0266] The present invention also relates to a process for the manufacture of paper or paperboard, comprising (1) adding a water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) according to the present invention to an aqueous suspension of fibers, and (2) forming paper or paperboard. Thus, the present invention relates to the use of a water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) in a papermaking process.

[0267] The different steps in the production process of paper, board or the like are known and correspond to the technology that is part of the knowledge of the person skilled in the art, and there is no need to describe them in further detail, as they are still known and classic to the person skilled in the art. If necessary, these steps can be referred to the document: Handbook for Pulp & Paper Technologists, 4th edition, GASmook.

[0268] According to the invention, the water-soluble dialdehyde-functionalized polymer, advantageously glyoxalated, is added during the papermaking process, before or after the formation of paper, board, etc. Thus, contacting the cellulosic material with the polymer of the invention can be carried out in different ways, in particular according to typical methods known to those skilled in the art.

[0269] The water-soluble dialdehyde functionalized polymer, advantageously glyoxalated, may be added to the cellulosic material in the form of a diluted or undiluted aqueous solution. It may be applied by an impregnation technique or may be added directly to the fiber suspension at any point in the papermaking process where dry strength agents are normally introduced.

[0270] Thus, the polymer according to the invention can be introduced into a thick stock or a thin stock. It can be added at the mixing pump, before the headbox or the filter screen. Preferably, the polymer is introduced before the headbox.

[0271] Preferably, the polymer according to the invention is injected industrially into the fiber suspension, ie before it is diluted with pulp water (thick stock).The consistency of the pulp is about 1 to 5% by weight of cellulose fibers.

[0272] The papermaking process according to the invention can be carried out with any type of pulp, for example virgin fiber pulp (kraft, bisulfite), recycled fiber, deinked pulp, mechanical pulp and thermomechanical pulp.

[0273] The water-soluble dialdehyde functionalized polymer (advantageously glyoxalated) is advantageously added directly to the fiber suspension prior to forming the paper.

[0274] It can be added at a single injection point, or at two injection points.

[0275] As required, the papermaking method according to the present invention may also include the addition of other additives and / or polymers; by way of example and not limitation, we may cite: biocides, coagulants, retention aids, flocculants, starches, etc.

[0276] use

[0277] The invention also relates to the use of the water-soluble dialdehyde-functionalized polymer (advantageously glyoxalated) in the recovery of hydrocarbons (oil and / or gas); in drilling or cementing wells; in the stimulation of hydrocarbon wells (oil and / or gas), for example, in hydraulic fracturing, consistency, diversion; in the treatment of water in open, closed or semi-closed cycles; in the treatment of fermentation mash; in the treatment of sludge; in construction; in the treatment of wood; in the treatment of hydraulic compositions (concrete, cement, mortar and aggregates); in the mining industry; in the formulation of cosmetics; in the formulation of detergents; in textile production; in the geothermal field; in the manufacture of sanitary napkins; or in agriculture.

[0278] The invention also relates to the use of water-soluble dialdehyde-functionalized polymers, advantageously glyoxalated, as flocculants, coagulants, binders, fixatives, viscosity reducers, thickeners, absorbents, friction reducers, drainage agents, charge retention agents, dehydrating agents, conditioners, stabilizers, fixatives, film formers, sizing agents, superplasticizers, clay inhibitors or dispersants.

[0279] The invention and its advantages will become more apparent in the following examples given in order to illustrate the invention in a non-limiting manner.

[0280] Example

[0281] List of abbreviations:

[0282] DADMAC: Diallyldimethylammonium chloride (monomer A)

[0283] AMD: Acrylamide (Monomer B)

[0284] DMAM: dimethylacrylamide (compound II)

[0285] SMS: Sodium methyl allyl sulfonate (Compound I)

[0286] SPS: Sodium persulfate (polymerization initiator)

[0287] MBA: Methylene bisacrylamide (cross-linking agent)

[0288] PEI: Polyethyleneimine

[0289] Description of the Characterization of Molecular Weight by GPC-Malls

[0290] Gel permeation chromatography is a method that allows the separation of macromolecules according to their hydrodynamic volume; gel permeation chromatography combined with a Malls detector makes it possible to measure the diffusion of light from multiple angles.

[0291] The synthesized polymers were analyzed under the following conditions:

[0292] -Instrument: GPC-2

[0293] - Column: Shodex SB-807-HQ and SB-805custom

[0294] -method:

[0295] * Temperature: 30℃

[0296] *Mobile phase: 0,5M NaNO 3 ,HEPES(pH=8),100ppm NaN 3

[0297] *Injection: 100μL

[0298] *Flow rate: 0,3mL / min

[0299] *Detection:

[0300] (i) Light scattering detector (MALS): absolute molar mass

[0301] (ii) Refractometer (RI): Concentration

[0302] Viscosity was measured using a Brookfield viscometer with a Brookfield LVI module at 25°C and a speed of 60 rpm.

[0303] Preparation of polymers 1 to 3 (INV) according to the invention

[0304] Base polymer 1 (P1)

[0305] Step 1: Gradient Polymer PG1

[0306] In a 1 liter reactor equipped with a mechanical stirrer, a thermometer, a condenser and a nitrogen-impregnated rod, a first portion F1 is introduced into the reactor, comprising 140 g of water, 89.3 g of acrylamide (50% by weight in water), 16.7 g of diallyldimethylammonium chloride (64% by weight in water), 1 g of citric acid, 0.5 g of dimethylacrylamide and 0.87 g of sodium methallyl sulfonate. The medium is heated using a water bath and maintained at a temperature of 79 to 81° C. The addition of 0.05 g of sodium persulfate makes it possible to initiate the initiator and start the polymerization of the monomer (PO1) to form the first gradient polymer PG1.

[0307] Step 2: Gradient Polymer PG2

[0308] When the exothermic reaction was over, pouring began: the initiator (44 g SPS, 0.33 wt % aqueous solution) was added over 130 minutes, while the second portion F2 was added over 50 minutes, consisting of: 24.3 g water, 178.6 g acrylamide (50 wt % aqueous solution), 16.7 g DADMAC (64 wt % aqueous solution), 0.5 g dimethylacrylamide and 0.41 g sodium methallyl sulfonate. After pouring portion F2, the gradient polymer PG2 was allowed to age for 10 minutes (polymerization PO2 was carried out during pouring portion F2 and during the aging period to form the gradient polymer PG2).

[0309] Step 3: Base Polymer 1 (P1)

[0310] Then, a third portion F3 is poured over 60 minutes, consisting of: 115.6 g of water, 89.3 g of acrylamide (50% by weight in water), 0.01 g of sodium methyl allyl sulfonate. At the end of the addition of portion F3, the polymer is allowed to age for 10 minutes (polymerization PO3 is carried out during the pouring of portion F3 and during the aging period to form the polymer).

[0311] After aging was complete, 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 60 minute aging was performed before cooling. The solution containing base polymer 1 (P1) had a pH of 3.5, 20 wt % active matter, a viscosity of 4,100 cps and a molecular weight of 4,300,000 Da obtained by GPC-Malls.

[0312] Glyoxalation of the base polymer 1 (P1) according to the invention (P1-A / B (INV))

[0313] Polymer 1-A (P1-A)

[0314] 64 g of base polymer 1 (P1) and 728 g of water were introduced into a 1 liter reactor equipped with a mechanical stirrer. The reactor was equipped with a pH probe. After stirring for 10 minutes, the pH was adjusted to 10.3 with a 10 wt % soda solution. The temperature was maintained at 20 to 22° C. 8 g of glyoxal (40 wt % aqueous solution) was added. The pH detection and viscosity monitoring made it possible to obtain a product of 39 cps after a reaction time of 58 minutes. When the desired viscosity was reached, the mixture was stirred by adding H 2 SO 4 (92 wt. % aqueous solution) The pH was lowered to less than 3.5 to stop the reaction and obtain polymer 1-A (P1-A) according to the present invention.

[0315] Polymer 1-B (P1-B)

[0316] The protocol for preparing polymer 1-A was repeated by varying the amount of glyoxal added to obtain polymer 1-B (P1-B) according to the invention. The compositions are summarized in Table 2.

[0317] Base polymers 2 and 3 (P2 and P3)

[0318] The protocol for the preparation of polymer 1 was repeated by varying the composition of the different parts in order to prepare base polymers 2 (P2) and 3 (P3) of the invention. The compositions of the different parts used to obtain these base polymers are summarized in Table 1a.

[0319] Glyoxalation of base polymers 2 and 3 according to the invention (P2-A / B and P3-A / B) (INV)

[0320] The protocol for preparing polymers 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.

[0321] Preparation of Comparative Example Polymers 4 to 7 (CE1 to CE4)

[0322] Polymer 4 (CE1)

[0323] The polymer is prepared in one step.

[0324] In a 1-liter reactor equipped with a mechanical stirrer, a thermometer, a condenser and a nitrogen-impregnated rod, 526 g of water, 33.1 g of DADMAC (64 wt.% aqueous solution) were introduced. 2 SO 4 The pH is adjusted to 2.5. The medium is heated using a water bath and maintained at a temperature of 79 to 81° C. 357.8 g of acrylamide (50% by weight aqueous solution) are added by continuous pouring over 90 minutes, and a sodium persulfate solution is added by pouring for 90 minutes. After aging for 10 minutes, 0.6 g of sodium bisulfite (40% by weight aqueous solution) is added to react any residual monomers. A new 60 minute aging phase is performed before cooling. The solution obtained containing base polymer 4 (CE1) has a pH of 5.0, 20.1% by weight of active substances, a viscosity of 4,100 cps, and a molecular weight of 429,000 Da obtained by GPC-Malls.

[0325] Glyoxalation of polymer 4 (CE1-A / B)

[0326] The protocol for the preparation of polymer 1-A was repeated while varying the amount of glyoxal added. Comparative glyoxalated polymers 4-A (CE1-A) and 4-B (CE1-B) were obtained, their compositions are summarized in Table 2.

[0327] Polymer 5 (CE2)

[0328] Polymer 5 (CE2) is obtained according to Example 4 of document FR2987375.

[0329] Glyoxalation of polymer 5 (CE2-A / B)

[0330] The protocol for preparing 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.

[0331] Polymer 6 (CE3)

[0332] Polymer 6 is obtained according to Example 12 of document FR2987375.

[0333] Glyoxalation of polymer 6 (CE3-A / B)

[0334] The protocol for preparing polymer 1-A was repeated while varying the amount of glyoxal added. Polymers 6-(CE3-A) and 6-B (CE3-B) were obtained, whose compositions are summarized in Table 2.

[0335] Polymer 7 (CE4-A / B)

[0336] Polymer 7 (CE4) was prepared according to the same protocol as polymer 1, but with only 2 steps. The compositions of the different parts of the polymerization process for preparing base polymers 1-3 (P1 to P3) according to the invention and comparative base polymer examples (CE1 to CE4) are summarized in Table 1a.

[0337] In this Table 1a, the monomer content described in each part represents the molar weight percentage of AMD (or DADMAC) monomer relative to the total molar amount of the corresponding monomer in the total part. Thus, for example, the sum of the percentages of AMD monomer in the three parts equals 100%.

[0338] The contents of compounds I (SMS) and II (DMAM) are expressed in ppm by weight, based on the total weight of the monomer or monomers in the three fractions.

[0339]

[0340]

[0341] Table 1a: Composition of the parts of the polymerization process or processes for obtaining the base polymers P1 to P3 according to the invention (P1-P3(INV)) and comparative examples P4 to P7 (CE1 to CE4).

[0342] The physicochemical properties of the base polymers obtained are described in Table 1b below:

[0343]

[0344] Table 1 b: Physicochemical properties of base polymers P1 to P3 according to the invention and comparative examples CE1 to CE4.

[0345] Table 2 describes the viscosity and composition of glyoxalated polymers 1 to 3 (P1-A to P3-B) according to the invention and comparative glyoxalated polymers CE1-A to CE4-B

[0346]

[0347]

[0348] Table 2: Viscosity results for inventive glyoxalated polymers P1-A to P3-B and comparative examples CE1-A to CE4-B.

[0349] Application Testing

[0350] The wet pulp used in all application examples was obtained by disintegrating dry pulp in order to obtain a final water mass concentration of 1%. This was a pH neutral pulp with 100% recycled paperboard fibers. Evaluation of the Drainage Vacuum (DDA) performance

[0351] The DDA (Dynamic Drainage Analyser) allows the automatic determination of the time (in seconds) required for vacuum dewatering of the fiber suspension on the fabric. The polymer was added to the wet pulp (0.6 liters of pulp to 1.0 mass %) in the DDA drum under stirring at 1000 rpm:

[0352] T=0s:Stirring pulp

[0353] T = 10s: Add one or more polymers

[0354] T=30s: Stop stirring and drain under vacuum at 200 mBar for 60s.

[0355] The pressure under the fabric is recorded as a function of time. As water is drained from the mat, air passes through the mat, which creates a sudden change in slope on the curve representing the pressure under the fabric as a function of time. The time (expressed in seconds) associated with the sudden change in slope on the curve corresponds to the drainage time. The shorter the time, the better the vacuum drainage.

[0356] Performance in dry-resistant applications, basis weight 80 g·m -2

[0357] The necessary amount of pulp is sampled in order to obtain a pulp having a final density of 80 g·m -2 Basis weight of paper.

[0358] The wet pulp is introduced into a dynamic handsheet former tank which is kept agitated. Different compounds are injected into the pulp according to a predetermined sequence. Typically, there is a contact time of 30 to 45 seconds between the addition of polymers.

[0359] Making Paper Hand Sheets with Automatic Dynamic Hand Sheet Former: Blotting paper and forming fabric were placed in the tank of the dynamic hand sheet former before starting the rotation of the tank at 1000 rpm and building a water wall. The treated pulp was distributed on the water wall to form a fiber mat on the forming fabric.

[0360] After the water was drained off, the fiber mat was recovered, pressed at a pressure of 4 bars and then dried at 117° C. The paper obtained was packaged overnight in a room with controlled humidity and temperature (50% relative humidity and 23° C.). The drying resistance properties of all the papers obtained by this procedure were then measured.

[0361] The burst strength was measured using a Messmer Buchel M 405 burst tester according to TAPPI T403 om-02 standard.

[0362] The amount of polymer added is expressed as kg of active polymer per ton of dry fibre. Tests with 1.5 kg / t were carried out and are summarized in Table 3. The results are expressed as a percentage increase compared to the blank (no polymer).

[0363]

[0364]

[0365] Table 3: Comparison of drainage and dry strength properties of glyoxalated polymers 1 to 3 (P1-A to P3-B) according to the invention and comparative polymers 4 to 6 (CE1-A to CE4-B)

[0366] It is interesting to note that the polymers of the invention (P1-A to P3-B) exhibit drainage properties (DDA) and mechanical properties (burst resistance; DBL; break in dry state) which are improved with respect to polymers prepared according to conventional methods (CE1-A and CE1-B) or polymers of the prior art (CE2-A to CE4-B).

Claims

1. A water-soluble dialdehyde functionalized polymer comprising - at least one monomer A: a cationic monomer or an anionic monomer; - at least one monomer B: a nonionic monomer; - At least one structured system comprising: (i) at least one compound I selected from the group consisting of allylsulfonic acid, methallylsulfonic acid, allyldisulfonic acid, methallyldisulfonic acid, salts thereof and mixtures thereof; (ii) at least one compound II of the formula (1) which is different from at least one monomer B: R1 and R2 are independently a hydrogen atom or a methyl, ethyl, isopropyl or CH2-OH group; R1 and R2 are not both hydrogen atoms; the polymer does not contain anionic monomers other than compound I; The polymer is obtained according to the following steps: a) forming a solution (S1) comprising at least a first part (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) subjecting part F1 to polymerization 1 (PO1) to form a solution of a first gradient polymer (PG1); c) adding a 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 to the solution comprising PG1; d) polymerizing part F2 on PG1 (PO2) to form a solution of a second gradient polymer (PG2); e) adding a 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 to the solution comprising PG2; f) polymerizing part F3 on PG2 (PO3) to form a solution comprising the base polymer; g) diluting a solution comprising a base polymer and reacting at least one dialdehyde with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer; at least one of the fractions F1, F2 or F3 contains at least one monomer A, at least one of the fractions F1, F2 or F3 contains at least one monomer B, At least one of the fractions F1, F2 or F3 contains at least one compound I, and at least one of the fractions F1, F2 or F3 contains at least one compound II; Monomer A is different from a mixture of a cationic monomer and an anionic monomer. 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 The at least one monomer A is a cationic monomer.

4. The water-soluble dialdehyde-functionalized polymer according to any one of claims 1 to 3, characterized in that At least one monomer A is selected from quaternized dimethylaminoethyl acrylate, quaternized dimethylaminoethyl methacrylate, diallyldimethylammonium chloride, acrylamidopropyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride and mixtures thereof, and the dialdehyde is selected from the group consisting of glyoxal, glutaraldehyde, furandialdehyde, adipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyacetaldehyde, diepoxides 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, methacrylamide, and the dialdehyde is glyoxal.

6. The water-soluble dialdehyde-functionalized polymer according to any one of the preceding claims, characterized in that The water-soluble dialdehyde-functional polymer comprises 500 to 50,000 ppm of compound I based on the total weight of monomers A and B.

7. The water-soluble dialdehyde-functionalized polymer according to any one of the preceding claims, characterized in that Based on the total weight of monomers A and B, the water-soluble dialdehyde-functionalized polymer comprises 500 to 50,000 ppm of compound II.

8. The water-soluble dialdehyde-functionalized polymer according to any one of the preceding claims, characterized in that Compound II is selected from the group consisting of N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-isopropylacrylamide, N-methylolacrylamide, and mixtures thereof.

9. The water-soluble dialdehyde-functionalized polymer according to any one of the preceding claims, characterized in that The mass ratio between compound I and compound II is 0.01 to 100.

10. A method for preparing a water-soluble dialdehyde functionalized polymer stepwise, comprising the steps of: a) forming a solution (S1) comprising at least a first part (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 an anionic monomer; At least one monomer B is a nonionic monomer; At least one compound I is selected from the group consisting of allylsulfonic acid, methallylsulfonic acid, Allyl disulfonic acid, methyl allyl disulfonic acid, their salts and mixtures thereof; At least one compound II has the formula (1) which is different from at least one monomer B: R1 and R2 are independently a hydrogen atom or a methyl, ethyl, isopropyl or CH2-OH group; R1 and R2 are not both hydrogen atoms; b) subjecting part F1 to polymerization 1 (PO1) to form a solution of a first gradient polymer (PG1); c) adding a 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 to the solution comprising PG1; d) polymerizing part F2 on PG1 (PO2) to form a solution of a second gradient polymer (PG2); e) adding a 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 to the solution comprising PG2; f) polymerizing part F3 on PG2 (PO3) to form a solution comprising the base polymer; g) diluting a solution comprising a base polymer and reacting at least one dialdehyde with the base polymer to obtain a water-soluble dialdehyde-functionalized polymer; at least one of the fractions F1, F2 or F3 contains at least one monomer A, at least one of the fractions F1, F2 or F3 contains at least one monomer B, At least one of the fractions F1, F2 or F3 contains at least one compound I, and at least one of the fractions F1, F2 or F3 contains at least one compound II; Monomer A is different from a mixture of a cationic monomer and an anionic monomer. 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.

11. The method according to claim 10, characterized in that At least one of the parts F1 , F2 or F3 is different from the other parts.

12. The method according to claim 10 or 11, characterized in that: The initiator was added continuously throughout the polymerization process and the dialdehyde was glyoxal.

13. The method according to any one of claims 10 to 12, characterized in that After step f) of polymerisation (PO3), the process comprises an ageing step of 10 to 100 minutes.

14. The method according to any one of claims 10 to 12, characterized in that The dialdehyde reaction comprises at least the following steps: g1) diluting a solution comprising a base polymer so as to form a diluted solution of the base polymer (SD1); g2) optionally adjusting the pH of SD1 to at least 10; g3) adding at least one dialdehyde to the solution obtained in step g1) or g2) so as to form a diluted solution (SD2); g4) Optionally acidifying the solution obtained in step g3) to a pH of 2 to 4, so as to form a diluted solution (SD3).

15. A method for making paper or paperboard, comprising adding a water-soluble dialdehyde-functionalized polymer according to any one of claims 1 to 9 to an aqueous solution of fibers and forming the paper or paperboard.

16. Use of a water-soluble dialdehyde-functionalized polymer according to any one of claims 1 to 9 in the recovery of hydrocarbons; in drilling or cementing wells; in the stimulation of hydrocarbon wells; in open-circuit water treatment; in the treatment of fermentation mash; in the treatment of sewage sludge; in construction; in the treatment of wood; in the treatment of hydraulic compositions; in the mining industry; in the formulation of cosmetics; in the formulation of detergents; in textile production; in the geothermal field; in the manufacture of sanitary napkins; or in agriculture.

17. Use of a water-soluble dialdehyde-functionalized polymer according to any one of claims 1 to 9 as a flocculant, coagulant, binder, fixative, viscosity reducer, thickener, absorbent, friction reducer, drainage agent, charge retention agent, dehydrating agent, conditioner, stabilizer, fixative, film former, sizing agent, superplasticizer, clay inhibitor or dispersant.

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