Novel water-soluble polymer complex in the form of an inverse emulsion and its use

Abstract

The present invention relates to polymer composites obtained by inverse emulsion polymerization of water-soluble monomers in the presence of cationic, water-soluble host polymers containing amine functional groups.

Description

[Technical Field]

[0001] The present invention relates to conjugates of water-soluble polymers derived from the inverse emulsion polymerization of one or more water-soluble monomers in the presence of a pre-prepared polymer.

[0002] Another aspect of the invention relates to the use of this complex as a dehydration agent, in particular for implementation in the manufacture of paper, cardboard or the like. [Background technology]

[0003] The problem of phase shift between polymers is overcome in the applicant's U.S. Patent No. 9,546,246, which discloses a polymer composite and its use as an agent for treating mineral fillers, particularly for use in the manufacture of paper, cardboard, or the like.

[0004] U.S. Patent Nos. 7,001,953 and 8,021,516 disclose water-soluble polymers that can be used in sludge treatment and papermaking. These polymers are obtained by polymerizing monomers in the presence of a previously prepared polymer. As shown in these documents, the previously synthesized polymer and the newly synthesized polymer do not substantially graft with each other.

[0005] Document EP 262945 A2 presents a mixture of cationic flocculants composed of two different polymers and a method for their production. The agent is formed by polymerizing cationic monomers into a high molecular weight cationic polymer component (flocculant) in the presence of a low molecular weight cationic polymer component (flocculant). The properties of these flocculants do not meet the speed and efficiency requirements imposed by technical flocculation processes. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 9,546,246 [Patent Document 2] U.S. Patent No. 7,001,953 [Patent Document 3] U.S. Patent No. 8,021,516 [Patent Document 4] EP262945A2 Summary of the Invention [Problem to be solved by the invention]

[0007] In any event, there is a need for polymer composites that are stable and satisfactory in terms of dewatering properties during implementation in the manufacture of paper, cardboard, or the like. [Means for solving the problem]

[0008] The present invention relates to a polymer composite comprising a cationic water-soluble polymer (host polymer) and one or more water-soluble monomers polymerized in the presence of the water-soluble host polymer.

[0009] The term "water soluble" refers to the amount of water dissolved in 20 g.L of water with stirring at 25°C for 4 hours. -1 It refers to a compound (especially a polymer complex or a polymer or monomer) that forms an aqueous solution free of insoluble particles when added at a concentration of 0.1%.

[0010] More particularly, the object of the present invention relates to polymer composites obtained by inverse emulsion polymerization of water-soluble monomers in the presence of one or more cationic, water-soluble host polymers containing amine functional groups.

[0011] The polymerization of water-soluble monomers corresponds to the polymerization of a single type of water-soluble monomer (eg, acrylamide) or of several types of water-soluble monomers (eg, acrylamide and ADAME quaternized with methyl chloride).

[0012] In the resulting composite, the polymer resulting from the polymerization of the monomers branches from the host polymer. This is a composite, not a mixture of polymers, where the host polymer acts as a chain transfer agent during the polymerization of the monomers.

[0013] The chain transfer agent, in this case the host polymer, makes it possible to control the length of the polymer chains formed during the polymerization of the water-soluble monomers.

[0014] The term "polymer" refers to a homopolymer or copolymer resulting from the polymerization of the same or different monomers, respectively.

[0015] Another aspect of the present invention is the use of this water-soluble polymer complex as a dewatering and turbidity reducing agent in the manufacture of paper, board, or the like.

[0016] *Host polymer The host polymer is preferably a polyamine having ammonium groups and preferably hydroxyl groups. The polyamine may also contain secondary amine groups.

[0017] The host polymer is advantageously a polyamine selected from the group comprising poly-(dimethylamine(co)epichlorohydrin) and poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine). Preferably, the polyamine is poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine).

[0018] According to a variant of the invention, the host polymer comprises repeating units -[N + (CH3)2CH2CHOHCH2]Cl - Poly(epichlorohydrin-dimethylamine) may also be used, which generally comprises -. Poly(epichlorohydrin-dimethylamine) can be obtained by reacting dimethylamine with epichlorohydrin, advantageously in stoichiometric ratio.

[0019] According to another variant of the invention, the host polymer may be poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine), which is obtainable by reacting dimethylamine, ethylenediamine, and epichlorohydrin.

[0020] According to a preferred feature of the invention, the host polymer is structured, in other words it may advantageously have a branched, star-shaped or comb-shaped configuration.

[0021] According to the present invention, the host polymer has a molecular weight of at least 1000 g / mol, preferably at least 2000 g / mol, and even more preferably at least 5000 g / mol. Typically, the molecular weight of the host polymer is preferably less than 2 million g / mol, and more preferably less than 1 million g / mol.

[0022] *Water-soluble polymer complex The water-soluble polymer composite is derived from the inverse emulsion polymerization of water-soluble monomers, during which the already present host polymer acts as a chain transfer agent. Thus, the present invention may be carried out in the absence of a non-polymeric chain transfer agent. Advantageously, the molecular weight of the non-polymeric chain transfer agent is less than 200 g / mol.

[0023] The water-soluble monomers used in the preparation of the conjugate of the water-soluble polymer may in particular be at least one cationic monomer and / or at least one nonionic monomer and / or at least one anionic monomer. The water-soluble monomers may also be zwitterionic monomers. Preferably, the water-soluble monomers used in the preparation of the conjugate of the water-soluble polymer are at least one cationic monomer and at least one nonionic monomer.

[0024] According to a preferred embodiment, the polymer conjugate is produced in the absence of water-insoluble monomers, in particular monomers of the (meth)acrylic acid ester type.

[0025] Cationic monomers which may be used in the context of the present invention may advantageously be chosen from diallyldialkylammonium salts, such as diallyldimethylammonium chloride (DADMAC); acidified or quaternized salts of dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates, in particular dialkylaminoethyl acrylate (ADAME) and dialkylaminoethyl methacrylate (MADAME); acidified or quaternized salts of dialkyl-aminoalkylacrylamides or dialkyl-aminoalkyl methacrylamides, such as methacrylamide-propyltrimethylammonium chloride (MAPTAC), acrylamido-propyltrimethylammonium chloride (APTAC), and Mannich products, such as quaternized dialkylaminomethylacrylamides.

[0026] The "alkyl" groups of these monomers may be linear, cyclic (substituted or unsubstituted), or branched. The alkyl groups may be identical or different. The alkyl groups advantageously have 1 to 10 carbon atoms, more advantageously 1 to 8, and even more advantageously 1 to 4 carbon atoms. The alkyl groups are preferably methyl or ethyl groups. Thus, the acidified or quaternized salts of ADAME and MADAME are advantageously the acidified or quaternized salts of dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate.

[0027] Acidified salts can be obtained by means known to those skilled in the art, in particular by protonation. Quaternized salts can also be obtained by means known to those skilled in the art, in particular by reaction with alkyl or aryl halides, such as benzyl chloride, methyl chloride (MeCl), aryl or alkyl chlorides, or dimethyl sulfate. The cationic monomer is preferably ADAME quaternized with methyl chloride.

[0028] According to the present invention, the proportion of cationic monomers used is advantageously 1% mol to 80% mol, preferably 2% mol to 60% mol, and even more preferably 5% mol to 40% mol, relative to the total number of water-soluble monomers used.

[0029] The nonionic monomers that may be used in the present invention may be selected from acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide. N-vinylformamide, N-vinylacetamide, N-vinylpyridine and N-vinylpyrrolidone, acryloylmorpholine (ACMO), and diacetone acrylamide may also be used. The preferred nonionic monomer is acrylamide.

[0030] According to the invention, the proportion of nonionic monomers used is advantageously between 20 mol% and 99 mol%, preferably between 40 mol% and 98 mol%, and even more preferably between 60 mol% and 95 mol%, relative to the total number of water-soluble monomers used.

[0031] Anionic monomers that may be used in the present invention may be selected from a large group. These monomers may have vinyl functionality, particularly acrylic, maleic, fumaric, or allyl functionality, or may contain carboxylate, phosphonic, phosphate, sulfate, sulfonic, or other groups with anionic charge. The monomers may be acidic or in the form of the corresponding alkaline earth metal, alkali metal, or ammonium (preferably quaternary ammonium) salts of such monomers. Examples of suitable monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and strong acid-type monomers with sulfonic or phosphonic acid functionality, such as 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, allylphosphonic acid, styrenesulfonic acid, and alkali metal, alkaline earth metal, and ammonium salts of these water-soluble monomers. A preferred monomer is acrylic acid.

[0032] According to the invention, the proportion of anionic monomers used is advantageously 0 mol % to 80 mol %, preferably 1 mol % to 60 mol %, and even more preferably 2 mol % to 40 mol %, relative to the total number of water-soluble monomers used.

[0033] The mass ratio of the water-soluble monomer to the host polymer is preferably from 99 / 1 to 1 / 99, and more preferably from 95 / 5 to 40 / 60.

[0034] Advantageously, the present invention uses at least two different types of water-soluble monomers, advantageously a nonionic monomer and a cationic monomer, more advantageously an acrylamide and a cationic monomer (e.g., ADAME quaternized with methyl chloride).

[0035] According to the present invention, the polymer conjugate is advantageously obtained by inverse emulsion polymerization. Inverse emulsion polymerization also includes inverse microemulsion polymerization. This polymerization technique is well known to those skilled in the art. Inverse emulsion polymerization consists of emulsifying an aqueous phase containing monomers in an oil phase. This emulsification is usually carried out using a water-in-oil surfactant. After polymerization of the monomers, an oil-in-water surfactant is optionally added to promote the subsequent phase inversion of the emulsion in water.

[0036] At the end of the polymerization reaction, the emulsion obtained can be diluted or concentrated, in particular by distillation, with or without the prior introduction of an oil-in-water (O / W) emulsifier.

[0037] Advantageously, the method for preparing the polymer conjugate comprises the following steps: - preparing an aqueous phase comprising at least one host polymer and a water-soluble monomer; - emulsifying said aqueous solution in an oil phase; - obtaining a polymer composite by polymerization of water-soluble monomers; may include:

[0038] Preferably, during the preparation of the composite, the host polymer is introduced into the reactor together with the monomers, and then the polymerization is initiated by adding the catalyst.

[0039] Preferably, the polymerization is carried out in the absence of polyfunctional ethylenic branching or crosslinking agents, for example in the absence of N,N-methylene-bis-acrylamide. The polymerization is advantageously carried out in the absence of branching or crosslinking agents with a molecular weight of less than 200 g / mol.

[0040] Another aspect of the present invention is the use of the water-soluble polymer composite in the manufacture of paper, cardboard, or the like.

[0041] The method for producing paper, board or the like according to the present invention comprises the following steps in a paper machine: - placing fibers, advantageously cellulose fibers, in an aqueous suspension; - adding the polymer composite object of the present invention to an aqueous suspension of fibers; - forming a sheet of paper, cardboard or the like on a wire surface of a paper machine; - Drying the sheets may include:

[0042] The polymer complex may be added to the fiber suspension of the thin stock and / or thick stock at one or more dosing points.

[0043] In addition to the complex, other compounds known to those skilled in the art may be combined, including, but not limited to, dispersants, biocides, or even antifoaming agents.

[0044] The method may also include the addition of polymers other than the composite according to the invention. Examples include coagulants, retention aids, flocculants, or even starch. These additives may be polymeric or mineral, such as bentonite.

[0045] Thus, the method of producing paper, board, or the like may comprise the step of adding, prior to the sheet-forming step, at least one additive selected from coagulants, retention aids, flocculants, and starches, different from the polymer composite.

[0046] Preferably, the polymer complex is added to the thick stock before the mixing pump.

[0047] The various steps of the method for manufacturing paper, cardboard or the like follow techniques that form part of the knowledge of a person skilled in the art.

[0048] The amount of complex added is advantageously between 3 g of active ingredient per tonne of fibre (dry mass of fibre, advantageously cellulose fibre) and 10,000 g / T, preferably between 10 g / T and 7000 g / T, and even more preferably between 30 g / T and 3000 g / T.

[0049] The use of polymer composites is part of a general principle to improve product performance. Therefore, reducing the amount of product required for an application implicitly contributes to reducing greenhouse gas emissions such as CO2. In addition, the use of polymer composites requires less steam during the drying process of the paper sheet, saving energy.

[0050] The following examples illustrate, but do not limit, the present invention. [Brief explanation of the drawings]

[0051] [Figure 1] 1 is a graph of UL viscosity versus monomer / polyamine ratio. [Figure 2] FIG. 1 shows the percentage of thick stock dewatering improvement and turbidity measurements compared to a reference test (Blank). [Figure 3] FIG. 1 shows the percentage of DDA improvement and turbidity measurements on diluted stock compared to a reference test (blank). [Figure 4] FIG. 1 shows vacuum dewatering performance and turbidity measurements on diluted stock compared to a reference test (blank). [Figure 5] FIG. 1 shows dryness values ​​before compression compared to a reference test (blank). [Figure 6] FIG. 1 shows the percentage improvement of vacuum dewatering and turbidity measurements in diluted stock compared to a reference test (blank). [Figure 7] FIG. 1 shows vacuum dewatering performance and turbidity measurements on diluted stock compared to a reference test (blank). [Figure 8] FIG. 1 shows the improvement (percentage) of vacuum dewatering and turbidity measurements on diluted stock compared to a reference test (blank). DETAILED DESCRIPTION OF THE INVENTION [Example]

[0052] In the following examples, - Polyamine H-1 is a 50% by weight active ingredient in water with a Brookfield viscosity of 850 cps (module LV2, 30 rpm) -1 , 23°C) structured poly-(dimethylamine / epichlorohydrin / ethylenediamine). - Polyamine H-2 is a 50% by weight active ingredient in water with a Brookfield viscosity of 30 cps (module LV1, 60 rpm) -1 , 23°C) is a linear poly(dimethylamine / epichlorohydrin). - P-3 is a 29% by weight active ingredient in water with a viscosity of UL = 8.16 cps (Brookfield viscosity, module UL, NaCl 1M, 60 rpm) -1 , 23°C), an anionic inverse emulsion polymer, linear poly-(acrylamide / acrylic acid). - P-4 is a 92% by weight active ingredient in water with a viscosity of UL = 4.11 cps (Brookfield viscosity, module UL, NaCl 1M, 60 rpm) -1, 23°C), a cationic powder form of polymer, linear poly-(acrylamide / dimethylaminoethyl acrylate, MeCl). - Bentonite: inorganic fine particles sold by Clariant under the name OPAZIL ABG.

[0053] *Synthesis of polymer P1 in inverse emulsion The aqueous phase is prepared by adding 359.8 g of acrylamide (50 wt.% solution in water), 262.6 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), and 90.2 g of water. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS (by weight of dry monomer) of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0054] The organic phase is prepared by adding to a reactor 234.2 g of Exxsol D100S oil, 4.7 g of sorbitan monooleate, 8.2 g of sorbitan monooleate 3EO (oxyethylene groups), 11.1 g of sorbitan monooleate 5EO (oxyethylene groups), and 4.8 g of oil-in-water surfactant polymer (Rhodibloc RS).

[0055] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0056] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0057] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 4.21 cps is obtained at 39% by weight of active ingredient.

[0058] *Synthesis of polymer P2 in inverse emulsion The aqueous phase is prepared by adding 491.3 g of acrylamide (50 wt.% solution in water), 92.9 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), and 149.2 g of water. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0059] The organic phase is prepared by adding 213.2 g of Exxsol D100S oil, 26 g of sorbitan monooleate, and 3.8 g of surfactant polymer (Rhodibloc RS) to a reactor.

[0060] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0061] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0062] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 4.26 cps is obtained at 32% by weight of active ingredient.

[0063] *Synthesis of the complex (I-1) in an inverse emulsion according to the invention The aqueous phase is prepared by adding 369.1 g of acrylamide (50 wt.% solution in water), 256.8 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), 2.2 g of water, and 82.5 g of polyamine H-1. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0064] The organic phase is prepared by adding to a reactor 234.2 g of Exxsol D100S oil, 4.7 g of sorbitan monooleate, 8.2 g of sorbitan monooleate 3EO (oxyethylene groups), 11.1 g of sorbitan monooleate 5EO (oxyethylene groups), and 4.8 g of surfactant polymer (Rhodibloc RS).

[0065] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0066] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0067] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 3.81 cps is obtained with 43.1% by weight of active ingredient.

[0068] *Synthesis of complex (I-2) in inverse emulsion according to the present invention The aqueous phase is prepared by adding 290.6 g of acrylamide (50 wt.% solution in water), 212.1 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), 1 g of water, and 213.4 g of polyamine H-1. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0069] The organic phase is prepared by adding to a reactor 234.2 g of Exxsol D100S oil, 4.7 g of sorbitan monooleate, 8.2 g of sorbitan monooleate 3EO (oxyethylene groups), 11.1 g of sorbitan monooleate 5EO (oxyethylene groups), and 4.8 g of surfactant polymer (Rhodibloc RS).

[0070] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0071] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0072] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 3.71 cps is obtained with 42.1% by weight of active ingredient.

[0073] *Synthesis of complex (I-3) in inverse emulsion according to the invention The aqueous phase is prepared by adding 287.8 g of acrylamide (50 wt.% solution in water), 210.1 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), 0.7 g of water, and 237.5 g of polyamine H-1. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0074] The organic phase is prepared by adding to a reactor 214.2 g of Exxsol D100S oil, 4.7 g of sorbitan monooleate, 8.2 g of sorbitan monooleate 3EO (oxyethylene groups), 11.1 g of sorbitan monooleate 5EO (oxyethylene groups), and 4.8 g of surfactant polymer (Rhodibloc RS).

[0075] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0076] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0077] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 3.46 cps is obtained with 43.1% by weight of active ingredient.

[0078] *Synthesis of complex (I-4) in inverse emulsion according to the present invention The aqueous phase is prepared by adding 250.9 g of acrylamide (50 wt.% solution in water), 183.1 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), 0.9 g of water, and 280.1 g of polyamine H-1. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0079] The organic phase is prepared by adding to a reactor 234.2 g of Exxsol D100S oil, 4.7 g of sorbitan monooleate, 8.2 g of sorbitan monooleate 3EO (oxyethylene groups), 11.1 g of sorbitan monooleate 5EO (oxyethylene groups), and 4.8 g of surfactant polymer (Rhodibloc RS).

[0080] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0081] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0082] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 3.01 cps is obtained with 41.2% by weight of active ingredient.

[0083] *Synthesis of complex (I-5) in inverse emulsion according to the invention The aqueous phase is prepared by adding 184.5 g of acrylamide (50 wt.% solution in water), 134.7 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), 0.5 g of water, and 396 g of polyamine H-1. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0084] The organic phase is prepared by adding to a reactor 234.2 g of Exxsol D100S oil, 4.7 g of sorbitan monooleate, 8.2 g of sorbitan monooleate 3EO (oxyethylene groups), 11.1 g of sorbitan monooleate 5EO (oxyethylene groups), and 4.8 g of surfactant polymer (Rhodibloc RS).

[0085] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0086] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0087] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 2.51 cps is obtained with 39.8% by weight of active ingredient.

[0088] *Synthesis of complex (I-6) in inverse emulsion according to the present invention The aqueous phase is prepared by adding 439.1 g of acrylamide (50 wt.% solution in water), 83.1 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), 0.2 g of water, and 214 g of polyamine H-1. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0089] The organic phase is prepared by adding 213.2 g of Exxsol D100S oil, 26 g of sorbitan monooleate, and 3.8 g of surfactant polymer (Rhodibloc RS) to a reactor.

[0090] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0091] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0092] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 3.61 cps is obtained with 39.3% by weight of active ingredient.

[0093] *Synthesis of complex (I-7) in inverse emulsion according to the invention The aqueous phase is prepared by adding 287.8 g of 50 wt% acrylamide in water, 210.1 g of dimethylaminoethyl acrylate, 80 wt% MeCl in water, 0.7 g of water, and 237.5 g of polyamine H-2. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0094] The organic phase is prepared by adding to a reactor 214.2 g of Exxsol D100S oil, 4.7 g of sorbitan monooleate, 8.2 g of sorbitan monooleate 3EO (oxyethylene groups), 11.1 g of sorbitan monooleate 5EO (oxyethylene groups), and 4.8 g of surfactant polymer (Rhodibloc RS).

[0095] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0096] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite using a syringe pump. The temperature is raised to 55°C and maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0097] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 3.31 cps is obtained with 43.1% by weight of active ingredient.

[0098] *Synthesis of complex (I-8) in inverse emulsion according to the invention The aqueous phase is prepared by adding 537.3 g of 50 wt% acrylamide in water, 101.7 g of dimethylaminoethyl acrylate, 80 wt% MeCl in water, 0.7 g of water, and 73 g of polyamine H-1. The pH of the solution is adjusted to 4-5 using adipic acid. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0099] The organic phase is prepared by adding 210.3 g of Exxsol D100S oil, 25.9 g of sorbitan monooleate, and 3.7 g of surfactant polymer (Rhodibloc RS) to a reactor.

[0100] The aqueous phase is then transferred to the organic phase and emulsified, for example using an Ultra-Turax, at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0101] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite using a syringe pump. The temperature is raised to 55°C and maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0102] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 4.01 cps is obtained with 38.6% by weight of active ingredient.

[0103] *Synthesis of complex (I-9) in inverse emulsion according to the present invention The aqueous phase is prepared by adding 280.5 g of acrylamide (50 wt.% solution in water), 204.7 g of dimethylaminoethyl acrylate, MeCl (80 wt.% solution in water), 0.7 g of water, and 227.5 g of polyamine H-1. The pH of the solution is adjusted to 4-5 using adipic acid. 2-25 ppm / MS of sodium hypophosphite is added as the limiting reagent, along with 2-25 ppm / MS of methylenebisacrylamide as the crosslinker. Then, 100-250 ppm / MS of potassium bromate and 800-1500 ppm / MS of sodium diethylenetriaminepentaacetate are added as initiators.

[0104] The organic phase is prepared by adding to a reactor 211.2 g of Exxsol D100S oil, 4.7 g of sorbitan monooleate, 8.2 g of sorbitan monooleate 3EO (oxyethylene groups), 11.1 g of sorbitan monooleate 5EO (oxyethylene groups), and 4.8 g of surfactant polymer (Rhodibloc RS).

[0105] The aqueous phase is then transferred to the organic phase and emulsified using an Ultra-Turax at 8000 rpm for 1 minute to obtain a homogeneous inverse emulsion.

[0106] The inverse emulsion is deoxygenated by nitrogen sparging for 30 minutes. Polymerization is initiated by adding sodium bisulfite and the temperature is maintained at 55°C for approximately 1.5 hours. The reaction medium is finally treated with excess sodium bisulfite to reduce free monomer.

[0107] Once the inverse emulsion is complete, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 2.31 cps is obtained with 41.8% active ingredients.

[0108] Regarding the stability of the inverse emulsions according to the invention (I-1 to I-9), after several weeks of storage at room temperature we do not observe any phase shift.

[0109] *Synthesis of a mixture of polymers in inverse emulsion (M-1) 767.8 g of P2 emulsion is weighed into a 1 L beaker and stirred using a half-moon stirring blade. 205.2 g of Polyamine H-1 is slowly added, and the mixture is left stirring for 10 minutes to ensure uniformity. The mixture has an active ingredient content of 35.8% by weight. After one week of storage at ambient temperature, a phase shift of the mixture is observed.

[0110] *Synthesis of polymer mixture (M-2) in inverse emulsion 571.8 g of emulsion P1 is weighed into a 1 L beaker and stirred using a half-moon stirring blade. 300 g of polyamine H-1 is slowly added, and the mixture is left stirring for 10 minutes to ensure homogeneity. The mixture has an active ingredient content of 38.2% by weight. After one week of storage at ambient temperature, a phase shift of the mixture is observed.

[0111] *Synthesis of a mixture of polymers in inverse emulsion (M-3) 759.9 g of P2 emulsion was weighed into a 1 L beaker and stirred using a half-moon stirring blade. 54 g of Polyamine H-1 was slowly added, and the mixture was left stirring for 10 minutes to ensure uniformity. The mixture had an active ingredient content of 33.2% by weight. After one week of storage at room temperature, a phase shift in the mixture was observed.

[0112] *Synthesis of powder-form polymer (C-1) A polymerization reactor is charged with 748.7 g of 50% acrylamide, 126.2 g of dimethylaminoethyl acrylate, 80% MeCl, 431.5 g of water, and 95 g of polyamine H-1. The pH of the solution is adjusted to 3-4 using adipic acid. The solution is cooled to 0-2°C and deoxygenated by nitrogen sparging for 15 minutes. Then, 1-15 ppm / MS of sodium persulfate and 1-15 ppm / MS of Mohr's salt are added as initiators.

[0113] The reaction temperature is increased from 0 to 90°C, obtaining the polymer in the form of a gel, which is then cut, chopped, dried at 75°C for 45 minutes, crushed, and finally sieved. In this way, the polymer is obtained in the form of a powder with a particle size of less than 1 mm.

[0114] Once the polymer in powder form is ready, measure the Brookfield viscosity (UL module, 1M NaCl, 60 rpm) -1 , 23°C). A UL viscosity of 3.76 cps is obtained at 92.8% by weight of active ingredient in water.

[0115] [Table 1]

[0116] [Table 2]

[0117] The studies in Table 2 were analyzed in groups: [2-4], [5-6], [7-8-9], [10-11-12], and [13-14-15].

[0118] *Evaluation test procedure *Recycled fiber paper stock: The wet stock is obtained by disaggregating the dry stock to a final aqueous concentration of 4% by weight in water to produce a thick stock, which is then diluted to 1% by weight in water to obtain a thin stock, which is a pH-neutral stock made from 100% recycled cardboard fibre.

[0119] *UL viscosity measurement: 500 mg of polymer (derived from the polymerization of monomers according to the invention or not) is added to 490 ml of deionized water. After complete dissolution, 29.25 grams of NaCl is added.

[0120] The viscosity is measured using a digital Brookfield DVII+ viscometer at 25° C. with a rotation speed of 60 rpm (UL module).

[0121] *Dewatering Performance Assessment (DDA): A DDA (Dynamic Freeness Analyzer) is used to automatically measure the time (in seconds) required to drain the fiber suspension under vacuum. The polymer is added to the wet stock (0.6 liters of 1.0% by weight stock) while stirring at 1000 rpm in a DDA cylinder. - For the evaluation of a single polymer, the following sequence is followed: T=0 seconds: Mixing the paper stock T = 10 seconds: Add cationic dehydrating agent (350 g / t) T=30 seconds: Stop stirring and dehydrate under a vacuum of 200 mBar for 60 seconds - The evaluation of polymer combinations follows the following sequence: T = 0 seconds: Mix the dough T=5 seconds: Add cationic dehydrating agent (350g / t) T = 10 seconds: Add cationic polymer (250 g / t) T = 20 seconds: Add anionic polymer (150 g / t) and / or bentonite (1.5 kg / t) T=30 seconds: Stop stirring and dehydrate under a vacuum of 200 mBar for 60 seconds

[0122] The dosages are expressed in grams of active ingredient per tonne of fibre (dry mass of fibre, advantageously cellulose fibre).

[0123] The pressure under the wire surface is recorded as a function of time. When all the water has been expelled from the fiber pad, air passes through it and a break appears in the slope of the curve showing the pressure under the wire surface as a function of time. The time recorded at this break in the slope, expressed in seconds, corresponds to the dewatering time. The shorter the time, the better the vacuum dewatering.

[0124] In addition, the turbidity of the white water resulting from the DDA measurement is measured: the lower the turbidity value, the higher the retention of solid particles in the fiber pad.

[0125] *Dryness The DDA test drains free water from the fiber suspension under vacuum. The purpose of the dryness test is to measure the amount of water bound to the fiber pad. For this purpose, the fiber pad cake resulting from the DDA test is collected and its mass is measured before and after drying in an oven at 105°C for 2 hours. The ratio of the two masses is the dryness; the higher this value, the more bound water the dehydrating polymer removes.

[0126] *Evaluation of dewatering performance in thick stock: 500 ml of thick stock at 4% in water is treated in a beaker and subjected to low shear (stirring speed 300 rpm) The polymer is added to this fibre suspension with a contact time T=1 min.

[0127] The treated stock is transferred to a Canadian Standard Freeness Tester.

[0128] The volume of water released over time is recorded: the more water released, the better the thick stock dewatering.

[0129] *Turbidity: Turbidity refers to the content of suspended solids that make a fluid cloudy. Turbidity is measured using a HANNA spectrophotometer, which measures the decrease in intensity of a light beam at an angle of 90° and a wavelength of 860 nm, expressed in NTU.

[0130] Figure 1 shows that, all other things being equal, the UL viscosity decreases as the monomer / polyamine ratio decreases, leading to the conclusion that the polyamine acts as a chain transfer agent for the polymer.

[0131] Figures 2 and 3 show that there is a synergistic effect between thick stock drainage, DDA, and turbidity improvement with any of the products of the invention (I-1 to I-5) compared to the polymer alone (P-1) and compared to the polyamine alone (H-1). In this case, a monomer / polyamine mass ratio of 70 / 30 (I-3) allows for the most favorable combination of thick stock drainage / DDA / turbidity increase.

[0132] Figures 4 and 5 show that the products of the present invention (I-3 to I-6) are much more efficient in vacuum dewatering, turbidity, and pre-compaction dryness of diluted stock compared to the corresponding blends (M-1 and M-2) and the products alone (H-1, P-1, and P-2).

[0133] Figure 6 shows that there is a synergistic effect between the improvement of vacuum dewatering (DDA) and turbidity of diluted stock with any of the products of the present invention (I-3 and I-7) compared to the products alone (P-1, H-1, H-2). It is noteworthy that in this particular case, the structure of the polyamine has a positive impact on application performance compared to linear polyamines.

[0134] Figure 7 shows that the polymerization in inverse emulsion form (I-8) remains much more effective than the corresponding powder form (C-1) and mixture (M-3). In addition, polymerization with polyamines in inverse emulsion form makes it possible to solve the stability problem of simple mixtures.

[0135] According to Figure 8, in tests 2-15, products I-3 and I-6 of the present invention in combination with retention systems (single or multiple components) were tested compared to products P-1 and P-2, respectively (Table 2; Test 4 vs. Test 2 and Test 3, Test 6 vs. Test 2 and Test 5, Test 9 vs. Test 7 and Test 8, Test 12 vs. Test 10 and Test 11, and Test 15 vs. Test 13 and Test 14), resulting in better performance in terms of improved diluted stock vacuum dewatering (DDA) and reduced turbidity.

Claims

1. A method for preparing a polymer composite, comprising inverse emulsion polymerization of water-soluble monomers in the presence of a cationic water-soluble host polymer, which is poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine).

2. 2. The method according to claim 1, wherein the weight ratio of the water-soluble monomer to the host polymer is from 99 / 1 to 1 / 99.

3. The water-soluble monomer is - Quaternary ammonium salts of dimethylaminoethyl acrylate (ADAME), quaternary ammonium salts of dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), - acrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N-vinylformamide, N-vinylpyrrolidone, - acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, allylphosphonic acid, styrenesulfonic acid, and water-soluble alkali metal salts, alkaline earth metal salts, or ammonium salts of these monomers 3. The method according to claim 1 or 2, characterized in that the compound is selected from the group comprising:

4. - preparing an aqueous solution comprising at least one of said host polymers and a water-soluble monomer; - emulsifying said aqueous solution in an oil phase; - obtaining a polymer composite by polymerization of water-soluble monomers; The method according to any one of claims 1 to 3, comprising:

5. 5. The process according to claim 1, wherein the polymerization is carried out in the absence of polyfunctional ethylenic branching or crosslinking agents.

6. 6. A method for producing a sheet of paper or cardboard, comprising adding a polymer composite obtained by the method of any one of claims 1 to 5 to a fiber suspension at one or more dosing points before forming the sheet.

7. 7. The method according to claim 6, wherein the amount of polymer complex added is between 3 g / ton of fiber and 10,000 g / ton of fiber, dry mass, and the fiber may be cellulose fiber.

8. 1. A method for producing paper or board, comprising the steps of: - placing fibers, which may be cellulosic fibers, in an aqueous suspension; - adding a polymer composite object obtained by the method according to any one of claims 1 to 5; - forming a sheet of paper or cardboard on a wire surface of a paper machine; - Drying the sheets A method comprising:

9. 9. A method for producing paper or board according to any one of claims 6 to 8, characterized in that it comprises, before the sheet-forming step, the step of adding at least one additive different from the composite obtained by the method according to any one of claims 1 to 5, selected from coagulants, retention aids, flocculants and starches.

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