EP2491177B1 - Procédé de fabrication de papier, carton souple et carton avec une grande résistance à sec - Google Patents

Procédé de fabrication de papier, carton souple et carton avec une grande résistance à sec Download PDF

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EP2491177B1
EP2491177B1 EP10765625.8A EP10765625A EP2491177B1 EP 2491177 B1 EP2491177 B1 EP 2491177B1 EP 10765625 A EP10765625 A EP 10765625A EP 2491177 B1 EP2491177 B1 EP 2491177B1
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EP
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Prior art keywords
nanocellulose
polymer
anionic
monomer
styrene
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German (de)
English (en)
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EP2491177A1 (fr
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Anton Esser
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Solenis Technologies Cayman LP
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Solenis Technologies Cayman LP
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents

Definitions

  • the invention relates to a process for the production of paper, cardboard and cardboard with high dry strength by adding an aqueous composition of a nanocellulose and at least one polymer selected from the group of anionic polymers and water-soluble cationic polymers, dewatering the paper stock and drying the paper products.
  • a dry strength agent can either be applied to the surface of a paper that has already dried or added to a paper stock before the sheet is formed.
  • the dry strength agents are usually applied in the form of a 1 to 10% strength aqueous solution. If such a solution of a dry strength agent is applied to the surface of a paper, then considerable amounts of water must be evaporated in the subsequent drying process. Since the drying step is very energy-intensive and since the capacity of the usual drying devices on paper machines is usually not so large that you can drive at the maximum possible production speed of the paper machine, the production speed of the paper machine must be reduced so that the dry-proofed paper dries to a sufficient extent becomes.
  • the dry strength agent is added to a paper stock before the sheet is formed, the finished paper only has to be dried once.
  • a water-soluble cationic polymer and then a water-soluble anionic polymer are first added to the paper stock.
  • Polyethyleneimine, polyvinylamine, polydiallyldimethylammonium chloride and epichlorohydrin-crosslinked condensation products of adipic acid and diethylenetriamine are described as water-soluble cationic polymers in the examples.
  • suitable water-soluble anionic polymers are homopolymers or copolymers of ethylenically unsaturated C 3 to C 5 carboxylic acids.
  • the copolymers contain, for example, 35 to 99% by weight of an ethylenically unsaturated C 3 to C 5 carboxylic acid such as, for example, acrylic acid.
  • WO 04/061235 A1 A process for the production of paper, in particular tissue, with particularly high wet and / or dry strengths is known, in which a water-soluble cationic polymer is first added to the paper stock, which contains at least 1.5 meq / g polymer of primary amino functionalities and a molecular weight of at least 10,000 daltons. Partly and completely hydrolyzed homopolymers of N-vinylformamide are particularly emphasized. A water-soluble anionic polymer is then added, which contains anionic and / or aldehydic groups.
  • the main advantage of this process is the variability of the two-component systems described with regard to various paper properties, including wet and dry strength.
  • the polymeric anionic compound comprises at least one water-soluble Copolymer used, which is obtainable by copo
  • a process for the production of paper with high dry strength by separately adding a water-soluble cationic polymer and an anionic polymer to a paper stock is known, the anionic polymer being an aqueous dispersion of a water-insoluble polymer with an acid group content of at most 10 mol% or an anionic adjusted aqueous dispersion of a nonionic polymer.
  • the paper stock is then dewatered and the paper products dried.
  • EP 09 152 163.3 discloses a process for producing paper, cardboard and cardboard with high dry strength, which is also characterized by adding a water-soluble cationic polymer and an anionic polymerate to a paper stock, dewatering the paper stock and drying the paper products. It is called anionic Polymer used an aqueous dispersion of at least one anionic latex and at least one degraded starch.
  • the object of the invention is to provide a further process for the production of paper with high dry strength and the lowest possible wet strength, the dry strength of the paper products being further improved as far as possible compared to the prior art.
  • the object is achieved according to the invention with a method for producing paper, cardboard and cardboard with high dry strength according to claim 1.
  • nanocellulose is understood to mean cellulose forms which are converted by a process step from the state of the natural fiber with the usual dimensions (length approx. 2000 - 3000 ⁇ m, thickness approx. 60 ⁇ m) into a form in which the thickness dimension is particularly strong is reduced.
  • nanocellulose is known in the literature.
  • WO 2007/091942 A1 discloses a grinding process which can be carried out using enzymes.
  • Processes are also known in which the cellulose is first dissolved in suitable solvents and then precipitated as nanocellulose in the aqueous medium (for example described in WO 2003/029329 A2 ).
  • nanocelluloses are commercially available, for example the products sold by J. Rettenmeier & Söhne GmbH & Co. KG under the trade name Arbocel®.
  • nanocelluloses which are used in the process according to the invention can be dissolved and used in any suitable solvent, for example in water, organic solvents or in any mixtures thereof.
  • suitable solvents for example in water, organic solvents or in any mixtures thereof.
  • Such solvents can also contain other constituents such as ionic liquids in any amount.
  • Nanocelluloses which contain ionic liquids are produced, for example, by micronizing celluloses present in ionic liquids in the form of the natural fibers in one of the processes described above.
  • Celluloses in the form of natural fibers, which are present in ionic liquids are among others US 6,824,599 B2 known. Reference is hereby expressly made to the content of this US patent.
  • nanocellulose should be understood to mean those celluloses whose linear expansion is below 1000 ⁇ m, preferably below 500 ⁇ m, but above 100 nm.
  • the linear expansion is accordingly preferably between 100 nm and 500 ⁇ m, particularly between 100 nm and 100 ⁇ m, particularly preferably between 100 nm and 50 ⁇ m and in particular between 100 nm and 10 ⁇ m.
  • the thickness of the cellulose is, for example, in the range between 50 ⁇ m and 3 nm. The thickness is preferably between 1 ⁇ m and 5 nm.
  • the values given here for thickness and linear expansion are of course average values, for example at least 50% of the cellulose fibers are in the ranges and preferably at least 80% of the cellulose fibers are in the ranges specified.
  • the nanocellulose of the process according to the invention is a nanocellulose whose fiber thickness of at least 80% of the cellulose fibers is between 50 ⁇ m and 3 nm, preferably between 1 ⁇ m and 5 nm, and between 5 ppm and 2% by weight, preferably between 10 ppm and Contains 1% by weight of ionic liquids.
  • the present invention therefore also relates to such a nanocellulose whose fiber thickness of at least 80% of the cellulose fibers is between 50 ⁇ m and 3 nm, preferably between 1 ⁇ m and 5 nm, and between 5 ppm and 2% by weight, preferably between 10 ppm and 1 wt .-% contains ionic liquids.
  • the length extension and the thickness of the cellulose fibers can be determined, for example, using Cryo-TEM images.
  • a nanocellulose that can be used in the method according to the invention has fiber thicknesses of up to 5 nm and length extensions of up to 10 mm.
  • These nanocellulose fibers can also be called fibrillia, the smallest superstructure in cellulose-based substances (5-30 nm wide depending on the plant variety; degrees of polymerization up to 10,000 anhydroglycose units). They typically have high moduli of elasticity of up to several hundred GPa, and the strength of such fibrils is in the GPa range.
  • the high stiffness is a result of the crystal structure in which the long parallel polysaccharide chains are held together by hydrogen bonds.
  • cryo-TEM means that the aqueous dipsersions of cellulose are frozen and measured by means of an electron transmission.
  • the nanocellulose fibers are typically present in intertwined networks of several fibers. This leads to a gel at the macroscopic level. This gel can be measured rheologically, showing that the memory module is larger in magnitude than the loss module. This gel behavior is typically already present at concentrations of 0.1 mass percent nanocellulose in water.
  • aqueous slurries of nanocelluloses which contain 0.1 to 25% by weight of nanocellulose, based on the total weight of the aqueous slurry.
  • the aqueous slurries preferably contain 1 to 20% by weight, particularly preferably 1 to 10% by weight and in particular 1 to 5% by weight of the nanocellulose.
  • aqueous compositions which can be used in the process according to the invention comprise at least one polymer which is selected from the group of anionic and water-soluble cationic polymers.
  • the aqueous composition contains at least one anionic polymer in addition to the nanocellulose. It is also possible that the aqueous composition contains at least one water-soluble cationic polymer in addition to the nanocellulose and the anionic polymer.
  • the aqueous composition contains a water-soluble cationic polymer in addition to the nanocellulose.
  • the anionic polymers for the purposes of this invention are practically insoluble in water.
  • the dispersions are anionic due to the content of acid groups in the polymer.
  • the water-insoluble polymer has, for example, an acid group content of 0.1 to 10 mol%, usually 0.5 to 9 mol% and preferably 0.5 to 6 mol%, in particular 2 to 6 mol%.
  • the content of acid groups in the anionic polymer is usually 2 to 4 mol%.
  • the acid groups of the anionic polymer are selected, for example, from carboxyl, sulfonic acid and phosphonic acid groups. Carboxyl groups are particularly preferred.
  • the anionic polymers contain at least 60 mol% and in particular at least 80 mol% of at least one monomer from group (a) polymerized. These monomers are practically water-insoluble or, when homopolymerized with them, give water-insoluble polymers.
  • the anionic polymers contain, as monomer of group (a), mixtures of (i) a C 1 to C 20 alkyl acrylate and / or a C 1 to C 20 alkyl methacrylate and (ii) styrene, ⁇ -methylstyrene, p-methylstyrene , ⁇ -butylstyrene, 4-n-butylstyrene, butadiene and / or isoprene polymerized in a weight ratio of 10:90 to 90:10.
  • Examples of individual monomers of group (a) of the anionic polymers are acrylic acid and methacrylic acid esters of saturated, monohydric C 1 to C 20 alcohols such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, n- Butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, 2-ethylhe
  • Mixtures of these monomers are also used in the preparation of the anionic polymers, e.g. B. mixtures of n-butyl acrylate and ethyl acrylate or mixtures of n-butyl acrylate and at least one propyl acrylate.
  • Other monomers of group (a) of the anionic polymers are: Vinyl esters of saturated carboxylic acids with 1 to 20 carbon atoms z.
  • Preferred monomers of group (a) are C 1 -C 20 alkyl (meth) acrylates and mixtures of the alkyl (meth) acrylates with vinyl aromatics, in particular styrene and / or hydrocarbons having two double bonds, in particular butadiene, or mixtures of such hydrocarbons with vinyl aromatics , especially styrene.
  • Particularly preferred monomers of group (a) of the anionic polymers are n-butyl acrylate, styrene and acrylonitrile, which can each be used alone or as a mixture.
  • the weight ratio of alkyl acrylates or alkyl methacrylates to vinyl aromatics and / or to hydrocarbons having two double bonds, such as butadiene can be, for example, 10:90 to 90:10, preferably 20:80 to 80:20.
  • Anionic monomers of group (b) of the anionic polymers are ethylenically unsaturated C 3 - to C 8 -carboxylic acids such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid and crotonic acid.
  • Suitable monomers of group (b) are also monomers containing sulfone groups, such as vinylsulfonic acid, acrylamido-2-methyl-propanesulfonic acid and styrene sulfonic acid and vinylphosphonic acid.
  • the monomers of this group can be used alone or in a mixture with one another, in partially or in completely neutralized form in the copolymerization.
  • neutralization for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or are used Alkanolamines.
  • alkali metal or alkaline earth metal bases ammonia, amines and / or are used Alkanolamines.
  • alkanolamines examples include sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylene triamine or tetraethylene pentamine.
  • the water-insoluble anionic polymers can, if appropriate, as further monomers (c) at least one monomer from the group of the C 1 -C 10 -hydroxyalkylacyrylates, C 1 -C 10 -hydroxyalkyl methacrylates, acrylamide, methacrylamide, NC 1 -C 20 -alkyl acrylamides and Contain NC 1 to C 20 alkyl methacrylamides. If these monomers are used to modify the anionic polymers, acrylamide or methacrylamide is preferably used.
  • the amounts of copolymerized monomers (c) in the anionic polymer are up to, for example, 20 mol%, preferably up to 10 mol% and, if these monomers are used in the polymerization, are in the range from 1 to 5 mol%.
  • the anionic polymers can optionally also contain monomers of group (d).
  • Suitable monomers of group (d) are compounds having at least two ethylenically unsaturated double bonds in the molecule.
  • Such connections are also referred to as crosslinkers. They contain, for example, 2 to 6, preferably 2 to 4 and usually 2 or 3 free-radically polymerizable double bonds in the molecule.
  • the double bonds can be, for example, the following groups: acrylic, methacrylic, vinyl ether, vinyl ester, allyl ether and allyl ester groups.
  • Examples of crosslinkers are 1,2-ethanediol di (meth) acrylate (the notation "... (meth) acrylate” or "(meth) acrylic acid” means here both "...
  • Allyl acrylate, divinylbenzene, 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate are preferred.
  • a crosslinker is used to modify the anionic polymers, the amounts polymerized in are up to 2 mol%. For example, they are in the range from 0.001 to 2, preferably 0.01 to 1, mol%.
  • the water-insoluble anionic polymers preferably contain, as monomers (a), mixtures of 20-50 mol% of styrene and 30-80 mol% of at least one alkyl methacrylate and / or polymerized at least one alkyl acrylate. If appropriate, they can also contain up to 30 mol% of copolymerized methacrylonitrile or acrylonitrile. Such polymers can optionally also be modified with the amounts of methacrylamide and / or acrylamide given above under monomers of group (c).
  • Anionic polymers which contain at least 80 mol% of at least one monomer from group (a) in copolymerized form are particularly preferred. They usually contain as a monomer of group (a) mixtures of (i) a C 1 - to C 20 -alkyl acrylate and / or a C 1 - to C 20 -alkyl methacrylate and (ii) styrene, ⁇ -methylstyrene, p-methylstyrene, Polymerized ⁇ -butylstyrene, 4-n-butylstyrene, butadiene and / or isoprene in a weight ratio of 10:90 to 90:10.
  • the anionic polymers are generally prepared by emulsion polymerization.
  • the anionic polymers are therefore emulsion polymers.
  • the preparation of aqueous polymer dispersions by the free-radical emulsion polymerization process is known per se (cf. Houben-Weyl, Methods of Organic Chemistry, Volume XIV, Macromolecular Substances, Georg Thieme Verlag, Stuttgart 1961, pages 133ff ).
  • ionic and / or non-ionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • the surface-active substance is usually used in amounts of 0.1 to 10% by weight, in particular 0.2 to 3% by weight, based on the monomers to be polymerized.
  • Common emulsifiers are e.g. B. ammonium or alkali metal salts of higher fatty alcohol sulfates, such as Na-n-lauryl sulfate, fatty alcohol phosphates, ethoxylated C 8 - to C 10 -alkylphenols with a degree of ethoxylation of 3 to 30 and ethoxylated C 8 - to C 25 -fatty alcohols with a degree of ethoxylation of 5 to 50.
  • Mixtures are also conceivable from nonionic and ionic emulsifiers.
  • phosphate or sulfate group-containing, ethoxylated and / or propoxylated alkylhenols and / or fatty alcohols are also suitable.
  • emulsifiers are in Houben-Weyl, Methods of Organic Chemistry, Volume XIV, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 209 listed.
  • Water-soluble initiators for emulsion polymerization for the preparation of the anionic polymers are e.g. B. ammonium and alkali metal salts of peroxidic sulfuric acid, e.g. As sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. B. tert-butyl hydroperoxide.
  • B. ammonium and alkali metal salts of peroxidic sulfuric acid e.g. As sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. B. tert-butyl hydroperoxide.
  • red-ox initiator systems are also suitable, for example combinations of peroxides, hydroperoxides or hydrogen peroxide with reducing agents such as ascorbic acid or sodium bisulfite.
  • reducing agents such as ascorbic acid or sodium bisulfite.
  • These initiator systems can additionally contain metal ions such as iron (II) ions.
  • the amount of initiators is generally 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the monomers to be polymerized. Several different initiators can also be used in emulsion polymerization.
  • regulators can optionally be used, e.g. B. in amounts of 0 to 3 parts by weight, based on 100 parts by weight of the monomers to be polymerized. This reduces the molecular weight of the resulting polymers.
  • Suitable regulators are e.g. B. Compounds with a thiol group such as tert-butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptopropyltrimethoxysilane or tert-dodecyl mercaptan or regulator without a thiol group, in particular, for. B. terpinolene.
  • the emulsion polymerization for the preparation of the anionic polymers generally takes place at 30 to 130 ° C., preferably at 50 to 100 ° C.
  • the polymerization medium can consist only of water, as well as mixtures of water and thus miscible liquids such as methanol. Preferably only water is used.
  • the emulsion polymerization can be carried out either as a batch process or in the form of a feed process, including a step or gradient procedure.
  • a polymer seed In the polymerization z. B. to better adjust the particle size, a polymer seed.
  • the manner in which the initiator is added to the polymerization vessel in the course of the free-radical aqueous emulsion polymerization is known to the person skilled in the art. It can either be completely introduced into the polymerization vessel or, depending on its consumption, be used continuously or in stages in the course of the free-radical aqueous emulsion polymerization. Specifically, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. A portion is preferably introduced and the remainder is fed to the polymerization zone in accordance with the consumption.
  • At least one initiator is again added and the reaction mixture is heated to the polymerization temperature or a temperature above it for a certain time.
  • the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor floor.
  • the acid groups contained in the anionic polymer can still be at least partially or completely neutralized.
  • This can be done, for example, with oxides, hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, preferably with hydroxides, to which any counterion or more can be associated, e.g. B. Li + , Na + , K + , Cs + , Mg 2+ , Ca 2+ or Ba 2+ .
  • Ammonia or amines are also suitable for neutralization. Aqueous ammonium hydroxide, sodium hydroxide or potassium hydroxide solutions are preferred.
  • aqueous dispersions of the anionic polymer are generally obtained with solids contents of from 15 to 75% by weight, preferably from 40 to 75% by weight.
  • the molecular weight M w of the anionic polymers is, for example, in the range from 100,000 to 1 million daltons. If the polymers have a gel phase, it is not readily possible to determine the molar mass. The molecular weights are then above the range mentioned above.
  • the glass transition temperature Tg of the anionic polymers is, for example, in the range from -30 to 100 ° C, preferably in the range from -5 to 70 ° C and particularly preferably in the range from 0 to 40 ° C (measured by the DSC method according to DIN EN ISO 11357).
  • the particle size of the dispersed anionic polymers is preferably in the range from 10 to 1000 nm, particularly preferably in the range from 50 to 300 nm (measured with a Malvern® Autosizer 2 C).
  • the anionic polymers can optionally contain small amounts of cationic monomer units in copolymerized form, so that amphoteric polymers are present, but the total charge of the polymers must be anionic.
  • anionic polymers are polymer dispersions of nonionic monomers which are emulsified with the aid of anionic surfactants or emulsifiers (such compounds were described above in the emulsion polymerization for the preparation of anionic polymers).
  • the surfactants or emulsifiers are used, for example, in amounts of 1 to 15% by weight, based on the total dispersion.
  • the aqueous composition can also contain a water-soluble cationic polymer in addition to the nanocellulose.
  • All water-soluble cationic polymers mentioned in the prior art cited at the beginning are suitable as cationic polymers. It is e.g. B. to amino or ammonium-bearing compounds. The amino groups can be primary, secondary, tertiary or quaternary groups. Polymers, polyaddition compounds or polycondensates are essentially suitable for the polymers, it being possible for the polymers to have a linear or branched structure up to hyperbranched or dendritic structures. Graft polymers can also be used.
  • the cationic polymers are referred to in the present context as water-soluble if their solubility in water under normal conditions (20 ° C., 1013 mbar) and pH 7.0 is, for example, at least 10% by weight.
  • the molecular weights M w of the cationic polymers are, for. B. at least 1,000 g / mol. For example, they are usually in the range from 5,000 to 5 million g / mol.
  • the charge densities of the cationic polymers are, for example, 0.5 to 23 meq / g polymer, preferably 3 to 22 meq / g polymer and mostly 6 to 20 meq / g polymer.
  • Suitable monomers for the preparation of cationic polymers are, for example: Esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C 2 -C 12 amino alcohols. These can be C 1 -C 8 -monoalkylated or dialkylated on the amine nitrogen.
  • As an acid component of these esters are, for. As acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Acrylic acid, methacrylic acid and mixtures thereof are preferably used.
  • N-methylaminomethyl (meth) acrylate N-methylaminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate ,
  • Suitable monomers are also N-vinylimidazoles, alkylvinylimidazoles, especially methylvinylimidazoles such as 1-vinyl-2-methylimidazole, 3-vinylimidazole-N-oxide, 2- and 4-vinylpyridines, 2- and 4-vinylpyridine-N-oxides, and betaine derivatives and Quaternization products of these monomers.
  • Monomers or monomer mixtures in which the number average of m in the above formula (II) is at least 2.1, usually 2.1 to 8, are preferred.
  • she are obtainable by reacting an ethylenically unsaturated carboxylic acid with an oligoalkyleneimine, preferably in the form of an oligomer mixture.
  • the product obtained can optionally be converted into the acid addition salt using a mineral acid HY.
  • Such monomers can be polymerized in an aqueous medium in the presence of an initiator which triggers a radical polymerization to give cationic homopolymers and copolymers.
  • Salts of the monomers (III) with mineral acids or organic acids and quaternization products of the monomers (III) with alkyl halides or dialkyl sulfates can be obtained by adding alkyleneimines to amino-C 2 -C 6 -alkyl vinyl ethers.
  • the aforementioned monomers can be polymerized alone to form water-soluble cationic homopolymers or together with at least one other neutral monomer to form water-soluble cationic copolymers or with at least one acid-containing monomer to form amphoteric copolymers which carry a total cationic charge with a molar excess of copolymerized cationic monomers.
  • Suitable neutral monomers which are copolymerized with the above-mentioned cationic monomers for the preparation of cationic polymers are, for example, esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 30 alkanols, C 2 -C 30 alkanediols, Amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, esters of vinyl alcohol and allyl alcohol with saturated C 1 -C 30 monocarboxylic acids, vinyl aromatics, vinyl halides, vinylidene halides, C 2 -C 8 monoolefins and Mixtures of these.
  • Suitable comonomers are e.g. B. methyl (meth) acrylate, methylethacrylate, ethyl (meth) acrylate, ethylethacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate and mixtures thereof.
  • acrylamide, substituted acrylamides, methacrylamide, substituted methacrylamides such as acrylic acid amide, methacrylic acid amide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) - (meth) acrylamide, tert-butyl (meth) acrylamide, n-octyl (meth) acrylamide, 1,1,3,3-tetramethylbutyl (meth) acrylamide and ethylhexyl (meth) acrylamide as well as acrylonitrile and methacrylonitrile and mixtures of the monomers mentioned ,
  • Further monomers for modifying the cationic polymers are 2-hydroxyethyl (meth) acrylate, 2-hydroxyethylethacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate etc. and mixtures thereof.
  • N-vinyl lactams and their derivatives which, for. B. can have one or more C 1 -C 6 alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. These include e.g. B.
  • N-vinylpyrrolidone N-vinylpiperidone, N-vinylcaprolactam
  • N-vinyl-5-methyl-2-pyrrolidone N-vinyl-5-ethyl-2-pyrrolidone
  • N-vinyl-6-methyl-2-piperidone N-vinyl-6-ethyl-2-piperidone
  • N-vinyl-7-methyl-2-caprolactam N-vinyl-7-ethyl-2-caprolactam, etc.
  • Suitable comonomers for the copolymerization with the above-mentioned cationic monomers are also ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • Another group of comonomers are ethylenically unsaturated compounds which carry a group from which an amino group can be formed in a polymer-analogous reaction. These include, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide and mixtures thereof.
  • the polymers formed from it can, as in EP 0 438 744 A1 described, by acid or basic hydrolysis in vinylamine and amidine units (formulas IV - VII) polymers are converted.
  • the substituents R 1 , R 2 are H, C 1 - to C 6 -alkyl and X is an anion equivalent of an acid, preferably a mineral acid.
  • the hydrolysis produces, for example, polyvinylamines, polyvinylmethylamines or polyvinylethylamines.
  • the monomers of this group can be polymerized in any manner with the cationic monomers and / or the above-mentioned comonomers.
  • Cationic polymers for the purposes of the present invention are also to be understood as meaning amphoteric polymers which carry a total cationic charge.
  • the content of cationic groups is, for example, at least 5 mol% above the content of anionic groups in the polymer.
  • Such polymers are e.g. B. accessible by copolymerizing a cationic monomer such as N, N-dimethylaminoethyl acrylamide in the form of the free base, in partially neutralized with an acid or in quaternized form with at least one monomer containing acid groups, the cationic monomer being used in a molar excess , so that the resulting polymers carry a total cationic charge.
  • the copolymers can be hydrolysed in the presence of acids or bases or also enzymatically. In the hydrolysis with acids, the vinylamine groups formed from the vinylcarboxamide units are in salt form.
  • the hydrolysis of vinyl carboxamide copolymers is in the EP 0 438 744 A1 , Page 8, line 20 to page 10, line 3, described in detail. The statements made there apply accordingly to the production of the amphoteric polymers to be used according to the invention with a total cationic charge.
  • These polymers have, for example, K values (determined according to H. Fikentscher in 5% aqueous saline solution at pH 7, a polymer concentration of 0.5% by weight and a temperature of 25 ° C.) in the range from 20 to 250, preferably 50 to 150.
  • the cationic homopolymers and copolymers can be prepared by solution, precipitation, suspension or emulsion polymerization.
  • Solution polymerization in aqueous media is preferred.
  • Suitable aqueous media are water and mixtures of water and at least one water-miscible solvent, e.g. B. an alcohol such as methanol, ethanol, n-propanol, etc.
  • the polymerization temperatures are preferably in a range from about 30 to 200 ° C., particularly preferably 40 to 110 ° C.
  • the polymerization is usually carried out under atmospheric pressure, but it can also take place under reduced or elevated pressure.
  • a suitable pressure range is between 0.1 and 5 bar.
  • the monomers can be polymerized with the aid of initiators which form free radicals.
  • the peroxo and / or azo compounds customary for this purpose can be used as initiators for the radical polymerization, for example alkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbamate, bis- (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl peris-butyl peroxide, tert-peryl butyl peroxide, tert.
  • Initiator mixtures or redox initiator systems such as, for. B. ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H 2 O 2 / Cu-I or iron (II) compounds.
  • the polymerization can be carried out in the presence of at least one regulator.
  • a regulator the usual compounds known to those skilled in the art, such as, for. B. sulfur compounds, e.g. B. mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid, sodium hypophosphite, formic acid or dodecyl mercaptan and tribromochloromethane or other compounds which act regulatingly on the molecular weight of the polymers obtained.
  • Cationic polymers such as polyvinylamines and their copolymers can also be prepared by Hofmann degradation of polyacrylamide or polymethacrylamide and their copolymers, cf. H. Tanaka, Journal of Polymer Science: Polymer Chemistry Edition 17, 1239-1245 (1979 ) and EI Achari, X. Coqueret, A. Lablache-Combier, C. Loucheux, Makromol. Chem., Vol. 194, 1879-1891 (1993 ).
  • All of the aforementioned cationic polymers can be modified by carrying out the polymerization of the cationic monomers and, if appropriate, of the mixtures of cationic monomers and the comonomers in the presence of at least one crosslinking agent.
  • a crosslinker is understood to mean those monomers which contain at least two double bonds in the molecule, e.g. B. methylene bisacrylamide, Glycol diacrylate, glycol dimethacrylate, glycerol triacrylate, pentaerythritol triallyl ether, at least twice polyalkylene glycols esterified with acrylic acid and / or methacrylic acid or polyols such as pentaerythritol, sobitol or glucose. If at least one crosslinker is used in the copolymerization, the amounts used are, for example, up to 2 mol%, for. B. 0.001 to 1 mole%.
  • Polymers that can be produced by polyaddition reactions are also suitable as cationic compounds. Both homopolymers can be formed, but also graft polymers that are produced by grafting aziridines onto other polymers. Again, it may be advantageous to add during or after the polyaddition, which have at least two groups that can react with the aziridines or the amino groups formed, such as. B. epichlorohydrin or dihaloalkanes. Crosslinker (s. Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, 1992 , Chapter on aziridines).
  • Preferred polymers of this type are based on ethyleneimine, e.g. B. Homopolymers of ethyleneimine prepared by polymerization of ethyleneimine or polymers grafted with ethyleneimine such as polyamidoamines.
  • Suitable cationic polymers are reaction products of dialkylamines with epichlorohydrin or with di- or multifunctional epoxides such as. B. reaction products of dimethylamine with epichlorohydrin.
  • polycondensates e.g. B. homo- or copolymers of lysine, arginine and histidine. They can be used as homopolymers or as copolymers with other natural or synthetic amino acids or lactams. For example, glycine, alanine, valine, Leucine, phenylalanine, tryptophan, proline, asparagine, glutamine, serine, threonine or caprolactam.
  • Condensation of difunctional carboxylic acids with multifunctional amines can furthermore be used as cationic polymers, the multifunctional amines having at least two primary amino groups and at least one further less reactive, i.e. wear secondary, tertiary or quaternary amino group.
  • Examples are the polycondensation products of diethylenetriamine or triethylenetetramine with adipic, malonic, glutaric, oxalic or succinic acid.
  • amino group-bearing polysaccharides such as B. Chitosan are suitable as cationic polymers.
  • graft polymers are described, the graft base of which is selected from the group of polymers containing vinylamine units, polyamines, polyamidoamines and polymers of ethylenically unsaturated acids and which contain only oligoalkyleneimine side chains as side chains.
  • Graft polymers with oligoalkyleneimine side chains are prepared by grafting at least one oligoalkyleneimine which contains a terminal aziridine group onto one of the graft bases mentioned.
  • a polymer having vinylamine units is used as the water-soluble cationic polymer.
  • the present invention also relates to an aqueous composition composed of a nanocellulose and at least one polymer, selected from the group of anionic polymers and water-soluble cationic polymer, as can be used in the process according to the invention described above.
  • pulps for the production of the pulps for example wood pulp, bleached and unbleached cellulose and pulps from all annual plants.
  • pulp includes wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP).
  • TMP thermomechanical material
  • CMP chemo-thermomechanical material
  • RMP refiner mechanical pulp
  • sulfate, sulfite and soda pulps are suitable as pulp.
  • Unbleached pulp which is also referred to as unbleached kraft pulp, is preferably used.
  • Suitable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf. Waste paper is mostly used to produce the pulps, either alone or as a mixture with others Fibrous materials are used or fiber mixtures of a primary material and recycled scrap are assumed, for example bleached pine sulfate in a mixture with recycled scrap.
  • the process according to the invention is of particular technical interest for the production of paper and cardboard from waste paper, because it significantly increases the strength properties of the returned fibers and is of particular importance for improving the strength properties of graphic papers and packaging papers.
  • the papers obtainable by the process according to the invention surprisingly have a higher dry strength than those by the process of WO 2006/056381 A1 manufacturable papers.
  • the pH of the stock suspension is, for example, in the range from 4.5 to 8, mostly from 6 to 7.5.
  • an acid such as sulfuric acid or aluminum sulfate can be used to adjust the pH.
  • the aqueous composition is first prepared from a nanocellulose and at least one polymer. It is irrelevant whether the nanocellulose is initially introduced and the at least one polymer is added to the nanocellulose or vice versa. If both an anionic polymer and a water-soluble cationic polymer are added, the order is also irrelevant.
  • the aqueous suspension of the nanocellulose is first heated, for example up to 60 ° C., preferably up to 50 ° C. and particularly preferably in a range between 30 and 50 ° C.
  • An aqueous dispersion of at least one anionic polymer is then metered in. It is also possible, if appropriate, to add at least one cationic polymer to this aqueous composition.
  • At least one cationic polymer is added to the aqueous composition, this at least one cationic polymer preferably being added to a heated aqueous slurry of nanocellulose as described above.
  • the anionic polymer is then optionally added.
  • the addition of the aqueous composition in the process according to the invention to the thick matter (fiber concentration> 15 g / l, for example in the range from 25 to 40 g / l up to 60 g / l) or preferably to a thin material ( Fiber concentration ⁇ 15 g / l, for example in the range of 5 to 12 g / l).
  • the addition point is preferably in front of the sieves, but can also be between a shear step and a screen or after.
  • the water-insoluble anionic polymer is, for. B. in an amount of 0.1 to 10 wt .-%, preferably 0.3 to 6 wt .-%, in particular from 0.5 to 5.5 wt .-%, based on dry paper, used.
  • the cationic polymer optionally used is used, for example, in an amount of 0.03 to 2.0% by weight, preferably 0.1 to 0.5% by weight, based on dry paper stock.
  • the weight ratio of any water-soluble cationic polymer to water-insoluble anionic polymer used is, based on the solids content, for example 1: 5 to 1:20 and is preferably in the range from 1:10 to 1:15 and particularly preferably in the range from 1: 10 to 1:12.
  • the process chemicals usually used in paper production can be used in the usual amounts, e.g. Retention agents, drainage agents, other dry strength agents such as starch, pigments, fillers, optical brighteners, defoamers, biocides and paper dyes.
  • the K value of the polymers was determined according to Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74 (1932 ) at a temperature of 20 ° C in 5 wt .-% aqueous saline solutions at a pH of 7 and a polymer concentration of 0.5%.
  • K k ⁇ 1000.
  • the stated average particle sizes were determined according to ISO 13321 by quasi-elastic light scattering using a Malvern® Autosizer 2 C on 0.01% by weight samples.
  • This polymer was made by hydrolysis of a poly-N-vinylformamide with hydrochloric acid.
  • the degree of hydrolysis of the polymer was 50 mol%, ie the polymer contained 50 mol% N-vinylformamide units and 50 mol% vinylamine units in salt form.
  • the K value of the water-soluble cationic polymer was 90.
  • the anionic polymer B was present as an anionic acrylate resin with a solids content of 50% and was obtained by the suspension polymerization of 68 mol% n-butyl acrylate, 14 mol% styrene, 14 mol% acrylonitrile and 4 mol% acrylic acid.
  • the average particle size of the dispersed polymer particles was 192 nm.
  • the anionic polymer C was present as an anionic acrylate resin with a solids content of 50% and was obtained by the suspension polymerization of 87 mol% of n-butyl acrylate, 5 mol% of styrene, 5 mol% of acrylonitrile and 3 mol% of acrylic acid.
  • the average particle size of the dispersed polymer particles was 184 nm.
  • a Spinnig disk reactor was used, which was equipped with an inlet for cellulose solution and four inlets for water.
  • the feed for the cellulose solution was positioned centrally above the axis of the disc 1 mm from the disc surface.
  • the water inlets were positioned at equal distances from each other, 5 cm from the axis and 1 mm from the disk surface.
  • the disc surface and the jacket of the spinning disc reactor were heated to 95 ° C.
  • the reactor was filled with nitrogen.
  • a 0.5% by weight aqueous stock suspension was produced from 100% mixed waste paper.
  • the pH of the suspension was 7.1, the degree of grinding of the material was 50 ° Schopper-Riegler (° SR).
  • the treated nanocellulose suspension was added to the waste paper pulp with stirring.
  • the metered amount of treated nanocellulose (solid) based on waste paper stock (solid) was 5%.
  • sheets with a basis weight of 120 g / m 2 were produced from the treated waste paper stock on a Rapid-Köthen sheet former according to ISO 5269/2. The sheets were dried over one-sided contact to a steam heated metal cylinder for 7 minutes at 90 ° C.
  • a 0.5% by weight aqueous stock suspension was produced from 100% mixed waste paper.
  • the pH of the suspension was 7.1, the degree of grinding of the material was 50 ° Schopper-Riegler (° SR).
  • the treated nanocellulose suspension is added to the waste paper pulp with stirring.
  • the metered amount of treated nanocellulose (solid) based on waste paper stock (solid) was 5%.
  • sheets with a basis weight of 120 g / m 2 were produced from the treated waste paper stock on a Rapid-Köthen sheet former according to ISO 5269/2. The sheets were dried over one-sided contact to a steam heated metal cylinder for 7 minutes at 90 ° C.
  • a 0.5% by weight aqueous stock suspension was produced from 100% mixed waste paper.
  • the pH of the suspension was 7.1, the degree of grinding of the material was 50 ° Schopper-Riegler (° SR).
  • the treated nanocellulose suspension was added to the waste paper pulp with stirring.
  • the metered amount of treated nanocellulose (solid) based on waste paper stock (solid) was 5%.
  • sheets with a basis weight of 120 g / m 2 were produced from the treated waste paper stock on a Rapid-Köthen sheet former according to ISO 5269/2. The sheets were dried over one-sided contact to a steam heated metal cylinder for 7 minutes at 90 ° C.
  • a 0.5% by weight aqueous stock suspension was produced from 100% mixed waste paper.
  • the pH of the suspension was 7.1, the degree of grinding of the material was 50 ° Schopper-Riegler (° SR).
  • Sheets with a basis weight of 120 g / m 2 were produced from the untreated waste paper stock on a Rapid Köthen sheet former according to ISO 5269/2. The sheets were dried over one-sided contact to a steam heated metal cylinder for 7 minutes at 90 ° C.
  • a 0.5% by weight aqueous stock suspension was produced from 100% mixed waste paper.
  • the pH of the suspension was 7.1, the degree of grinding of the material was 50 ° Schopper-Riegler (° SR).
  • the cationic polymer A was added undiluted to this fiber suspension.
  • the amount of polymer used, based on the fiber content, was 0.3% by weight (polymer, solid).
  • the substance pretreated with the cationic polymer was stirred gently for about 30 seconds.
  • the dispersion of anionic polymer B was diluted by a factor of 10 with water.
  • the diluted dispersion was then added to the fiber suspension with gentle stirring.
  • the amount of acrylate resin used was 5% by weight (polymer, solid, based on the fiber content).
  • Sheets with a basis weight of 80 g / m 2 were produced from the pretreated fibrous material on a Rapid-Köthen sheet former according to ISO 5269/2. The sheets were dried over one-sided contact to a steam heated metal cylinder for 7 minutes at 90 ° C.

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Claims (9)

  1. Procédé de fabrication de papier, de carton souple et de carton faisant preuve d'une résistance élevée à l'état sec, caractérisé en ce qu'on fabrique dans un premier temps une composition aqueuse constituée d'une nano-cellulose, que l'on met en œuvre sous la forme d'une suspension aqueuse, contenant de 0,1 à 25 % en poids de nano-cellulose en rapport au poids total de la suspension aqueuse et au moins un polymérisat, sélectionné dans le groupe des polymérisats anioniques et des polymérisats cationiques hydrosolubles, on ajoute par dosage la composition aqueuse à la pâte à papier, on déshydrate la pâte à papier et on fait sécher les produits du papier, la nano-cellulose faisant preuve d'une extension longitudinale inférieure à 1000 µm et au moins 80 % des fibres de cellulose de la nano-cellulose présentant une épaisseur de fibres de l'ordre de 50 µm et 3 nm,
    les polymérisats anioniques contenant, en liaison polymère
    (a) au moins 60 % en moles d'au moins un monomère du groupe composé d'un acrylate d'alkyle en C1 à C20, d'un méthacrylate d'alkyle en C1 à C20, de l'acétate de vinyle, du propionate de vinyle, du styrène, de l'α-méthylstyrène, du p-méthylstyrène, de l'α-butylstyrène, du 4-n-butylstyrène, du 4-n-décylstyrène, de l'acrylonitrile, du méthacrylonitrile, du butadiène et de l'isoprène,
    (b) de 0,5 à 9 % en moles d'au moins un monomère anionique du groupe des acides carboxyliques éthyléniquement insaturés en C3 à C5, ainsi que de leurs sels,
    (c) le cas échéant, au moins un monomère du groupe des acrylates d'hydroxyalkyle en C1 à C10, des méthacrylates d'hydroxyalkyle en C1 à C10, de l'acrylamide, du méthacrylamide, des n-alkyl acrylamides en C1 à C20 et des n-alkylméthacrylamides en C1 à C20, et
    (d) le cas échéant au moins un monomère avec au moins deux doubles liaisons éthyléniquement insaturées dans la molécule,
    en tant que polymérisat cationique hydrosoluble étant mis en œuvre un polymérisat contenant des unités vinylamine.
  2. Procédé selon la revendication 1, caractérisé en ce qu'au moins 80 % des fibres de cellulose de la nanocellulose présentent une épaisseur de fibres de l'ordre de 1 µm à 5 nm.
  3. Procédé selon la revendication 1, caractérisé en ce que la nano-cellulose fait preuve d'une extension longitudinale inférieure à 1000 µm, l'épaisseur de fibres se situe dans l'ordre de 50 µm et 3 nm et la nano-cellulose contient entre 5 ppm et 2 % en poids de liquides ioniques.
  4. Procédé selon la revendication 3, caractérisé en ce qu'au moins 80 % des fibres de cellulose de la nanocellulose présentent une épaisseur de fibres comprise entre 50 µm et 3 nm et entre 5 ppm et 2 % en poids de liquides ioniques.
  5. Procédé selon la revendication 1, caractérisé en ce que les polymérisats anioniques contiennent, en liaison polymère au moins 80 % en moles d'au moins un monomère du groupe (a).
  6. Procédé selon l'une quelconque des revendications 1 ou 5, caractérisé en ce que les polymérisats anioniques contiennent, en liaison polymère en tant que monomère du groupe (a) des mélanges (i) d'un acrylate d'alkyle en C1 à C20, et/ou d'un méthacrylate d'alkyle en C1 à C20 et (ii) de styrène, d'α-méthylstyrène, de p-méthylstyrène, d'α-butylstyrène, de 4-n-butylstyrène, butadiène et/ou d'isoprène en rapport en poids de 10 : 90 à 90 : 10.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la masse molaire Mw des polymérisats cationiques se situe dans l'ordre de 5 000 à 5 millions de g/mole.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les densités de charge des polymérisats cationiques se situent dans l'ordre de 0,5 à 23 meq/g.
  9. Composition aqueuse, constituée d'une nano-cellulose, la nano-cellulose étant mise en œuvre sous la forme d'une suspension aqueuse contenant de 0,1 à 25 % en poids de nano-cellulose en rapport au poids total de la suspension aqueuse, faisant preuve d'une extension longitudinale inférieure à 1000 µm et au moins 80 % des fibres de cellulose de la nano-cellulose présentant une épaisseur de fibres de l'ordre de 50 µm et 3 nm et au moins un polymérisat, sélectionné dans le groupe des polymérisats anioniques et des polymérisats cationiques hydrosolubles,
    les polymérisats anioniques contenant, en liaison polymère
    (a) au moins 60 % en moles d'au moins un monomère du groupe composé d'un acrylate d'alkyle en C1 à C20, d'un méthacrylate d'alkyle en C1 à C20, de l'acétate de vinyle, du propionate de vinyle, du styrène, de l'α-méthylstyrène, du p-méthylstyrène, de l'α-butylstyrène, du 4-n-butylstyrène, du 4-n-décylstyrène, de l'acrylonitrile, du méthacrylonitrile, du butadiène et de l'isoprène,
    (b) de 0,5 à 9 % en moles d'au moins un monomère anionique du groupe des acides carboxyliques éthyléniquement insaturés en C3 à C5, ainsi que de leurs sels,
    (c) le cas échéant, au moins un monomère du groupe des acrylates d'hydroxyalkyle en C1 à C10, des méthacrylates d'hydroxyalkyle en C1 à C10, de l'acrylamide, du méthacrylamide, des n-alkyl acrylamides en C1 à C20 et des n-alkylméthacrylamides en C1 à C20, et
    (d) le cas échéant au moins un monomère avec au moins deux doubles liaisons éthyléniquement insaturées dans la molécule,
    en tant que polymérisat cationique hydrosoluble étant mis en œuvre un polymérisat contenant des unités vinylamine,
    susceptible d'être mise en œuvre dans un procédé selon les revendications 1 à 8.
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US20120205065A1 (en) 2012-08-16
WO2011048000A1 (fr) 2011-04-28
US8647470B2 (en) 2014-02-11
BR112012009141B1 (pt) 2020-10-13
US20140102649A1 (en) 2014-04-17
US9206551B2 (en) 2015-12-08
EP2491177A1 (fr) 2012-08-29
CN102666984A (zh) 2012-09-12
BR112012009141A2 (pt) 2016-08-30
JP2013508568A (ja) 2013-03-07
CA2777115A1 (fr) 2011-04-28
CA2777115C (fr) 2018-06-12

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