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EP2315875B1 - Procédé pour améliorer la résistance à sec du papier, du carton-pâte et du carton - Google Patents

Procédé pour améliorer la résistance à sec du papier, du carton-pâte et du carton Download PDF

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Publication number
EP2315875B1
EP2315875B1 EP09781661.5A EP09781661A EP2315875B1 EP 2315875 B1 EP2315875 B1 EP 2315875B1 EP 09781661 A EP09781661 A EP 09781661A EP 2315875 B1 EP2315875 B1 EP 2315875B1
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units
polymer
acid
polymers
groups
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EP2315875A1 (fr
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Hans-Joachim HÄHNLE
Christian Jehn-Rendu
Rainer Blum
Ellen KRÜGER
Norbert Schall
Martin Rübenacker
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BASF SE
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BASF SE
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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
    • 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
    • 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
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/48—Condensation polymers of aldehydes or ketones with phenols
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides

Definitions

  • the invention relates to a process for the production of paper, paperboard and cardboard with high dry strength by adding at least one cationic polymer and a polymeric anionic compound to a pulp, dewatering of the pulp under sheet formation and drying of the paper products.
  • CA patent 1 110 019 discloses a process for the production of paper with high dry strength, in which one adds to the paper material first a water-soluble cationic polymer, then dosed a water-soluble anionic polymer, then dewatered the paper stock on the paper machine with sheet formation and the paper products dried.
  • Suitable anionic polymers are, for example, hydrolyzed polyacrylamides which may have up to 30 mol% of acrylic acid units.
  • cationic polymers for example, water-soluble homo- and copolymers of cationic monomers such as vinylpyridine, vinylimidazolidine, diallylamines, ethyleneimine and basic acrylates and basic methacrylates are used.
  • the basic (meth) acrylates can each be copolymerized with acrylamide or methacrylamide.
  • These cationic polymers and also polyacrylamides can be modified to form other cationic polymers which are suitable for the process described, for example they can be subjected to a Mannich reaction or Hofmann degradation.
  • From the DE-A 35 06 832 discloses a process for the production of paper with high dry strength, in which one adds to the stock first a water-soluble cationic polymer and then a water-soluble anionic polymer.
  • Suitable anionic polymers are, for example, homopolymers or copolymers of ethylenically unsaturated C 3 -C 5 -carboxylic acids.
  • the copolymers contain at least 35 wt .-% of an ethylenically unsaturated C 3 - C 5 carboxylic acid (eg acrylic acid) in copolymerized form.
  • polyethyleneimine polyvinylamine, polydiallyldimethylammonium chloride and epichlorohydrin crosslinked condensation products of adipic acid and diethylenetriamine are described.
  • the JP-A 1999-140787 relates to a process for the production of corrugated board, wherein to improve the strength properties of a paper product to the pulp 0.05 to 0.5 wt .-%, based on dry pulp, of a polyvinylamine obtained by hydrolysis of polyvinylformamide having a degree of hydrolysis of 25 to 100 %, is added in combination with an anionic polyacrylamide, the stock is then dewatered to form sheets and the paper is dried.
  • a paper product having improved strength properties obtainable by applying to the surface of a paper product a polyvinylamine and a polymeric anionic compound which can form a polyelectrolyte complex with polyvinylamine, or a polymeric compound having aldehyde functions such as aldehyde group-containing polysaccharides.
  • a polyvinylamine and a polymeric anionic compound which can form a polyelectrolyte complex with polyvinylamine or a polymeric compound having aldehyde functions such as aldehyde group-containing polysaccharides.
  • WO 2004/061235 discloses a process for the production of paper, especially tissue, with particularly high wet and / or dry strengths, in which the paper stock is first added a water-soluble cationic polymer containing at least 1.5 meq / g of polymer to primary amino functionalities and a molecular weight of at least 10,000 daltons. Particular emphasis is placed here partially and fully hydrolyzed homopolymers of N-vinylformamide. Subsequently, a water-soluble anionic polymer is added which contains anionic and / or aldehydic groups.
  • WO 2006/120235 describes a process for producing papers having a filler content of at least 15% by weight, in which filler and fibers are treated together with cationic and anionic polymers, the treatment taking place alternately with cationic and anionic polymers and comprising at least 3 steps.
  • the invention has for its object to provide a further process for the production of paper, paperboard and cardboard with high dry strength available, the dry strength properties of the paper products compared to those of known products are further improved as possible. Another object of the invention is to achieve faster dewatering of the stock compared to known methods.
  • Examples of monomers of the formula I are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide and N-vinyl-N-methylpropionamide and N-vinylbutyramide.
  • the monomers of group (i) can be used alone or mixed in the copolymerization with the monomers of the other groups.
  • Preferably used monomer of this group is N-vinylformamide.
  • These polymers may optionally be modified by copolymerizing the N-vinylcarboxamides (i) together with (ii) at least one other monoethylenically unsaturated monomer and then hydrolyzing the copolymers to form amino groups. If anionic monomers are used in the copolymerization, the hydrolysis of the copolymerized vinylcarboxamide units is carried out so far that the molar excess of amine units compared to the anionic units in the polymer is at least 5 mol%.
  • Examples of monomers of group (ii) are esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 30 -alkanols, C 2 -C 30 -alkanediols and C 2 -C 30 -aminoalcohols, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, esters of vinyl alcohol and allyl alcohol with C 1 -C 30 monocarboxylic acids, N-vinyl lactams, nitrogen-containing Heterocycles with ⁇ , ⁇ -ethylenically unsaturated double bonds, vinyl aromatics, vinyl halides, vinylidene halides, C 2 -C 8 monoolefins and mixtures thereof
  • Suitable representatives are, for example, methyl (meth) acrylate (this notation symbolizes both "acrylates” and “methacrylates” here as well as in the following text), methyl methacrylate, Ethyl (meth) acrylate, ethyl ethacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-o-cytriethyl (meth) acrylate, 1,1,3, 3-Tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate and mixtures thereof.
  • Suitable additional monomers of group (ii) are furthermore the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols, preferably C 2 -C 12 -aminoalcohols. These may be C 1 -C 8 -monoalkylated or -dialkylated on the amine nitrogen.
  • the acid component of these esters are z.
  • Preference is given to using acrylic acid, methacrylic acid and mixtures thereof.
  • 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 of group (ii) are 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( meth) acrylate, 6-hydroxyhexyl (meth) acrylate and mixtures thereof.
  • Suitable monomers of group (ii) are acrylamide, methacrylamide, 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, ethylhexyl (meth) acrylamide and mixtures thereof.
  • monomers of group (ii) are nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids such as, for example, acrylonitrile and methacrylonitrile.
  • the presence of units of these monomers in the copolymer leads during or after the hydrolysis to products which have amidine units, cf. eg EP-A 0 528 409 or DE-A 43 28 975 , Namely, in the hydrolysis of N-vinylcarboxylic acid amide polymers, amidine units are formed in a secondary reaction by reacting vinylamine units with an adjacent vinylformamide unit or, if a nitrile group is present as an adjacent group in the polymer.
  • the indication of vinylamine units in the amphoteric Copolymers or in unmodified homo- or copolymers always the sum of vinylamine and amidine units.
  • Suitable monomers of group (ii) are furthermore N-vinyllactams and derivatives thereof which, for. B. one or more C 1 -C 6 alkyl substituents (as defined above) may have.
  • 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 and mixtures thereof.
  • suitable monomers of group (ii) are N-vinylimidazoles and alkylvinylimidazoles, in particular methylvinylimidazoles such as 1-vinyl-2-methylimidazole, 3-vinylimidazoleN-oxide, 2- and 4-vinylpyridine N-oxides and betaine derivatives and quaternization products of these monomers and ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • methylvinylimidazoles such as 1-vinyl-2-methylimidazole, 3-vinylimidazoleN-oxide, 2- and 4-vinylpyridine N-oxides and betaine derivatives and quaternization products of these monomers and ethylene, propylene, isobutylene, butad
  • the aforementioned monomers can be used individually or in the form of any mixtures. Typically, they are used in amounts of 1 to 90 mol%, preferably 10 to 80 mol% and particularly preferably 10 to 60 mol%.
  • amphoteric Copoylmerisaten come as other monoethylenically unsaturated monomers of group (ii) also anionic monomers into consideration, which are referred to above as monomers (ii, a). They may optionally be copolymerized with the neutral and / or cationic monomers (ii, b) described above. However, the amounts of anionic monomers (ii, a) is at most 45 mol%, so that the resulting amphoteric copolymer has a total cationic charge.
  • anionic monomers of group (ii, a) are ethylenically unsaturated C 3 to C 8 carboxylic acids such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itoconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • monomers containing sulfo groups such as vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid, and monomers containing phosphono groups, such as vinylphosphonic acid.
  • the monomers of this group can be used alone or in admixture with each other, in partially or completely neutralized form in the copolymerization.
  • neutralization for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines are used. Examples of these are sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium bicarbonate, magnesium oxide, calcium hydroxide, calcium oxide, Triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • a further modification of the copolymers is possible by using in the copolymerization monomers of group (iii) which contain at least two double bonds in the molecule, for. B. triallylamine, methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, glycerol triacrylate, pentaerythritol triallyl ether, at least two times with acrylic acid and / or methacrylic acid esterified polyalkylene glycols or polyols such as pentaerythritol, Sobit or glucose. If at least one monomer of the above group is used in the polymerization, the amounts used are up to 2 mol%, e.g. B. 0.001 to 1 mol%.
  • regulators are typically used 0.001 to 5 mol%. All regulators known in the literature can be used, eg. For example, sulfur compounds such as mercaptoethanol, 2-Ethylhexylthioglycolat, thioglycolic acid and dodecyl mercaptan and sodium hypophosphite, formic acid or Tribromchlormethan.
  • the polymers containing vinylamine units also include hydrolyzed graft polymers of, for example, N-vinylformamide on polyalkylene glycols, polyvinyl acetate, polyvinyl alcohol, polyvinylformamides, polysaccharides such as starch, oligosaccharides or monosaccharides.
  • the graft polymers are obtainable by free-radically polymerizing, for example, N-vinylformamide in aqueous medium in the presence of at least one of the stated grafting bases together with copolymerizable other monomers and then hydrolyzing the grafted vinylformamide units in a known manner to give vinylamine units.
  • the hydrolysis of the copolymers can be carried out in the presence of acids or bases or else enzymatically.
  • the vinylamine groups formed from the vinylcarboxamide units are present in salt form.
  • the hydrolysis of vinylcarboxylic acid amide copolymers is described in U.S. Pat EP-A 0 438 744 , Page 8, line 20 to page 10, line 3, described in detail.
  • the explanations made there apply correspondingly to the preparation of the cationic and / or amphoteric polymers containing vinylamine units to be used according to the invention and having a total cationic charge.
  • the polymers containing vinylamine units can also be used in the form of the free bases in the process according to the invention. Such polymers are useful, for example, in the hydrolysis of polymers containing vinylcarboxylic acid units with bases.
  • the polymers containing vinylamine units have, for example, K values (determined according to H. Fikentscher in 5% strength aqueous sodium chloride 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 preparation of the homopolymers and copolymers containing vinylamine units described above can be carried out by solution, precipitation, suspension or emulsion polymerization. Preference is given to solution polymerization in aqueous media. Suitable aqueous media are water and mixtures of water and at least one water-miscible solvent, e.g. As an alcohol such as methanol, ethanol, n-propanol or isopropanol.
  • the cationic polymers are water-soluble.
  • the charge density of the cationic polymers (without counterions) is for example at least 1.0 meq / g and is preferably in the range of 4 to 10 meq / g.
  • polymers containing vinylamine units the reaction products which are obtainable by Hofmann degradation of homopolymers or copolymers of acrylamide or methacrylamide in an aqueous medium in the presence of sodium hydroxide solution and sodium hypochlorite and subsequent decarboxylation of the carbamate groups of the reaction products in the presence of an acid are also suitable .
  • Such polymers are for example made EP-A 0 377 313 and WO 2006/075115 known.
  • the preparation of polymers containing vinylamine groups is described, for example, in WO 2006/075115 , Page 4, line 25 to page 10, line 22 and in the examples on pages 13 and 14 are treated in detail.
  • acrylamide and / or methacrylamide units are homopolymers or copolymers of acrylamide and methacrylamide.
  • Suitable comonomers are, for example, dialkylaminoalkyl (meth) acrylamides, diallylamine, methyldiallylamine and also the salts of the amines and the quaternized amines.
  • Dimethyldiallylammonium salts acrylamidopropyltrimethylammonium chloride and / or Methacrylamidopropyltrimethylammoniumchlorid
  • N-vinylformamide N-vinylacetamide
  • N-vinylpyrrolidone vinyl acetate
  • acrylic and methacrylic acid esters Dimethyldiallylammonium salts, acrylamidopropyltrimethylammonium chloride and / or Methacrylamidopropyltrimethylammoniumchlorid, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, vinyl acetate and acrylic and methacrylic acid esters.
  • comonomers are optionally also anionic monomers such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid, acrylamidomethylpropanesulfonic acid, methallylsulfonic acid and vinylsulfonic acid and the alkali metal, Erdalkylimetall- and Ammonium salts of said acidic monomers into consideration, wherein not more than 5 mol% of these monomers are used in the polymerization.
  • the amount of water-insoluble monomers is chosen in the polymerization so that the resulting polymers are soluble in water.
  • comonomers may also be used crosslinkers, for. B. ethylenically unsaturated monomers containing at least two double bonds in the molecule such as triallylamine, methylenebisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triallylamine and trimethylol trimethacrylate. If a crosslinker is used, the amounts used are, for example, 5 to 5000 ppm.
  • the polymerization of the monomers can be carried out by any known method, for. B. by free-radical initiated solution, precipitation or suspension polymerization. If appropriate, it is possible to work in the presence of customary polymerization regulators.
  • Hofmann degradation is for example from 20 to 40 wt .-% aqueous solutions of at least one acrylamide and / or methacrylamide units containing polymers.
  • the ratio of alkali metal hypochlorite to (meth) acrylamide units in the polymer is decisive for the resulting content of amine groups in the polymer.
  • the molar ratio of alkyl metal hydroxide to alkyl metal hypochlorite is, for example, 2 to 6, preferably 2 to 5.
  • the amount of alkali metal hydroxide required for the degradation of the polymer is calculated.
  • the Hofmann degradation of the polymer takes place z.
  • the aqueous reaction solution is passed into a reactor in which an acid is introduced for the decarboxylation of the reaction product.
  • the pH of the reaction product containing vinylamine units is adjusted to a value of 2 to 7.
  • the concentration of the decomposition products containing vinylamine units is, for example, more than 3.5% by weight, in most cases above 4.5% by weight.
  • the aqueous polymer solutions can be concentrated for example by means of ultrafiltration.
  • the polymers containing ethyleneimine units include all polymers obtainable by polymerization of ethyleneimine in the presence of acids, Lewis acids or haloalkanes, such as homopolymers of ethyleneimine or graft polymers of ethyleneimine, cf. US 2,182,306 or in US 3,203,910 , If desired, these polymers can subsequently be subjected to crosslinking. As crosslinkers z. B.
  • multifunctional epoxides such as bisglycol ethers of oligo- or polyethyleneoxides or other multifunctional alcohols such as glycerol or sugars, multifunctional carboxylic acid esters, mulifunctional isocyanates, polyfunctional acrylic or methacrylic acid esters, multifunctional acrylic or methacrylic acid amides, epichlorohydrin, multifunctional acid halides, multifunctional nitriles, ⁇ , ⁇ -chlorohydrin ethers of oligo- or polyethylene oxides or of other multifunctional alcohols such as glycerol or sugars, divinyl sulfone, maleic anhydride or ⁇ -halocarboxylic acid chlorides, multifunctional haloalkanes in particular ⁇ , ⁇ -dichloroalkanes.
  • Other crosslinkers are in WO 97/25367 , Pages 8 to 16 described.
  • polymers containing ethyleneimine units are made EP-A-0411400 . DE 2434816 and US 4,066,494 known.
  • a method for producing such compounds is, for example, in DE-A-2434816 wherein ⁇ , ⁇ -chlorohydrin ethers of oligo- or polyethylene oxides are used as crosslinkers application.
  • Reaction products of polyethylenimines with monobasic carboxylic acids to amidated polyethylenimines are known from the WO 94/12560 known.
  • Michael addition products of polyethyleneimines with ethylenically unsaturated acids, salts, esters, amides or nitriles of monoethylenically unsaturated carboxylic acids are the subject of WO 94/14873 , Phosphonomethylated polyethylenimines are described in detail in U.S. Pat WO 97/25367 described.
  • Carboxylated polyethyleneimines are obtainable, for example, by means of a plug synthesis by reacting polyethyleneimines with formaldehyde and ammonia / hydrogen cyanide and hydrolysing the reaction products.
  • Alkoxylated polyethyleneimines can be prepared by reacting Polyethyleiminen with alkylene oxides such as ethylene oxide and / or propylene oxide.
  • the polymers containing ethyleneimine units have, for example, molecular weights of from 10,000 to 3,000,000.
  • the cationic charge of the polymers containing ethyleneimine units is e.g. at least 4 meq / g. It is usually in the range of 8 to 20 meq / g.
  • the weight ratio of polymers containing (a) vinylamine units to polymers containing (b) ethyleneimine units in the process of the present invention is, for example, 10: 1 to 1:10, preferably 5: 1 to 1: 5.
  • the combination of polymers containing ethyleneimine units and polymers containing vinylamine units used in the inventive method for producing paper for example in an amount of 0.01 to 2.0 wt .-%, preferably 0.1 to 1.0 wt .-%, based on dry pulp.
  • Suitable monomers of group (1.1) are compounds which have an organic radical having a polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond and at least one sulfonic acid or phosphonic acid group per molecule. Also suitable are the salts and esters of the aforementioned compounds. The esters of phosphonic acids may be mono- or diesters. Suitable monomers (1.1) are furthermore esters of phosphoric acid with alcohols having a polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond. In this case, a proton of the phosphoric acid group or the other two protons of the phosphoric acid group can be neutralized by suitable bases or esterified with alcohols which have no polymerizable double bonds.
  • Suitable bases for the partial or complete neutralization of the acid groups of the monomers (1.1) are, for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines. Examples of these are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • Suitable alcohols for the esterification of phosphoric acid are, for example, C 1 -C 6 -alkanols, such as, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol and their isomers.
  • component (1.1) exclusively monomers in which all protons of the acid groups are esterified, such as.
  • component (1.2) at least one monoethylenically unsaturated mono- and / or dicarboxylic acid or a salt thereof is used for the polymerization, as described below as component (1.2). This ensures that the copolymers used according to the invention have anionic groups.
  • the abovementioned monomers (1.1) can be used individually or in the form of any desired mixtures in the preparation of the anionic polymers.
  • Suitable monomers of group (1.2) are monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts such as alkali metal, alkaline earth metal or ammonium salts of these carboxylic acids and the monoethylenically unsaturated carboxylic acid anhydrides.
  • This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, aconitic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • the monomers of group (1.2) can be used alone or mixed with each other, in partially or completely neutralized form in the homo- or copolymerization. Suitable bases for neutralization are the compounds mentioned above in component (1.1).
  • the water-soluble anionic polymer contains at least one monomer from the group (1) which is selected from the subgroups (1.1) and / or (1.2).
  • the water-soluble copolymer may also contain mixtures of monomers from subgroups (1.1) and (1.2) in copolymerized form.
  • the copolymers may contain at least one further monomer of group (2) in copolymerized form for modification.
  • These monomers are preferably selected from esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 30 -alkanols, C 2 -C 30 -alkanediols and C 2 -C 30 -aminoalcohols, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, esters of vinyl alcohol and allyl alcohol with C 1 -C 30 monocarboxylic acids, N-vinyl lactams, nitrogen-containing heterocycles having ⁇ , ⁇ -ethylenically unsaturated double bonds, vinyl aromatics, vinyl halides, vinylidene halides, C 2 C 8 monoolefins and mixtures thereof.
  • Suitable representatives of group (2) are z. Methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-ocytl ( meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate and mixtures thereof.
  • Suitable additional monomers (2) are furthermore acrylic acid amide, methacrylamide, 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, ethylhexyl (meth) acrylamide and mixtures thereof.
  • 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) are suitable.
  • Suitable monomers of group (2) are nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, such as, for example, acrylonitrile and methacrylonitrile.
  • Suitable monomers of group (2) are also N-vinyl lactams and derivatives thereof, the z. B. one or more C 1 -C 6 alkyl substituents (as defined above) may have. These include 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 and mixtures thereof.
  • Suitable monomers of group (2) are ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • the aforementioned monomers of group (2) can be used in the copolymerization with at least one anionic monomer, individually or in the form of any mixtures.
  • a further modification of the copolymers is possible by using in the copolymerization monomers of group (3) which contain at least two double bonds in the molecule, for.
  • group (3) which contain at least two double bonds in the molecule
  • methylenebisacrylamide glycol diacrylate, glycol dimethacrylate, glycerol triacrylate, pentaerythritol triallyl ether, at least two times with acrylic acid and / or methacrylic acid esterified polyalkylene glycols or polyols such as pentaerythritol, soba or glucose.
  • the amounts used are up to 2 mol%, z. B. 0.001 to 1 mol%.
  • regulators in the polymerization.
  • All known literature can be used Regulators such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid, dodecyl mercaptan, sodium hypophosphite, formic acid and / or tribromochloromethane.
  • the anionic polymeric compound used is preferably homopolymers of ethylenically unsaturated C 3 - to C 5 -carboxylic acids, in particular polyacrylic acid and polymethacrylic acid, and also hydrolyzed homopolymers of maleic anhydride and of itaconic anhydride.
  • Preferred anionic copolymers comprise, for example, (1) 10 to 99% by weight of at least one ethylenically unsaturated C 3 to C 5 carboxylic acid and (2) 90 to 1% by weight of at least one amide, nitrile and / or one Esters of an ethylenically unsaturated C 3 - to C 5 -carboxylic acid in copolymerized form.
  • copolymers of acrylic acid and acrylamide Copoylmerisate of acrylic acid and acrylonitrile
  • copolymers of acrylic acid and N-vinylformamide copolymers of methacrylic acid and methacrylamide, copolymers of Methacrylic acid and N-vinylformamide
  • copolymers of acrylic acid and methacrylamide copolymers of acrylic acid and methacrylonitrile
  • copolymers of methacrylic acid and methacrylonitrile copolymers of methacrylic acid and methacrylonitrile and copolymers of acrylic acid, acrylamide and acrylonitrile.
  • the anionic polymers are water-soluble. They can be used in the form of the free acids and / or as alkali metal, alkaline earth metal or ammonium salt in the process according to the invention. They have, for example, a K value of 50 to 250 (determined according to H. Fikentscher in 5% strength by weight aqueous sodium chloride solution at 25 ° C. and pH 7).
  • the water-soluble anionic polymer is used in the process according to the invention in an amount of, for example, from 0.01 to 2.0% by weight, preferably from 0.05 to 1.0% by weight, in particular from 0.1 to 0.5% by weight. %, based on dry pulp, used.
  • the weight ratio of cationic polymers (a) polymers containing vinylamine units and (b) polymers containing ethyleneimine units to the water-soluble polymeric anionic compounds is for example 3: 1 to 1: 3 and is preferably 1: 1.
  • the pulps used for producing the pulps are all grades which are customary for this purpose, for example wood pulp, bleached and unbleached pulp and paper pulp from all annual plants.
  • Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp, and refiner mechanical pulp (RMP).
  • TMP thermomechanical pulp
  • CMP chemothermomechanical pulp
  • RMP refiner mechanical pulp
  • pulp for example, sulphate, sulphite and soda pulps come into consideration.
  • unbleached pulp also referred to as unbleached kraft pulp
  • Suitable annual plants For example, rice, wheat, sugar cane and kenaf are used to make paper stocks.
  • the inventive method is particularly suitable for the production of dry-proof papers from waste paper (comprising deinked waste paper), which is used either alone or in admixture with other fibers. It is also possible to start with fiber blends of a primary material and recycled coated broke, e.g. B. bleached pine sulfate in admixture with recycled coated broke.
  • the inventive method is for the production of paper, cardboard and cardboard from waste paper and in special cases from deinked waste paper of technical interest, because it significantly increases the strength properties of the recycled fibers. It is of particular importance for improving the strength properties of graphic papers and packaging papers.
  • the pH of the stock suspension is, for example, in the range of 4.5 to 8, most 6 to 7.5.
  • an acid such as sulfuric acid or aluminum sulphate.
  • the cationic polymers namely (a) polymers comprising vinylamine units and polymers containing ethyleneimine units, are preferably first metered into the pulp.
  • the cationic polymers can be added to the thick material (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, eg in in the range of 5 to 12 g / l).
  • the point of addition is preferably in front of the screens, but it can also be between a shearing stage and a screen or afterwards.
  • the dosage of the cationic polymers (a) and (b) to the paper stock can be carried out, for example, successively, simultaneously or else as a mixture of (a) and (b).
  • the anionic component is usually added only after the addition of the cationic polymers (a) and (b) to the paper stock, but can also be metered simultaneously to the stock, but separately from the cationic polymers. Furthermore, it is also possible first to add the anionic and subsequently the cationic component or first to meter one of the cationic components (a) or (b) to the paper stock, then to add the anionic polymer and then to add the other cationic component.
  • the process chemicals commonly used in papermaking can be used in the usual amounts, for.
  • dehydrating agents other dry strength such as Starch, pigments, fillers, optical brighteners, defoamers, biocides and paper dyes.
  • the process according to the invention gives dry-proof papers whose dry strength relative to papers produced by known processes has an increased dry strength.
  • the dewatering rate is improved in comparison with known methods.
  • the percentages in the examples are by weight unless otherwise specified.
  • the K value of the polymers was after Fikentscher, Cellulose Chemie, Vol. 13, 58-64 and 71-74 (1932 ) at a temperature of 25 ° C in 5 wt .-% aqueous saline solutions at a pH of 7 and a polymer concentration of 0.5%.
  • a paper made of 100% waste paper (mixture of the grades: 1.02, 1.04,4.01) was pitched with drinking water at a consistency of 4% in a laboratory pulper without specks and ground in a laboratory refiner to a freeness of 40 ° SR. This substance was then diluted with drinking water to a consistency of 0.7%.
  • the polymers listed in the table were added successively to the above-described paper stock with stirring.
  • the polymer concentration of the aqueous solutions of cationic and anionic polymers was 1% each.
  • the amounts of polymers used in each case are given in percent by weight, based on the solids content of the paper stock.

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Claims (11)

  1. Procédé de fabrication de papier, de carton-pâte et de carton à résistance à sec élevée par ajout d'au moins un polymère cationique soluble dans l'eau et d'au moins un composé anionique polymère soluble dans l'eau à une pâte à papier, déshydratation de la pâte à papier avec formation de feuilles et séchage des produits de papier, caractérisé en ce qu'en tant que polymères cationiques solubles dans l'eau,
    (a) des polymères contenant des unités vinylamine et
    (b) des polymères contenant des unités éthylène-imine
    sont ajoutés dans un ordre quelconque ou sous la forme d'un mélange à une pâte à papier, le rapport en poids entre (a) les polymères contenant des unités vinylamine et (b) les polymères contenant des unités éthylène-imine étant de 10:1 à 1:10, et les produits de réaction qui peuvent être obtenus
    - par polymérisation d'au moins un monomère de formule
    Figure imgb0012
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    puis clivage partiel ou total des groupes -CO-R1 à partir des unités des monomères (I) polymérisées dans le polymère avec formation de groupes amino et/ou
    - par décomposition de Hoffmann de polymères comprenant des unités acrylamide et/ou méthacrylamide,
    étant utilisés en tant que (a) polymères contenant des unités vinylamine.
  2. Procédé selon la revendication 1, caractérisé en ce que les produits de réaction qui peuvent être obtenus par polymérisation de
    (i) au moins un monomère de formule
    Figure imgb0013
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    (ii) au moins un autre monomère monoéthyléniquement insaturé et éventuellement
    (iii) au moins un monomère à effet réticulant contenant au moins deux doubles liaisons par molécule,
    puis clivage partiel ou total des groupes -CO-R1 à partir des unités des monomères (I) polymérisées dans le polymère avec formation de groupes amino,
    sont utilisés en tant que (a) polymères contenant des unités vinylamine.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les produits de réaction qui peuvent être obtenus par polymérisation de
    (i) au moins un monomère de formule
    Figure imgb0014
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    (ii,a) au moins à chaque fois un acide sulfonique monoéthyléniquement insaturé, un acide phosphonique monoéthyléniquement insaturé, un acide carboxylique monoéthyléniquement insaturé contenant 3 à 8 atomes C par molécule et/ou leurs sels de métaux alcalins, de métaux alcalino-terreux ou d'ammonium, et éventuellement
    (ii,b) au moins un autre monomère neutre et/ou cationique, et éventuellement
    (iii) au moins un monomère à effet réticulant contenant au moins deux doubles liaison par molécule,
    puis clivage partiel ou total des groupes -CO-R1 à partir des monomères de formule I polymérisés dans le polymère avec formation de groupes amino, la teneur en groupes amino du copolymère étant au moins 5 % en moles supérieure à la teneur en groupes acides polymérisés des monomères (ii,a),
    sont utilisés en tant que (a) polymères contenant des unités vinylamine.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les produits de réaction qui peuvent être obtenus par polymérisation de N-vinylformamide, puis clivage des groupes formyle à partir des unités vinylformamide polymérisées dans le polymère avec formation de groupes amino sont utilisés en tant que (a) polymères contenant des unités vinylamine.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les produits de réaction qui peuvent être obtenus par copolymérisation de
    (i) vinylformamide et
    (ii) acrylonitrile,
    puis clivage des groupes formyle à partir des unités vinylformamide polymérisées dans le copolymère avec formation de groupes amino,
    sont utilisés en tant que (a) polymères contenant des unités vinylamine.
  6. Procédé selon la revendication 3, caractérisé en ce que les produits de réaction qui peuvent être obtenus par copolymérisation de
    (i) N-vinylformamide,
    (ii,a) acide acrylique, acide méthacrylique et/ou leurs sels de métaux alcalins, de métaux alcalino-terreux ou d'ammonium, et éventuellement
    (ii,b) acrylonitrile et/ou méthacrylonitrile,
    puis clivage partiel ou total des groupes formyle du N-vinylformamide polymérisé dans le polymère avec formation de groupes amino, la teneur en groupes amino du copolymère étant au moins 5 % en moles supérieure à la teneur en groupes acides polymérisés des monomères (ii,a),
    sont utilisés en tant que (a) produits de réaction contenant des unités vinylamine.
  7. Procédé selon la revendication 1, caractérisé en ce que les produits de réaction qui peuvent être obtenus par décomposition de Hoffmann d'homo- ou de copolymères d'acrylamide ou de méthacrylamide dans un milieu aqueux en présence de soude caustique et d'hypochlorite de sodium, puis décarboxylation des groupes carbamate du produit de réaction en présence d'un acide, sont utilisés en tant que (a) polymères contenant des unités vinylamine.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'au moins un polymère cationique soluble dans l'eau du groupe constitué par
    - les homopolymères d'éthylène-imine,
    - les polyéthylène-imines mises en réaction avec des agents de réticulation au moins bifonctionnels,
    - les polyamidoamines greffées avec de l'éthylène-imines, qui sont mises en réaction avec des agents de réticulation au moins bifonctionnels,
    - les produits de réaction de polyéthylène-imines avec des acides carboxyliques monobasiques pour former des polyéthylène-imines amidées,
    - les produits d'addition de Michael de polyéthylène-imines sur des acides éthyléniquement insaturés, des sels, des esters, des amides ou des nitriles d'acides carboxyliques monoéthyléniquement insaturés,
    - les polyéthylène-imines phosphonométhylées,
    - les polyéthylène-imines carboxylées et
    - les polyéthylène-imines alcoxylées,
    est utilisé en tant que (b) polymères contenant des unités éthylène-imine.
  9. Procédé selon la revendication 8, caractérisé en ce que des homopolymères d'éthylène-imine et/ou des polyamidoamines greffées avec de l'éthylène-imines, puis mises en réaction avec des agents de réticulation au moins bifonctionnels sont utilisés en tant que (b) polymères contenant des unités éthylène-imine.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'un polymère soluble dans l'eau, comprenant des groupes acides, présentant une densité de charge > 0,5 meq/g, ou ses sels, est utilisé en tant que composé anionique polymère.
  11. Procédé selon la revendication 10, caractérisé en ce qu'au moins un composé soluble dans l'eau du groupe constitué par l'acide polyacrylique, l'acide polyméthacrylique, les copolymères d'acrylamide et d'acide acrylique, les copolymères de N-vinylformamide et d'acide acrylique, les copolymères hydrolysés de N-vinylformamide et d'acide acrylique, et à chaque fois leurs sels, est utilisé en tant que composé anionique polymère.
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CA2590489C (fr) * 2004-12-17 2015-02-10 Basf Aktiengesellschaft Papiers ayant une forte teneur en matiere de charge et une resistance a la traction a l'etat sec elevee
FR2880901B1 (fr) 2005-01-17 2008-06-20 Snf Sas Soc Par Actions Simpli Procede de fabrication de papier et carton de grande resistance a sec et papiers et cartons ainsi obtenus
FR2882373B1 (fr) 2005-02-24 2007-04-27 Snf Sas Soc Par Actions Simpli Procede de fabrication de papier et carton de grande resistance a sec et papiers et cartons ainsi obtenus
BRPI0608971B8 (pt) 2005-05-11 2017-03-21 Stora Enso Ab processo para a produção de um papel e um papel produzido de acordo com o processo
ATE539126T1 (de) 2007-07-05 2012-01-15 Basf Se Wässrige anschlämmungen von feinteiligen füllstoffen, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von papieren mit hohem füllstoffgehalt und hoher trockenfestigkeit
JP2010533214A (ja) 2007-07-05 2010-10-21 ビーエーエスエフ ソシエタス・ヨーロピア 微粒子充填剤の水性懸濁液、その製造方法、並びに高充填材含有量及び高乾燥強度を有する紙を製造するためのその使用
EP2164908A1 (fr) 2007-07-05 2010-03-24 Basf Se Procédé pour préparer des suspensions de charges en fines particules et leur utilisation pour produire des papiers à teneur en charges et à résistance à sec élevées
WO2009004080A2 (fr) 2007-07-05 2009-01-08 Basf Se Procédé pour préparer des suspensions aqueuses de charges en fines particules et leur utilisation pour produire des papiers à teneur en charges et à résistance à sec élevées

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CN102124161B (zh) 2014-09-10
CA2733503A1 (fr) 2010-02-25
WO2010020551A1 (fr) 2010-02-25
EP2315875A1 (fr) 2011-05-04
US20110132559A1 (en) 2011-06-09
CN102124161A (zh) 2011-07-13
CA2733503C (fr) 2018-07-03
US8404083B2 (en) 2013-03-26

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