EP2288750B1 - Procédé de production de papier, de carton-pâte, et de carton présentant une résistance à sec élevée - Google Patents

Procédé de production de papier, de carton-pâte, et de carton présentant une résistance à sec élevée Download PDF

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EP2288750B1
EP2288750B1 EP09745789A EP09745789A EP2288750B1 EP 2288750 B1 EP2288750 B1 EP 2288750B1 EP 09745789 A EP09745789 A EP 09745789A EP 09745789 A EP09745789 A EP 09745789A EP 2288750 B1 EP2288750 B1 EP 2288750B1
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Prior art keywords
polymer
anionic
mol
process according
acid
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EP2288750A1 (fr
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Anton Esser
Hans-Joachim HÄHNLE
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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
    • D21H17/41—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

Definitions

  • the invention relates to a process for the production of paper, cardboard and cardboard with high dry strength by adding water-soluble cationic polymers and anionic polymers to a pulp, draining the pulp and drying the paper products.
  • a dry strength agent may either be applied to the surface of already dried paper or added to a stock prior to sheet formation.
  • the dry strength agents are usually used in the form of a 1 to 10% aqueous solution. If such a solution of a dry strength agent is applied to the surface of a paper, considerable amounts of water must be evaporated during the subsequent drying process. Since the drying step is very energy consuming and since the capacity of the usual drying equipment 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 lowered so that dried dry-treated paper dried sufficiently becomes.
  • Suitable water-soluble anionic polymers are, for example, homopolymers or copolymers of ethylenically unsaturated C 3 - to C 5 -carboxylic acids.
  • the copolymers contain, for example, from 35 to 99% by weight of an ethylenically unsaturated C 3 - to C 5 -carboxylic acid, for example acrylic acid, in copolymerized form.
  • WO-A-2004/061235 is a process for the production of paper, especially tissue, with particularly high wet and / or dry strengths known, in which one first adds to the paper a water-soluble cationic polymer which contains at least 1.5meq / g polymer of primary amino functionalities and a molecular weight of at least 10,000 daltons. Particularly emphasized here are partially and fully hydrolyzed homopolymers of N-vinylformamide. Subsequently, a water-soluble anionic polymer is added which contains anionic and / or aldehydic groups.
  • the method is mainly the variability of the two-component systems described in terms of various paper properties, including wet and dry strength, exposed.
  • DE 10 2005 029 010 teaches a method of making paper by separately adding a vinylamine moiety-containing polymer and a water-soluble polymeric anionic compound to the stock.
  • the anionic copolymer is composed of the monomers N-vinylcarboxamide and acrylic acid, wherein the acrylic acid content of the monomer composition is 30%. Such acrylic acid contents render the copolymer water-soluble.
  • From the CA 1 110 019 discloses a process for the production of paper with high dry strength, in which one adds to the paper stock first a water-soluble cationic polymer and then a water-soluble anionic polymer.
  • the anionic polymers are acrylamide / acrylic acid copolymers having an acrylic acid content of 2-30 mol%.
  • the US 5,185,062 teaches a papermaking process in which a mineral slurry, first a mineral filler, then a high molecular weight cationic polymer and then a water soluble anionic polymer of average molecular weight, is added to a cellulose slurry.
  • the anionic polymers are polymers based on acrylic acid or copolymers which contain at least 65 mol% of anionically ionizable radicals.
  • the US 2003/0188840 teaches the addition of a mixture of a water-soluble anionic resin and a water-soluble cationic or amphoteric starch in the papermaking process.
  • anionic polymers copolymers based on acrylamide / acrylic acid are used, which are water-soluble.
  • the US 5,338,406 teaches a process for producing high dry strength paper using a polyelectrolyte complex formed from a water-soluble cationic polymer and a water-soluble anionic polymer.
  • the invention has for its object to provide a further process for the production of paper with high dry strength and lowest possible wet strength available, the dry strength of the paper products over the prior art is further improved as possible.
  • the object is achieved according to the invention by a process for the production of paper, paperboard and cardboard with high dry strength by separately adding a water-soluble cationic polymer and an anionic polymer to a paper stock, dewatering the paper stock and drying the paper products, if the anionic polymer is an aqueous dispersion a water-insoluble polymer having an acid group content of 0.1 to 10 mol% or an anionic aqueous dispersion of a nonionic polymer.
  • the cationic polymer is added to the pulp in the form of dilute aqueous solutions having a polymer content of, for example, from 0.1 to 10% by weight
  • the addition of the anionic polymer is always carried out as an aqueous dispersion.
  • the polymer concentration The aqueous dispersion can be varied within a wide range.
  • the aqueous dispersions are preferably metered in diluted form; for example, the polymer concentration of the anionic dispersions is 0.5 to 10% by weight.
  • the water-dispersed anionic polymers are practically insoluble in water. For example, at a pH of 7.0 under normal conditions (20 ° C., 1013 mbar) at most 2.5 g of polymer / liter of water, usually at most 0.5 g / l and preferably not more than 0.1 g, dissolve / l.
  • the dispersions are anionic due to the content of acid groups in the polymer.
  • the water-insoluble polymer has a content of acid groups 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, for example, selected from carboxyl, sulfonic acid and phosphonic acid groups. Particularly preferred are carboxyl groups.
  • the anionic polymers contain z. B. at least 40 mol%, preferably at least 60 mol% and in particular at least 80 mol% of at least one monomer of group (a) copolymerized. These monomers are practically water-insoluble or, when homopolymerized, result in water-insoluble polymers.
  • the anionic polymers preferably 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 copolymerized 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 -C 20 -alcohols such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, n-butyl 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, 2-ethylhexyl acryl
  • esters of acrylic acid and of methacrylic acid with saturated, monohydric C 1 - to C 10 -alcohols are preferably used.
  • Mixtures of these monomers are also used in the preparation of the anionic polymers, for example mixtures of n-butyl acrylate and ethyl acrylate or mixtures of n-butyl acrylate and at least one propyl acrylate.
  • Preferred monomers of group (a) are C 1 -C 20 -alkyl (meth) acrylates and mixtures of alkyl (meth) acrylates with vinylaromatics, in particular styrene and / or double bonds containing hydrocarbons, in particular butadiene, or mixtures of such hydrocarbons with vinylaromatics , in particular 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 in a mixture.
  • the weight ratio of alkyl acrylates or alkyl methacrylates to vinyl aromatics and / or to double-bond hydrocarbons such as butadiene may 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, 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 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.
  • the water-insoluble anionic polymers may optionally contain as further monomers (c) at least one monomer from the group of C 1 to C 10 hydroxyalkyl acrylates, C 1 to C 10 hydroxyalkyl methacyrylates, acrylamide, methacrylamide, NC 1 to C 20 alkylacrylamides and NC 1 to C 20 alkyl methacrylamides included. If these monomers are used to modify the anionic polymers, it is preferable to use acrylamide or methacrylamide.
  • the amounts of polymerized 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, in the range of 1 to 5 mol%.
  • Suitable monomers of group (d) are compounds having at least two ethylenically unsaturated double bonds in the molecule. Such compounds 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 may 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” here and in the following text means both "...
  • Allyl acrylate, divinylbenzene, 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate are preferred. If a crosslinker is used to modify the polymers, the amounts polymerized in are up to 2 mol%. They are, for example, in the range of 0.001 to 2, preferably 0.01 to 1 mol%.
  • the water-insoluble anionic polymers preferably comprise, as monomers (a), mixtures of 20-50 mol% of styrene and 30-80 mol% of at least one alkyl methacrylate and / or at least one alkyl acrylate in copolymerized form. If appropriate, they may additionally contain up to 30 mol% of methacrylonitrile or acrylonitrile in copolymerized form. If appropriate, such polymers may also be modified with the amounts of methacrylamide and / or acrylamide stated above under monomers of group (c).
  • anionic polymers which comprise at least 80 mol% of at least one monomer of group (a) in copolymerized form. They 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, ⁇ -Butylstyrol, 4-n-butylstyrene, butadiene and / or isoprene in a weight ratio of 10: 90 to 90: 10 copolymerized.
  • the preparation of the anionic polymers is usually carried out by emulsion polymerization. It is therefore in the anionic polymers are emulsion polymers.
  • the preparation of aqueous polymer dispersions by the process of free-radical emulsion polymerization is known per se (cf. Houben-Weyl, Methods of Organic Chemistry, Volume XIV, Macromolecular Materials, Georg Thieme Verlag, Stuttgart 1961, pages 133ff ).
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • the surface-active substance is usually used in amounts of from 0.1 to 10% by weight, in particular from 0.2 to 3% by weight, based on the monomers to be polymerized.
  • Common emulsifiers are z. 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 having a degree of ethoxylation of 3 to 30 and ethoxylated C 8 - to C 25 -fatty alcohols having a degree of ethoxylation of 5 to 50. Also conceivable are mixtures of nonionic and ionic emulsifiers. Also suitable are phosphate- or sulfate-containing, ethoxylated and / or propoxylated alkylhenols and / or fatty alcohols. Other suitable emulsifiers are in Houben-Weyl, Methods of Organic Chemistry, Volume XIV, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 209 listed.
  • Water-soluble initiators for the emulsion polymerization for the preparation of anionic polymers are, for.
  • red-ox reduction-oxidation initiator systems
  • peroxides 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 may additionally contain metal ions such as iron (II) ions.
  • the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the monomers to be polymerized. Several different initiators can also be used in the emulsion polymerization.
  • regulators may be used, e.g. in amounts of from 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 z.
  • the emulsion polymerization for the preparation of the anionic polymers is generally carried out at 30 to 130 ° C, preferably at 50 to 100 ° C.
  • the polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the emulsion polymerization can be carried out both as a batch process and in the form of a feed process, including a stepwise or gradient procedure.
  • the feed process in which one submits a portion of the polymerization, heated to the polymerization, polymerized and then the rest of the polymerization, usually over several spatially separate feeds, one or more of which monomers in pure or in emulsified form, continuously , gradually or with the addition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies.
  • the polymerization can also z. B. be presented for better adjustment of the particle size of 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 one of ordinary skill in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. In detail, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.
  • To remove the residual monomers is usually also after the end of the actual emulsion polymerization, ie after a conversion of the monomers of at least 95%, added again at least one initiator and the reaction mixture heated for a certain time to the polymerization or an overlying temperature.
  • the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor bottom.
  • 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 one or more counterions may be associated, eg Li + , Na + , K + , Cs + , Mg 2+ , Ca 2 + or Ba 2+ .
  • Also suitable for neutralization are ammonia or amines. Preference is given to aqueous ammonium hydroxide, sodium hydroxide or potassium hydroxide solutions.
  • aqueous dispersions of the anionic polymer are generally obtained with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-%.
  • the molecular weight M w of the anionic polymers is, for example, in the range of 100,000 to 1 million daltons. If the polymers have a gel phase, a molecular weight determination is not readily possible. The molar masses are then above the above-mentioned range.
  • the glass transition temperature Tg of the anionic polymers is for example in the range of -30 to 100 ° C, preferably in the range of -5 to 70 ° C and particularly preferably in the range of 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 of 10 to 1000 nm, more preferably in the range of 50 to 300 nm (measured using a Malvern ® Autosizer 2 C).
  • the anionic polymers may optionally contain polymerized small amounts of cationic monomer units, so that there are amphoteric polymers, but the total charge of the polymers must be anionic.
  • the net anionic charge is less than -0.2 meq / g. It is usually in the range of -0.5 to -2.0 meq / g.
  • polymer dispersions of nonionic monomers which are emulsified with the aid of anionic surfactants or emulsifiers are also suitable as anionic polymers are.
  • the surfactants or emulsifiers are used for this application, for example, in amounts of 1 to 15 wt .-%, based on the total dispersion.
  • Suitable cationic polymers are all water-soluble cationic polymers mentioned in the cited prior art. It is z. B. to amino or ammonium compounds carrying compounds. The amino groups may be primary, secondary, tertiary or quaternary groups. For the polymer are in the main polymers, polyaddition compounds or polycondensates into consideration, wherein the polymers may have a linear or branched structure up to hyperbranched or dendritic structures. Furthermore, graft polymers are also applicable.
  • 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, for example, at least 10% by weight.
  • the molecular weights M w of the cationic polymers are, for example, at least 1000. For example, they are mostly in the range of 5,000 to 5 million.
  • the charge densities of the cationic polymers are, for example, 0.5 to 23 meq / g of polymer, preferably 3 to 22 meq / g of polymer and most often 6 to 20 meq / g of polymer.
  • Suitable monomers are furthermore N-vinylimidazoles, alkylvinylimidazoles, in particular methylvinylimidazoles such as 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridines, 2- and 4-vinylpyridine N-oxides and betainic derivatives and Quaternization products of these monomers.
  • Monomers or monomer mixtures in which the number average of m in the above formula is at least 2.1, usually 2.1 to 8, are preferred. They are obtainable by reacting an ethylenically unsaturated carboxylic acid with an oligoalkyleneimine, preferably in the form of an oligomer mixture. The resulting product may optionally be converted with a mineral acid HY in the acid addition salt.
  • Such monomers can be polymerized in an aqueous medium in the presence of an initiator which initiates a free radical polymerization to cationic homo- and copolymers.
  • the abovementioned 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 group-containing monomer to form amphoteric copolymers which carry a total cationic charge in a molar excess of copolymerized cationic monomers.
  • Suitable neutral monomers which are copolymerized with the abovementioned 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 thereof.
  • Suitable comonomers are e.g. Methyl (meth) acrylate, methylethacrylate, ethyl (meth) acrylate, ethylethacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butylethacrylate, 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, for example, 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 and ethylhexyl (meth) acrylamide and also acrylonitrile and methacrylonitrile and mixtures of the stated monomers.
  • Further monomers for modifying the cationic polymers 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, etc., and mixtures thereof.
  • N-vinyllactams and derivatives thereof which contain, for example, one or more C 1 -C 6 -alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. Butyl, tert-butyl, etc. 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, etc.
  • Suitable comonomers for the copolymerization with the abovementioned cationic monomers are furthermore 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 bearing a moiety 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 therefrom can, as in EP-A-0438744 described, by acidic or basic hydrolysis in vinylamine and amidine units (formulas IV - VII) containing polymers are transferred
  • 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.
  • polyvinylamines polyvinyl-methylamines or polyvinylethylamines are formed during the hydrolysis.
  • the monomers of this group may be polymerized in any manner with the cationic monomers and / or the above-mentioned comonomers.
  • Cationic polymers should also be understood as meaning amphoteric polymers which carry a total cationic charge.
  • the content of cationic groups is, for example, at least 5 mol% higher than the content of anionic groups in the polymer.
  • Such polymers are z. B. accessible by copolymerizing a cationic monomer such as N, N-Dimethylaminoethylacrylamid in the form of the free base, partially neutralized with an acid or in quaternized form with at least one acid group-containing monomer, wherein the cationic monomer is used in a molar excess so that the resulting polymers carry a cationic total charge.
  • 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 statements made there apply correspondingly to the preparation of the amphoteric polymers to be used according to the invention having 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. 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, etc.
  • the polymerization temperatures are preferably in a range of about 30 to 200 ° C, more preferably 40 to 110 ° C.
  • the polymerization is usually carried out under atmospheric pressure, but it can also proceed under reduced or elevated pressure.
  • a suitable pressure range is between 0.1 and 5 bar.
  • the monomers can be polymerized by means of free-radical initiators.
  • the peroxo and / or azo compounds customary for this purpose can be used, for example alkali 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 permalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide tert-butyl hydroperoxide
  • initiator mixtures or redox initiator systems such as, for example, 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 -Links.
  • the polymerization can be carried out in the presence of at least one regulator.
  • a regulator the usual compounds known in the art, such.
  • B. sulfur compounds for. As mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid, sodium hypophosphite, formic acid or dodecyl mercaptan and Tribromchlormethan or other compounds which act regulating the molecular weight of the polymers obtained, are used.
  • 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 ).
  • 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 crosslinker.
  • a crosslinker is understood as meaning those monomers which contain at least two double bonds in the molecule, eg.
  • 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. If at least one crosslinker is used in the copolymerization, the amounts used, for example, up to 2 mol%, z. B. 0.001 to 1 mol%.
  • Suitable cationic compounds are polymers which can be produced by polyaddition reactions, in particular polymers based on aziridines. Both homopolymers can be formed but also graft polymers which are produced by grafting aziridines to other polymers. Again, it may be advantageous during or after the polyaddition add crosslinkers having at least 2 groups that can react with the aziridines or the amino groups formed, such as. For example, 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. produced by polymerization of ethyleneimine homopolymers of ethyleneimine or grafted with ethyleneimine polymers such as polyamidoamines.
  • Suitable cationic polymers are reaction products of dialkylamines with epichlorohydrin or with di- or multifunctional epoxides such.
  • cationic polymers are also polycondensates, eg. 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 else caprolactam are suitable for the copolymerization.
  • cationic polymers it is also possible to use condensates of difunctional carboxylic acids with polyfunctional amines, the polyfunctional amines bearing at least 2 primary amino groups and at least one further less reactive, ie secondary, tertiary or quaternary amino group.
  • examples are the polycondensation products of diethylenetriamine or triethylenetetramine with adipic, malonic, glutaric, oxalic or succinic acid.
  • amino groups carrying polysaccharides such as B. Chitosan are suitable as cationic polymers.
  • graft polymers which carry primary or secondary amino groups, can be modified by means of reactive oligoethyleneimines as in the older one EP application 07 150 232.2 described.
  • graft polymers are described whose graft base is selected from the group of polymers comprising vinylamine units, polyamines, polyamidoamines and polymers of ethylenically unsaturated acids, and which contain exclusively oligoalkyleneimine side chains as side chains.
  • the preparation of graft polymers with Oligoalkylenimintimketten done by grafting on one of said grafting at least one Oligoalkylenimin containing a terminal Aziridinruppe.
  • Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp, and refiner mechanical pulp (RMP).
  • TMP thermomechanical pulp
  • CMP chemo-thermo-mechanical 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 the production of pulps are, for example, rice, wheat, sugar cane and kenaf.
  • waste paper is mostly used, which is used either alone or in admixture with other fibers or it is based on fiber blends of a primary material and recycled coated Committee, z. B. bleached pine sulfate in admixture with recycled coated broke.
  • the process according to the invention is of technical interest for the production of paper and paperboard because it significantly increases the strength properties of the recycled 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 according to the process of WO 2006/056381 manufacturable papers.
  • the pH of the stock suspension is, for example, in the range of 4.5 to 8, usually 6 to 7.5.
  • an acid such as sulfuric acid or aluminum sulphate.
  • the cationic polymer is preferably first metered to the paper stock.
  • the cationic polymer 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 may also be between a shearing stage and a screen or afterwards.
  • the anionic component is usually added to the paper stock only after the cationic component has been added, but it can also be metered into the paper stock at the same time, but separately from the cationic component. Furthermore, it is also possible first to add the anionic and subsequently the cationic component.
  • Particularly advantageous is a process variant in which the pulp is heated to a temperature of at least 40 ° C, e.g. 45 to 55 ° C, preferably heated to at least 50 ° C and then dosed first the water-soluble cationic polymer and then or simultaneously, but separately, the water-insoluble anionic polymer.
  • a temperature of at least 40 ° C e.g. 45 to 55 ° C
  • the water-soluble anionic polymer preferably heated to at least 50 ° C
  • the water-soluble cationic polymer used is preferably a polymer containing vinylamine units.
  • the cationic polymer is used, for example, in an amount of 0.03 to 2.0 wt .-%, preferably 0.1 to 0.5 wt .-%, based on dry pulp.
  • the water-insoluble anionic polymer is e.g. in an amount of 0.5 to 10 wt .-%, preferably 1 to 6 wt .-%, in particular from 2.5 to 5.5 wt .-%, based on dry pulp, used.
  • the weight ratio of water-soluble cationic polymer to water-insoluble anionic polymer is, for example, 1: 5 to 1:20, based on the solids content, and is preferably in the range of 1:10 to 1:15, and more preferably in the range of 1:10 to 1:12.
  • 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 percentages in the examples are by weight unless otherwise specified.
  • the K value of the polymers was calculated according to Fikentscher, Cellulose Chemistry, 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.
  • This polymer was prepared by hydrolysis of a poly-N-vinylformamide with hydrochloric acid.
  • the degree of hydrolysis of the polymer was 50 mole%, i. the polymer contained 50 mole% of N-vinylformamide units and 50 mole% of vinylamine units in salt form.
  • the K value of the water-soluble cationic polymer was 90.
  • the water-soluble cationic polymer contained 70 mol% of N-vinylformamide units and 30 mol% of vinylamine units in salt form.
  • the K value of the water-soluble cationic polymer was 90.
  • a 0.5% aqueous pulp suspension was prepared.
  • the pH of the suspension was 7.1, the freeness of the substance 50 ° Schopper-Riegler (° SR).
  • the stock suspension was then divided into 8 equal parts and in Examples 1 to 3 and in Comparative Examples 1 to 5 under the conditions specified in the Examples and Comparative Examples on a Rapid Köthen sheet former according to ISO 5269/2 sheets of a basis weight of 120 gsm processed.
  • the stock was heated to a temperature of 50 ° C.
  • polymer B polymer, based on dry pulp.
  • the dispersion of an anionic acrylate resin (solid content 50%) obtainable by the suspension polymerization of 68 mol% of n-butyl acrylate, 14 mol% of styrene, 14 mol% of acrylonitrile and 4 mol% of acrylic acid was increased by a factor 10 diluted.
  • the mean particle size of the dispersed polymer particles was 192 nm.
  • the dilute dispersion was metered into the pulp suspension heated to 50 ° C. with gentle stirring. The used
  • Acrylate resin amount was 5% (polymer solid) based on dry pulp. After an exposure time of 1 minute leaves were formed, which were then dried at 90 ° C for 7 minutes.
  • the dilute dispersion the temperature of which was about 20 ° C.
  • the amount of acrylate used was 5% (polymer solid), based on dry pulp. After an exposure time of 1 minute leaves were formed, which were then dried at 90 ° C for 7 minutes.
  • the dispersion of an anionic acrylate resin (solids content 50%) obtainable by the suspension polymerization of 68 mol% of n-butyl acrylate, 14 mol% of styrene, 14 mol% of acrylonitrile and 4 mol% of acrylic acid was diluted by a factor of 10. The diluted dispersion was then added to the pulp suspension with gentle stirring. The amount of acrylate used was 5% (polymer solid), based on dry pulp. The mean particle size of the dispersed particles was 192 nm. The pulp suspension pretreated with the dispersion was then heated to 50 ° C. To the heated stock suspension was metered 0.25% polymer B (polymer solid, based on dry pulp). After an exposure time of 1 minute leaves were formed, which were then dried at 90 ° C for 7 minutes.
  • Comparative Examples 2 to 4 were according to Example 1 of WO 2006/056381 carried out.
  • a sample of the stock suspension described above was mixed at a fabric temperature of 22 ° C. with 0.25% of polymer A (polymer solid, based on dry pulp). After a residence time of 5 minutes, 0.25% of a water-soluble copolymer of 30% acrylic acid and 70% vinylformamide was added. The copolymer was in the form of a sodium salt and had a K value of 90. After an exposure time of 1 minute, leaves were formed, which were then dried at 90 ° C. for 7 minutes.

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Claims (14)

  1. Procédé de fabrication de papier, de bristol et de carton présentant une résistance à sec élevée par ajout séparé d'un polymère cationique soluble dans l'eau et d'un polymère anionique à une pâte à papier, déshydratation de la pâte à papier et séchage des produits de papier, caractérisé en ce qu'une dispersion aqueuse d'un polymère insoluble dans l'eau ayant une teneur en groupes acides de 0,1 à 10 % en moles ou une dispersion aqueuse ajustée anioniquement d'un polymère non ionique est utilisée en tant que polymère anionique.
  2. Procédé selon la revendication 1, caractérisé en ce que le polymère insoluble dans l'eau présente une teneur en groupes acides de 0,1 à 9 % en moles.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le polymère insoluble dans l'eau présente une teneur en groupes acides de 0,5 à 6 % en moles.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le polymère soluble dans l'eau présente une teneur en groupes acides de 2 à 6 % en moles.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les groupes acides sont choisis parmi les groupes carboxyle, acide sulfonique et acide phosphonique.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les polymères anioniques contiennent sous forme copolymérisée
    (a) au moins un monomère du groupe constitué par les acrylates d'alkyle en C1 à C20, les méthacrylates d'alkyle en C1 à C20, les esters de vinyle d'acides carboxyliques saturés contenant jusqu'à 20 atomes C, les composés aromatiques de vinyle contenant jusqu'à 20 atomes C, les nitriles éthyléniquement insaturés, les éthers de vinyle d'alcools monovalents saturés contenant 1 à 10 atomes C, les halogénures de vinyle et les hydrocarbures aliphatiques contenant 2 à 8 atomes C et une ou deux doubles liaisons,
    (b) au moins un monomère anionique du groupe constitué par les acides carboxyliques en C3 à C8 éthyléniquement insaturés, l'acide vinylsulfonique, l'acide acrylamido-2-méthylpropanesulfonique, l'acide styrènesulfonique, l'acide vinylphosphonique et leurs sels, et éventuellement
    (c) au moins un monomère du groupe constitué par les acrylates d'hydroxyalkyle en C1 à C10, les méthacrylates d'hydroxyalkyle en C1 à C10, l'acrylamide, le méthacrylamide, les N-alkyle en C1 à C20-acrylamides et les N-alkyle en C1 à C20-méthacrylamides, et éventuellement
    (d) au moins un monomère contenant au moins deux doubles liaisons éthyléniquement insaturées par molécule.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les polymères anioniques contiennent sous forme copolymérisée
    (a) au moins 60 % en moles d'au moins un monomère du groupe constitué par un acrylate d'alkyle en C1 à C20, un méthacrylate d'alkyle en C1 à C20, l'acétate de vinyle, le propionate de vinyle, le styrène, l'α-méthylstyrène, le p-méthylstyrène, l'α-butylstyrène, le 4-n-butylstyrène, le 4-n-décylstyrène, l'acrylonitrile, le méthacrylonitrile, le butadiène et l'isoprène,
    (b) 0,5 à 9 % en moles d'au moins un monomère anionique du groupe constitué par les acides carboxyliques en C3 à C5 éthyléniquement insaturés.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que les polymères anioniques contiennent sous forme copolymérisée au moins 80 % en moles d'au moins un monomère du groupe (a).
  9. Procédé selon la revendication 8, caractérisé en ce que les polymères anioniques contiennent sous forme copolymérisée en tant que monomère du groupe (a) des mélanges de (i) un acrylate d'alkyle en C1 à C20 et/ou un méthacrylate d'alkyle en C1 à C20 et (ii) le styrène, l'α-méthylstyrène, le p-méthylstyrène, l'α-butylstyrène, le 4-n-butylstyrène, le butadiène et/ou l'isoprène en une proportion de 10:90 à 90:10.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que les polymères anioniques ont une température de transition vitreuse Tg de -30 à 100 °C (mesurée selon DIN EN ISO 11357).
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que les polymères anioniques ont une température de transition vitreuse de -5 à 70 °C.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que la température de la pâte à papier est d'au moins 40 °C.
  13. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que la température de la pâte à papier est d'au moins 50 °C.
  14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce qu'un polymère comprenant des unités vinylamine est utilisé en tant que polymère cationique soluble dans l'eau.
EP09745789A 2008-05-15 2009-05-14 Procédé de production de papier, de carton-pâte, et de carton présentant une résistance à sec élevée Not-in-force EP2288750B1 (fr)

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EP09150237 2009-01-08
PCT/EP2009/055837 WO2009138457A1 (fr) 2008-05-15 2009-05-14 Procédé de production de papier, de carton-pâte, et de carton présentant une résistance à sec élevée
EP09745789A EP2288750B1 (fr) 2008-05-15 2009-05-14 Procédé de production de papier, de carton-pâte, et de carton présentant une résistance à sec élevée

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EP2373745B1 (fr) 2008-12-03 2019-03-13 Omya International AG Suspensions aqueuses de matières de charge fines, procédé de fabrication et utilisation de ces suspensions pour la fabrication de papiers contenant des matières de charge

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WO2009138457A1 (fr) 2009-11-19
JP2011521114A (ja) 2011-07-21
EP2288750A1 (fr) 2011-03-02
CN102027170B (zh) 2012-11-21
PT2288750E (pt) 2012-09-26
KR20110013480A (ko) 2011-02-09

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