EP3234259A1 - Procédé de fabrication de papier et de carton - Google Patents

Procédé de fabrication de papier et de carton

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Publication number
EP3234259A1
EP3234259A1 EP15820441.2A EP15820441A EP3234259A1 EP 3234259 A1 EP3234259 A1 EP 3234259A1 EP 15820441 A EP15820441 A EP 15820441A EP 3234259 A1 EP3234259 A1 EP 3234259A1
Authority
EP
European Patent Office
Prior art keywords
polymer
groups
acid
mol
amino groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15820441.2A
Other languages
German (de)
English (en)
Inventor
Hans-Joachim Haehnle
Christoph Hamers
Anton Esser
Hubert Meixner
Matthew BUCHAN
Norbert Schall
Stefan Spange
Katja TROMMLER
Hendrik WÜRFEL
Susan SEIFERT
Tina WALTHER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3234259A1 publication Critical patent/EP3234259A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/51—Methods thereof
    • B01F23/511—Methods thereof characterised by the composition of the liquids or solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/80—After-treatment of the mixture
    • B01F23/804—Drying the mixture
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/02—Homopolymers or copolymers of vinylamine
    • 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
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/10—Composite fibres
    • 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
    • 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
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • 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
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • 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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/47—Mixing of ingredients for making paper pulp, e.g. wood fibres or wood pulp
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
    • D21H11/04—Kraft or sulfate pulp
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/08—Mechanical or thermomechanical pulp

Definitions

  • the invention relates to a process for the production of paper and cardboard with high dry strength by adding at least one aqueous composition and a polymeric anionic compound to a paper stock, dewatering the paper stock to form sheets and drying the paper products.
  • Today's papermaking processes are geared towards reducing resources or making better use of resources.
  • developments are taking place to use shorter fiber lengths, to reduce the basis weights and to use a higher proportion of filler. All these innovations in turn have a negative impact on the strength, especially the dry strength of paper, so that especially in this direction new solidifiers are sought.
  • the strength of the paper is an important requirement, particularly in the packaging paper sector, as recycled fibers are an important basis for this, as they lose their length due to recycling and thus gradually reduce the strength of the paper.
  • a process for producing paper having high dry strength by adding a water-soluble cationic polymer and various water-soluble anionic polymers to the paper stock are known and are described, for example, in DE 35 06 832, WO 2006/0751 15 and DE-A 10 2004 056 551.
  • a process for the production of paper, in particular tissue, with particularly high wet and / or dry strengths is known, in which one first admits to the paper a water-soluble cationic polymer that at least 1, 5 meq / g of polymer contains primary amino functionalities and has 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.
  • the older European application 14188666.3 relates to aqueous composition containing polymers having primary amino groups and / or amidine groups and 0.01 to 50 mol% of 1, 4-cyclohexanedione based on the primary amino groups and amidine groups of the polymers, as well as the use of the aqueous composition for the preparation of Paper and cardboard which has increased strength.
  • the present invention was based on a process for the production of paper and board as a task that allows a reduction in basis weight of the paper or cardboard with the same properties, in particular the same strength or leads to increased strength of the paper at the same basis weight. Accordingly, a process for the production of paper or paperboard comprising the separate addition of
  • Amino groups and amidine groups of the polymers are Amino groups and amidine groups of the polymers.
  • the present invention relates to the paper and the cardboard produced hereafter. It has been found that the separate addition of aqueous composition and water-soluble polymeric anionic compound according to the invention leads to the papermaking process for solidification of the paper.
  • An explanatory approach states that the composition leads to a crosslinking reaction of the primary amino groups and optionally present amidine groups of the polymers with the 1, 4-cyclohexanedione.
  • Such a crosslinking reaction would be a pH-dependent equilibrium which, when added to the pulp, which generally has a pH in the range of 7 to 8, is shifted towards the crosslinked structure. As the paper dries, the balance would shift to the right side. The equilibrium of the aqueous composition is shifted to the side of the starting materials in the acid, so that the composition is particularly stable in acidic form.
  • the total content of primary amino groups and amidine groups is to be understood as the sum of the molar fractions of these groups given in milliequivalent per gram of polymer (solid).
  • polymer having primary amino groups and / or amidine groups (solid) is mentioned, this is understood to mean the amount of polymer without counterions, taking into account potentially charge-carrying structural units in the charged form, ie, for example, amino groups in the protonated form and acid groups in the deprotonated form, counterions of the charged structural units such as Na, chloride, phosphate, formate, acetate, etc. are not taken into account
  • charge-carrying structural units in the charged form ie, for example, amino groups in the protonated form and acid groups in the deprotonated form
  • counterions of the charged structural units such as Na, chloride, phosphate, formate, acetate, etc.
  • aqueous compositions comprising polymers having primary amino groups and / or amidine groups having a total content of these groups of .alpha.1.5 meq / g of polymer and 0.01 to 50 mol% of 1,4-cyclohexanedione (b) based on the total amount primary amino groups and amidine groups of the polymers (solid) and ⁇ 50 wt .-% water based on the aqueous composition.
  • Particularly preferred are aqueous compositions containing 60 to 98 wt .-%, in particular 70 to 95 wt .-% water, based on the aqueous composition.
  • composition according to the invention has a pH of 6. It therefore has an acidic pH.
  • compositions have a pH in the range of 2 to 6.
  • the polymers having primary amino groups and / or amidine groups are polymers having primary amino groups and optionally amidine groups. They usually have average molecular weights M w (determined by means of static light scattering) in the range from 10,000 to 10,000,000 daltons, preferably in the range from 20,000 to 5,000,000 daltons, more preferably in the range from 40,000 to 3,000,000 daltons on. Very particularly preferred is an upper limit of the average molecular weight of 2,000,000 Dalton.
  • the average molecular weight M w is understood here and below as the weight-average molecular weight.
  • Polymers with primary amino groups and / or amidine groups are cationizable by addition of protons and therefore have a cationic charge in aqueous solution at pH 7.
  • the polymers having primary amino groups and / or amidine groups may also be amphoteric, as long as they have a total cationic charge.
  • the content of cationic groups in the polymer should be at least 5 mol%, preferably at least 10 mol%, above the content of anionic groups.
  • Polymers having primary amino groups and / or amidine groups are known, cf. the DE 35 06 832 A1 and DE 10 2004 056 551 A1 referred to in the prior art.
  • copolymers encompasses polymers of two monomers as well as of more than two monomers, for example terpolymers, where the term below refers to a copolymer which is obtainable by "polymerizing" with a subsequent list of monomers understand that the monomer composition comprises these monomers as the main ingredient.
  • the monomer composition Preferably exists the monomer composition to at least 95 wt .-%, in particular to 100 wt .-%, of these monomers.
  • the polymers are selected with primary amino groups and / or amidine groups from the group of polymer classes consisting of:
  • (G) polymers containing ethyleneimine units The polymers having primary amino groups and / or amidine groups from the group of polymer classes consisting of:
  • N-vinylcarboxamide Partially and fully hydrolyzed homopolymers of N-vinylcarboxamide are obtainable by polymerizing at least one N-vinylcarboxamide of the formula
  • R 1 signifies H or C 1 to C 6 alkyl, preferably R 1 signifies H
  • R 1 signifies H
  • compounds (iii) which have at least two ethylenically unsaturated double bonds in the molecule, and subsequent partial or complete hydrolysis of the copolymerized into the polymer.
  • the hydrolysis of the carboxylic acid amide radicals of the copolymerized units of the monomers (I) converts the group -NH-CO-R 1 into the group -NH 2.
  • Hydrolyzed homopolymers of N-vinylcarboxamide are commonly referred to as polyvinylamines, which are characterized by their degree of hydrolysis.
  • the degree of hydrolysis of the polyvinylamines is equivalent to the molar percent total content of the primary amino groups and amidine groups of the polymers based on the N-vinylcarboxamide units originally present.
  • the degree of hydrolysis can be determined by analysis of the formic acid released in the hydrolysis. For example, the latter can be achieved enzymatically with the help of a test kit from Boehminger Mannheim.
  • the total content of primary amino groups and amidine groups of the partially / fully hydrolyzed vinylformamide homopolymers is determined in a manner known per se from the degree of hydrolysis determined by means of analysis and the ratio of amidine / primary determined by 13 C-NMR spectroscopy. Calculated amino group.
  • the molar composition of the structural units of the polymer present at the end of the reaction is determined on the basis of the amounts of monomers used, the particular degree of hydrolysis, the ratio of amidine to prim amino groups and optionally the proportion which has been reacted polymer-analogously , With the aid of the molar mass of the individual structural units, the molar fraction of primary amino groups and / or amidine units in meq, which is in 1 g of polymer, can be calculated therefrom.
  • Amidine groups can form as is well known in partially hydrolyzed homo- and copolymers of vinylformamide. In the case of adjacent amino and formamide groups, ring closure and hence amidine formation can occur. This results in a six-membered ring with amide structure.
  • amidine unit Since the amidine unit is in dynamic equilibrium with adjacent vinylamine and vinylformamide units and is also reactive with the 1,4-cyclohexanedione, they also contribute to the effectiveness in the inventive composition.
  • the determination of the degree of hydrolysis recorded in the same way the formation of primary amino groups as well as amidine units, since in both cases exactly one molecule of formic acid is released.
  • ester group is usually hydrolyzed to the alcohol under the hydrolysis conditions to form vinyl alcohol units. This also applies to the copolymers (C) and (D) described below.
  • R 1 H or C 1 -C 6 -alkyl
  • monomers selected from monoethylenically unsaturated sulphonic acids, monoethylenically unsaturated phosphonic acids, monounsaturated esters of phosphoric acid, monoethylenically unsaturated carboxylic acids having 3 to 8 C Atoms in the molecule and / or their alkali metal, alkaline earth metal or ammonium salts, and
  • R 1 H or Cr to C 6 -alkyl
  • (Iic) optionally one or more monomers selected from quaternized monoethylenically unsaturated monomers or protonatable secondary or tertiary
  • Examples of monomers of the formula I are N-vinylformamide, N-vinylacetamide, N-vinylpropionamide and N-vinylbutyramide.
  • the monomers of group (i) may be used alone or in admixture in the copolymerization with the monomers of the other groups.
  • Preferably used monomer of this group is N-vinylformamide. If N-vinylcarboxamides (i) are copolymerized together with (ii) at least one other monoethylenically unsaturated monomer and the copolymers then hydrolyzed to form amino groups, the copolymers (B), (C) and (D) are obtained.
  • “Further monomers (iia)” are to be understood as meaning monomers which do not fall under the monomers of the formula I. Furthermore, they are neutral (uncharged), meaning that they bear neither cationic nor anionic radicals, and are therefore unsaturated from the monomers of the groups (ov) and (iic) different.
  • Examples of neutral monomers of group (iia) are monoesters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with ⁇ -C3o-alkanols, C2-C3o-alkanediols, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and ⁇ , ⁇ -dialkyl derivatives, nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, esters of vinyl alcohol and allyl alcohol with C 1 -C 3 -monocarboxylic acids, N-vinyllactams, non-nitrogen-containing heterocycles having ⁇ , ⁇ -ethylenically unsaturated double bonds, Vinylaromatics, vinyl halides, vinylidene halides, C 2 -C 8 monoolefins and mixtures thereof.
  • Suitable representatives are e.g. Methyl (meth) acrylate (this notation symbolizes here as well as in the following text both “acrylates” and “methacrylates”), methyl methacrylate,
  • Suitable monomers of group (iia) 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 (iia) are acrylamide, methacrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (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 (iia) are nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids such as, for example, acrylonitrile and methacrylonitrile.
  • nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids such as, for example, acrylonitrile and methacrylonitrile.
  • amidine units cf.
  • EP-A 0 528 409 or DE-A 43 28 975 In the hydrolysis of these copolymers, 5-ring amidine units are formed in a secondary reaction by reacting vinylamine units with an adjacent nitrile group in the polymer.
  • 5-ring amidines also contribute to the reactivity with the 1,4-cyclohexanedione. Since exactly one molecule of formic acid is also formed in the formation of a 5-ring amidi- um, these are also included in the determination of the degree of hydrolysis and thus also in the calculation of the total proportion of primary amino groups and amidine groups.
  • Suitable monomers of the group (iia) are furthermore N-vinyllactams and derivatives thereof which, for. B. one or more Ci-C6-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 (iia) are ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, vinyl formate, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • Particularly preferred monomers of group (iia) are acrylonitrile and vinyl acetate.
  • the aforementioned monomers (iia) can be used individually or in the form of any desired mixtures. Typically, they are used in amounts of 1 to 90 mol%, preferably 10 to 80 mol% and particularly preferably 10 to 60 mol%, based on the total monomer composition.
  • suitable monoethylenically unsaturated monomers of group (ii) are also anionic monomers, which are referred to above as monomers (Ub). They may optionally be copolymerized with the neutral monomers (iia) and / or cationic monomers (iic) described above.
  • Anionic monomers are formed from monomers containing acidic groups by cleavage of protons.
  • anionic monomers of the group (c) are ethylenically unsaturated C3 to Ce carboxylic acids such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methyl enmalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • monomers of this group are monomers containing sulfo groups, such as vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid, allyl- and methallylsulfonic acid and styrenesulfonic acid, phosphono-containing monomers, such as vinylphosphonic acid and monoalkylphosphate groups.
  • 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.
  • sodium hydroxide solution sodium hydroxide solution
  • potassium hydroxide solution soda, potash
  • sodium bicarbonate sodium bicarbonate
  • magnesium oxide calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • Particularly preferred monomers of the group (a) are acrylic acid, methacrylic acid, vinylsulfonic acid, vinylphosphonic acid, and acrylamido-2-methylpropanesulfonic acid.
  • Cationic monomers contain basic groups and are cationizable either by quaternization cationic or by addition of protons.
  • Suitable cationic monomers (üc) which are copolymerizable are the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols, preferably C 2 -C 12 -aminoalcohols. These may be C 1 -C 12 monoalkylated or dialkylated on the amine nitrogen.
  • the acid component of these esters are z.
  • Preferred monomers are dialkylaminoethyl (meth) acrylamides, dialkylaminopropyl (meth) acrylamides, diallyldimethylammonium chloride, vinylimidazole, alkylvinylimidazoles, and the cationic monomers neutralized and / or quaternized with mineral acids.
  • esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols are 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, N, N-dimethylaminocyclohexyl (meth) acrylate.
  • dialkylated amides of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines examples include dialkylaminoethyl (meth) acrylamides, dialkylaminopropyl (meth) acrylamides, N- [2- (dimethylamino) ethyl] acrylamide, N- [2 - (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (di-) methylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [2- (diethylamino) ethyl] methacrylamide.
  • vinylimidazoles which may be mentioned are 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridine N-oxides and also betaine derivatives of these monomers.
  • Particularly preferred monomers of group (iic) are diallyldimethylammonium chloride (DADMAC).
  • DADMAC diallyldimethylammonium chloride
  • the cationic monomers may be completely or even partially neutralized or quaternized, e.g. each to 1 to 99%.
  • Quatem istsstoff for the cationic monomers is methyl chloride.
  • the quaternization of the monomers can also be carried out with dimethyl sulfate, diethyl sulfate or with other alkyl halides such as ethyl chloride or benzyl chloride.
  • 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, eg. B. triallylamine, methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, glycerol intriacrylate, pentaerythritol triallyl ether, ⁇ , ⁇ -divinylethyleneurea, tetraallylammonium chloride, at least two times with acrylic acid and / or methacrylic acid esterified polyalkylene glycols or polyols such as pentaerythritol, sorbitol and glucose.
  • Monomers of group (iii) act as crosslinkers.
  • the monomer DADMAC is not counted to this group but to the cationic monomers. 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% based on the total monomer composition.
  • All the literature known regulators can be used, eg.
  • sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecyl mercaptan and sodium hypophosphite, formic acid or Tribromchlormethan.
  • the preparation of the above-described polymers having primary amino groups and / or amine groups of the classes (A), (B), (C) and (D) 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. Example, an alcohol such as methanol, ethanol, n-propanol or isopropanol.
  • the hydrolysis of the copolymers can be carried out in the presence of acids or bases or else enzymatically.
  • the amino groups formed from the vinylcarboxylic acid amide units are present in salt form.
  • the remarks made there apply correspondingly to the preparation of the polymers to be used according to the invention with primary amino groups and / or amidine groups.
  • the polymers having primary amino groups and / or amidine groups 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.
  • R 1 denotes H or C 1 to C 6 -alkyl, 0 to 70 mol% of one or more further neutral monoethylenically unsaturated monomers (iia),
  • one or more monomers selected from monoethylenically unsaturated sulfonic acids, monoethylenically unsaturated phosphonic acids, monounsaturated esters of phosphoric acid, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms in the molecule and / or their alkali metal, alkaline earth metal or ammonium salts,
  • optionally compounds which have at least two ethylenically unsaturated double bonds in the molecule with the proviso that the sum of the proportions of the monomers (iia), (trans) and (iic) is in total 1 to 70 mol%, and subsequent partial or complete hydrolysis of the in the polymer polymerized units of the monomers (I) to form amino groups, wherein the content of amino groups in the copolymer by at least 5 mol% exceeds the content of polymerized acid groups of the monomers (ii, b).
  • such copolymers are preferred with a degree of hydrolysis ⁇ 30 mol%.
  • this monomer being selected from acrylonitrile, vinyl acetate, sodium acrylate, DADMAC, [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide and the available by reaction with methyl chloride
  • those having a degree of hydrolysis are preferably 30 mol%.
  • Very particular preference is given to partially or fully hydrolyzed copolymers of N-vinylcarboxamide with sodium acrylate, and a degree of hydrolysis of> 30 mol%.
  • polymer-analogously reacted polymers of polymers of class A ie polymer-analogously reacted polyvinylamines
  • Suitable polymer-analogous reactions are the reaction with Michael systems as described in WO2007 / 136756. Michael systems are compounds with an unsaturated double bond which are conjugated to an electron-withdrawing group. Suitable Michael systems fall under the general formula II
  • R 2 and R 3 independently of one another are H, alkyl, alkenyl, carbonyl, carboxyl or carboxamide and X 1 is an electron-withdrawing group or an amino group.
  • Examples thereof are known as Michael systems: acrylamide, N-alkylacrylamide, methacrylamide, ⁇ , ⁇ -dimethylacrylamide, N-alkylmethacrylamide, N- (2-methylpropanesulphonic acid acrylamide, N- (glycolic acid) acrylamide, N- [3- (propyl) trimethylammonium chloride] acrylamide, Acrylonitrile, methacrylonitrile, acrolein, methyl acrylate, alkyl acrylate, methyl methacrylate, alkyl methacrylate, aryl acrylate, aryl methacrylates, [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride, N- [3- (dimethylamino) propyl] meth
  • reaction products preferably contain structural units selected from the group of polymer units (III), (IV), (V), (VI) and (VII)
  • X- is an anion, preferably, chloride, bromide or iodide
  • Y is carbonyl or methylene or a single bond
  • R6 linear or branched Ci-Ci2-alkylene, which is optionally substituted with hydroxyl, preferably CH 2 CH (OH) CH 2 - or -Ethylen
  • R7 is hydrogen, linear or branched C 1 -C 22 -alkyl, preferably methyl or ethyl
  • Rs is hydrogen, linear or branched C 1 -C 22 -alkyl, linear or branched C 1 -C 22 -alkoxy, amino, linear or branched C 1 -C 2 -alkylamino, linear or branched C 1 -C 2 2-dialkylamino, preferably amino
  • Rg is linear or branched C 1 -C 12 -alkylene, preferably ethylene
  • R 10 is hydrogen, linear or branched C 1 -C 22 -alkyl, preferably methyl or ethyl
  • the reaction conditions for the reaction are described in WO2009 / 017781, the disclosure of which is expressly incorporated by reference.
  • Reaction products containing units of the formula III are obtainable by polymer-analogous reaction of the primary amino groups and / or amidine groups of the polyvinylamines (polymers A) with alkylating agents.
  • the alkylation can furthermore be carried out with alkyl glycidyl ethers, glycidol (2,3-epoxy-1-propanol) or chloropropanediol.
  • Preferred alkyl glycidyl ethers are butyl glycidyl ether, 2-ethylhexyl glycidyl ether, hexadecyl glycidyl ether and C12 / C14 glycidyl ether.
  • the reaction with alkyl glycidyl ethers is generally carried out in water, but can also be carried out in aqueous / organic solvent mixtures.
  • reaction products of structures IV and VI may include anionic groups according to the definitions of substituents below.
  • the content of cationic groups of the reaction products must be at least 5 mol%, above the content of anionic groups of the reaction products.
  • Such acylating agents are selected from succinic anhydride, substituted succinic anhydrides substituted by linear or cross-linked C 1 -C 18 -alkyl or linear or cross-linked C 1 -C 18 -alkenyl, maleic anhydride, glurar anhydride, 3-methylglutaric anhydride.
  • 2,2-dimethylsuccinic anhydride 2,2-dimethylsuccinic anhydride, cyclic alkylcarboxylic anhydrides, cyclic alkenylcarboxylic anhydrides, alkenylsuccinic anhydrides (ASA), chloroacetic acid, salts of chloroacetic acid, bromoacetic acid, salts of bromoacetic acid, halogen-substituted alkanoic acid acrylamides and halogen-substituted alkenyl acrylamides.
  • ASA alkenylsuccinic anhydrides
  • alkylating agents are selected from 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2- (diethylamino) ethyl chloride hydrochlorides, (dialkylamino) alkyl chlorides such as 2- (dimethylamino) ethyl chloride, 3-chloro-2-hydroxypropylalkyl-dimethylammonium chlorides such as 3-chloro 2-hydroxypropyl lauryldimethyl ammonium chloride, 3-chloro-2-hydroxypropyl cocoalkyl dimethyl ammonium chloride, 3-chloro-2-hydroxypropyl stearyldimethyl ammonium chloride, (haloalkyl) trimethyl ammonium chlorides such as (4-chlorobutyl) trimethyl ammonium chloride, (6-chlorohexyl) trimethyl ammonium chloride, (8- Chloroctyl) trimethylammonium chloride and glycidylpropyl) trimethylammonium chlorides
  • suitable polymers having primary amino groups are the reaction products obtained by Hofmann degradation of homopolymers or copolymers of acrylamide or methacrylamide in an aqueous medium 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 available.
  • Such polymers are for example from EP-A 0 377 313 and WO 2006/0751 5 known.
  • the preparation of polymers containing vinylamine groups is discussed in detail, for example, in WO 2006/075115, page 4, line 25 to page 10, line 22 and in the examples on pages 13 and 14.
  • the polymer content without counterion and the content of the amino groups of this type of polymers is determined in a manner known per se by means of polyelectrolyte titration and NMR measurements.
  • 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.
  • comonomers are dimethyldiallylammonium salts, acrylamidopropyltrimethylammonium chloride and / or methacrylamidopropyltrimethylammonium chloride, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, vinyl acetate and acrylic and methacrylic acid esters.
  • Comonomers are also optionally anionic monomers such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid, acrylamidomethylpropanesulfonic acid, methylallyl sulfonic acid and vinylsulfonic acid and the alkali metal, Erdalkylimetall- and ammonium salts of said acidic monomers into consideration.
  • 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 which contain at least two double bonds in the molecule such as triallylamine, methylenebisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triallylamine and Trimethyloltrimethacry-Iat. 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. For example, the concentration of the degradation product containing vinylamine units is more than
  • aqueous polymer solutions can be concentrated, for example, by means of ultrafiltration.
  • ethyleneimine units-containing polymers typically have a mixture of primary, secondary and tertiary amino groups. The content of the amino groups and their distribution to primary, secondary and tertiary ethyleneimine units containing polymers is determined in a conventional manner by NMR.
  • 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. For example, all multifunctional compounds containing groups reactive with primary amino groups, e.g.
  • multifunctional epoxides such as bisglycol ethers of oligo- or polyethyleneoxides or other multifunctional alcohols such as glycerol or sugars, polyfunctional carboxylic acid esters, mucin-functional isocyanates, polyfunctional acrylic or methacrylic acid esters, polyfunctional 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, divinylsulfone, maleic anhydride or ⁇ -halocarboxylic acid chlorides, multifunctional haloalkanes, in particular ⁇ , ⁇ -dichloroalkanes.
  • Further crosslinkers are described in WO 97/25367, pages 8 to 16.
  • polymers containing ethyleneimine units are known from EP-A-041 1400,
  • the primary amine content is usually 10 to 40 mol% in the described ethyleneimine polymers.
  • alkoxylated polyethyleneimines Polymers which are obtained by first condensing at least one polycarboxylic acid with at least one polyamine to form polyamidoamines, then grafting with ethyleneimine and then crosslinking the reaction products with one of the abovementioned compounds belong to the compounds preferably containing ethyleneimine units.
  • a process for preparing such compounds is described, for example, in DE-A-2434816, where ⁇ , ⁇ -chlorohydrin ethers of oligo- or polyethylene oxides are used as crosslinkers.
  • Reaction products of polyethyleneimines with monobasic carboxylic acids to amidated polyethyleneimines are known from WO 94/12560.
  • Michael addition products of polyethyleneimines to ethylenically unsaturated acids, salts, esters, amides or nitriles of mono- ethylenically unsaturated carboxylic acids are the subject of WO 94/14873.
  • Phosphonomethylated polyethyleneimines are described in detail in WO 97/25367.
  • Carboxylated polyethyleneimines are obtainable, for example, by means of a stretching synthesis by reacting polyethyleneimines with formaldehyde and ammonia / hydrogen cyanide and hydrolysing the reaction products.
  • Alkoxylated polyethyleneimines can be prepared by reacting polyethylenimines 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 polymers having primary amino groups and / or amidine 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 can be obtained by free-radically polymerizing, for example, N-vinylformamide in an aqueous medium in the presence of at least one of the cited graft bases together with copolymerizable other monomers and subsequently hydrolyzing the grafted vinylformamide units in a known manner.
  • Such graft polymers are described, for example, in DE-A-19515943, DE-A-4127733, DE-A-100412 1.
  • aqueous composition according to the invention is prepared by combining the individual components.
  • the aqueous solution of the polymer having primary amino groups and / or amidine groups is prepared, adjusted to a pH of -6, at which the crosslinking occurs to an insignificant extent, and the 1,4-cyclohexanedione is present as Solid substance too.
  • the addition of the 1, 4-cyclohexanedione can also be carried out as an aqueous solution.
  • the preparation of the mixture is preferably carried out at room temperature, but may optionally also be carried out at reduced temperatures to 0 ° C. Likewise, the preparation of the mixture can also be carried out at elevated temperature up to 100 ° C. Preferably, the addition is at room temperature.
  • all commercially available mixing units can be used, which can handle the viscosities of the polymer solutions.
  • the mixing process should be carried out at least until a homogeneous aqueous composition is present. If 1, 4-cyclohexadione was used as a solid, the mixing process should be continued until the 1, 4-Cyclolhexadion has completely dissolved. It is beneficial to stir for at least one hour, but is not mandatory. It is also possible to mix 1, 4-cyclohexanedione as an aqueous solution in line in the solution of the polymer having primary amino groups and / or amidine groups.
  • the aqueous composition contains polymers having primary amino groups and / or amidine groups with a total content of these groups of -.1.5 meq / g of polymer (milliequivalent / gram of polymer).
  • the aqueous composition according to the invention preferably contains
  • aqueous composition according to the invention consisting of at least 95% by weight, in particular consisting of 100% by weight,
  • the water-soluble polymeric anionic compounds include all polymers which carry acid groups or their salts and have an anionic charge density of> 0.1 meq / g (at pH 7).
  • the acid groups may be carboxyl groups, sulfonic acid groups and phosphonic acid groups. Also esters of phosphoric acid belong to this, wherein at least one acid function of the phosphoric acid is not esterified.
  • polymers which have been modified by polymer-analogous reactions such as Strecker reaction or by phosphonomethylation with acidic groups.
  • polymers are preferably obtainable by polymerization of:
  • 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.
  • Suitable monomers (1.1) are also mono- and diesters of phosphoric acid with alcohols having a polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and mono- and diamides of phosphoric acid with amines having a polymerizable compound , ⁇ , ⁇ -ethylenically unsaturated double bond.
  • 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 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 also their isomers ,
  • the aforementioned monomers (1.1) may be used alone or in the form of any mixtures in the preparation of the water-soluble polymeric anionic compound.
  • 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 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, mesa-carboxylic acid, citraconic acid, glutaconic acid, aconitic acid, methyl enmalonic 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 polymeric anionic compound contains at least one monomer selected from the group (1) 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 C1-C30-alkanols, C2-C3o-alkanediols and C2-C3o-aminoalcohols, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl- and ⁇ , ⁇ -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-vinyllactams, non-nitrogen-containing heterocycles having ⁇ , ⁇ -ethylenically unsaturated double bonds, vinylaromatics, Vinylar
  • Suitable representatives of group (2) are e.g. Methyl (meth) acrylate, methyl methacrylate,
  • Such monomers of group (2) 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 additional monomers of group (2) are furthermore N-vinylformamide, N-vinylacetamide, N-methyl, N-vinylacetamide, N-vinylpropionamide and N-vinylbutyramide, acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (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 (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 Ci-C6-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
  • the amounts used are up to 2 mol%, z. B. 0.001 to 1 mol%.
  • regulators in the polymerization.
  • Homopolymers of ethylenically unsaturated C.sub.3- to C.sub.-carboxylic acids in particular polyacrylic acid and polymethacrylic acid, and hydrolyzed homopolymers of maleic anhydride and of itaconic anhydride are preferably used as the water-soluble polymeric anionic compound.
  • a polymeric anionic compound which is a copolymer of acrylic acid with at least one monomer selected from vinylformamide, vinyl acetate, acrylonitrile and acrylamide.
  • the polymeric anionic compounds are water-soluble.
  • Water-soluble in the sense of the inventions are polymers which can be dissolved in water at least in a concentration of 0.1 wt .-% at 25 ° C and atmospheric pressure. 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).
  • paper is to be understood as meaning a weight per unit area of 7 g / m 2 to 225 g / m 2 and, under paperboard, a basis weight of more than 225 g / m 2 .
  • paper stock also referred to as pulp
  • pulp is understood below to mean a mixture of substances suspended in water and consisting of one or more types of processed fibers and of various auxiliaries, prior to sheet formation.
  • the paper stock thus additionally contains the composition according to the invention, optionally filler and optionally paper auxiliaries. If it is a reference to dry paper stock, the total paper stock of pulp, cationic composition used according to the invention, anionic polymeric compound, optionally filler and optionally paper auxiliaries without water to understand (pulp solid).
  • Suitable fillers are all pigments customarily used in the paper industry on the basis of metal oxides, silicates and / or carbonates, in particular of pigments from the group consisting of calcium carbonate used in the form of ground (GCC) lime, chalk, marble or precipitated calcium carbonate (PCC) talc, kaolin, bentonite, satin white, calcium sulfate, barium sulfate and titanium dioxide. It is also possible to use mixtures of two or more pigments.
  • the inventive method is used to produce paper and cardboard comprising dewatering a filler-containing paper stock.
  • the filler content of the paper or the cardboard can be 5 to 40 wt .-% based on the paper or cardboard.
  • a process for producing paper whose filler content is 20 to 30% by weight is preferred.
  • Such papers are, for example, wood-free papers.
  • a method for the production of paper is preferred whose filler content is 5 to 20 wt .-%.
  • Such papers are used primarily as packaging papers.
  • a process for the production of paper is preferred whose filler content is 5 to 15 wt .-%. Such papers are used primarily for newspaper printing. According to another preferred embodiment, preference is given to a process for producing paper whose filler content is from 25 to 40% by weight, for example SC papers. Particularly preferred is a process for the production of testliners and fluting and of wood-free papers.
  • native and / or recovered fibers can be used as the fibrous material.
  • All types of coniferous and deciduous woods commonly used in the paper industry can be used, for example.
  • 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).
  • pulp for example, sulphate, sulphite and soda pulps come into consideration.
  • unbleached pulp also referred to as unbleached kraft pulp, is used.
  • Waste paper may also be used to make the pulps, either alone or blended with other pulps.
  • the waste paper can come from a deinking process. However, it is not necessary for the waste paper to be used to undergo such a process. Furthermore, it is also possible to start from fiber blends of a primary material and recycled coated broke.
  • a pulp having a freeness of 20 to 30 SR can be used.
  • a pulp with a freeness of about 30 SR is used, which is ground during the production of the pulp.
  • pulp is used which has a freeness of -30 ° SR.
  • the aqueous composition is metered into the paper stock.
  • the addition of the aqueous composition can be made into a thick material (fiber concentration> 15 g / l, for example in the range of 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 water-soluble polymeric anionic compound is usually added to the paper stock only after the addition of the aqueous composition, but can also be metered into the stock at the same time but separately from the aqueous composition. Further, it is also possible to first add the water-soluble polymeric anionic compound and subsequently the aqueous composition.
  • the aqueous composition is added to the stock at a time prior to the addition of the filler.
  • the aqueous composition is preferably added in an amount of from 0.01 to 6% by weight of the polymer having primary amino groups and / or amidine groups (solid) based on pulp (solid).
  • the aqueous composition is used in a ratio to the pulp, which is 0.05 to 5 wt .-% of the polymer having primary amino groups and / or amidine (solids) based on the pulp (solid).
  • the water-soluble polymeric anionic compound is in the process according to the invention in an amount of for example 0.01 to 6.0 wt .-%, preferably 0.05 to 1, 0 wt .-%, in particular 0.1 to 0.5 wt. -%, based on dry pulp, used.
  • the weight ratio of polymers having primary amino groups and / or amidine groups (solid) to the water-soluble polymeric anionic compounds is for example 4: 1 to 1: 1 and is preferably 2: 1 to 1: 1.
  • the dry content of the paper and pulp is the ratio of the mass of a sample which has been dried at a temperature of (105 ⁇ 2) ° C under defined conditions to a constant mass to the mass of the sample before drying.
  • the dry content is usually expressed as mass fractions in percent.
  • the determination of the dry content is carried out according to DIN EN ISO 638 DE with the oven cabinet method. From the dry content of the pulp, the amount of pulp (solid) can be determined.
  • Typical application rates of the aqueous composition are, based on the polymer, for example 0.2 to 120 kg, preferably 0.3 to 100 kg, in particular 0.5 to 50 kg at least of the polymer having primary amino groups and / or amidine groups, per ton of a dry pulp.
  • the amounts used of the aqueous composition according to the invention with respect to the polymer having primary amino groups and / or amidine groups are particularly preferably 0.4 to 3 kg, preferably 0.6 to 3 kg polymer (solid), per ton of dry pulp.
  • the exposure time of the aqueous composition according to the invention to a pure pulp or pulp after metering to sheet formation is, for example, 0.5 seconds to 2 hours, preferably 1.0 seconds to 15 minutes, more preferably 2 to 20 seconds.
  • fillers having an average particle size (volume average) ä10 pm preferably from 0.3 to 5 pm, in particular from to 0.5 to 2 pm used.
  • the determination of the average particle size (volume average) of the fillers and of the particles of the powder composition is carried out in the context of this document generally by the method of quasi-elastic light scattering (DIN-ISO 13320-1), for example with a Mastersizer 2000 from. Malvern Instruments Ltd.
  • the filler is preferably metered after the addition of the aqueous composition according to the invention. In this case, according to a preferred embodiment, the addition takes place in the stage in which the pulp is already present as a thin material, ie at a pulp concentration of 5 to 15 g / l.
  • the filler is metered both in the thin and in the thick matter, wherein the ratio of the two addition amounts (addition of thick material / addition of thin material) is preferably from 5/1 to 1/5.
  • customary paper auxiliaries can optionally be mixed with the paper stock, generally at a pulp concentration of 5 to 15 g / l.
  • Conventional paper auxiliaries are, for example, sizing agents, wet strength agents, cationic or anionic retention aids based on synthetic polymers, and dual systems, dehydrating agents, other dry strength agents, optical brighteners, defoamers, biocides and paper dyes. These conventional paper additives can be used in the usual amounts.
  • the sizing agents to be mentioned are alkylketene dimers (AKD), alkenylsuccinic anhydrides (ASA) and rosin size.
  • Suitable retention agents are, for example, cationic polyacrylamides, cationic starch, cationic polyethylenimine or cationic polyvinylamine.
  • retention aids of this kind, which can be added to the thin material, for example.
  • Microparticular systems are used to further improve retention. Typical microparticular systems are based on silica sols, bentonites and mixtures as well as on anionic cross-linked microparticles.
  • Dry strength agents are synthetic dry strength agents such as polyvinylamine, polyethylene enimine, glyoxylated polyacrylamide (PAM), or natural dry strength agents such as starches based on derivatized starches (cationic) or natural starches which are oxidatively or enzymatically degraded.
  • synthetic dry strength agents are recommended, which can preferably be added to the thick stock but also to the thin stock.
  • the papers obtained with the aqueous composition according to the invention show very good performance properties.
  • the addition of the aqueous composition of the invention results in excellent strengths, especially dry strength.
  • the use of less expensive fibers is possible (eg increase of the waste paper content in semi-kraft pulp or increase of the chemo-thermal Pulps in folding box cartons or food cartons), increasing the proportion of filler in packaging papers and graphic papers.
  • aqueous compositions containing, as polymer having primary amino groups and / or amidine groups, a hydrolyzed homopolymer of N-vinylcarboxamide, preferably having a degree of hydrolysis of 30 mol%, for the preparation of testliners.
  • aqueous compositions containing a polymer having primary amino groups and / or amidine groups are selected from hydrolyzed copolymers of N-vinylcarboxamide and other neutral monoethylenically unsaturated monomers, hydrolyzed copolymers of N-vinylcarboxamide and anionic monoethylenically unsaturated monomers, hydrolyzed copolymers of N-Vinylcarbonklareamid and cationic monoethylenically unsaturated monomers, used for the production of wood-free papers.
  • aqueous compositions comprising as polymer having primary amino groups and / or amidine groups a partially or fully hydrolyzed copolymers of N-vinylcarboxamide with further neutral, anionic and / or cationic monoethylenically unsaturated monomers, this monomer being selected from acrylonitrile, vinyl acetate, sodium acrylate , Diallyldimethylammonium chloride, [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, [3- (trimethylammonium) propyl] acrylamido chloride and N- [3- (trimethylammonium) propyl] methacrylamide chloride, for the preparation of used wood-free papers.
  • DADMAC diallyldimethylammonium chloride
  • PVFA polyvinylformamide
  • Copo VFA / NaAS Copolymer of vinylformamide and sodium acrylate
  • Copo VFA / VAc copolymer of vinylformamide and vinylacetate
  • Copo VFA / AN / Na-itaconate Copolymer of vinylformamide, acrylonitrile, sodium itaconate
  • Copo VFA / NaAS / AN Copolymer of vinylformamide, sodium acrylate and acrylonitrile
  • Copo VFA / DADMAC Copolymer of vinylformamide and DADMAC
  • the K values were measured according to H. Fikentscher, Cellulose Chemistry, Vol. 13, 48-64 and 71-74 under the particular conditions indicated.
  • the figures in parenthesis indicate the concentration of the polymer solution and the solvent.
  • Solid contents of the polymers were determined by distributing 0.5 to 1.5 g of the polymer solution in a 4 cm diameter tin cover and then drying in a circulating air drying cabinet at 140 ° C. for two hours. The ratio of the mass of the sample after drying under the above conditions to the mass during sampling gives the solids content of the polymer.
  • Example P1 VFA homopolymer, K value 45
  • Feed 1 was 423.1 g of N-vinylformamide (BASF)
  • a 2 l glass apparatus with anchor stirrer, descending condenser, internal thermometer and nitrogen inlet tube was charged with 585.2 g of water and 4.6 g of 75% strength by weight phosphoric acid.
  • At a speed of 100 rpm about 8.2 g of a 25 wt .-% sodium hydroxide solution was added, so that a pH of 6.6 was reached.
  • the initial charge was heated to 80 ° C. and the pressure in the apparatus was reduced to such an extent that the reaction mixture began to boil at 80 ° C. (about 460 mbar). Feeds 1 and 2 were then started simultaneously and dosed synchronously at a constant 80 ° C. over a period of 3 hours.
  • reaction mixture was postpolymerized at 80 ° C for three more hours. During the entire polymerization and postpolymerization about 100 g of water were distilled off. Subsequently, the batch was cooled to room temperature under normal pressure. A slightly yellow, viscous solution with a solids content of 36.4% by weight was obtained. The K value of the polymer was 45 (1.0% by weight in water).
  • Feed 1 provided 234 g of N-vinylformamide.
  • reaction mixture was postpolymerized for three more hours at 73 ° C. During the entire polymerization and postpolymerization about 190 g of water were distilled off. Subsequently, the batch was cooled to room temperature under normal pressure.
  • Feed 1 was a mixture of 293.7 g of water, 242.96 g of aqueous 32% by weight Na acrylate solution adjusted to pH 6.4, and 237.2 g of N-vinylformamide.
  • the feed 2, 4 g of 2,2-azobis (2-methylpropionamidine) dihydrochloride were dissolved in 203.6 of water at room temperature for 1 '.
  • a 2 l glass apparatus with anchor stirrer, descending condenser, internal thermometer and nitrogen inlet tube was charged with 659.4 g of water and 3.5 g of 75% strength by weight phosphoric acid.
  • 6.0 g of a 25 wt .-% sodium hydroxide solution was added, so that a pH of 6.6 was reached.
  • the original was heated to 80 ° C and reduced the pressure in the apparatus to about 460 mbar, so that the reaction mixture at 80 ° C just began to boil.
  • feeds 1 and 2 were started simultaneously. At constant 80 ° C, the feed 1 was added in two hours and the feed 2 in 2.5 hours.
  • reaction mixture was re-polymerized at 80 ° C. for a further 2.5 hours. During the entire polymerization and postpolymerization about 170 g of water were distilled off. Subsequently, the batch was cooled to room temperature under normal pressure.
  • feed 1 a mixture of 147.3 g of water, 317.6 g of aqueous 32% by weight Na acrylate solution pH adjusted to pH 6.4 and 181.0 g of N-vinylformamide.
  • the feed 1 was added in two hours and the feed 2 in 2.5 hours. After completion of the addition of feed 2, the reaction mixture was re-polymerized at 80 ° C. for a further 2.5 hours. During the entire polymerization and postpolymerization about 70 g of water were distilled off. Subsequently, the batch was cooled to room temperature under normal pressure.
  • feed 1 a mixture of 340.0 g of water, 176.5 g of 32% aqueous Na acrylate solution adjusted to pH 6.4 and 100.6 g of N-vinylformamide were provided.
  • feed 2 5.8 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were dissolved in 164.2 g of water at room temperature.
  • the feed 3 was added in 5 minutes and further polymerized at 80 ° C. for a further two hours. During the entire polymerization and postpolymerization, about 100 g of water were distilled off. Subsequently, the batch was cooled to room temperature under normal pressure.
  • the K value of the copolymer was 85 (determined 0.5 wt .-% in 5gew .-% aqueous NaCl)
  • Feed 1 was a mixture of 100.0 g of water, 224.6 g of aqueous 32 wt .-% sodium acrylate solution, which was adjusted to pH 6.4, and 128.0 g of N-vinylformamide provided as feed 2 azobis (2-methylpropionamidine) dihydrochloride was added 0.9 g of 2,2 'dissolved in 125.8 g of water at room temperature.
  • the reaction mixture was postpolymerized for a further 2.5 hours at 80.degree. During the entire polymerization and postpolymerization, about 143 g of water were distilled off. Subsequently, the batch was cooled to room temperature under normal pressure. Obtained was a yellow, viscous solution with a solids content of 23.8 wt .-%.
  • the K value of the copolymer was 90 (0.5% by weight in 5% strength by weight aqueous NaCl solution).
  • Feed 1 was a mixture of 330 g of water, 217.8 g of aqueous 32% by weight Na acrylate solution adjusted to pH 6.4, and 124.2 g of N-vinylformamide.
  • feed 2 0.3 g of 2,2-azobis (2-methylpropionamidine) dihydrochloride were 'dissolved in 66.8 g of water at room temperature.
  • a 2 l glass apparatus with anchor stirrer, descending condenser, internal thermometer and nitrogen inlet tube was charged with 668.3 g of water and 1.9 g of 75% strength by weight phosphoric acid.
  • 3.1 g of a 25 wt .-% sodium hydroxide solution was added, so that a pH of 6.6 was reached.
  • the original was heated to 73 ° C and the pressure in the apparatus reduced to about 340 mbar, so that the reaction mixture at 73 ° C just began to boil.
  • feeds 1 and 2 were started simultaneously. At constant 73 ° C, the feed 1 was added in two hours and the feed 2 in 3 hours.
  • the reaction mixture was postpolymerized for a further 2 hours at 73.degree. Then, the feed 3 was added in 5 minutes and further polymerized at 73 ° C. for a further two hours. During the entire polymerization and postpolymerization about 190 g of water were distilled off. Subsequently, the batch was cooled to room temperature under normal pressure.
  • Feed 1 was a mixture of 423.5 g of aqueous 32% by weight Na-acrylate solution adjusted to pH 6.4 and 155.1 g of N-vinylformamide
  • the reaction mixture was postpolymerized for a further 2.5 hours at 80.degree. During the entire polymerization and postpolymerization about 200 g of water were distilled off. Subsequently, the batch was cooled to room temperature under normal pressure. This gave a slightly yellow, viscous solution with a solids content of 25.0 wt .-%.
  • the K value of the copolymer was 92 (0.5% strength by weight in 5% strength by weight aqueous NaCl solution).
  • Feed 1 provided 76.5 g of vinyl acetate As feed 2 0.4 g of 2,2-azobis (2-methylpropionamidine) dihydrochloride were 'dissolved in 98.2 g of water at room temperature.
  • feed 1 was added in 5 minutes and then the feed 2 in 5 h. 1, 0 h after the start of feed 2, feed 4 is additionally started and added in 2.5 hours.
  • polymerization was continued at 65 ° C. for one hour, then feed 3 was added in 5 minutes, and the reaction mixture was heated to 70 ° C. At this temperature, polymerization was continued for a further 2 hours. Thereafter, the reflux condenser is replaced by a descending radiator.
  • the pressure in the apparatus was lowered to 580 mbar and distilled off at 80 ° C about 68 g of water. At atmospheric pressure, the product was cooled to room temperature.
  • Feed 1 provided 100.1 g of vinyl acetate
  • feed 1 was added in 5 min and then the feed 2 in 5 hours. 1.5 hours after the start of feed 2, feed 4 is additionally started and added in 2.5 hours.
  • polymerization was continued at 65 ° C. for 1 hour, then feed 3 was added in 5 minutes and the reaction mixture was heated to 70 ° C. At this temperature, polymerization was continued for a further two hours.
  • the reflux cooler is replaced by a descending cooler. The pressure in the apparatus was lowered to 540 mbar and distilled off at 80 ° C about 102 g of water. At atmospheric pressure, the product was cooled to room temperature.
  • a finely divided, white suspension having a solids content of 15.7% by weight was obtained.
  • the K value of the copolymer was 74 (0.5% by weight in formamide))
  • Feed 1 was 127.3 g of vinyl acetate
  • feed 1 was added in 5 minutes and then the feed 2 in 5 hours. 2h after the start of feed 2, feed 4 was additionally started and added in 2.5 hours. After the end of feed 2, polymerization was continued at 65 ° C. for one hour, then feed 3 was added in 5 minutes, and the reaction mixture was heated to 70 ° C. At this temperature, polymerization was continued for a further two hours. Thereafter, the reflux condenser is replaced by a descending radiator. The pressure in the apparatus was lowered to 540 mbar and distilled off at 80 ° C about 200 g of water. The vacuum was broken and the product cooled to room temperature.
  • a finely divided, white suspension having a solids content of 16.5% by weight was obtained.
  • the K value of the copolymer was 68 (0.5% by weight in formamide))
  • Feed 1 provided 221.3 g of acrylonitrile
  • feeds 1 to 3 were started simultaneously. At constant 60 ° C, the feed 1 in 3.5 hours, the feed 2 in three hours and the feed 3 in 4 hours were added. Then, the reaction mixture was postpolymerized at 60 ° C for a further 2.5 hours.
  • feed 1 342.7 g of a 32% strength by weight aqueous Na acrylate solution were provided.
  • feed 2 139.5 g of N-vinylformamide were provided
  • Feed 3 provided 41.2 g of acrylonitrile
  • Nitrogen was introduced into the receiver at 10 l / h for half an hour to remove the oxygen present. Meanwhile, the original was heated to 66 ° C. In the apparatus, the pressure was reduced to about 240 mbar, so that the reaction mixture at 66 ° C just boil began. Then feeds 1 and 2 were started simultaneously. At constant 66 ° C, the feed 1 was added in two hours and the feed 2 in 4 hours. After completion of the addition of feed 2, the reaction mixture was postpolymerized for a further hour at 66 ° C. Then, the pressure was increased to 360 mbar and the internal temperature to 75 ° C and then the mixture was further post-polymerized at 74 ° C for two hours. Under these conditions, the reaction mixture was still boiling.
  • the required amount of acid was chosen in such a way that the sodium ita conate units contained in the polymer were additionally protonated.
  • the degree of hydrolysis is the proportion in mol% of the hydrolyzed VFA units based on the VFA units originally present in the polymer.
  • the degree of hydrolysis of the hydrolyzed homopolymers or copolymers of N-vinylformamide was determined by enzymatic analysis of the formic acid / formates released during the hydrolysis (test set from Boehringer Mannheim).
  • the polymer content without counter-ions indicates the content of polymer in the aqueous solution in% by weight, counterions being ignored. It represents the sum of the parts by weight of all the structural units of the polymer in g which are present in 100 g of the solution. He is determined by calculation. In this case, potentially charge-carrying structural units in the charged form are included, ie, for example, amino groups in the protonated form and acid groups in the deprotonated form. Counter ions of the charged structural units such as Na, chloride, phosphate, formate, acetate, etc. are not considered.
  • the calculation can be carried out by determining the molar amounts of the structural units of the polymer present at the end of the reaction for an approach starting from the amounts of monomers used, the degree of hydrolysis and, if appropriate, the amount of polymer analog, and using the molar masses of the polymer Structural units are converted into the weight fractions.
  • the sum of the parts by weight gives the total amount of the polymer in this approach.
  • the polymer content without Jacobion results from the ratio of the total amount of polymer to the total mass of the approach.
  • the total content of primary amino groups and amidine groups can be carried out analogously to the procedure described above for the polymer content.
  • 250.0 g of the polymer solution obtained according to P1 were mixed in a 500 ml four-necked flask with paddle stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm with 6.4 g of a 40% strength by weight aqueous sodium bisulphite solution and then at 80.degree ° C heated. Then 147.8 g of a 25 wt .-% aqueous sodium hydroxide solution were added. The mixture was kept at 80 ° C for three hours. The resulting product was cooled to room temperature and adjusted to pH 2.0 with 163.1 g of 37% strength by weight hydrochloric acid. A slightly yellow polymer solution was obtained. The degree of hydrolysis of the vinylformamide units was 70 mol%.
  • 250.0 g of the polymer solution obtained according to P3 were mixed in a 500 ml four-necked flask with paddle stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm with 2.3 g of a 40% strength by weight aqueous sodium bisulfite solution and then to 80 ° C heated. Then, 34.7 g of a 25 wt .-% aqueous sodium hydroxide solution was added. The mixture was kept at 80 ° C for three hours. The resulting product was cooled to room temperature and adjusted to pH 3.0 with 31.7 g of 37% strength by weight hydrochloric acid. A slightly yellow polymer solution was obtained. The degree of hydrolysis of the vinylformamide units was 48 mol%.
  • 600.0 g of the polymer solution obtained according to P6 were mixed in a 21 four-necked flask with paddle stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm with 4.5 g of a 40% strength by weight aqueous sodium bisulphite solution and then heated to 80.degree , Then, 150.0 g of a 25% aqueous sodium hydroxide solution was added. The mixture was kept at 80 ° C for 7 hours. The resulting product was cooled to room temperature.
  • 200.0 g of the polymer solution obtained according to P12 were in a 500 ml four-necked flask with paddle stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm with 1, 1 g of a 40 wt .-% aqueous sodium bisulfite solution and then to 80 ° C heated. Then, 72.8 g of a 25 wt .-% sodium hydroxide solution was added. The mixture was held at 80 ° C for three hours, during which the suspension went into solution. The resulting product was cooled to room temperature.
  • the conversion of the subsequent reactions was determined by determining the residual content of the reagent in the final product.
  • the methods used are given in the examples.
  • the viscous solution obtained had a residual content of acrylamide of 20 ppm (HPLC) and had a polymer content without Gegenion of 5.4 wt .-%.
  • the viscous solution obtained had a residual content of acrylamide (HPLC) of 40 ppm and had a polymer content without counterion of 13.3 wt .-%.
  • the polymer used was identical to the Hofmann degradation product designated in WO 2006/0751 15 on page 13 in the table as C8 beta 2. It was prepared by reacting polyacrylamide with sodium hypochlorite in the molar ratio 1: 1, and sodium hydroxide, wherein the molar ratio of sodium hydroxide to sodium hypochlorite 2: 1.
  • the polymer content without Jacobion was 4.5% and the content of primary amino groups 9.8 meq / g.
  • the water-soluble polymeric anionic compound A has the following monomer composition: 70 mole% acrylamide and 30 mole% acrylic acid. Furthermore, it has an M w of 800 000 g / mol and has an anionic charge density of - 3.8 meq / g.
  • Retention agent Percol 540 (polyacrylamide emulsion having a solids content of 43% of a cationic charge density of 1.7 mmol / 100 g and a K value of 240).
  • Pretreatment of the pulp :
  • a paper stock made of 100% waste paper (mixture of varieties: 1.02, 1.04, 4.01) was pitched with drinking water at a consistency of 4 wt .-% in a pulper speck-free and ground in a refiner to a freeness of 40 ° SR. This substance was then diluted with drinking water to a consistency of 0.8% by weight.
  • the aqueous compositions of Examples EF1-EF44 given in Table 4 were added to the thus-pretreated paper stock based on waste paper paper with stirring.
  • the addition amount of the aqueous composition was selected such that 0.5% by weight of polymer having primary amino groups and / or amidine groups (solid) based on waste paper pulp (solid) was used.
  • the water-soluble polymeric anionic compound A was added.
  • the addition amount of the water-soluble polymeric anionic compound was 0.3% by weight based on waste paper pulp (solid).
  • the retention agent (Percol 540) in the form of a 1 wt .-% aqueous solution was metered to the pulp, with 0.04 wt .-% polymer (solid) based on waste paper fiber (solid) were used.
  • the pH of the stock was kept constant at pH 7 (using 5% by weight sulfuric acid).
  • base papers were produced by means of a dynamic sheet former from Tech Pap, France.
  • the paper was then dried with contact dryers to a paper moisture content of 5% by weight.
  • the addition amount of the polymer H 4 was selected such that 0.5 wt .-% polymer with primary amino groups (solid) based on recycled paper pulp (solid) was used.
  • the water-soluble polymeric anionic compound in an amount of 0.3 wt .-% based on waste paper pulp (solid) were added.
  • The% value for CMT, SCT and Burst represents the increase in% compared to the reference.
  • the water-soluble polymeric anionic compound P4 was used.
  • the water-soluble polymeric anionic compound P7 was used.
  • the water-soluble polymeric anionic compound P8 was used.
  • the aqueous composition of example EF7 was added to the pretreated paper stock based on waste paper (see above) with stirring.
  • the addition amount of the aqueous composition was selected such that 0.5% by weight of polymer having primary amino groups and / or amidine groups (solid) based on recovered paper pulp (solid) was used.
  • the respective water-soluble polymeric anionic compound was added.
  • the addition amount of the water-soluble polymeric anionic compound was 0.3% by weight based on waste paper pulp (solid).
  • the retention agent (Percol 540) in the form of a 1 wt .-% aqueous solution was metered to the pulp, with 0.04 wt .-% polymer (solid) based on waste paper fiber (solid) were used.
  • the pH of the stock was kept constant at pH 7 (using 5% by weight sulfuric acid).
  • base papers were produced by means of a dynamic sheet former from Tech Pap, France.
  • the paper was then dried with contact dryers to a paper moisture content of 5% by weight.
  • a paper stock suspension and paper sheets thereof were produced without addition of the aqueous composition and without addition of the water-soluble polymeric anionic compound.
  • The% value for CMT, SCT and Burst represents the increase in% compared to the reference.

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Abstract

L'invention concerne un procédé de fabrication de papier ou de carton par addition (I) d'une composition aqueuse d'un pH ≤ 6 et (II) d'au moins un composé anionique polymère soluble dans l'eau à une pâte à papier d'un pH situé entre 6 et 8, après quoi la pâte à papier est déshydratée avec formation de feuilles et séchage. La composition aqueuse contient (a) des polymères présentant des groupes aminés primaires et/ou des groupes amidine, la teneur totale de ces groupes étant ≥ 1,5 meq/g de polymère, et (b) 0,01 à 50 % en moles de 1,4-cyclohexanedione (b) sur la base de la quantité totale de groupes aminés primaires et/ou de groupes amidine des polymères. L'invention concerne également du papier fabriqué par ledit procédé ou du carton fabriqué par ledit procédé.
EP15820441.2A 2014-12-16 2015-12-04 Procédé de fabrication de papier et de carton Withdrawn EP3234259A1 (fr)

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US11203838B2 (en) * 2017-10-11 2021-12-21 Solenis Technologies Cayman, L.P. Method for manufacturing paper or cardboard
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EP3850020A1 (fr) 2018-09-14 2021-07-21 Solenis Technologies Cayman, L.P. Procédé de production de papier ou de carton
WO2022243820A1 (fr) * 2021-05-17 2022-11-24 Stora Enso Oyj Papier cannelé ou doublure comprenant de la pâte nssc

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US20170362776A1 (en) 2017-12-21
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