EP0438755B1 - Procédé de fabrication de papier et de carton à partir de matières de papier contenant des produits perturbateurs - Google Patents

Procédé de fabrication de papier et de carton à partir de matières de papier contenant des produits perturbateurs Download PDF

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Publication number
EP0438755B1
EP0438755B1 EP90125089A EP90125089A EP0438755B1 EP 0438755 B1 EP0438755 B1 EP 0438755B1 EP 90125089 A EP90125089 A EP 90125089A EP 90125089 A EP90125089 A EP 90125089A EP 0438755 B1 EP0438755 B1 EP 0438755B1
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Prior art keywords
paper
polymers
units
formula
mol
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German (de)
English (en)
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EP0438755A1 (fr
Inventor
Enrique Dr. Freudenberg
Friedrich Dr. Linhart
Rainer Tresch
Heinrich Dr. Hartmann
Walter Denzinger
Michael Dr. Kroener
Norbert Dr. Sendhoff
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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
    • 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

Definitions

  • US Pat. No. 4,421,602 discloses hydrolyzed homopolymers of N-vinylformamide which contain 90 to 10 mol% of vinylamine units and 10 to 90 mol% of N-vinylformamide units.
  • the hydrolyzed polyvinylformamides are used as retention and drainage agents in the manufacture of paper. Because of the vinylamine units, the polymers have a positive charge in aqueous solution. They are therefore adsorbed by the negatively charged surfaces of the solid particles in the paper stock and thus facilitate the binding of the originally negatively charged particles to one another. As a result, an increased drainage rate and improved retention are observed.
  • the effectiveness of the cationic products is known to be significantly adversely affected by the presence of contaminants in the paper stock. Interfering substances are understood to mean oligomeric or polymeric substances with an anionic charge character, which worsen the drainage rate and the retention in the manufacture of paper. Such contaminants accumulate increasingly in the water cycles of paper machines because the used water is recycled to an increasing extent.
  • EP-A-0 249 891 discloses a process for the production of paper, cardboard and cardboard, in which paper materials containing impurities are dewatered in the presence of nonionic polymers, such as homopolymers of N-vinylformamide or of N-vinylpyrrolidone.
  • nonionic polymers such as homopolymers of N-vinylformamide or of N-vinylpyrrolidone.
  • the polymers mentioned act as retention aids and drainage aids.
  • Their effectiveness is considerably increased if non-ionic condensation products, e.g. Condensation products of phenol and formaldehyde of the resol and novolak type are present.
  • EP-A-0071050 describes a method according to the preamble of claim 1.
  • the present invention has for its object to provide dewatering, retention and flocculants for the papermaking process, which have a better effectiveness in paper containing impurities than the polymers described above.
  • a paper stock containing interfering substances is dewatered, for the production of which all fiber qualities are considered either alone or in a mixture with one another.
  • Inorganic fillers such as clay, chalk, gypsum or titanium dioxide and mixtures of these fillers can be added to the fibrous materials in customary amounts.
  • water is used for the production of the paper stock, which is at least partially or completely returned from the paper machine. These are clarified or untreated white water as well as mixtures of such water qualities.
  • the returned water contains more or less large amounts of so-called contaminants, which - as mentioned - severely impair the effectiveness of the previously used cationic retention and drainage aids.
  • Such effects are described for example in the technical literature, cf.
  • the content of such contaminants in the paper stock can be characterized, for example, with the sum parameter "Chemical oxygen demand” (COD value).
  • COD value the sum parameter
  • this sum parameter also includes nonionic or low molecular weight substances that do not directly interfere with dewatering or retention, but which, for example, as degradation products of wood constituents, always occur as accompanying substances for contaminants.
  • the COD values of the pulp-containing paper stock to be dewatered according to the invention are 300 to 30,000, preferably 1,000 to 20,000 mg oxygen / kg of the aqueous phase of the pulp-containing paper.
  • Fibers for the production of pulps that contain contaminants are, for example, wood pulp, unbleached pulp, waste paper pulp and paper pulp from all annual plants.
  • wood pulps include wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP).
  • TMP thermomechanical material
  • CMP chemo-thermomechanical material
  • RMP refiner mechanical pulp
  • unbleached pulp the unbleached kraft pulp is particularly suitable, but also the unbleached sulfite pulp.
  • waste paper all qualities are suitable, both sorted and unsorted. Are particularly suitable deinked waste paper.
  • Usable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf.
  • the following compounds are to be regarded as interfering substances: sodium silicate, which comes from deinking and the peroxide bleaching of waste paper materials, polyphosphates and polyacrylates from filler dispersions that are used in paper manufacture, humic acids from raw water, carboxymethyl cellulose from waste paper or coated scrap, anionic starches from waste paper or deleted committee, lignin derivatives from sulfate pulp, wood pulp, TMP or CTMP substances, hemicelluloses and their degradation products from wood pulp, TMP or CTMP substances and lignin sulfonates from unbleached sulfite pulps.
  • sodium silicate which comes from deinking and the peroxide bleaching of waste paper materials
  • polyphosphates and polyacrylates from filler dispersions that are used in paper manufacture humic acids from raw water, carboxymethyl cellulose from waste paper or coated scrap, anionic starches from waste paper or deleted committee
  • lignin derivatives from sulfate pulp, wood pulp, TMP or CTMP substances
  • R1 and R2 can have the same or different meanings.
  • they each represent H and / or C1- to C3-alkyl, preferably R1 and R2 each represent a hydrogen atom.
  • the polymers which contain the units of the formulas I and II have K values of at least 130 (determined according to H. Fikentscher in 5% by weight saline solution at 25 ° C. and a polymer concentration of 0.1% by weight).
  • the polymers are obtainable by homopolymerization or copolymerization of N-vinylamides of the formula
  • the substituents R1 and R2 have the meaning given in the formulas I and II.
  • Compounds of the formula III are, for example, N-vinylformamide, N-vinylacetamide, N-ethyl-N-vinylformamide, N-ethyl-N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide and N-vinylpropionamide.
  • the homo- and copolymerization of the N-vinylamides of the formula III leads to homo- or copolymers which contain units of the formula I in copolymerized form.
  • the homopolymers and copolymers of the vinylamides of the formula III are subjected to hydrolysis in the presence of acids or bases at temperatures up to 170 ° C., for example in the Range from 20 to 170 ° C, preferably 50 to 120 ° C.
  • the degree of hydrolysis of the polymerized units of the formula I is essentially dependent on the concentration of the amounts of acid or base used and the temperature.
  • Mineral acids such as hydrogen halide, sulfuric acid, nitric acid and phosphoric acid, and organic acids, for example, are suitable for the hydrolysis of the copolymers.
  • Acetic acid, propionic acid, benzenesulfonic acid and alkylsulfonic acids such as dodecylsulfonic acid.
  • bases can also be used for the hydrolysis, for example metal hydroxides of metals of the 1st and 2nd main group of the Periodic Table of the Elements, for example lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide.
  • Ammonia and derivatives of ammonia for example triethylamine, monomethanolamine, diethanolamine, triethanolamine and morpholine, can also be used as bases.
  • the hydrolysis of the homo- and copolymers of the N-vinylamides of the formula III is carried out to such an extent that less than 10, preferably 1 to 9 mol% of the units of the formula I contained in the polymers are converted into units of the formula II.
  • copolymers are also suitable which contain up to 50% by weight, preferably up to 30% Wt .-%, at least one other ethylenically unsaturated monomer copolymerized.
  • Suitable comonomers for the N-vinylamides of the formula III are, for example, vinyl acetate, vinyl propionate, C1- to C4-alkyl vinyl ether, N-vinylpyrrolidone, and also esters, nitriles and amides of ethylenically unsaturated C3- to C8-carboxylic acids, in particular esters, nitriles and amides of acrylic acid or methacrylic acid. Processes for the preparation of the hydrolyzed homopolymers and copolymers of compounds of the formula III are known.
  • the hydrolyzed polymers can be present as an aqueous solution, as a water-in-oil polymer emulsion, as a powder or as a bead polymer.
  • Bead polymers are prepared, for example, by the known reverse suspension polymerization process.
  • the above-described homopolymers and copolymers containing less than 10 mol% of vinylamine units of the formula II are, according to the invention, a pulp containing impurities as drainage, retention and flocculants in amounts of 0.002 to 0.1, preferably 0.005 to 0.05,% by weight. -%, based on dry paper stock added.
  • the Polymers to be used according to the invention are added to the paper stock in a very dilute aqueous solution, as is customary when using other high molecular weight water-soluble polymers.
  • concentration in the aqueous solution is generally between 0.01 and 0.1% by weight.
  • the main advantages of the process according to the invention are the low sensitivity of the polymers containing less than 10 mol% of units of formula II to the presence of interfering substances and the fact that that no additional fixative for the high molecular weight polymer, as described in EP-A-0 249 891, has to be used.
  • the parts given in the examples are parts by weight. The percentages relate to the weight of the fabrics.
  • 1 l of the pulp suspension to be tested is dewatered in a Schopper-Riegler test device.
  • the time that is determined for different outlet volumes is evaluated as a criterion for the drainage rate of the substance suspension examined in each case.
  • the drainage times were determined after a run of 500 or 600 ml of water.
  • the charge density of the hydrolyzed polymers based on poly-N-vinylformamide was determined using an enzymatic formic acid determination method (company publication “Methods of Enzymatic Food Analysis” by Boehringer Mannheim GmbH, 1984).
  • Polymer 4 homopolymer of N-vinylformamide with a K value of 218.
  • Polymer 5 Hydrolyzed poly-N-vinylformamide, which contained 89.9 mol% of N-vinylformamide units and 10.1 mol% of vinylamine units and had a K value of 218.
  • a pulp with a consistency of 4 g / l was produced from 100% mixed waste paper.
  • the pH in the stock suspension was 8.1.
  • 4% water glass, based on dry paper stock was added to the paper stock.
  • Samples of this paper stock were each dewatered in the presence of the polymers shown in Table 1.
  • the polymers were used in an amount of 0.04%, based on dry paper stock.
  • the drainage times for 600 ml of filtrate in the Schopper-Riegler test device and the optical transmittance of the filtrate obtained in this way are given in Table 1.
  • the paper stock described above was dewatered without any further addition.
  • a pulp with a consistency of 4 g / l was produced from 80 parts of TMP fabric, 20 parts of bleached sulfate pulp and 30 parts of kaolin as filler.
  • the pH was adjusted to 6.0 by adding alum.
  • 50 ml of an aqueous TMP extract from an industrial-scale TMP production were added per liter.
  • the polymers given in Table 2 were added to samples of this paper stock in an amount of 0.02% polymer, based on dry paper stock, and the dewatering time for 500 ml of filtrate in the Schopper-Riegler test device and the optical transmission were determined. The following results were obtained:
  • a pulp was made from 100% unbleached sulfate pulp with a consistency of 5 g / l.
  • the pH was 7.9.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Making Paper Articles (AREA)
  • Machines For Manufacturing Corrugated Board In Mechanical Paper-Making Processes (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Claims (3)

  1. Procédé de fabrication de papier et de carton à partir de pâtes à papier contenant des matières perturbatrices, par déshydratation en présence de polymères qui contiennent en liaison polymère, en tant que constituants caractéristiques, des motifs de formules
    Figure imgb0009
     dans lesquelles R¹, R² représentent des atomes d'hydrogène et/ou des restes alkyle en C₁-C₃, et qui présentent des valeurs K d'au moins 130 (déterminées par la methode de H. Fikentscher dans une solution aqueuse à 5% en poids de chlorure de sodium, à 25°C et avec une concentration de polymère de 0,1% en poids), caractérisé en ce qu'on utilise des polymères dont la teneur en motifs de formule II est inférieure à 10% en moles.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des polymères qui contiennent les motifs de formule II dans des proportions de 1 à 9% en moles.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les substituants R¹ et R² dans les formules I et II représentent chacun un atome d'hydrogène.
EP90125089A 1990-01-25 1990-12-21 Procédé de fabrication de papier et de carton à partir de matières de papier contenant des produits perturbateurs Expired - Lifetime EP0438755B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4002065A DE4002065A1 (de) 1990-01-25 1990-01-25 Verfahren zur herstellung von papier, pappe und karton aus stoerstoffe enthaltenden papierstoffen
DE4002065 1990-01-25

Publications (2)

Publication Number Publication Date
EP0438755A1 EP0438755A1 (fr) 1991-07-31
EP0438755B1 true EP0438755B1 (fr) 1994-03-16

Family

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EP90125089A Expired - Lifetime EP0438755B1 (fr) 1990-01-25 1990-12-21 Procédé de fabrication de papier et de carton à partir de matières de papier contenant des produits perturbateurs

Country Status (10)

Country Link
US (1) US5098521A (fr)
EP (1) EP0438755B1 (fr)
JP (1) JP2921609B2 (fr)
AT (1) ATE103023T1 (fr)
CA (1) CA2034869C (fr)
DE (2) DE4002065A1 (fr)
DK (1) DK0438755T3 (fr)
ES (1) ES2050350T3 (fr)
FI (1) FI102688B (fr)
NO (1) NO176526C (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005090678A1 (fr) * 2004-03-16 2005-09-29 Basf Aktiengesellschaft Procede de fabrication de papier, de carton-pate et de carton

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5232553A (en) * 1992-01-24 1993-08-03 Air Products And Chemicals, Inc. Fines retention in papermaking with amine functional polymers
US5401588A (en) * 1992-12-23 1995-03-28 Georgia-Pacific Resins Inc. Gypsum microfiber sheet material
US5380403A (en) * 1993-03-22 1995-01-10 Air Products And Chemicals, Inc. Amine functional poly(vinyl alcohol) for improving properties of recycled paper
DE4493351T1 (de) * 1993-05-10 1996-08-22 Grace W R & Co Papierherstellungsverfahren
US5720888A (en) * 1993-11-12 1998-02-24 Betzdearborn Inc. Water-soluble cationic copolymers and their use as flocculants
US5529699A (en) * 1993-11-12 1996-06-25 W. R. Grace & Co.-Conn. Water-soluble cationic copolymers and their use as flocculants
US5700893A (en) * 1993-11-12 1997-12-23 Betzdearborn Inc. Water-soluble cationic copolymers and their use as flocculants and drainage aids
US5516852A (en) * 1993-11-12 1996-05-14 W. R. Grace & Co.-Conn. Method of producing water-soluble cationic copolymers
US5473033A (en) * 1993-11-12 1995-12-05 W. R. Grace & Co.-Conn. Water-soluble cationic copolymers and their use as drainage retention aids in papermaking processes
US6273998B1 (en) 1994-08-16 2001-08-14 Betzdearborn Inc. Production of paper and paperboard
US20030192664A1 (en) * 1995-01-30 2003-10-16 Kulick Russell J. Use of vinylamine polymers with ionic, organic, cross-linked polymeric microbeads in paper-making
DE19716821A1 (de) * 1997-04-22 1998-10-29 Basf Ag Verfahren zur Herstellung von Papier, Pappe und Karton
CN1906359A (zh) * 2004-03-30 2007-01-31 日油瑞新株式会社 沥青控制剂
EP2640891B1 (fr) 2010-11-16 2016-03-30 Basf Se Fabrication de feuilles de pâte cellulosique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI70230C (fi) * 1981-07-18 1986-09-15 Basf Ag Rakkedjiga basiska polymerisat foerfarande foer deras framstaellning och deras anvaendning
DE3128478A1 (de) * 1981-07-18 1983-02-03 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von linearen, basischen polymerisaten
DE3620065A1 (de) * 1986-06-14 1987-12-17 Basf Ag Verfahren zur herstellung von papier, pappe und karton

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005090678A1 (fr) * 2004-03-16 2005-09-29 Basf Aktiengesellschaft Procede de fabrication de papier, de carton-pate et de carton
CN1934315B (zh) * 2004-03-16 2010-08-18 巴斯福股份公司 生产纸、纸板和卡片纸板的方法

Also Published As

Publication number Publication date
NO176526B (no) 1995-01-09
ATE103023T1 (de) 1994-04-15
FI910328A (fi) 1991-07-26
NO910283D0 (no) 1991-01-24
NO176526C (no) 1995-04-19
DE4002065A1 (de) 1991-08-01
FI102688B1 (fi) 1999-01-29
DK0438755T3 (da) 1994-04-05
JPH04333698A (ja) 1992-11-20
NO910283L (no) 1991-07-26
FI910328A0 (fi) 1991-01-22
ES2050350T3 (es) 1994-05-16
CA2034869C (fr) 2001-08-14
DE59005019D1 (de) 1994-04-21
JP2921609B2 (ja) 1999-07-19
US5098521A (en) 1992-03-24
FI102688B (fi) 1999-01-29
EP0438755A1 (fr) 1991-07-31
CA2034869A1 (fr) 1991-07-26

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