EP0418343A1 - Process for manufacturing paper, paperboard and cardboard in the presence of copolymerizates containing n-vinyl formamide units. - Google Patents

Process for manufacturing paper, paperboard and cardboard in the presence of copolymerizates containing n-vinyl formamide units.

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Publication number
EP0418343A1
EP0418343A1 EP90904264A EP90904264A EP0418343A1 EP 0418343 A1 EP0418343 A1 EP 0418343A1 EP 90904264 A EP90904264 A EP 90904264A EP 90904264 A EP90904264 A EP 90904264A EP 0418343 A1 EP0418343 A1 EP 0418343A1
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EP
European Patent Office
Prior art keywords
weight
copolymers
cardboard
paper
vinylformamide
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EP90904264A
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German (de)
French (fr)
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EP0418343B1 (en
Inventor
Dietmar Moench
Heinrich Hartmann
Enrique Freudenberg
Andreas Stange
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BASF SE
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BASF SE
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Priority to AT90904264T priority Critical patent/ATE89879T1/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—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
    • 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
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised

Definitions

  • the invention relates to a process for the production of paper, cardboard and cardboard by dewatering a paper stock in the presence of
  • JP-A-118 406/86 discloses water-soluble polyvinylamines which are obtained by polymerizing N-vinylformamide or mixtures of N-vinylformamide with other water-soluble monomers, such as acrylamide, N, N-dialkylacrylamides or diallyldialkylammonium salts and subsequent hydrolysis of the polymers with bases , e.g. Ethylamine, diethylamine, ethylenediamine or morpholine can be produced.
  • the polyvinylamines are used as dewatering and retention agents in papermaking and as flocculants for waste water.
  • Polymers are known from US Pat. No. 4,421,602, which are obtainable by partial hydrolysis of poly-N-vinylformamide with acids or bases. Due to the hydrolysis, these polymers contain vinylamine and N-vinylformamide units. They are used, for example, in the manufacture of paper as drainage aids, flocculants and retention aids.
  • EP-A-0 220 603 inter alia, known to subject N-vinylformamide together with basic acrylic esters such as dimethylaminoethyl acrylate or N-vinylimidazole in supercritical carbon dioxide to the copolymerization.
  • the resulting fine-particle copolymers are used in partially hydrolyzed form in which they contain vinylamine units, for example as retention aids and flocculants in the production of paper.
  • a dry strength agent is a mixture of cationic polymers which, as characteristic monomers, can also contain units of vinylamine copolymerized and natively Potato starch is used, the potato starch being converted into a water-soluble form by heating in an aqueous medium in the presence of the cationic polymer to temperatures above the gelatinization temperature of the native potato starch in the absence of oxidizing agents, polymerization initiators and alkali.
  • the object of the invention is to provide aids for paper production which are as effective as possible than those known hitherto and which are more technically accessible.
  • the object is achieved according to the invention with a process for the production of paper, cardboard and cardboard by dewatering a paper stock in the presence of polymers containing N-vinylformamide units, if the polymers containing N-vinylformamide units are non-hydrolyzed copolymers which
  • R 5 , R 6 C 1 to C 10 alkyl
  • N-vinylformamide can be considered as monomer (a) of the copolymers.
  • Suitable monomers of group (b) are the compounds of the formula I, of which the following compounds may be mentioned by way of example:
  • N-ethyldimethylammonium propylacrylamide ethosulfate N-ethyldimethylammonium propylacrylamide ethosulfate.
  • N-Trimethylammonium propyl methacrylamide chloride is preferred.
  • the compounds of formula II are also suitable as monomers of group (b).
  • Compounds of this type are, for example, diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldiethylammonium chloride and diallyldiethylammonium bromide.
  • Diallyldimethylammonium chloride is preferably used.
  • the anion is an acid residue and is preferably chloride, bromide, iodide, sulfate, methosulfate and ethosulfate.
  • the compounds of the formula I or II can be involved in the synthesis of the copolymers either alone or as a mixture with one another. It is also possible to use several compounds of the formula I or II in the copolymerization with the monomer (a).
  • the monomers of group (b) make up 99 to 1, preferably 40 to 5 mol%, of the copolymers.
  • the monomers (a) and (b) are copolymerized in aqueous solution in the presence of polymerization initiators which decompose into free radicals under the polymerization conditions.
  • Suitable polymerization initiators are, for example, hydrogen peroxide, alkali and ammonium salts of peroxidic sulfuric acid, peroxides, hydroperoxides, redox catalysts and particularly non-oxidizing initiators, such as azo compounds which break down into free radicals.
  • azo compounds which break down into free radicals.
  • water-soluble azo compounds such as 2,2'-azo-bis (2-amidinopropane) dihydrochloride, 2,2'-azo-bis (N, N'-methylene-isobutyramidine) dihydrochloride or 2,2'-azo-bis [2-methyl-N- (2-hydroxyethyl) propionamide].
  • the polymerization initiators are used in customary amounts, for example in amounts of 0.01 to 5.0% by weight, based on the monomers to be polymerized.
  • the polymerization can be carried out in a wide temperature range, if appropriate under reduced or also under increased pressure in appropriately designed apparatus.
  • the polymerization is preferably carried out at normal pressure and temperatures up to 100 ° C., in particular in the range from 30 to 80 ° C.
  • the concentration of the monomers in the aqueous solution is preferably selected so that polymer solutions are obtained whose solids content is 10 to 90, preferably 20 to 70,% by weight.
  • the pH of the reaction mixture is adjusted in the range from 4 to 10, preferably 5 to 8.
  • copolymers of different molecular weights are obtained.
  • the K value according to H. Fikentscher is given instead of the molecular weight.
  • the K values (measured in 5% aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.1% by weight) are 5 to 350.
  • Copolymers with low molecular weights and correspondingly low K values are obtained using the customary methods, ie Use of larger amounts of peroxide in the copolymerization or use of polymerization regulators or combinations of the two measures mentioned.
  • Polymers with a high K value and with high molecular weights are obtained, for example, by polymerizing the monomers in the form of the reverse suspension polymerization or by polymerizing the monomers (a) and (b) by the water-in-oil polymerization method.
  • saturated hydrocarbons for example hexane, heptane, cyclohexane, decalin or aromatic hydrocarbons such as benzene, toluene, xylene and cumene, are used as the oil phase.
  • the ratio of oil phase to aqueous phase in the reverse suspension polymerization is, for example, 10: 1 to 1:10, preferably 7: 1 to 1: 1.
  • a protective colloid In order to disperse the aqueous monomer solution in an inert hydrophobic liquid, a protective colloid is required, which has the task of Stabilize suspension of the aqueous monomer solution in the inert hydrophobic liquid.
  • the protective colloids also have an influence on the particle size of the polymer beads formed by polymerization.
  • Protective colloids which can be used are, for example, those substances which are described in US Pat. No. 2,982,749. Also suitable are the protective colloids known from DE-PS 2 634486, which are obtainable, for example, by reacting oils and / or resins, each of which has allyl-containing hydrogen atoms, with maleic anhydride.
  • 27 10 372 known which are obtainable by thermal or radical solution or bulk polymerization from 60 to 99.9% by weight of dicyclopentadiene, 0 to 30% by weight of styrene and 0.1 to 10% by weight of maleic anhydride.
  • graft polymers which can be obtained by grafting polymers (A) from a) 40 to 100% by weight of monovinylaromatic monomers, b) 0 to 60% by weight of monoethylenically unsaturated carboxylic acids with 3 to
  • the polymers A) have a molecular weight (Number average) from 500 to 20,000 and hydrogenation iodine numbers (according to DIN 53 241) from 1.3 to 51, with monomer mixtures
  • an aliphatic hydrocarbon is used as the inert hydrophobic liquid in the reverse suspension polymerization, a mixture of an inorganic suspending agent based on modified finely divided minerals and a nonionic surfactant has proven to be very advantageous as a protective colloid.
  • the inorganic suspending agents that have a low hydrophilic-lyophilic balance are the agents commonly used in reverse suspension polymerization processes.
  • the mineral component of these substances is formed, for example, by bentonite, montmorillonite or kaolin.
  • the finely divided minerals are treated to C 24 amines or quaternary ammonium salts for modifying with salts of long chain amines, for example C 8 _, wherein a storage of the amine salts or the quaternary ammonium salts between the individual layers of finely divided minerals.
  • the optionally quaternized ammonium salts used for the modification preferably contain 1 to 2 C 10 to C 22 alkyl radicals.
  • the other substituents of the ammonium salts are C 1 to C 4 alkyl or hydrogen.
  • the content of free ammonium salts of the amine-modified minerals is at most 2% by weight. Finely divided minerals modified with ammonium salts are commercially available.
  • the inorganic suspending agents for the reverse suspension polymerization also include silicon dioxide which has been reacted with organosilicon compounds.
  • a suitable organosilicon compound is, for example, trimethylsilyl chloride.
  • the aim of modifying the inorganic fine-particle minerals is to improve the wettability of the minerals with the aliphatic hydrocarbon used as the outer phase of the reverse suspension polymerization.
  • the modification with amines ensures that the modified minerals swell in the aliphatic hydrocarbon and thereby break down into very fine particles.
  • the Particle size is about 1 micron and is generally in the range of 0.5 to 5 microns.
  • the silicas reacted with organosilicon compounds have a particle size in the range from about 10 to 40 nm.
  • the modified, finely divided minerals are wetted both by the aqueous monomer solution and by the solvent and thereby accumulate in the phase interface between the aqueous and organic phases. They prevent coagulation when two aqueous monomer droplets collide in the suspension.
  • part of the water is distilled off azeotropically, so that copolymers having a solids content of 70 to 99, preferably 80 to 95,% by weight are obtained.
  • the copolymers are in the form of fine beads with a diameter of 0.05 to 1 mm.
  • the copolymers described above are used in the non-hydrolyzed form in the manufacture of paper, cardboard and cardboard as an additive to the paper stock.
  • copolymers contain no vinylamine units. They cause an increase in the dewatering speed of the paper stock, so that the production speed in paper production can be increased.
  • the copolymers act as retention agents for fibers and fillers and at the same time as flocculants.
  • the copolymers are added to the paper stock in amounts of from 0.01 to about 0.8% by weight, based on dry paper stock. Higher amounts of copolymers cause dry consolidation.
  • the polymers are used in amounts of approximately 0.5 to 3.5% by weight, based on dry paper stock. It is particularly preferred to use the copolymers mentioned together with native potato starch as a dry strength agent.
  • Mixtures have good retention compared to paper fibers in the paper stock.
  • the COD value in the white water is significantly reduced with these mixtures compared to native starch.
  • the interfering substances contained in the water circuits of paper machines affect the effectiveness of the mixtures of the copolymers to be used according to the invention and native starch only slightly.
  • the pH of the pulp suspension can be in the range from 4 to 9, preferably 6 to 8.5.
  • These mixtures of native starch and cationic polymer, which are added to the paper stock for dry strengthening are preferably prepared by mixing native potato starch in the presence of the non-hydrolyzed copolymers in aqueous solution to temperatures above the gelatinization temperature of the native potato starch in the absence of oxidizing agents, polymerization initiators and Alkali heated.
  • the native potato starch is modified in this way.
  • the gelatinization temperature of the starch is the temperature at which the birefringence of the starch grains is lost, cf. Ullmann's Encyclopedia of Technical Chemistry, Urban and Schwarzenberg, Kunststoff-Berlin, 1965, 16th volume, page 322.
  • the modification of the native potato starch can be done in different ways.
  • a previously excluded native potato starch which is in the form of an aqueous solution, can be reacted with the cationic polymers in question to temperatures in the range from 15 to 70 ° C. Longer contact times are required at even lower temperatures. If the reaction is carried out at even higher temperatures, e.g. up to 110 ° C, shorter contact times are required, e.g. 0.1 to 15 min.
  • the simplest way of modifying the native potato starch is to heat an aqueous slurry of the starch in the presence of the cationic copolymers in question to a temperature above the gelatinization temperature of the native potato starch.
  • the starch is modified to temperatures in the range of Heated from 70 to 110 ° C, the reaction being carried out in pressure-tight apparatus at temperatures above 110 ° C.
  • the starch is solubilized in the absence of oxidizing agents, initiators and alkali in about 3 minutes to 5 hours, preferably 5 to 30 minutes. Higher temperatures here require a shorter dwell time.
  • aqueous phase of the reaction mixture increases.
  • a 3.5% by weight aqueous solution of the dry strength agent has viscosities in the range from 50 to 10,000 mPas (measured according to Brookfield at 20 rpm and 20 ° C.).
  • the copolymers to be used according to the invention can be used in the production of all known paper, cardboard and cardboard qualities, for example for the production of writing, printing and packaging papers.
  • the papers can be made from a variety of different types of fiber materials, such as sulfite or Sulphate filler in bleached or unbleached condition. Wood pulp, waste paper, thermomechanical material (TMP) and chemothermomechanical material (CTMP).
  • TMP thermomechanical material
  • CTMP chemothermomechanical material
  • the basis weight of the papers can be between 30 and 200, preferably 35 and 150 g / m2, while for cardboard it can be up to 600 g / m 2 .
  • the papers which are produced using the copolymers to be used according to the invention in a mixture with native potato starch have a markedly improved strength compared to papers which are obtainable in the presence of the same amount of native potato starch.
  • the parts given in the examples are parts by weight, the percentages relate to the weight.
  • the viscosities were determined in aqueous solution at a solids concentration of 3.5% by weight and at a temperature of 20 ° C. in a Brookfield viscometer at 20 rpm.
  • the sheet formation was carried out in a Rapid Köthen laboratory sheet former.
  • the dry tear length was determined according to DIN 53 112, sheet 1, the dry burst pressure according to Müllen, DIN 53 141, the CMT value according to DIN 53 143 and tear propagation resistance according to Brecht-Inset according to DIN 53 115.
  • the leaves were tested after 24-hour air conditioning at a temperature of 23 ° C and a relative humidity of 50%.
  • copolymer 1 The following feedstocks were used: copolymer 1
  • Copolymer of 90 mol% N-vinylformamide (VFA) and 10 mol% 3-methacrylamidopropyltrimethylammonium chloride (MAPTAC) copolymer 1 was prepared by 800 g in a 2 1 flask equipped with a stirrer, thermometer, gas inlet tube and reflux condenser Cyclohexane and 3 g of the protective colloid, which is described in Example 1 of EP-A-0 290 753. The initial charge was heated to a temperature of 50 ° C. under a nitrogen atmosphere and with stirring at a speed of the stirrer of 300 revolutions per minute.
  • Copolymer 6 Homopolymer of N-vinylformamide with a
  • Copolymer 7 Partially hydrolyzed polymer 6, which by
  • a degree of hydrolysis of 90% means that 90% of the formamide groups originally present in the polymer have been converted into amino groups or the corresponding ammonium salt groups.
  • Examples A newsprint stock containing wood and kaolin was first produced with a consistency of 2 g / l and a pH of 6 with an alum content of 0.5% by weight. This paper stock was used as a model substance for all examples and comparative examples. First the Schopper-Riegler device was used to determine the degree of grinding (° SR), the drainage time (ie the time in which 600 ml of white water ran out of the device) and the degree of transmittance (optical transmission of the white water in%) for the above Paper stock model. Then 1 1 samples each of the paper stock described above were tested with the amounts of copolymers 1 to 8 given in Table 2. The measurement results obtained in this way are given in Table 2.
  • the strengthening agents 1 to 5 specified below were tested, which were each prepared by heating native potato starch with the copolymers given in Table 3.
  • the consolidators 1 to 5 described above were each tested on the paper stock specified above.
  • the amount added was 3.0% by weight, based on dry paper stock.
  • the test results are shown in Table 4.
  • Further strengthening agents were prepared by heating native potato starch in an aqueous slurry to a temperature of 90 to 110 ° C. for 15 minutes in the presence of the copolymers given in Table 5.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Selon un procédé de fabrication de papier, de carton-pâte et de carton, on déshydrate la pâte de papier en présence de copolymères non hydrolysés qui contiennent: (a) entre 99 et 1 moles % de N-vinylformamide et (b) entre 1 et 99 moles % d'au moins un monomère basique soluble dans l'eau ayant les formules (I) ou (II), dans lesquelles R1 = H, CH3, C2H5; R2, R3 et R4 = H, CH3, C2H5, (-CH2-CH2-O-)nH; R5, R6 = C1-C10-alkyle; A = C1-C6-alkylène; n = 1 à 6 et Y = un anion, le tout étant polymérisé. La quantité de ces deux éléments est comprise entre 0,01 et 3,5 % en poids de la pâte déshydratée de papier.According to a paper, pulpboard and cardboard manufacturing process, the paper pulp is dehydrated in the presence of unhydrolyzed copolymers which contain: (a) between 99 and 1 mole% of N-vinylformamide and (b) between 1 and 99 mole% of at least one basic water soluble monomer having the formulas (I) or (II), wherein R1 = H, CH3, C2H5; R2, R3 and R4 = H, CH3, C2H5, (-CH2-CH2-O-) nH; R5, R6 = C1-C10-alkyl; A = C1-C6-alkylene; n = 1 to 6 and Y = an anion, the whole being polymerized. The amount of these two elements is between 0.01 and 3.5% by weight of the dehydrated paper pulp.

Description

Verfahren zur Herstellung von Papier, Pappe und Karton in Gegenwart von N-Vinylformamid-Einheiten enthaltenden Copolymerisaten Process for the production of paper, cardboard and cardboard in the presence of copolymers containing N-vinylformamide units
Beschreibung description
Die Erfindung betri fft ein Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Papierstoffs in Gegenwart von The invention relates to a process for the production of paper, cardboard and cardboard by dewatering a paper stock in the presence of
N-Vinylformamid-Einheiten enthaltenden Copolymerisaten. Aus der JP-A-118 406/86 sind wasserlösliche Polyvinylamine bekannt, die durch Polymerisieren von N-Vinylformamid oder Mischungen aus N-Vinylformamid mit anderen wasserlöslichen Monomeren, wie Acrylamid, N,N-Dialkylacrylamiden oder Diallyldialkylammoniumsalzen und anschließende Hydrolyse der Polymerisate mit Basen, z.B. Ethylamin, Diethylamin, Ethylendiamin oder Morpholin, hergestellt werden. Die Polyvinylamine werden als Entwässerungsmittel und Retentionsmittel bei der Papierherstellung und als Flockungsmittel für Abwässer verwendet. Copolymers containing N-vinylformamide units. JP-A-118 406/86 discloses water-soluble polyvinylamines which are obtained by polymerizing N-vinylformamide or mixtures of N-vinylformamide with other water-soluble monomers, such as acrylamide, N, N-dialkylacrylamides or diallyldialkylammonium salts and subsequent hydrolysis of the polymers with bases , e.g. Ethylamine, diethylamine, ethylenediamine or morpholine can be produced. The polyvinylamines are used as dewatering and retention agents in papermaking and as flocculants for waste water.
Aus der US-PS 4421 602 sind Polymerisate bekannt, die durch partielle Hydrolyse von Poly-N-Vinylformamid mit Säuren oder Basen erhältlich sind. Diese Polymerisate enthalten aufgrund der Hydrolyse Vinylamin- und N- Vinylformamid-Einheiten. Sie werden beispielsweise bei der Herstellung von Papier als Entwässerungshilfsmittel, Flockungsmittel und Retentionsmittel verwendet. Polymers are known from US Pat. No. 4,421,602, which are obtainable by partial hydrolysis of poly-N-vinylformamide with acids or bases. Due to the hydrolysis, these polymers contain vinylamine and N-vinylformamide units. They are used, for example, in the manufacture of paper as drainage aids, flocculants and retention aids.
Aus der EP-A-0 220 603 ist u.a. bekannt, N-Vinylformamid zusammen mit basischen Acrylsäureestern, wie Dimethylaminoethylacrylat oder N-Vinylimidazol inen, in überkritischem Kohlendioxid der Copolymerisation zu unterwerfen. Die dabei anfallenden feinteiligen Copolymerisate werden in partiell hydrolysierter Form, in der sie Vinylamin-Einheiten enthalten, beispielsweise als Retentionsmittel und Flockungsmittel bei der Herstellung von Papier verwendet. From EP-A-0 220 603, inter alia, known to subject N-vinylformamide together with basic acrylic esters such as dimethylaminoethyl acrylate or N-vinylimidazole in supercritical carbon dioxide to the copolymerization. The resulting fine-particle copolymers are used in partially hydrolyzed form in which they contain vinylamine units, for example as retention aids and flocculants in the production of paper.
Aus der EP-A-0 282 761 ist ein Verfahren zur Herstellung von Papier, Pappe und Karton mit hoher Trockenfestigkeit bekannt, bei dem man als Trockenverfestigungsmittel eine Mischung aus kationischen Polymerisaten, die als charakteristische Monomere u.a. auch Einheiten von Vinylamin einpolymerisiert enthalten können und nativer Kartoffelstärke verwendet, wobei die Kartoffelstärke durch Erhitzen in wäßrigem Medium in Gegenwart des kationischen Polymerisats auf Temperaturen oberhalb der Verkleisterungstemperatur der nativen Kartoffel stärke in Abwesenheit von Oxidationsmitteln, Polymerisationsinitiatoren und Alkali in eine wasserlösliche Form überführt wird. Der Erfindung liegt die Aufgabe zugrunde, Hilfsmittel für die Papierherstellung zur Verfügung zu stellen, die möglichst wirksamer sind als die bisher bekannten und die technisch leichter zugänglich sind. Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Papierstoffs in Gegenwart von N-Vinylformamid-Einheiten enthaltenden Polymerisaten, wenn man als N-Vinylformamid-Einheiten enthaltende Polymerisate nicht hydrolysierte Copolymerisate, die From EP-A-0 282 761 a process for the production of paper, cardboard and cardboard with high dry strength is known, in which a dry strength agent is a mixture of cationic polymers which, as characteristic monomers, can also contain units of vinylamine copolymerized and natively Potato starch is used, the potato starch being converted into a water-soluble form by heating in an aqueous medium in the presence of the cationic polymer to temperatures above the gelatinization temperature of the native potato starch in the absence of oxidizing agents, polymerization initiators and alkali. The object of the invention is to provide aids for paper production which are as effective as possible than those known hitherto and which are more technically accessible. The object is achieved according to the invention with a process for the production of paper, cardboard and cardboard by dewatering a paper stock in the presence of polymers containing N-vinylformamide units, if the polymers containing N-vinylformamide units are non-hydrolyzed copolymers which
(a) 99 bis 1 Mol% N-Vinylformamid und (a) 99 to 1 mole% N-vinylformamide and
(b) 1 bis 99 Mol% mindestens eines wasserlöslichen basischen (b) 1 to 99 mol% of at least one water-soluble basic
Monomers der Formeln (I) oder Monomers of the formulas (I) or
CH2=CH- -CH=CH2 (II),CH 2 = CH- -CH = CH 2 (II),
in denen  in which
R1 = H, CH3, C2H5, R2, R3 und R4= H, CH3, C2H5, (-CH2-CH2-O-)nH, R 1 = H, CH 3 , C 2 H 5 , R 2 , R 3 and R 4 = H, CH 3 , C 2 H 5 , (-CH 2 -CH 2 -O-) n H,
R5, R6 = C1- bis C10-Alkyl R 5 , R 6 = C 1 to C 10 alkyl
A = C1- bis C6-Alkylen n = 1 bis 6 und = ein Anion bedeuten, einpolymerisiert enthalten, in Mengen von 0,01 bis 3,5 Gew.%, bezogen auf trockenen Papierstoff, einsetzt. Der Vorteil der nicht hydrolysierten N-Vinylformamid-Einheiten enthaltenden Copolymerisate gegenüber den bisher verwendeten hydrolysierten Copoly merisate, die nach der Hydrolyse Vinylamin-Einheiten enthalten, ist darin zu sehen, daß die in vielen Fällen schwierig durchzuführende Hydrolyse fortfällt und durch direkte Copolymerisation wirksame Hilfsmittel für die Herstellung von Papier erhältlich sind. A = C 1 to C 6 alkylene n = 1 to 6 and = an anion, contained in copolymerized form, in amounts of 0.01 to 3.5% by weight, based on dry paper stock. The advantage of the copolymers containing non-hydrolyzed N-vinylformamide units over the previously used hydrolyzed copoly Merisates which contain vinylamine units after hydrolysis can be seen in the fact that the hydrolysis which is difficult to carry out in many cases is eliminated and effective auxiliaries for the production of paper can be obtained by direct copolymerization.
Als Monomer (a) der Copolymerisate kommt N-Vinylformamid in Betracht. N-vinylformamide can be considered as monomer (a) of the copolymers.
Dieses Monomer ist zu 1 bis 99, vorzugsweise 60 bis 95 Mol%, am Aufbau der Copolymerisate beteiligt. Als Monomere der Gruppe (b) eignen sich die Verbindungen der Formel I, von denen folgende Verbindungen beispielhaft genannt seien: This monomer makes up 1 to 99, preferably 60 to 95 mol%, of the copolymers. Suitable monomers of group (b) are the compounds of the formula I, of which the following compounds may be mentioned by way of example:
N-Trimethylammoniumethylacrylamidchlorid, N-trimethylammonium ethyl acrylamide chloride,
N-Trimethylammoniumethylmethacrylamidchlorid,  N-trimethylammoniumethyl methacrylamide chloride,
N-Trimethylammoniumethylacrylamidmethosulfat, N-trimethylammonium ethyl acrylamide methosulfate,
N-Trimethylammoniumethylmethacrylamidmethosulfat,  N-trimethylammonium ethyl methacrylamide methosulfate,
N-Ethyldimethylammoniummethylmethacrylamidethosulfat,  N-ethyldimethylammonium methyl methacrylamide ethosulfate,
N-Ethyldimethylammoniummethylacrylamidethosulfat,  N-ethyldimethylammonium methyl acrylamide ethosulfate,
N-Trimethylammoniumpropylacrylamidehlorid,  N-trimethylammoniumpropylacrylamidehlorid,
N-Trimethylammoniumpropylmethacrylamidchlorid, N-trimethylammonium propyl methacrylamide chloride,
N-Trimethylammoniumpropylacrylamidmethosulfat,  N-trimethylammonium propylacrylamide methosulfate,
N-Trimethylammoniumpropylmethacrylamidmethosulfat,  N-trimethylammonium propyl methacrylamide methosulfate,
N-Ethyldimethylammoniumpropylmethacrylamidethosulfat,  N-ethyldimethylammonium propyl methacrylamide ethosulfate,
N-Ethyldimethylammoniumpropylacrylamidethosulfat.  N-ethyldimethylammonium propylacrylamide ethosulfate.
Bevorzugt ist N-Trimethylammoniumpropylmethacrylamidchlorid. N-Trimethylammonium propyl methacrylamide chloride is preferred.
Als Monomere der Gruppe (b) kommen außerdem die Verbindungen der Formel II in Betracht. Verbindungen dieser Art sind beispielsweise Diallyldimethylammoniumchlorid, Diallyldimethylammoniumbromid, Diallyldiethylammoniumchlorid und Diallyldiethylammoniumbromid. Vorzugsweise verwendet man Diallyldimethylammoniumchlorid. Das Anion ist ein Säurerest und steht vorzugsweise für Chlorid, Bromid, Jodid, Sulfat, Methosulfat und Ethosulfat. The compounds of formula II are also suitable as monomers of group (b). Compounds of this type are, for example, diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldiethylammonium chloride and diallyldiethylammonium bromide. Diallyldimethylammonium chloride is preferably used. The anion is an acid residue and is preferably chloride, bromide, iodide, sulfate, methosulfate and ethosulfate.
Am Aufbau der Copolymerisate können von den Monomeren der Gruppe (b) die Verbindungen der Formel I oder II entweder allein oder in Mischung untereinander beteiligt sein. Ebenso ist es auch möglich, mehrere Verbindungen der Formel I oder II bei der Copolymerisation mit dem Monomer (a) einzusetzen. Die Monomeren der Gruppe (b) sind zu 99 bis 1, vorzugsweise 40 bis 5 Mol%, am Aufbau der Copolymerisate beteiligt. Die Copolymerisation der Monomeren (a) und (b) erfolgt in wäßriger Lösung in Gegenwart von Polymerisationsinitiatoren, die unter den Polymerisationsbedingungen in Radikale zerfallen. Geeignete Polymerisationsinitiatoren sind beispielsweise Wasserstoffperoxid, Alkali- und Ammoniumsalze der Peroxidischwefelsäure, Peroxide, Hydroperoxide, Redoxkatalysatoren und besonders nicht-oxidierende Initiatoren, wie in Radikale zerfallende Azoverbindungen. Vorzugsweise verwendet man wasserlösliche Azoverbindungen, wie 2,2'-Azo-bis(2-amidinopropan)dihydrochlorid, 2,2'-Azo-bis(N,N'-di- methylenisobutyramidin)dihydrochlorid oder 2,2'-Azo-bis[2-methyl-N-(2-hydroxyethyl)propionamid]. Die Polymerisationsinitiatoren werden in üblichen Mengen eingesetzt, z.B. in Mengen von 0,01 bis 5,0 Gew.%, bezogen auf die zu polymerisierenden Monomeren. Die Polymerisation kann in einem weiten Temperaturbereich, gegebenenfalls unter vermindertem oder auch unter erhöhtem Druck in entsprechend ausgelegten Apparaturen, vorgenommen werden. Vorzugsweise erfolgt die Polymerisation bei Normaldruck und Temperaturen bis zu 100°C, insbesondere in dem Bereich von 30 bis 80°C. Die Konzentration der Monomeren in der wäßrigen Lösung wird vorzugsweise so gewählt, daß Polymerisatlösungen anfallen, deren Feststoffgehalt 10 bis 90, vorzugsweise 20 bis 70 Gew.%, beträgt. Der pH-Wert des Reaktionsgemisches wird in dem Bereich von 4 bis 10, vorzugsweise 5 bis 8, eingestellt. Of the monomers of group (b), the compounds of the formula I or II can be involved in the synthesis of the copolymers either alone or as a mixture with one another. It is also possible to use several compounds of the formula I or II in the copolymerization with the monomer (a). The monomers of group (b) make up 99 to 1, preferably 40 to 5 mol%, of the copolymers. The monomers (a) and (b) are copolymerized in aqueous solution in the presence of polymerization initiators which decompose into free radicals under the polymerization conditions. Suitable polymerization initiators are, for example, hydrogen peroxide, alkali and ammonium salts of peroxidic sulfuric acid, peroxides, hydroperoxides, redox catalysts and particularly non-oxidizing initiators, such as azo compounds which break down into free radicals. Preference is given to using water-soluble azo compounds, such as 2,2'-azo-bis (2-amidinopropane) dihydrochloride, 2,2'-azo-bis (N, N'-methylene-isobutyramidine) dihydrochloride or 2,2'-azo-bis [2-methyl-N- (2-hydroxyethyl) propionamide]. The polymerization initiators are used in customary amounts, for example in amounts of 0.01 to 5.0% by weight, based on the monomers to be polymerized. The polymerization can be carried out in a wide temperature range, if appropriate under reduced or also under increased pressure in appropriately designed apparatus. The polymerization is preferably carried out at normal pressure and temperatures up to 100 ° C., in particular in the range from 30 to 80 ° C. The concentration of the monomers in the aqueous solution is preferably selected so that polymer solutions are obtained whose solids content is 10 to 90, preferably 20 to 70,% by weight. The pH of the reaction mixture is adjusted in the range from 4 to 10, preferably 5 to 8.
In Abhängigkeit von den Polymerisationsbedingungen erhält man Copolymerisate eines unterschiedlichen Molekulargewichts. Zur Charakterisierung der Copolymerisate wird anstelle des Molekulargewichts der K-Wert nach H. Fikentscher angegeben. Die K-Werte (gemessen in 5%iger wäßriger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 0,1 Gew.%) betragen 5 bis 350. Copolymerisate mit niedrigen Molekulargewichten und entsprechend niedrigen K-Werten erhält man mit Hilfe der üblichen Methoden, d.h. Einsatz größerer Peroxidmengen bei der Copolymerisation oder Verwendung von Polymerisationsreglern oder Kombinationen der beiden genannten Maßnahmen. Polymerisate mit einem hohen K-Wert und mit hohen Molekulargewichten erhält man beispielsweise durch Polymerisieren der Monomeren in Form der umgekehrten Suspensionspolymerisation oder durch Polymerisieren der Monomeren (a) und (b) nach dem Verfahren der Wasser-in-öl-Polymerisation. Bei dem Verfahren der umgekehrten Suspensionspolymerisation sowie der Wasserin-öl-Polymerisation verwendet man als ölphase gesättigte Kohlenwasserstoffe, beispielsweise Hexan, Heptan, Cyclohexan, Dekalin oder aromatische Kohlenwasserstoffe, wie Benzol, Toluol, Xylol und Cumol. Das Verhältnis von ölphase zu wäßriger Phase beträgt bei der umgekehrten Suspensionspolymerisation beispielsweise 10 : 1 bis 1 : 10, vorzugsweise 7 : 1 bis 1 : 1. Depending on the polymerization conditions, copolymers of different molecular weights are obtained. To characterize the copolymers, the K value according to H. Fikentscher is given instead of the molecular weight. The K values (measured in 5% aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.1% by weight) are 5 to 350. Copolymers with low molecular weights and correspondingly low K values are obtained using the customary methods, ie Use of larger amounts of peroxide in the copolymerization or use of polymerization regulators or combinations of the two measures mentioned. Polymers with a high K value and with high molecular weights are obtained, for example, by polymerizing the monomers in the form of the reverse suspension polymerization or by polymerizing the monomers (a) and (b) by the water-in-oil polymerization method. In the process of reverse suspension polymerization and water-in-oil polymerization, saturated hydrocarbons, for example hexane, heptane, cyclohexane, decalin or aromatic hydrocarbons such as benzene, toluene, xylene and cumene, are used as the oil phase. The ratio of oil phase to aqueous phase in the reverse suspension polymerization is, for example, 10: 1 to 1:10, preferably 7: 1 to 1: 1.
Um die wäßrige Monomerlösung in einer inerten hydrophoben Flüssigkeit zu dispergieren, benötigt man ein Schutzkolloid, das die Aufgabe hat, die Suspension der wäßrigen Monomerlösung in der inerten hydrophoben Flüssigkeit zu stabilisieren. Die Schutzkolloide haben außerdem einen Einfluß auf die Teilchengröße der durch Polymerisation entstehenden Polymerperlen. Als Schutzkolloide können beispielsweise diejenigen Substanzen verwendet werden, die in der US-PS 2 982 749 beschrieben sind. Außerdem eignen sich die aus der DE-PS 2 634486 bekannten Schutzkolloide, die beispielsweise durch Umsetzung von ölen und/oder Harzen, die jeweils allylständige Wasserstoffatome aufweisen, mit Maleinsäureanhydrid erhältlich sind. In order to disperse the aqueous monomer solution in an inert hydrophobic liquid, a protective colloid is required, which has the task of Stabilize suspension of the aqueous monomer solution in the inert hydrophobic liquid. The protective colloids also have an influence on the particle size of the polymer beads formed by polymerization. Protective colloids which can be used are, for example, those substances which are described in US Pat. No. 2,982,749. Also suitable are the protective colloids known from DE-PS 2 634486, which are obtainable, for example, by reacting oils and / or resins, each of which has allyl-containing hydrogen atoms, with maleic anhydride.
Weitere geeignete Schutzkolloide sind beispielsweise aus der DE-PS Other suitable protective colloids are for example from DE-PS
27 10 372 bekannt, die erhältlich sind durch thermische oder radikalische Lösungs- oder Substanzpolymerisation aus 60 bis 99,9 Gew.% Dicyclopentadien, 0 bis 30 Gew.% Styrol und 0,1 bis 10 Gew.% Maleinsäureanhydrid. Außerdem eignen sich als Schutzkolloide Pfropfpolymerisate, die erhältlich sind durch Pfropfen von Polymeriaten (A) aus a) 40 bis 100 Gew.% monovinylaromatischen Monomeren, b) 0 bis 60 Gew.% monoethylenisch ungesättigten Carbonsäuren mit 3 bis  27 10 372 known, which are obtainable by thermal or radical solution or bulk polymerization from 60 to 99.9% by weight of dicyclopentadiene, 0 to 30% by weight of styrene and 0.1 to 10% by weight of maleic anhydride. Also suitable as protective colloids are graft polymers which can be obtained by grafting polymers (A) from a) 40 to 100% by weight of monovinylaromatic monomers, b) 0 to 60% by weight of monoethylenically unsaturated carboxylic acids with 3 to
6 C-Atomen, Maleinsäureanhydrid und/oder Itaconsäureanhydrid und c) 0 bis 20 Gew.% anderen monoethylenisch ungesättigten Monomeren, mit der Maßgabe, daß die Summe der Gewichtsprozente (a) bis (c) immer 100 beträgt, die Polymerisate A) ein Molekulargewicht (Zahlenmittel) von 500 bis 20 000 und Hydrierjodzahlen (nach DIN 53 241) von 1,3 bis 51 aufweisen, mit Monomermischungen aus  6 carbon atoms, maleic anhydride and / or itaconic anhydride and c) 0 to 20% by weight of other monoethylenically unsaturated monomers, with the proviso that the sum of the percentages by weight (a) to (c) is always 100, the polymers A) have a molecular weight (Number average) from 500 to 20,000 and hydrogenation iodine numbers (according to DIN 53 241) from 1.3 to 51, with monomer mixtures
1) 70 bis 100 Gew.% Acrylsäureester und/oder Methacrylsäureester von 1 bis 20 C-Atome enthaltenden einwertigen Alkoholen, 1) 70 to 100% by weight of acrylic acid esters and / or methacrylic acid esters of monohydric alcohols containing 1 to 20 carbon atoms,
2) 0 bis 15 Gew.% monoethylenisch ungesättigten Carbonsäuren mit 3 bis 6 C-Atomen, Maleinsäureanhydrid und/oder2) 0 to 15% by weight of monoethylenically unsaturated carboxylic acids with 3 to 6 carbon atoms, maleic anhydride and / or
Itaconsäureanhydrid, Itaconic anhydride,
3) 0 bis 10 Gew.% Acrylsäuremonoester und/oder Methacrylsäuremonoester von mindestens zweiwertigen Alkohlen, 3) 0 to 10% by weight of acrylic acid monoesters and / or methacrylic acid monoesters of at least dihydric alcohols,
4) 0 bis 15 Gew.% monovinylaromatischen Monomeren und 5) 0 bis 7,5 Gew.% Acrylamid und/oder Methacrylamid, mit der Maßgabe, daß die Summe der Gewichtsprozente a) bis e) immer 100 beträgt, bei Temperaturen bis zu 150°C in einem inerten hydrophoben Verdünnungsmittel in Gegenwart von Polymerisationsinitiatoren, wobei die Monomeren in einer Menge von 97,5 bis 50 Gew.%, bezogen auf die Mischung aus Polymerisat (A) und Monomeren, eingesetzt werden. Schutzkolloide dieser Art werden in der EP-A-0 290 753 beschrieben. 4) 0 to 15% by weight of monovinyl aromatic monomers and 5) 0 to 7.5% by weight of acrylamide and / or methacrylamide, with the proviso that the sum of the percentages by weight a) to e) is always 100, at temperatures up to 150 ° C. in an inert hydrophobic diluent in the presence of polymerization initiators , the monomers being used in an amount of 97.5 to 50% by weight, based on the mixture of polymer (A) and monomers. Protective colloids of this type are described in EP-A-0 290 753.
Wenn bei der umgekehrten Suspensionspolymerisation ein aliphatischer Kohlenwasserstoff als inerte hydrophobe Flüssigkeit eingesetzt wird, hat sich als Schutzkolloid eine Mischung aus einem anorganischen Suspensionsmittel auf Basis modifizierter feinteiliger Mineralien und einem nichtionischen Tensid als sehr vorteilhaft erwiesen. If an aliphatic hydrocarbon is used as the inert hydrophobic liquid in the reverse suspension polymerization, a mixture of an inorganic suspending agent based on modified finely divided minerals and a nonionic surfactant has proven to be very advantageous as a protective colloid.
Die anorganischen Suspensionsmittel, die eine niedrige hydrophile-lyophile Balance haben, sind die bei den umgekehrten Suspensionspolymerisationsverfahren üblicherweise eingesetzten Mittel. Die mineralische Komponente dieser Stoffe wird beispielsweise von Bentonit, Montmorillonit oder Kaolin gebildet. Die feinteiligen Mineralien werden zur Modifizierung mit Salzen langkettiger Amine, z.B. C8 _ bis C24-Aminen oder quaternären Ammoniumsalzen behandelt, wobei eine Einlagerung der Aminsalze bzw. der quaternären Ammoniumsalze zwischen die einzelnen Schichten der feinteiligen Mineralien erfolgt. Die zur Modifizierung verwendeten gegebenenfalls quaternisierten Ammoniumsalze enthalten vorzugsweise 1 bis 2 C10- bis C22- Alkylreste. Die anderen Substituenten der Ammoniumsalze sind C1- bis C4- Alkyl oder Wasserstoff. Der Gehalt an freien Ammoniumsalzen der aminmodifizierten Mineralien beträgt höchstens 2 Gew.%. Mit Ammoniumsalzen modifizierte feinteilige Mineralien sind im Handel erhältlich. The inorganic suspending agents that have a low hydrophilic-lyophilic balance are the agents commonly used in reverse suspension polymerization processes. The mineral component of these substances is formed, for example, by bentonite, montmorillonite or kaolin. The finely divided minerals are treated to C 24 amines or quaternary ammonium salts for modifying with salts of long chain amines, for example C 8 _, wherein a storage of the amine salts or the quaternary ammonium salts between the individual layers of finely divided minerals. The optionally quaternized ammonium salts used for the modification preferably contain 1 to 2 C 10 to C 22 alkyl radicals. The other substituents of the ammonium salts are C 1 to C 4 alkyl or hydrogen. The content of free ammonium salts of the amine-modified minerals is at most 2% by weight. Finely divided minerals modified with ammonium salts are commercially available.
Zu den anorganischen Suspensionsmitteln für die umgekehrte Suspensionspolymerisation gehört auch Siliciumdioxid, das mit siliciumorganischen Verbindungen umgesetzt worden ist. Eine geeignete siliciumororganische Verbindung ist beispielsweise Trimethylsilylchlorid. The inorganic suspending agents for the reverse suspension polymerization also include silicon dioxide which has been reacted with organosilicon compounds. A suitable organosilicon compound is, for example, trimethylsilyl chloride.
Ziel der Modifizierung der anorganischen feinteiligen Mineralien ist es, die Benetzbarkeit der Mineralien mit dem als äußere Phase der umgekehrten Suspensionspolymerisation verwendeten aliphatischen Kohlenwasserstoff zu verbessern. Bei den schichtförmig aufgebauten natürlichen Mineralien, z.B. Bentonit und Montmorillonit, wird durch die Modifizierung mit Aminen erreicht, daß die modifizierten Mineralien in dem aliphatischen Kohlenwasserstoff quellen und dabei zu sehr feinen Teilchen zerfallen. Die Teilchengröße beträgt etwa 1 μm und liegt im allgemeinen in dem Bereich von 0,5 bis 5 μm. Die mit siliciumorganischen Verbindungen umgesetzten Siliciumdioxide haben eine Teilchengröße in dem Bereich von etwa 10 bis 40 nm. Die modifizierten feinteiligen Mineralien werden sowohl von der wäßrigen Monomerlösung als auch von dem Lösungsmittel benetzt und lagern sich dadurch in die Phasengrenzfläche zwischen wäßriger und organischer Phase an. Sie verhindern bei einer Kollision zweier wäßriger Monomertröpfchen in der Suspension eine Koagulation. Nach Beendigung der Copolymerisation wird ein Teil des Wassers azeotrop abdestilliert, so daß man Copolymerisate mit einem Feststoffgehalt von 70 bis 99, vorzugsweise 80 bis 95 Gew.%, erhält. Die Copolymerisate liegen in Form feiner Perlen eines Durchmessers von 0,05 bis 1 mm vor. Die oben beschriebenen Copolymerisate werden zum Unterschied gegenüber dem Stand der Technik in der nicht hydrolysierten Form bei der Herstellung von Papier, Pappe und Karton als Zusatz zum Papierstoff verwendet. Diese Copolymerisate enthalten keine Vinylamin-Einheiten. Sie bewirken dabei eine Erhöhung der Entwässerungsgeschwindigkeit des Papierstoffs, so daß die Produktionsgeschwindigkeit bei der Papierherstellung erhöht werden kann. Außerdem wirken die Copolymerisate als Retentionsmittel für Faser- und Füllstoffe und sich gleichzeitig Flockungsmittel. Um die genannten Effekte zu erzielen, setzt man dem Papierstoff die Copolymerisate in Mengen von 0,01 bis etwa 0,8 Gew.%, bezogen auf trockenen Papierstoff, zu. Höhere Einsatzmengen an Copolymerisaten bewirken eine Trockenverfestigung. Um Trockenverfestigungseffekte zu erzielen, verwendet man die Polymerisate in Mengen von etwa 0,5 bis 3,5 Gew.%, bezogen auf trockenen Papierstoff. Besonders bevorzugt ist der Einsatz der genannten Copolymerisate zusammen mit nativer Kartoffelstärke als Trockenverfestigungsmittel. Solche The aim of modifying the inorganic fine-particle minerals is to improve the wettability of the minerals with the aliphatic hydrocarbon used as the outer phase of the reverse suspension polymerization. In the case of the layered natural minerals, for example bentonite and montmorillonite, the modification with amines ensures that the modified minerals swell in the aliphatic hydrocarbon and thereby break down into very fine particles. The Particle size is about 1 micron and is generally in the range of 0.5 to 5 microns. The silicas reacted with organosilicon compounds have a particle size in the range from about 10 to 40 nm. The modified, finely divided minerals are wetted both by the aqueous monomer solution and by the solvent and thereby accumulate in the phase interface between the aqueous and organic phases. They prevent coagulation when two aqueous monomer droplets collide in the suspension. When the copolymerization has ended, part of the water is distilled off azeotropically, so that copolymers having a solids content of 70 to 99, preferably 80 to 95,% by weight are obtained. The copolymers are in the form of fine beads with a diameter of 0.05 to 1 mm. In contrast to the prior art, the copolymers described above are used in the non-hydrolyzed form in the manufacture of paper, cardboard and cardboard as an additive to the paper stock. These copolymers contain no vinylamine units. They cause an increase in the dewatering speed of the paper stock, so that the production speed in paper production can be increased. In addition, the copolymers act as retention agents for fibers and fillers and at the same time as flocculants. To achieve the effects mentioned, the copolymers are added to the paper stock in amounts of from 0.01 to about 0.8% by weight, based on dry paper stock. Higher amounts of copolymers cause dry consolidation. In order to achieve dry strengthening effects, the polymers are used in amounts of approximately 0.5 to 3.5% by weight, based on dry paper stock. It is particularly preferred to use the copolymers mentioned together with native potato starch as a dry strength agent. Such
Mischungen weisen eine gute Retention gegenüber Papierfasern im Papierstoff auf. Der CSB-Wert im Siebwasser wird mit diesen Mischungen im Vergleich zu nativer Stärke erheblich reduziert. Die in den Wasserkreisläufen von Papiermaschinen enthaltenen Störsubstanzen beeinträchtigen die Wirksamkeit der Mischungen aus den erfindungsgemäß einzusetzenden Copolymerisäten und nativer Stärke nur geringfügig. Der pH-Wert der Papierstoffsuspension kann in dem Bereich von 4 bis 9, vorzugsweise 6 bis 8,5, liegen. Diese Mischungen aus nativer Stärke und kationischem Polymerisat, die zur Trockenverfestigung dem Papierstoff zugesetzt werden, werden vorzugsweise dadurch hergestellt, daß man native Kartoffelstärke in Gegenwart der nicht hydrolysierten Copolymerisate in wäßriger Lösung auf Temperaturen oberhalb der Verkleisterungstemperatur der nativen Kartoffelstärke in Abwesenheit von Oxidationsmitteln, Polymerisationsinitiatoren und Alkali erhitzt. Die native Kartoffelstärke wird auf diese Weise modifiziert. Die Verkleisterungstemperatur der Stärke ist dabei diejenige Temperatur, bei der die Doppelbrechung der Stärkekörner verlorengeht, vgl. Ullmanns Enzyklopädie der technischen Chemie, Urban und Schwarzenberg, MünchenBerlin, 1965, 16. Band, Seite 322. Mixtures have good retention compared to paper fibers in the paper stock. The COD value in the white water is significantly reduced with these mixtures compared to native starch. The interfering substances contained in the water circuits of paper machines affect the effectiveness of the mixtures of the copolymers to be used according to the invention and native starch only slightly. The pH of the pulp suspension can be in the range from 4 to 9, preferably 6 to 8.5. These mixtures of native starch and cationic polymer, which are added to the paper stock for dry strengthening, are preferably prepared by mixing native potato starch in the presence of the non-hydrolyzed copolymers in aqueous solution to temperatures above the gelatinization temperature of the native potato starch in the absence of oxidizing agents, polymerization initiators and Alkali heated. The native potato starch is modified in this way. The gelatinization temperature of the starch is the temperature at which the birefringence of the starch grains is lost, cf. Ullmann's Encyclopedia of Technical Chemistry, Urban and Schwarzenberg, Munich-Berlin, 1965, 16th volume, page 322.
Die Modifizierung der nativen Kartoffelstärke kann in verschiedener Weise vorgenommen werden. Eine bereits ausgeschlossene native Kartoffelstärke, die als wäßrige Lösung vorliegt, kann mit den in Betracht kommenden kationischen Polymerisaten auf Temperaturen in dem Bereich von 15 bis 70°C zur Reaktion gebracht werden. Bei noch tieferen Temperaturen sind längere Kontaktzeiten erforderlich. Wird die Umsetzung bei noch höheren Temperaturen, z.B. bis zu 110°C vorgenommen, so benötigt man kürzere Kontaktzeiten, z.B. 0,1 bis 15 min. Die einfachste Art der Modifizierung der nativen Kartoffelstärke besteht darin, daß man eine wäßrige Aufschlämmung der Stärke in Gegenwart der in Betracht kommenden kationischen Copolymerisate auf eine Temperatur oberhalb der Verkleisterungstemperatur der nativen Kartoffelstärke erhitzt, im allgemeinen wird die Stärke zur Modifizierung auf Temperaturen in dem Bereich von 70 bis 110°C erwärmt, wobei man bei Temperaturen oberhalb von 110°C die Umsetzung in druckdichten Apparaturen ausführt. Man kann jedoch auch so vorgehen, daß man zunächst eine wäßrige Anschlämmung von nativer Kartoffelstärke auf eine Temperatur in dem Bereich von 70 bis 110°C erwärmt und die Stärke in Lösung bringt und danach das zur Modifizierung erforderliche kationische Copolymerisat zusetzt. Das Löslichmachen der Stärke geschieht dabei in Abwesenheit von Oxidationsmitteln, Initiatoren und Alkali in etwa 3 min bis 5 Std., vorzugsweise 5 bis 30 min. Höhere Temperaturen erfordern hier eine kürzere verweilzeit. The modification of the native potato starch can be done in different ways. A previously excluded native potato starch, which is in the form of an aqueous solution, can be reacted with the cationic polymers in question to temperatures in the range from 15 to 70 ° C. Longer contact times are required at even lower temperatures. If the reaction is carried out at even higher temperatures, e.g. up to 110 ° C, shorter contact times are required, e.g. 0.1 to 15 min. The simplest way of modifying the native potato starch is to heat an aqueous slurry of the starch in the presence of the cationic copolymers in question to a temperature above the gelatinization temperature of the native potato starch. In general, the starch is modified to temperatures in the range of Heated from 70 to 110 ° C, the reaction being carried out in pressure-tight apparatus at temperatures above 110 ° C. However, it is also possible to proceed by first heating an aqueous slurry of native potato starch to a temperature in the range from 70 to 110 ° C. and bringing the starch into solution and then adding the cationic copolymer required for modification. The starch is solubilized in the absence of oxidizing agents, initiators and alkali in about 3 minutes to 5 hours, preferably 5 to 30 minutes. Higher temperatures here require a shorter dwell time.
Auf 100 Gew. -Teile native Kartoffelstärke verwendet man 1 bis 20, vorzugsweise 8 bis 12 Gew.-Teile eines einzigen oder einer Mischung der in Betracht kommenden nicht hydrolysierten kationischen Copolymerisate. Durch die Umsetzung mit den kationischen Copolymerisaten wird die native Kartoffelstärke in eine in Wasser lösliche Form überführt. Die Viskosität der wäßrigen Phase des Reaktionsgemisches steigt dabei an. Eine 3,5 gew.%ige wäßrige Lösung des Trockenverfestigungsmittels hat dabei Viskositäten in dem Bereich von 50 bis 10.000 mPas (gemessen nach Brookfield bei 20 Upm und 20°C). 1 to 20, preferably 8 to 12 parts by weight of a single or a mixture of the non-hydrolyzed cationic copolymers in question are used per 100 parts by weight of native potato starch. The native potato starch is converted into a water-soluble form by the reaction with the cationic copolymers. The viscosity of the aqueous phase of the reaction mixture increases. A 3.5% by weight aqueous solution of the dry strength agent has viscosities in the range from 50 to 10,000 mPas (measured according to Brookfield at 20 rpm and 20 ° C.).
Die erfindungsgemäßen zu verwendenden Copolymerisate können bei der Herstellung von sämtlichen bekannten Papier-, Karton- und Pappenqualitäten verwendet werden, z.B. zur Herstellung von Schreib-, Druck- und Verpackungspapieren. Die Papiere können aus einer Vielzahl verschiedenartiger Fasermaterialien hergestellt werden, beispielsweise aus Sulfit- oder Sulfat-Füllstoff in gebleichtem oder ungebleichtem Zustand. Holzschliff, Altpapier, thermomechanischem Stoff (TMP) und chemothermomechanischem Stoff (CTMP). Das Flächengewicht der Papiere kann zwischen 30 und 200, vorzugsweise 35 und 150 g/m2 betragen, während es bei Karton bis zu 600 g/m2 betragen kann. Die Papiere, die unter Einsatz der erfindungsgemäß zu verwendenden Copolymerisate in Mischung mit nativer Kartoffelstärke hergestellt werden, haben gegenüber Papieren, die in Gegenwart der gleichen Menge an nativer Kartoffelstärke erhältlich sind, eine merklich verbesserte Festigkeit. The copolymers to be used according to the invention can be used in the production of all known paper, cardboard and cardboard qualities, for example for the production of writing, printing and packaging papers. The papers can be made from a variety of different types of fiber materials, such as sulfite or Sulphate filler in bleached or unbleached condition. Wood pulp, waste paper, thermomechanical material (TMP) and chemothermomechanical material (CTMP). The basis weight of the papers can be between 30 and 200, preferably 35 and 150 g / m2, while for cardboard it can be up to 600 g / m 2 . The papers which are produced using the copolymers to be used according to the invention in a mixture with native potato starch have a markedly improved strength compared to papers which are obtainable in the presence of the same amount of native potato starch.
Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Prozentangaben beziehen sich auf das Gewicht. Die Viskositäten wurden in wäßriger Lösung bei einer Feststoffkonzentration von 3,5 Gew.% und einer Temperatur von 20°C in einem Brookfield Viskosimeter bei 20 Upm bestimmt. The parts given in the examples are parts by weight, the percentages relate to the weight. The viscosities were determined in aqueous solution at a solids concentration of 3.5% by weight and at a temperature of 20 ° C. in a Brookfield viscometer at 20 rpm.
Die Blattbildung wurde in einem Rapid-Köthen-Laborblattbildner vorgenommen. Die Trockenreißlänge wurde nach DIN 53 112, Blatt 1, der Trockenberstdruck nach Müllen, DIN 53 141, der CMT-Wert nach DIN 53 143 und Weiterreißwiderstand nach Brecht-Inset gemäß DIN 53 115 bestimmt. Die Prüfung der Blätter erfolgte jeweils nach einer 24stündigen Klimatisierung bei einer Temperatur von 23°C und einer relativen Luftfeuchtigkeit von 50 %. The sheet formation was carried out in a Rapid Köthen laboratory sheet former. The dry tear length was determined according to DIN 53 112, sheet 1, the dry burst pressure according to Müllen, DIN 53 141, the CMT value according to DIN 53 143 and tear propagation resistance according to Brecht-Inset according to DIN 53 115. The leaves were tested after 24-hour air conditioning at a temperature of 23 ° C and a relative humidity of 50%.
Der K-Wert der Copolymerisate wurde nach H. Fikentscher, Cellulosechemie Bd. 13, 58 - 64 und 71 - 74 (1932) bei einer Temperatur von 25°C in 5%iger wäßriger Kochsalzlösung und einer Polymerkonzentration von 0,1 Gew.% bestimmt; dabei bedeutet K = k · 103. The K value of the copolymers was determined according to H. Fikentscher, Cellulosechemie Vol. 13, 58-64 and 71-74 (1932) at a temperature of 25 ° C. in 5% aqueous sodium chloride solution and a polymer concentration of 0.1% by weight. certainly; where K = k · 10 3 .
Folgende Einsatzstoffe wurde verwendet: Copolymerisat 1 The following feedstocks were used: copolymer 1
Copolymerisat aus 90 Mol% N-Vinylformamid (VFA) und 10 Mol% 3-Methacrylamidopropyltrimethylammoniumchlorid (MAPTAC) Copolymerisat 1 wurde hergestellt, indem man in einem 2 1-Kolben, der mit einem Rührer, Thermometer, Gaseinleitungsrohr und Rückflußkühler versehen war, 800 g Cyclohexan und 3 g des Schutzkolloids vorlegte, das in Beispiel 1 der EP-A-0 290 753 beschrieben ist. Die Vorlage wurde unter einer Stickstoffatmosphäre und unter Rühren bei einer Drehzahl des Rührers von 300 Umdrehungen pro Minute auf eine Temperatur von 50°C erwärmt. Sobald diese Temperatur erreicht war, gab man innerhalb von 30 Minuten eine Lösung von 117 g N-Vinylformamid, 80 g einer 50gew.%igen wäßrigen Lösung von 3-Meth- acrylamidopropyltrimethylammoniumchlorid, 0,15 g Diethylentriaminpenta essigsäure-Natriumsalz, 0,65 g 2,2'-Azo-bis(2-amidinopropan)dihydrochlorid und 100 g Wasser hinzu. Der pH-Wert der wäßrigen Phase betrug 6,5. Anschließend wurde das Reaktionsgemisch 16 Stunden bei 50°C gerührt. Danach wurde die Temperatur auf 78°C erhöht und mit Hilfe eines Wasserabscheiders 134 g Wasser azeotrop abdestilliert. Der anfallende weiße perlförmige Feststoff wurde abfiltriert, mit 200 g Cyclohexan gewaschen und im Vakuum vom restlichen Lösemittel befreit. Man erhielt 163 g eines Copolymerisats mit einem Feststoffgehalt von 96,4 Gew.%. Der K-Wert betrug 180. Analog zu der oben angegebenen Herstellvorschrift wurden die Copolymerisate 2 bis 5 hergestellt, deren Zusammensetzung in Tabelle 1 angegeben ist. Copolymer of 90 mol% N-vinylformamide (VFA) and 10 mol% 3-methacrylamidopropyltrimethylammonium chloride (MAPTAC) copolymer 1 was prepared by 800 g in a 2 1 flask equipped with a stirrer, thermometer, gas inlet tube and reflux condenser Cyclohexane and 3 g of the protective colloid, which is described in Example 1 of EP-A-0 290 753. The initial charge was heated to a temperature of 50 ° C. under a nitrogen atmosphere and with stirring at a speed of the stirrer of 300 revolutions per minute. As soon as this temperature had been reached, a solution of 117 g of N-vinylformamide, 80 g of a 50% by weight aqueous solution of 3-methacrylamidopropyltrimethylammonium chloride, 0.15 g of diethylenetriaminepenta was added within 30 minutes acetic acid sodium salt, 0.65 g of 2,2'-azobis (2-amidinopropane) dihydrochloride and 100 g of water. The pH of the aqueous phase was 6.5. The reaction mixture was then stirred at 50 ° C. for 16 hours. The temperature was then raised to 78 ° C. and 134 g of water were distilled off azeotropically with the aid of a water separator. The resulting white pearly solid was filtered off, washed with 200 g of cyclohexane and freed from the remaining solvent in vacuo. 163 g of a copolymer with a solids content of 96.4% by weight were obtained. The K value was 180. Analogously to the preparation instructions given above, copolymers 2 to 5 were prepared, the composition of which is given in Table 1.
Copolymerisat 6: Homopolymerisat des N-Vinylformamids mit einem  Copolymer 6: Homopolymer of N-vinylformamide with a
Feststoffgehalt von 96,6 % und einem K-Wert von 203 hergestellt analog der Vorschrift für Copolymerisat 1 durch Homopolymerisation von N-vinylformamid. Copolymeriat 7: Partiell hydrolysiertes Polymerisat 6, das durch  Solids content of 96.6% and a K value of 203 prepared analogously to the procedure for copolymer 1 by homopolymerization of N-vinylformamide. Copolymer 7: Partially hydrolyzed polymer 6, which by
Homopolymerisation von N-Vinylformamid nach der für das Copolymerisat 1 angegebenen Herstellvorschrift erhalten wurde, wobei jedoch vor dem Entfernen des Wassers 105 g einer 38%igen Salzsäure zugegeben und die Mischung 3 Stunden bei 50°C gerührt wurde und erst danach das Wasser azeotrop abdestilliert wurde. Der Hydrolysegrad betrug 42 %, der K-Wert 185, der Feststoffgehalt 93,5 %. Copolymerisat 8: Ist ebenfalls ein hydrolysiertes Homopolymerisat des N-Vinylformamids, das analog Copolymerisat 7 hergestellt wurde, jedoch wurden bei der Hydrolyse 211 g 38%ige Salzsäure eingesetzt. Der Hydrolysegrad betrug ca. 90 %, der K-Wert 195 und der Feststoffgehalt 90,6 %. Homopolymerization of N-vinylformamide was obtained in accordance with the preparation instructions given for copolymer 1, but 105 g of 38% hydrochloric acid were added before the water was removed, and the mixture was stirred at 50 ° C. for 3 hours and only then was the water distilled off azeotropically . The degree of hydrolysis was 42%, the K value 185, the solids content 93.5%. Copolymer 8: Is also a hydrolyzed homopolymer of N-vinylformamide, which was prepared analogously to copolymer 7, but 211 g of 38% hydrochloric acid were used in the hydrolysis. The degree of hydrolysis was approximately 90%, the K value 195 and the solids content 90.6%.
Ein Hydrolysegrad von 90 % bedeutet, daß 90 % der ursprünglich im Polymerisat vorhandenen Formamidgruppen in Aminogruppen bzw. die entsprechenden Ammoniumsalzgruppen überführt worden sind. A degree of hydrolysis of 90% means that 90% of the formamide groups originally present in the polymer have been converted into amino groups or the corresponding ammonium salt groups.
Beispiele Man stellte zunächst einen holz- und kaolinhaltigen Zeitungspapierstoff mit einer Stoffdichte von 2 g/l und einem pH-Wert von 6 bei einem Alaungehalt von 0,5 Gew.% her. Dieser Papierstoff wurde für sämtliche Beispiele und Vergleichsbeispiele als Modellsubstanz verwendet. Man bestimmte zunächst mit Hilfe des Schopper-Riegler-Gerätes den Mahlgrad (°SR), die Entwässerungszeit (d.h. die Zeit, in der 600 ml Siebwasser aus dem Gerät liefen) sowie den Durchlaßgrad (optische Transmission des Siebwassers in %) für das oben beschriebene Papierstoffmodell. Dann prüfte man jeweils 1 1- Proben des oben beschriebenen Papierstoffs mit den in Tabelle 2 angegebenen Mengen an Copolymerisaten 1 bis 8. Die dabei erhaltenen Meßergebnisse sind in Tabelle 2 angegeben. Examples A newsprint stock containing wood and kaolin was first produced with a consistency of 2 g / l and a pH of 6 with an alum content of 0.5% by weight. This paper stock was used as a model substance for all examples and comparative examples. First the Schopper-Riegler device was used to determine the degree of grinding (° SR), the drainage time (ie the time in which 600 ml of white water ran out of the device) and the degree of transmittance (optical transmission of the white water in%) for the above Paper stock model. Then 1 1 samples each of the paper stock described above were tested with the amounts of copolymers 1 to 8 given in Table 2. The measurement results obtained in this way are given in Table 2.
zur Prüfung der Papierverfestigung wurden die im folgenden angegebenen Verfestiger 1 bis 5 getestet, die durch Erhitzen von nativer Kartoffelstärke mit den in Tabelle 3 angegebenen Copolymerisaten jeweils hergestellt wurden. To test the paper strengthening, the strengthening agents 1 to 5 specified below were tested, which were each prepared by heating native potato starch with the copolymers given in Table 3.
Die oben beschriebenen Verfestiger 1 bis 5 wurden jeweils an dem oben angegebenen Papierstoff getestet. Die Zugabemenge betrug in allen Fällen 3,0 Gew.%, bezogen auf trockenen Papierstoff. Die Testergebnisse sind in Tabelle 4 angegeben.  The consolidators 1 to 5 described above were each tested on the paper stock specified above. The amount added was 3.0% by weight, based on dry paper stock. The test results are shown in Table 4.
5 - 126 136 2667 1625 - 126 136 2667 162
6 native Kartoffel 6 native potatoes
stärke 145 148 2836 276 strength 145 148 2836 276
7 4 148 149 2971 3277 4 148 149 2971 327
8 5 200 194 3349 1468 5 200 194 3349 146
Weitere Verfestiger wurde dadurch hergestellt, daß man native Kartoffelstärke in wäßriger Anschlämmung 15 Minuten auf eine Temperatur von 90 bis 110°C in Gegenwart der in Tabelle 5 angegebenen Copolymerisate erwärmte. Further strengthening agents were prepared by heating native potato starch in an aqueous slurry to a temperature of 90 to 110 ° C. for 15 minutes in the presence of the copolymers given in Table 5.
Um die Verfestiger 6 bis 8 bezüglich ihrer Wirksamkeit zu testen, wurden sie in einer Menge von 3,0 Gew.%, bezogen auf trockenen Papierstoff, zu dem in Beispiel 1 beschriebenen Papierstoff zugesetzt. Die dabei erhaltenen Ergebnisse sind in Tabelle 6 angegeben.  In order to test the strength of the strengthening agents 6 to 8, they were added in an amount of 3.0% by weight, based on dry paper stock, to the paper stock described in Example 1. The results obtained are shown in Table 6.
Um die Copolymerisate 1, 3 und 5 sowie Copolymerisat 6 (Vergleich) bezüglich ihrer Wirksamkeit als Trockenverfestiger auch ohne Stärkezusatz zu testen, wurden sie in einer Menge von 0,5 Gew.%, bezogen auf trockenen Papierstoff, zu dem in Beispiel 1 beschriebenen Papierstoff zugesetzt. Die dabei erhaltenen Ergebnisse sind in Tabelle 7 angegeben. In order to test the copolymers 1, 3 and 5 and copolymer 6 (comparison) with regard to their effectiveness as dry strength agents even without adding starch, they were added to the paper stock described in Example 1 in an amount of 0.5% by weight, based on dry paper stock added. The results obtained are shown in Table 7.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Papierstoffs in Gegenwart von N-Vinylformamid-Einheiten enthaltenden Polymerisaten, dadurch gekennzeichnet, daß man als1. A process for the production of paper, cardboard and cardboard by dewatering a paper stock in the presence of polymers containing N-vinylformamide units, characterized in that as
N-Vinylformamid-Einheiten enthaltende Polymerisate nicht hydrolysierte Copolymerisate, die Polymers containing N-vinylformamide units, non-hydrolyzed copolymers
(a) 99 bis 1 Mol% N-Vinylformamid und (a) 99 to 1 mole% N-vinylformamide and
(b) 1 bis 99 Mol% mindestens eines wasserlöslichen basischen (b) 1 to 99 mol% of at least one water-soluble basic
Monomers der Formeln Monomers of the formulas
CH2=CH- -CH=CH2 (II),CH 2 = CH- -CH = CH 2 (II),
in denen  in which
R1 = H, CH3, C2H5, R 1 = H, CH 3 , C 2 H 5 ,
R2, R3 und R4= H, CH3, C2H5, (-CH2-CH2-O-)nH, R 2 , R 3 and R 4 = H, CH 3 , C 2 H 5 , (-CH 2 -CH 2 -O-) n H,
R5, R6 = C1- bis C10-Alkyl R 5 , R 6 = C 1 to C 10 alkyl
A = C1- bis C6-Alkylen n = 1 bis 6 und = ein Anion bedeuten, einpolymerisiert enthalten, in Mengen von 0,01 bis 3,5 Gew.%, bezogen auf trockenen Papierstoff, einsetzt. A = C 1 to C 6 alkylene n = 1 to 6 and = an anion, contained in copolymerized form, in amounts of 0.01 to 3.5% by weight, based on dry paper stock.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man zum Papierstoff eine wäßrige Lösung zusetzt, die durch Erhitzen von nativer Kartoffelstärke in Gegenwart der nicht hydrolysierten Copolymerisate in wäßriger Lösung auf Temperaturen oberhalb der Verkleisterungstemperatur der nativen Kartoffelstärke in Abwesenheit von Oxidations- mitteln, Polymerisationsinitiatoren und Alkali erhältlich ist. 2. The method according to claim 1, characterized in that an aqueous solution is added to the pulp by heating native potato starch in the presence of the non-hydrolyzed copolymers in aqueous solution to temperatures above the gelatinization temperature of the native potato starch in the absence of oxidizing agents, polymerization initiators and alkali is available.
EP90904264A 1989-03-18 1990-03-14 Process for manufacturing paper, paperboard and cardboard in the presence of copolymerizates containing n-vinyl formamide units Expired - Lifetime EP0418343B1 (en)

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