EP0362770B1 - Trockenfestigkeitszusatz für Papier - Google Patents

Trockenfestigkeitszusatz für Papier Download PDF

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Publication number
EP0362770B1
EP0362770B1 EP89118245A EP89118245A EP0362770B1 EP 0362770 B1 EP0362770 B1 EP 0362770B1 EP 89118245 A EP89118245 A EP 89118245A EP 89118245 A EP89118245 A EP 89118245A EP 0362770 B1 EP0362770 B1 EP 0362770B1
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cationic
anionic
polymer
mixture
polymers
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French (fr)
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EP0362770A3 (de
EP0362770A2 (de
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Douglas Charles Smith
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Hercules LLC
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Hercules LLC
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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
    • 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
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/31—Gums
    • D21H17/32—Guar or other polygalactomannan gum
    • 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
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents

Definitions

  • This invention relates to a mixture of cationic and anionic polymers useful as a strengthening additive in papermaking processes, and to the use of the mixture in a conventional aqueous suspension of cellulosic fibers in a process for making paper.
  • Polyacrylamides are disclosed in a number of patents to improve dry strength, and acrylamide copolymers have been developed in attempting to provide increased dry strength to papers made from unbleached pulps, and, more particularly, those containing black liquor.
  • US-A- 3,819,555 discloses autodispersible, nonionic, anionic, cationic and amphoteric vinyl polymers containing at least 60 weight percent acrylamide linkages and at least 5 weight percent of acrolein linkages, including anionic and cationic polymers that are said to provide improved dry and wet strength when added to unbleached pulps, and pulps containing black liquor.
  • US-A- 3,840,489 discloses substantially autodispersible vinylamide polymers comprising at least 60 weight percent of unsubstituted vinylamide linkages as dry strengthening components and at least 5 weight percent of hydrophobic linkages as components for improving absorptivity to cellulose.
  • the latter polymers may also carry a small amount of anionic or cationic substituents.
  • US-A- 4,167,439 discloses that a nonionic copolymer composed of 5 to 30 weight % N-vinyl pyrrolidone, 15 to 60 weight % acrylamide, and 30 to 70 weight % methyl methacrylate is useful as dry strength additive when used in the presence of black liquor.
  • acrylamide copolymers disclosed to be water-insoluble or dispersible, are stated to be useful as dry strength additives for use with unbleached pulps containing black liquors.
  • US-A- 3,874,994, US-A- 3,875,097, and US-A- 3,875,098 disclose use of a water-insoluble polymer containing at least about 60 weight percent of unsubstituted acrylamide linkages, at least about 5 weight percent of hydrophobic linkages, and at least about 2 weight percent of N-[di-(C1 ⁇ 3alkyl)amino methyl]acrylamide.
  • US-A- 4,002,588 discloses a polysalt that consists essentially of an anionic acrylamide-styrene-acrylic acid interpolymer (molar ratio, respectively, of 94-65:5-15:1-20) and a water-soluble cationic polyamine having a molecular weight in excess of 1,000 is an efficient strengthening agent, even when used with unbleached pulps containing black liquor.
  • US-A- 3,660,338 and US-A- 3,677,888 disclose a strength additive consisting essentially of (a) an ionically self-crosslinked polysalt of a normally water-soluble polyanionic polymer with a normally water-soluble polycationic polymer, at least one polymer of which is a weak electrolyte having an ionization constant less than 10 ⁇ 3 and (b) a water-soluble ionization suppressor.
  • South African Patent Application 78/2037 discloses water-soluble dry strength polymers, which are asserted to be suitable for the manufacture of paper from unbleached fibers, both in the presence of and in the absence of black liquor, comprising acrylamide linkages and N-[di-(C1 ⁇ 3alkyl) aminomethyl]acrylamide linkages having the specified formulae in a mole ratio of 98:2 to 50:50, respectively.
  • These polymers may have additional linkages, which are nonionic, anionic or cationic, including cationic dimethyl diallyl ammonium chloride and 2-dimethylaminoethyl acrylate linkages. They have a viscosity of 2 to 10 mPas (centipoises (cps)), preferably 3 to 8 mPas (cps), in a 0.5% aqueous solution at pH 11 and 25°C.
  • US-A- 4,347,100 discloses that addition of an anionic organic surface active agent into mechanical or thermomechanical pulp at elevated temperature and pressure is effective to cause dispersion of the lignin and to retard redeposition or coating of the lignin on the fibers during defibering of the wood and during subsequent cooling of the pulp.
  • Useful water-soluble anionic agents are disclosed to be relatively high molecular weight anionic organic polyelectrolytes or polymers, such as sodium lignin sulfonates, or relatively lower molecular weight anionic detergents.
  • the resultant pulp is disclosed to have improved strength.
  • Yamashita in JP-A- 191394-82, discloses the addition of low molecular weight cationic polymers having a charge density of at least (or more than) 3.0 meq/g, preferably at least 5.0 meq/g, to unbleached pulp containing at least 3 percent, based on the weight of the pulp, of lignin to improve the dry strength of the resultant paper.
  • This lignin is generally present in the black liquor. However, where sufficient lignin is not present in the pulp, additional amounts may be added.
  • Yamashita also describes that the prior art includes use of an anionic or weakly cationic water-soluble polymeric substance, of greater molecular weight than his cationic polymers, in combination with lignin to improve dry strength, but that the prior art processes do not provide improved dry strength.
  • CA-A- 1,110,019 discloses a process for manufacturing paper having improved dry strength using, first, a water-soluble cationic polymer having a viscosity greater than about 5 mPas (cps) in a 10% aqueous solution at 25°C and, subsequently, a cation content of greater than about 1.0 gram ion/kg polymer in combination with a water soluble anionic polymer.
  • a water-soluble cationic polymer having a viscosity greater than about 5 mPas (cps) in a 10% aqueous solution at 25°C and, subsequently, a cation content of greater than about 1.0 gram ion/kg polymer in combination with a water soluble anionic polymer.
  • Exemplary cationic components include a copolymer of acrylamide and methacryloyloxyethyltrimethyl ammonium chloride having a viscosity of 9800 mPas (cps) (10% solution) and a cationic content of 2.68 gram ion/kg polymer, a copolymer of acrylamide and methacryloyloxyethyltrimethyl ammonium chloride having a viscosity of 9700 mPas (cps) (10% solution) and a cationic content of 1.64 gram ion/kg polymer, and a copolymer of acrylamide and dimethyldiallyl ammonium chloride having a viscosity of 33 mPas (cps) and a cationic content of 2.21 gram ion/kg polymer.
  • Guar and its derivatives are also known as dry strength additives.
  • US-A- 3,303,184 discloses use of aminoethyl gums, such as aminoethyl ethers of guar, as dry strength additives.
  • a mixture of water-soluble cationic and anionic polymers useful as a strengthening additive in papermaking processes is characterized in that it comprises a water-soluble, linear, cationic polymer having a reduced specific viscosity (0.05 weight % in a 2 M NaCl solution at 30°C) greater than 2 dl/g and a charge density of 0.2 to 4 meq/g, and a water-soluble, anionic polymer having a charge density of less than 5 meq/g that is reactable in the presence of water with the cationic polymer to form a polyelectrolyte complex.
  • a process for making the mixture of cationic and anionic polymers according to claim 14 is provided.
  • the invention also includes a process for improving the dry strength of paper according to claim 16.
  • the amount of the cationic polymer is 0.2 to 3%, by dry weight of the fibers.
  • the use of the mixture of cationic and anionic polymers according to the invention is characterized in that the said mixture is incorporated into a conventional aqueous suspension of cellulosic fibers in a process for making paper.
  • the polymers useful in this invention are water-soluble cationic and anionic polymers.
  • water-soluble it is meant that the polymers form a non-colloidal 1% aqueous solution.
  • linear it is meant that the polymers are straight-chained, with no significant branching present. Exemplary polymers are described below.
  • Charge Density can be determined based on the known structure of the polymer by calculating as follows: It may also be determined by experimentation, for instance, by using the colloidal titration technique described by L. K. Wang and W. W. Schuster in Ind. Eng. Chem., Prd. Res. Dev., 14(4)312 (1975).
  • molecular weight is expressed in terms of the polymers reduced specific viscosity (RSV) measured in a 2 M NaCl solution containing 0.05 weight percent of the polymer at 30°C. Under these conditions, a cationic acrylamide copolymer of molecular weight 1 x 106 has a RSV of approximately 2 dl/g.
  • the polyelectrolyte complex that may form from the mixture of cationic and anionic polymers may be soluble, partially soluble or insoluble in water. Thus, it forms what may be conventionally termed a "solution”, “suspension”, “dispersion”, etc.
  • aqueous system will be used to refer to the same. In some instances the term “aqueous system” is also used with respect to aqueous solutions of the water-soluble polymers that form the polyelectrolyte complex.
  • the cationic polymers of this invention have a RSV greater than 2 dl/g, preferably in the range of about 10 to about 25 dl/g. They have a charge density in the range of from 0.2 to 4 meq/g, preferably 0.5 to 1.5 meq/g. Optimum performance is obtained with cationic polymers having a charge density of about 0.8 meq/g.
  • Exemplary cationic polymers include polysaccharides such as cationic guar (e.g., guar derivatized with glycidyltrimethylammonium chloride) and other natural gum derivatives, and synthetic polymers such as copolymers of acrylamide.
  • the latter include copolymers of acrylamide with diallyldimethylammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethyl ammonium methylsulfate, methacryloyloxyethyltrimethyl ammonium chloride (MTMAC) or methacrylamidopropyltrimethylammonium chloride, etc.
  • DADMAC diallyldimethylammonium chloride
  • MTMAC methacryloyloxyethyltrimethyl ammonium chloride
  • methacrylamidopropyltrimethylammonium chloride etc.
  • copolymers of acrylamide with DADMAC or MTMAC are preferred.
  • Some of the cationic polymers described above may undergo hydrolysis of their ester linkages under conditions of high temperature, extreme pH's, or extended storage. This hydrolysis results in the loss of cationic charge and the introduction of anionic sites into the polymer. If sufficient hydrolysis occurs, the polymer solution may become hazy. However, this hydrolysis has been found to have no significant effect on the performance of the polymer so long as the net cationic charge density (sum of cationic polymer charge density (meq. +/g) plus anionic polymer charge density (meq. -/g)) remains within the ranges specified.
  • the anionic components of this invention include those normally present in unbleached pulps such as solubilized lignins and hemicelluloses; synthetic anionic polymers; and anionically modified natural polymers (i.e., those other than lignins and hemicelluloses). When present in the papermaking process in sufficient quantity, the anionic polymer normally present in unbleached pulps are preferred.
  • Solubilized lignins and hemicelluloses are normally present in unbleached pulps as a result of incomplete removal of materials solubilized during manufacture of the pulp. Such products result from both chemical and mechanical pulping.
  • black liquors such as kraft black liquor or neutral sulfite brown liquor
  • black liquors comprise solubilized lignin and hemicellulose. Washed, unbleached pulp normally contains 1 to 10 weight percent black liquors.
  • Exemplary synthetic anionic polymers and anionically modified natural polymers useful in the present invention include copolymers of acrylamide and sodium acrylate, sodium methacrylate and sodium-2-acrylamide-2-methylpropane sulfonate; sodium carboxymethylcellulose; sodium carboxymethyl guar; sodium alginate; sodium polypectate; and poly-(sodium-2-acrylamide-2-methylpropane sulfonate). They may be used by themselves or in any combination.
  • lignin and hemicellulose are obtained, e.g., by oxidation, sulfonation or carboxymethylation.
  • Oxidized and sulfonated lignins and hemicelluloses are naturally present as by-products of the pulping process and are normally present in unbleached pulps useful in this invention.
  • the naturally present lignins and hemicellulose may also be modified by synthetic processes such as oxidation, sulfonation and carboxymethylation.
  • the polyelectrolyte complex of this invention provides paper having improved dry strength in most papermaking systems. It is especially useful in the presence of the anionic materials found in unbleached papermaking systems, i.e., black liquors, as prior dry strength additives show reduced effectiveness in such systems.
  • the process for manufacturing paper comprises three principal steps: (1) forming an aqueous suspension of cellulosic fibers; (2) adding the strengthening additive; and (3) sheeting and drying the fibers to form the desired cellulosic web.
  • the first step of forming an aqueous suspension of cellulosic fibers is performed by conventional means, such as known mechanical, chemical and semichemical, etc., pulping processes. After the mechanical grinding and/or chemical pulping step the pulp is washed to remove residual pulping chemicals and solubilized wood components. These steps are well known, for instance, as described in Casey, Pulp and Paper (New York, Interscience Publishers, Inc. 1952).
  • the second step may be carried out by adding the polyelectrolyte complex, or cationic component, or cationic and anionic components, or blends of the anionic and cationic components directly to the papermaking system.
  • the individual components and blends of the components may be dry or they may be in aqueous systems. Further, this step may be carried out by forming an aqueous system comprising the polyelectrolyte complex, or polymer, or polymers, and adding the same to the papermaking system.
  • the third step is carried out according to well-known and conventional means, such as those described in, e.g., Casey, Pulp and Paper, cited above.
  • the polyelectrolyte complex forms when the components are mixed in an aqueous system, preferably under high shear. It may be formed and then added during the papermaking process, or may be formed in the papermaking process. In the latter instance, the cationic component may be added by itself to react with naturally present anionic polymers or may be simultaneously or successively added with an anionic component. When added successively, the anionic polymer is generally added prior to the cationic polymer in order to avoid flocculating the pulp. Here, the amount of each anionic polymer to be incorporated in the polyelectrolyte complex is reduced to take into account the amount of that polymer already in the system.
  • the specific amount and type of polyelectrolyte complex that is preferable will depend on, among other things, the characteristics of the pulp; the presence or absence of black liquors and, where present, the amount and nature thereof; characteristics of the polymers used to form the complex; the characteristics of the complex; the desirability of transporting an aqueous system comprising the polyelectrolyte complex; and the nature of the papermaking process in which the aqueous system is to be used.
  • the polyelectrolyte complex will typically comprise polymers in a ratio of cationic polymer(s):anionic polymer(s) of 4:100 to 40:1, preferably 1:4 to 4:1.
  • Aqueous systems formed prior to addition to the pulp normally comprise 0.1 to 10 weight percent, based on the weight of the water in the system, of the polyelectrolyte complex.
  • the polyelectrolyte complex is effective when added to the stock in an amount of 0.1 to 15%, preferably 0.2 to 3%, by dry weight of the pulp.
  • anionic polymer to be used is dependent on the source of the anionic material. Naturally present anionic polymers are typically found at a level of 0.1 to 5%, based on the dry weight of the pulp. When anionic polymers are added to the system, the total weight of anionic polymers generally falls in the range of 0.1 to 10%, based on the dry weight of the pulp. Preferably, the total weight of added anionic polymers is in the range of 0.1 to 2.5%, based on the dry weight of the pulp.
  • the level of cationic polymer required is highly dependent on the level of anionic material present.
  • the level of cationic polymer is generally 0.1 to 5%, preferably 0.1 to 2.5%, based on the dry weight of the pulp.
  • the anionic charge fraction is indicative of the nature of the polyelectrolyte complex. It can be determined by the following formula: in which the total anionic charge is determined by multiplying the absolute value of the charge density (electrostatic charge per weight of polymer, e.g., in meq/g) of each anionic polymer forming the polyelectrolyte complex by the weight of that polymer in the polyelectrolyte complex and adding the total charge of all of the anionic polymers.
  • the total cationic charge is determined by multiplying the charge density of each cationic polymer forming the poly-electrolyte complex by the weight of that polymer in the polyelectrolyte complex and adding the total charge of all of the cationic polymers.
  • polyelectrolyte complex is completely soluble at an anionic charge fraction of less than 0.2, colloidal at an anionic charge fraction of 0.2 to 0.4, and fibrous (in some instances as a stringy gel that precipitates from solution, but which becomes colloidal under high shear) at an anionic charge fraction greater than 0.4.
  • Polyelectrolyte complexes of this invention generally have an anionic charge fraction of 0.1 to 0.98, preferably an anionic charge fraction of 0.3 to 0.8, and more preferably 0.45 to 0.6. All polyelectrolyte complexes per this invention provide enhanced dry strength, particularly in the presence of black liquors.
  • the fibrous polyelectrolyte complexes (particularly those having the more preferred anionic charge fraction listed above) provide larger improvement in dry strength than colloidal or water-soluble polyelectrolyte complexes prepared from the same polymers. Under high shear in papermaking, these fibrous particles break into colloidal particles that provide excellent dry strength properties.
  • Unique properties are obtained by forming the polyelectrolyte complex by mixing the anionic and cationic components in an aqueous system at a temperature of at least 75°C and letting the mixture cool to less than about 60°C, preferably less than 50°C. This can be achieved by adding the dry powder polymers to water heated to at least 75°C and, then, allowing the resultant aqueous system to cool to less than about 60°C. Premixing of the polymers into a dry polymer mixture may facilitate handling.
  • the same properties can be obtained by preparing separate aqueous systems of the anionic and cationic polymers, heating each of the aqueous systems to at least 75°C, mixing them together, and, then, allowing the resultant aqueous system to cool to less than about 60°C.
  • Polyelectrolyte complexes prepared by these processes generally have an anionic charge fraction of 0.1 to 0.98, preferably 0.4 to 0.9, and most preferably 0.65 to 0.85. High shear mixing aids in the rapid preparation of these polyelectrolyte complexes, but is not necessary. Maintaining the temperature of the preparation solution, dispersion, or slurry at above about 75°C for one hour aids in the homogenization of the mixture.
  • Polyelectrolyte complexes having an anionic charge fraction of less than about 0.2 prepared by heating to at least 75°C and cooling will be water-soluble and perform in the same manner to those having the same anionic charge fraction prepared at lower temperatures.
  • Polyelectrolyte complexes with anionic charge fractions of from about 0.2 to less than about 0.65 form colloidal particles that perform similar to the colloidal and fibrous particles prepared without heating to at least 75°C and cooling.
  • the anionic charge fraction is about 0.65 or higher and the polyelectrolyte complexes are prepared by heating to at least 75°C followed by cooling, water-soluble polyelectrolyte complexes are obtained that perform even better as dry strength additives than the other species of this invention.
  • These soluble polyelectrolyte complexes are also useful as shear activated flocculants, retention aids on high speed paper machines, viscosifiers and drag reduction agents, and in water treatment.
  • Such water-soluble complexes can be prepared from all of the aforementioned types of anionic components.
  • temperatures are not normally sufficiently high during papermaking for formation of such a water-soluble polyelectrolyte complex. Therefore, to use those anionic polymers normally present in unbleached pulps, it is necessary to separate the anionic component from the pulp. This separation is normally carried out in the papermaking process, making such anionic components readily available.
  • Water-soluble polyelectrolyte complexes can be prepared from, for example, poly(acrylamide-co-dimethyldiallyammonium chloride) and Marasperse N-3 sodium lignin sulfonate (Reed Lignin Inc., Greenwich, CT), or Aqualon® CMC 7M (Aqualon Company, Wilmington, DE), or southern pine black liquor; quaternary amine modified waxy maize starch and Marasperse® N-22 sodium lignin sulfonate (Reed Lignin Inc., Greenwich, CT); poly(acrylamide-co-methylacryloxyethyltrimethylammonium chloride) and Marasperse® N-3 sodium lignin sulfonate; and poly(acrylamide-co-methylacryloxyethyltrimethylammonium chloride) and Marasperse® N-3 sodium lignin sulfonate.
  • additives useful in the papermaking process of this invention include sizes, defoamers, fillers, wetting agents, optical brighteners, inorganic salts, etc.
  • Handsheets were made on a Noble and Wood Sheet Machine (Noble and Wood Machine Co., Hoosick Falls, NY) using the following: 1. Pulp: unbleached southern kraft pulp beaten to 550 Canadian Standard Freeness (CSF) at pH 8. 2. Standard Hard Water: Standard hard water having 50 ppm alkalinity and 100 ppm hardness was prepared by adding CaCl2 and NaHCO3 to distilled water, and adjusting the pH to 6.5 with H2SO4. 3.
  • Pulp unbleached southern kraft pulp beaten to 550 Canadian Standard Freeness (CSF) at pH 8.
  • CSF Canadian Standard Freeness
  • Standard Hard Water Standard hard water having 50 ppm alkalinity and 100 ppm hardness was prepared by adding CaCl2 and NaHCO3 to distilled water, and adjusting the pH to 6.5 with H2SO4. 3.
  • Black Liquor (Union Camp Corp., Worcester, GA): Total Solids: 15.9% (measured by Tappi Standard T650) Sulfate Ash: 8.9% Sodium: 2.6% (by atomic absorption spectroscopy) Sulfur: 0.7% (by x-ray fluoresence) Lignin: 5.2% (by UV spectroscopy) Charge density (by colloidal titration): .057 meq/g at pH 5.5 .103 meq/g at pH 9.0 4. Defoamer: Defoamer 491A (Hercules Incorporated, Wilmington, DE).
  • a clean thoroughly wetted screen was placed on an open deckle.
  • the deckle was clamped closed and then filled with the 6.5 pH standard hard water (described above), from the white water return tank, to the bottom mark on the deckle box.
  • a one liter aliquout of stock was drawn from the proportioner and poured into the deckle.
  • the stock in the deckle was stirred using three rapid strokes of the dasher, the dasher was removed, and the deckle was drawn into the white water return tank. The screen and retained pulp was then transferred to the open felt at the entrance to the press.
  • the felted sheets were run through the press with the press weights adjusted so as to obtain a pressed sheet having 33-34% solids. Then, the sheet and screen were placed in the drum dryer, having an internal temperature of 116°C (240°F) and a throughput time of 50-55 seconds, and run through two times (during the first run the sheet was in contact with the drum and during the second run the screen was in contact with the drum.). The sheets were conditioned at 22°C (72°F) and 50% relative humidity for 24 hours. Eight sheets were prepared in this manner, with the last five being used for testing.
  • the handsheets were evaluated by way of the following tests: Mullen Burst: Tappi Standard T403 ("Bursting Strength of Paper”). STFI Compression: Tappi Standard T826 ("Short Span Compressive Strength of Paperboard”).
  • Table 1 shows that improved results are obtained with respect to both the STFI Compression Strength and Mullen Burst tests when a cationic polymer of this invention is added to a pulp containing black liquor. Looking at the rows of data it can be seen that best STFI Compression Strength results were obtained with samples containing black liquor. Similarly, Mullen Burst results were better for samples containing black liquor than samples that did not contain black liquor at polymer levels of 0.2% or more, despite the fact that better results were obtained when the control did not contain black liquor. Looking at the columns, it can be seen that results were significantly better with samples containing black liquor having 0.2% or more of the cationic polymer. Thus, this example demonstrates formation of a polyelectrolyte complex between the cationic polymer added and the anionic polymers present in the black liquor, and that improved dry strength is obtained with the polyelectrolyte complex of this invention.
  • the data in Table 4 shows that improved STFI Compression Strength and Mullen Burst results are obtained using the cationic polymers of this invention.
  • the samples prepared with cationic polymers per this invention performed better than the control sample.
  • STFI Compression Strength was better in each instance with black liquor.
  • Mullen Burst results were better with the samples prepared with black liquor than samples that were not prepared with black liquor, except with respect to sample No. 22.
  • the results indicate that a polyelectrolyte complex forms between the cationic polymers of this invention and anionic polymer present in black liquors.
  • Example 1 show the effect of addition of both anionic and cationic polymers during papermaking and the beneficial effect of addition of higher levels of anionic component.
  • the procedures of Example 1 were repeated using 0.5% of the cationic polymer used in example 2-6 and the anionic polymers listed in Table 5, below. The results are shown below in Table 5.
  • Table 5 demonstrates that superior dry strength properties are obtained when both an anionic and cationic polymer are added during papermaking so as to form a polyelectrolyte complex.
  • example 25 shows that improved results are achieved when the amount of anionic polymer is such that the cationic and anionic changes are nearly balanced (i.e., the charges are neutralized).
  • Table 6 shows the superior dry strength properties of paper prepared with the polyelectrolyte complex of this invention.
  • Example No. 35 the sample prepared with black liquor performed better than the sample prepared without black liquor.
  • a polyelectrolyte complex forms with the cationic polymers and the naturally present anionic polymers in black liquor, providing improved dry strength.
  • Examples 29 and 30 have superior dry strength compared to example 28 in the absence of black liquor, indicating formation of a polyelectrolyte complex by the cationic polymer and CMC.
  • Similar results were found to occur with other cationic/anionic polymer combination per this invention, in the absence of black liquor, in examples 31 to 33.
  • the lower STFI value achieved with poly(sodium) acrylate (no black liquor present) indicates that additive anionic polymers per the instant invention provide superior dry strength as compared to other additive anionic polymers.
  • results obtained in example 34 in the presence of black liquor can be attributed to formation of a polyelectrolyte complex between the cationic polymer and the anionic polymers forming the black liquor.
  • Sample 35 is a comparative example showing the use of a cationic polymer outside the scope of the instant invention.
  • the STFI value was lower in the presence of black liquor using this cationic polymer.
  • this invention provides superior dry strength in the presence of black liquor than in the absence of black liquor, whereas a decrease in dry strength occurs in the presence of black liquor using dry strength additives outside the scope of this invention.
  • examples illustrate the effect of premixing a portion of the anionic component with the cationic polymer so as to form an aqueous system containing a polyelectrolyte complex and adding the aqueous system to a papermaking furnish.
  • the procedure of examples 1-6 were repeated so as to prepare a control example having no cationic polymer, example 36, and a sample prepared with a cationic copolymer comprised of 87.6 mole % acrylamide units and 12.4% diallyldimethylammonium chloride units, Example 37.
  • Sample 38 was prepared using an additive composition comprising 86 parts of the aforementioned acrylamide copolymer and 14 parts sodium lignin sulfonate, which was premixed in a Waring blender so as to form a water-insoluble particulate polyelectrolyte complex prior to addition to the papermaking furnish according to the following procedure.
  • Table 7 demonstrates that excellent dry strength properties are obtained using an anionic and cationic polymer per this invention, particularly when they are premixed to form a particulate polyelectrolyte complex prior to addition to the papermaking process. Excellent dry strength properties occur in the presence of black liquor, and superior performance to the cationic polymer only is shown in the absence of black liquor.
  • Examples 1-6 illustrates the performance of comparative polymers.
  • the procedure of Examples 1-6 was repeated using the following polymers: no cationic polymer, (sample No. 39); Corcat® P600 polyethyleneimine (PEI) (Cordova Chemical Co. Muskegon, MI) (sample No. 40); poly(diallyldimethylammonium chloride) (sample No. 41); poly(acryloyloxyethyltrimethylammonium chloride) (sample No. 42); polyaminoamide epichlorohydrin resin (sample No.
  • Example No. 44 copolymer prepared from 11 mole % styrene, 5 mole % sodium acrylate and 84 mole % acrylamide, prepared according to the procedures of Example 12 of US-A- 3,840,489) (sample No. 44); a copolymer prepared by mixing the copolymer of Example 44 with polyaminoamide epichlorohydrin resin according to the procedures of US-A- 4,002,588 (the polymers were mixed at an equal charge ratio) (sample No.
  • Marasperse® N-3 sodium lignin sulfonate Rosin Inc., Greenwich, CT
  • Table 9 Ex. Anionic Charge Fraction Sodium Lignin Sulfonate(g) Nature of Polyelectrolyte Complex Brookfield Viscosity1 47 0 0 None formed 37 mPas (cps) 48 0.6 0.993 0.6 micrometer colloidal particle 5.7 mPas (cps) 49 0.8 2.648 soluble 4.6 mPas (cps) 1. 60 rpm, #2 spindle.
  • a dry powder was prepared by mixing 0.98 g of copolymer of acrylamide and diallyldimethylammonium chloride (6 mole %) and the amount of Marasperse® N-3 sodium lignin sulfonate (Reed Lignin Inc., Greenwich, CT) listed in the following table.
  • the dry powder mixture was then added to 200 g of water that had been heated to 80°C and the mixture was stirred using a Cowles disperser blade in a baffled, heated vessel for 5 minutes at 750 rpm, while the temperature was maintained at 80°C, and then allowed to cool to room temperature.
  • polyelectrolyte complex of Example 56 provides improved dry strength, particularly in papers prepared with unbleached pulp and black liquor. Therefore, the polyelectrolyte complex of this invention is suitable for use as dry strength additive in all types of paper and is particularly useful as a dry strength additive for unbleached paper and paper board.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (22)

  1. Als Verstärkungsadditiv in Papiererzeugungsverfahren geeignetes Gemisch aus wasserlöslichen kationischen und anionischen Polymeren, dadurch gekennzeichnet, daß es ein lineares, kationisches Polymer mit einer reduzierten spezifischen Viskosität (0,05 Gew.-% in einer 2 M-NaCl-Lösung bei 30°C) von über 2 dl/g und einer Ladungsdichte von 0,2 bis 4 Milliäquivalenten/g und ein anionisches Polymer mit einer Ladungsdichte von weniger als 5 Milliäquivalenten/g, das in Anwesenheit von Wasser mit dem kationischen Polymer unter Ausbildung eines Polyelektrolytkomplexes reaktionsfähig ist, umfaßt.
  2. Gemisch aus kationischen und anionischen Polymeren nach Anspruch 1, weiterhin dadurch gekennzeichnet, daß das kationische Polymer eine reduzierte spezifische Viskosität von 10 bis 25 dl/g aufweist.
  3. Gemisch aus kationischen und anionischen Polymeren nach Anspruch 1 oder 2, weiterhin dadurch gekennzeichnet, daß das kationische Polymer eine Ladungsdichte von 0,5 bis 1,5 Milliäquivalenten/g aufweist.
  4. Gemisch aus kationischen und anionischen Polymeren nach Anspruch 1, 2 oder 3, weiterhin dadurch gekennzeichnet, daß das kationische Polymer aus der Gruppe ausgewählt ist, die aus kationischem Guar und Copolymeren von Acrylamid und Diallyldimethylammoniumchlorid, Acryloyloxyethyltrimethylammoniumchlorid, Methacryloyloxyethyltrimethylammoniummethylsulfat, Methacryloyloxyethyltrimethylammoniumchlorid und Methacrylamidopropyltrimethylammoniumchlorid besteht.
  5. Gemisch von kationischen und anionischen Polymeren nach Anspruch 4, weiterhin dadurch gekennzeichnet, daß das kationische Polymer aus der aus Copolymeren von Acrylamid mit Diallyldimethylammoniumchlorid und Methacryloyloxyethyltrimethylammoniumchlorid bestehenden Gruppe ausgewählt ist.
  6. Gemisch aus kationischen und anionischen Polymeren nach einem der vorstehenden Ansprüche, weiterhin dadurch gekennzeichnet, daß das anionische Polymer aus der Gruppe ausgewählt ist, die aus Copolymeren von Acrylamid und Natriumacrylat, Natriummethacrylat und Natrium-2-acrylamid-2-methylpropansulfonat, Natriumcarboxymethylcellulose, Natriumcarboxymethylguar, Natriumalginat, Natriumpolypectat und Poly(natrium-2-acrylamid-2-methylpropansulfonat) besteht.
  7. Gemisch aus kationischen und anionischen Polymeren nach einem der vorstehenden Ansprüche, weiterhin dadurch gekennzeichnet, daß das Polymergemisch in Form eines Polyelektrolytkomplexes vorliegt.
  8. Gemisch aus kationischen und anionischen Polymeren nach Anspruch 7, weiterhin dadurch gekennzeichnet, daß der Polyelektrolytkomplex einen anionischen Ladungsanteil von 0,1 bis 0,98 aufweist.
  9. Gemisch aus kationischen und anionischen Polymeren nach Anspruch 7, weiterhin dadurch gekennzeichnet, daß der Polyelektrolytkomplex einen anionischen Ladungsanteil von 0,3 bis 0,8 aufweist.
  10. Gemisch aus kationischen und anionischen Polymeren nach Anspruch 7, weiterhin dadurch gekennzeichnet, daß der Polyelektrolytkomplex einen anionischen Ladungsanteil von 0,65 bis 0,85 aufweist.
  11. Gemisch aus kationischen und anionischen Polymeren nach Anspruch 7, weiterhin dadurch gekennzeichnet, daß der Polyelektrolytkomplex einen anionischen Ladungsanteil von 0,45 bis 0,6 aufweist und faserig ist.
  12. Gemisch aus kationischen und anionischen Polymeren nach einem der vorstehenden Ansprüche, weiterhin dadurch gekennzeichnet, daß das Gewichtsverhältnis des kationischen Polymers zum anionischen Polymer 4:100 bis 40:1 beträgt.
  13. Gemisch aus kationischen und anionischen Polymeren nach Anspruch 12, weiterhin dadurch gekennzeichnet, daß das Gewichtsverhältnis des kationischen Polymers zum anionischen Polymer 1:4 bis 4:1 beträgt.
  14. Verfahren zur Ausbildung des Gemisches aus kationischen und anionischen Polymeren nach einem der Ansprüche 1 bis 13, wobei das kationische Polymer und das anionische Polymer zu Wasser mit einer Temperatur von wenigstens etwa 75°C zugesetzt werden und das resultierende wäßrige System auf unter etwa 60°C abgekühlt wird.
  15. Verwendung des Gemisches aus kationischen und anionischen Polymeren nach einem der Ansprüche 1 bis 13 in einem Papiererzeugungsprozeß, wobei dieses Gemisch in eine konventionelle wäßrige Suspension von Zellulosefasern aufgenommen wird.
  16. Verfahren zur Verbesserung der Trockenfestigkeit von Papier, wobei ein wasserlösliches kationisches Polymer in eine konventionelle wäßrige Suspension von Zellulosefasern aufgenommen wird, worin die Suspension von Zellulosefasern ein wasserlösliches anionisches Polymer enthält, wonach die Fasern in Blattform gebracht und zur Ausbildung der Zellulosebahn getrocknet werden, dadurch gekennzeichnet, daß das kationische Polymer ein lineares Polymer mit einer reduzierten spezifischen Viskosität (0,05 Gew.-% in einer 2M NaCl-Lösung bei 30°C) von über 2 dl/g und einer Ladungsdichte von 0,2 bis 4 Milliäquivalenten/g ist und in die Suspension von Zellulosefasern in einer Menge von 0,1 bis 5 %, bezogen auf das Trockengewicht der Fasern, eingebracht wird und daß das anionische Polymer eine Ladungsdichte von unter 5 Milliäquivalenten/g aufweist.
  17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß die Menge des kationischen Polymers 0,2 bis 3 %, bezogen auf das Trockengewicht der Fasern, beträgt.
  18. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß die Menge des kationischen Polymers 0,1 bis 2,5 %, bezogen auf das Trockengewicht der Fasern, beträgt.
  19. Verfahren nach Anspruch 16, 17 oder 18, dadurch gekennzeichnet, daß die Menge des anionischen Polymers 0,1 bis 5%, bezogen auf das Trockengewicht der Fasern, beträgt.
  20. Verfahren nach einem der Ansprüche 16 bis 19, dadurch gekennzeichnet, daß 0,1 bis 5 % des anionischen Polymers, bezogen auf das Trockengewicht der Fasern, zu der Zellulosefasersuspension zugesetzt werden.
  21. Verfahren nach Ansopruch 16 oder 17, dadurch gekennzeichnet, daß das anionische Polymer aus der Gruppe ausgewählt wird, die aus in ungebleichten Pulpen vorliegenden anionischen Polymeren, synthetischen anionischen Polymeren und anionisch modifizierten natürlichen Polymeren besteht.
  22. Verfahren nach Anspruch 16, umfassend die folgenden Stufen:
    (1) Ausbilden einer wäßrigen Suspension aus ungebleichten Pulpefasern mit einem Gehalt an etwa 0,1 bis etwa 5%, bezogen auf das Trockengewicht der Pulpe, an anionischen Polymeren, die normalerweise in ungebleichter Pulpe vorliegen,ausgewählt aus der aus solubilisierten Ligninen und Hemizellulosen bestehenden Gruppe, welche anionischen Polymere eine Ladungsdichte von unter 5 Milliäquivalenten aufweisen;
    (2) Zusetzen von etwa 0,1 bis etwa 5 %, bezogen auf das Trockengewicht der Pulpe, eines Polymers zu der Pulpe, welches Polymer im wesentlichen aus wenigstens einem wasserlöslichen linearen hochmolekularen kationischen Polymer niedriger Ladungsdichte mit einer reduzierten spezifischen Viskosität von über 2 dl/g und einer Ladungsdichte von 0,2 bis 4 Milliäquivalenten besteht, in einer solchen Menge, daß sich mit dem normalerweise in der ungebleichten Pulpe vorliegenden anionischen Polymer der Polyelektrolytkomplex ausbilden wird, und Ausbilden eines Polyelektrolytkomplexes aus dem kationischen Polymer und den normalerweise in ungebleichter Pulpe vorliegenden anionischen Polymeren; und
    (3) Überführen in Blattform und Trocknen der Fasern der Pulpe zur Ausbildung der gewünschten Zellulosebahn.
EP89118245A 1988-10-03 1989-10-02 Trockenfestigkeitszusatz für Papier Expired - Lifetime EP0362770B1 (de)

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KR101349076B1 (ko) * 2011-07-20 2014-01-14 현대자동차주식회사 연료전지 스택용 매니폴드 블록의 산화층 형성 장치 및 방법
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EP0362770A3 (de) 1991-01-09
EP0362770A2 (de) 1990-04-11
KR0159921B1 (ko) 1999-01-15
JPH02251696A (ja) 1990-10-09
DE68917069D1 (de) 1994-09-01
FI98941B (fi) 1997-05-30
AU619599B2 (en) 1992-01-30
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DE68917069T2 (de) 1994-12-08
JP2862913B2 (ja) 1999-03-03
FI894684A (fi) 1990-04-04
AU4252389A (en) 1990-04-05
BR8905018A (pt) 1990-05-08

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