WO1998006898A1 - Polyacrylamides amphoteres utilises comme additifs de resistance a l'etat sec pour la fabrication de papier - Google Patents

Polyacrylamides amphoteres utilises comme additifs de resistance a l'etat sec pour la fabrication de papier Download PDF

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Publication number
WO1998006898A1
WO1998006898A1 PCT/US1997/014010 US9714010W WO9806898A1 WO 1998006898 A1 WO1998006898 A1 WO 1998006898A1 US 9714010 W US9714010 W US 9714010W WO 9806898 A1 WO9806898 A1 WO 9806898A1
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Prior art keywords
monomer
cationic
paper
anionic
group
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PCT/US1997/014010
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English (en)
Inventor
Elliott Echt
Richard Perlee Geer
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Hercules Incorporated
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Priority to AU39131/97A priority Critical patent/AU3913197A/en
Publication of WO1998006898A1 publication Critical patent/WO1998006898A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H21/20—Wet strength agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/38—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides

Definitions

  • This invention relates to a process for making paper, which paper has improved dry strength.
  • U.S. Patent No. 2,884,058 discloses improving the dry strength (tensile) of paper utilizing an amphoteric acrylamide polymer wherein the cationic groups are supplied by quaternary ammonium groups.
  • the monomers used to supply the quaternary ammonium groups do not include methacryloyloxyethyltrimethylammonium chloride (MTMAC), acryloyloxyethyltrimethylammonium chloride (ATMAC), methacryloyloxyethylbenzyldimethylammonium chloride (MBMAC), dimethylaminoethylmethacrylate (DMAEMA) and salts of DMAEMA.
  • MTMAC methacryloyloxyethyltrimethylammonium chloride
  • ATMAC acryloyloxyethyltrimethylammonium chloride
  • MBMAC methacryloyloxyethylbenzyldimethylammonium chloride
  • DMAEMA dimethylaminoeth
  • U.S. Patent No. 5,032,226 discloses a base paper for photographic layer carriers containing cationic wet strength resin and an amphoteric poly(meth)acrylamide for structural strength. It is stated diat the molar ratio of the amide components to the sum of the anionic and cationic groups is preferably in the region of from about 60:40 to 95:5 in the amphoteric polymer, and that the ratio of the number of cationic groups to the number of anionic groups is between 10: 1 and 1 :2. In the examples the molar ratio of anionic monomer plus cationic monomer to uncharged monomer is 9:91 or greater.
  • 5,391 ,225 discloses an alkenylsuccinic acid emulsion sizing agent wherein the emulsifying dispersant is an amphoteric acrylamide polymer containing from 0.1 to 20 mole % cationic monomer, from 0.1 to 20 mole % anionic monomer and from 50 to 99.8 mole % acrylamide or methacrylamide.
  • European Patent Application No. 0 580 529 A discloses the use in paper of a predominantly cationic polyelectrolyte obtained from acrylamide, at least one anionic monomer at the 5-15 mole % level, and at least one cationic monomer at the 10-50 mole % level.
  • Japanese Patent Application No. 57047998(82)- A discloses that the strength of paper can be improved by using an amphoteric polyacrylamide copolymer, an anionic paper strength improver, and aluminum sulfate.
  • Japanese Patent Application No. 88063678(88)-B discloses that paper with high strength is obtained by addition of first, an amphoteric acrylamide polymer, second, A1 2 0 3 , and third, an amphoteric acrylamide polymer.
  • the acrylamide polymers contain 1 to 20 mole % anionic groups and 1 to 30 mole % cationic groups.
  • Japanese Patent Application No. 63050597(88)-A teaches that a paper strength intensifier comprises (meth)acrylamide, cationic monomer, ⁇ , ⁇ - unsaturated mono- or dicarboxylic acid, and difunctional vinyl monomer as constituent monomers.
  • the cationic monomers disclosed are dimethylaminoethyl (meth)acrylate and diethylaminopropyl (mett ⁇ )acrylamide. Summary of the Invention
  • the present invention relates to a process for making paper comprising: a) providing an aqueous pulp slurry; b) adding to the aqueous pulp slurry cationic polymer selected from the group consisting of cationic starch and cationic wet strength resin, and water- soluble amphoteric polymer made from monomers comprising: i) nonionic monomer selected from the group consisting of acrylamide and methacrylamide; ii) anionic monomer; and iii) cationic monomer, wherein the amount of anionic monomer plus cationic monomer is less than 9 mole percent of the total of anionic, cationic and nonionic monomer in the amphoteric polymer.
  • amphoteric polymer is made from monomers comprising: i) nonionic monomer selected from the group consisting of acrylamide and methacrylamide; ii) anionic monomer; iii) cationic monomer; and iv) crosslinking monomer comprising at least one water-soluble divinyl monomer.
  • the invention also relates to paper made by said process and paper with improved dry strength made by said process.
  • amphoteric polymers of the invention are made from nonionic monomer selected from the group consisting of acrylamide and methacrylamide, anionic monomer, and cationic monomer, wherein the amount of anionic monomer plus cationic monomer is less than 9 mole percent of the total of anionic, cationic and nonionic monomer in the amphoteric polymer.
  • the preferred nonionic monomer is acrylamide.
  • Anionic monomers for use in the invention are preferably ⁇ , ⁇ -unsaturated carboxylic acids such as e.g., acrylic acid, methacrylic acid, itaconic acid and salts thereof. More preferred anionic monomers are acrylic acid and methacrylic acids, or salts thereof; and the most preferred anionic monomer is acrylic acid or salts thereof.
  • the preferable salts are sodium salts.
  • Cationic monomers for use in the invention include unsaturated monomers containing amino groups or quaternary amino groups. When monomers containing amino groups are used, cationic sites are obtainable by forming salts of the amino groups with mineral acids.
  • Preferred unsaturated cationic monomers include methacryloyloxyethyltrimethylammonium chloride (MTMAC), acryloyloxyethyltrimethylammonium chloride (ATMAC), methacryloyloxyethylbenzyldimethylammonium chloride (MBMAC) and d e hydrochloride salt of dimethylaminoethylmethacrylate (DMAEMA-HC1).
  • MTMAC methacryloyloxyethyltrimethylammonium chloride
  • ATMAC acryloyloxyethyltrimethylammonium chloride
  • MBMAC methacryloyloxyethylbenzyldimethylammonium chloride
  • DMAEMA-HC1 d e
  • amphoteric polymers for use in the invention will have an amount of anionic monomer plus cationic monomer that is less than 9 mole percent, preferably less than about 8 mole percent, and more preferably less than about 7 mole percent, of the total of anionic, cationic and nonionic monomers.
  • the range of mole percent of anionic monomer plus cationic monomer will be from about 1 to 9, preferably from about 5 to 9, and more preferably from about 5 to about 8.
  • the relative ratio of anionic monomer to cationic monomer in the amphoteric polymers may vary over a wide range.
  • the molar ratio of cationic monomer to anionic monomer will be from about 0.5: 1 to about 2: 1. More preferably the ratio will be from about 0.6: 1 to about 1.5: 1, and most preferably from about 0.7: 1 to about 1 : 1.
  • a small amount of water soluble, divinyl monomer may also be incorporated to increase the molecular weight of the amphoteric polymer without crosslinking it so that it becomes insoluble.
  • Suitable divinyl- monomers include N,N'-methylenebisacrylamide, ethyleneglycol dimethacrylate and ethyleneglycol diacrylate.
  • the amphoteric polymers may be prepared by the general procedures described in U.S. Patent No. 5,543,446 to Rodriguez. The procedures involve dissolving the monomers in water, adjusting the pH to 3.0-6.0, preferably 4.0- 5.0, purging with nitrogen to remove oxygen, and adding a binary redox free- radical initiator to convert the monomers to polymer.
  • the monomer concentration in water is preferably from 10-25 weight percent.
  • Copper ions may be included to control the polymer molecular weight. Twenty-five to 35 parts cupric ion per million parts acrylamide monomer are typically included to control molecular weight depending upon the monomers used and the monomer concentration. Copper ion is generally added as copper sulfate.
  • the redox initiator consists of a reactive pair which forms free radicals on reaction with each other.
  • a particularly useful pair consists of potassium bromate and sodium metabisulfite. Other pairs will be apparent to those skilled in e art.
  • Aqueous solutions of the redox initiator components are added continuously to the purged monomer solution to cause polymerization of the monomers to polymer.
  • the polymer solutions so formed have Brookfield viscosities of about 2,000-20,000 cps at polymer concentrations of about 15-20 weight percent.
  • the polymers are further characterized by having reduced specific viscosities of about 0.5-2.0 dl/g at 0.05% concentration in 2 molal sodium chloride solution.
  • the paper of the instant invention is prepared by any of the procedures well known in the art.
  • the amount of amphoteric polymer used will be any amount which is effective to increase the dry strength of the paper.
  • the amount of polymer will be from about 0.05% to about 4% based on the dry weight of pulp. More preferably the amount of polymer will be from about 0.1 % to about 3 % , and most preferably from about 0.15% to about 2% based on the dry weight of pulp.
  • cationic polymer selected from the group consisting of cationic starch or cationic wet strength resin is utilized in addition to amphoteric polymer.
  • cationic wet strength resin is meant cationic polymers which when used alone in paper impart significant wet strength to the paper.
  • Exemplary cationic wet strength resins for use in the invention are polymeric amine/epihalohydrin resins, glyoxal-modified acrylamide copolymer resins, polyethyleneimines and polyvinylamines.
  • Polymeric amine/epihalohydrin resins are selected from the group consisting of poiyaminoamide/epihalohydrin resins, polyalkylenepolyamine/epihalohydrin resins, aminopolymer/epihalohydrin resins, and polyaminoamide ureylene/epihalohydrin resins.
  • the preferred epihalohydrin is epichlorohydrin.
  • Cationic glyoxal-modified acrylamide copolymer resins and their use in paper for wet strength are disclosed in U.S. Patent No. 3,556,932 to Coscia et al.
  • Polyaminoamide ureylene/epihalohydrin resins are disclosed in U.S. Patent No. 4,537,657 to Keim.
  • Polyalkylenepolyamine/epihalohydrin resins include resins made by reaction of epihalohydrin, preferably epichlorohydrin, with diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis(3-aminopropyl)amine, hexamethylenediamine or polyethyleneimine.
  • Amino polymer/epihalohydrin resins include resins made by reaction of epihalohydrin, preferably epichlorohydrin, with poly(diallylamine) or poly(meU ⁇ yldiallylamine).
  • Polyalkylenepolyamine/epihalohydrin resins and amino polymer/epihalohydrin resins are discussed by H.H.
  • the most preferred cationic wet strength resins for the practice of ttie invention are the polyaminoamide/epihalohydrin resins.
  • These resins are produced by reacting a saturated aliphatic dicarboxylic acid containing two to ten carbon atoms, preferably adipic acid, with a polyalkylenepolyamine containing from two to four ethylene groups, two primary amine groups, and one to three secondary amine groups, such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine, preferably diethylenetriamine, to form a polyaminoamide having secondary amine groups that are men alkylated with epihalohydrin, preferably epichlorohydrin, to form tertiary aminochlorohydrin groups.
  • These groups self-alky late to form hydroxyazetidinium groups, which are considered responsible for wet strength in paper.
  • polyaminoamides containing tertiary amines in the backbone are disclosed in U.S. Patent Nos. 4,487,884 and 4,515,657 to Maslanka. If tertiary amines are present in the polyaminoamide or polyamine backbone, quaternary epoxide groups are produced. The actual procedure for synthesizing these wet strength resins differs from product to product, but the objective, to generate aminopolyamide/epihalohydrin functionality, remains the same.
  • Kymene ® wet strength resins are the preferred polyaminoamide/ epihalohydrin resins.
  • Kymene ® 557H adipic acid is reacted with diethylenetriamine to form a polyaminoamide that is alkylated and crosslinked with epichlorohydrin to form a polyaminoamide/epichiorohydrin resin.
  • Kymene*Plus is a higher solids version of Kymene ® 557H.
  • Kymene ® 557LX, Kymene ® 557SLX and Kymene ® 557ULX are versions of Kymene ® 557H that contain low amounts of halide by-products.
  • Polyaminoamide/epichiorohydrin resins containing low amounts of halide byproducts are disclosed in U.S. Patent No. 5,171,795, to Miller et al., European Patent Application Publication No. 0 488 767 A2, to Bower, and European Patent Application Publication No. 0 510 987A1 , to Bull et al.
  • Kymene ® 450 wet strength resin is a polyaminoamide ureylene/ epichlorohydrin resin prepared by reacting oxalic acid, methyl bis(aminopropylamine) and urea to form a polyaminoamide ureylene, which is then alkylated with epichlorohydrin.
  • Kymene ® 736 is a polyalkylenepolyamine/epichlorohydrin resin prepared from hexa ethylenediamine and epichlorohydrin as described in European Patent Application Publication No. 0508203, October 14, 1992.
  • the level of cationic polymer used will generally be in the range of from about 0.1 % to about 5 % on a dry basis based on the dry weight of pulp.
  • a preferred level is from about 0.2% to about 4% , and a more preferred level from about 0.3 % to about 3 % .
  • the most preferred level will be in the range of from about 0.3 % to about 2% .
  • aqueous pulp suspension of step (a) of the process of this invention is obtained by conventional means well known in the art, such as mechanical, chemical, semichemical, thermomechanical and chemi-thermomechanical pulping processes. After the mechanical grinding and/or chemical pulping step, the pulp is washed to remove residual pulping chemicals and solubilized wood components. Either bleached or unbleached pulp fiber may be utilized in the process of this invention. Recycled pulp fibers are also suitable for use.
  • step (b) of the process the cationic polymer and amphoteric polymer may be added to the pulp suspension separately in any order, or they may be mixed together and thus added to the pulp simultaneously.
  • the amphoteric polymer and the cationic polymer will be added as aqueous solutions.
  • they may be added to the suspension in the neat form.
  • Step (c) sheeting and drying the pulp slurry, is carried out according to conventional means well known in the paper making art.
  • the paper of this invention has dry strength greater than that of paper that is the same except that it contains no amphoteric polymer.
  • Conventionally used indicators of dry strength are tensile strength, Z-direction tensile strength (tensile strength in the thickness direction), Mullen burst strength and ring crush.
  • T e tensile strength of the paper of this invention is found to be from about 1 % to about 15% greater, more particularly, from about 1 % to about 10% greater, than mat of paper that is the same except that it contains no amphoteric polymer.
  • Values of the tensile strength of the papers of this invention fall in the range of from about 4.5 to about 7.1 kg/cm width (25 to about 40 lb/inch width).
  • the process of this invention is of use in a large variety of paper types, e.g. , liner board, liquid packaging board, corrugating medium, printing or writing paper, newsprint, and tissue or towel. It is of particular significance for use in making liner board and corrugating medium from recycled pulp where chemicals often work poorly because of high levels of anionic materials present due to the recycling operations.
  • Examples 1-23 In these examples, which describe preparation of the amphoteric polymers of this invention, the equipment utilized was typically a two-liter resin kettle having a bottom valve with a stopcock. Fittings included a mechanical stirrer (paddle), thermocouple, nitrogen sparge inlet, and a nitrogen outlet passing through an aqueous sodium metabisulfite trap. Initiator solutions were continuously injected into the reactor through hypodermic tubing using a syringe pump.
  • a solution of the monomers and copper sulfate in deionized water was prepared, and the pH was adjusted to 4-5 using aqueous sodium hydroxide.
  • the solution was transferred to a polymerization reactor, and then sparged with nitrogen to remove oxygen. A blanket of nitrogen was maintained on the reactants during polymerization.
  • Polymerization was initiated by adding die redox initiator (potassium bromate/sodium metabisulfite) over a period of 30-60 minutes.
  • % aqueous potassium bromate (1 weight percent based on total monomers) and 10 wt. % aqueous sodium metabisulfite (2 weight percent based on total monomers) were added to the reactor over 60 minutes at an addition rate of 15 ml per hour.
  • the initial temperature was 24.4°C, and the maximum temperature reached after 25 minutes was 50.1 °C.
  • the reaction was stirred an additional fifteen minutes, and the thick reaction product was drained from the reactor and analyzed.
  • the polymer reduced specific viscosity (RSV) at 0.05% polymer concentration was measured by diluting 30.67 g. of a 1 % aqueous solution of the reaction product to 50.00 g. with distilled water, and men to 107.1 g. with 19.6% aqueous sodium chloride solution. This provided a 0.05% polymer solution in 2 m sodium chloride solution.
  • the flow time of the polymer solution in a Ubbelohde capillary viscometer at 30°C was 78.3 seconds compared to the flow time of 73.1 seconds for the 2 m sodium chloride control.
  • the RSV was calculated using the following formula where 71.5 is the kinetic correction factor for the particular Ubbelohde viscometer.
  • the RSV was calculated to be 1.46 dl/g.
  • the Brookfield viscosity of the original 16.3 % polymer solution was 3950 cps measured with a #4 spindle at 60 rpm and 25 °C using a Brookfield LVT viscometer.
  • ATMAC aciyloyloxyemyltrimethylam onium chloride
  • DMAEMA-HCl dimemylarninoethylmethacrylate hydrochloride salt
  • MBMAC methacryloyloxyethylbenzyldimethylammonium chloride
  • MBA methylenebisacrylamide
  • amphoteric polymers for evaluation of the amphoteric polymers in paper, handsheets or paper from a continuous laboratory former were prepared. The Z-direction tensile strength, tensile strength, and ring crush was determined and compared with controls in which no amphoteric polymer was added. In all cases an additional cationic polymer, either cationic starch or Kymene ® 557H wet strength resin, an epichlorohydrin/polyaminoamide available from Hercules Incorporated, Wilmington, DE, were also incorporated.
  • Example 24-32 and Comparative Example A Several of the polymers made in Example 1-23 were tested as dry strength additives in paper handsheets prepared using 50:50 hardwood/softwood pulp at pH 7.0, to a nominal basis weight of 130 g/m 2 (80 lbs/ream). All paper included 0.4% Kymene 557 ® H wet strength resin and 0.225 % Aquapel ® 649 alkylketene dimer sizing agent (both available from Hercules Incorporated, Wilmington, DE), added in that order after ti e addition of 0.1-0.3% of the dry strength additives.
  • the paper samples were aged under ambient conditions for at least two weeks before testing the tensile strength (TAPPI test method 541) and die tensile strength in the diickness direction (Z-Direction Tensile, TAPPI test method 494).
  • the latter test is a good indicator of tiie strength of the internal bonding between paper fibers.
  • the properties of samples containing dry strength additives was compared to those of the controls, which contained only d e wet strength and sizing agents.
  • the data in Table 2 demonstrate from about 2 to about 15% improvement in tensile strength for die papers of this invention as compared to paper with the same cationic polymer but no amphoteric polymer.
  • All handsheets contain Kymene*557 wet strength resin and Aquapel*649 alkylketene dimer size at 0.4% and 0.225% respectively, based on the weight of the dry pulp used to prepare the handsheets.
  • MTMAC methacryloyloxyethyltrimethylammonium chloride
  • AA acrylic acid
  • the polymers contain acrylamide and the indicated mo!e%'s of comonomer.
  • Fxamples 33-51 and Comparative Example R Paper was made on a continuous laboratory former using mixtures of hardwood and softwood pulp. Paper testing was carried out as described for Examples 24-32 except mat tensile strength was determined in both machine and cross direction and then averaged using die geometric mean of die machine and cross machine direction values. The results are presented in Table 3. The data in Table 3 demonstrate tensile strength improvements of up to about 9% for d e papers of mis invention as compared to paper witii the same cationic polymer but no amphoteric polymer.
  • Paper was made on a continuous laboratory former using repulped old corrugated containers as pulp. Paper testing was carried out as described for Examples 24-32 except mat tensile strength was determined in both machine direction and cross direction and then averaged using the geometric mean of e machine and cross machine direction values. In these examples cationic starch was utilized instead of Kymene 557 ® H wet strengtii resin. In some of the examples (so indicated) Aquapel ® 649 alkylketene dimer sizing agent was replaced by rosin size plus alum. The results are presented in Table 4. The data in Table 4 demonstrate tensile strengtii improvements of up to about 7.5% for the papers of ti ⁇ s invention as compared to paper with die same cationic polymer but no amphoteric polymer.
  • All handsheets contain Kymene*557 wet strength resin and Aquapel*649 alkylketene dimer size at 0.4% and 0.225% respectively, based on the weight of the dry pulp used to prepare the handsheets.
  • the pulp used was a mixture of hardwood and softwood pulps.
  • MTMAC methacryloyloxyethylrrimethylammoruum chloride
  • AA acrylic acid
  • MBA methylenebisacrylamide
  • the polymers contain acrylamide and the indicated mole%'s of comonomer.
  • MTMAC methacryloyloxyethyltrimethylammonium chloride
  • AA acrylic acid
  • the polymers contain acrylamide and the indicated mole%'s of comonomer.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne un procédé de fabrication de papier consistant (a) à prendre une pâte aqueuse; b) à ajouter à la pâte aqueuse un polymère cationique sélectionné dans le groupe constitué par un amidon cationique et une résine cationique conférant la résistance humide, et par un polymère amphotère soluble dans l'eau obtenu à partir de monomères. Lesdits monomères comprennent: i) un monomère non ionique sélectionné dans le groupe constitué par acrylamide et méthacrylamide; ii) un monomère anionique; et iii) un monomère cationique, les quantités additionnées de monomère anionique et de monomère cationique étant inférieures à 9 moles pour cent de la quantité totale des monomères anionique, cationique et non ionique contenue dans le polymère amphotère. L'invention concerne aussi du papier ayant une résistance à sec améliorée, obtenu par ledit procédé.
PCT/US1997/014010 1996-08-15 1997-08-08 Polyacrylamides amphoteres utilises comme additifs de resistance a l'etat sec pour la fabrication de papier WO1998006898A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39131/97A AU3913197A (en) 1996-08-15 1997-08-08 Amphoteric polyacrylamides as dry strength additives for paper

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000011046A1 (fr) * 1998-08-19 2000-03-02 Hercules Incorporated Polyacrylamides anioniques et amphoteres modifies par dialdehyde utiles pour ameliorer la resistance du papier
WO2000034584A1 (fr) * 1998-12-07 2000-06-15 Hercules Incorporated Polyacrylamides glyoxales utilises comme agents de renforcement du papier
WO2000059965A1 (fr) * 1999-04-06 2000-10-12 Minerals Technologies Inc. Polymeres bifonctionnels
WO2000077302A1 (fr) * 1999-06-16 2000-12-21 Nopco Paper Technology Holding As Utilisation d'ethers gras a longue chaine
EP1180559A1 (fr) * 2000-08-04 2002-02-20 Armstrong World Industries, Inc. Composition de liant pour une feuille fibreuse
WO2003087473A1 (fr) * 2002-04-08 2003-10-23 Hercules Incorporated Procede d'augmentation la resistance a sec du papier
EP1849803A1 (fr) * 2006-04-28 2007-10-31 Harima Chemicals, Inc. Procédé de préparation d'un polymère hydrosoluble et additive pour la fabrication du papier
US7442280B1 (en) 1998-04-27 2008-10-28 Akzo Nobel Nv Process for the production of paper
WO2010145956A1 (fr) * 2009-06-16 2010-12-23 Basf Se Procédé permettant d'augmenter la résistance à l'état sec du papier, du carton souple et du carton
WO2012067877A1 (fr) * 2010-11-15 2012-05-24 Kemira Oyj Composition et processus d'augmentation de la force à l'état sec d'un produit papetier
WO2012175392A1 (fr) * 2011-06-21 2012-12-27 Basf Se Procédé de fabrication de papier, de papier-carton et de carton compact
US20120325420A1 (en) * 2011-06-21 2012-12-27 Basf Se Production of paper, card and board
CN103469687A (zh) * 2012-06-07 2013-12-25 金东纸业（江苏）股份有限公司 增干强剂及其制备方法，应用该增干强剂的浆料
US8816031B2 (en) 2006-03-06 2014-08-26 Harima Chemicals, Inc. Water-soluble polymer and additive for paper manufacture
WO2016100020A1 (fr) * 2014-12-16 2016-06-23 Ecolab Usa Inc. Procédé de contrôle et de réaction en ligne pour ajustement de ph
EP3044366A4 (fr) * 2013-09-12 2017-04-19 Ecolab USA Inc. Composition d'adjuvants pour la fabrication de papier et procédé permettant d'augmenter la rétention de cendres du papier fini
WO2017116795A1 (fr) * 2015-12-31 2017-07-06 Ecolab Usa Inc. Polymère amphotère et émulsion d'anhydride d'acide alcényl-succinique comprenant celui-ci
US9873983B2 (en) 2013-09-12 2018-01-23 Ecolab Usa Inc. Process and compositions for paper-making
WO2019221692A1 (fr) * 2018-05-14 2019-11-21 Kemira Oyj Composition améliorant la résistance du papier, fabrication de celle-ci et son utilisation dans la production de papier
WO2020012074A1 (fr) * 2018-07-12 2020-01-16 Kemira Oyj Procédé de fabrication d'une bande fibreuse multicouche et bande fibreuse multicouche
US10982391B2 (en) * 2016-06-01 2021-04-20 Ecolab Usa Inc. High-efficiency strength program used for making paper in higher charge demand system
WO2021130411A1 (fr) * 2019-12-23 2021-07-01 Kemira Oyj Composition et son utilisation pour la fabrication de papier, de carton ou analogue
CN113105587A (zh) * 2021-03-12 2021-07-13 深圳市瑞成科讯实业有限公司 造纸增强剂及其制备方法
CN115053035A (zh) * 2020-03-06 2022-09-13 凯米拉公司 用于制造纸、纸板等的组合物和方法

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US5032226A (en) * 1988-02-16 1991-07-16 Felix Schoeller Jr. Gmbh & Co., Kg Base paper for photographic layer support
JPH0551895A (ja) * 1991-08-12 1993-03-02 Seiko Kagaku Kogyo Co Ltd 中性紙の製造方法

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US2884058A (en) * 1955-05-02 1959-04-28 American Cyanamid Co Cellulose web of improved dry strength containing a polymer comprising carboxylic groups, amide groups, and quaternary ammonium groups and method for producing same
US5032226A (en) * 1988-02-16 1991-07-16 Felix Schoeller Jr. Gmbh & Co., Kg Base paper for photographic layer support
JPH0551895A (ja) * 1991-08-12 1993-03-02 Seiko Kagaku Kogyo Co Ltd 中性紙の製造方法

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7442280B1 (en) 1998-04-27 2008-10-28 Akzo Nobel Nv Process for the production of paper
WO2000011046A1 (fr) * 1998-08-19 2000-03-02 Hercules Incorporated Polyacrylamides anioniques et amphoteres modifies par dialdehyde utiles pour ameliorer la resistance du papier
WO2000034584A1 (fr) * 1998-12-07 2000-06-15 Hercules Incorporated Polyacrylamides glyoxales utilises comme agents de renforcement du papier
WO2000059965A1 (fr) * 1999-04-06 2000-10-12 Minerals Technologies Inc. Polymeres bifonctionnels
WO2000077302A1 (fr) * 1999-06-16 2000-12-21 Nopco Paper Technology Holding As Utilisation d'ethers gras a longue chaine
EP1180559A1 (fr) * 2000-08-04 2002-02-20 Armstrong World Industries, Inc. Composition de liant pour une feuille fibreuse
WO2003087473A1 (fr) * 2002-04-08 2003-10-23 Hercules Incorporated Procede d'augmentation la resistance a sec du papier
US6723204B2 (en) 2002-04-08 2004-04-20 Hercules Incorporated Process for increasing the dry strength of paper
US8816031B2 (en) 2006-03-06 2014-08-26 Harima Chemicals, Inc. Water-soluble polymer and additive for paper manufacture
EP1849803A1 (fr) * 2006-04-28 2007-10-31 Harima Chemicals, Inc. Procédé de préparation d'un polymère hydrosoluble et additive pour la fabrication du papier
WO2010145956A1 (fr) * 2009-06-16 2010-12-23 Basf Se Procédé permettant d'augmenter la résistance à l'état sec du papier, du carton souple et du carton
US8926797B2 (en) 2009-06-16 2015-01-06 Basf Se Method for increasing the dry strength of paper, paperboard, and cardboard
WO2012067877A1 (fr) * 2010-11-15 2012-05-24 Kemira Oyj Composition et processus d'augmentation de la force à l'état sec d'un produit papetier
US8980056B2 (en) 2010-11-15 2015-03-17 Kemira Oyj Composition and process for increasing the dry strength of a paper product
WO2012175392A1 (fr) * 2011-06-21 2012-12-27 Basf Se Procédé de fabrication de papier, de papier-carton et de carton compact
US20120325420A1 (en) * 2011-06-21 2012-12-27 Basf Se Production of paper, card and board
US8753479B2 (en) * 2011-06-21 2014-06-17 Basf Se Production of paper, card and board
CN103469687A (zh) * 2012-06-07 2013-12-25 金东纸业（江苏）股份有限公司 增干强剂及其制备方法，应用该增干强剂的浆料
US9873986B2 (en) 2013-09-12 2018-01-23 Ecolab Usa Inc. Paper-making aid composition and process for increasing ash retention of finished paper
EP3044366A4 (fr) * 2013-09-12 2017-04-19 Ecolab USA Inc. Composition d'adjuvants pour la fabrication de papier et procédé permettant d'augmenter la rétention de cendres du papier fini
US9873983B2 (en) 2013-09-12 2018-01-23 Ecolab Usa Inc. Process and compositions for paper-making
WO2016100020A1 (fr) * 2014-12-16 2016-06-23 Ecolab Usa Inc. Procédé de contrôle et de réaction en ligne pour ajustement de ph
US10316469B2 (en) 2014-12-16 2019-06-11 Ecolab Usa Inc. On-line control and reaction process for pH adjustment
WO2017116795A1 (fr) * 2015-12-31 2017-07-06 Ecolab Usa Inc. Polymère amphotère et émulsion d'anhydride d'acide alcényl-succinique comprenant celui-ci
CN106928400A (zh) * 2015-12-31 2017-07-07 埃科莱布美国股份有限公司 一种两性聚合物及包含其的烯基琥珀酸酐乳液
US10982391B2 (en) * 2016-06-01 2021-04-20 Ecolab Usa Inc. High-efficiency strength program used for making paper in higher charge demand system
WO2019221692A1 (fr) * 2018-05-14 2019-11-21 Kemira Oyj Composition améliorant la résistance du papier, fabrication de celle-ci et son utilisation dans la production de papier
US11453979B2 (en) 2018-05-14 2022-09-27 Kemira Oyj Paper strength improving composition, manufacture thereof and use in paper making
CN112384655A (zh) * 2018-07-12 2021-02-19 凯米拉公司 制造多层纤维网的方法和多层纤维网
WO2020012074A1 (fr) * 2018-07-12 2020-01-16 Kemira Oyj Procédé de fabrication d'une bande fibreuse multicouche et bande fibreuse multicouche
CN112384655B (zh) * 2018-07-12 2022-12-27 凯米拉公司 制造多层纤维网的方法和多层纤维网
WO2021130411A1 (fr) * 2019-12-23 2021-07-01 Kemira Oyj Composition et son utilisation pour la fabrication de papier, de carton ou analogue
CN114867913A (zh) * 2019-12-23 2022-08-05 凯米拉公司 用于制造纸张、纸板等的组合物及其用途
CN115053035A (zh) * 2020-03-06 2022-09-13 凯米拉公司 用于制造纸、纸板等的组合物和方法
CN113105587A (zh) * 2021-03-12 2021-07-13 深圳市瑞成科讯实业有限公司 造纸增强剂及其制备方法
CN113105587B (zh) * 2021-03-12 2022-12-06 深圳市瑞成科讯实业有限公司 造纸增强剂及其制备方法

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Publication number Publication date
AU3913197A (en) 1998-03-06
ID17876A (id) 1998-02-05
ZA977367B (en) 1998-02-16

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