EP1910616A1 - Procede d'amelioration de la retention et de l'egouttage dans la fabrication du papier - Google Patents

Procede d'amelioration de la retention et de l'egouttage dans la fabrication du papier

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Publication number
EP1910616A1
EP1910616A1 EP05854765A EP05854765A EP1910616A1 EP 1910616 A1 EP1910616 A1 EP 1910616A1 EP 05854765 A EP05854765 A EP 05854765A EP 05854765 A EP05854765 A EP 05854765A EP 1910616 A1 EP1910616 A1 EP 1910616A1
Authority
EP
European Patent Office
Prior art keywords
starch
starches
anionic
associative polymer
cationic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05854765A
Other languages
German (de)
English (en)
Inventor
Fushan Zhang
John C. Harrington
Frank J. Sutman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hercules LLC
Original Assignee
Hercules LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hercules LLC filed Critical Hercules LLC
Publication of EP1910616A1 publication Critical patent/EP1910616A1/fr
Withdrawn legal-status Critical Current

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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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes

Definitions

  • This invention relates to the process of making paper and paperboard from a cellulosic stock, employing a flocculating system.
  • the making of cellulosic fiber sheets includes the following: 1) producing an aqueous slurry of cellulosic fiber which may also contain inorganic mineral extenders or pigments; 2) depositing this slurry on a moving papermaking wire or fabric; and 3) forming a sheet from the solid components of the slurry by draining the water. [0005] The foregoing is followed by pressing and drying the sheet to further remove water. Organic and inorganic chemicals are often added to the slurry prior to the sheet-forming step to make the papermaking method less costly, more rapid, and/or to attain specific properties in the final paper product. [0006] The paper industry continuously strives to improve paper quality, increase productivity, and reduce manufacturing costs. Chemicals are often added to the fibrous slurry before it reaches the papermaking wire or fabric to improve drainage/dewatering and solids retention; these chemicals are called retention and/or drainage aids.
  • Drainage or dewatering of the fibrous slurry on the papermaking wire or fabric is often the limiting step in achieving faster paper machine speeds. Improved dewatering can also result in a drier sheet in the press and dryer sections, resulting in reduced energy consumption.
  • the retention and/or drainage aid can impact performance attributes of the final paper sheet.
  • papermaking retention aids are used to increase the retention of fine furnish solids in the web during the turbulent method of draining and forming the paper web. Without adequate retention of the fine solids, they are either lost to the mill effluent or accumulate to high levels in the recirculating white water loop, potentially causing deposit buildup. Additionally, insufficient retention increases the papermakers' cost due to loss of additives intended to be adsorbed on the fiber. Additives can provide opacity, strength, sizing or other desirable properties to the paper.
  • High molecular weight (MW) water-soluble polymers with either cationic or anionic charge have traditionally been used as retention and drainage aids.
  • U.S. Patent Nos. 4,294,885 and 4,388,150 teach the use of starch polymers with colloidal silica.
  • U.S. Patent Nos. 4,643,801 and 4,750,974 teach the use of a coacervate binder of cationic starch, colloidal silica, and anionic polymer.
  • 4,753,710 teaches flocculating the pulp furnish with a high MW cationic flocculant, inducing shear to the flocculated furnish, and then introducing bentonite clay to the furnish.
  • the efficacy of the polymers or copolymers used will vary depending upon the type of monomers from which they are composed, the arrangement of the monomers in the polymer matrix, the molecular weight of the synthesized molecule, and the method of preparation.
  • a method of improving retention and drainage in a papermaking process is disclosed.
  • the method provides for the addition of an associative polymer and starch or a starch derivative to a papermaking slurry.
  • a composition comprising an associative polymer and starch or a starch derivative and optionally further comprising cellulose fiber is disclosed.
  • composition comprising an associative polymer, a starch or a starch derivative, a siliceous material and optionally further comprising cellulose fiber is disclosed.
  • the present invention provides for a synergistic combination comprising a water soluble copolymer prepared under certain conditions (herein after referred to as "associative polymer”) and starch or starch derivative. It has surprising been found that this synergistic combination results in retention and drainage performance superior to that of the individual components. Synergistic effects occur when the combination of components are used together. [0018] It has been found, unexpectedly, that the use of starch or starch derivative in combination with an associative polymer, such as the polymer disclosed in WO 03/050152 A1 or US 2004/0143039 A1, results in enhanced retention and drainage.
  • an associative polymer such as the polymer disclosed in WO 03/050152 A1 or US 2004/0143039 A1
  • the present invention also provides for a novel composition comprising an associative polymer and starch or a starch derivative.
  • the present invention also provides for a composition comprising an associative polymer, starch or a starch derivative a siliceous material.
  • the present invention also provides for a composition comprising an associative polymer and starch or a starch derivative and cellulose fiber.
  • the present invention also provides for a composition comprising an associative polymer, starch or a starch derivative, a siliceous material and cellulose fiber.
  • the use of the associative polymer as a retention and drainage aid has an impact on the performance of other additives in the papermaking system. Improved retention and/or drainage can have both a direct and indirect impact.
  • a direct impact refers to the retention and drainage aid acting to retain the additive.
  • An indirect impact refers to the efficacy of the retention and drainage aid to retain filler and fines onto which the additive is attached by either physical or chemical means.
  • filler refers to particulate materials, typically inorganic in nature, that are added to the cellulosic pulp slurry to provide certain attributes or be a lower cost substitute of a portion of the cellulose fiber.
  • Their relatively small size, on the order of 0.2 to 10 microns, low aspect ratio and chemical nature results in their not being adsorbed onto the large fibers yet too small to be entrapped in the fiber network that is the paper sheet.
  • fines refers to small cellulose fibers or fibrils, typically less than 0.2 mm in length and /or ability to pass through a 200 mesh screen.
  • the amount of additive retained in the sheet increases. This can provide either an enhancement of the property, providing a sheet with increased performance attribute, or allows the papermaker to reduce the amount of additive added to the system, reducing the cost of the product. Moreover, the amount of these materials in the recirculating water, or Whitewater, used in the papermaking system is reduced. This reduced level of material, that under some conditions can be considered to be an undesirable contaminant, can provide a more efficient papermaking process or reduce the need for scavengers or other materials added to control the level of undesirable material.
  • additive refers to materials added to the paper slurry to provide specific attributes to the paper and/or improve the efficiency of the papermaking process. These materials include, but are not limited to, sizing agents, wet strength resins, dry strength resins, starch and starch derivatives, dyes, contaminant control agents, antifoams, and biocides.
  • sizing agents include, but are not limited to, sizing agents, wet strength resins, dry strength resins, starch and starch derivatives, dyes, contaminant control agents, antifoams, and biocides.
  • a water-soluble copolymer composition comprising the formula:
  • B is a nonionic polymer segment formed from the polymerization of one or more ethylenically unsaturated nonionic monomers
  • F is an anionic, cationic or a combination of anionic and cationic polymer segment(s) formed from polymerization of one or more ethylenically unsaturated anionic and/or cationic monomers
  • the molar % ratio of B:F is from 95:5 to 5:95
  • the water-soluble copolymer is prepared via a water-in-oil emulsion polymerization technique that employs at least one emulsification surfactant consisting of at least one diblock or triblock polymeric surfactant wherein the ratio of the at least one diblock or triblock surfactant to monomer is at least about 3:100 and wherein;
  • the water-in- oil emulsion polymerization technique comprises the steps of: (a) preparing an aqueous solution of monomers, (b) contacting the
  • the associative polymer can be an anionic copolymer.
  • the anionic copolymer is characterized in that the Huggins' constant (k 1 ) determined between 0.0025 wt. % to 0.025 wt. % of the copolymer in 0.01 M NaCI is greater than 0.75 and the storage modulus (G') for a 1.5 wt. % actives copolymer solution at 4.6 Hz greater than 175 Pa.
  • the associative polymer can be a cationic copolymer.
  • the cationic copolymer is characterized in that its Huggins' constant (k 1 ) determined between 0.0025 wt. % to 0.025 wt. % of the copolymer in 0.01 M NaCI is greater than 0.5; and it has a storage modulus (G') for a 1.5 wt. % actives copolymer solution at 6.3 Hz greater than 50 Pa.
  • the associative polymer can be an amphoteric copolymer.
  • the amphoteric copolymer is characterized in that its Huggins' constant (k') determined between 0.0025 wt. % to 0.025 wt. % of the copolymer in 0.01 M NaCI is greater than 0.5; and the copolymer has a storage modulus (G') for a 1.5 wt. % actives copolymer solution at 6.3 Hz greater than 50 Pa.
  • Inverse emulsion polymerization is a standard chemical process for preparing high molecular weight water-soluble polymers or copolymers.
  • an inverse emulsion polymerization process is conducted by 1) preparing an aqueous solution of the monomers, 2) contacting the aqueous solution with a hydrocarbon liquid containing appropriate emulsification surfactant(s) or surfactant mixture to form an inverse monomer emulsion, 3) subjecting the monomer emulsion to free radical polymerization, and, optionally, 4) adding a breaker surfactant to enhance the inversion of the emulsion when added to water.
  • Inverse emulsions polymers are typically water-soluble polymers based upon ionic or non-ionic monomers. Polymers containing two or more monomers, also referred to as copolymers, can be prepared by the same process. These co-monomers can be anionic, cationic, zwitterionic, nonionic, or a combination thereof.
  • Typical nonionic monomers include, but are not limited to, acrylamide; methacrylamide; N-alkylacrylamides, such as N-methylacrylamide; N,N-dialkylacrylamides, such as N,N-dimethylacrylamide; methyl acrylate; methyl methacrylate; acrylonitrile; N-vinyl methylacetamide; N-vinyl formamide; N-vinyl methyl formamide; vinyl acetate; N-vinyl pyrrolidone; hydroxyalky(meth)acrylates such as hydroxyethyl(meth)acrylate or hydroxypropyl(meth)acrylate; mixtures of any of the foregoing and the like.
  • Nonionic monomers of a more hydrophobic nature can also be used in the preparation of the associative polymer.
  • the term 'more hydrophobic' is used here to indicate that these monomers have reduced solubility in aqueous solutions; this reduction can be to essentially zero, meaning that the monomer is not soluble in water. It is noted that the monomers of interest are also referred to as polymerizable surfactants or surfmers.
  • Exemplary materials include, but are not limited to, methylmethacrylate, styrene, t-octyl acrylamide, and an allyl phenyl polyol ether sulfate marketed by Clariant as Emulsogen APG 2019.
  • Exemplary anionic monomers include, but are not limited to, the free acids and salts of: acrylic acid; methacrylic acid; maleic acid; itaconic acid; acrylamidoglycolic acid; 2-acrylamido-2-methyl-1-propanesulfonic acid; 3- allyloxy-2 ⁇ hydroxy-1-propanesulfonic acid; styrenesulfonic acid; vinylsulfonic acid; vinylphosphonic acid; 2-acrylamido-2-methylpropane phosphonic acid; mixtures of any of the foregoing and the like.
  • Exemplary cationic monomers include, but are not limited to, cationic ethylenically unsaturated monomers such as the free base or salt of: diallyldialkylammonium halides, such as diallyldimethylammonium chloride; the (meth)acrylates of dialkylaminoalkyl compounds, such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethyl aminopropyl (meth)acrylate, 2-hydroxydimethyl aminopropyl (meth)acrylate, aminoethyl (meth)acrylate, and the salts and quaternaries thereof; the N 1 N- dialkylaminoalkyl(meth)acrylamides, such as N.N-dimethylaminoethylacrylamide, and the salts and quaternaries thereof and mixture of the foregoing and the like.
  • the co-monomers may be present in any ratio. The result
  • the molar ratio of nonionic monomer to anionic monomer may fall within the range of 95:5 to 5:95, preferably the range is from about 75:25 to about 25:75 and even more preferably the range is from about 65:35 to about 35:65 and most preferably from about 60:40 to about 40:60.
  • the molar percentages of B and F must add up to 100%. It is to be understood that more than one kind of nonionic monomer may be present in the Formula I. It is also to be understood that more than one kind of anionic monomer may be present in the Formula I.
  • the associative polymer when it is an anionic copolymer, is defined by Formula I where B, the nonionic polymer segment, is the repeat unit formed after polymerization of acrylamide; and F, the anionic polymer segment, is the repeat unit formed after polymerization of a salt or free acid of acrylic acid and the molar percent ratio of B: F is from about 75:25 to about 25:75
  • the physical characteristics of the associative polymer when it is an anionic copolymer, are unique in that their Huggins 1 constant (k 1 ) as determined in 0.01 M NaCI is greater than 0.75 and the storage modulus (G') for a 1.5 wt. % actives polymer solution at 4.6 Hz is greater than 175 Pa, preferably greater than 190 and even more preferably greater than 205.
  • the Huggins 1 constant is greater than 0.75, preferably greater than 0.9 and even more preferably greater than 1.0
  • Formula I may fall within the range of 99:1 to 50:50, or 95:5 to 50:50, or 95:5 to 75:25, or 90:10 to 60:45, preferably the range is from about 85:15 to about 60:40 and even more preferably the range is from about 80:20 to about 50:50.
  • the molar percentages of B and F must add up to 100%. It is to be understood that more than one kind of nonionic monomer may be present in the Formula I. It is also to be understood that more than one kind of cationic monomer may be present in the Formula I.
  • the minimum amount of each of the anionic, cationic and non-ionic monomer is 1 % of the total amount of monomer used to form the copolymer.
  • the maximum amount of the non-ionic, anionic or cationic is 98% of the total amount of monomer used to form the copolymer.
  • the minimum amount of any of anionic, cationic and non-ionic monomer is 5%, more preferably the minimum amount of any of anionic, cationic and non-ionic monomer is 7% and even more preferably the minimum amount of any of anionic, cationic and non-ionic monomer is 10% of the total amount of monomer used to form the copolymer.
  • the molar percentages of anionic, cationic and non-ionic monomer must add up to 100%. It is to be understood that more than one kind of nonionic monomer may be present in the Formula I, more than one kind of cationic monomer may be present in the Formula I, and that more than one kind of anionic monomer may be present in the Formula I.
  • the physical characteristics of the associative polymer when it is a cationic or amphoteric copolymer, are unique in that their Huggins' constant (k 1 ) as determined in 0.01 M NaCI is greater than 0.5 and the storage modulus (G') for a 1.5 wt. % actives polymer solution at 6.3 Hz is greater than 50 Pa, preferably greater than 10 and even more preferably greater than 25, or greater than 50, or greater than 100, or greater than 175, or greater than 200.
  • the Huggins' constant is greater than 0.5, preferably greater than 0.6, or greater than 0.75, or greater than 0.9 or greater than 1.0.
  • the emulsification surfactant or surfactant mixture used in an inverse emulsion polymerization system have an important effect on both the manufacturing process and the resultant product.
  • Surfactants used in emulsion polymerization systems are known to those skilled in the art. These surfactants typically have a range of HLB (Hydrophilic Lipophilic Balance) values that is dependent on the overall composition.
  • HLB Hydrophilic Lipophilic Balance
  • One or more emulsification surfactants can be used.
  • the emulsification surfactant(s) of the polymerization products that are used to produce the associative polymer include at least one diblock or triblock polymeric surfactant. It is known that these surfactants are highly effective emulsion stabilizers.
  • the choice and amount of the emulsification surfactant(s) are selected in order to yield an inverse monomer emulsion for polymerization.
  • one or more surfactants are selected in order to obtain a specific HLB value.
  • Diblock and triblock polymeric emulsification surfactants are used to provide unique materials.
  • diblock and triblock polymeric emulsification surfactants are used in the necessary quantity, unique polymers exhibiting unique characteristic result, as described in WO 03/050152 A1 and US 2004/0143039 A1 , the entire contents of each is herein incorporated by reference.
  • Exemplary diblock and triblock polymeric surfactants include, but are not limited to, diblock and triblock copolymers based on polyester derivatives of fatty acids and poly[ethyleneoxide] (e.g., Hypermer® B246SF, Uniqema, New Castle, DE), diblock and triblock copolymers based on polyisobutylene succinic anhydride and poly[ethyleneoxide], reaction products of ethylene oxide and propylene oxide with ethylenediamine, mixtures of any of the foregoing and the like.
  • the diblock and triblock copolymers are based on polyester derivatives of fatty acids and poly[ethyleneoxide].
  • the triblock contains two hydrophobic regions and one hydrophilic region, i.e., hydrophobe-hydrophile-hydrophobe.
  • the amount (based on weight percent) of diblock or triblock surfactant is dependent on the amount of monomer used to form the associative polymer.
  • the ratio of diblock or triblock surfactant to monomer is at least about 3 to 100.
  • the amount of diblock or triblock surfactant to monomer can be greater than 3 to 100 and preferably is at least about 4 to 100 and more preferably 5 to 100 and even more preferably about 6 to 100.
  • the diblock or triblock surfactant is the primary surfactant of the emulsification system.
  • a secondary emulsification surfactant can be added to ease handling and processing, to improve emulsion stability, and/or to alter the emulsion viscosity.
  • secondary emulsification surfactants include, but are not limited to, sorbitan fatty acid esters, such as sorbitan monooleate (e.g., Atlas G-946, Uniqema, New Castle, DE), ethoxylated sorbitan fatty acid esters, polyethoxylated sorbitan fatty acid esters, the ethylene oxide and/or propylene oxide adducts of alkylphenols, the ethylene oxide and/or propylene oxide adducts of long chain alcohols or fatty acids, mixed ethylene oxide/propylene oxide block copolymers, alkanolamides, sulfosuccinates and mixtures thereof and the like.
  • sorbitan fatty acid esters such as sorbitan monooleate (e.g., Atlas G-946, Uniqema, New Castle, DE), ethoxylated sorbitan fatty acid esters, polyethoxylated sorbitan fatty acid esters,
  • Polymerization of the inverse emulsion may be carried out in any manner known to those skilled in the art. Examples can be found in many references, including, for example, Allcock and Lampe, Contemporary Polymer Chemistry, (Englewood Cliffs, New Jersey, PRENTICE-HALL, 1981), chapters 3- 5.
  • a representative inverse emulsion polymerization is prepared as follows. To a suitable reaction flask equipped with an overhead mechanical stirrer, thermometer, nitrogen sparge tube, and condenser is charged an oil phase of paraffin oil (135.Og, Exxsol® D80 oil, Exxon - Houston, TX) and surfactants (4.5g Atlas® G-946 and 9.Og Hypermer® B246SF). The temperature of the oil phase is then adjusted to 37°C.
  • paraffin oil (135.Og, Exxsol® D80 oil, Exxon - Houston, TX
  • surfactants 4.5g Atlas® G-946 and 9.Og Hypermer® B246SF
  • An aqueous phase is prepared separately which comprised 53-wt. % acrylamide solution in water (126.5g), acrylic acid (68.7g), deionized water (70.Og) 1 and Versenex® 80 (Dow Chemical) chelant solution (0.7g).
  • the aqueous phase is then adjusted to pH 5.4 with the addition of ammonium hydroxide solution in water (33.1g, 29.4 wt. % as NH 3 ).
  • the temperature of the aqueous phase after neutralization is 39°C.
  • the aqueous phase is then charged to the oil phase while simultaneously mixing with a homogenizer to obtain a stable water-in-oil emulsion.
  • This emulsion is then mixed with a 4-blade glass stirrer while being sparged with nitrogen for 60 minutes. During the nitrogen sparge the temperature of the emulsion is adjusted to 50+1 0 C. Afterwards, the sparge is discontinued and a nitrogen blanket implemented.
  • the polymerization is initiated by feeding a 3-wt. % solution of 2,2'- azobisisobutyronitrile (AIBN) in toluene (0.213g). This corresponds to an initial AIBN charge, as AIBN, of 250 ppm on a total monomer basis.
  • AIBN 2,2'- azobisisobutyronitrile
  • the batch temperature was allowed to exotherm to 62°C ( ⁇ 50 minutes), after which the batch was maintained at 62+1 0 C. After the feed the batch was held at 62+1 0 C for 1 hour.
  • 3-wt. % AIBN solution in toluene (0.085g) is then charged in under one minute. This corresponds to a second AIBN charge of 100 ppm on a total monomer basis. Then the batch is held at 62+1 0 C for 2 hours. Then batch is then cooled to room temperature, and breaker surfactant(s) is added.
  • the associative polymer emulsion is typically inverted at the application site resulting in an aqueous solution of 0.1 to 1% active copolymer. This dilute solution of the associative polymer is then added to the paper process to affect retention and drainage.
  • the associative polymer may be added to the thick stock or thin stock, preferably the thin stock.
  • the associative polymer may be added at one feed point, or may be split fed such that the associative polymer is fed simultaneously to two or more separate feed points.
  • Typical stock addition points include feed point(s) before the fan pump, after the fan pump and before the pressure screen, or after the pressure screen.
  • the associative polymer may be added in any effective amount to achieve flocculation.
  • the amount of copolymer could be more than 0.5 Kg per metric ton of cellulosic pulp (dry basis).
  • the associative polymer is employed in an amount of at least about 0.03 Ib. to about 0.5 Kg. of active copolymer per metric ton of cellulosic pulp, based on the dry weight of the pulp.
  • the concentration of copolymer is preferably from about 0.05 to about 0.5 Kg of active copolymer per metric ton of dried cellulosic pulp.
  • the copolymer is added in an amount of from about 0.05 to 0.4 Kg per metric ton cellulose pulp and, most preferably, about 0.1 to about 0.3 Kg per metric ton based on dry weight of the cellulosic pulp.
  • the second component of the retention and drainage system is starch and derivatives thereof.
  • Starch is the common name for a polymer of glucose that contains a/pfra-1,4 linkages. Starch is a naturally occurring material; this carbohydrate can be found in the leaves, stems, roots and fruits of most land plants.
  • the commercial sources of starch include, but are not limited to, the seeds of cereal grains (corn, wheat, rice, etc.), and certain roots (potato, tapioca, etc.). Starch is described by its plant source; reference would be made to, for example, corn starch, potato starch, tapioca starch, rice starch, and wheat starch.
  • Glucose is composed of carbon, hydrogen, and oxygen in the ratio of 6:10:5 (C ⁇ H-IOO S ), placing it in the class of carbohydrate organic compounds.
  • Starch can be considered to be a condensation polymer of glucose.
  • Most starches consist of a mixture of two polysaccharide types: amylose, an essentially linear polymer, and amylopectin, a highly branched polymer. The relative amounts of amylose and amylopectin vary with the source, with the ratio of amylose to amylopectin typically being 17:83 for tapioca, 21 :79 for potato, 28:72 for corn and 0:100 for waxy maize corn. Although these are the typical starch ratios found the present invention contemplates that any ratio of amylose to amylopectin can be useful in the present invention.
  • waxy maize is consisted a type of corn starch.
  • Amylose is a linear polymer consisting of a chain of glucose units connected to each other by alpha- ⁇ ,4 linkages.
  • the molecular weight can range from about 30,000 to about 1 ,000,000.
  • Amylopectin is a highly branched structure of short amylose chains having molecular weight from about 2000 to about 10,000 connected via alpha-
  • Starch is synthesized by plants and accumulates in granules that are distinctive for each plant. Starch granules are separated from the plant through a milling and grinding process. The granules are insoluble in cold water and must be heated above a critical temperature in order for the granules to swell and rupture, allowing the polymer to dissolve in solution.
  • Starch can be modified to provide specific properties of value in selected applications. This includes modification to either or both the physical and chemical structure of the material. Physical modification includes reduction in molecular weight, which is most often achieved by hydrolysis. Such modified materials are often referred to as derivatized starch or starch derivatives.
  • Chemical modifications include, but are not limited to, reactions that result in oxidized starches, such as by reaction with hypochlorite; reactions to form crosslinked starch, such as by using crosslinkers such as epichlorohydrin, sodium trimetaphosphate, isocyanates, or N,N-methylenebisacrylamide; reactions to form starch ester, such as by reaction with acetic acid or succinic anhydride; reactions to form hydroxyalkyl starches, such as by reaction with ethylene oxide or propylene oxide; reactions to form phosphate monoesters, such as by reaction with sodium tripolyphosphate; reactions to form cationic starch, such as by reaction with diethylamino ethyl chloride, tertiary amines and epichlorohydrin, or ethyleneamine; reactions to form dialdehyde starch, such as by acid oxidation, or starch xanthates; and the like.
  • any type of chemically modified starch is contemplate
  • Blends of cationic and anionic starches are useful in the present invention. Low charge starches are also useful in the present invention.
  • the second component of the retention and drainage system can be added at amounts up to 20 Kg of active material per metric ton of cellulose pulp based on dry weight of the pulp, with the ratio of the associative polymer to second component being 1 :100 to 100:1. It is contemplated that more than one second component can be used in the papermaking system.
  • siliceous materials can be used as an additional component of a retention and drainage aid used in making paper and paperboard.
  • the siliceous material may be any of the materials selected from the group consisting of silica based particles, silica microgels, amorphous silica, colloidal silica, anionic colloidal silica, silica sols, silica gels, polysilicates, polysilicic acid, and the like. These materials are characterized by the high surface area, high charge density and submicron particle size.
  • This group includes stable colloidal dispersion of spherical amorphous silica particles, referred to in the art as silica sols.
  • the term sol refers to a stable colloidal dispersion of spherical amorphous particles.
  • Silica gels are three dimensional silica aggregate chains, each comprising several amorphous silica sol particles, that can also be used in retention and drainage aid systems; the chains may be linear or branched.
  • Silica sols and gels are prepared by polymerizing monomeric silicic acid into a cyclic structure that result in discrete amorphous silica sols of polysilicic acid. These silica sols can be reacted further to produce a three dimensional gell network.
  • the various silica particles (sols, gels, etc.) can have an overall size of 5-50 nm.
  • Anionic colloidal silica can also be used.
  • the siliceous material can be added to the cellulosic suspension in an amount of at least 0.005 Kg per metric ton based on dry weight of the cellulosic suspension.
  • the amount of siliceous material may be as high at 50 Kg per metric ton.
  • the amount of siliceous material is from about 0.05 to about 25 Kg per metric ton. Even more preferably, the amount of siliceous material is from about 0.25 to about 5 Kg per metric ton based on the dry weight of the cellullosic suspension.
  • an additional component of the retention and drainage aid system can be a conventional flocculant.
  • a conventional flocculant is generally a linear cationic or anionic copolymer of acrylamide.
  • the additional component of the retention and drainage system is added in conjunction with the aluminum compound and the associative polymer to provide a multi-component system which improves retention and drainage.
  • the conventional flocculant can be an anionic, cationic or non-ionic polymer.
  • the ionic monomers are most often used to make copolymers with a non-ionic monomer such as acrylamide.
  • These polymers can be provided by a variety of synthetic processes including, but not limited to, suspension, dispersion and inverse emulsion polymerization. For the last process, a microemulsion may also be used.
  • the co-monomers of the conventional flocculant may be present in any ratio.
  • the resultant copolymer can be non-ionic, cationic, anionic, or amphoteric (contains both cationic and anionic charge).
  • alum aluminum sulfate
  • polyaluminum sulfate polyaluminum chloride
  • aluminum chlorohydrate aluminum sources
  • the components of a retention and drainage system may be added substantially simultaneously to the cellulosic suspension.
  • the term retention and drainage system is used here to encompass two or more distinct materials added to the papermaking slurry to provide improved retention and drainage.
  • the components may be added to the cellulosic suspension separately either at the same stage or dosing point or at different stages or dosing points.
  • any two of more of the materials may be added as a blend.
  • the mixture may be formed in-situ by combining the materials at the dosing point or in the feed line to the dosing . point.
  • the inventive system comprises a preformed blend of the materials.
  • the components of the inventive system are added sequentially. A shear point may or may not be present between the addition points of the components. The components can be added in any order.
  • the inventive system is typically added to the paper process to affect retention and drainage.
  • the inventive system may be added to the thick stock or thin stock, preferably the thin stock.
  • the system may be added at one feed point, or may be split fed such that the inventive system is fed simultaneously to two or more separate feed points.
  • Typical stock addition points include feed points(s) before the fan pump, after the fan pump and before the pressure screen, or after the pressure screen.
  • a series of drainage tests were conducted utilizing a synthetic alkaline furnish.
  • This furnish is prepared from hardwood and softwood dried market lap pulps, and from water and further materials.
  • the hardwood and softwood dried market lap pulp are refined separately. These pulps are then combined at a ratio of about 70 percent by weight of hardwood to about 30 percent by weight of softwood in an aqueous medium.
  • the aqueous medium utilized in preparing the furnish comprises a mixture of local hard water and deionized water to a representative hardness.
  • Inorganic salts are added in amounts so as to provide this medium with a total alkalinity of 75 ppm as CaCO 3 and hardness of 100 ppm as CaCU 3 ..
  • Precipitated calcium carbonate is introduced into the pulp furnish at a representative weight percent to provide a final furnish containing 80% fiber and 20% PCC filler.
  • the drainage tests were conducted by mixing the furnish with a mechanical mixer at a specified mixer speed, and introducing the various chemical components into the furnish and allowing the individual components to mix for a specified time prior to the addition of the next component.
  • the specific chemical components and dosage levels are described in the data tables.
  • VDT Vacuum Drainage Test
  • the VDT test is conducted by first setting the vacuum to the desired level, typically 10 inches Hg, and placing the funnel properly on the cylinder. Next, 25Og of 0.5% wt. % paper stock is charged into a beaker and then the required additives according to treatment program (e.g., starch, alum, and testing flocculants) are added to the stock under the agitation provided by an overhead mixer. The stock is then poured into the filter funnel and the vacuum pump is turned on while simultaneously starting a stopwatch. The drainage efficacy is reported as the time, in seconds, required to obtain 230 ml of filtrate. Lower quantitative drainage time values represent higher levels of drainage or dewatering, which is the desired response.
  • treatment program e.g., starch, alum, and testing flocculants
  • starch materials utilized in the evaluation of the current invention are presented in Table 1.
  • Stalok and lnterbond are trade names of A. E. Staley (Decatur, IL); Cato, Microcat, and Optiplus are trade names of National Starch and Chemical (Bridgewater, NJ).
  • the evaluated starches are described in the table by product designation and starch type or source,.
  • the starch materials used for evaluation in the present invention are listed in table 1.
  • the additive(s) of interest are added sequentially to the furnish as Kilograms (Kg) of additive per metric ton (MT) of paper furnish (dry basis).
  • Kg Kilograms
  • MT additive per metric ton
  • Alum aluminum sulfate octadecahydrate as a 50% solution (Delta Chemical Corporation, Baltimore, MD).
  • SP 9232 is PerForm® SP9232, a retention and drainage aid produced under certain conditions (see PCT WO 03/050152 A1)
  • PC8138 is PerForm® PC8138, a cationic copolymer of polyacrylamide
  • PA8137 is PerForm® PA8137, an anionic copolymer of acrylamide.
  • PerForm is a trade name of Hercules Incorporated, Wilmington, DE

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un procédé d'amélioration de la rétention et de l'égouttage dans la fabrication du papier. Le procédé comprend l'addition d'un polymère associatif, d'amidon ou d'un dérivé d'amidon, et éventuellement d'un matériau siliceux à la pâte à papier. L'invention concerne également une composition comprenant un polymère associatif, de l'amidon ou un dérivé d'amidon, et comprenant éventuellement en outre une fibre de cellulose.
EP05854765A 2005-06-24 2005-12-22 Procede d'amelioration de la retention et de l'egouttage dans la fabrication du papier Withdrawn EP1910616A1 (fr)

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US69385405P 2005-06-24 2005-06-24
US11/313,579 US20060289139A1 (en) 2005-06-24 2005-12-21 Retention and drainage in the manufacture of paper
PCT/US2005/046105 WO2007001470A1 (fr) 2005-06-24 2005-12-22 Procede d'amelioration de la retention et de l'egouttage dans la fabrication du papier

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AU2011295397B2 (en) * 2010-08-25 2015-07-02 Solenis Technologies Cayman, L.P. Method for increasing the advantages of starch in pulped cellulosic material in the production of paper and paperboard
AU2012299794B2 (en) 2011-08-25 2017-03-02 Solenis Technologies Cayman, L.P. Method for increasing the advantages of strength aids in the production of paper and paperboard
FI126733B (en) * 2013-09-27 2017-04-28 Upm Kymmene Corp Procedure for the manufacture of stock and paper product
BR102013026713A2 (pt) * 2013-10-16 2015-08-18 Nicepel Produtos Químicos Ltda Epp Formulação e processo de obtenção de composto a base de dextrina de mandioca para uso na indústria de papel e conversão de papel

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KR20080024139A (ko) 2008-03-17
AU2005333560A1 (en) 2007-01-04
US20060289139A1 (en) 2006-12-28
MX2007015821A (es) 2008-02-22
BRPI0520383A2 (pt) 2009-05-05
TW200700615A (en) 2007-01-01
WO2007001470A1 (fr) 2007-01-04
JP2008544106A (ja) 2008-12-04

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