EP0414496A1 - Verfahren und Zellstoff für die Verbesserung der Retention von Papierpulvern und -füllstoffen - Google Patents

Verfahren und Zellstoff für die Verbesserung der Retention von Papierpulvern und -füllstoffen Download PDF

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Publication number
EP0414496A1
EP0414496A1 EP90309154A EP90309154A EP0414496A1 EP 0414496 A1 EP0414496 A1 EP 0414496A1 EP 90309154 A EP90309154 A EP 90309154A EP 90309154 A EP90309154 A EP 90309154A EP 0414496 A1 EP0414496 A1 EP 0414496A1
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EP
European Patent Office
Prior art keywords
pulp
paper
weight percent
copolymer
acrylamide
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Withdrawn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
EP90309154A
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English (en)
French (fr)
Inventor
Paul F. Richardson
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.)
ChampionX LLC
Original Assignee
Nalco Chemical Co
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 Nalco Chemical Co filed Critical Nalco Chemical Co
Publication of EP0414496A1 publication Critical patent/EP0414496A1/de
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised

Definitions

  • This invention in general, relates to specific polymeric additives useful in the processing of paper. More particularly, to certain polymeric additives having greatly improved activity for the retention of fillers and fiber fines in paper manufacture.
  • the pulp fibers were the only constituents of a paper sheet, the usefulness of the paper would be very restricted because the sheet would be soft, have a yellowish colour, and could not be written or printed upon with ink successfully. If the sheet were thin, it would be transparent to matter printed upon the opposite side. It is necessary, then, to add other substances, such as sizing, colouring agents, and fillers, to the cellulosic fibers to produce paper suited to its many uses.
  • the fillers are inorganic substances and may be either naturally-occurring materials such as talc, agalite, pearl filler, barytes and certain clays such as china clay or artificial fillers such as suitably precipitated calcium carbonate, crown filler (pearl hardening), blanc fixe, and titanium dioxide pigments.
  • Sizing is added to the paper, other than absorbent papers and filter paper, to impart resistance to penetration by liquids. Common sizing agents added to the pulp before it is formed into a sheet are wax emulsions or soaps made by the saponification of rosin with alkali. The sizes are precipitated with alum.
  • Pulp stock is prepared for formation into paper by two general processes, beating and refining. Mills use either one or the other alone or both together. Beating the fibers makes the paper stronger, more uniform, more dense, and less porous. It is in the beater that fillers, colouring agents and sizing may be added. The standard practice in making the finer grades of paper is to follow the beaters with the refiners, the latter being continuous machines.
  • filler, sizing and colour While the usual practice is to add filler, sizing and colour to the beaters, they may be added to prior to the refiner or to a combination of points in the system or subsequent to the beating operation but prior to the refining steps, as for example, prior to beating.
  • the order in which the materials are added to the beaters may vary with different mills.
  • the filler is first added to the blended pulp, and after sufficient beating, the sizing and the colouring are added.
  • all or part of the sizing is surface applied to the formed, dried sheet, using animal glues, starches, or gelatin as the sizing.
  • alum is most generally added to the beater, but in some mills, this practice is varied, and the pulp may be treated with this chemical during the refining step or even later in the paper processing scheme.
  • the machines used for the actual formation of the paper sheet are of two general types, the Fourdrinier machine and the cylinder machine.
  • the basic principles of operation are essentially the same for both machines.
  • the sheet is formed on a travelling screen or cylinder, dewatered under rollers, dried by heated rollers and finished by calender rolls.
  • the Fourdrinier machine the stock of the foregoing operations is sent to the headbox from which it flows onto a moving endless screen known as a wire.
  • the pulp fibers remain on the screen while a greater portion of the water, containing unretained fiber fines and unretained filler, drains through.
  • the paper While still on the Fourdrinier wire, the paper passes over suction boxes to remove water and under a dandy roll which smooths the top of the sheet.
  • the cylinder machine there are several parallel vats into which similar dissimilar dilute paper stocks are charged.
  • a wire-covered rotating cylinder rotates in each vat.
  • the paper stock is deposited on the turning screen as the water inside the cylinder is removed.
  • the paper stock reaches a point where the wet layer comes in contact with and adheres to the moving felt.
  • This felt and paper after removal of some water, come into contact with the top of the next cylinder and pick up another layer of wet paper.
  • a composite wet sheet or board is built up and passed through press rolls and onto the drying and smoothing rolls.
  • an additive for improving filler and fines retention must be capable of acting both upon the filler and fines in the system to efficiently cause such materials to be retained in the finished sheet rather than with one being preferentially acted upon by the additive.
  • Another important characteristic that must be possessed by any chemical used as a filler and fines retention additive is that it must be capable of operating on a large variety of stocks.
  • Cationic charges are generated by introducing sulfonium, phosphonium, or ammonium groups onto the polymer backbone.1
  • the ammonium ion is the one most commonly used for producing paper additives.
  • An example of a monomer used as a copolymer agent is METAMS (methacryloyloxyethyl trimethyl ammonium methylsulfate), shown below:
  • the cationic polymers have the advantage of being readily adsorbed by the normally negative surfaces encountered in the wet-end system, thus eliminating the necessity of using intermediaries such as alum.
  • the high molecular weight allows for the formation of many loops on adsorption, thus providing many bonding points. This results in a strong, tenacious bridge.
  • a further object is to provide polymeric chemical retention aids for improving filler and fines retention which are effective at low economical dosage, which will not interfere with other additives and substances used in the make-up and manufacture of paper, and which have no adverse effects on the chemical and/or physical characteristics of the finished paper sheet. They are easy and safe to handle and will impart to the finished paper sheet certain and desirable characteristics which have not been so far available relative to retention of fines and fillers used in the manufacture of paper.
  • a method of improving fine and filler retention of paper during its manufacture into a sheet from pulp comprises treating the pulp prior to sheet formation with a copolymer which contains between 40-60 weight percent diallyldimethylammonium chloride and between about 60-40 weight percent of acrylamide which polymer has a molecular weight sufficient to provide a reduced specific viscosity (RSV) equal to at least 5.0 deciliters per gram.
  • a copolymer which contains between 40-60 weight percent diallyldimethylammonium chloride and between about 60-40 weight percent of acrylamide which polymer has a molecular weight sufficient to provide a reduced specific viscosity (RSV) equal to at least 5.0 deciliters per gram.
  • RSV specific viscosity
  • the copolymer is a 50/50 weight percent copolymer of diallyldimethylammonium chloride and acrylamide.
  • the polymer preferably has a reduced specific viscosity of at least 7.5 deciliters per gram. Most preferably, the copolymer has a sufficient molecular weight to provide for a reduced specific viscosity of at least 8.0 deciliters per gram.
  • the polymers of our invention are copolymers which have as few as possible NH2 units hydrolysed to COOH. They should contain less than 2 weight percent hydrolysis-converted acrylamide monomers, in which the conversion by hydrolysis yields a carboxylate mer unit. Preferably, our polymers contain less than one and even more preferably less than 0.1 weight percent of such a hydrolysis product of the acrylamide mer unit originally present in the polymerization.
  • the starting monomers for our copolymer are acrylamide and diallyldimethylammonium chloride ("DADMAC"). These monomers are well known in the art and may be polymerized by free radical initiation in aqueous solution or in a water-in-oil emulsion. It is preferable to obtain the high molecular weight polymers of our invention to synthesize our polymers using free radical initiation of an appropriate aqueous solution of the admixture of monomers, after this aqueous solution containing the monomers of this invention has been emulsified in oil by the techniques taught in Vanderhoff, U.S.
  • Patent 3,284,393 the disclosure of which is incorporated herein by reference, or in other patents, such as Frisque/Anderson, U.S. 3,624,019, U.S. 3,734,873, and RE-28,474, which are also incorporated herein by reference.
  • a mixture of 50 weight ratios of acrylamide and DADMAC was dissolved in water to form a solution which contained between 40-60 weight percent total monomer.
  • This aqueous solution was then added to a hydrophobic oil in the presence of a water-in-oil emulsifying agent and was vigorously stirred to form a water-in-oil emulsion, which emulsion contains, in its aqueous phase, the acrylamide and DADMAC monomers.
  • This emulsion is formed by the use of water-in-oil emulsifiers, such as those exemplified in Vanderhoff, U.S. Patent 3,284,393.
  • This emulsion is deoxygenated by blowing nitrogen, or any other inert gas, through the emulsion, then a free radical initiator is added.
  • a free radical initiator Any of the free radical initiators known in the art may be used, including, but not limited to, peroxides, redox initiators, U.V. light, and the like.
  • the emulsion is normally purged with an inert gas, such as nitrogen, and heated to a temperature of about 40-50°C.
  • a free radical initiator is added and a polymerization reaction maintained temperatures ranging between about 40-60°C for reaction times of at least one hour.
  • reaction is stopped, preferably by blowing air into the reaction emulsion and the contents of the reaction vessel are cool to room temperature.
  • the polymerization procedure and its utilization in preparing typical copolymers of this invention is to form the water-in-oil emulsions containing the DADMAC and acrylamide and containing the following four basic components. These components and their weight percentages in the water-in-oil emulsions are listed below:
  • a water-in-oil emulsifying agent D.
  • water-in-oil emulsions of water soluble polymers of this invention with respect to the aqueous phase of these emulsions.
  • This aqueous phase is generally defined as the sum of the copolymer present in the emulsion plus the amount of water present in the emulsion. This terminology may also be utilized in describing the water-in-oil emulsions useful in our invention.
  • the aqueous phase of the water-in-oil emulsions of this invention generally consists of 25-95 percent by weight of the emulsion and preferably the aqueous phase is between 40-90 weight percent of the emulsion. Most preferably, the emulsions containing the copolymers of this invention have an aqueous phase ranging between about 55-85 weight percent.
  • emulsions may also be characterized in relation to the water/oil ratios. This figure is simply a ratio of the amount of water present in the emulsion divided by the amount of hydrophobic liquid present in the emulsion.
  • the water-in-oil emulsions of this invention have a water/oil ratio ranging from about 0.25 to about 18.
  • the water-in-oil ratio will range from 0.5-14, and most preferably, this ratio will range between about 1.0-5.
  • the oily liquid may be chosen from any hydrocarbon oil, which oil is essentially immiscible with water.
  • a common paraffin oil such as LOPS, may be used.
  • the water-in-oil emulsifiers are exemplified by sorbitan monooleate or a mixture of sorbitan monooleate with a ethylene oxide adduct of sorbitan monostearate.
  • the combination can provide for rapid invertibility of the emulsion of the polymers of this invention when the emulsion is added directly to an aqueous solution, as taught in the Anderson/Frisque patents U.S. 3,624,019, U.S. 3,734,873 and RE-28,576.
  • the polymer may be added to the pulp in any form, e.g. as a water-in-oil emulsion or as a previously inverted oil-in-water emulsion.
  • the figure presents the results of three polymers having reduced specific viscosities of 4.0, 5.6, and 8.2, all polymers being a 50/50 mixture of acrylamide and DADMAC, all polymers having been made as water-in-oil emulsions using techniques similar to those described above. These materials were tested to demonstrate their retention abilities using a Britt jar screening technique known in the art. This Britt jar test measures small particle retention in terms of the present transmittance of simulated white water, plotted on the Y axis in Figure 1 vs. polymer dose in kg/t. An increased percent transmittance indicates improved performance.
  • polymers of this invention having reduced specific viscosities above 5.0 gives preferred and improved performance, even against polymer D, which is another type of cationic polymer commercially used as a retention aid, which polymer does not contain DADMAC and which polymer has a higher molecular weight than the highest molecular weight described herein. It is however highly viscous and difficult to handle.
  • the effective paper fine and filler retaining amount of our polymer is at least 0.1 kg of polymer (as active polymer) per metric ton of paper pulp solids (or active) being treated (i.e. about 0.25 lb/ton). Although as much as about 2.5 kg/t (approx. 5 lbs/ton) active polymer may be used, preferably the fines and filler effective retaining amount of polymer is between about 0.25 to 1.25 kg/t (about 0.5 to about 2.5 lbs/ton) of paper pulp.
  • copolymers of the instant invention are an improvement over the art, even when other cationic polymers derived from different cationic monomers and having higher molecular weight are tested, which higher molecular weight polymers do not contain the DADMAC monomer.
  • Products of our invention having reduced specific viscosities above 5 show significantly improved retention aid performance when the polymers contain between 40-60 weight percent DADMAC and between 60-40 weight percent acrylamide and the acrylamide contained within the polymer is hydrolyzed below 2 weight percent, based on starting acrylamide monomer, and preferably below 0.1 weight percent based on starting acrylamide monomer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
EP90309154A 1989-08-23 1990-08-21 Verfahren und Zellstoff für die Verbesserung der Retention von Papierpulvern und -füllstoffen Withdrawn EP0414496A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US39722489A 1989-08-23 1989-08-23
US397224 1989-08-23

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EP0414496A1 true EP0414496A1 (de) 1991-02-27

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EP (1) EP0414496A1 (de)
AU (1) AU5113090A (de)
CA (1) CA2005896A1 (de)
FI (1) FI902129A0 (de)
MX (1) MX174066B (de)
ZA (1) ZA902389B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0536580A1 (de) * 1991-10-07 1993-04-14 Nalco Chemical Company Verwendung von Emzyme und Flockungsmitteln zur Erhöhung der Entwässerungsneigung
WO2001063050A1 (en) * 2000-02-24 2001-08-30 Calgon Corporation An organic coagulant composition for treating coated broke

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2245671A1 (de) * 1973-10-01 1975-04-25 Calgon Corp
EP0320512A1 (de) * 1985-04-30 1989-06-21 Sumitomo Chemical Company, Limited Verfahren zur herstellung von papier
EP0362770A2 (de) * 1988-10-03 1990-04-11 Hercules Incorporated Trockenfestigkeitszusatz für Papier

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2245671A1 (de) * 1973-10-01 1975-04-25 Calgon Corp
EP0320512A1 (de) * 1985-04-30 1989-06-21 Sumitomo Chemical Company, Limited Verfahren zur herstellung von papier
EP0362770A2 (de) * 1988-10-03 1990-04-11 Hercules Incorporated Trockenfestigkeitszusatz für Papier

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0536580A1 (de) * 1991-10-07 1993-04-14 Nalco Chemical Company Verwendung von Emzyme und Flockungsmitteln zur Erhöhung der Entwässerungsneigung
WO2001063050A1 (en) * 2000-02-24 2001-08-30 Calgon Corporation An organic coagulant composition for treating coated broke

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AU5113090A (en) 1991-02-28
FI902129A0 (fi) 1990-04-27
CA2005896A1 (en) 1991-02-23
MX174066B (es) 1994-04-19
ZA902389B (en) 1991-03-27

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