US3902958A - Method of making improved paper and paper products - Google Patents

Method of making improved paper and paper products Download PDF

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US3902958A
US3902958A US438050*A US43805074A US3902958A US 3902958 A US3902958 A US 3902958A US 43805074 A US43805074 A US 43805074A US 3902958 A US3902958 A US 3902958A
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pulp
water
polymers
paper
weight
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Danny L Breen
Alvin J Frisque
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ChampionX LLC
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Nalco Chemical Co
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375Poly(meth)acrylamide
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54Synthetic 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

Definitions

  • This invention is based upon the concept that improved paper and paper products are afforded by adding to an aqueous pulp slurry a liquid dispersion of a water-soluble anionic vinyl addition polymer and a water-soluble cationic polymer.
  • the water-soluble anionic vinyl addition polymer may be in the form of a water-in-oil emulsion which contains dispersed therein the finely divided water-soluble anionic vinyl addition polymer. This emulsion or latex contains unformly distributed therethroughout a water-soluble cationic polymer. Latices of this type are preferred for use in the practice of the invention.
  • the invention also contemplates utilizing metastable dispersions of water-soluble anionic vinyl addition polymers and water-soluble cationic polymers which are dispersed in aqueous brines.
  • Michaels polymers Metastable dispersions of this type are commonly known to the art as Michaels polymers or dispersions.
  • the Michaels polymers are prepared by adding a water-soluble anionic vinyl addition polymer to an aqueous brine and then adding a cationic water-soluble polymer to such brine to form a metastable solution or dispersion of the oppositely charged polymers.
  • the reverse order of addition also may be used. It is now known that when the salt concentration of such brines is within the range of 5-30% by weight, and the proportions of anionic and cationic polymers are properly adjusted, it is possible to produce dispersions of the two polymers which do not form precipitates or gels.
  • brine dispersions are stable over periods of time ranging from a few minutes up to several months depending upon the particular polymers selected, the concentra" tions and ratios of the polymers, the molecular weight of the polymers. the concentration of the'brine, and the particular salt in the brine.
  • concentration of the'brine the concentration of the'brine
  • salt the particular salt in the brine.
  • polar water-miscible organic solvents such as dioxane.
  • the water-soluble anionic vinyl addition polymers that are used to prepare the liquid dispersions may be illustrated by the following list of polymers:
  • the above polymers may vary in molecular weight. They may be as low as 10,000 or as high as 12 million or more. In most instances, significant effects in the finished paper are noticed when the molecular weight is greater than 1 million.
  • the invention contemplates using as preferred watersoluble anionic vinyl addition polymers the homoand eopolymers of acrylic acid as well as the water-soluble salts thereof.
  • Ethylene dichloride-ammonia condensation polymers Tetraethylene pentamine-epichlorov hydrin condensation polymers 3 Epichlorohydrin-ammonia condensation polymers Polyethylene imine Ethylene diamine Polydiallyl amine Dimethylamino ethyl methacrylate The methyl chloride quaternary of Number l The benzol chloride quaternary of Number 7 Guanidine formaldehyde condensation TABLE II-Continued Number Name polymers 1 l Acrylamide-diallylamine (3W7:
  • the above polymers are illustrative of typical watersoluble cationic polymeric materials that may be used in the practices of the invention.
  • a preferred class of these polymers may be described as alkylene polyamines which are illustrated by polymers 1, 2, 3, 4, 5 and 8 above. I Many of the above polymers have been described with respect to the reactants from which they are prepared. A detailed discussion of the above polymers and other cationic polymers appears in Canadian Pat. No. 731,212, the disclosure of which is incorporated herein by reference.
  • the polymers may be employed as solutions or in the form of a water-in-oil latex or emulsion. When the polymers are of the vinyl addition type, they may be copolymers of other ethylinically saturated monomers. Such copolymers should contain at least 5% by weight of the cationic monomer.
  • the invention in its preferred embodiment contemplates utilizing the water-soluble anionic vinyl addition polymers in the form of water-in-oil emulsion which contains dispersed therein the water-soluble anionic vinyl addition polymer.
  • Emulsions of this type are prepared by dispersing the anionic vinyl addition polymer into a water-in-oil emulsion. These polymers are produced by most manufacturing processes are in the form of powders or lump-like agglomerates of varying particle size.
  • the particles before being placed into the emulsion, be comminuted by grinding, abrading or the like so that their average particle size is less than 5 millimeters and preferably is within the range of 1-5 microns.
  • the powders may be dispersed into the waterinoil emulsion by means of agitation provided by such devices as stirrers, shakers and the like.
  • the amount of polymer in the emulsion should be at least 2% by weight.
  • the invention contemplates using emulsions containing between 575% by weight with preferred emulsions having a polymer concentration within the range of 1045% by weight. In some cases the starting emulsions are converted to suspensions due to the nature and the amount of the polymer present therein.
  • the polymer emulsions thus described be stable, yet at the same time contain relatively large amounts of polymers.
  • One method of insuring that the polymers do not precipitate when dispersed in the emulsion is that the particle size of the polymer be as small as possible.
  • polymers dispersed in the emulsions are quite stable when the particle size is within the range of 5 millimicrons up to about 5 microns.
  • spray dryers with appropriate size nozzles may be used. It also is possible to prepare the polymer-containing emulsion of the watersoluble vinyl addition polymers directly from the vinyl monomers from which these polymers are synthesized.
  • Such polymer-containing emulsions may be synthesized by using the water-in-oil emulsion polymerization technique set forth in US. Pat. No. 3,284,393.
  • the teachings of this patent comprise forming a water-in-oil emulsion of water-soluble ethylenic unsaturated monomers.
  • the emulsion is formed by utilizing a water-in-oil emulsifying agent.
  • a free radical-type polymerization catalyst To this monomer is added a free radical-type polymerization catalyst and then heat is applied under free radical-forming conditions to form water'soluble polymer latices,
  • the polymeric latices produced by this patent are relatively unstable and frequently must be treated with additional emulsifiers to render the products stable.
  • the water-in-oil emulsions used to prepare the above polymers may be formulated by any number of known techniques.
  • oils used in preparing these emulsions may be selected from a large group of organic liquids which include liquid hydrocarbons and substituted liquid hydrocarbons. Aliphatic liquid hydrocarbons are preferred.
  • the oil should be inert to the polymer or the monomer from which the polymer is prepared.
  • a preferred group of organic liquids are the hydrocarbon liquids which include both aromatic and aliphatic compounds, with the latter being most preferred
  • organic hydrocarbon liquids as benzene, xylene, toluene, mineral oils, kerosenes, naphthas, and, in certain instances, petrolatums may be used.
  • a particularly useful oil from the standpoint of its physical and chemical properties is the branch-chain isoparaffinic solvent sold by Humble Oil & Refining Company under the Tradename ISOPAR M. Typical specifications of this narrow-cut isoparaffinic solvent are set forth below in TABLE III.
  • the amount of oil used in relation to the water to prepare the emulsion may be varied over wide ranges.
  • the amount of oil-to-water may vary between 5:1 lzlO with preferable emulsions being prepared in the ratio of 1:2 1:10. These ratios are illustrative of emulsions that can be prepared, although it should be understood that the invention is not limited thereby.
  • the emulsions may be prepared by any number of techniques.
  • the emulsions may be prepared by using high speed agitation or ultrasonic techniques.
  • the amount of emulsifying agent to provide an emulsion will have to be determined by routine experimentation. As a general rule it may be said that the amount of oil-soluble emulsifier may range from 0.1 30% by weight based on the weight of the oil. To produce stable emulsions the amount of emulsifier will normally be within the range of l2 205 by weight of the oil.
  • tants may be used as long as they are capable of pro- DISPERSION A ducmg these emulsions.
  • we lave iound To emulsion in TABLE IV COMPOSITION certalllhlgh rl l Z i BER VI there was added 30% by weight of an aqueous f 1 W L emu typlcl Ow w dispersion containing 23% by weight of an alkylene H B emu ls sot monoo Cate polyamine prepared from the condensation of ethylene PREPARATION OF THE STABLE LIQUID dichloride ancli1 ammonia.
  • f:I"he;1p oly(igner prepalged DISPERSIONS using the tee niques set ort 1n ana ian Pat. 0.
  • the water'soluble DISPERSION B cationic polymers are combined therewith by the utili- To COMPOSITION NUMBER VI in TABLE IV zation of conventional mixing techniques.
  • an aqueous dispersion which conthe water-soluble cationic polymers are in the form of tained by weight of an ammonia ethylene dichloaqueous solutions which contain 5 40% by weight of 40 ride polymer of the type used in DISPERSION A above the polymer and are added to the polymeric latex. Alwith the exception it had been quaternized with methyl ternatively, they may be nearly water-free. After unichloride.
  • ble liquid dispersion of a water-soluble anionic vinyl TABLE V is presented below: addition polymer and a water-soluble cationic polymer.
  • the proportions of the two polymers may be varied to a considerable degree.
  • the ratio of the ANIONIC LATEX /(by 7r by water-soluble anionic vinyl addition polymer to water- TABLE W weght CATIOMC POLYMER soluble cationic polymer may vary between 1:10 10:1 1 60 30% solution of a tetra- 40 on a weight basis.
  • a preferred ratio is 1:5 to 5:1.
  • the ehylcne i chlorohydrin reaction most preferred ratio is 1:2 2:1. product (Canadian Pat.
  • the amount of the water-soluble vinyl addition polymers plus the water-soluble cationic polymers present VI 50 Ethylene di'dmine in the finished liquid dispersion may be varied over a v 70 75% acwlamidm 25,7! 30 wide range of concentrations, e.g. dispersions containmethylamino ethyl mething from 0.001 75% by weight are useful. In many inf m orin of a latex (WJUEFII'I- stances the total weight of the two polymers contained oil A see TABLE II. US.
  • dispersions in the dispersion will be within the range of 5 40% by weight, with a very beneficial dispersion being one 13()/b' eihtofthetwo g buwebn 0 y w g All of the above dispersions were stable and were cap0 yn pable of being stored under a variety of conditions The finished dispersions are stable at room temperawithout interreaction of the two polymers. ture for periods of time ranging between several days AS pre iously in i ated, i i possible i tilize m mto as long as 6 months since they may be prepared over stable dispersions of water-soluble anionic vinyl addia wide variety of concentrations.
  • Concentrates containing large amounts of polymers may be prepared and tion polymers and cationic water-soluble addition polymers which are dispersed in an aqueous brine.
  • such dispersions are preferably prepared at the paper mill at a point at or near the addition point in the pulp processing portion of the papermaking operation. Also. as indicated, since these dispersions are stable for periods of time ranging from several hours up to several months it is possible to make small batches which would be continuously fed to the pulp system. It has been found that a convenient way to prepare such metastable dispersions is to take a small portion of the pulp and use it as the brine into which the anionic and cationic polymer are added.
  • Example 1 in U.S. Pat. No. 3,271,496 which shows the preparation of such a dispersion.
  • the liquid dispersions of the type described above are used to treat aqueous suspensions of paper pulp at dosages ranging from as little as 0.1 by weight, based on the dry weight of the pulp. In most applications the dosage ranges between 0.5 571 by weight.
  • the dosage used in the practice of the invention is dependent upon many factors. Illustrative of some of these factors is the effect sought to be achieved, the nature of the pulp, the type of pulping process used and the particular chemical makeup of the stable liquid dispersion. Also factors are the pH of the pulp, the pulp concentration, the temperature of the pulp and the dissolved solids and other additives present in the aqueous phase of the pulp suspension. Therefore, it is evident that While a dosage range has been given, it is dependent upon the particular pulp system sought to be treated and the particular effect sought to be achieved in the finished paper produced from such pulp.
  • liquid dispersions are added to either concentrated brine solutions, which solutions include concentrated alum and sodium aluminate solutions. These brine dispersed suspensions remain relatively stable. When the brine is removed from the diluted stable liquid dispersion, it tends to release into the aqueous phase the anionic vinyl addition polymer and the cationic polymer. These two polymers. upon release into water, tend to react with each other, forming a cross-linked, gel-like structure which is water and oil insoluble and is flexible and somewhat porous in nature.
  • the stable liquid dispersion be either added to a brine or it may be first diluted with an appropriate hydrocarbon oil or other hydrophobic liquid to dilute the polymer concentration to between 5-10% by weight.
  • these diluted materials may be then added to the paper pulp which in many instances contains a sufficient amount of dissolved solids, such as alum, sodium aluminate and the like, where the polymers tend to uniformly distribute themselves throughout the pulp slurry allowing them to combine with and upon the individual fiber surfaces in a surprisingly uniform manner.
  • the pulp is then processed in accordance with known papermaking methods to form a water laid sheet on a device such a fourdrinier machine.
  • metastable liquid dispersions When used, they are added to the pulp system in the same manner as that used for adding the stable latices. When added to the pulp system, the oppositely charged polymers do not react with each other to form a cross-linked gel-like structure but rather tend to disperse themselves into the and about the cellulosic fibers in a uniform manner, thereby producing a homogeneity of treatment heretofore unobtainable by prior art processes.
  • the anionic and cationic polymers react with each other to form a flexible three-dimensional cross-linked structure which imparts outstanding properties to the finished paper formed from the pulp containing such polymers.
  • the polymeric mixtures of anionic and cationic polymers tend to react with each other upon dilution of the pulp just prior to or during the sheet-formation stage of the papermaking process.
  • the cross-linking reaction of the polymers is further increased which tends to additionally improve the characteristics of the finished paper.
  • the pH of the papermaking sys tem will invert the liquid dispersion of polymers that has been added thereto and thereby cause the gel-like structures to form about the paper fibers.
  • the dispersions give excellent results when the pH of the pulp is or is adjusted to between 4.59.5 and preferably 4.58.5.
  • Each of the numerous liquid dispersions that can be prepared and their method of reaction in the presence of the pulp may be suitably selected for the particular conditions and effects sought to be achieved while at the same time allowing ease of feed and application of the dispersions to the paper pulp.
  • the various liquid dispersions used in the practice of the invention allow special effects to be achieved in paper products using relatively low dosages.
  • By controlling the amount and nature of the polymeric components of the liquid dispersions it is possible to produce paper and paper products having improved wet and dry strength. Sizing effects are readily achieved heretofore unobtainable by wet end addition of sizing agents such as rosin.
  • Specialty papers, such as waterproof and greasproof papers can be easily produced.
  • Paper products can be manufactured where high amounts of the liquid dispersion polymers are used, which products resemble plastic laminates which can be used in the manufacture of high grade industrial paper products, such as felts, building materials, and the like.
  • Dispersion A would be used by diluting it with kerosene to provide a polymer concentration of 5% by weight. This concentration would then be added to a kraft or sulfate pulp to give a dosage of 2% by weight based on dry pulp. If the pulp contains suffieient alum or sodium aluminate to produce a dissolved salt content of about 2% by weight, then the diluted dispersion added thereto would uniformly distribute itself throughout the pulp without reacting to cause the anionic vinyl addition polymer to react with the cationic polymer.
  • a small amount of nonionic dispersant e.g. 0.1% by weight of the pulp, is added to invert the liquid dispersion of the polymer so that it uniformly reacts so that the polymeric components react with each other to form an insoluble mass about the individual fiber surfaces.
  • the pulp is processed by forming into finished kraft paper.
  • the paper, thus treated would have improved wet and dry strength, would be slightly waxy to the feel, and would be capable of acting as heavy duty wrapping paper.
  • the same paper untreated would have far less wet or dry strength and is only of use in light duty service.
  • a process for manufacturing paper having improved properties which comprises the steps of:
  • a polymeric latex composed of a water-in-oil emulsion which contains dispersed therein a finely divided water-soluble anionic vinyl addition polymer; said polymeric latex having uniformly distributed throughout,
  • b a water-soluble cationic polymer: With the ratio of (a) to (b) being within the range of 1:10 to 10:1 and the total amount of a and b present within said dispersion being within the range of from 0.001 to wherein a stable dispersion of pulp containing uniformly dispersed polymers without gellation is formed,
  • weight ratio of (a) to (b) is within the range of from 1:5 to 5:1 and the amount of (a) plus (17) present within said dispersion is within the range of from 54()% by weight.

Abstract

Improved paper and paper products are produced by adding to an aqueous suspension of paper pulp fibers from 0.01 - 10% by weight, based on the dry weight of the pulp, of a liquid dispersion of a water-soluble anionic vinyl addition polymer and a water-soluble cationic polymer.

Description

United States Patent [1 1 Breen et al.
[4 1 Sept. 2, 1975 METHOD OF MAKING IMPROVED PAPER AND PAPER PRODUCTS [75] Inventors: Danny L. Breen, Plover, Wis.; Alvin ,I. Frisque, Lagrange, Ill.
[73] Assignee: Nalco Chemical Company, Oak
Brook, 111.
[22] Filed: Jan. 30, 1974 [211' Appl. No.: 438,050
[52] U.S. Cl. 162/164; 162/168; 162/183 [51] Int. Cl. D2ID 3/00 [58] Field of Search 162/168, 164, 183;
260/296 RW, 29.6 R, 29.6 NR
[56] References Cited UNITED STATES PATENTS 11/1966 Vanderhofi et a1 260/342 7/1967 Reynolds 162/164 3,660,338 5/1972 Economou 162/164 3,790,514 2/1974 Econonou 3,799,902 3/1974 Anderson 260/296 R 0TH ER PUBLICATIONS Casey Pulp & Paper, Vol. II, 2nd ed. (1960) p. 947.
Primary ExaminerS. Leon Bashore Assistant Examiner-Peter Chin Attorney, Agent, or Firm-John G. Premo; Robert A. Miller [5 7 ABSTRACT 4 Claims, No Drawings METHOD OF MAKING IMPROVED PAPER AND PAPER PRODUCTS INTRODUCTION Many substances are placed into aqueous suspensions of paper pulp fibers in an attempt to produce improved paper and paper products. Chemicals are fre quently added to various types of paper pulps to pro duce finished paper having improved properties, such as wet and dry strength, increased tear resistance, better surface characteristics and the like. Also, chemicals are added to paper pulps to improve the manufacturing characteristics of the pulp as it is processed from an aqueous slurry into a finished sheet. For example, chemicals are added to improve fine and filler retention, to improve the receptivity of the paper for various additives, all of which processes have as their main objective producing better paper with less wastage or better utilization of raw material.
It would be a valuable contribution to the art if a paper-making process and additive or additives could be provided which could produce finished paper products having improved chemical and mechanical characteristics. could be used either along or in conjunction with other known additives for paper at low economical doses and which would incorporate itself into the paper and be intimately combined therewith to provide a fin ished paper having improved characteristics.
Also of importance would be a chemical additive for paper pulp which could be used in the various types of papermaking processes such as, for example, mechanical pulping, soda processing, sulfite processing, sulfate processing and semichcmical processing. Of further utility would be an additive which would work over a wide variety of pH ranges, would be relatively compatible with other known papermaking additives and would uniformly distribute itself throughout the pulp so that the finished paper contained as an integral part thereof the additives.
THE INVENTION This invention is based upon the concept that improved paper and paper products are afforded by adding to an aqueous pulp slurry a liquid dispersion of a water-soluble anionic vinyl addition polymer and a water-soluble cationic polymer. The water-soluble anionic vinyl addition polymer may be in the form of a water-in-oil emulsion which contains dispersed therein the finely divided water-soluble anionic vinyl addition polymer. This emulsion or latex contains unformly distributed therethroughout a water-soluble cationic polymer. Latices of this type are preferred for use in the practice of the invention.
In addition to using anionic latices which contain uniformly distributed therethroughout a water-soluble cat ionic polymer, the invention also contemplates utilizing metastable dispersions of water-soluble anionic vinyl addition polymers and water-soluble cationic polymers which are dispersed in aqueous brines.
Metastable dispersions of this type are commonly known to the art as Michaels polymers or dispersions. The Michaels polymers are prepared by adding a water-soluble anionic vinyl addition polymer to an aqueous brine and then adding a cationic water-soluble polymer to such brine to form a metastable solution or dispersion of the oppositely charged polymers. The reverse order of addition also may be used. It is now known that when the salt concentration of such brines is within the range of 5-30% by weight, and the proportions of anionic and cationic polymers are properly adjusted, it is possible to produce dispersions of the two polymers which do not form precipitates or gels. These brine dispersions are stable over periods of time ranging from a few minutes up to several months depending upon the particular polymers selected, the concentra" tions and ratios of the polymers, the molecular weight of the polymers. the concentration of the'brine, and the particular salt in the brine. To improve the stability of such eopolymer brine mixtures it is sometimes beneficial to add quantities of polar water-miscible organic solvents such as dioxane.
The water-soluble anionic vinyl addition polymers that are used to prepare the liquid dispersions may be illustrated by the following list of polymers:
TABLE I Number Name The above polymers may vary in molecular weight. They may be as low as 10,000 or as high as 12 million or more. In most instances, significant effects in the finished paper are noticed when the molecular weight is greater than 1 million.
The invention contemplates using as preferred watersoluble anionic vinyl addition polymers the homoand eopolymers of acrylic acid as well as the water-soluble salts thereof.
THE WATER-SOLUBLE CATIONIC POLYMERS These polymers also may be selected from a wide variety of known polymeric materials. Several of these polymers are listed below in TABLE II.
TABLE II Number Name 1 Ethylene dichloride-ammonia condensation polymers Tetraethylene pentamine-epichlorov hydrin condensation polymers 3 Epichlorohydrin-ammonia condensation polymers Polyethylene imine Ethylene diamine Polydiallyl amine Dimethylamino ethyl methacrylate The methyl chloride quaternary of Number l The benzol chloride quaternary of Number 7 Guanidine formaldehyde condensation TABLE II-Continued Number Name polymers 1 l Acrylamide-diallylamine (3W7:
The above polymers are illustrative of typical watersoluble cationic polymeric materials that may be used in the practices of the invention. A preferred class of these polymers may be described as alkylene polyamines which are illustrated by polymers 1, 2, 3, 4, 5 and 8 above. I Many of the above polymers have been described with respect to the reactants from which they are prepared. A detailed discussion of the above polymers and other cationic polymers appears in Canadian Pat. No. 731,212, the disclosure of which is incorporated herein by reference. The polymers may be employed as solutions or in the form of a water-in-oil latex or emulsion. When the polymers are of the vinyl addition type, they may be copolymers of other ethylinically saturated monomers. Such copolymers should contain at least 5% by weight of the cationic monomer.
THE ANIONIC VINYL ADDITION POLYMER POLYMERIC LATEX The invention in its preferred embodiment contemplates utilizing the water-soluble anionic vinyl addition polymers in the form of water-in-oil emulsion which contains dispersed therein the water-soluble anionic vinyl addition polymer. Emulsions of this type are prepared by dispersing the anionic vinyl addition polymer into a water-in-oil emulsion. These polymers are produced by most manufacturing processes are in the form of powders or lump-like agglomerates of varying particle size. It is desirable that the particles, before being placed into the emulsion, be comminuted by grinding, abrading or the like so that their average particle size is less than 5 millimeters and preferably is within the range of 1-5 microns. After the powders have been comminuted, they may be dispersed into the waterinoil emulsion by means of agitation provided by such devices as stirrers, shakers and the like. To be commer cially practical, the amount of polymer in the emulsion should be at least 2% by weight. The invention contemplates using emulsions containing between 575% by weight with preferred emulsions having a polymer concentration within the range of 1045% by weight. In some cases the starting emulsions are converted to suspensions due to the nature and the amount of the polymer present therein.
From a commercial standpoint it is beneficial that the polymer emulsions thus described be stable, yet at the same time contain relatively large amounts of polymers. One method of insuring that the polymers do not precipitate when dispersed in the emulsion is that the particle size of the polymer be as small as possible. Thus, polymers dispersed in the emulsions are quite stable when the particle size is within the range of 5 millimicrons up to about 5 microns. To produce particle sizes within these limitations, spray dryers with appropriate size nozzles may be used. It also is possible to prepare the polymer-containing emulsion of the watersoluble vinyl addition polymers directly from the vinyl monomers from which these polymers are synthesized. Such polymer-containing emulsions may be synthesized by using the water-in-oil emulsion polymerization technique set forth in US. Pat. No. 3,284,393. The teachings of this patent comprise forming a water-in-oil emulsion of water-soluble ethylenic unsaturated monomers. The emulsion is formed by utilizing a water-in-oil emulsifying agent. To this monomer is added a free radical-type polymerization catalyst and then heat is applied under free radical-forming conditions to form water'soluble polymer latices, The polymeric latices produced by this patent are relatively unstable and frequently must be treated with additional emulsifiers to render the products stable.
The water-in-oil emulsions used to prepare the above polymers may be formulated by any number of known techniques.
The oils used in preparing these emulsions may be selected from a large group of organic liquids which include liquid hydrocarbons and substituted liquid hydrocarbons. Aliphatic liquid hydrocarbons are preferred. The oil should be inert to the polymer or the monomer from which the polymer is prepared.
A preferred group of organic liquids are the hydrocarbon liquids which include both aromatic and aliphatic compounds, with the latter being most preferred Thus, such organic hydrocarbon liquids as benzene, xylene, toluene, mineral oils, kerosenes, naphthas, and, in certain instances, petrolatums may be used. A particularly useful oil from the standpoint of its physical and chemical properties is the branch-chain isoparaffinic solvent sold by Humble Oil & Refining Company under the Tradename ISOPAR M. Typical specifications of this narrow-cut isoparaffinic solvent are set forth below in TABLE III.
The amount of oil used in relation to the water to prepare the emulsion may be varied over wide ranges. As a general rule, the amount of oil-to-water may vary between 5:1 lzlO with preferable emulsions being prepared in the ratio of 1:2 1:10. These ratios are illustrative of emulsions that can be prepared, although it should be understood that the invention is not limited thereby.
The emulsions may be prepared by any number of techniques. For example, the emulsions may be prepared by using high speed agitation or ultrasonic techniques. In most instances, however, it is desirable that the emulsion be a stable emulsion and to achieve this end it is often necessary to employ an oil-soluble emulsifying agent. The amount of emulsifying agent to provide an emulsion will have to be determined by routine experimentation. As a general rule it may be said that the amount of oil-soluble emulsifier may range from 0.1 30% by weight based on the weight of the oil. To produce stable emulsions the amount of emulsifier will normally be within the range of l2 205 by weight of the oil.
Rather than provide a listing of suitable emulsifiers, recommended as being satisfactory are the so-called low HLB materials which are well documented in the shipped to a use point and then diluted with an organic liquid just prior to use.
PREPARATION OF THE LIQUID DISPERSIONS To illustrate the preparation of liquid dispersions a literature and are summarized in the Atlas I-ILB Surtacvariety of emulsions were prepared containing different tant Selector. Although these emulsifiers are useful in water-soluble anionic vinyl addition polymers. These producing good water-in-oil emulsions. other surfacemulsions are set forth below in TABLE IV.
TABLE IV Com- Water ()il /r In position (A by (/1 by Emul- Polymer Particle Num- Weight) Weight) Polymer sion Size Range her 9371 acrylamidc I 72 28 (I) 7'71 methacrylic acid 3571 ().()57.() microns 93% acrylamide II 72 28 (I) 7% methacrylic acid 35% (l.()57.() microns 70% acrylaniide III 72 28 (T) 307: acrylic acid 357! O.()57.() microns 93% acrylamide IV 67 33 (I) 77: methacrylic acid 327: 30 microns 70% acrylamide V 70 30 (I) 3092 acrylic acid 3471 .()l-l() microns VI 7] 29 (I) Sodium Polyacrylate 37% 1 mm.
tants may be used as long as they are capable of pro- DISPERSION A ducmg these emulsions. For instance, we lave iound To emulsion in TABLE IV COMPOSITION certalllhlgh rl l Z i BER VI, there was added 30% by weight of an aqueous f 1 W L emu typlcl Ow w dispersion containing 23% by weight of an alkylene H B emu ls sot monoo Cate polyamine prepared from the condensation of ethylene PREPARATION OF THE STABLE LIQUID dichloride ancli1 ammonia. f:I"he;1p oly(igner prepalged DISPERSIONS using the tee niques set ort 1n ana ian Pat. 0.
785,829. Once latices containing the water-soluble anionic vinyl addition polymers are prepared the water'soluble DISPERSION B cationic polymers are combined therewith by the utili- To COMPOSITION NUMBER VI in TABLE IV zation of conventional mixing techniques. Preferably there was added an aqueous dispersion which conthe water-soluble cationic polymers are in the form of tained by weight of an ammonia ethylene dichloaqueous solutions which contain 5 40% by weight of 40 ride polymer of the type used in DISPERSION A above the polymer and are added to the polymeric latex. Alwith the exception it had been quaternized with methyl ternatively, they may be nearly water-free. After unichloride. formly mixing the two components there results a Sta- To illustrate other novel dispersions of the invention, ble liquid dispersion of a water-soluble anionic vinyl TABLE V is presented below: addition polymer and a water-soluble cationic polymer. TABLE V The proportions of the two polymers may be varied to a considerable degree. For instance, the ratio of the ANIONIC LATEX /(by 7r by water-soluble anionic vinyl addition polymer to water- TABLE W weght CATIOMC POLYMER soluble cationic polymer may vary between 1:10 10:1 1 60 30% solution of a tetra- 40 on a weight basis. A preferred ratio is 1:5 to 5:1. The ehylcne i chlorohydrin reaction most preferred ratio is 1:2 2:1. product (Canadian Pat.
. 731.212 The amount of the water-soluble vinyl addition polymers plus the water-soluble cationic polymers present VI 50 Ethylene di'dmine in the finished liquid dispersion may be varied over a v 70 75% acwlamidm 25,7! 30 wide range of concentrations, e.g. dispersions containmethylamino ethyl mething from 0.001 75% by weight are useful. In many inf m orin of a latex (WJUEFII'I- stances the total weight of the two polymers contained oil A see TABLE II. US. in the dispersion will be within the range of 5 40% by weight, with a very beneficial dispersion being one 13()/b' eihtofthetwo g buwebn 0 y w g All of the above dispersions were stable and were cap0 yn pable of being stored under a variety of conditions The finished dispersions are stable at room temperawithout interreaction of the two polymers. ture for periods of time ranging between several days AS pre iously in i ated, i i possible i tilize m mto as long as 6 months since they may be prepared over stable dispersions of water-soluble anionic vinyl addia wide variety of concentrations. Concentrates containing large amounts of polymers may be prepared and tion polymers and cationic water-soluble addition polymers which are dispersed in an aqueous brine. In the practice of the invention. such dispersions are preferably prepared at the paper mill at a point at or near the addition point in the pulp processing portion of the papermaking operation. Also. as indicated, since these dispersions are stable for periods of time ranging from several hours up to several months it is possible to make small batches which would be continuously fed to the pulp system. It has been found that a convenient way to prepare such metastable dispersions is to take a small portion of the pulp and use it as the brine into which the anionic and cationic polymer are added. This approach for making up the metastable dispersions works very well in those cases where the pulp contains relatively large amounts of dissolved solids of polyvalent metal salts such as aluminum salts (e.g., alum or sodium aluminate) in addition to other metal salts such as calcium or magnesium salts which are often times normally associated with the make up water used to prepare the pulp. The ratio of anionic to cationic polymer may be varied in the same proportions used in preparing the stable latices previously described. A preferred ratio is 1:5 to 5:1.
In preparing the metastable dispersions a certain amount of experimental trial-and-error techniques are required to determine the ratio of anionic to cationic polymer, their concentration, and the like in order to produce a dispersion that does not cause the two polymers to interact and form a precipitate or gel. Such experimentation is well within the skill of an ordinary papermaking chemist or mill operator.
To illustrate typical dispersions which may be used, reference should be made to Example 1 in U.S. Pat. No. 3,271,496 which shows the preparation of such a dispersion.
TREATMENT OF THE PULP WITH THE LIQUID DISPERSIONS As previously indicated, the liquid dispersions of the type described above are used to treat aqueous suspensions of paper pulp at dosages ranging from as little as 0.1 by weight, based on the dry weight of the pulp. In most applications the dosage ranges between 0.5 571 by weight. The dosage used in the practice of the invention is dependent upon many factors. Illustrative of some of these factors is the effect sought to be achieved, the nature of the pulp, the type of pulping process used and the particular chemical makeup of the stable liquid dispersion. Also factors are the pH of the pulp, the pulp concentration, the temperature of the pulp and the dissolved solids and other additives present in the aqueous phase of the pulp suspension. Therefore, it is evident that While a dosage range has been given, it is dependent upon the particular pulp system sought to be treated and the particular effect sought to be achieved in the finished paper produced from such pulp.
The above-described liquid dispersions are added to either concentrated brine solutions, which solutions include concentrated alum and sodium aluminate solutions. These brine dispersed suspensions remain relatively stable. When the brine is removed from the diluted stable liquid dispersion, it tends to release into the aqueous phase the anionic vinyl addition polymer and the cationic polymer. These two polymers. upon release into water, tend to react with each other, forming a cross-linked, gel-like structure which is water and oil insoluble and is flexible and somewhat porous in nature.
In using the liquid latex dispersions in the papermaking process, it is desirable that when the concentrated dispersions are initially supplied such as, for example, by a manufacturer shipping concentrates containing as much as 10-30% by weight of the polymer, that the stable liquid dispersion be either added to a brine or it may be first diluted with an appropriate hydrocarbon oil or other hydrophobic liquid to dilute the polymer concentration to between 5-10% by weight. These diluted materials may be then added to the paper pulp which in many instances contains a sufficient amount of dissolved solids, such as alum, sodium aluminate and the like, where the polymers tend to uniformly distribute themselves throughout the pulp slurry allowing them to combine with and upon the individual fiber surfaces in a surprisingly uniform manner. After the pulp has thus been treated, it is then processed in accordance with known papermaking methods to form a water laid sheet on a device such a fourdrinier machine.
When the metastable liquid dispersions are used, they are added to the pulp system in the same manner as that used for adding the stable latices. When added to the pulp system, the oppositely charged polymers do not react with each other to form a cross-linked gel-like structure but rather tend to disperse themselves into the and about the cellulosic fibers in a uniform manner, thereby producing a homogeneity of treatment heretofore unobtainable by prior art processes.
When the pulp is diluted by washing at a point at or about the fourdrinier wire or papermaking felt, the anionic and cationic polymers react with each other to form a flexible three-dimensional cross-linked structure which imparts outstanding properties to the finished paper formed from the pulp containing such polymers.
Using the practices described above, far superior paper and paper products are produced as opposed to similar paper pulp which has been treated by separate additions of anionic and cationic polymers of the type described. The success of the invention is believed to be predicated on the fact that by adding the polymers jointly and simultaneously with each other, a more homogenous coating of the individual fibers by these polymers is achieved and that cross-linking, when it does occur, tends to produce more intimate and rigidly bonded structures about the fiber surfaces, thus assuring a paper having improved properties.
The polymeric mixtures of anionic and cationic polymers tend to react with each other upon dilution of the pulp just prior to or during the sheet-formation stage of the papermaking process. When the thus-formed sheet is subjected to the usual drying steps, the cross-linking reaction of the polymers is further increased which tends to additionally improve the characteristics of the finished paper.
In certain instances the pH of the papermaking sys tem will invert the liquid dispersion of polymers that has been added thereto and thereby cause the gel-like structures to form about the paper fibers. The dispersions give excellent results when the pH of the pulp is or is adjusted to between 4.59.5 and preferably 4.58.5.
Each of the numerous liquid dispersions that can be prepared and their method of reaction in the presence of the pulp may be suitably selected for the particular conditions and effects sought to be achieved while at the same time allowing ease of feed and application of the dispersions to the paper pulp.
The various liquid dispersions used in the practice of the invention allow special effects to be achieved in paper products using relatively low dosages. By controlling the amount and nature of the polymeric components of the liquid dispersions, it is possible to produce paper and paper products having improved wet and dry strength. Sizing effects are readily achieved heretofore unobtainable by wet end addition of sizing agents such as rosin. Specialty papers, such as waterproof and greasproof papers can be easily produced. Paper products can be manufactured where high amounts of the liquid dispersion polymers are used, which products resemble plastic laminates which can be used in the manufacture of high grade industrial paper products, such as felts, building materials, and the like.
Since papers can be modified to produce a variety of different effects, it is possible to produce such papers having superior qualities which qualities are achieved by chemicals which are uniformly distributed through out the sheet and which are closely associated with each of the individual fibers. This phenomenon allows papers to be uniform in their properties throughout the entire sheet and does not rely upon surface effects which are frequently the mcchnism by which many additives work. Since the polymers form flexible, threedimensional, cross-linked substances, they provide a remarkable degree of adhesiveness and cohesiveness for the individual fibers, thus allowing papers to be produced having unusual properties of physical and mechanical strength.
To illustrate the practices of the invention, the following is given by way of example:
EXAMPLE 1 Dispersion A would be used by diluting it with kerosene to provide a polymer concentration of 5% by weight. This concentration would then be added to a kraft or sulfate pulp to give a dosage of 2% by weight based on dry pulp. If the pulp contains suffieient alum or sodium aluminate to produce a dissolved salt content of about 2% by weight, then the diluted dispersion added thereto would uniformly distribute itself throughout the pulp without reacting to cause the anionic vinyl addition polymer to react with the cationic polymer. After being added to the pulp and thoroughly admixed therewith, a small amount of nonionic dispersant, e.g., 0.1% by weight of the pulp, is added to invert the liquid dispersion of the polymer so that it uniformly reacts so that the polymeric components react with each other to form an insoluble mass about the individual fiber surfaces. After the reaction has taken place, the pulp is processed by forming into finished kraft paper. The paper, thus treated, would have improved wet and dry strength, would be slightly waxy to the feel, and would be capable of acting as heavy duty wrapping paper. The same paper untreated would have far less wet or dry strength and is only of use in light duty service.
Having thus described our invention, it is claimed as follows:
1. A process for manufacturing paper having improved properties which comprises the steps of:
A. Adding to a concentrated aqueous suspension of paper pulp fibers containing at least 2% by weight of a polyvalent metal salt from 0.1 to 10% by weight based on the dry weight of the pulp of a stable liquid dispersion of a water-soluble anionic vinyl addition polymer and a water-soluble cationic polymer comprising:
a. a polymeric latex composed of a water-in-oil emulsion which contains dispersed therein a finely divided water-soluble anionic vinyl addition polymer; said polymeric latex having uniformly distributed throughout,
b. a water-soluble cationic polymer: With the ratio of (a) to (b) being within the range of 1:10 to 10:1 and the total amount of a and b present within said dispersion being within the range of from 0.001 to wherein a stable dispersion of pulp containing uniformly dispersed polymers without gellation is formed,
B. Diluting the stable dispersion of pulp containing uniformly dispersed polymers with water to effect gellation of the said polymers; and then C. Processing the pulp into a paper having improved properties.
2. The process of claim 1 where the weight ratio of (a) to (b) is within the range of from 1:5 to 5:1 and the amount of (a) plus (17) present within said dispersion is within the range of from 54()% by weight.
3. The process of claim 1 where the weight ratio of (a) to (b) is within the range of from 1:2 to 2:1 and the amount of (a) plus (b) present within said dispersion is within the range of from 10-30% by weight.
4. The process of claim 1 where the pulp is a sulfate pulp.

Claims (4)

1. A PROCESS FOR MANUFACTURING PAPER HAVING IMPROVED PROPERTIES WHICH COMPRISES THE STEPS OF: A. ADDING TO A CONCENTRATED AQUEOUS SUSPENSION OF PAPER PULP FIBERS CONTAINING AT LEAST 2% BY WEIGHT OF A POLYVALENT METAL SALT FROM 0.1 TO 10% BY WEIGHT BASED ON THE DRY WEIGHT OF THE PULP OF A STABLE LIQUID DISPERSION OF A WATERSOLUBLE ANIONIC VINYL ADDITION POLYMER AND A WATER-SOLUBLE CATIONIC POLYMER COMPRISING: A. APOLYMERIC LATEX COMPOUND OF A WATER-IN-OIL EMULSION WHICH CONTAINS DISPERSED THEREIN A FINELY DIVIDED WATERSOLUBLE ANIONIC VINYL ADDITION POLYMER, SAID POLYMERIC LATEX HAVING UNFROMLY DISTRIBUTED THROUGHOUT, B. A WATER-SOLUBLE CATIONIC POLYMER: WITH THE RATIO OF (A) TO (B) BEING WITHIN THE RANGE OF 1:10 TO 10:1 AND THE TOTAL AMOUNT OF A AND B PRESENT WITHIN SAID DISPERSION BEING WITHIN THE RANGE OF FROM 0.001 TO 75% WHEREIN A STABLE DISPERSION OF PULP CONTAINING UNIFORMLY DISPERSED POLYMERS WITHOUT GELLATION IS FORMED, B. DILUTING THE STABLE DISPERSION OF PULP CONTAINING UNIFORMLY DISPERSED POLYMERS WITH WATER TO EFFECT GELLATION OF THE SAID POLYMERS: AND THEN C. PROCESSING THE PULP INTO A PAPER HAVING IMPROVED PROPERTIES.
2. The process of claim 1 where the weight ratio of (a) to (b) is within the range of from 1:5 to 5:1 and the amount of (a) plus (b) present within said dispersion is within the range of from 5-40% by weight.
3. The process of claim 1 where the weight ratio of (a) to (b) is within the range of from 1:2 to 2:1 and the amount of (a) plus (b) present within said dispersion is within the range of from 10-30% by weight.
4. The process of claim 1 where the pulp is a sulfate pulp.
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Cited By (18)

* Cited by examiner, † Cited by third party
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FR2314297A1 (en) * 1975-06-12 1977-01-07 Borden Products Ltd HIGH DRY RESISTANCE PAPER DUE TO ADDITIVES EXERCISING A SYNERGIC ACTION AND ITS MANUFACTURING PROCESS
US4042748A (en) * 1972-07-26 1977-08-16 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for improving coating compositions for paper and paper substitutes by use of poly(hydroxyaldehydocarboxylate) dispersing agent
US4152200A (en) * 1977-12-15 1979-05-01 American Cyanamid Company Process for draining formed paper
US4256807A (en) * 1978-07-20 1981-03-17 Northern Telecom Limited Synthetic latex modified pulp insulated conductors
EP0100370A1 (en) * 1982-07-31 1984-02-15 Teijin Limited Process for producing paper or non-woven fabric
US4510019A (en) * 1981-05-12 1985-04-09 Papeteries De Jeand'heurs Latex containing papers
WO1986000350A1 (en) * 1984-06-20 1986-01-16 Weyerhaeuser Company Latex treated cationic cellulose product and method for its preparation
JPS63218246A (en) * 1987-03-06 1988-09-12 Mitsui Saianamitsudo Kk Water-in-oil type polymer emulsion composition
US5883181A (en) * 1993-11-24 1999-03-16 Cytec Technology Corp. Multimodal emulsions and processes for preparing multimodal emulsions
US5935383A (en) * 1996-12-04 1999-08-10 Kimberly-Clark Worldwide, Inc. Method for improved wet strength paper
US6077887A (en) * 1995-11-29 2000-06-20 Akzo Nobel Surface Chemistry Ab Polyelectrolyte composition
USRE36780E (en) * 1988-12-19 2000-07-18 Cytec Technology Corp. Mannich acrylamide polymers
USRE36884E (en) * 1988-12-19 2000-09-26 Cytec Technology Corp. Mannich acrylamide polymers
USRE37037E1 (en) 1988-12-19 2001-01-30 Cytec Technology Corp. Emulsified mannich acrylamide polymers
WO2006065928A2 (en) 2004-12-14 2006-06-22 Hercules Incorporated Retention and drainage aids
US20090165975A1 (en) * 2006-02-03 2009-07-02 Nanopaper, Llc Functionalization of paper components
KR100923611B1 (en) * 2001-12-07 2009-10-23 허큘레스 인코포레이티드 Anionic copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions
EP3397811A4 (en) * 2015-12-31 2019-05-22 Ecolab USA, Inc. Dry strength agent composition and method for enhancing the dry strength of paper

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042748A (en) * 1972-07-26 1977-08-16 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for improving coating compositions for paper and paper substitutes by use of poly(hydroxyaldehydocarboxylate) dispersing agent
FR2314297A1 (en) * 1975-06-12 1977-01-07 Borden Products Ltd HIGH DRY RESISTANCE PAPER DUE TO ADDITIVES EXERCISING A SYNERGIC ACTION AND ITS MANUFACTURING PROCESS
US4152200A (en) * 1977-12-15 1979-05-01 American Cyanamid Company Process for draining formed paper
US4256807A (en) * 1978-07-20 1981-03-17 Northern Telecom Limited Synthetic latex modified pulp insulated conductors
US4510019A (en) * 1981-05-12 1985-04-09 Papeteries De Jeand'heurs Latex containing papers
EP0100370A1 (en) * 1982-07-31 1984-02-15 Teijin Limited Process for producing paper or non-woven fabric
WO1986000350A1 (en) * 1984-06-20 1986-01-16 Weyerhaeuser Company Latex treated cationic cellulose product and method for its preparation
US4584357A (en) * 1984-06-20 1986-04-22 Weyerhaeuser Company Latex treated cationic cellulose product and method for its preparation
JPS63218246A (en) * 1987-03-06 1988-09-12 Mitsui Saianamitsudo Kk Water-in-oil type polymer emulsion composition
JPH0716597B2 (en) * 1987-03-06 1995-03-01 三井サイテック株式会社 Water-in-oil type polymer emulsion composition
USRE37037E1 (en) 1988-12-19 2001-01-30 Cytec Technology Corp. Emulsified mannich acrylamide polymers
USRE36780E (en) * 1988-12-19 2000-07-18 Cytec Technology Corp. Mannich acrylamide polymers
USRE36884E (en) * 1988-12-19 2000-09-26 Cytec Technology Corp. Mannich acrylamide polymers
US5883181A (en) * 1993-11-24 1999-03-16 Cytec Technology Corp. Multimodal emulsions and processes for preparing multimodal emulsions
US5914366A (en) * 1993-11-24 1999-06-22 Cytec Technology Corp. Multimodal emulsions and processes for preparing multimodal emulsions
US6077887A (en) * 1995-11-29 2000-06-20 Akzo Nobel Surface Chemistry Ab Polyelectrolyte composition
US5935383A (en) * 1996-12-04 1999-08-10 Kimberly-Clark Worldwide, Inc. Method for improved wet strength paper
KR100923611B1 (en) * 2001-12-07 2009-10-23 허큘레스 인코포레이티드 Anionic copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions
WO2006065928A2 (en) 2004-12-14 2006-06-22 Hercules Incorporated Retention and drainage aids
WO2006065928A3 (en) * 2004-12-14 2006-11-30 Hercules Inc Retention and drainage aids
US20090165975A1 (en) * 2006-02-03 2009-07-02 Nanopaper, Llc Functionalization of paper components
US8123906B2 (en) * 2006-02-03 2012-02-28 Nanopaper, Llc Functionalization of paper components
EP3397811A4 (en) * 2015-12-31 2019-05-22 Ecolab USA, Inc. Dry strength agent composition and method for enhancing the dry strength of paper
US10704201B2 (en) 2015-12-31 2020-07-07 Ecolab Usa Inc. Dry strength agent composition and method for enhancing the dry strength of paper

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