US20030127204A1 - Amphoteric polymer resins that increase the rate of sizing development - Google Patents

Amphoteric polymer resins that increase the rate of sizing development Download PDF

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US20030127204A1
US20030127204A1 US09/947,300 US94730001A US2003127204A1 US 20030127204 A1 US20030127204 A1 US 20030127204A1 US 94730001 A US94730001 A US 94730001A US 2003127204 A1 US2003127204 A1 US 2003127204A1
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formula
monomers
monomer
paper
cationic
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Daniel Varnell
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Priority to US09/947,300 priority Critical patent/US20030127204A1/en
Priority to RU2004110407/04A priority patent/RU2293090C2/ru
Priority to ES02798104T priority patent/ES2306809T3/es
Priority to AU2002332792A priority patent/AU2002332792B2/en
Priority to CNB028175085A priority patent/CN100343295C/zh
Priority to CA2455980A priority patent/CA2455980C/en
Priority to MXPA04001371A priority patent/MXPA04001371A/es
Priority to BRPI0212305-3A priority patent/BR0212305B1/pt
Priority to PCT/US2002/027874 priority patent/WO2003022898A1/en
Priority to DE60226876T priority patent/DE60226876D1/de
Priority to EP02798104A priority patent/EP1423444B9/en
Priority to PT02798104T priority patent/PT1423444E/pt
Priority to KR1020047003306A priority patent/KR100869638B1/ko
Priority to JP2003526969A priority patent/JP4121955B2/ja
Priority to PL02368384A priority patent/PL368384A1/xx
Priority to AT02798104T priority patent/ATE397026T1/de
Priority to TW091120453A priority patent/TW589328B/zh
Assigned to CREDIT SUISSE FIRST BOSTON, AS COLLATERAL AGENT reassignment CREDIT SUISSE FIRST BOSTON, AS COLLATERAL AGENT NOTICE OF GRANT OF SECURITY INTEREST Assignors: HERCULES INCORPORATED
Priority to US10/424,502 priority patent/US7270727B2/en
Publication of US20030127204A1 publication Critical patent/US20030127204A1/en
Priority to ZA2004/02703A priority patent/ZA200402703B/en
Assigned to HERCULES CORPORATION reassignment HERCULES CORPORATION PATENT TERMINATION CS-013599-0200 Assignors: CREDIT SUISSE, CAYMAN ISLANDS BRANCH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C08F226/04—Diallylamine
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • This invention relates to paper sizing promoter compounds, compositions of the sizing promoter compounds, methods of using the sizing promoter compositions and paper made using the sizing promoter compositions.
  • a sizing agent is often employed to provide desirable characteristics sought in the ultimate paper product.
  • Sizing is a measure of the resistance of a manufactured paper or paperboard product to the penetration or wetting by an aqueous liquid.
  • Sizing agents are internal additives employed during papermaking or external additives employed as coating agents during paper finishing that increase this resistance.
  • Papermaking can be carried out under acidic, neutral, or alkaline pH conditions, and the selection of a sizing agent is usually dependent on the pH used.
  • rosin-derived sizing agents are typically used under acidic papermaking conditions.
  • alkaline pH conditions which are widely used in fine paper manufacturing applications, typical sizing agents include alkyl ketene or alkenyl dimers or acid anhydrides such as alkenyl succinic anhydrides.
  • the rate at which the sizing property develops in the sized paper is very important.
  • the sizing property is advantageously developed as quickly as possible after the sizing agent has been added or applied. It is known that the level of size development increases as sized paper is dried to remove moisture.
  • a fast rate of size development is desired for reducing or controlling the water and additive pick-up at the size press of a paper machine.
  • a fast rate of sizing is also important for accurately measuring final paper properties at the end of the paper machine without waiting or additional heating.
  • the sized paper is typically dried to about 0.8-3 wt. % moisture to obtain adequate development of the sizing property before the paper reaches the size press; at the end of the size press treatment, the paper is typically dried to about 4-6 wt. % moisture.
  • the sizing property is not fully developed at the end of the paper machine, corrective measures must be taken, e.g., the paper must be stored for sufficient time (hours or days) until the sizing property develops adequately for the intended use of the paper, or an excess of sizing agent must be used to provide adequate sizing property if the benefit is required (e.g., during the paper finishing or converting steps) before the sizing property has completely developed.
  • the sizing properties provided by conventional paper sizing agents may be improved by the use of sizing promoters, also called sizing accelerators.
  • sizing promoters also called sizing accelerators.
  • Numerous paper sizing promoters are known; see, e.g., U.S. Pat No., 4,040,984; U.S. Pat. No., 4,764,365; U.S. Pat. No., 4,772,462, U.S. Pat. No. 4,478,682; U.S. Pat. No. 4,847,315; U.S. Pat. No. 4,895,621, U.S. Pat. No. 5,498,648 and U.S. Pat. No. 5,853,542.
  • the interaction of the optical brighteners may inhibit the performance of the sizing promoter.
  • the interaction of the optical brighteners may inhibit the performance of the sizing promoter.
  • Cationic polymers and copolymers based on the cyclopolymerization of dimethyldiallylammonium chloride are well known for use in a wide variety of industrial applications.
  • Poly(diallyldimethylammonium chloride) homopolymers are well known cationic polymeric compounds that have been used commercially in papermaking for a wide variety of purposes, e.g., for aiding furnish retention and additive retention in paper; for increasing the dewatering rate of wet paper web; for neutralizing anionic materials in white water; and for size enhancement, to improve paper sizing efficiency and its rate of development.
  • Reten® 203 retention aid Hercules Incorporated, Wilmington, Del.
  • a product which contains a diallyldimethylammonium chloride homopolymer is one such product.
  • Copolymers and terpolymers containing diallylamine-type compounds such as diallyldimethylammonium chloride (DADMAC), methylaldiallyl ammonium chloride or diallylammonium chloride (also referred to as DAA.HCl or DAAC), as one of the monomeric components are known.
  • DADMAC diallyldimethylammonium chloride
  • methylaldiallyl ammonium chloride or diallylammonium chloride also referred to as DAA.HCl or DAAC
  • Japanese Patent 57 161197 discloses use of copolymers of sulfur dioxide and diallyldialkylammonium salts, such as DADMAC, or diallylammonium salts, as a dispersing agent with a paper sizing agent.
  • European Patent 282 081 discloses (meth)acrylamide terpolymers that also contain DADMAC or diallylamine, useful in combination with aluminum sulfate for increasing paper strength.
  • Japanese Patent 52 47883 discloses copolymers of acrylamide and diallylamine-type compounds, useful for producing stronger paper.
  • U.S. Pat. Nos. 4,279,794 and 4,295,931 disclose the use of poly(diallylamine) epihalohydrin resins as paper sizing accelerators.
  • Japanese Patent 62 99494 discloses use of copolymers of diallylammonium salts and certain non-ionic water-soluble monomers (e.g. acrylamide) with a paper sizing agent to provide improved sizing property development.
  • Japanese Patent No. Hei (8) 1996-49193 describes polymers derived from hydrophilic vinyl monomers with amino groups and/or quaternary ammonium groups and hydrophobic vinyl monomers.
  • the hydrophillic vinyl monomers would function as cations if they are quanterized.
  • Polymers with up to 5% acrylic acid are shown in this report. The resultant polymers are used to coat papers to provide superior printability.
  • White paper is achieved by adding optical brighteners in the form of fluorescent dyes. These dyes are very effective when used with highly bleached pulps. These fluorescent dyes absorb light in the ultraviolet region (below 370 nm) and re-emit the light in true visible range (usually the blue region). This gives a fluorescent effect that produces a bright white in daylight masking the inherent yellowness of the bleached pulp. [Principles of Wet End Chemistry, William F. Scott, TAPPI Press, 1996, page 47].
  • the fluorescent dyes are generally anionic and under use conditions their effectiveness is significantly inhibited by the cationic sizing promoters.
  • Optical brightener producers such as the Clariant Corporation, Charlotte N.C. or The Bayer Corporation, Pittsburgh, Pa. advise that the optical brighteners should be added at points in the paper making process significantly removed from cationic chemicals such as the common sizing promoter resins.
  • diallyl-based cationic polymers for a variety of industrial purposes, there has not been found any suggestion in the prior art of the usefulness of co- and terpolymers of diallyldialkylammonium salts, optionally, diallylammonium salts, and unsaturated organic acids for improving the sizing property characteristics of sized paper, while not adversely effectiveness paper brightness from optical brightners.
  • One aspect of the current invention is a polymerization reaction product of one or more selected cationic unsaturated monomers capable of free radical polymerization and one or more selected anionic unsaturated monomers also capable of free radical polymerization.
  • compositions of the present invention which employ polymers which have significant fractions of certain cationic components can be employed as successfully as they are in the present invention. Specifically, it was expected that the use of a polymer with cationic components greater than 50% would interfere with the use of certain other additives, such as optical brightening agents, which, depending on the particular market, can be of economic importance.
  • these resins which have anionic and cationic components are found to be effective promoter resins even when used in relatively low amounts. These resins are called amphoteric promoter resin to denote the cationic and anionic properties of their components.
  • amphoteric promoter resins do not interfere with such additives when the amphoteric promoter resins are employed in low amounts and have considerably less interference even at high levels versus nonamphoteric cationic resins.
  • Additives especial notable are the optical brighteners which are added to whiten and brighten paper.
  • the new polymer amphoteric promoter resins are polymers which include: a) at least one type of quarternary amine based segments that improve the rate of sizing development and b) at least one type of anionic segments that will offset the effect the cationic portion of the polymer has on optical brightening agents (OBA).
  • OBA optical brightening agents
  • a subset of the polymer amphoteric resin of this invention is prepared from one or more of a quaternary diallylammonium monomers, optionally diallylammonium monomer and an unsaturated organic acid monomer is a novel compound when the molar percentage of the unsaturated organic acid is at least 25% on a molar basis and the molar sum of the quaternary diallyl ammonium monomer and the diallyl ammonium monomer is at least 25% on a molar basis.
  • composition of the invention is of a water soluble amphoteric promoter resin composition that consists essentially of recurring units product of a monomer comprising at least one polymerizable cationic amine of formula(I)
  • G is selected from alkenyl, allyl, alkenyl, styrenyl, and J, K, and L are selected from hydrogen, alkyl, akenyl, allyl, styrenyl or aryl;
  • R x , R y , and R z are hydrogen, alkyl, alkenyl or aryl and E is an organic substituent selected from the group COO ⁇ , SO 3 ⁇ , HSO 4 ⁇ , and H 2 PO 4 ⁇ .
  • a more preferred aspect of the present invention is a paper sizing promoter that consists essentially of recurring units of at least one quaternary diallylammonium monomer of formula (III):
  • R 1A , R 1B , R 1C , and R 1D are hydrogen or C 1 -C 8 straight chain or branched alkyl;
  • R 2 and R 3 are alkyl, alkenyl, aryl, heteroatom interrupted alkyl or alkenyl,
  • heteroatoms are selected from the group N, S, and O;
  • R 4 is hydrogen, alkyl, alkenyl, aryl, heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O
  • X ⁇ is a monovalent anion or a multivalent equivalent of a monovalent anion
  • R x , R y , and R z hydrogen, alkyl, alkenyl or aryl heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and E is an organic substituent selected from the group COO, SO3, HSO4, and H2PO4.
  • Still another aspect of the invention is a method of producing sized paper with enhanced sizing property characteristics by employing the paper sizing promoter of this invention.
  • Yet another aspect of the invention is sized paper containing the paper sizing promoter of this invention.
  • the sizing promoters increase the rate at which the sizing property develops in paper when the sizing promoters are used with sizing agents. Sized paper made with the sizing promoter of this invention exhibits an accelerated rate of sizing property development, and may require the use of less sizing agent. Other benefits and advantages of the present invention will be apparent herein.
  • Drawing 1 is a chart depicting how commercial cationic promoter resins inhibit optical brighteners.
  • Drawing 2 is a chart depicting that two commercially used cationic promoter resins, poly(DADMAC) and Poly(DADMAC/DAA. HCL) reduce the effectiveness of optical brighteners.
  • Drawing 3 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin.
  • Drawing 4 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin showing the effect of different concentration of the Amphoteric Promoter Resin.
  • Drawing 5 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin showing the effect of different ratios of the monomer components of the Amphoteric Promoter Resin.
  • Drawing 6 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin showing the effect of different ratios of the monomer components of the Amphoteric Promoter Resin.
  • Drawing 7 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin showing the effect of different ratios of the monomer components of the Amphoteric Promoter Resin.
  • Drawing 8 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin.
  • Drawing 9 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin showing the effect of alkenyl sulfonate monomer components on the Amphoteric Promoter Resin.
  • Drawing 10 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin showing the effect of alkenyl sulfonate monomer components on the Amphoteric Promoter Resin.
  • Drawing 11 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin showing the effect of other monomer components on the Amphoteric Promoter Resin.
  • Drawing 12 is a chart depicting paper sizing efficiency of the Amphoteric Promoter Resin with the optical brightness of the final products.
  • paper and papermaking are intended to cover not only paper (and its manufacture), but also paperboard, molded paper and other similar cellulosic-web based materials (and their manufacture), that are typically manufactured with papermaking equipment and procedures and that require additives such as sizing agents for modification of the sizing property of the resultant product.
  • PAPER SIZING Treatment of paper to resist liquid penetration, either by means of wet end additives or surface application.
  • SIZE Any material used for internal, or surface sizing, for example rosin with alum, starch, animal glue, gelatin, latex, alkyl ketene dimer, alkyl succinic anhydride, and the like
  • PROMOTER RESINS Chemicals added to the paper making process which accelerates the activity of a paper size.
  • BRIGHTNESS The reflectance by white or near white papers. It is a primarly a measure of freedom from pulp yellowness associated with the presence of lignin and other impurities left by incomplete bleaching.
  • OPTICAL BRIGHTENERS FOR PAPER Fluorescent dyes that absorb light in the ultraviolet region of the spectrum (below 370 nm) and re-emit the light in the visible blue range (peaking at 435 nm, giving a flurorscent effect that produces a bright whie in daylight, masking the inherent yellowness of the bleached pulp.
  • the new polymer amphoteric promoter resins are polymers which include: a) at least one type of cationic based segments that improve the rate of sizing development and b) at least one type of anionic segments that offsets the effect the cationic portion of the polymer has on optical brightening agents.
  • Addition of a third type of segment consisting of a units formed when diallylamine hydrochloride (DAA-HCl) is included in the polymerization mixture.
  • DADMAC diallylamine hydrochloride
  • acrylic acid as the anionic segment
  • DAA.HCl as the optional third monomer. This DADMAC, DAA.HCl and acrylic acid polymerization mixture was found to give a significant boost in performance.
  • Optical Brightener Agent can also be included in the polymer which can be any repeat units provided they do not absorb UV light such as to quench the effect of the Optical Brightener Agent (OBA) and they do not render the polymer water insoluble and they are not added at a level that brings the polymer composition outside prescribed ranges.
  • OBA Optical Brightener Agent
  • the cationic based segments in the polymer of interest are those that lead to promoted sizing.
  • the cationic based segments of interest are those that will promote sizing without the addition of anionic segments of the current invention.
  • useful segments or monomers are those that lead to a polymer with a relatively strong absorption of light in the same ultraviolet spectrum region utilized by an Optical Brightener Agent (OBA) to give brightness.
  • OBA Optical Brightener Agent
  • useful monomer or segments are DADMAC, methyl-diallyl ammonium chloride, DAA-HCl, dicyandiamide amine bisaminopropylpiperazine and ethyleneimine as well as many derivatives of these materials.
  • any anionic monomer that leads to a polymer with a relatively strong absorption of light in the same ultraviolet spectrum region utilized by an OBA to give brightness is not desirable for the current invention.
  • the anionic monomers may be either based on carboxylic acid or sulfonate functionality or other anionic functionality that will reduce the interaction of the polymer with OBAs.
  • the anionic nature might also be created by reaction of another monomer segment of the polymer such as reaction of an acrylamide.
  • the partial anionic and partial cationic nature of the final polymer is what is important and not the means of getting there.
  • the anionic monomers with carboxylic acid functionality are preferred.
  • a paper sizing promoter of this invention is a polymerization reaction product prepared from at least one quaternary diallylammonium monomer, optionally at least one diallylammonium monomer and at least one alpha, beta unsaturated carboxylic acid.
  • the polymerization reaction product is preferably prepared from the monomers:
  • the unsaturated organic acid can be an unsaturated carboxylic acid of formula (V).
  • R 1 radicals R 1A , R 1B , R 1C and R 1D are each either hydrogen or methyl.
  • the R 1 radicals are preferably hydrogen.
  • R 2 is alkyl, alkenyl or aryl, preferably C 1 -C 22 alkyl, C 1 -C 22 alkenyl, or aryl.
  • R 3 is alkyl, alkenyl or aryl, preferably C 1 -C 22 alkyl, C 1 -C 122 alkenyl, or aryl.
  • R 4 is C 1 -C 22 alkyl, C 1 -C 22 alkenyl, aryl or hydrogen with hydrogen being the preferred structure.
  • the R 2 , R 3 and R 4 structures may be unsubstituted or substituted, e.g., alkyl may be hydroxyalkyl, carboxy, alkoxy, mercapto or thio.
  • the R 2 , R 3 and R 4 alkyl structures, alkenyl structures and aryl structures may include ester groups and may be interrupted by heteroatoms, e.g., N or S, or by heterogroups, e.g., —NH—CO— or —CO—NH—.
  • R 2 , R 3 and R 4 alkyl structures and alkenyl structures may be straight chained or branched.
  • the radicals R 2 , R 3 and R 4 are preferably uninterrupted alkyl radicals with 1-18 carbon atoms, more preferably 1-4 carbon atoms.
  • R 2 , R 3 and/or R 4 examples of suitable alkyl structures are n-docosyl, n-pentadecyl, n-decyl, i-octyl, i-heptyl, n-hexyl, i-pentyl and, preferably, n-butyl, i-butyl, sec-butyl, i-propyl, ethyl and methyl.
  • the radicals R 2 , R 3 and R 4 are preferably identical and are preferably methyl.
  • Preferred alkenyl groups for the R 2 , R 3 and R 4 structures in formulas (III) and (IV) include octadecenyl, hexadecenyl, undecenyl, octadec-dienyl, hexadec-dienyl, or mixtures of these.
  • Preferred aryl groups for R 2 , R 3 and R 4 radicals in formulas (III) and (IV) include benzyl and phenyl.
  • the R 2 and R 3 structures are preferably selected from, in decreasing order of preference: methyl, benzyl, C 2 -C 22 alkyl, phenyl, octadec-dienyl or hexadec-dienyl, octadecenyl or hexadecenyl or undecenyl, and other alkyl and aryl.
  • R 4 structures is preferably: hydrogen,
  • R x , R y , and R z are hydrogen, alkyl alkenyl, aryl, alkenylaryl and heteroatom interrupted alkyl, aryl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O.
  • X ⁇ is a sizing compatible anion. Salts of inorganic acids and common organic acids may be used.
  • X ⁇ is selected from halide, nitrate, acetate, benzoate, sulfate or phosphate.
  • Preferred halides are chloride, fluoride and bromide. More preferably, X ⁇ is chloride or fluoride. Most preferably X ⁇ is chloride.
  • More preferred monomers of formulas (III) and (IV) are those in which R 1A , R 1B , R 1C and R 1D are and R 4 are hydrogen and R 2 and R 3 are methyl.
  • the monomer of formula (III) is diallyldimethylammonium chloride, sometimes referred to herein as DADMAC
  • the monomer of formula (IV) is diallylammonium chloride, sometimes referred to herein as DAA.HCl.
  • R 1 , R 2 , R 3 and R 4 are limited in that the final polymer must be water soluble. The nature of this limitation is that it depends on the chemistry of R 1 , R 2 , R 3 and R 4 and the level to which it is present.
  • More preferred alpha, beta unsaturated carboxylic acids of formula (V) are cinnamic acid, crotonic acid, sorbic acid, acrylic acid, methacrylic acid, itaconic acid, propiolic acid, maleic acid, and fumaric acid. Acrylic and methacrylic acids are preferred.
  • polymeric reaction products of the polymerization of monomer of formula (III), monomer of formula (IV) and formula (II) preferably contain only these monomeric components in the polymer; and not significant amounts of other monomeric components in addition to the formula (III) monomer, formula (IV) monomer and formula (II) monomer.
  • the portion of the polymer that is derived from monomer formula III and formula IV are in their cationic state for all conditions anticipated for use in this invention.
  • the monomers of formulas III and IV are described as quarternary cationic amines.
  • the groups that make up the 4 groups substituted on the nitrogen can be hydrogen, alkyl, akenyl, aryl, allyl, and the like. This in this definition both (CH 3 ) 4 N + Cl and (CH 3 ) 3 N + HCl are considered quarternary cationic amine.
  • the portion of the polymer that is derived from the monomer formula V is anionic under the conditions that is experienced during the alkaline paper making process.
  • the combination of the cationic components [formula (III) and formula (IV)] and the anionic component [formula (II)] produce a polymerization product, which is amphoteric under papermaking conditions.
  • [0087] is in its acidified form and thus unchanged during the polymer synthesis.
  • the ratio of monomers or segments with cationic amine anionic functionality in the polymer effects how well the polymer promotes sizing and how little effect it will have on OBA efficacy.
  • the final polymer must consist of, on a molar basis, at least 25% total amine based cationic monomer units including the amount of DAA.HCl, if it is present. More preferred is a level of at least 30%. Most preferred is a level of at least 40%.
  • the amount of specific cationic groups and anionic groups is best expressed as a percentage, on a molar basis, of the total cationic monomer units. Of the cationic segments it is preferred that up to 65% and most preferably 10 to 50% on percentage of the cationic segments are DAA.HCl.
  • anionic groups there should be at least 33% as many anionic groups as there are cationic groups.
  • the more preferred range is 50% or higher.
  • the most preferred range is 65% or higher.
  • a polymer in the preferred range would be one that consists on a molar basis of 40%, DADMAC; 20%, DAA-HCl; and 40% acrylic acid.
  • the anionic molar % based on the cationic components would be 67%.
  • compositions of the present invention that employ polymers which have significant fractions of cationic components can be employed as successfully as they are in the present invention.
  • a polymer with cationic components greater than 50% would interfere with the use of certain other additives, such as optical brightening agents, which, depending on the particular market, can be of economic importance.
  • amphoteric promoter resins are found to be effective promoter resins even when used in relatively low amounts and, surprisingly, the amphoteric promoter resins do not interfere with such additives when the amphoteric promoter resins are employed in low amounts and have considerably less interference even at high levels versus nonamphoteric cationic resins.
  • sizing and the amphoteric promoter resins can be applied to many types of paper preferred papers are those papers used in printing where contrast of the paper and the printing is important. Other preferred papers are also those where high brightness levels are the goal. Most preferred papers are those generally classified as “fine papers” used such uncoated papers made for electroreprographic or ink-jet printing. A very common application where the usefulness of the current invention would be especially obvious is in high brightness cut-sheet copy paper.
  • a key to this invention is the understanding of how optical brighteners are used to make paper appear brighter, or more white.
  • Optical brightening agents (“OBA's”) are discussed for example, in Encyclopedia of Chemical Technology, Kirk & Othmer, eds, 3rd. edition (1978), John Wiley and Sons, New York, As noted therein, with the aid of optical brighteners, also referred to as fluorescent whitening agents (FWA) or fluorescent brightening agents, optical compensation of the yellow cast (bleached paper or textile has a yellowish color, ) may be obtained. The yellow cast is produced by the absorption of short-wavelength light (violet-to-blue).
  • optical brighteners With optical brighteners this short-wavelength light is in part replaced, thus a complete white is attained without loss of light. This additional light is produced by the brightener by means of fluorescence.
  • Optical brightening agents absorb the invisible portion of the daylight spectrum and convert this energy into the longer-wavelength visible portion of the spectrum, i.e., into blue to blue-violet light. Optical brightening, therefore, is based on the addition of light.
  • Two requirements are indispensable for an optical brightener: it should be optically colorless on the substrate, and it should not absorb in the visible part of the spectrum. Paper OBA's are almost exclusively stilbene based, that is based on one or two stilbene residues.
  • OBA's are disodium salt of distyrlbiphenyl disulfonic acid, 4,4′-di-triazinylamino-2,2′-di-sulfostilbene.
  • OBAs have a negative charge. Therefore, they are electrostatically attracted by cationic polymers. This interaction interferes with the fluorescence of the OBA, often in such a way that the fluorescence is quenched and the OBA loses its effect. For this reason papermakers are careful with not only the addition of cationic polymers that promote sizing to their papermaking system, but also the location of adding these cationic promoter resin relative to the OBA. Some cationic polymers are worse than others and size promoters have a strong fluorescence-quenching effect. Fine paper, and in particular printing & writing paper, generally contains OBA's.
  • Brightness is a commonly used industry term for the numerical value of the reflectance factor of a sample with respect to blue light of specific spectral and geometric characteristics. (TAPPI test method 452 om-92).
  • the brightness unit is a relative one.
  • the measured brightness is expressed as the ratio between the reflectance factor of the sample (at effective 457 nm) and the reflectance factor of a perfect reflecting sample times 100%.
  • the brightness can be larger than 100% when OBA's are used (they fluoresce in this wavelength area, that is, they emit light). Further information on the measurement of brightness can be found in “Pulp and Paper Chemistry and Chemical Technology, 3 rd edition, Vol. V, James P. Casey, ed.”, John Wiley & Sons, New York (1981): 1828-1833.
  • the amphoteric promoter polymers of this invention are water-soluble polymers possessing relatively high average molecular weights.
  • the weight average molecular weight (M w ) for these polymers, (not including residual monomer) is at least about 10,000 and more preferably at least about 30,000. While not wishing to be bound by theory, it is expected that the polymer produced by free radical polymerization of these monomers will result in a random or alternating polymer.
  • the polymerization reaction conditions are controlled to facilitate the random distribution of monomers. Experimental strategies to control polymerization conditions are shown in the examples.
  • the most preferred polymerization is a free-radial, chain polymerization that leads to less than 4% residual monomers and less than 5% of the product, (including monomers) with a number average molecular weight less than 500 g/mole.
  • the monomeric components utilized for preparation of the polymerization reaction products of this invention are either known and are available commercially (e.g., DADMAC from CPS Chemical Company, Inc. (Old Bridge, N.J.) and from Pearl River Polymers (Pearl River, La.); DADMAC and DAA.HCl from Sigma Chemical Company (St. Louis, Mo.)) or may be prepared by conventional processes, typically used for the preparation of diallyl-type compounds.
  • Acrylic acid is available from many commercial sources, including Rohm & Haas, Philadelphia, Pa.
  • the preparation of the polymeric reaction product is preferably carried out by a chain polymerization of the monomers of formulas (I) and (II).
  • the monomers of formulas (III), (IV) and (V) can be polymerized by a chain polymerization in the presence of a free radical polymerization initiator.
  • the polymerization reaction of the diallyl-type monomer components and organic acid is carried out in a suitable solvent, polar solvents being preferred. Water is a particularly preferred solvent for the polymerization reaction. Other polar solvents which do not adversely affect the polymerization reaction may also be used.
  • polar solvents which do not adversely affect the polymerization reaction may also be used.
  • One factor to be considered in the selection of a suitable solvent is the potential for reaction between the initiator employed and the solvent, causing the polymerization reaction to be quenched.
  • Suitable solvents also include water mixed with a water-miscible solvent or solvents and do not adversely affect the polymerization reaction.
  • the amount of water or organic solvent used in the polymerization reaction medium is desirably minimized, to provide high concentrations of the monomers in the reaction medium.
  • the lower limit for the amount of reaction medium is generally dictated by the need to obtain adequate mixing of the reaction medium throughout the polymerization reaction and the need to provide adequate heat transfer to avoid having the polymerization exotherm and overheat the run. Since the viscosity of the reaction medium normally increases as high molecular weight polymers are formed from the monomer components, it may be advantageous to add additional solvent during the course of the polymerization reaction to adjust the viscosity of the reaction medium.
  • the concentration of monomeric reactants in the polymerization solvent is from about 5 to about 60 wt. %, and more preferably, from about 10 to about 50 wt. %, based on the weight of the reaction medium.
  • the pH of the reaction medium Before the start of the polymerization, it is advantageous to adjust the pH of the reaction medium to bring the pH to a value of about 1.5 to about 6.
  • An acid preferably an inorganic acid such as a hydrohalo acid like HCl, is typically used for this adjustment of the pH.
  • the polymerization reaction temperature employed is normally based on the performance characteristics of the initiator used and is also dictated by the rate of polymerization and degree of polymerization (molecular weight) desired.
  • the polymerization is typically carried out at a temperature of about 40° C. to about 100° C., preferably about 50° C. to about 95° C. and more preferably at a temperature of about 60° C. to about 90° C., at ambient pressure (one atmosphere).
  • the polymerization reaction is ordinarily characterized by being very exothermic in its early stages. The polymerization may require many hours, to ensure relatively complete reaction of the monomer components.
  • the polymerization reaction of the monomer components is started in the customary manner, typically by addition of a suitable initiator, preferably one that is water-soluble.
  • ammonium persulfate, t-butyl hydroperoxide, 2,2′-azobis-(2-amidinopropane) dihydrochloride, 2,2′-azobis-(2-imidazol-2-yl-propane) dihydrochloride, 2,2′-azobis-(2-carbamoylpropane) dihydrate or 2,2′-azobis-(2-methoxycarbonylpropane) is used as the initiator.
  • Suitable initiators i.e., substances which form free radicals, include hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, lauryl peroxide, t-butyl perbenzoate, di-t-butyl perphthalate, azobisisobutyronitrile, 2,2′-azobis-(2,4-dimethylvaleronitrile), 2-phenyl-azo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazoformamide, azodiisobutyramide, dimethyl, diethyl or di-n-butyl azobismethylvalerate, t-butyl perneodecanoate, di-isononanoyl peroxide, t-amyl perpivalate, di-2-ethyl-hexyl peroxydicarbonate, dilauroyl peroxide
  • initiator About 0.01 to about 10% by weight, preferably about 0.1 to about 5% by weight, of initiator is used, based on the amount (weight) of the monomer components. It is advantageous to carry out the polymerization with the exclusion of oxygen, to minimize the amount of initiator used and to maximize the polymer molecular weight. This can be effected in a conventional manner, for example, by flushing or degassing with an inert gas, such as nitrogen or argon. The initiator may be added at the outset of the reaction or, alternatively, may be added continuously or in aliquots during the course of the polymerization reaction, until the majority of the monomer components are consumed. Utilization of the monomer components, including their rate of consumption, during the polymerization may be monitored by carbon 13 NMR or liquid and ion chromatography.
  • the molecular weight of the polymer product was determined by Size Exclusion Chromatography using a waters 717 Wisp instrument with a Waters 515 HPLC Pump, Waters Temperature Control Module and a column heater module.
  • the Mobile Phase was 50:50 aqueous 1% sodium nitrate, 0.1% trifluoroacetic acid: acetonitrile.
  • the columns used were a: Eichrom CATSEC 4000 (10 um particle size)+1000 (7 um particle size)+300 (5 um particle size)+100A (5 um particle size) columns in series. Silica gel base material with bonded polyamine surface.
  • the column Temperature was 35 C. and the injection volume: 100 ul.
  • the detector was a differential refractive index detector: Hewlett Packard 1047A.
  • the flow rate was 1.0 ml/min.
  • the calibration standards American Polymer Standards Poly(2-vinyl pyridine) 2,900-1,250,000 daltons, 1-propyl pyridinium bromide.
  • Residual monomers were measured by nuclear magnetic resonance spectrometry. Samples were dissolved in D2O for a lock solvent and acetonitrile used an internal reference set to 119 ppm. 13C NMR was run at 100 or 125 MHz. The relative weight percents were determined by integration of the peaks attributed to the residual monomers with respect to all integrated area of polymer and monomer.
  • the polymerization reaction product of this invention is a water-soluble polymer and consequently may be utilized as an aqueous solution.
  • aqueous solutions of the polymerization reaction product may be employed as a paper sizing promoter in the manufacture of sized paper and may optionally contain the sizing agent in the aqueous medium.
  • the polymerization reaction products of this invention serve as highly effective paper sizing promoters in combination with conventional alkaline papermaking sizing agents.
  • Sizing agents based on alkyl(straight chain or branched) or alkenyl ketene dimers or multimers and alkenyl succinic anhydride sizing agents are preferred. Combinations of these with other paper sizing agents may also be employed.
  • Paper sizing agents are usually employed as aqueous emulsions, aqueous dispersions or aqueous solutions.
  • emulsion is used herein, as is customary in the art, to mean either a dispersion of the liquid-in-liquid type or of the solid-in-liquid type.
  • AKD emulsion stability is defined as an emulsion that can be made and when left at 22 degrees centigrade will not develop significant nonuniformity within 24 hours. Significant nonuniformity is that which would make it unusable on a paper machine for its intended purpose.
  • Ketene dimers used as paper sizing agents are well known. Alkyl ketene dimers, containing one ⁇ -lactone ring, are typically prepared by the dimerization of alkyl ketenes made from two fatty acid chlorides. Commercial alkyl ketene dimer sizing agents are often prepared from palmitic and/or stearic fatty acids, e.g., Hercon® sizing agents (Hercules Incorporated, Wilmington, Del.). Similar alkyl ketene dimer sizing agents may be prepared from branched alkyl ketene dimers. An example of a source of alkyl for a branched ketene dimer is the isostearic group from isostearic acid.
  • Alkenyl ketene dimer sizing agents are also commercially available, e.g., Aquapel® sizing agents (Hercules Incorporated, Wilmington, Del.) and Precis® sizing agents (Hercules Incorporated, Wilmington, Del.). Ketene multimers, containing more than one ⁇ -lactone ring, may also be employed as paper sizing agents, and these may be alkyl or alkenyl ketene dimers.
  • Ketene dimers used as paper sizing agents are generally dimers having the formula
  • R 5 alkyl group derived from fatty acids where R 5 is a hydrocarbon radical, such as alkyl having at least 8 carbon atoms, cycloalkyl having at least 6 carbon atoms, aryl, aralkyl and alkaryl.
  • R 5 is a hydrocarbon radical, such as alkyl having at least 8 carbon atoms, cycloalkyl having at least 6 carbon atoms, aryl, aralkyl and alkaryl.
  • the radical “R 5 ” is named followed by “ketene dimer”.
  • ketene dimers include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, decosyl, tetracosyl, phenyl, benzyl, beta-naphthyl and cyclohexyl ketene dimers, as well as the ketene dimers prepared from montamic acid, naphthenic acid, ⁇ 9,10-decylenic acid, ⁇ 9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, and eleostearic acid, as well as ketene dimers prepared from naturally occurring mixtures of fatty acids, such as those mixtures in coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rapeseed
  • Hydrophobic acid anhydrides are useful as sizing agents for paper such as:
  • R 6 is a saturated or unsaturated hydrocarbon radical, the hydrocarbon radical being a straight or branched chain alkyl radical, an aromatic substituted alkyl radical, or an alkyl substituted aromatic radical so long as the hydrocarbon radical contains a total of from about 14 to about 36 carbon atoms; and
  • R 7 represents a dimethylene or trimethylene radical and where R 8 is a hydrocarbon radical containing more than 7 carbon atoms which are selected from the group consisting of alkyl, alkenyl, aralkyl or aralkenyl.
  • R 8 is a hydrocarbon radical containing more than 7 carbon atoms which are selected from the group consisting of alkyl, alkenyl, aralkyl or aralkenyl.
  • Preferred substituted cyclic dicarboxylic acid anhydrides falling within the above formula (VIII) are substituted succinic and glutaric anhydrides.
  • each R 6 can be the same hydrocarbon radical or each R 6 can be a different hydrocarbon radical.
  • anhydrides of formula (VII) are myristoyl anhydride; palmitoyl anhydride; oleoyl anhydride; and stearoyl anhydride.
  • anhydrides of formula (VIII) are i- and n-octadecenyl succinic acid anhydride; i- and n-hexadecenyl succinic acid anhydride; i- and n-tetradecenyl succinic acid anhydride; dodecyl succinic acid anhydride; decenyl succinic acid anhydride; ectenyl succinic acid anhydride; and heptyl glutaric acid anhydride.
  • Hydrophobic organic isocyanates e.g., alkylated isocyanates
  • alkylated isocyanates are another class of compounds used as paper sizing agents that are well known in the art.
  • the hydrocarbon chains of the isocyanates are alkyls that contain at least 12 carbon atoms, preferably from 14 to 18 carbon atoms.
  • Such isocyanates include rosin isocyanate; dodecyl isocyanate; octadecyl isocyanate; tetradecyl isocyanante; hexadecyl isocyanate; eicosyl isocyanate; docosyl isocyanate; 6-ethyldecyl isocyanate; 6-phenyldecyl isocyanate; and polyisocyanates such as 1,18-octadecyl diisocyanate and 1,12-dodecyl diisocyanate, wherein one long chain alkyl group serves two isocyanate radicals and imparts hydrophobic properties to the molecule as a whole.
  • alkyl carbamoyl chlorides alkylated melamines such as stearylated melamines.
  • the polymerization reaction product of the invention may be used as a paper sizing amphoteric promoter resin according to this invention via an internal addition method or via a surface application (external) method, or via a combination of these methods. Satisfactory performance of the polymerization reaction product as an amphoteric promoter resin is generally obtained regardless of the particular method of application employed.
  • the sizing promoter is introduced into the paper furnish during the papermaking process.
  • the sizing promoter is introduced in combination with the paper sizing agent (or agents), either as separately introduced feed streams or as an aqueous medium containing both components. Addition of premixed sizing promoter and paper sizing agent (or agents) is preferred. Other conventional papermaking compounds or additions may also be employed with the sizing promoter and/or sizing agent.
  • the optical brighteners should not be added at the same time as a cationic promoter resin. However, the amphoteric promoter resin may be added at the same time as the optical brightener, thus minimizing paper machine addition points.
  • amphoteric promoter resin at a location other than the optical brightener would also be advantageous. Considering the complexity of paper making process—pulp sources, other chemical additives—the optimum addition point for the amphoteric resin in a specific paper mill would need to be determined by trial and error. In Examples 11 to 19 the sizing agent, the amphoteric promoter resin, and the optical brightener was added simultaneously in the base sheet as part of a starch solution with a pH of 8.
  • the sizing promoter is ordinarily applied as a size press treatment or as a coating, by conventional coating or spraying techniques, to the preformed paper, and then the paper or treatment or coating is dried. The paper is then treated with an appropriate paper sizing agent (or agents) and it is dried again.
  • the paper sizing agent and sizing promoter may be applied in a surface treatment method in a single application, with an aqueous treatment/coating medium containing paper sizing agent, sizing promoter and, optionally, other conventional components.
  • the optical brighteners should not be added at the same time as a cationic promoter resin.
  • amphoteric promoter resin may be added with the optical brightener, thus minimizing paper machine addition points. Addition of the amphoteric promoter resin at a location other than the optical brightener would also be advantageous. Considering the complexity of paper making process—pulp sources, other chemical additives—the optimum addition point for the amphoteric resin in a specific paper mill would need to be determined by trial and error.
  • Preferred papers are those papers used in printing where contrast of the paper and the printing is important. Other preferred papers are also those where high brightness levels are the foal. Most preferred papers are those generally classified as “fine papers” used such uncoated papers made for electroreprographic or ink-jet printing. A very common application where the usefulness of the current invention would be obvious is in high brighness cut-sheet copy paper.
  • additives conventionally used in papermaking such as starch, fillers, pulp, retention aids, strengthening additives, drainage aids, colorants, optical brighteners, defoamers and the like.
  • polymer the polymerization reaction product amphoteric promoter resin (“polymer”) and the paper sizing agent (“size”) should be utilized in a respective weight ratio of from about 0.05:1 to about 4:1 polymer:size; preferably, from about 0.1:1 to about 1:1 polymer:size and most preferably 0.10:1 to 0.5:1.
  • the paper sizing agent (or agents) is ordinarily used in an amount to provide good sizing property characteristics in the paper.
  • Sized paper typically contains from about 0.005 to about 1.5 wt. %, preferably, from about 0.025 to about 0.5 wt. % and, more preferably, from about 0.05 to about 0.25 wt. % paper sizing agent, based on the weight of the dried sized paper.
  • the amount of paper sizing agent in the sized paper may be decreased without sacrifice of the paper sizing property.
  • the sizing promoter of this invention can also be used in combination with other, conventional sizing promoters or sizing additives.
  • Sufficient amphoteric promoter resin should be employed to yield sized paper containing the sizing promoter in an amount of from about 0.002 to about 0.6 wt. %, preferably, from 0.007 to about 0.3 wt. %, and, more preferably, from about 0.012 to about 0.15 wt. %, based on the weight of the dried sized paper.
  • One advantage of the sizing promoter of this invention is that the sized paper need only be dried to a residual moisture level of from about 8 wt. % to about 12 wt. %, based on the weight of the paper, to provide satisfactory immediate sizing property characteristics. Without the sizing promoter, such sized paper typically needs to be dried to a residual moisture level of about 4-6 wt. % to achieve equivalent immediate sizing property characteristics.
  • immediate sizing means the properties of the paper at the end of the paper making and finishing processes without undo aging as is often necessary with unprompted AKD Sizing.
  • sized paper employing the sizing promoter of this invention provide increased sizing property characteristics if under the conditions of the process the unpromoted sizing agent did not fully develop its sizing property characteristics.
  • a second advantage is that sized paper produced with the amphoteric promoter resin will exhibit increased whiteness or brightness when optical brighteners are used versus use of common cationic promoter resins known prior to this invention.
  • the sizing property performance in sized paper may be characterized by the Hercules Size Test, a well-recognized test for measuring sizing performance.
  • the Hercules Size Test is described in Pulp and Paper Chemistry and Chemical Technology, J. P. Casey, Ed., Vol. 3, p. 1553-1554 (1981).
  • the Hercules Size Test determines the degree of water sizing obtained in paper, by measuring the change in reflectance of the paper's surface as an aqueous solution of dye penetrates from the opposite surface side.
  • the aqueous dye solution e.g., naphthol green dye in 1% formic acid in the Examples described below, is contained in a ring on the top surface of the paper, and the change in reflectance is measured photoelectrically from the bottom surface.
  • Test duration is limited by choosing a convenient end point, e.g., a reduction in reflected light of 20%, corresponding to 80% reflectance, in the Examples described below.
  • a timer measures the time (in seconds) for the end point of the test to be reached. Longer times correlate with increased sizing performance, i.e., resistance to water penetration increases. Unsized paper will typically fail at 0 seconds, lightly sized paper will register times of from about 1 to about 20 seconds, moderately sized paper from about 21 to about 150 seconds, and hard sized paper from about 151 to about 2000 seconds or more.
  • a water-soluble polymer of diallyldimethyl-ammonium chloride (DADMAC), diallylammonium chloride (DAA.HCl) and acrylic acid may be prepared by the following general procedure.
  • An aqueous mixture of the three monomer components is made by adding the respective monomer components in water in the appropriate mole ratio sought in the polymerization reaction product.
  • the aqueous reaction mixture is degassed with an inert gas, such as nitrogen or argon.
  • Both the monomer mixture and an aqueous solution of a water-soluble free radical polymerization initiator, such as 2,2′-azobis(2-amidinopropane) dihydrochloride are added slowly and continuously to a reaction vessel at 80° C., until the majority of the monomer components have been consumed in the polymerization reaction.
  • Water is usually added to the reaction mixture during the polymerization reaction to prevent the viscosity in the aqueous reaction mixture from becoming excessive.
  • the concentration of the monomer components in the aqueous reaction mixture should not be dilute, since high concentrations of the monomers provide better polymerization results.
  • DAA.HCl is added with some water to a vessel along with approximately 90% of the DADMAC and approximately 20% of the AA.
  • a solution of initiators prepared and a mixture of the remaining DADMAC and AA is prepared. All solutions are degassed. The reaction vessel is heated to 60° C. the initiator solution and monomer solution are slowly added over time (12 hour). The monomer solution is added at a decreasing rate and the temperature is slowly increased to 95° over 10 hours.
  • Examples 1-8 are exemplary of this general procedure for obtaining the polymerization reaction products of this invention.
  • the sizing property of the paper was determined using the Hercules Size Test (as described above) immediately after the paper was made and also (in several of the Examples) after the paper was aged at 50% relative humidity and at a temperature of 22° C., for seven days or longer (as noted in the Examples).
  • a water-soluble copolymer of diallyldimethyl-ammonium chloride (DADMAC), diallylammonium chloride (DAA.HCl) and acrylic acid (AA) was prepared as follows.
  • the monomer mole ratio used in the polymerization reaction product was about 45:45:10 DADMAC:AA DAA.HCl.
  • Part I The DAA.HCl was prepared by adding 6.75 parts of DAA a reaction vessel. While agitating the DAA 25.35 parts 10 % HCl solution (2.54 parts HCl, 22.81 parts water) was added. The resultant pH was 3.5.
  • Part II A mixture of DADMAC and AA were prepared in a separate mixing vessel. 106.1 parts water was added to the vessel 19.4 parts AA followed by 8.2 parts of a 65% aqueous solution of DADMAC. The solution was mixed. Final pH was ⁇ 2. This mixture was added over time to the reaction vessel which has DAA-HCl present.
  • Part III was made in the reaction vessel by adding to part I 74.07 parts 65% solution of DADMAC and 4.87 parts AA.
  • Part IV To a second mixing vessel 30.71 parts water was added with 2.78 parts of V50 initiator. The mix was stirred to dissolve the V50 in the water.
  • Part III reaction mixture was heated to 60° C. and 3.35 parts of Part IV added.
  • Part II monomer mixture and the Part IV initiator solution were slowly and constantly added at constant prescribed addition rates to the reaction vessel.
  • the addition profile is shown in following table: Reaction Monomer Addition over Time Temp. time Initiator Addition 0 to 60 60 C.
  • Add 1/2 of Part 2 Add 8.2% of solution minutes over 1 hour of Part 4 over 1 hour (The reaction is exothermic and the temperature will rise if cooling is not provided, the temperature rise is the most significant in the first hour, during the first 2 hours the temperature should be kept below 75 C.)
  • 60 to 240 70 Add 1/4 of solution Add 25% of solution of minutes of Part 2 Part 3 over 3 hours over 3 hours 240 to 600 85 C.
  • the resulting aqueous solution of amphoteric promoter resin was 20% polymer by weight, 80% water. Residual monomers levels on a mole % of original monomers were determined by C-13 NMR and were found to be approximately: acrylic acid, less than 0.1%; DAA.HCl, less than 0.4% and DADMAC, less than 1%. Other properties include Brookfield viscosity at 22° C. of less than 300 cps, pH 2-4, color off-white, and specific gravity of 1.05 g/cc.
  • Solution A 26.8 g of a 50% DAA-HCl solution in water (made by mixing DAA and HCl (see ex. 1))+48.3 g 60% DADMAC solution+55.0 g water (deionized water was used in the experiments)
  • Solution B 14.4 g AA+5.4 g 60% DADMAC solution+100.0 g water
  • Solution C 1.8 g 2,2′-AZOBIS(2-AMIDINOPROPANE) DIHYDROCHLORIDE+50 ml water
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up to be pumped slowly into the reaction vessel.
  • reaction was allowed to slowly cool to room temperature after the hour at 95 C.
  • sample was diluted to approximately 20% solids with water.
  • the flask was then opened and the polymer solution analyzed.
  • the polymer solution was 22.5% solids.
  • the solution contained a polymer with 43 parts (on a molar basis) acrylic acid units, 38 parts DADMAC units, and 7 parts DAA-HCl units. On the same basis it contained 1 part residual AA, 8 parts residual DADMAC and 3 parts residual DAA-HCl.
  • Solution A 9.9 g of a 68% DAA-HCl solution in water (see above)+60.4 g of a 60% DADMAC solution+30.0 g water (deionized water was used in the experiments)
  • Solution B 16.2 g AA+50.0 g water
  • Solution C 1.77 g 2,2′-AZOBIS(2-AMIDINOPROPANE) DIHYDROCHLORIDE+50 g water
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up the be pumped slowly into the reaction vessel.
  • the temperature of the reaction was kept at 75° C. for 4 hours then increased to 85° C. for 3 hours and then increased to 95° C. for 1 hour.
  • the reaction was allowed to slowly cool to room temperature after the hour at 95 C.
  • the sample was diluted to approximately 20% solids with water.
  • the flask was then opened and the polymer solution analyzed.
  • the polymer solution was 24.7% solids.
  • the solution contained a polymer with 48 parts (on a molar basis) acrylic acid units, 45 parts DADMAC units, and 5 parts DAA-HCl units. On the same basis it contained less than 1 part residual AA, 1 part residual DADMAC and less than 1 part residual DAA-HCl.
  • Solution A 44.6 g of a 50% DAA-HCl solution in water (see above)+201.3 g 60% DADMAC solution+100 g water (deionized water was used in the experiments)
  • Solution B 54.0 g AA+200.0 g water
  • Solution C 5.9 g 2,2′-AZOBIS(2-AMIDINOPROPANE) DIHYDROCHLORIDE+50 ml water
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up the be pumped slowly into the reaction vessel.
  • the temperature of the reaction was kept at 75° C. for 4 hours then increased to 85° C. for 2 hours and then increased to 95° C. for 2 hours.
  • the polymer solution was 23.0% solids.
  • the solution contained a polymer with 49 parts (on a molar basis) acrylic acid units, 47 parts DADMAC units, and 2 parts DAA-HCl units. On the same basis it contained less than 1 part residual AA, 1 part residual DADMAC and 0.4 parts residual DAA-HCl.
  • Solution A 9.9 g of a 68% DAA-HCl solution in water (see above)+60.4 g of a 60% DADMAC solution+30.0 g water (deionized water was used in the experiments).
  • Solution B 16.2 g AA+44.0 g water
  • Solution C 1.77 g 2,2′-AZOBIS(2-AMIDINOPROPANE) DIHYDROCHLORIDE+50 g water.
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up the be pumped slowly into the reaction vessel.
  • the temperature of the reaction was kept at 65° C. for 6 hours then increased to 85° C. for 2 hours and then increased to 85° C. for 2 hours.
  • reaction was allowed to slowly cool to room temperature after the 2 hours at 95 C.
  • sample was diluted to approximately 20% solids with water.
  • the flask was then opened and the polymer solution analyzed.
  • the polymer solution was 24.7% solids.
  • the solution contained a polymer with 47 parts (on a molar basis) acrylic acid units, 44 parts DADMAC units, and 5 parts DAA-HCl units. On the same basis it contained less than 1 part residual AA, 3 parts residual DADMAC and 0.6 part residual DAA-HCl.
  • Solution A 66.7 g of a 60% DADMAC solution+33.3 g water (deionized water was used in the experiments)
  • Solution B 18.0 g AA+122.0 g water
  • Solution C 1.74 g 2,2′-AZOBIS(2-AMIDINOPROPANE) DIHYDROCHLORIDE+50 g water
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up the be pumped slowly into the reaction vessel.
  • the temperature of the reaction was kept at 75° C. for 4 hours then increased to 85° C. for 2 hours and then increased to 95° C. for 2 hours.
  • reaction was allowed to slowly cool to room temperature after the hour at 95 C.
  • sample was diluted to approximately 25% solids with water.
  • the flask was then opened and the polymer solution analyzed.
  • the polymer solution was 25.5% solids.
  • the solution contained a polymer with 51 parts (on a molar basis) acrylic acid units and 44 parts DADMAC units. On the same basis it contained less than 1 part residual AA and 4 parts residual DADMAC.
  • Solution A 26.8 g of a 50% DAA-HCl solution in water (see above)+48.3 g of a 60% DADMAC solution+55.0 g water (deionized water was used in the experiments)
  • Solution B 14.4 g AA+5.4 g of a 60% DADMAC solution+100.0 g water
  • Solution C 1.8 g 2,2′-AZOBIS(2-AMIDINOPROPANE) DIHYDROCHLORIDE+50 ml water
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up the be pumped slowly into the reaction vessel.
  • the temperature of the reaction was kept at 75° C. for 4 hours then increased to 85° C. for 2 hours and then increased to 95° C. for 2 hours.
  • the polymer solution was 22.5% solids.
  • the solution contained a polymer with 43 parts (on a molar basis) acrylic acid units, 38 parts DADMAC units, and 7 parts DAA-HCl units. On the same basis it contained less than 1 part residual AA, 8 parts residual DADMAC and 3 parts residual DAA-HCl.
  • Solution A 53.6 g of a 50% DAA-HCl solution in water (see above)+53.7 g of a 60% DADMAC solution+50.0 g water (deionized water was used in the experiments)
  • Solution B 14.4 g AA+100.0 g water
  • Solution C 2.2 g 2,2′-AZOBIS(2-AMIDINOPROPANE) DIHYDROCHLORIDE+50 ml water
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up the be pumped slowly into the reaction vessel.
  • the temperature of the reaction was kept at 75° C. for 4 hours then increased to 85° C. for 2 hours and then increased to 95° C. for 2 hours.
  • the polymer solution was 22.2% solids.
  • the solution contained a polymer with 35 parts (on a molar basis) acrylic acid units, 32 parts DADMAC units, and 24 parts DAA-HCl units. On the same basis it contained less than 1 part residual AA, 4 parts residual DADMAC and 5 parts residual DAA-HCl.
  • amphoteric promoter resins are used to promote sizing agents.
  • the sizing agents were prepared according to descriptions below or were obtained from commericially available sources:
  • Hercon® 195 reactive size is a highly efficient, alkyl ketene dimer (AKD) emulsion specifically designed to enhance drainage and optimize sizing efficiency in most papermaking systems. While Hercules Hercon 195 reactive size is a cationically stabilized emulsion and self-retaining, the addition of either cationic starch or cationic resins is recommended for maximum size retention and performanc. (Hercules Incorporated, Wilmington, Del.)
  • HERCON® 79 cellulose-reactive sizing emulsion is designed to function at alkaline pH in the presence of low alkalinity.
  • Hercon 79 is slightly cationic and has an affinity for the fiber. Additional promoter resin or cationic starch may be required for retention.
  • Hercon 79 sizing develops rapidly on the paper machine to control pickup of size press or calender solutions. Full sizing typically is attained off the rewinder. Hercon 79 has minimal interference with wet-end optical whitening agents compared with more cationic grades of Hercon. (Hercules Incorporated, Wilmington, Del.)
  • HERCON® 70 reactive size is a highly efficient, reactive sizing emulsion for use against a wide variety of penetrants. It is not dependent on alum and reacts directly with cellulose to provide sizing. Operation at near-neutral pH provides an opportunity for the utilization of calcium carbonate as an inexpensive, high-brightness filler and for the production of stronger, permanent, highly sized paper. (Hercules Incorporated, Wilmington, Del.)
  • AQUAPEL® 364 is an alkylketene dimer derived from long-chain fatty acids. It reacts chemically, under mild conditions, with many substances having active hydrogen atoms in their structural makeup. Resulting products can have new and desirable properties. For example, Aquapel 364 is especially outstanding for imparting water repellency to various forms of cellulosic materials.
  • R alkyl group derived from fatty acids
  • RETEN® 201 cationic resin and retention aid is an efficient cationic source designed to coagulate fines and other anionic contaminants typically present in bleached and unbleached papers. —It is a low molecular weight, high charge density polyamine/epichlorohydrin polymer (Hercules Incorporated, Wilmington, Del.)
  • Hercon® 70 paper sizing agent Hercules Incorporated, Wilmington, Del.
  • an aqueous alkyl ketene dimer (AKD) sizing dispersion The (AKD) sizing agent was evaluated at a concentration of 0.09 wt %, and the Hercon® 70 sizing agent was evaluated at two different concentrations, 0.06 wt % and 0.07 wt %. All sizing agent concentrations noted in this Example and in subsequent Examples are based on the dry weight of the paper furnish.
  • Polyethyleneimine can be purchased from a commercial source such as Sigma-Aldrich, Milwaukee, Wis. The sample had a reported molecular weight of 10000.
  • Poly(acrylamide) can be purchased from a commercial source such as Sigma-Aldrich, Milwaukee, Wis.
  • Example 1-8 The performance of the polymerization reaction products prepared in Example 1-8 was evaluated in sized paper at several different use levels, with different commercial sizing agents. Commercially available sizing promoters were also included in the evaluation to provide a performance benchmark for the polymerization reaction product sizing promoter of this invention. These are reported as comparative examples. Several experiments were completed that had no sizing promoter present. These are reported as comparative examples.
  • the commercial sizing agents utilized were Precis® 2000 paper sizing agent (Hercules Incorporated, Wilmington, Del.), an aqueous starch-stabilized reactive alkaline sizing dispersion.
  • the laboratory work with a size press provided a model closer to what would happen if the additives were applied at a size press. Nevertheless, it was shown to provide a good relative measure of the effectiveness of the new promoter resins of the current invention versus more traditional promoter resins.
  • the laboratory size press work is not very far from modeling the wet-end performance of the additives in terms of how sizing develops in the first dryer section of a paper machine. Paper going into a dryer section of a fine paper machine is approximately 50% water. The base sheet paper after treatment in the laboratory size press picked up its weight in water and thus was also at about a 50% level of water before drying.
  • amphoteric promoter resins are listed based on the monomer ratio that was added to the polymerization. These amphoteric promoter resins were synthesized by procedures described in Synthetic Examples 1-8 or similar polymerization procedures.
  • This example shows two amphoteric promoter resins performance relative to a commercial sizing and promoted sizing agents.
  • the pilot paper machine was set up to run with an 80/20 by weight mix of hardwood and soft wood pulp. To the pulp slurry was added various chemicals. The amounts of the chemicals added are listed below. The percentages listed are based on the assumption that they were completely retained in the paper. The assumption is a good approximation for the paper machine used in the study. The values listed are predicted weight percentages in the final paper, again assuming perfect retention. If an example states that 0.5% starch was added it means that the final paper consisted of approximately 99.5% dried pulp and other additives and 0.5% starch.
  • the addition of chemicals was as follows: 0.5% low molecular weight cationic starch, 14% ground calcium carbonate, 0.1% of a microparticle retention/drainage aid combined with a 0.015% of an acrylamide based retention aid. 0.05% optical brightening agent was added and 0.075% AKD was added. The AKD was added as an emulsion.
  • the type and level of promoter resin is listed below along with the results obtained. The promoter resins were used in the preparation of the AKD emulsion and were added as part of the emulsion.
  • Comparative Example 2 contained a pure cationic promoter resin, had a better rate of sizing development (104 vs 80 and 285 to 231 seconds of HST at two different dryer cans on the paper machine).
  • Comparative Example 2 shows that the addition of a typical cationic promoter resin, poly(DADMAC), dropped the paper brightness from 91.2 to 90.3.
  • the experimental promoter resins of the current invention both improved rate of sizing development as measured by HST at the two different dryer cans.
  • the new amphoteric promoter resins had less impact on brightness compared to the pure cationic resin.
  • the pilot paper machine was set up to run with an 80/20 by weight mix of hardwood and soft wood pulp. To the pulp slurry was added various chemicals. The amounts of the chemicals added are listed below. The percentages listed are based on the assumption that they were completely retained in the paper. The assumption is a good approximation for the paper machine used in the study. The values listed are predicted weight percentages in the final paper, again assuming perfect retention. If an example states that 0.5% starch was added it means that the final paper consisted of approximately 99.5% dried pulp and other additives and 0.5% starch.
  • the addition of chemicals was as follows: 0.5% low molecular weight cationic starch, 14% ground calcium carbonate, 0.1% of a microparticle retention/drainage aid combined with a 0.015% of an acrylamide based retention aid. 0.05% optical brightening agent was added and 0.075% AKD was added. The AKD was added as an emulsion.
  • the type and level of promoter resin is listed below along with the results obtained.
  • Example 10-1 the promoter resin was premixed with the AKD emulsion and was therefore added as part of the emulsion. Comparative Example 3 had no promoter resin added. Comparative Example 4 was made with a sizing agent product which contains AKD and p(DADMAC) as a cationic promoter resin. The ratio of AKD to cationic resin was 4:1.
  • HST (sec) At reel After Promoter Level of HST (sec) 11 th Dryer Resin Promoter After 7 th Can & Sample Brightness Resin Dryer Can Calendar 10-1 B 0.0075% 203 404 91.2 Comparative None None None 189 324 91.4 Example 3 Comparative C 0.019% 218 334 90.0 Example 4
  • Example 10-1 with the amphoteric promoter resin had a better rate of sizing development (203 vs 189 and 404 to 324 seconds of HST at two different places on the paper machine).
  • Example 7-2 shows that the addition of the amphoteric promoter resin dropped the paper brightness only slightly from 91.4 to 91.2.
  • Comparative example 4 which was made with a typical AKD emulsion containing a cationic non-amphoteric promoter resin showed a large negative impact on the brightness, 91.4 to 90.0.
  • a base sheet was prepared ahead of time on a pilot paper machine at Western Michigan University using an 75:25 mixture of hardwood and softwood bleached pulp.
  • the base sheet was similar to copy paper made in the United States. It had a basis weight of 75 grams per square meter and contained 15% precipitate calcium carbonate. For the current use it was made without addition of starch or sizing agent.
  • the base sheet was treated in a laboratory size press.
  • the base sheet was passed through a puddle in a size press and between its two rollers.
  • Each treated sample was immediately dried on a drum drier which was at 65° C.
  • the time in the drier was varied to simulate different times and levels of drying along a paper machine.
  • the relative sizing generated for different drying times was measured immediately for each sample.
  • the size press solution used to treat the paper consisted of approximately a 0.5% cationic starch solution.
  • the pick-up of the solution into the paper was approximately 100%. Therefore, the level of starch added to the paper on a dry basis was 0.5 grams of starch for every 100 grams of paper, or a treatment of 0.5% on a dry basis.
  • the exact pick-up of the base sheet was determined ahead of time for each set of experiments and the solids level of the starch adjusted to yield the desired treatment level.
  • the additives being tested were added to the starch solution in a level based on the pick-up of the base sheet and by doing so the desired level of treatment was obtained.
  • Samples for HST testing were cut out at drying times (measured in seconds) and then tested via HST. The time between sampling and testing was routinely done at about the same time interval to assure that a good comparison can be made. The optical brightness was measured on the final paper.
  • the levels of amphoteric promoter resins added are noted below. The sizing obtained at different drying times is reported. The approximate moisture content at the drying times was 29% ⁇ 5%.
  • the AKD was added as an emulsion.
  • the amphoteric promoter resins were added with the AKD emulsion in the size press starch solution. The level of AKD added to the paper in every case was 0.09%. With no promoter resin or OBA the paper brightness was 90.1.
  • the starch solution was used within a few hours. It was stored and used at 75° C.
  • the mixture was fed through a microfluidizer (impinging streams) system set at 3000 psi which transformed the mixture into an emulsion.
  • the AKD was added in the form of Hercules' Hercon 70 sizing agent emulsion. The promoter resins were added with the AKD emulsion in the size press starch solution. The level of AKD added to the paper in every case was 0.09%.
  • amphoteric promoter resins were added to Hercon 79 formulations and tested.
  • the resultant AKD emulsion with the promoter resins were stable.
  • Examples 16-1 and 16-2 The amphoteric promoter resin with DADMAC and AA without any DAA performed about the same as the Hercon 79 formulation.
  • This modest performance of the amphoteric promoter resin is attributed to the high level of OBA and the high amphoteric promoter resin to AKD ratio.
  • the optical brightness of both 16-1 and 16-2 is much better than the comparative example 9.
  • amphoteric promoter resin in this example was made by a synthetic technique similar to Synthetic Example #1, with the ratio of DADMAC:AA:DAA::45:45:10.
  • the paper was prepared in a manner identical to the previous examples except that the precipitated calcium carbonate was 18% not 15%.
  • Optical Bright- ness H70 + ⁇ 79 Dryer time 32 39 47 57 63 71 (600 gal) seconds HST, Sec 3 6 6 36 546 730 93.7 Comp. Ex. 10 Dryer time, 40 46 54 64 75 89 seconds H70 + R203 HST, Sec 5 4 7 42 75 505 92
  • Hercon 70 Reactive size (abbreviated here as H70 was promoted with the 45:45:10 amphoteric promoter resin. Comparative example 10 had no amphoteric promoter resin, but did have Retene 203 cationic resin and retention aid (obtained from Hercules Incorporated, Wilmington Del.). The data for this Example 17 is shown in Drawing 12 .
  • Solution A 80.0 g water+0.5 g V-50.
  • Solution B 40.25 g 65% DADMAC solution+84.4 g water+57.25 g AMPS (the pH was adjusted to 3.7 with a 1% HCl solution)
  • Solution C 1.5 g V-50+50 ml water
  • Solution D 1.0 g V-50+10.0 g water
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up the be pumped slowly into the reaction vessel.
  • the polymer solution was 18.3% solids.
  • the solution contained a polymer with 48 parts (on a molar basis) AMPS units and 35 parts DADMAC units. On the same basis it contained 18 parts residual DADMAC.
  • Solution A 80.0 g water+0.5 g V-50.
  • Solution B 60.4 g 65% DADMAC solution+126.7 g water+42.9 g AMPS (the pH was adjusted to 3.8 with a 1% HCl solution)
  • Solution C 1.5 g V-50+50 ml water
  • Solution D 1.0 g V-50+10.0 g water
  • Solution A was added to a closed reaction vessel equipped with an overhead stirrer and a nitrogen purge.
  • Solution B was added to an addition funnel set-up to drip into the reaction vessel.
  • the funnel was set to drop directly onto the liquid in the vessel and not on the sides of the flask.
  • Solution C was set-up the be pumped slowly into the reaction vessel.
  • the polymer solution was 18.1% solids.
  • the solution contained a polymer with 27 parts (on a molar basis) AMPS units and 42 parts DADMAC units. On the same basis it contained 31 parts residual DADMAC.
  • Monomers that contain an alkenyl sulfonate as the anionic monomer component of the polymer also promotes sizing.
  • the following results are for samples with 0.075% OBA added to the paper and compare cationic promoter resins with amphoteric promoter resins with alkenyl sulfonates.
  • the synthesis of the alkenyl sulfonate containing APR's is given in polymer synthesis Examples 18 and 19.
  • the levels of promoter resins added are noted below.
  • the AKD was added in the form of Hercules' AKD sizing agent emulsion.
  • the promoter resins were added with the AKD emulsion in the size press starch solution.
  • Example 20 The data of Example 20 is shown in Drawing 9 .
  • Paper making example 23 Amphoteric promoter Resins with other monomeric components.
  • Amphoteric promoter resins were prepared with other monomers in the monomer mixture.
  • the synthesis technique was nearly identical to Synthetic Examples 1-8 with the other monomer being added to one of the monomer streams added to the polymer reaction mixtures.
  • Examples of other monomers are listed in the following table. Mole ratios are indicated in the fomulation in the following table.
  • TEGDMA is triethylene glycol dimethacrylate
  • Amphoteric Promoter Resins can be prepared with other monomer units such as styrene and TEGDMA.
  • the data for Example 23 is shown in Drawing 11
  • a water-soluble copolymer of diallyldimethyl-ammonium chloride (DADMAC) and diallylammonium chloride (DAA.HCl) was prepared in this Example as follows.
  • the monomer mole ratio used in the polymerization reaction product was about 8:2 DADMAC:DAA.HCl.
  • An aqueous mixture was made by combining 53.8 parts of 65 wt % diallyldimethylammonium chloride in water with 14.5 parts of 49.8 wt % diallylammonium chloride in water.
  • the aqueous reaction mixture of the two monomer components was degassed with nitrogen for 40 minutes and warmed to a temperature of 55° C. with stirring.
  • a water-soluble free radical polymerization initiator 4.23 parts of 9.09 wt % 2,2′-azobis(2-amidinopropane) hydrochloride in degassed water was added to the aqueous solution at a rate of 0.4 g/minute. After the addition of the initiator was complete, 16.9 parts of degassed water was added to reduce the viscosity of the reaction medium, and the mixture was maintained at a temperature of about 90° C.
  • Typical cationic promoter resins were used to make paper and the optical brightness measured. These typical materials were poly(DADMAC), high molecular weight, poly(DADMAC) medium molecular weight, poly(dimethylamine/epichloridrin), polyethyleneimine and a neutral resin, poly(acrylamide).
  • the poly(DADMAC)s, polyethyleneimine and poly(acrylamide) were purchased from Sigma Aldrich Chemical, Milwaukee, Wis.
  • the poly(dimethylamine/epichloridrin) was obtained as RETEN® 201 cationic resin and retention aid. The cationic nature of the cationic promoter resin and the amount of cationic promoter resin added will reduce the effectiveness of optical brighteners.
  • the cationic density of each of these was determined by titration of the cationic component.
  • the charge density of cationic resin products was measured at pH 8.0. A colloid titration is used. Charge density is the amount of cationic charge per unit weight in milliequivalents per gram of product solids.
  • the sample is titrated with potassium poly(vinyl sulfate), KPVS, to form a colloid. Once all of the charge has been titrated, the excess KPVS reacts with the end point indicator, toluidine blue, which changes from blue to purple.
  • a dip probe colorimeter set at 620 nm and an automatic titrator (analog or digital) are used to perform the titration.
  • the charge density is calculated from the titration results, on a dry solids basis. The charge density is reported in milliequivalents/gram.
  • the total charge due to the cationic promoter resin is the charge density times the amount of cationic promoter resin in lbs/ton.
  • Comparative Paper Making Example 2 Reduction in brightness when poly(DADMAC) and poly(DADMAC/DAA-HCL) cationic promoter resins are used.
  • the poly(DADMAC) and poly(DADMAC/DAA-HCL) were synthesized by comparative Polymer Synthesis Examples 1 and 2 respectively.
  • the OBA was added at 1 lb/ton.
  • These cationic promoter resins were used to make paper and the optical brightness measured. As more cationic promoter resin is added the deleterious effect on paper brightness increases. This data is shown in Drawing 2 .

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US09/947,300 US20030127204A1 (en) 2001-09-06 2001-09-06 Amphoteric polymer resins that increase the rate of sizing development
PT02798104T PT1423444E (pt) 2001-09-06 2002-08-30 Resinas de polímero anfotérico que aumentam a velocidade do desenvolvimento de colagem
KR1020047003306A KR100869638B1 (ko) 2001-09-06 2002-08-30 사이징 전개 속도를 상승시키는 양쪽성 중합체 수지
ES02798104T ES2306809T3 (es) 2001-09-06 2002-08-30 Resinas polimericas anfoteras que aumentan la velocidad de desarrollo de encolado.
CNB028175085A CN100343295C (zh) 2001-09-06 2002-08-30 提高施胶速率的两性聚合物树脂
CA2455980A CA2455980C (en) 2001-09-06 2002-08-30 Amphoteric polymer resins that increase the rate of sizing development
MXPA04001371A MXPA04001371A (es) 2001-09-06 2002-08-30 Resinas de polimeros anfotermicos, que aumentan el regimen de desarrollo de encolado.
BRPI0212305-3A BR0212305B1 (pt) 2001-09-06 2002-08-30 composiÇço de resina promotora anfotÉrica solével em Água para promoÇço de colagem de papel, mÉtodo de fabricaÇço de papel colado e papel colado.
PCT/US2002/027874 WO2003022898A1 (en) 2001-09-06 2002-08-30 Amphoteric polymer resins that increase the rate of sizing development
JP2003526969A JP4121955B2 (ja) 2001-09-06 2002-08-30 サイジング発現速度を高める両性重合体樹脂
EP02798104A EP1423444B9 (en) 2001-09-06 2002-08-30 Amphoteric polymer resins that increase the rate of sizing development
RU2004110407/04A RU2293090C2 (ru) 2001-09-06 2002-08-30 Способ изготовления проклеенной бумаги (варианты)
AU2002332792A AU2002332792B2 (en) 2001-09-06 2002-08-30 Amphoteric polymer resins that increase the rate of sizing development
DE60226876T DE60226876D1 (de) 2001-09-06 2002-08-30 Amphotere polymerharze, die die geschwindigkeit der leimungsentwicklung erhöhen
PL02368384A PL368384A1 (en) 2001-09-06 2002-08-30 Amphoteric polymer resins that increase the rate of sizing development
AT02798104T ATE397026T1 (de) 2001-09-06 2002-08-30 Amphotere polymerharze, die die geschwindigkeit der leimungsentwicklung erhöhen
TW091120453A TW589328B (en) 2001-09-06 2002-09-09 Water soluble amphoteric promoter resin composition for promoting sizing of paper, method of producing sized paper, and sized paper
US10/424,502 US7270727B2 (en) 2001-09-06 2003-04-28 Paper sized with a sizing agent and a selected sizing promoter
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US7270727B2 (en) 2007-09-18
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US20040016528A1 (en) 2004-01-29
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