CN101133211A - Improved retention and drainage in the manufacture of paper - Google Patents
Improved retention and drainage in the manufacture of paper Download PDFInfo
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- CN101133211A CN101133211A CNA2005800488372A CN200580048837A CN101133211A CN 101133211 A CN101133211 A CN 101133211A CN A2005800488372 A CNA2005800488372 A CN A2005800488372A CN 200580048837 A CN200580048837 A CN 200580048837A CN 101133211 A CN101133211 A CN 101133211A
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Abstract
A method of improving retention and drainage in a papermaking process is disclosed. The addition of an associative polymer, a poly(vinylamine) and optionally a siliceous material to the papermaking slurry to improve retention and drainage is disclosed. Additionally a method to improve retention and drainage comprising addition of an organic microparticle, a poly(vinylamine) and optionally a siliceous material to the papermaking slurry is disclosed. A composition comprising an associative polymer, and a poly(vinylamine) and optionally further comprising cellulose fiber is disclosed.
Description
The cross reference of related application
The application requires in the rights and interests of the US provisional application 60/640,164 of proposition on December 29th, 2004, and its full content is incorporated herein by reference at this.
Technical field
The present invention relates to use flocculation system to make the method for paper and cardboard by cellulosic material.
Background technology
Keep with drainage is the importance of papermaking.Known certain material can provide keeping and/or water filtering performance of improvement in the production of paper and cardboard.
The manufacturing of cellulosic fiber sheets, especially paper and cardboard comprises the steps: 1) preparation also can contain the aqueous slurry of the cellulose fibre of inorganic mineral extender or pigment; 2) this slurry is deposited on the mobile papermaking wire-cloth or fabric; With 3) form page by drainage by the solid constituent of slurry.
After abovementioned steps, page squeezing and drying are anhydrated further to remove.Usually before page forms step, organic and inorganic chemical are added in the slurry so that papermaking process is cheaper, quicker and/or obtain particular characteristic in final paper product.
Paper industry ongoing effort with the quality of improving paper, increase productivity and reduce manufacturing cost.Before fibre stuff arrives papermaking wire-cloth or fabric, chemicals is added wherein usually and keep to improve drainage/dehydration and solid; These compounds are called retention and/or filter aid.
Drainage or dewater the normally conditioning step of realization faster paper machine speed of fibre stuff on papermaking wire-cloth or fabric.Improved dehydration also can obtain more dry page in squeezing and drying nest, causes energy consumption to reduce.In addition, because this is the step of the final performance of the many pages of decision in papermaking process, retention and/or filter aid can influence the performance of final page.
About solid, at drainage and form in the process of turbulent flow method of paper web, Retention Aid in Papermaking is used for increasing fine furnish solids keeping at the width of cloth.Do not have keeping fully of micro-solid, then they or be lost in the plant chimney stalk or in the white water loop that refluxes the paramount level of accumulation, cause deposit buildup potentially.In addition, inadequate keeping owing to the loss that is intended to be adsorbed on the additive on the fiber has increased the papermaking cost.Additive can provide opacity, intensity, applying glue (sizing) or other desired properties for paper.
High molecular (MW) water-soluble polymer that has cationic charge or anionic charge traditionally is used as retention and filter aid.The immediate development of inorganic particles shows that it better keeps and drainage efficient having than the high MW water-soluble polymer of routine when the retention and filter aid in conjunction with high MW water-soluble polymer.US patent 4,294,885 and 4,388,150 have instructed the purposes of starch polymer and cataloid.US patent 4,643,801 and 4,750,974 have instructed the purposes of the cohesion adhesive of cationic starch, cataloid and anionic polymer.US patent 4,753,710 has been instructed with high MW cationic flocculant flocculation intermittent pulp proportioning, and the batching of flocculation is induced shearing, then bentonite is introduced in the batching.US patent 5,274,055 and 5,167,766 disclose in paper technology organic little polymer with chemical crosslinking as retention and filter aid.
The efficient of used polymer or copolymer changes according to the arrangement in polymer matrix of the type of the monomer of its composition, monomer, the molecular weight and the preparation method of institute's synthetic molecules.
Recently the water solubility copolymer that has been found that preparation under given conditions demonstrates unique physical property.These polymer prepare under the chemical cross-linking agent not having.In addition, this copolymer provides unexpected activity in application-specific (comprising that the papermaking application is as retention and filter aid).The anionic copolymer of described demonstration peculiar property is disclosed among the WO 03/050152A1, and its full content is hereby incorporated by.Cationic and the ampholyte copolymer that demonstrates peculiar property is disclosed in the US sequence 10/728,145, and its full content is hereby incorporated by.
The purposes of inorganic particle and acrylamide linear copolymers is well known in the art.Recent patent has been instructed the purposes of these inorganic particles and water soluble anion type polymer (US 6,454,902) or special cross-linked material (US 6,454,902, US 6,524,439 and US 6,616,806).
Yet, still need to improve drainage and retention performance.
Summary of the invention
A kind of method of improving in the papermaking process of keeping with drainage is disclosed.This method provides association polymer, organic fine particles is added in the paper making pulp.
In addition, a kind ofly comprise association polymer and organic fine particles and optionally comprise that also the composition of cellulose fibre is disclosed.
In addition, a kind ofly comprise association polymer, organic fine particles, material and optionally comprise that also the composition of cellulose fibre is disclosed.
The specific embodiment
The invention provides a kind of synergistic combination, it comprises the water solubility copolymer (hereinafter referred to as " association polymer ") and the organic fine particles of preparation under given conditions.Find that surprisingly this synergistic combination obtains to be better than keeping and water filtering performance of its single component.Cooperative effect takes place when using the combination of component together.Be surprised to find that keeping and drainage that particulate and association polymer cause when for example WO 03/050152A1 or the disclosed copolymer of US 2004/0143039A1 are used in combination strengthening.
The present invention also provides the new compositions that comprises association polymer and organic fine particles.
The present invention also provides the new compositions that comprises association polymer, organic fine particles and material.
The present invention also provides the new compositions that comprises association polymer, organic fine particles and cellulose fibre.
The present invention also provides the new compositions that comprises association polymer, organic fine particles, material and cellulose fibre.
Using multicomponent system to provide in the manufacturing of paper and cardboard may by what utilize that the material that this method and/or product are had a Different Effects makes that performance strengthened.In addition, affiliated combination can provide with the unavailable performance of independent component.Cooperative effect takes place in multicomponent system of the present invention.
Also observe association polymer is had influence as retention and filter aid to the performance of other auxiliary agent in the papermaking systems.Improved keep and/or drainage can have direct and indirect influence.Directly influence is meant that the retention and filter aid work is in order to keep additive.Remote-effects are meant that retention and filter aid keeps the effect of filler and fines (fines), and additive is adsorbed on described filler and the fines by physical method or chemical method.Therefore, keep the filler in page or the amount of fines by increase, the amount that is accompanied by the additive of keeping is increased.The term filler is meant and joins in the cellulose pulp particular characteristic to be provided or to become the part cellulose fibre granular materials of substitute more cheaply, it typically is inorganic in nature.The micron-sized size of they less 0.2-10, low draw ratio and chemical property cause it not to be attracted on the big fiber can not accumulating in the network of fibers of page but they are too little.Term " fines " is meant little cellulose fibre or fubril, and its length is less than 0.2mm and/or can pass 200 mesh screens usually.
With the increase of the usage level of retention and filter aid, the amount of keeping the additive in page increases.This or performance is strengthened and make page have augmented performance, perhaps can allow paper manufacturers to reduce the amount of the additive in the adding system and the cost of product is minimized.In addition, the amount of these materials in recirculation water that is used for papermaking systems or plain boiled water is minimized.The decline of the level of described material (can regard undesired pollutant as under certain conditions) can provide more effective paper technology or reduction to be used to control the level of not wishing material and the scavenger that adds or the needs of other material.
As used herein, the term additive is meant and adds in the paper pulp so that the material of property and/or improvement papermaking process efficient to be provided to paper.These materials include, but are not limited to sizing agent, wet-strength resins, dry strength resin, starch and starch derivatives, dyestuff, pollutant controlling agent, defoamer and biocide.
Can be used for association polymer of the present invention can be explained as follows:
The water solubility copolymer composition that comprises following formula:
[-B-co-F-](I)
The B non-ionic polymers segment that the unsaturated non-ionic monomer of one or more ethylenic forms of serving as reasons wherein; F the serve as reasons polymerization of unsaturated anion of one or more ethylenic and/or cationic monomer and the anionic polymer segment, cation type polymer segment or the anionic that form and the combination of cation type polymer segment; The mole % ratio of B: F is 95: 5-5: 95; And this water solubility copolymer prepares via the water-in-oil emulsion polymerization technique, this technology has been used at least a emulsifying surfactant of being made up of at least a diblock or three block polymerization surfactants, wherein said at least a diblock or three block surfactants are at least about 3: 100 to the ratio of monomer, and wherein said water-in-oil emulsion polymerization technique comprises the steps: the aqueous solution of (a) preparation monomer, (b) this aqueous solution is contacted to form reversed-phase emulsion with the hydrocarbon liquid that contains surfactant or surfactant mixture, (c) make monomer in the emulsion in about 2 polymerizations under less than 7 pH by radical polymerization.
Described association polymer can be anionic copolymer.Described anionic copolymer be characterised in that the Huggins constant that the copolymer of its 0.0025-0.025 weight % measured in 0.01M NaCl (k ') greater than storage modulus under 4.6Hz of the active copolymer solution of 0.75 and 1.5 weight % (G ') greater than 175Pa.
Described association polymer can be cationic copolymer.Described cationic copolymer be characterised in that the Huggins constant that the copolymer of its 0.0025-0.025 weight % measured in 0.01M NaCl (k ') greater than storage modulus under 6.3Hz of the active copolymer solution of 0.5 and 1.5 weight % (G ') greater than 50Pa.
Described association polymer can be ampholyte copolymer.Described ampholyte copolymer be characterised in that the Huggins constant that the copolymer of its 0.0025-0.025 weight % measured in 0.01M NaCl (k ') greater than storage modulus under 6.3Hz of the active copolymer solution of 0.5 and 1.5 weight % (G ') greater than 50Pa.
Inverse emulsion polymerization is the standard chemical process of preparation molecular weight water-soluble polymers or copolymer.Usually, the inverse emulsion polymerization method is carried out as follows: the 1) aqueous solution of preparation monomer, 2) this aqueous solution is contacted to form anti-phase monomer emulsions with the hydrocarbon liquid that contains suitable emulsifying surfactant or surfactant mixture, 3) make this monomer emulsions carry out radical polymerization and optional 4) add demulsifier surfactant (breaker surfactant) and strengthen emulsion inverts with in adding entry the time.
Inverse emulsion polymer is generally the water-soluble polymer based on ion or non-ionic monomer.Contain two or more monomers polymer also be called copolymer, it can prepare by same procedure.These comonomers can be anion, CATION, amphion, nonionic or its combination.
Typical non-ionic monomer includes, but are not limited to acrylamide, Methacrylamide, N-alkyl propyl amides such as N methacrylamide, N, N-dialkyl group acrylamide such as N,N-DMAA, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl formamide, N-vinyl methylformamide, vinyl acetate, N-vinyl pyrrolidone, hydroxyalkyl (methyl) acrylate are as (methyl) hydroxy-ethyl acrylate or (methyl) hydroxypropyl acrylate, above-mentioned any mixture etc.
Can also in the preparation of association polymer, use more hydrophobic non-ionic monomer.Terminology used here " more hydrophobic " represents that these monomers have the dissolubility of reduction in the aqueous solution; It is zero substantially that this reduction can be arrived, and means that this monomer is insoluble in water.It should be noted that described monomer also is called polymerisable surfactant or surface active monomer.These monomers include, but are not limited to alkyl acrylamide; Ethylenically unsaturated monomers with side aryl and alkyl; And formula CH
2=CR ' CH
2OA
mThe ethers of R, wherein R ' is hydrogen or methyl, and A is the polymer of one or more ring-type ethers such as oxirane, expoxy propane and/or epoxy butane, and R is a hydrophobic group; The vinyl alkoxide; The allyl alkoxide; And ally phenylpolyolether sulfates.Exemplary material includes, but are not limited to methyl methacrylate, styrene, uncle's octyl acrylamide and by the ally phenylpolyolether sulfates of Clariant as Emulsogen APG 2019 marketizations.
Exemplary anionic monomer includes, but are not limited to following free acid and salt: acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamido glycollic acid, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid, 3-allyloxy-2-hydroxyl-1-propane sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphonate, 2-acrylamido-2-methylpropane phosphonic acids, above-mentioned any mixture etc.
Exemplary cationic monomer includes, but are not limited to CATION ethylenically unsaturated monomers such as following free alkali or salt: poly (dially dialkyl) base ammonium halide such as diallyldimethylammonium chloride; (methyl) acrylate of dialkyl aminoalkyl compound is as (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine ethyl ester, (methyl) acrylic acid dimethylamino propyl ester, (methyl) acrylic acid 2-hydroxyl dimethylamino propyl ester, (methyl) acrylic-amino ethyl ester, and their salt and quaternary ammonium salt; N, N-dialkyl aminoalkyl (methyl) acrylamide such as N, N-dimethylaminoethyl acrylamide and its esters and quaternary ammonium salt; With above-mentioned mixture etc.
Described comonomer can exist by arbitrary proportion.The gained association polymer can be nonionic, cationic, anionic or amphoteric ion type (not only containing cationic charge but also contain anionic charge).
Non-ionic monomer and anionic monomer (B among the formula I: mol ratio F) can be 95: 5-5: 95, be preferably about 75: and about 25: 75 of 25-, and be more preferably about 65: about 35: 65 of 35-most preferably is about 60: about 40: 60 of 40-.At this, the mole percent of B and F must add up to 100%.Be understood that in formula I and can exist more than a kind of non-ionic monomer.What will also be understood that is can exist more than a kind of anionic monomer in formula I.
In a preferred embodiment of the invention, association polymer is defined by formula I by anionic copolymer the time, B wherein, and the non-ionic polyalcohol segment is the repetitive that forms behind the acrylamide polymerization; F, the anionic polymer segment be the repetitive that forms after acrylic acid salt or the free acid polymerization, and the molar percentage of B: F is about 75: about 25: 75 of 25-.
Association polymer its unique distinction when the anionic copolymer be its Huggins constant of in 0.01M NaCl, being measured (k ') greater than storage modulus under 4.6Hz of the active copolymer solution of 0.75 and 1.5 weight % (G ') greater than 175Pa, be preferably greater than 190, more preferably greater than 205.The Huggins constant is preferably greater than 0.9, more preferably greater than 1.0 greater than 0.75.
(B among the formula I: mol ratio F) can be 99: 1-50: 50 for non-ionic monomer and cationic monomer, perhaps 95: 5-50: 50, perhaps 95: 5-75: 25, perhaps 90: 10-60: 45, be preferably about 85: about 60: 40 of 15-, more preferably 80: about 50: 50 of 20-.At this, the mole percent of B and F must add up to 100%.Be understood that in formula I and can exist more than a kind of non-ionic monomer.What will also be understood that is can exist more than a kind of cationic monomer in formula I.
About the molar percentage of the ampholyte copolymer among the formula I, the minimum separately of anion, CATION and non-ionic monomer be used to form polymer the monomer total amount 1%.The maximum of nonionic, anion and cationic monomer be used to form polymer the monomer total amount 98%.The minimum of preferred any anion, CATION and non-ionic monomer be used to form copolymer the monomer total amount 5%, the minimum of more preferably any anion, CATION and non-ionic monomer be used to form copolymer the monomer total amount 7%, the minimum of more preferably any anion, CATION and non-ionic monomer be used to form copolymer the monomer total amount 10%.At this, the mole percent of anion, CATION and non-ionic monomer must add up to 100%.Be understood that in formula I, can exist, in formula I, can exist, and in formula I, can exist more than a kind of anionic monomer more than a kind of cationic monomer more than a kind of non-ionic monomer.
Association polymer unique distinction the time for CATION or ampholyte copolymer be its Huggins constant of in 0.01M NaCl, being measured (k ') greater than storage modulus under 6.3Hz of the active copolymer solution of 0.5 and 1.5 weight % (G ') greater than 50Pa, be preferably greater than 10, more preferably greater than 25, perhaps greater than 50, or greater than 100 or greater than 175 or greater than 200.The Huggins constant is preferably greater than 0.6 greater than 0.5, or greater than 0.75 or greater than 0.9 or greater than 1.0.
The emulsifying surfactant or the surfactant mixture that are used for the inverse emulsion polymerization system all have material impact to manufacture method and products therefrom.The surfactant that is used for emulsion polymerization systems is known to those skilled in the art.The scope of the HLB that these surfactants have usually (hydrophile-lipophile balance) value depends on total composition.Can use one or more emulsifying surfactants.The emulsifying surfactant that is used to produce the polymerization product of association polymer comprises at least a diblock or three block polymerization surfactants.Known these surfactants are emulsion stabilizer efficiently.The kind of selection emulsifying surfactant and amount are in order to obtain being used for the anti-phase monomer emulsions of polymerization.Preferably, select one or more surfactants to obtain specific HLB value.
Diblock and three block polymerization emulsifying surfactants are used to the material that provides special.When using described diblock and three block polymerization emulsifying surfactants with requirement, obtain demonstrating the distinct polymer of peculiar property, describe as WO 03/050152A1 and US 2004/0143039A1, its separately full content be hereby incorporated by.Exemplary diblock and three block polymerization surfactants comprise but are not limited to based on the diblock of the polyester derivatives of aliphatic acid and poly-[oxirane] and triblock copolymer (Hypermer B246SF for example, Uniqema, New Castle, DE), based on diblock and the product of triblock copolymer, oxirane and expoxy propane and ethylenediamine, above-mentioned any mixture etc. of polyisobutylene butanedioic anhydride and poly-[oxirane].Preferred diblock and triblock copolymer are based on polyester derivatives and poly-[oxirane] of aliphatic acid.When using three block surfactants, preferred three blocks contain two hydrophobic regions and a hydrophilic area, and are promptly hydrophobic-hydrophilic-hydrophobic.
The amount of diblock or three block surfactants (based on percentage by weight) depends on the amount of the monomer that is used to form association polymer.Diblock or three block surfactants are at least about 3-100 to the ratio of monomer.Diblock or three block surfactants can be preferably at least about 4-100 for greater than 3 to 100 the amount of monomer, and more preferably 5-100 is more preferably about 6-100.Diblock or three block surfactants are main surfactants of described emulsification system.
Can add secondary emulsification surfactant improves stability of emulsion and/or changes emulsion viscosity to be easy to handle and process.The example of secondary emulsification surfactant includes, but are not limited to D-sorbite fatty acid ester such as dehydrated sorbitol mono-fatty acid ester (Atlas G-946 for example, Uniqema, New Castle, DE), the D-sorbite fatty acid ester of ethoxylation, the D-sorbite fatty acid ester of polyethoxylated, the oxirane of alkyl phenol and/or propylene oxide adduct, the oxirane of long-chain alcohol or aliphatic acid and/or the adduct of expoxy propane, the ethylene oxide/propylene oxide block copolymer that mixes, alkanolamide, sulfosuccinate and composition thereof etc.
Inverse emulsion polymerization can any mode well known by persons skilled in the art carry out.Example can find in many documents, comprises for example Allcock and Lampe, Contemporary Polymer Chemistry (Englewood Cliffs, New Jersey, PRENTICE-HALL, 1981), chapters 3-5.
Representational inverse emulsion polymerization is by being prepared as follows.Oil phase (the 135.0g that in the suitable reaction flask of being furnished with overhead mechanical agitator, thermometer, nitrogen tube spray and condenser, adds paraffin oil, Exxsol D80 oil, Exxon-Houston, TX) and surfactant (4.5g Atlas G-946 and 9.0g Hpermer B246SF).Then with oil phase adjustment to 37 ℃.
The water that separately prepares the aqueous solution (126.5g), acrylic acid (68.7g), deionized water (70.0g) and Versenex 80 (Dow Chemical) chelating agent solution (0.7g) of the acrylamide that comprises 53 weight %.The aqueous solution (33.1g, the NH that add ammonium hydroxide then
3Be 29.4 weight %) and water is adjusted to pH is 5.4.Water temperature after the neutralization is 39 ℃.
Then water is added in the oil phase, mix to obtain stable water-in-oil emulsion with homogenizer simultaneously.With four blade sheet glass agitator this emulsion is mixed then, sprayed into nitrogen simultaneously 60 minutes.In the process that nitrogen feeds, emulsion temperature is adjusted to 50 ± 1 ℃.Subsequently, stop to spray into and realizing blanket of nitrogen.
Polymerization is by adding 2,2 '-azodiisobutyronitrile (AIBN) in toluene (0.213g) 3 weight % solution and cause.This is 250ppm AIBN corresponding to the initial reinforced of AIBN based on total monomer.In reinforced process, allow batch temperature heat release to 62 ℃ (～50 minutes), make batch of material remain on 62 ± 1 ℃ then.After reinforced, batch of material was remained on 62 ± 1 ℃ of temperature following 1 hour.Then, in 1 minute, add the 3 weight % solution of AIBN in toluene (0.085g).This feeds in raw material based on total monomer corresponding to secondary AIBN is 100ppm AIBN.Then batch of material was remained on 62 ± 1 ℃ of temperature following 2 hours.Then batch of material is cooled to room temperature, and adds demulsifier surfactant.
Usually the association polymer emulsion is reversed at point of application and form the aqueous solution of 0.1-1% active copolymer.Keep and drainage with influence in the dilute solution adding paper technology with described association polymer then.Association polymer can be added in underflow material or the grout, preferably add in the grout.Association polymer can be added at a feed point, perhaps can separately add so that association polymer is joined the feed point that two or more separate simultaneously.Typical feed point comprise fan pump (fan pump) before, after the fan pump and before the pressurized screen or the feed point after the pressurized screen.
Can any effective amount add association polymer to realize flocculation.The amount of per metric ton cellulose pulp (butt) copolymer can be greater than 0.5kg.The dry weight that is preferably based on paper pulp is at least the amount of the about 0.5kg of about 0.031b-and uses association polymer with the per metric ton active copolymer.The concentration of copolymer is preferably the active copolymer of the about 0.5kg of the about 0.05kg-of cellulose pulp of per metric ton drying.More preferably the dry weight per metric ton cellulose pulp copolymer addition based on cellulose pulp is about 0.05-0.4kg, and most preferably per metric ton is the about 0.3kg of about 0.1kg-.
Described second component of keeping with drainage system can be organic fine particles (also being called little polymer or microballon).For the purpose of the present invention, term microparticles, little polymer or microballon are used interchangeably.Organic fine particles is crosslinked ion organic polymer materials.They are the copolymer of non-ionic monomer, ion monomer and crosslinking agent.In addition, ion monomer can be anion or CATION.In same polymer, not only use anionic monomer but also use cationic monomer to obtain Amphoteric Materials.Particulate forms by the polymerization of ethylenically unsaturated monomers usually, and described ethylenically unsaturated monomers can be anion, CATION or nonionic.Though can use other polymerization well known by persons skilled in the art, prepare these materials with inverse emulsion polymerization usually.
The unsaturated non-ionic monomer of preferred ethylenic for preparing described organic fine particles is selected from acrylamide, Methacrylamide, N, N-dialkyl group acrylamide, N-alkyl acrylamide, N-vinyl methylacetamide, N-vinyl formamide, N-vinyl methylformamide, N-vinyl pyrrolidone, and their mixture.
The exemplary anionic monomer that is used to prepare described organic fine particles includes, but are not limited to following salt and free acid: acrylic acid; Methacrylic acid; Ethylacrylic acid; 2-acrylamido-2-alkyl sulfonic acid, wherein alkyl contains 1-6 carbon atom, as 2-acrylamido-2-propane sulfonic acid; Or above-mentioned any mixture etc.; And their basic salt.The salt or the acid of preferred especially acrylic acid, methacrylic acid and 2-acrylamido-2-methyl propane sulfonic acid.Preferred salt is CATION with sodium.
The exemplary cationic monomer that is used to prepare described organic fine particles includes, but are not limited to be selected from the following free alkali or the ethylenically unsaturated monomers of salt: the acryloxy ethyl-trimethyl salmiac, diallyldimethylammonium chloride, 3-(methyl) acrylamido-oxypropyl trimethyl ammonium chloride, 3-acrylamido-oxypropyl trimethyl ammonium-2-hydroxypropyl acrylic acid methylsulfuric acid ester (3-acrylamido-propyltrimethylammonium-2-hydroxypropylacry late methosulfate), trimethyl ammonium methyl acrylic acid methylsulfuric acid ester, 1-trimethyl ammonium-2-hydroxypropyl-methacrylic acid methyl sulfuric ester, the methacryloxyethyl trimethyl ammonium chloride, and above-mentioned any mixture etc.
The unsaturated anion of ethylenic, CATION and the non-ionic monomer polymerization that these can be constituted organic fine particles are to form anionic, cationic or ampholyte copolymer, and described three class monomers exist with any ratio.Acrylamide is preferred non-ionic monomer.
The polyfunctional crosslinking agent existence that is aggregated in of described monomer is carried out to form crosslinked composition down.Multifunctional crosslinking agent comprises the molecule with at least two two keys or two key and reactive group or two reactive groups.The example that contains the multifunctional crosslinking agent of at least two two keys includes, but are not limited to N, N-methylene-bisacrylamide, N, N-di-2-ethylhexylphosphine oxide Methacrylamide, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, N-vinyl acrylamide, divinylbenzene, triallyl ammonium, N-methacrylic acrylamide etc.Contain the multifunctional crosslinking agent of at least one two key and at least one reactive group or the example of branching agent and include, but are not limited to acrylic acid glycerine ether-ether, acrolein, n-methylolacrylamide etc.The example that contains the multifunctional branching agent of at least two reactive groups include, but are not limited to aldehydes such as glyoxal, di-epoxy compounds, epoxychloropropane etc.Must use the crosslinking agent of q.s to guarantee cross-linked composition.
The example of organic fine particles is disclosed in US 5,171, in 808.Particulate can trade name Polyflex CP.3 (Ciba, Tarrytown, NY) commercial.
Keep with second component of drainage system and can add with the amount that the per metric ton cellulose pulp reaches the 0.5kg active material based on the paper pulp dry weight, association polymer is 1 to the ratio of second component: 100-100: 1.Expectation can be used in papermaking systems more than the second a kind of component.
Randomly can be with the additional component of material as the retention and filter aid in paper and the cardboard manufacturing.Material can be for being selected from any material of following group: silica-based particles, silica microgel, amorphous silica, cataloid, anionic colloidal silica, silicon dioxide gel, silica dioxide gel, polysilicate, poly-silicic acid etc.These materials are characterised in that the particle size of high surface area, high charge density and sub-micron.
Such material comprises the stable colloid dispersion of spherical amorphous silica particles, and it is called silicon dioxide gel in the art.Term colloidal sol is meant the stable aqueous colloidal dispersion of spherical amorphous granular.Silica dioxide gel is a three dimensional silica aggregate chains, and each dimension comprises some and also can be used for amorphous silica sol particle in the retention and filter aid system, and described chain can be line style or side chain.Silicon dioxide gel and gel prepare by the dispersion amorphous silica colloidal sol that thereby the monomer silicic acid polymerization is obtained poly-silicic acid in the circulus.These silicon dioxide gels can further react and form the three dimensional gel network.Various silica dioxide granules (colloidal sol, gel etc.) can have the overall size of 5-50nm.Can also use anionic colloidal silica.
Can based on the dry weight of cellulosic suspension with per metric ton at least the amount of 0.005kg material is added in the cellulosic suspension.The amount of material can be as high as per metric ton 50kg.The amount of preferred material is the about 25kg of the about 0.05kg-of per metric ton.The amount that is more preferably material is the about 5kg of the about 0.25kg-of per metric ton based on the dry weight of cellulosic suspension.
Randomly, the additional component of retention and filter aid system can be conventional flocculant.Conventional flocculant is generally the linear cationic or the anionic copolymer of acrylamide.Described keep to add to provide with aluminium compound and association polymer with the additional component of drainage system improve the multicomponent system of keeping with drainage.
Conventional flocculant can be anionic, cationic or non-ionic polymers.The most normal ion monomer is used for preparing copolymer with non-ionic monomer such as acrylamide.These polymer can provide by multiple synthetic method, and wherein said synthetic method includes, but are not limited to suspension polymerization, dispersin polymerization and inverse emulsion polymerization.For last method, can also use microemulsion.
The comonomer of conventional flocculant can exist by arbitrary proportion.The gained copolymer can be nonionic, cationic, anionic or amphoteric (containing CATION and anionic charge).
Other additional component of system of the present invention can also be aluminium source, for example alum (aluminum sulfate), polyaluminium sulfate, aluminium polychloride and aluminum chlorohydrate.
The component of keeping with drainage system can be added in the cellulosic suspension substantially simultaneously.Terminology used here is kept with drainage system and is comprised that two or more different materials that add in paper making pulps keep and drainage to provide improved.For example, can component be added in the cellulosic suspension respectively at same phase or feeding point (dosing point) or in different phase or feeding point.In the component that adds system of the present invention, any two or more described materials can be added as blend.This mixture can be by in the feeding point or in that the original place forms in conjunction with any two or more materials to the feeding line of feeding point.Perhaps, system of the present invention comprises the pre-formation blend of described any two or more materials.In another kind of form of the present invention, add the component of system of the present invention successively.Between the interpolation point of component, can maybe cannot there be shearing point (shear point).Can add component with any order.
Usually system of the present invention is added in the paper technology and keep and drainage with influence.System of the present invention can be added in underflow material or the grout, preferably add in the grout.System can be added at a feed points, perhaps can separately add so that system of the present invention is joined the feed points that two or more separate simultaneously.Typical feed point comprises before the fan pump, after the fan pump and before the pressurized screen or the feed point after the pressurized screen.
Embodiment
In order to estimate performance of the present invention, utilize synthetic alkali batching to carry out a series of drainage test.This batching is by the commercially available pulp lap (market lap pulp) of hardwood and softwood dried and water and other material and prepare.Finish grind the commercially available pulp lap of hardwood and softwood dried at first, respectively.Then the hardwood of these paper pulp with about 70 weight % is combined in water-bearing media with the ratio of the cork of about 30 weight %.The water-bearing media that is used to prepare batching comprises that the mixture of local hard water and deionized water is to reach representative hardness.The addition of inorganic salts should be this medium the CaCO as 75ppm is provided
3Total alkalinity and 100ppm CaCO
3Hardness.With winnofil (PCC) with typical weight than adding in the intermittent pulp proportioning so that the final batching that contains 80% fiber and 20%PCC filler to be provided.Drainage test mixes with specific mixer speed and adds various chemical constituents in the batching and single component mixing special time is carried out with mechanical mixer by prepare burden.Concrete chemical constituent and dosage are described in the tables of data.Drainage activity of the present invention uses Canadian Standard Freeness (CSF) to measure.Can use the CSF tester, a kind of commercially available instrument (Lorentzen﹠amp; Wettre, Stockholm Sweden) measures relative filtration rate, and perhaps dehydration rate also is known in the art; Standard method of test (tappi test program T-227) is a typical method.The CSF instrument is made up of the straining chamber and the speed measurement funnel that all are installed on the suitable holder.Straining chamber is a cylindrical shape, is furnished with perforated screen and hinge plate in the bottom and is furnished with vacuum-packed twisting on top to cover.Described speed measurement funnel is furnished with bottom outlet and side spout hole.
The test of CSF drainage is carried out with 1 liter of batching.The preparation batching is used for carrying out described external treatment by the CSF instrument among square beaker and mixes so that turbulent flow to be provided.After adding additive and mixing order are finished, the batching of handling is poured in the straining chamber, close top lid and open the plate of bottom at once.Make water freely enter the speed measurement funnel; Surpass by the current of bottom outlet decision and will overflow and be collected in the graduated cylinder by side opening.The value that is produced is represented with milliliter filtrate (ml); The drainage or the dehydration of higher numeric representation higher degree.
Table 1 (as follows) is for example understood purposes of the present invention.Sample is by being prepared as follows: in the batching of preparation as mentioned above per metric ton batching (butt) at first add the 5kg cationic starch (Stalok 400, AE., Staley, Decatur, IL).Per metric ton batching (butt) adding 2.5kg alum (derives from Delta ChemicalCorporation then, Baltimore, the 50% Patent alum solution of MD), per metric ton batching (butt) adds 0.25kg PerForm PC8138 cation type polymer (Hercules Incorporated then, Wilmington, De).
In the listed embodiment of table 1, add interested additive as shown in table 1 then.SP9232 is PerForm SP9232, a kind of retention and filter aid association polymer (referring to PCT WO03/050152A), and it is Hercules Incorporated, Wilmington, the product of DE; Polyflex is Polyflex CP.3, and is a kind of by Ciba Specialty Chemicals, Tarrytown, the organic fine particles that NY sells; And silica is NP780, a kind of Eka Chemicals, Marietta, the colloidal silicon dioxide products of GA.
Table 1
| Interested | Add | The CSF freedom | ||||
| Embodiment | Additive (a) | Mode (b) | (ml) | |||
| 1 | Do not have | - | 430 | |||
| 2 | SP9232 | - | 654 | |||
| 3 | Silica | - | 606 | |||
| 4 | Polyflex | 634 | ||||
| 5 | Polyflex/SP9232 | SIM | 677 | |||
| 6 | Polyflex/ silica/SP9232 | SIM | 698 | |||
| 7 | Polyflex/SP9232 | SEQ | 660 | |||
| 8 | Polyflex/ silica/SP9232 | SEQ | 688 |
(a) additive therefor is per metric ton batching 0.25kg.
(b) SIM represents to add simultaneously, and SEQ represents to add successively.
These data representations use independent material to have cooperative effect when using any two kinds or all three kinds of materials relatively.Preferably add simultaneously, also demonstrate than using homogenous material that improvement is arranged though add test for data successively.
Claims (16)
1. method of improving in the paper technology with drainage kept, wherein said improvement comprises association polymer and at least a polymer particle is added in the paper making pulp that wherein said association polymer comprises following formula:
[-B-co-F-] (I)
Wherein B is the non-ionic polymers segment that comprises the unsaturated non-ionic monomer of one or more ethylenic; F is the polymer segment that comprises unsaturated anion of at least a ethylenic or cationic monomer; The molar percentage of B: F is 99: 1-1: 99; And wherein said association polymer has the association performance that the emulsifying surfactant at least that is selected from diblock or three block polymerization surfactants by effective dose provides, and the surfactant of wherein said at least a diblock or three blocks is at least about 3: 10 to the amount of monomer.
2. the method for claim 1, wherein said polymer particle is by comprising that at least a monomer that is selected from following non-ionic monomer forms: acrylamide, Methacrylamide, N, N-dialkyl group acrylamide, N-alkyl acrylamide, N-vinyl methylacetamide, N-vinyl formamide, N-vinyl methylformamide, N-vinyl pyrrolidone, and their mixture.
3. the method for claim 2, wherein said polymer particle is by comprising that also at least a monomer that is selected from the anionic monomer of following free acid or salt forms: acrylic acid; Methacrylic acid; Sodium styrene sulfonate; 2-acrylamido-2-alkyl sulfonic acid, wherein said alkyl contain 1-6 carbon atom; Or their mixture.
4. the method for claim 3, wherein said at least a anionic monomer is selected from the free acid or the salt of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid or its mixture.
5. the method for claim 1, it also comprises material.
6. the method for claim 5, wherein said material be selected from silica-based particles, silica microgel, amorphous silica, cataloid, anionic colloidal silica, silicon dioxide gel, silica dioxide gel, polysilicate, poly-silicic acid with and combination.
7. the process of claim 1 wherein described particulate and association polymer are added in the paper making pulp successively or simultaneously or as blend.
8. the process of claim 1 wherein that described association polymer is an anionic.
9. the process of claim 1 wherein that non-ionic monomer comprises that acrylamide and anionic monomer comprise acrylic acid free acid or salt.
10. the process of claim 1 wherein that described association polymer is cationic.
11. the process of claim 1 wherein that described association polymer comprises anion and cationic monomer.
12. a composition that comprises association polymer and polymer particle, wherein said water solubility copolymer comprises following formula:
[-B-co-F-] (I)
Wherein B is the non-ionic polymers segment that comprises the unsaturated non-ionic monomer of one or more ethylenic; F is the polymer segment that comprises unsaturated anion of at least a ethylenic or cationic monomer; The molar percentage of B: F is 99: 1-1: 99; And wherein said association polymer has the association performance that the emulsifying surfactant at least that is selected from diblock or three block polymerization surfactants by effective dose provides, and wherein said at least a diblock or three block surfactants are at least about 3: 10 to the amount of monomer.
13. the composition of claim 12, it also comprises cellulose fibre.
14. the composition of claim 12, wherein said polymer particle is by comprising that at least a monomer that is selected from following non-ionic monomer forms: acrylamide, Methacrylamide, N, N-dialkyl group acrylamide, N-alkyl acrylamide, N-vinyl methylacetamide, N-vinyl formamide, N-vinyl methylformamide, N-vinyl pyrrolidone, and their mixture.
15. the composition of claim 14, wherein said polymer particle is by comprising that also at least a monomer that is selected from the anionic monomer of following free acid or salt forms: acrylic acid; Methacrylic acid; Sodium styrene sulfonate; 2-acrylamido-2-alkyl sulfonic acid, wherein said alkyl contain 1-6 carbon atom; Or their mixture.
16. the composition of claim 12, it also comprises material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64016704P | 2004-12-29 | 2004-12-29 | |
| US60/640,167 | 2004-12-29 | ||
| US11/313,506 | 2005-12-21 |
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| CNA2005800488372A Pending CN101133211A (en) | 2004-12-29 | 2005-12-22 | Improved retention and drainage in the manufacture of paper |
| CNA2005800488442A Pending CN101142359A (en) | 2004-12-29 | 2005-12-22 | Improved retention and drainage in the manufacture of paper |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2005800488442A Pending CN101142359A (en) | 2004-12-29 | 2005-12-22 | Improved retention and drainage in the manufacture of paper |
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| CN (2) | CN101133211A (en) |
| MX (1) | MX2007007903A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603342A (en) * | 2015-10-12 | 2018-09-28 | 索伦伊斯技术有限合伙公司 | Improve the method and its product of pulp drainage performance in paper product manufacturing process |
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| CA2763508C (en) * | 2009-06-16 | 2018-07-17 | Basf Se | Method for increasing the dry strength of paper, paperboard, and cardboard |
| FI20145063L (en) * | 2014-01-22 | 2015-07-23 | Kemira Oyj | Substance composition for paper production and process for treating fiber pulp |
| CN103865060B (en) * | 2014-03-20 | 2016-06-29 | 江南大学 | The preparation method of a kind of polymeric retention aid retention aid and filter containing phenylboric acid functional group and application thereof |
-
2005
- 2005-12-22 CN CNA2005800488372A patent/CN101133211A/en active Pending
- 2005-12-22 MX MX2007007903A patent/MX2007007903A/en unknown
- 2005-12-22 CN CNA2005800488442A patent/CN101142359A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603342A (en) * | 2015-10-12 | 2018-09-28 | 索伦伊斯技术有限合伙公司 | Improve the method and its product of pulp drainage performance in paper product manufacturing process |
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| Publication number | Publication date |
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| MX2007007903A (en) | 2007-08-20 |
| ZA200706299B (en) | 2008-12-31 |
| CN101142359A (en) | 2008-03-12 |
| ZA200706301B (en) | 2010-04-28 |
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