CN101208478A - 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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- CN101208478A CN101208478A CNA2005800502435A CN200580050243A CN101208478A CN 101208478 A CN101208478 A CN 101208478A CN A2005800502435 A CNA2005800502435 A CN A2005800502435A CN 200580050243 A CN200580050243 A CN 200580050243A CN 101208478 A CN101208478 A CN 101208478A
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Abstract
A method of improving retention and drainage in a papermaking process is disclosed. The method provides for the addition of an associative polymer, prepared by an inverse emulsion polymerization process that utilizes multiple, discrete additions of initiator. Additionally, a process for preparation of an associative polymer, prepared by an inverse emulsion polymerization process that utilizes multiple discrete additions of initiator is disclosed.
Description
The cross reference of related application
The application advocates the rights and interests of No. the 60/693rd, 852, the U.S. Provisional Application submitted on June 24th, 2005, and its full content is combined in this by reference.
Technical field
The present invention relates to the method that adopts flocculation system, make paper and cardboard by cellulosic material.
Background technology
Keep with drainage is the importance of papermaking.Known some material can provide improved and keep and/or the drainage characteristic in the production of paper and cardboard.
The manufacturing of cellulosic fibrous web, particularly paper and cardboard may further comprise the steps: 1) preparation also can contain the cellulose fibre aqueous slurry of inorganic mineral filler or pigment; 2) this slurry is deposited on the mobile papermaking wire-cloth or fabric; With 3) form sheet material by drainage by the solid constituent of slurry.
After above-mentioned steps, carry out the extruding of sheet material and dry further to remove moisture.Before the step that sheet material forms, often organic and inorganic chemicals is added in the slurry, so that papermaking is more economical, faster and/or obtain special nature in final paper product.
Paper industry making great efforts to improve always paper quality, boost productivity and reduce production costs.Adding chemicals to it before the cellulose paste of being everlasting arrives papermaking wire-cloth or fabric keeps to improve drainage/dehydration and solid; These chemicals are called retention agent and/or drainage agent.
In realizing faster paper machine speed, drainage or the dehydration of cellulose paste on papermaking wire-cloth or fabric usually is conditioning step.Improved dehydration also can obtain dried sheet material in press and drying machine parts, thereby reduces energy consumption.In addition, because this is the step of many final performances of decision sheet material in papermaking, so retention agent and/or drainage agent can influence the attribute of performance of the final scraps of paper.
For solid, at drainage and form in the turbulene method process of paper web, Retention Aid in Papermaking is used for increasing solid the keeping at paper web of fine furnish.Do not having enough tiny solids to keep down, they or run off in plant chimney stalk, or in the white water circuit cycle, assemble paramount concentration, thereby may cause sediment pile.In addition, because tendency is adsorbed in the loss of the additive of fiber, the inadequate cost that has increased papermaker of keeping.Additive can be paper opacity, intensity, applying glue (sizing) or other characteristic that needs is provided.
Have or high molecular (MW) water-soluble polymer of cationic charge or anionic charge is often used as retention agent and drainage agent.The effect basis of used polymer or copolymer is by the molecular weight of the arrangement in polymeric matrix of the type of its monomer of forming, monomer, synthetic molecules and preparation method's difference and change.
When the newly-developed of inorganic particles is presented at the combination of itself and high MW water-soluble polymer as retention agent and drainage agent, compares it with common high MW water-soluble polymer and have and better keep and water filtering performance.US 4,294, and 885 and 4,388,150 have instructed the use of starch polymer and colloidal silica.US 4,643, and 801 and 4,750,974 have instructed the use of the cohesion binding agent of cationic starch, colloidal silica and anionic polymer.US 4,753, and 710 have instructed to induce with high MW cationic flocculant flocculating intermittent pulp proportioning, to the batching of flocculation and shear and introduce bentonite to batching then.
The water solubility copolymer that recent findings prepares under certain conditions demonstrates unique physical characteristic.This base polymer is to prepare under the situation of chemical cross-linking agent not having.In addition, described copolymer provides surprising activity in some that comprises that papermaking uses used as retention agent and drainage agent.The anionic copolymer that shows unique property is disclosed in WO 03/050152 A1, and its full content is combined in this by reference.The cation copolymer and the ampholyte copolymer that show unique property are disclosed in U.S. Patent Application Publication 2004/0143039 A1, and its full content is combined in this by reference.
The use of inorganic particulate and acrylamide linear copolymer is as known in the art.Recently patent has been instructed the use of this class inorganic particulate and water-soluble anionic 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 have here and improve the needs of keeping with water filtering performance.
Summary of the invention
A kind of method of keeping with drainage of improving in paper technology is disclosed.This method provides and added improved association polymer in pulp, and the improvement of wherein said polymer provides by discontinuous repeatedly interpolation of radical initiator.
In addition, the method for preparing improved association polymer is disclosed.
In addition, disclose and comprised improved association polymer and other material, and optional further comprise to be used in the improved composition of keeping with the cellulose fibre of drainage is provided in the paper technology.
The specific embodiment
The invention provides the improved water solubility copolymer (being called " association polymer " here) that under certain condition, prepares.Be surprised to find that and in the polymerization technique process, adopt a succession of discontinuous interpolation initator to obtain association polymer (such as the polymer that is disclosed in WO 03/050152 A1 or US 2004/0143039 A1, the full content of its each piece is combined in this by reference), it has improved characteristic as keeping and water filtering performance of strengthening, and has surpassed the association polymer that is disclosed in WO 03/050152 A1 or US 2004/0143039.
For purposes of the present invention, " the discontinuous interpolation of initator " refer to that initator is after the initial aliquot initator of beginning polymerisation adds and be used for reducing those interpolations that the monomer residual content is carried out to the interpolation of feed consumption (burnout) the aliquot initator of commercial permissible level before.The aliquot of feed consumption is to finish in reaction to surpass those that are added after about 95%.
The present invention also provides the new compositions that comprises association polymer and other material.
The present invention also provides the new compositions that comprises association polymer, other material and cellulose fibre.
Also observe when using association polymer influential to the performance of other additive in the paper manufacturing systems as retention agent and drainage agent.Improved keep and/or drainage can have directly and indirect two kinds of influences.Directly influence is meant that retention agent and drainage agent work to keep additive.No matter remote-effects refer to it is by physical method or chemical method, filler and the attritive powder effect to the appended additive is kept in retention agent and drainage agent.Therefore, by increasing the filler kept in the described sheet material or the amount of attritive powder, it has increased the amount of the additive of keeping in the mode of following.The term filler refers to add in the cellulose pulp slurry certain attribute to be provided or to become the particulate material of the low-cost substitute of part cellulose fibre, is generally the natural inorganic thing.They can not be attracted on the crude fibre it in the micron-sized relatively little size of 0.2-10, low length-width ratio and chemical characteristic, and little as to be not enough to be captured in the network of fibers of the scraps of paper.Term attritive powder (fines) refers to little cellulose fibre or fibrillation, and typically length is less than 0.2mm and/or can pass 200 purpose sieves.
By the use of retention agent and drainage agent, increased the amount of the additive of keeping in the described sheet material, the influence of additive increases.The enhancing that this provides performance makes sheet material have the augmented performance attribute, or the amount that makes papermaker can reduce to add to the additive in the system, has reduced the cost of product.In addition, these materials used recirculated water or amount in the white water in paper manufacturing systems reduced.This content that do not need to be considered to impurity under certain conditions reduces can provide more effective papermaking process, or is reduced to that control does not need the content of material and the scavenger that adds or the needs of other material.
Above-mentioned used term additive refers to add material in the paper pulp to for the efficient that paper provides specific properties and/or improves papermaking process.This class material includes but not limited to sizing agent, wet-strength resins, dry strength resin, starch and starch derivatives, dyestuff, Control of Impurities agent, antifoaming agent and biocide.
As what habitually practise in this area, the polymerization of reversed-phase emulsion adopts one of initator of several types to cause.Usually, add initator and reaction and carry out a few hours, and often accompany by heat release.The initator of this single introducing induces reaction, and reaction proceeds to all free radicals always and is consumed.At the halt of reaction, most of monomer (greater than 95%) is attached in the polymer.Yet residual monomer can exist based on the content of molar weight several ten thousand ppm.The second aliquot initator that adds common more volume is with the remaining residual monomer of polymerization, and it often is called feed consumption.This step produces the material of lower molecular weight.Can add extra aliquot to reduce content of monomer to the content based on the hundreds of ppm of molar weight, this also is regarded as feed consumption.
Method is included in and adds most of initator in the polymerization process continuously alternatively, adds the mixture of monomer and initator after the polymerization of initial reactor charging for the second time, and the mixture that adds initator and particular polymeric conditioning agent.
Method of the present invention is different from the standard convention part and is, discontinuous aliquot initator adds at the batch (-type) of reaction initial period.For order of the present invention, initiator mixture is added in the polyblend under the situation without any other material.Described initiator mixture is the mixture of initator and carrier solvent.Do not have other monomer to add, or after polymerization is initiated, just do not add other monomer with initator.For example, polymerisation typical or standard can comprise that initial aliquot initator adds, and with afterreaction 4 hours, and does not add other initator in this course of reaction of 4 hours, reacts greater than 90% monomer therebetween.Usually after this 4 hour reaction time, when reacting completely (reaction) when thinking, final aliquot initator is added in the reactant mixture to exhaust residual monomer greater than 95%.Can in the reaction time before any feed consumption aliquot, add the aliquot initator more than once among the present invention.These are the discontinuous interpolations that finally exhaust that do not relate to monomer.For example, add first aliquot and begin polymerization, can add the second aliquot initator after 1 hour, can add the initator of C grade portions after 2 hours.The step of invention is: in initial two hours course of reaction, use up to 5 times, preferred up to 3 times and more preferably 2 extra aliquot initators, produce new free radical when in batch of material, still having obvious monomer, thus guarantee most of monomer reaction form use in available high molecular weight products.
In one embodiment of the invention, add initial aliquot initator with the beginning polymerisation.Preferably to finish about 1%-about 90% the time when polymerisation, carries out the discontinuous interpolation of one or many of initator.To finish about 5%-about 90% the time when polymerisation, carries out the discontinuous interpolation of one or many of initator.To finish about 5%-about 80% the time when polymerisation, carries out the discontinuous interpolation of one or many of initator.To finish about 5%-about 60% the time when polymerisation, carries out the discontinuous interpolation of one or many of initator.To finish about 10%-about 60% the time when polymerisation, carries out the discontinuous interpolation of one or many of initator." finish percentage " and refer to be attached to the percentage of the initial monomer in the polymer chain.When during reaction finishing, can add the initator of other five equilibrium with reaction.
In one embodiment of the invention, add the initator of initial five equilibrium with the beginning polymerisation.To finish about 5%-about 50% the time when polymerisation, adds in the reactant mixture initator is discontinuous, finished about 15%-at about 60% o'clock in reaction, and discontinuous five equilibrium initator is added reactant mixture.When during reaction finishing, can add the initator of other discontinuous interpolation with reaction.
In another embodiment of the invention, add initial initiator with the beginning polymerisation.To finish about 30%-about 75% the time when polymerisation, and the initator of second five equilibrium is added in the reactant mixture, finished about 50%-at about 90% o'clock in reaction, and the initator that C grade is divided adds in the reactant mixture.When during reaction finishing, can add the initator of extra five equilibrium with reaction.
In another embodiment of the invention, in the process of reaction, except that the initial aliquot of beginning polymerisation, can there be as many as 5 times or more times different five equilibrium initator to be added in the reactant mixture.After the initial aliquot that begins to react, can add few initator to 1 time or more, preferred few extra five equilibrium to 2 times to reactant mixture.In the process of reaction, except that the initial aliquot of beginning polymerisation, can there be the initator of different five equilibriums to add in the reactant mixture up to 6 times.
The repeatedly discontinuous interpolation of radical initiator has tangible influence to the polymer properties characteristic.For purposes of the present invention, term " the discontinuous interpolation of initator " does not comprise the initial interpolation that is used to cause initiator of polyreaction, does not comprise the interpolation of branch initators such as feed consumption yet.Initator is influential to the relative concentration that free radical forms speed and/or free radical.Be not bound by any theory, think that molal weight, copolymer that this conversely can impact polymer form and other physical attribute.In addition, the reactivity that free radical forms the relative concentration of speed, free radical and/or initator can influence the amount of used initator, molal weight and other physical attribute that this conversely again can impact polymer.
The preferred thermal initiator that uses.Thermal initiator is to decompose under the initator characteristic temperature, and formation can cause ethylenically unsaturated monomers, also be known as the free radical material group of vinyl, allyl or acrylic monomer polymerization.These materials are initators the most universal in the commercial Application.Thermal initiator includes but not limited to peroxide, persulfate and azo-compound.Exemplary peroxide includes but not limited to benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide or the like and their mixture.Exemplary persulfate includes but not limited to ammonium persulfate, potassium peroxydisulfate and their mixture or the like.Exemplary azo-compound includes but not limited to 2,2-azo two (2-methyl propionitrile), and it also is generally called azodiisobutyronitrile or AIBN; 4,4 '-azo two (cyanopentanoic acid); 1,1 '-azo two (cyclohexanenitriles) and their mixture or the like.
For purposes of the present invention, selected initator can be a kind of initator, perhaps can be the combination of two or more thermal initiators.
Association polymer by the inventive method preparation can be described below:
The composition that contains the water solubility copolymer of following formula:
-[B-co-F]- (I)
The B non-ionic polymers segment that the unsaturated non-ionic monomer polymerization of one or more ethylenic forms of serving as reasons wherein; F anion, CATION or anion and the CATION combination of polymers segment that the unsaturated anion of one or more ethylenic and/or cationic monomer polymerization form of serving as reasons; The molar percentage of B: F is 95: 5-5: 95; And described water solubility copolymer prepares through the water-in-oil emulsion polymerization technique, this technology adopts at least a emulsifying surfactant of being made up of at least a two blocks or three block nonionic polymeric surfactants, wherein at least a two blocks or three block surfactants are at least about 3: 100 with the ratio of monomer, and wherein the water-in-oil emulsion polymerization technique comprises the steps: (a) preparation monomer solution, (b) described monomer solution is contacted with the hydrocarbon liquid that contains surfactant or surfactant mixture and form reversed-phase emulsion, (c) at the about 2-of pH less than 7 times, use specific initiator to make the monomer in the emulsion carry out polymerization through the mode of radical polymerization.
In an advantageous embodiment of the present invention, described initator is a thermal initiator.
Association polymer can be anionic copolymer.Described anionic copolymer is characterised in that this copolymer is that its Huggins constant (k ') of measuring under the 0.0025 weight %-0.025 weight % is greater than 0.75 in 0.01M NaCl, in concentration; And for 1.5 weight % active copolymer its storage moduluss of solution (G ') is greater than 75Pa under 6.3Hz.In one embodiment of the invention, the described storage modulus (G ') for 1.5 weight % active copolymer solution is 75Pa-170Pa under 6.3Hz.
Association polymer can be cationic copolymer.Described cation copolymer is characterised in that its Huggins constant (k ') that this copolymer is measured is greater than 0.5 in 0.01M NaCl, under 0.0025 weight %-0.025 weight %; And for 1.5 weight % active copolymer its storage moduluss of solution (G ') is greater than 30Pa under 6.3Hz.
Association polymer can be an ampholyte copolymer.Described ampholyte copolymer is characterised in that its Huggins constant (k ') that this copolymer measures for greater than 0.5 in 0.01M NaCl, under 0.0025 weight %-0.025 weight %, and is greater than 30Pa under 6.3Hz for 1.5 weight % active copolymer its storage moduluss of solution (G ').
Inverse emulsion polymerization is the standard chemical process that is used to prepare molecular weight water-soluble polymers or copolymer.Generally speaking, reversed emulsion polymerization is undertaken by following steps: 1) preparation monomer solution, 2) the described aqueous solution is contacted with the hydrocarbon liquid that contains suitable emulsifying surfactant or surfactant mixture and form anti-phase monomer emulsions, 3) make monomer emulsions carry out radical polymerization, and, randomly 4) add demulsifier surfactant to strengthen the anti-phase conversion of emulsion in adding entry the time.
Inverse emulsion polymer is typical water-soluble polymer based on ion monomer or non-ionic monomer.The polymer that contain two or more monomers, is also referred to as copolymer can be prepared by same method.This class comonomer can be anionic, cationic, zwitterionic, non-ionic or its combination.
Typical non-ionic monomer, include but not limited to: acrylamide, Methacrylamide, N-alkyl acrylamide 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, vinylacetate, N-vinyl pyrrolidone, hydroxyalkyl (methyl) acrylate such as ethoxy (methyl) acrylate or hydroxypropyl (methyl) acrylate, above-mentioned any mixture or the like.
Exemplary anionic monomer includes but not limited to following free acid and salt: acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamido glycolic 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 or the like.
Exemplary cationic monomer includes but not limited to the CATION ethylenically unsaturated monomers, as following free alkali or salt: poly (dially dialkyl) ammonium chloride such as diallyldimethylammonium chloride; (methyl) acrylate of dialkyl aminoalkyl compound is such as dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate, dimethylaminopropyl (methyl) acrylate, 2-hydroxyl dimethylaminopropyl (methyl) acrylate, aminoethyl (methyl) acrylate and salt and its quaternary ammonium salt; N, N-dialkyl aminoalkyl (methyl) acrylamide, such as N, N-dimethyl aminoethyl acrylamide, and salt and its quaternary ammonium salt and above-mentioned mixture or the like.
Comonomer can exist by arbitrary proportion.The association polymer that obtains can be nonionic, cationic, anionic or both sexes (containing two kinds of electric charges of CATION and anion).
Association polymer can be an anionic copolymer, the mol ratio of non-ionic monomer and the anionic monomer (B of formula 1: F) 95: 5-5: in 95, be preferably about 75: about 25: 75 of 25-, more preferably about 65: about 35: 65 of 35-, most preferably from about 60: about 40: 60 of 40-.Thus, the mole percent of B and F must add up to 100%.Should be understood to exist more than a kind of non-ionic monomer in the formula 1.Should be understood to equally can exist more than a kind of anionic monomer in the formula 1.
In a preferred embodiment of the invention, the association polymer that is defined by formula 1 is an anionic copolymer, and wherein non-ionic polymer segment B is the repetitive that forms behind the acrylamide polymerization; Anionic polymer segment F is 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-.
The unique distinction of the physical characteristic of the association polymer when it is anionic copolymer is, its Huggins constant (k ') of measuring in 0.01M NaCl is greater than 0.75, and its storage modulus (G ') for 1.5 weight % living polymer solution is greater than 75Pa under 6.3Hz, be preferably greater than 90Pa, even more preferably greater than 105Pa.Described Huggins constant is greater than 0.75, is preferably greater than 0.9, even more preferably greater than 1.0.
Association polymer can be a cation copolymer, the mol ratio of non-ionic monomer and the cationic monomer (B of formula 1: can be 99 F): 1-50: 50, or 95: 5-50: 50, or 95: 5-75: 25, or 90: 10-60: 45, preferred about 85: about 60: 40 of 15-, even more preferably from about 80: about 50: 50 of 20-.Thus, the mole percent of B and F must add up to 100%.Should be understood to exist more than a kind of non-ionic monomer in the formula 1.Should be understood to equally can exist more than a kind of cationic monomer in the formula 1.
Association polymer can be the ampholyte copolymer of formula 1, and the minimum mole percent of each anion, CATION and non-ionic monomer is to form 1% of the used monomer total amount of copolymer.The maximum of nonionic, anion or cationic monomer is to form 98% of the used monomer total amount of copolymer.The preferred minimum of anion, CATION and non-ionic monomer arbitrarily is to form 5% of the used monomer total amount of copolymer, more preferably the described minimum of anion, CATION and non-ionic monomer is 7% arbitrarily, even the described minimum of more preferably any anion, CATION and non-ionic monomer is 10%.Thus, the mole percent of anion, CATION and non-ionic monomer must add up to 100%.Be to be understood that to exist in the formula 1, can exist more than a kind of cationic monomer in the formula 1, and can exist more than a kind of anionic monomer in the formula 1 more than a kind of non-ionic monomer.
When it was CATION or ampholyte copolymer, the unique distinction of the physical characteristic of association polymer was when its Huggins constant (k ') is measured to be greater than 0.5 in 0.01M NaCl.The storage modulus (G ') of expection its 1.5 weight % living polymer solution for CATION or ampholyte copolymer is greater than 30Pa under 6.3Hz, is preferably greater than 50Pa.Huggins constant is greater than 0.5, is preferably greater than 0.6, 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 can have significant effects to manufacturing technique and synthetic product.The surfactant that is used in the emulsion polymerization systems is well known by persons skilled in the art.This class surfactant typically has the value scope of the HLB (hydrophilic lipophilic balance) based on total composition.Can use one or more emulsifying surfactants.The emulsifying surfactant that is used to prepare the polymerization product of described association polymer comprises the surfactant of at least a two blocks or three block polymerizations.Known these surfactants are emulsion stabilizers efficiently.Selecting with quantity of emulsifying surfactant selected, so that produce the anti-phase monomer emulsions that polymerization is used.
The emulsifying surfactant of two blocks and three block polymerizations is used to provide the material of uniqueness.When the emulsifying surfactant of two blocks that adopt necessary amounts and three block polymerizations, obtain demonstrating the particular polymer of unique property, described in WO 03/050152 A1 and US 2004/0143039 A1, the full content of its each piece is combined in this by reference.The surfactant of exemplary two blocks and three block polymerizations comprises but is not limited to two blocks and triblock copolymer based on the polyester derivatives of aliphatic acid and poly-(oxirane), such as Uniqema, and New Castle, the product Hypermer B246SF of DE; Two blocks and triblock copolymer based on polyisobutylene succinic anhydride and poly-(oxirane); The product of oxirane and expoxy propane and ethylenediamine; Above-mentioned any mixture or the like.Preferred two blocks and triblock copolymer are the polyester derivatives based on aliphatic acid and poly-(oxirane).When adopting three block surfactants, preferred described three blocks comprise two hydrophobic regions and a hydrophilic area, that is, and and hydrophobic body-hydrophilic body-hydrophobic body.Preferably select one or more surfactants so that obtain special HLB value.
The amount of two blocks or three block surfactants (based on weight %) depends on the amount that forms the used monomer of association polymer.Two blocks or three block surfactants are at least about 3: 100 with the ratio of monomer.Two blocks or three block surfactants can be greater than 3: 100 to the amount of monomer, preferably at least about 4: 100, and more preferably 5: 100, even more preferably from about 6: 100.Two blocks or three block surfactants are the first-selected surfactant of emulsification system.
Can add second emulsifying surfactant processing and processing are become easily,, or change emulsion viscosity with the improvement stability of emulsion.The example of second emulsifying surfactant includes but not limited to that sorbitan fatty ester is such as dehydrating sorbitol monooleate, such as Uniqema, New Castle, the product A tlas G-946 of DE), the sorbitan fatty ester of ethoxylation, the sorbitan fatty ester of polyethoxylated, the oxirane of alkyl phenol and/or propylene oxide adduct, the oxirane of long-chain alcohol or aliphatic acid and/or propylene oxide adduct, the ethylene oxide/propylene oxide block copolymer that mixes, alkanolamide, sulfosuccinate, and their mixture or the like.
The polymerization of reversed-phase emulsion can be carried out by any-mode well known by persons skilled in the art.Example is found in Allcock and the Lampe in other list of references, Contemporary Polymer Chemistry, (Englewood Cliffs, New Jersey, PRENTICE-HALL, 1981), 3-5 chapter.
Association polymer dilutes in application places usually, to obtain the aqueous solution of 0.1-1% active copolymer.Then the weak solution of this association polymer is added in the paper technology, exert an influence keeping with drainage.Association polymer can be added in underflow or the thin pulp to preferred thin pulp.Associative polymer copolymer can be added at a feed points, maybe can separate charging, makes association polymer simultaneously in the feed points charging of two or more separation.Before typical raw material adds point and is included in fan pump, behind the fan pump and the feed points before pressurized screen or behind the pressurized screen.
Association polymer of the present invention can add the flocculation that needing to realize level with effective dose.The consumption of preferred association polymer is at least about the about 0.5Kg active copolymer of 0.03-/metric ton cellulose pulp based on the paper pulp dry weight.The amount of used copolymer can be greater than the 1.0Kg/ metric ton among the application.The concentration of copolymer is preferably the cellulose pulp that the about 0.5Kg active copolymer of about 0.05-/metric ton is done.More preferably the addition of copolymer is the dried cellulose pulp of about 0.05-0.4kg/ metric ton, and most preferably from about the about 0.3Kg/ metric ton of 0.1-is based on the dry weight of cellulose pulp.
Association polymer of the present invention can with one or more other or second component use.Described other or second component can be selected from several materials.
Siliceous material can be used as second or other component.Siliceous material can be the material that is selected from arbitrarily in following group: based on the particle of silica, silica microgel, amorphous silica, colloidal silica, anion colloidal silica, Ludox, silicon gel, polysilicate, poly-silicic acid or the like.These materials be characterized as high surface, high charge density and submicron particle size.
This group material comprises the stable aqueous colloidal dispersion of spherical amorphous silica particles, and this area is called Ludox.Term colloidal sol refers to the stable colloid dispersion of spherical amorphous particle.The silicon gel is the aggregation chain of the silica of three-dimensional, its each self-contained several amorphous silicon sol particleses that also can be used in retention agent and the drainage agent system; The aggregation chain can be linear or branching.Ludox and the silicon gel silicic acid polymerization by the making monomer structure discrete amorphous silicon colloidal sol that produces poly-silicic acid circlewise prepares.These Ludox can further react and produce three-dimensional gel network.The whole dimension of various silicon dioxide granules (colloidal sol, gel, or the like) can be 5-50nm.Also can adopt the anion colloidal silica.
The inorganic particulate of the another kind of type of using is a clay.The term clay is applicable to the mineral of the phyllosilicate of the subclass that is considered to silicate in a large number.Therefore, clay comprises chlorite, illite, kaolin, imvite, reaches terre verte.
The term bentonite is applicable to the material group of the aggregation of two or more mineral usually in this area.The natural existence of these mineral aggregations is although can carry out the processing of chemistry and/or physical method with modification to these materials.Because itself and water mutual effect, an important component is a smectite clay mineral.Smectite minerals is long, the uniform thickness＜1nm of 300nm at the most, and by oxygen, silica and be generally aluminium and/or three-dimensional particle that the metal ion of magnesium is formed.Before keep with the drainage commercial Application in the most frequently used clay bentonite be imvite.Typically, imvite is the terre verte that is used to make colloid bentonite particulate.Imvite has dioctahedron structure and strong negative electrical charge in water.High just anionic charge, the electric double layer in the solution, and little particle size and make imvite be colloidal particle.
Any inorganic particulate be can use, aluminium hydroxide and perlite included but not limited to.
Keep that optionally other or second component can be organic little polymer or microballon with screening system.Organic little polymer is a material crosslinked, ion, organic polymer.They are copolymers of non-ionic monomer, ion monomer and crosslinking agent.In addition, ion monomer can be anionic or cationic.The use of anion and cationic monomer obtains amphiprotic substance.Little polymer normally forms with two polymerization of unsaturated monomers by being that anionic, cationic or non-ionic ethylenic list is unsaturated.Inverse emulsion polymerization typically is used to prepare these materials.An example of little polymer is Polyflex CP.3. (Ciba Specialty Chemicals, Tarrytown, New York).
Keep with screening system another optional second or other component can be one of different kinds of ions polymeric material or polyelectrolyte.These materials often are called coagulating agent or flocculant, thickener, wet-strength resins, dry strength resin, reach the rheology control additive by those skilled in the art.Expect that the dispersible polyelectrolyte of any water soluble or water can use with described association polymer.Described material can be the blend composition of single product or material.These materials are can be on their chemical characteristic different, chemical characteristic then be subjected to monomer compositions, ionic functional degree characteristic, ionic functional number of degrees amount, ionic functional degree along the distribution of polymer chain and polymer physics characteristic such as molecular weight, charge density, reach the influence of secondary/tertiary structure.
Keep with screening system another optional second or other component can be one of several aluminium compounds.Particularly preferably be alum (aluminum sulfate).
Aluminium compound include but not limited to aluminium chloride, aluminum chlorohydrate (aluminum chlorohydrate) (ACH), poly aluminium sulfate silicate (PASS) and aluminium polychloride (PAC).PAC is the title that the compound of the poly-polymeric aluminum chloride with following general formula is given:
Al
n(OH)
mCl
3n-m
The simplest PAC is the dimer with following chemical formula:
Al
n(OH)
2(H
2O)
8 +
And the general formula of generally acknowledging for polymer is:
[AlO
4Al
12(OH)
24(H
2O)
12]
+7
Keep with screening system another optionally other component be polyvinylamine, its typical case is by the polymerization of N-vinyl formamide, forms the copolymer that amine produces with posthydrolysis.Described material can adopt the condition of acidity or alkalescence to be hydrolyzed; Preferred alkalescence.Hydrolysis degree and the charge density that obtains can be reacted by control hydrolysis and be changed.Polyvinylamine can and comprise that also above-listed those copolymerization of copolymerization monomer prepares by vinyl formamide.Can use the synthetic route of other polyvinylamine.
And keep with screening system another optional second or other component be starch and derivative thereof.Starch is the common name that contains the glucose polymer of α-1,4 key.Starch is naturally occurring material; This carbohydrate can find in leaf, stem, root and the fruit of most of terrestrial plants.The industrial source of starch includes but not limited to seed and some root (potato, cassava or the like) of cereal (corn, wheat, rice, or the like).Starch is described according to its plant origin; Reference example such as cornstarch, farina, tapioca, rice starch and wheaten starch.
Glucose by carbon, hydrogen and oxygen with 6: 10: 5 (C
6H
10O
5) ratio form, belong to carbon water organic compound class.Starch can be regarded as the condensation polymer of glucose.
Majority starch is made up of the mixture of two kinds of polysaccharide types: be the amylose of linear polymer and the amylopectin of highly branched polymer basically.The relative quantity of amylose and amylopectin is different with the source, the ratio of amylose and amylopectin typically is cassava 17: 83, potato 21: 79, corn 28: 72 and wax yellow corn 0: 100.Though these are typical starch proportions of finding, the present invention wishes that the amylose of any ratio and amylopectin all can be used among the present invention.
Amylose is the linear polymer of forming by by the interconnective glucose unit chain of α-1,4 key.Molecular weight can be about 30, and 000-about 1,000,000.
Amylopectin is the short amylose chain of the about 2000-of the molecular weight of highly branched structure about 10,000, is connected to form very complicated, the polymer of high molecular (10,000,000-100,000,000) very via α-1,6 key.
Starch is synthesized by plant and assembles with the particulate that every kind of plant has nothing in common with each other.The starch particulate separates from plant with grinding (grinding) step by mill (milling).Described particulate is insoluble to cold water and must be heated to above critical-temperature so that particulate swelling and breaking, thereby makes polymer dissolution in solution.
Can carry out modification so that the special performances value to be provided in selected application to starch.This comprises one of the physics of material and chemical constitution or both modifications.Physical modification comprises the most frequent reduction molecular weight of finishing by hydrolysis.So-called starch of deriving of the material of modification or starch derivatives like this.
Chemical modification includes but not limited to obtain the reaction of oxidized starch, such as by reacting with hypochlorite; Form the reaction of crosslinked starch, such as passing through to adopt crosslinking agent such as chloropropylene oxide, sodium trimetaphosphate, isocyanates or N, the reaction of N-methylene-bisacrylamide; Form the reaction of starch ester, such as by with the reaction of acetic acid or succinyl oxide; Form the reaction of hydroxyalkyl starch, such as by with the reaction of oxirane or expoxy propane; Form the reaction of phosphate monoester, such as by with the reaction of sodium phosphate trimer; Form the reaction of cationic starch, such as by with the reaction of diethylamino chloroethanes, tertiary amine and chloropropylene oxide or ethylenediamine; Form the reaction of dialdehyde starch, such as passing through acid oxidase or starch xanthate or the like.Be in purpose of the present invention, the starch of the chemical modification of expectation any type should be available.
Optionally other or second component often are but needn't necessarily be called the inorganic material of mineral with another of screening system and keep.These materials include but not limited to clay, calcium carbonate, talcum, titanium dioxide, diatomite, calcium sulfate, zinc oxide and zeolite.These materials are found in nature or synthetic via chemical method.In addition, described material can carry out modification via the processing of chemistry or physics; Can carry out chemistry and two kinds of processing of physics to these materials, or successively or simultaneously.Calcium carbonate can be grind or the precipitation.
Zeolite is the crystalline solid with micropore of fine fixed structure.They comprise silicon atom, aluminium atom and oxygen atom usually.Zeolite can be natural, synthetic or modification.
Optionally other or second component can be the polymer of another water compatible with another of screening system and keep." water compatible " be meant polymer can be water miscible or water-swellable or water dispersible.
The water miscible polymer that is used to refer to of term is dissolved in the solvent, and does not remain visual solid matter in the described solvent.The free energy that be dissolved in mixing of polymer in solvent takes place when being negative.The example of water-soluble substances includes but not limited to the natural materials or the synthetic of exudate or natural gum, extract, natural materials, modification.An example of exudate or natural gum is a gum tragacanth.An example of extract is a pectin.An example of natural materials is a guar gum.An example of modified natural material is the cellulose such as the methylcellulose of deriving.An example of synthetic is a polyacrylic acid.Synthetic polymer can be formed by being used to supply with selected one or more monomers of final polymer special nature.
The water-swellable polymer is that those can suck aqueous solvent and swell to a certain degree polymer.This swelling behavior is subjected to the influence of many factors, includes but not limited to crosslinked.Therefore, the interaction between polymer and the solvent is limited, though what obtain is visual homogeneous solution, can not obtain uniform molecular dispersoid.Example has crosslinked polymer, and the acrylate copolymer and the copolymer that are used as absorbent or high absorbent in this area are concrete examples.They can be the dispersible with water of water compatible.
The water compatible material is that those can not be dissolved in the water, the but material of not phase-splitting.Typically, these materials have can make its modified surface that remains the discrete particle material that is suspended in the water, maybe can become dispersibility by adding other material.Example comprises latex particle, emulsion oil-in-water and the clay or the pigment that disperse.
Keep with screening system another optional second or other component can be slaine, include but not limited to following salt: magnesium, calcium, barium, iron, cobalt, nickel, copper, zinc, aluminium and silicon.Form each other by the CATION in the structural arrangement of maximum shielding and anion by obtaining two kinds of interionic minimum ranges and identical charges for simple salt.The slaine of being given can be soluble or insoluble according to its composition.Solubility in water-bearing media can be subjected to the influence of other material of temperature, pH and existence.The preferred salt that uses solubility.
Soluble material can interact with other ionic material in the solution, thereby changes characteristic and activity in its concrete application.These species can be regulated the activity of another material with multiple mode, include but not limited to build bridge and neutralization.These species can influence polyelectrolyte especially significantly, because the existence of salt ion can the structure of appreciable impact polymer in solution and its charge density.An example of the modification of soluble-salt is to produce soluble metal silicate, as US 6,379, and 501 and 6,358, described in 365.These patents have instructed univalent cation silicate and bivalent metal ion to mix in water environment to form the compound of water-soluble metal silicate.Described compound comprises at least a aluminium compound and at least a water-soluble silicate.Water-soluble silicate can be the silicate or the water-soluble metal silicate composite of univalent cation.The water-soluble metal silicate composite can be the product of univalent cation silicate and bivalent metal ion.Aluminium compound and water-soluble silicate are based on Al
2O
3And SiO
2Mol ratio be about 0.1-10, preferably about 0.2-5 and 0.5-2 more preferably from about.
The example of available slaine includes but not limited to metal silicate, frerrous chloride (II), anhydrous FeCl among the present invention
3, ZnSO
44H
2O, MgCl
2And combination.
Keep that optionally other or second component are the ring-type organic matters with another of screening system.A unique aspect of these materials is the ability of itself and other typical low-molecular-weight molecule or ion forming complex.This class interacts and is called as " host-guest " chemistry, and wherein the annular material of main body and the less position of guest molecule supposition in ring-type " main body " form complex compound.The examples for compounds that this class is also referred to as macrocyclic compound includes but not limited to crown ether, cyclodextrin and macrocyclic antibiotic.
Crown ether is the cyclic oligomer that comprises the ethylene glycol of carbon, hydrogen and oxygen.Two carbon atoms of each oxygen atom bonding obtain the ring of " hat " shape.This quasi-molecule makes the atomic ratio of certain metallic element such as sodium and potassium oneself to be attached on the oxygen atom that exposes in the ring, makes its chelating.Because its chemistry and ring size, these materials have high selectivity to particular molecule.
Cyclodextrin is that natural existence maybe can adopt enzyme such as the synthetic cyclic starch derivative of cyclodextrin glycosyltransferase.Naturally occurring cyclodextrin refer to α-, β-and gamma-cyclodextrin.Cyclodextrin and other compound form stable complex compound.
Macrocyclic antibiotic is the term that a series of cyclic compounds with antibiosis activity are provided.Because its structure, the complexing of they and molecular selectivity.Exemplary macrocyclic antibiotic includes but not limited to rifamycin, vancomycin and ristocetin A.
Keep that optionally other or second component can be based on one of several materials of siloxanes with another of screening system.An example is a silicone oil, and this term originally was applicable to the dimethyl silicone polymer of clear fluid.Other analog includes but not limited to gather (phenyl methyl siloxanes) and poly-(tetramethyl tetraphenyl siloxanes).
Keep the bridging agent that is based on metal such as aluminium, titanium or zirconium with another optional second component of screening system.These materials are by working with the reaction of other material, and can interact in the multi-section position and form bridge between the polymer chain; Bridge formation can pass through hydroxyl, amino, acylamino-, carboxyl or sulfenyl to be taken place.This class is built bridge to react and be can be used for viscosity Control and surface modification.Organic titanate and zirconate are used to strengthen in coating, printing seal China ink and the adhesive.
Titanate esters and zirconate are examples of these materials, and wherein the tetraalkyl ester is the most frequently used.The alkyl that is suitable for organic titanate and organic zirconium acid esters includes but not limited to isopropyl, butyl and ethylhexyl.
Organic sequestering agent also can be used as bridging agent.Described chelating agent can comprise acetylacetonate, ethyl acetoacetate, lactate, ethyl glycolate and triethanolamine derivative.Exemplary material have with the Tyzor trade name sell (DuPont, Wilmington, DE).
Also can use zirconium carbonate, wherein zirconium carbonate ammonium is the most frequently used.Zirconium carbonate ammonium is as bridging agent and insolubilizer (insolubilizer) in the paper industry.
The addition of keeping with other or second component of screening system can be up to the cellulose pulp of 0.5kg active matter/metric ton based on the paper pulp dry weight, and association polymer is 1 with the ratio of other or second component: 1-100: 1.Hope can be added in paper manufacturing systems more than a kind of other or second component.
Randomly, above-described silicon-containing material can as follow in paper and the cardboard manufacturing another second or other or the 3rd component of the retention agent of other component and drainage agent.Silicon-containing material can be the arbitrary substance that is selected from following group: based on the particle of silica, silica microgel, amorphous silica, colloidal silica, anion colloidal silica, Ludox, silicon gel, polysilicate, poly-silicic acid etc.These materials be characterized as high surface, high charge density and submicron particle size.
This thing group comprises the aqueous colloidal dispersion that spherical amorphous silica particles is stable, and this area is referred to as Ludox.Term colloidal sol refers to the stable colloid dispersion of spherical amorphous particle.The silicon gel is a three dimensional silica aggregate body chain, its each self-contained several amorphous silicon sol particleses that also can be used in retention agent and the drainage agent system; Described chain can be linearity or branching.The circulus that Ludox and the gel silicic acid by polymerization single polymerization monomer becomes the discrete amorphous silicon colloidal sol that produces poly-silicic acid prepares.These Ludox can further react and produce three-dimensional gel network.The whole dimension of various silicon dioxide granules (colloidal sol, gel, or the like) is 5-50nm.Also can adopt anion silica gel.
As the 3rd or the silicon-containing material of other component can add in the cellulose suspension based on the amount of cellulose suspension dry weight with 0.005Kg/ metric ton at least.The amount of silicon-containing material can be up to the 50Kg/ metric ton.The amount of preferred silicon-containing material is the about 25Kg/ metric ton of about 0.05-.Even more preferably the amount of silicon-containing material is the dry weight of the about 5Kg/ metric ton of about 0.25-based on cellulose suspension.
Randomly, other component of retention agent and drainage agent system can be conventional flocculant.This can be the 3rd or the 4th component.Conventional flocculant generally is the linear CATION or the anionic copolymer of acrylamide.Other component of retention agent and drainage agent system is added together with aluminium compound and association polymer, improves the multicomponent system of keeping with drainage to provide.
Conventional flocculant can be anion, CATION or non-ionic polymers.Ion monomer is the most frequent to be used to make copolymer with non-ionic monomer such as acrylamide.These polymer can be provided by various synthetic methods, and described method includes but not limited to suspension, dispersion and inverse emulsion polymerization.For last method, also can use microemulsion.
The comonomer of conventional flocculant can exist with arbitrary proportion.The copolymer that obtains can be nonionic, cationic, anionic or both sexes (containing CATION and anionic charge).
And can be that other component of part system of the present invention is the aluminium source, such as alum (aluminum sulfate), polyaluminium sulfate, aluminium polychloride and aluminum chlorohydrate.This material can be regarded as the 3rd, the 4th or the 5th component of system.
Keep with the component of screening system and can add in the cellulose suspension simultaneously basically.Terminology used here is kept and is comprised adding to be used to provide in the paper making pulp with screening system and improve two or more the different materials keep with drainage.For example, can add component to cellulose suspension respectively, no matter at same stage or stoichiometric point, still at different phase or stoichiometric point.When the component of system of the present invention was added simultaneously, two or more materials can add by mixture arbitrarily.By mixing described material, can form mixture on the spot at stoichiometric point or in the feeding line of stoichiometric point.System perhaps of the present invention comprises the pre-mixture of described material.In optional mode of the present invention, the component of system of the present invention is added successively.Shearing point can be in or be not between the interpolation point of component.Described component can be added in random order.
Typically 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 or the thin pulp, preferred thin pulp.Described system can be added at a feed points, maybe can separate charging, makes the invention system to add at the feed points of two or more separation the while.Before typical raw materials point is included in fan pump, behind the fan pump and the feed points before pressurized screen or behind the pressurized screen.
Associativity copolymer of the present invention provides improved and has kept and the drainage characteristic, surpasses the discontinuous similar polymer that makes that repeatedly adds that does not use initator in polymerization process.Associativity copolymer of the present invention provides at least 2% the improvement of keeping, preferred at least 3% keep improvement, more preferably at least 4% keep improvement.Associativity copolymer of the present invention provides the improvement of at least 5% drainage time, and preferred at least 7% drainage time improves, and more preferably at least 10% drainage time improves.
Embodiment
Embodiment 1 (Comparative Examples)
To contain surfactant (10.00 gram Hypermer B246SF (Uniqema, New Castle, DE) and 5.00 the gram dehydrated sorbitol mono-fatty acid esters) paraffin oil (139.72 the gram, Escaid 110 oil, ExxonMobil, Houston, oil phase TX) be fed to be furnished with the overhead system mechanical agitator, in the reaction flask that is fit to of thermometer, nitrogen bubble pipe and condenser.
Carry out the preparation of water separately, water is included in water (129.13 grams, based on 50 moles of % of total monomer), acrylamide (AAm) solution of 50 weight % in glacial acrylic acid (66.11 gram, based on 50 moles of % of total monomer), deionized water (106.91 gram) and Versenex 80 (Dow Chemical) chelating agent solution (0.69 gram).NaOH solution with 50% is adjusted to about 5-6 with the pH of water.
Mix down with homogenizer at the same time that subsequently water is fed in the oil phase, to obtain stable water-in-oil emulsion.Then this emulsion is mixed with 4-chip glassed agitator, and accompanied by nitrogen bubble 60 minutes.In the nitrogen bubble process, the temperature of emulsion is adjusted to 57 ± 1 ℃., stop bubbling, form blanket of nitrogen thereafter.
The solution of AIBN in toluene by reinforced 3 weight % comes initiated polymerization, and it is equivalent to initial AIBN charging and is the 75ppm based on the total monomer molar weight.In course of reaction, the temperature of reversed-phase emulsion is remained on 57 ± 1 ℃.Initial AIBN charging is after 4 hours, and the solution of AIBN in toluene of 3 weight % was fed in the reactor through～30 seconds, and it is equivalent to the 2nd AIBN charging and is the 75ppm based on the total monomer molar weight.Then batch of material is remained on 57 ± 1 ℃ 1.5 hours, and in 0.5 hour, be heated to 65 ± 1 ℃.The final AIBN charging of the solution of 3 weight %AIBN in toluene was added in the reactor through～30 seconds, and it is equivalent to the 100ppm based on the total monomer molar weight.Continue about 1 hour of reaction after the final initiator feed.Then this batch of material is cooled to room temperature and collects product.
Except that hereinafter mentioned change, the preparation of copolymer is carried out according to the method for embodiment 1 among the embodiment 2-4.
Embodiment 2
Embodiment 2 is prepared as described in example 1 above, the initator that polymerization begins injects except making, after polymerization half an hour, polymerization after one hour and polymerization comprise respectively after 1.5 hours that the AIBN of 3 weight % of 75 molar ppm AIBN, 25 molar ppm AIBN, 25 molar ppm AIBN and 25 molar ppm is at the solution of toluene.All ppm values are based on total monomer.
Embodiment 3
Embodiment 3 is prepared as described in example 1 above, the initator that polymerization begins injects except making, polymerization after a hour, polymerization after 1.5 hours and polymerization comprise the toluene solution of the 3 weight % of 75 molar ppm AIBN, 25 molar ppm AIBN, 25 molar ppm AIBN and 25 molar ppm AIBN after 4 hours respectively.All ppm values are based on total monomer.
Embodiment 4
Embodiment 4 is prepared as described in example 1 above, the initator that polymerization begins injects except making, polymerization after one hour and polymerization comprise the toluene solution of the 3 weight % of 50 molar ppm AIBN, 50 molar ppm AIBN and 50 molar ppm AIBN after 4 hours respectively.All ppm values are based on total monomer.
In order to assess performance of the present invention, adopt synthetic alkalescence batching to carry out a series of drainage tests.This batching is by commercially available lapped pulp (lab pulp) and the water and the preparation of other material of hardwood and softwood dried.At first, the commercially available lapped pulp of hardwood and softwood dried is made with extra care respectively.Then in water-bearing media with the softwood mix of these paper pulp with hardwood and the about 30 weight % of about 70 weight %.The water-bearing media that uses in the preparation batching comprises the mixture of local hard water and deionized water, thereby has obtained representative hardness.The addition of inorganic salts makes this medium that the total alkalinity (CaCO of 75ppm is provided
3Meter) and the hardness (CaCO of 100ppm
3Meter).Precipitation method calcium carbonate (PCC) is added in the intermittent pulp proportioning, so that the final batching that contains 80% fiber and 20%PCC filler to be provided with typical percetage by weight.
The active Britt Jar of employing (dynamic drainage instrument) that keeps of the present invention measures.The result of this test illustrates that by the magnitude of keeping fine powder dynamic drainage instrument powder keeps the ability that retention agent is distinguished in test.Dynamic drainage instrument powder is kept method by the sieve of container, the 76 μ m mesh sizes of band blade, backer board with remain on the rotor set formation of 3.2mm on sieve of original position with suitable locating rack (spacer).Rotor uses under the speed of 1000rpm.Mixes with rotor and introduce various chemical constituents in batching by batching, and before next component interpolation, make each component mixing fixed time keep test.Collect the filtrate of known volume and measure the turbidity of filtrate.Via the sieve of littler mesh size filtrate is carried out the second time then and filter, with the percentage of powder/fiber of determining to pass 76 μ m mesh size sieves.
By with the mixer speed mix of mechanical mixer, various chemical constituents are introduced in the batching, and before next component is added, made each component mixing fixed time carry out the drainage test with appointment.Concrete chemical constituent and stoichiometric level are described in the tables of data.Drainage activity of the present invention adopts Vacuum Drainage Test vacuum drainage method of inspection (VDT) to measure.The result of this test has illustrated that by the length of drainage time VDT distinguishes the ability of drainage agent.Experimental rig is similar to Buchner funnel test Buchner funnel method of inspection, describing in various filtration reference books, for example referring to Perry ' s Chemical Engineers ' Handbook, the 7th edition, (McGraw-Hill, New York, 1999) 18-78 page or leaf.
VDT is by the magnetic Gelman filter tunnel of 300-ml, 250-ml measuring graduates, decoupler (disconnect), dehydrator and have vacuum meter and the vavuum pump of control valve is formed fast.The VDT test is undertaken by the vavuum pump that at first is provided with vacuum meter and control valve.VDT test by at first be provided with vacuum to usually at the desired level of 250mm Hg, and funnel be placed on the graduated cylinder rightly carry out.Then, 250 paper making raw materials that restrain 0.5 weight % are fed in the beaker, under the stirring that the overhead system agitator provides, will add in the described raw material subsequently according to the additive (for example, starch, alum and test flocculant) of handling procedure needs.Then described raw material is poured in the filter tunnel, and when connecting vavuum pump, picked up counting.The drainage effect is recited as the time required when obtaining 230ml filtrate (in second).The low more quantitative drainage time value high-caliber more drainage of representative or dehydration obtain and this proper business is desired.
Table 1 has illustrated effectiveness of the present invention.Sample is following to be prepared: (Stalok 400 at first to add the 5Kg cationic starch in the batching of preparation as mentioned above, AE., Staley, Decatur, IL)/metric ton batching (butt), 2.5Kg alum is (from Delta Chemical Corporation then, Baltimore, the Patent alum that MD obtains with 50% solution)/metric ton batching (butt), be PerForm PC8138 (the Hercules Incorporated of 0.25Kg afterwards, Wilmington, DE)/metric ton batching (butt), next be material of the present invention.These data have shown that the initator that adds extra five equilibrium between beginning stage of reaction of 90 minutes has produced and has the product of better keeping unexpectedly with water filtering performance.
Storage modulus in the table 1 (G ') is measured according to method therefor among U.S. Patent Application Publication 2004/0143039 A1.G ' measures under the polymer of 1.5 weight % and frequency 6.3Hz.
Table 1 is kept and the drainage result
| Embodiment | Keep 0.2Kg/MT (%) | Improvement (%) to embodiment 1 | Drainage time 0.4Kg/MT (s) | Improvement (%) to embodiment 1 | G′ (Pa) |
| 1 | 76.3 | -- | 16.4 | -- | 256 |
| 2 | 79.4 | 4.06 | 13.9 | 15.2 | 146 |
| 3 | 79.7 | 4.46 | 14.4 | 12.2 | 136 |
| 4 | 80.5 | 5.50 | 13.5 | 17.7 | 151 |
Claims (15)
1. one kind is improved the method for keeping with drainage in paper technology, wherein said improvement comprises that the association polymer that will prepare by the discontinuous interpolation initator of one or many adds in the paper making pulp, wherein for not having the discontinuous association polymer that repeatedly adds initator and prepare, described association polymer provides at least 2% keep and improve and the improvement of at least 5% drainage time, and 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, wherein said association polymer has the association performance that emulsifying surfactant provided at least that is selected from two blocks or three block polymerization type surfactants by effective dose, and wherein said at least a two blocks or three block surfactants are at least about 3: 100 to the amount of monomer.
2. the process of claim 1 wherein that described association polymer is formed by the monomer that comprises at least a non-ionic monomer in the following group of choosing: acrylamide, Methacrylamide, N-dialkyl group acrylamide, N-alkyl acrylamide, N-vinyl methylacetamide, N-vinyl formamide, N-vinyl methylformamide, N-vinyl pyrrolidone, reach their mixture.
3. the method for claim 2, wherein said association polymer is formed by the monomer of at least a anionic monomer that comprises the free acid that is selected from following group or salt in addition: acrylic acid, methacrylic acid, Sodium styrene sulfonate, 2-acrylamido-2-alkyl sulfonic acid, wherein said alkyl comprises 1-6 carbon atom or their mixture.
4. the process of claim 1 wherein that discontinuous being added on when about 1-90% is finished in described reaction of the one or many of initator carry out.
5. the process of claim 1 wherein that discontinuous being added on when about 5-60% is finished in described reaction of the one or many of initator carry out.
6. the process of claim 1 wherein that discontinuous being added on when about 10-60% is finished in described reaction of the one or many of initator carry out.
7. the process of claim 1 wherein that described anionic monomer comprises acrylic acid.
8. the process of claim 1 wherein that described non-ionic monomer comprises acrylamide.
9. the process of claim 1 wherein that described anionic monomer comprises acrylic acid, described non-ionic monomer comprises acrylamide.
10. one kind prepares the method for polymer by radical polymerization process, and wherein association polymer prepares by the discontinuous interpolation initator of one or many in polymerization process.
11. the method for claim 10, wherein discontinuous being added on when about 1-90% is finished in reaction of the one or many of initator carried out.
12. the method for claim 10, wherein discontinuous being added on when about 5-60% is finished in reaction of the one or many of initator carried out.
13. the method for claim 10, wherein discontinuous being added on when about 10-60% is finished in reaction of the one or many of initator carried out.
14. the composition of a water solubility copolymer, it comprises:
The reversed-phase emulsion that contains at least a associativity anionic copolymer, the association performance of wherein said at least a associativity anionic copolymer is provided by at least a emulsifying surfactant that is selected from two blocks and three block polymerization type surfactants of effective dose, and wherein said at least a associativity anionic copolymer comprises:
The segment B of at least a non-ionic polymers that constitutes by the unsaturated non-ionic monomer of one or more ethylenic and
The segment F of at least a anionic polymer that constitutes by the unsaturated anionic monomer of one or more ethylenic;
The molar percentage of B: F is 95: 5-5: 95; And
The Huggins constant (k ') that wherein said at least a associativity anionic copolymer is measured in 0.01M NaCl is greater than 0.75; And described at least a associativity anionic copolymer storage modulus (G ') under 6.3Hz in the living polymer solution of 1.5 weight % is greater than 75Pa.
15. the composition of the water solubility copolymer of claim 14, wherein the storage modulus (G ') under 6.3Hz is 75Pa-170Hz in 1.5 weight % living polymer solution.
Applications Claiming Priority (3)
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|---|---|---|---|
| US69385205P | 2005-06-24 | 2005-06-24 | |
| US60/693,852 | 2005-06-24 | ||
| US11/313,505 | 2005-12-21 |
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|---|---|---|---|---|
| CN108547173A (en) * | 2018-05-07 | 2018-09-18 | 东升新材料（山东）有限公司 | A method of anion drying strengthening agent is prepared using inverse emulsion polymerization |
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| CN108547173A (en) * | 2018-05-07 | 2018-09-18 | 东升新材料（山东）有限公司 | A method of anion drying strengthening agent is prepared using inverse emulsion polymerization |
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