CN102226324B - A process for the production of paper - Google Patents

A process for the production of paper Download PDF

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Publication number
CN102226324B
CN102226324B CN201110144308XA CN201110144308A CN102226324B CN 102226324 B CN102226324 B CN 102226324B CN 201110144308X A CN201110144308X A CN 201110144308XA CN 201110144308 A CN201110144308 A CN 201110144308A CN 102226324 B CN102226324 B CN 102226324B
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Prior art keywords
polymer
paper
acrylamide
monomer
water
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CN102226324A (en
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F·索尔哈格
J·卡伦
B·约翰松
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Nouryon Chemicals International BV
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Akzo Nobel NV
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06—Controlling the addition
    • D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
    • D21H23/18—Addition at a location where shear forces are avoided before sheet-forming, e.g. after pulp beating or refining
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D21H23/765—Addition of all compounds to the pulp

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  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The present invention relates to a process for producing paper which comprises: (i) providing an aqueous suspension comprising cellulosic fibres, (ii) adding to the suspension after all points of high shear: a first polymer being a cationic polymer having a charge density above 2.5 meq/g; a second polymer; and a third polymer being an organic or inorganic anionic polymer; and (iii) dewatering the obtained suspension to form paper.

Description

Produce the method for paper
The application is that application number is dividing an application of 200580044329.7 application for a patent for invention, and the applying date of original application is on December 7th, 2005, and denomination of invention is " method of producing paper ".
Technical field
The present invention relates to produce the method for paper.More specifically, the present invention relates to produce the method for paper, the method is included in after all high shear points, adds first, second, and third polymer in aqueous cellulosic suspension, and makes the dehydration of gained suspension, forms paper.
Background technology
In field of papermaking, the aqueous suspension (being called paper stock) that contains the optional filler of cellulose fiber peacekeeping and additive is fed in the flow box (headbox) by pump, screen cloth and cleaner (these operations make paper stock accept high shearing force), and described flow box is ejected into paper stock on the shaping copper mesh.By the discharge water from paper stock of shaping copper mesh, in order to form the wet net width of cloth of paper on the net, in the drying nest of paper machine, the net width of cloth is dehydration and dry further.Difference place in paper stock flows introduces discharging and keeps auxiliary agent routinely, so that promote discharging and increase particulate, for example microfibre, filler and the additive absorption on cellulose fibre, they are retained on the copper mesh with fiber as a result.The example of the conventional discharging of using and reservation auxiliary agent includes organic polymer, inorganic material and bond thereof.
US6103065 discloses the reservation of improvement papermaking batching and the method for discharging, the method comprises the steps: that after last high shear point adding at least a molecular weight is 100,000-2, the polymer of 000,000 CATION high charge density is in described batching; Add at least a molecular weight greater than 2,000,000 polymer; And the POLARGEL NF of interpolation swellable.
EP1238161B1 discloses the method for making paper or cardboard, be that the basically water miscible cation synthesising copolymer of at least 4dl/g is in the thin paper stock logistics of cellulose suspension by adding intrinsic viscosity wherein, thereby make the cellulose suspension flocculation, wherein the cellulose suspension of flocculation carried out mechanical shearing, then by add subsequently comprise (i) material and (ii) intrinsic viscosity be the again flocculation to the centrifugal screen of the again flocculation system of the basically water-soluble anionic polymer of 4dl/g at least.Claimed method provides the improvement of reservation and discharging aspect.
WO2004/015200 discloses by shearing paper material, followed by last shearing step, before the material agglomeration, the microparticle system that interpolation is comprised of cationic polymer and particulate inorganic component is in paper material, make the paper material dehydration, so that the formation scraps of paper, and the dry described scraps of paper, thereby the method for producing paper and cardboard.Claimed the method provides the improvement of reservation and discharging aspect.
Advantageously can provide discharging, reservation and shaping aspect further improved paper technology.
Summary of the invention
The present invention relates to produce the method for paper, the method comprises:
(i) provide the aqueous suspension of containing cellulose fiber,
(ii) after all high shear points, add following substances in suspension:
The first polymer, it is the cationic polymer that charge density is higher than 4.0meq/g;
Molecular weight is higher than the second polymer of 500,000; With
Terpolymer, it is a kind of anionic polymer; With
(iii) make the dehydration of gained suspension, form paper.
The invention still further relates to the method for producing paper, the method comprises:
(i) provide the aqueous suspension of containing cellulose fiber,
(ii) after all high shear points, add following substances in suspension:
The first polymer, it is the cation acrylamide based polyalcohol that charge density is higher than 2.5meq/g;
The second polymer, it is that molecular weight is higher than 500,000 acrylamide-based polymers;
Terpolymer, it is a kind of anionic polymer; With
(iii) make the dehydration of gained suspension, form paper.
The invention further relates to the method for producing paper, the method comprises:
(i) provide the aqueous suspension of containing cellulose fiber,
(ii) after all high shear points, add following substances in suspension:
The first polymer, it is the cationic polymer that charge density is higher than 2.5meq/g,
The second polymer, it is a kind of water dispersible polymers; With
Terpolymer, it is a kind of anionic polymer; With
(iii) make the dehydration of gained suspension, form paper.
The specific embodiment
According to the present invention, find, can be by following method, in without any the situation that infringement is shaped significantly, perhaps even improving in the situation that paper is shaped, improve discharging and keep, described method is included in after all high shear points, add the discharging that contains first, second, and third polymer and keep auxiliary agent in cellulose suspension, then make the dehydration of gained suspension, form paper.By all types of paper stocks, especially the paper stock that contains machinery or circulation paper pulp, produce in the paper with the paper stock with high content of salt (high conductivity) and colloidal materials, and hold back (closure) at the plain boiled water with high level, be in the paper technology that large-scale plain boiled water circulates and limited fresh water is supplied, the improvement that the invention provides discharging and keep.So the invention enables the speed that can increase paper machine and use the polymer than low dosage to be discharged accordingly and/or retention, thereby cause improved paper technology and economic advantages.
Term as used herein " discharging and reservation auxiliary agent " refers to two or more following components, and in the time of wherein in joining aqueous cellulosic suspension, it is better than the discharging that obtains when not adding described two or more components and reservation to obtain.
The first polymer according to the present invention to be charge density be 2.5meq/g at least, 3.0meq/g at least suitably, the preferred at least cationic polymer of 4.0meq/g.Suitable is that the charge density scope is 2.5-10.0, preferred 3.0-8.5meq/g..
The first polymer can be selected from inorganic and organic cationic polymer.Preferably, the first polymer is water miscible.The example of the first suitable polymer comprises poly-aluminium compound, for example polyaluminium chloride, poly aluminium sulfate, contain the two poly-aluminium compound of chlorion and sulfate ion, poly-silicic acid-aluminum sulfate, and composition thereof.
The further example of the first suitable polymer comprises cationic organic polymer, for example the cation acrylamide based polyalcohol; Poly-(poly (dially dialkyl) base ammonium halide), for example poly-(diallyldimethylammonium chloride); Polymine; Polyamide-based amine; Polyamines; With the vinyl amine based polyalcohol.The example of suitable cationic organic polymer comprises by the unsaturated cationic monomer of polywater dissolubility ethylenic, perhaps preferably contains the unsaturated cationic monomer of one or more of water-soluble olefinic bond formulas and the randomly monomer mixture of one or more of other water-soluble olefinic bond formula unsaturated monomers and the polymer for preparing.The example of the suitable unsaturated cationic monomer of water-soluble olefinic bond formula comprises poly (dially dialkyl) base ammonium halide, diallyldimethylammonium chloride for example, and with the cationic monomer of following general structural formula (I) expression:
Figure BDA0000065252960000041
R wherein 1H or CH 3R 2And R 3Respectively do for oneself H or, preferred alkyl has 1-3 carbon atom suitably, preferably the alkyl of 1-2 carbon atom; A is O or NH; B has 2-8 carbon atom, the suitably alkyl of 2-4 carbon atom or alkylidene, perhaps hydroxy propylidene; R 4H or preferred alkyl, have suitably 1-4 carbon atom, the alkyl of preferred 1-2 carbon atom, the substituting group that perhaps contains aryl, suitably phenyl or substituted-phenyl, the wherein said substituting group that contains aryl can be by having 1-3 carbon atom usually, and the alkylidene of 1-2 carbon atom links to each other with nitrogen suitably, suitable R 4Comprise benzyl (CH 2-C 6H 5); And X -Anionic counter-ion, common halogen ion, for example chlorion.
Example with the suitable monomer of general structure (I) expression comprises by process (methyl) propenoic acid dialkyl ammonia alkane ester with methyl chloride or benzyl chloride, (methyl) acrylic acid dimethylamino ethyl ester for example, (methyl) acrylic acid diethyl amino ethyl ester and (methyl) acrylic acid dimethylamino hydroxypropyl acrylate, with dialkyl amino alkyl (methyl) acrylamide, dimethylaminoethyl (methyl) acrylamide for example, diethyl aminoethyl (methyl) acrylamide, dimethyl aminopropyl (methyl) acrylamide and diethyl amino propyl group (methyl) acrylamide and the season type monomer that obtains.The preferred cationic monomer of general formula (I) comprises acrylic acid dimethylamino ethyl ester methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, acrylic acid dimethylamino ethyl ester benzyl chloride quaternary salt and dimethylaminoethyl acrylate methyl base ammonia ethyl ester benzyl chloride quaternary salt.
Monomer mixture can contain the undersaturated non-ionic monomer of one or more of water-soluble olefinic bond formulas.But the example of the non-ionic monomer of suitable copolymerization comprises acrylamide and acrylamido monomer, for example Methacrylamide, N-alkyl (methyl) acrylamide, for example N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-n-pro-pyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, the N-tert-butyl group (methyl) acrylamide and N-isobutyl group (methyl) acrylamide; N-alkoxyalkyl (methyl) acrylamide, for example N-n-butoxy methyl (methyl) acrylamide and N-isobutoxy methyl (methyl) acrylamide; N, N-dialkyl group (methyl) acrylamide, N for example, N-dimethyl (methyl) acrylamide; Dialkyl amino alkyl (methyl) acrylamide; Acrylate-based monomer, for example (methyl) propenoic acid dialkyl ammonia alkane ester; And vinyl amine.Monomer mixture also can contain the undersaturated anion of one or more of water-soluble olefinic bond formulas or latent anionic monomer, is preferably low amount.Term as used herein " dive anionic monomer " refers to comprise the monomer with potential ionogenic group, and described potential ionogenic group will become anion in being included in the polymer that is applied on the cellulose suspension time.But the anion of suitable copolymerization and the example of latent anionic monomer comprise ethylenic unsaturated carboxylic acid and salt thereof, for example (methyl) acrylic acid and salt thereof, (methyl) sodium acrylate suitably, ethylenic unsaturated sulfonic acid and salt thereof, for example 2-acrylamide-2-methylpro panesulfonic acid salt, (methyl) acrylic acid sulphur ethyl ester, vinyl sulfonic acid and salt thereof, styrene sulfonate, and 4-Vinyl phenol (hydroxy styrenes) and salt thereof.But the example of the monomer of preferred copolymerization comprises acrylamide and Methacrylamide, i.e. (methyl) acrylamide, comprise the cation acrylamide based polyalcohol with the example of preferred cationic organic polymer, the cationic polymer that is namely prepared by the monomer mixture that contains one or more of acrylamides and acrylamido monomer.
The weight average molecular weight of the first polymer of cationic organic polymer form can be at least 10,000, usually at least 50,000, and more frequent is that it is at least 100,000, and usually at least about 500,000, suitably at least about 100 ten thousand, and preferably is higher than about 200 ten thousand.The upper limit is not crucial, and it can be about 3,000 ten thousand, common 2,000 ten thousand.
The second polymer of the present invention is organic polymer preferably, and described organic polymer can be selected from nonionic, CATION, anion and amphiphilic polymers.The second polymer can be water-soluble or water is dispersible.Suitably by the one or more of ethylenically unsaturated monomers of polymerization, preferred one or more of water-soluble olefinic bond formula unsaturated monomers, thus prepare the second polymer.The example of preferred the second polymer comprises acrylamide-based polymers.
The example of the second suitable polymer comprises the dispersible nonionic organic polymer of water-soluble and water that obtains by the unsaturated non-ionic monomer of the one or more of water-soluble olefinic bond formulas of polymerization.The example of suitable non-ionic monomer comprises acrylamide and above-mentioned nonionic acrylamido and acrylate-based monomer and vinyl amine.The example of preferred non-ionic monomer comprises acrylamide and Methacrylamide, i.e. (methyl) acrylamide, and the example of preferred the second polymer comprises the nonionic acrylamide-based polymers.
The further example of the second suitable polymer comprises by the unsaturated cationic monomer of polywater dissolubility ethylenic, or preferably contain the unsaturated cationic monomer of one or more of water-soluble olefinic bond formulas and randomly one or more of other the monomer mixture of water-soluble olefinic bond formula unsaturated monomer and the cationic organic polymer that obtains.The example of suitable cationic monomer comprises those that represent with above-mentioned general structure (I), wherein R 1, R 2, R 3, R 4, A, B and X -As defined above, and poly (dially dialkyl) base ammonium halide, for example diallyldimethylammonium chloride.Monomer mixture can contain the undersaturated non-ionic monomer of one or more of water-soluble olefinic bond formulas.But the example of the non-ionic monomer of suitable copolymerization comprises acrylamide and above-mentioned nonionic acrylamido and acrylate-based monomer and vinyl amine.Monomer mixture also can contain the unsaturated anion of one or more of water miscible ethylenic or latent anionic monomer, is preferably low amount.But the anion of suitable copolymerization and the example of latent anionic monomer comprise ethylenic unsaturated carboxylic acid and salt thereof, and ethylenic unsaturated sulfonic acid and salt thereof, for example above-mentioned any in those.But the example of the monomer of preferred copolymerization comprises acrylamide and Methacrylamide, i.e. (methyl) acrylamide, and the example of preferred the second polymer comprises the cation acrylamide based polyalcohol.
The further example of the second suitable polymer comprises by the unsaturated anion of polywater dissolubility ethylenic or latent anionic monomer, perhaps preferably contains the unsaturated anion of one or more of water-soluble olefinic bond formulas or latent anionic monomer and the randomly monomer mixture of one or more of other water-soluble olefinic bond formula unsaturated monomers and the anionic organic polymer that obtains.Suitable anion and the example of latent anionic monomer comprise ethylenic unsaturated carboxylic acid and salt thereof, and ethylenic unsaturated sulfonic acid and salt thereof, for example above-mentioned any in those.Monomer mixture can contain the unsaturated non-ionic monomer of one or more of water miscible ethylenic.But the example of the non-ionic monomer of suitable copolymerization comprises acrylamide and above-mentioned nonionic acrylamido and acrylate-based monomer and vinyl amine.Monomer mixture also can contain the unsaturated CATION of one or more of water-soluble olefinic bond formulas and checking exuberance of yang ion monomer, is preferably low amount.Term as used herein " checking exuberance of yang ion monomer " refers to comprise the monomer with potential ionogenic group, and described potential ionogenic group will become CATION in being included in the polymer that is applied on the cellulose suspension time.But the example of the CATION of suitable copolymerization and checking exuberance of yang ion monomer comprises monomer and poly (dially dialkyl) base ammonium halide, for example diallyldimethylammonium chloride with above general structure (I) expression.But the example of the monomer of preferred copolymerization comprises (methyl) acrylamide, and the example of preferred the second polymer comprises the anion acrylamide-based polymers.
The further example of the second suitable polymer comprises by polymerization and contains the unsaturated anion of one or more of water-soluble olefinic bond formulas or latent anionic monomer and the unsaturated CATION of one or more of water-soluble olefinic bond formulas or checking exuberance of yang ion monomer, and randomly one or more of other the monomer mixture of water-soluble olefinic bond formula unsaturated monomer and the both sexes organic polymer that obtains.Suitable anion and the example of latent anionic monomer comprise ethylenic unsaturated carboxylic acid and salt thereof, and ethylenic unsaturated sulfonic acid and salt thereof, for example above-mentioned any in those.The example of suitable CATION and checking exuberance of yang ion monomer comprises monomer and poly (dially dialkyl) base ammonium halide, for example diallyldimethylammonium chloride with above general structure (I) expression.Monomer mixture can contain the unsaturated non-ionic monomer of one or more of water-soluble olefinic bond formulas.But the example of the non-ionic monomer of suitable copolymerization comprises acrylamide and above-mentioned nonionic acrylamido and acrylate-based monomer and vinyl amine.But the example of the monomer of preferred copolymerization comprises (methyl) acrylamide, and the example of preferred the second polymer comprises the both sexes acrylamide-based polymers.
In preparing the second suitable polymer, monomer mixture also can contain one or more of multi-group crosslink agents except containing above-mentioned ethylenically unsaturated monomers.In monomer mixture, there is the multi-group crosslink agent so that can prepare dispersible the second polymer of water.The multi-group crosslink agent can be nonionic, CATION, anion or both sexes crosslinking agent.Suitable multi-group crosslink agent's example comprises the compound with at least two ethylenic unsatisfied chemical bonds, N for example, N-methylene-two (methyl) acrylamide, polyethylene glycol two (methyl) acrylate, N-vinyl (methyl) acrylamide, divinylbenzene, triallyl ammonium and N-methacrylic (methyl) acrylamide; Compound with ethylenic unsaturated bond and reactive group, for example (methyl) glycidyl acrylate, acrolein and methylol (methyl) acrylamide; With the compound with at least two reactive groups, dialdehyde for example, glyoxal for example, bicyclic oxygen compound, and chloropropylene oxide.Can be based on the monomer that exists in the monomer mixture, perhaps based on the monomeric unit that exists in the polymer, use at least 4 molar part/1,000,000 part multi-functional crosslinking agent, preferred about 6000 molar part of about 4-/1,000,000 parts, most preferably 20-4000 molar part/1,000,000 part multi-functional crosslinking agent prepares dispersible the second polymer of suitable water.The example of the suitable dispersible organic polymer of water is included in those disclosed in the U.S. Patent No. 5167766, is introduced into by reference at this.The further example of the second suitable polymer comprises the dispersible anion of water, CATION and both sexes organic polymer, comprise the dispersible anionic organic polymer of water with preferred the second polymer, the dispersible anion acrylamide-based polymers of preferred water.
The second polymer of the present invention, the weight average molecular weight that preferably has water miscible the second polymer can be at least about 500,000.Usually weight average molecular weight is at least about 100 ten thousand, suitably at least about 200 ten thousand, and preferably at least about 500 ten thousand.The upper limit is not crucial, and it can be about 5,000 ten thousand, common 3,000 ten thousand.
The charge density of the second polymer of the present invention can be less than about 10meq/g, suitably less than about 6meq/g, preferably less than about 4meq/g, is more preferably less than 2meq/g.Suitably, the charge density scope is 0.5-10.0meq/g, preferred 1.0-4.0meq/g.The second suitable polymer comprises charge density less than 10.0meq/g, suitably less than 6.0meq/g, preferably less than the anionic organic polymer of 4.0meq/g.The second suitable polymer further comprises charge density less than 6.0meq/g, suitably less than 4.0meq/g, preferably less than the cationic organic polymer of 2.0meq/g.
Terpolymer of the present invention is anionic polymer, and it can be selected from inorganic and the organic anion polymer.The example of suitable terpolymer comprises water-soluble and the dispersible inorganic and organic anion polymer of water.
The example of suitable terpolymer comprises the inorganic anion polymer based on silicic acid and silicate, i.e. the anionic silica-based polymer.Can be by the polycondensation silicon-containing compound, for example silicic acid and silicate (described polymerization can be homopolymerization or copolymerization), thus prepare suitable anionic silica-based polymer.Preferably, the anionic silica-based polymer comprises the anionic silica-based particles of colloidal state particle size range.Anionic silica-based particles is supplied with aqueous, colloidal dispersion (so-called colloidal sol) usually.The correctability silica-based sols also contains and can be present in water and/or be present in other element in the silica-based particles, for example aluminium, boron, nitrogen, zirconium, gallium and titanium.The example of suitable anionic silica-based particles comprises poly-silicic acid, the silica that gathers silicic acid microgel, polysilicate, polysilicate microgels, colloidal silica, colloidal aluminium modification, aluminium silicate polymer, aluminium silicate polymer microgel, poly-borosilicate etc.The example of suitable anionic silica-based particles is included in those disclosed in the United States Patent(USP) Nos. 4388150,4927498,4954220,4961825,4980025,5127994,5176891,5368833,5447604,5470435,5543014,5571494,5573674,5584966,5603805,5688482 and 5707493, is introduced into by reference at this.
The example of suitable anionic silica-based particles comprises particle mean size less than about 100 nanometers, and preferably less than about 20 nanometers, and more preferably scope is those of about 10 nanometers of about 1-.Routine is in the silica chemistry, and granularity refers to the average-size of primary granule, and described primary granule can be assembled or not assemble.Preferably, the anionic silica-based polymer comprises the anionic silica-based particles of gathering.The specific area of silica-based particles is suitably at least 50m 2/ g, and preferred 100m at least 2/ g.Usually, specific area can mostly be about 1700m most 2/ g, and preferred at most 1000m 2/ g.Removing suitably or regulating any compound that may disturb titration that is present in the sample, for example after aluminium and the borohydride species, by measuring specific area with the NaOH titration, as G.W.Sears described in Analytical Chemistry28 (1956): 12,1981-1983 and the U.S. Patent No. 5176891.So given area represents the average specific surface area of particle.
In a preferred embodiment of the invention, the specific area scope of anionic silica-based particles is 50-1000m 2/ g, more preferably 100-950m 2/ g.Preferably, silica-based particles is with 8-50%, and the scope of preferred 10-40% is present in the colloidal sol with S value, and it is 300-1000m that described colloidal sol contains the specific area scope 2/ g, suitably 500-950m 2/ g, and preferred 750-950m 2The silica-based particles of/g, the as described above modification of described colloidal sol.As Lier ﹠amp; Dalton described in the 955-957, measures and calculates the S value in J.Phys.Chem.60 (1956).The degree that the S value representation is assembled or microgel forms, and lower S value is the indication of higher aggregation extent.
Again in the preferred embodiment, silica-based particles has high specific area, is higher than suitably about 1000m in the present invention 2/ g.The specific area scope can be 1000-1700m 2/ g, and preferred 1050-1600m 2/ g.
The further example of suitable terpolymer comprises by the unsaturated anion of polymerization ethylenic or latent anionic monomer, perhaps preferably contain the unsaturated anion of one or more of ethylenic or latent anionic monomer, and the randomly monomer mixture of one or more of other ethylenically unsaturated monomers and the dispersible organic anion polymer of water-soluble and water that obtains.Preferably, ethylenically unsaturated monomers is water miscible.Suitable anion and the example of latent anionic monomer comprise ethylenic unsaturated carboxylic acid and salt thereof, ethylenic unsaturated sulfonic acid and salt thereof, for example above-mentioned any in those.Monomer mixture can contain the unsaturated non-ionic monomer of one or more of water-soluble olefinic bond formulas.But the example of the non-ionic monomer of suitable copolymerization comprises acrylamide and above-mentioned nonionic acrylamido and acrylate-based monomer and vinyl amine.Monomer mixture also can contain the unsaturated CATION of one or more of water-soluble olefinic bond formulas and checking exuberance of yang ion monomer, is preferably low amount.But the example of the cationic monomer of suitable copolymerization comprises the monomer with above-mentioned general structure (I) expression, and poly (dially dialkyl) base ammonium halide, for example diallyldimethylammonium chloride.Monomer mixture also can contain one or more of multi-group crosslink agents.In monomer mixture, there is the multi-group crosslink agent so that can prepare the dispersible terpolymer of water.Suitable multi-group crosslink agent's example comprises above-mentioned multi-group crosslink agent.Can use these reagent of above-mentioned content.The example of the dispersible organic anion polymer of suitable water is included in those disclosed in the U.S. Patent No. 5167766, is introduced into by reference at this.But the example of the monomer of preferred copolymerization comprises (methyl) acrylamide, and the example of preferred terpolymer comprises water-soluble and the dispersible anion acrylamide-based polymers of water.
The weight average molecular weight of terpolymer (it is a kind of organic anion polymer of the present invention, preferred water miscible organic anion polymer) is at least about 500,000.Usually weight average molecular weight is at least about 100 ten thousand, suitably at least about 200 ten thousand, and preferably at least about 500 ten thousand.The upper limit is not crucial, and it can be about 5,000 ten thousand, common 3,000 ten thousand.
The charge density of terpolymer (it is a kind of organic anion polymer) can be less than about 14meq/g, suitably less than about 10meq/g, preferably less than about 4meq/g, suitably, the charge density scope is 1.0-14.0meq/g, preferred 2.0-10.0meq/g.
The present invention preferably discharges and the example that keeps auxiliary agent comprises:
(i) the first polymer, it is a kind of cation acrylamide based polyalcohol; The second polymer, it is a kind of cation acrylamide based polyalcohol; With terpolymer, it is a kind of anionic silica-based particles;
(ii) the first polymer, it is the poly-aluminium compound of a kind of CATION; The second polymer, it is a kind of cation acrylamide based polyalcohol; With terpolymer, it is a kind of anionic silica-based particles;
(iii) the first polymer, it is a kind of cation acrylamide based polyalcohol; The second polymer, it is a kind of water-soluble or dispersible anion acrylamide-based polymers of water; With terpolymer, it is a kind of anionic silica-based particles;
(iv) the first polymer, it is the poly-aluminium compound of a kind of CATION; The second polymer, it is a kind of water-soluble or dispersible anion acrylamide-based polymers of water; With terpolymer, it is a kind of anionic silica-based particles;
(v) the first polymer, it is a kind of cation acrylamide based polyalcohol; The second polymer, it is a kind of cation acrylamide based polyalcohol; With terpolymer, it is a kind of water-soluble or dispersible anion acrylamide-based polymers of water; With
(vi) the first polymer, it is the poly-aluminium compound of a kind of CATION; The second polymer, it is a kind of cation acrylamide based polyalcohol; With terpolymer, it is a kind of water-soluble or dispersible anion acrylamide-based polymers of water.
According to the present invention,, by after all stages of high mechanical shearing and before discharging first, second, and third polymer is joined in the aqueous cellulosic suspension at it.The example in high shear stage comprises pumping and cleaning stage.For example, when cellulose suspension passes through air blast, pressure screen cloth and centrifugal screen, comprise this shear stage.Suitably, last high shear point occurs at the centrifugal screen place, therefore subsequently first, second, and third polymer is joined in the centrifugal screen suitably.Preferably, after adding first, second, and third polymer, cellulose suspension is fed in the flow box, described flow box spray suspension to the shaping copper mesh for discharging.
Can further comprise in the method for the invention extra material ideally.Preferably, these materials are joined in the cellulose suspension, make it afterwards to flow through the rearmost point of high shear.The example of this extra material comprises starch, for example CATION, anion and amphoteric starch, preferred cationic starch; Water-soluble organic polymer flocculant, cationic polyamine for example, daiamid, polymine, dicyano diamides condensation polymer and low-molecular-weight high-cation vinyl addition polymer; And inorganic flocculating agent, for example aluminium compound, for example alum and poly-aluminium compound.
First, second, and third polymer can join in the cellulose suspension independently.Suitably, the first polymer is joined in the cellulose suspension, add afterwards second and terpolymer.The second polymer can be before adding terpolymer, add simultaneously or afterwards.Perhaps, suitably the first polymer and the second polymer are joined in the cellulose suspension simultaneously, then add terpolymer.
First, second, and third polymer of the present invention can be joined in the cellulose suspension to be drained off, its consumption can change in wide scope.Usually, to obtain than the discharging that when not adding polymer, obtains and to keep and to add first, second, and third polymer by good consumption.Calculate with the dry polymer on the dried fibres element suspension, usually with at least about 0.001wt%, usually the consumption at least about 0.005wt% adds the first polymer, and the upper limit is generally about 2.0wt% and is suitably about 1.5wt%.Equally, calculate with the dry polymer on the dried fibres element suspension, usually with at least about 0.001wt%, usually the consumption at least about 0.005wt% adds the second polymer, and the upper limit is generally about 2.0wt% and be about 1.5wt% suitably.Similarly, with dry polymer or dry SiO on the dried fibres element suspension 2Calculate, usually with at least about 0.001wt%, usually the consumption at least about 0.005wt% adds terpolymer, and the upper limit is generally about 2.0wt% and be about 1.5wt% suitably.
When using in the method starch and/or cationic coagulant, calculate with the dry additive on the dried fibres element suspension, usually can be added in an amount of this additive at least about 0.001wt%.Suitably, amount ranges is about 3.0% for about 0.05-, and preferable range is about 0.1-about 2.0%.
Method of the present invention can be applicable in all paper technologies and the cellulose suspension, and it especially can be used for by the high paper stock papermaking of conductance.In this case, the conductance of the paper stock that dewaters at copper mesh is generally at least about 1.5mS/cm, preferred 3.5mS/cm at least, and more preferably 5.0mS/cm at least.Can pass through standard device, the WTWLF 539 apparatus measures conductances of for example being supplied by Christian Berner.
The present invention further comprises paper technology, wherein plain boiled water circulates on a large scale, perhaps recirculation, the plain boiled water interception that namely has high level, for example use the fresh water of 0-30 ton for the dry paper of production per ton, usually less than 20, preferably less than 15, be more preferably less than 10, and especially less than 5 tons of fresh waters/ton paper.Can in any stage of this technique, introduce fresh water, for example can mix fresh water and cellulose fibre, so that formation cellulose suspension, with can mix fresh water and thick cellulose suspension, dilute it, in order to form first, second, and third polymer adding rare cellulose suspension wherein.
Method of the present invention is for the production of paper.Term as used herein " paper " not only comprises paper and production thereof certainly, and comprises other net width of cloth shape product, for example plate and cardboard, and produce.Can use the method being produced in the paper by dissimilar cellulose fibre suspension, and suspension should contain preferably based on dry matter, at least 25%, and the more preferably this fiber of 50wt% at least.Suspension can be based on by chemical pulp, for example sulfate and sulfite pulp, thermomechanical pulp, chemistry-thermomechanical pulp, organic solvent paper pulp, refining paper pulp or the fiber that obtains from the two ground wood pulp of hardwood and cork, perhaps by 1 year living plant, the fiber that such as napier grass (elephant grass), bagasse, flax, straw etc. obtains, and also can be used in the suspension based on recycled fibre.Advantageous applications of the present invention is in the method by the suspension papermaking that contains timber.
Suspension also can contain the inorganic filler of general type, for example kaolin, clay, titanium dioxide, gypsum, talcum, and natural and synthetic calcium carbonate the two, for example calcium carbonate of the marble of chalk, pulverizing, pulverizing and winnofil.Paper stock also can contain the additive for paper making of general type certainly, and for example wet strength agent, sizing agent are such as based on those of rosin, dicthenone, ketenes polymer, alkenyl succinic anhydrides etc.
Preferably, the present invention is applied in and produces the paper contain timber and based on the paper of recycled fibre, for example on the paper machine of SC, LWC and dissimilar books and newspaper, and be applied in production and do not contain the printing of timber and write on the machine of paper, term does not contain timber and refers to contain fiber less than about 15% timber.The example of advantageous applications of the present invention comprises by containing at least machinery and/or the cellulose suspension production paper of recycled fibre and the layer in the multi-layered paper of 50wt%.Preferably, the present invention is applied in 300-3000m/min, and on the paper machine of the more preferably speed running of 500-2500m/min.
Set forth in the following embodiments the present invention, yet described embodiment does not plan to limit the present invention.Umber and percentage relate separately to weight portion and wt%, except as otherwise noted.
Embodiment
Use in an embodiment following additives:
C-PAM-1: by the cation acrylamide based polyalcohol of polypropylene acid amides (40mol%) and acryloxy ethyl-trimethyl salmiac (60mol%) preparation, the weight average molecular weight of this polymer be about 300 ten thousand and cationic charge density be about 4.2meq/g
C-PAM-2: by the cation acrylamide based polyalcohol of polypropylene acid amides (60mol%) and acryloxy ethyl-trimethyl salmiac (40mol%) preparation, the weight average molecular weight of this polymer be about 300 ten thousand and cationic charge density be about 3.3meq/g
C-PAM-3: by the cation acrylamide based polyalcohol of polypropylene acid amides (88mol%), acryloxy ethyl-trimethyl salmiac (10mol%) and DMAA (2mol%) preparation, the weight average molecular weight of this polymer be about 600 ten thousand and cationic charge density be about 1.2meq/g
C-PAM-4: by the cation acrylamide based polyalcohol of polypropylene acid amides (90mol%) and acryloxy ethyl-trimethyl salmiac (10mol%) preparation, the weight average molecular weight of this polymer be about 600 ten thousand and cationic charge density be about 1.2meq/g
PAC: cationic charge density is the CATION polyaluminium chloride of about 8.0meq/g
C-PAI 1: weight average molecular weight be about 200,000 and cationic charge density be the cationic polyamine of about 7meq/g
C-PAI 2: weight average molecular weight be about 400,000 and cationic charge density be the cationic polyamine of about 7meq/g
A=PAM: by the anion acrylamide-based polymers of polypropylene acid amides (80mol) and acrylic acid (20mol%) preparation, the weight average molecular weight of this polymer be about 1,200 ten thousand and anionic charge density be about 2.6meq/g
A-X-PAM: by the anion crosslink propylene amido polymer of polypropylene acid amides (30mol%) and acrylic acid (70mol%) preparation, the weight average molecular weight of this polymer be about 100,000 and anionic charge density be about 8.0meq/g
Silica: the anionic inorganic condensation polymer of the silicic acid of the Ludox form of colloidal aluminium modification, its S value is for about 21 and contain specific area for about 800m 2The silica-based particles of/g
Bentonite: bentonite
Embodiment 1
By the Dynamic Drainage Analyser (DDA) available from Sweden Akribi, estimate discharging (dehydration) performance, described apparatus measures is when removing stopper and apply vacuum when existing on the opposite copper mesh side of thereon a side with paper stock, the time of the paper stock by copper mesh emission regulation volume.
Employed paper stock is based on 75%TMP and 25%DIP fibrous material in test, and from the plain boiled water of the sedimentation of newsprint factory.The denseness of paper stock is 0.78%.The conductance of paper stock is that 1.5mS/cm and pH are 6.8.
In order to simulate the interpolation after all high shear points, in baffled tank, under different agitator speeds, stir paper stock.Stir and add according to following:
(i) under 1000rpm, stirred 20 seconds,
(ii) under 2000rpm, stirred 10 seconds,
(iii) under 1000rpm, stirred 15 seconds, add simultaneously, and
(iv) make deckering, automatically record simultaneously dewatering time.
As described below joining in the paper stock: before dehydration, carry out adding for the first time in 15 seconds (addition is 5kg/t), before dehydration, carry out adding for the second time (addition is 0.8kg/t) in 10 seconds, and before dehydration, carry out for the third time interpolation (addition is 0.5kg/t) in 5 seconds.
Table 1 shows the dewatering time under different interpolation patterns.Polymer and bentonitic addition calculate with the dry products form on the dry paper stock system, and the colloidal sol of silica-based particles calculates with the SiO2 form and take the paper stock system of drying as the basis.
Test No.1 shows the result with any additive.Test Nos.2-4 has illustrated and has been used for more employed technique, and test Nos.5-7 has illustrated according to technique of the present invention.
Table 1
Figure BDA0000065252960000151
Table 1 shows that the method according to this invention causes improved dehydration.
Embodiment 2
Use the DDA of embodiment 1 to estimate discharge performance.
This tests employed paper stock based on 75%TMP and 25%DIP fibrous material, and from the bleaching water of paper mill.The denseness of paper stock is 0.77%.The conductance of paper stock is that 1.6mS/cm and pH are 7.2.
In order to simulate before all high shear points and interpolation afterwards, in baffled tank, under different agitator speeds, stir paper stock.Stir and add according to following:
(i) 0-2 interpolation carried out in stirring in 20 seconds simultaneously under 1000rpm,
(ii) under 2000rpm, stirred 10 seconds,
(iii) under 1000rpm, stirred 15 seconds, carry out simultaneously 0-3 time and add, and
(iv) make deckering, automatically record simultaneously dewatering time.
As described below joining in the paper stock: if any, before dehydration, carry out adding for the first time in 45 or 15 seconds, if any, before dehydration, carry out adding for the second time in 25 or 10 seconds, and if any, before dehydration, carry out adding for the third time in 5 seconds.
Table 2 shows the dewatering time under different interpolation patterns.Before dehydration, provided interpolation time (unit: second), and for first, second, and third interpolation (1/2/3), provided respectively addition.The addition of polymer calculates with the dry products form on the dry paper stock system, and silica-based particles is with SiO 2Form is calculated and take the paper stock system of drying as the basis.
Test No.1 shows the result with any additive.Test Nos.2-7 has illustrated and has been used for more employed technique, and test Nos.8-10 has illustrated according to technique of the present invention.
Table 2
Figure BDA0000065252960000161
According to table 2, it is evident that method of the present invention causes improved dehydration.
Embodiment 3
Operation according to embodiment 2 is estimated discharge performance.
By the nephelometer available from Switzerland Novasina, by the filtrate of measuring the acquisition of discharging paper stock, the turbidity of plain boiled water, estimate retention property.Measure turbidity take NTU (Nephelometric TurbidityUnits) as unit.
In this embodiment, use similarly employed paper stock and stirring and interpolation pattern in embodiment 2.
Table 3 shows the dehydrating effect under different interpolation patterns.Test No.1 shows the result with any additive.Test Nos.2 and 3 has illustrated and has been used for more employed technique, and test Nos.4 has illustrated according to technique of the present invention.
Table 3
Figure BDA0000065252960000171
Table 3 shows that the inventive method causes improved discharge performance.
Embodiment 4
Operation evaluation discharging and retention property according to embodiment 3.In this embodiment, use similarly embodiment 2 employed paper stocks and stirring and interpolation pattern.
Table 4 shows the dehydrating effect under different interpolation patterns.Test No.1 shows the result with any additive.Test Nos.2-7 has illustrated and has been used for more employed technique, and test Nos.8-9 has illustrated according to technique of the present invention.
Table 4
Figure BDA0000065252960000181
Table 4 shows that method of the present invention causes improved discharging (dehydration) and retention property.
Embodiment 5
Operation evaluation discharging and retention property according to embodiment 3.In this embodiment, use similarly embodiment 2 employed stirrings and interpolation pattern.
The employed paper stock of this embodiment is based on 75%TMP and 25%DIP fibrous material, and from the bleaching water of paper mill.The denseness of paper stock is 0.82%.The conductance of paper stock is that 1.7mS/cm and pH are 7.2.
Table 5 shows the dehydrating effect under different interpolation patterns.Test No.1 shows the result with any additive.Test Nos.2-8 has illustrated and has been used for more employed technique, and test Nos.9 has illustrated according to technique of the present invention.
Table 5
Figure BDA0000065252960000182
Table 5 shows that method of the present invention causes improved discharging (dehydration) and retention property.
Embodiment 6
Operation according to embodiment 2 is estimated discharge performance.In this embodiment, use similarly embodiment 5 employed paper stocks and stirring and interpolation pattern.
Table 6 shows the dehydrating effect under different interpolation patterns.Test No.1 shows the result with any additive.Test Nos.2-6 has illustrated the technique (Ref) that is used for more employed use additive, and test No.7 has illustrated according to technique of the present invention.
Table 6
Figure BDA0000065252960000191
Table 6 shows that method of the present invention causes improved dewatering.
Embodiment 7
Operation according to embodiment 2 is estimated discharge performance.In this embodiment, use similarly embodiment 5 employed paper stocks and stirring and interpolation pattern.
Table 7 shows the dehydrating effect under different interpolation patterns.Test No.1 shows the result with any additive.Test Nos.2-7 has illustrated and has been used for more employed technique, and test No.8 has illustrated according to technique of the present invention.
Table 7
Figure BDA0000065252960000192
Table 7 shows that method of the present invention causes improved dewatering.

Claims (7)

1. produce the method for paper, the method comprises:
(i) provide the aqueous suspension of containing cellulose fiber,
(ii) after all high shear points, add following substances in suspension:
The first polymer, it is the poly-aluminium compound that charge density is higher than 4.0meq/g;
The second polymer, it is that weight average molecular weight is higher than 2,000,000 cation acrylamide based polyalcohol; With
Terpolymer, it is that a kind of weight average molecular weight is higher than 2,000,000 anion acrylamide-based polymers; With
(iii) make the dehydration of gained suspension, form paper.
2. the process of claim 1 wherein that poly-aluminium compound is selected from polyaluminium chloride, poly aluminium sulfate, contains the two poly-aluminium compound, poly-silicic acid-aluminum sulfate of chlorion and sulfate ion, and composition thereof.
3. the process of claim 1 wherein that poly-aluminium compound is polyaluminium chloride.
4. claim 1 or 2 method, wherein the weight average molecular weight of the second polymer is higher than 5,000, and 000.
5. claim 1 or 2 method, wherein the weight average molecular weight of terpolymer is higher than 5,000,000.
6. the process of claim 1 wherein that the charge density of the second polymer is less than 4.0meq/g.
7. the process of claim 1 wherein that the charge density of terpolymer is less than 4.0meq/g.
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