EP2601346B1 - Manufacturing process of paper or cardboard having improved retention and draining properties - Google Patents
Manufacturing process of paper or cardboard having improved retention and draining properties Download PDFInfo
- Publication number
- EP2601346B1 EP2601346B1 EP11752300.1A EP11752300A EP2601346B1 EP 2601346 B1 EP2601346 B1 EP 2601346B1 EP 11752300 A EP11752300 A EP 11752300A EP 2601346 B1 EP2601346 B1 EP 2601346B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- retention
- retention aid
- polymer
- main
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000014759 maintenance of location Effects 0.000 title claims description 146
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000011111 cardboard Substances 0.000 title description 5
- 239000011087 paperboard Substances 0.000 title description 5
- 229920000642 polymer Polymers 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 24
- 125000002091 cationic group Chemical group 0.000 claims description 23
- 125000000129 anionic group Chemical group 0.000 claims description 21
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- 239000002585 base Substances 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 238000006731 degradation reaction Methods 0.000 claims description 15
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 8
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 6
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
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- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 5
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 claims description 5
- ZKYCLDTVJCJYIB-UHFFFAOYSA-N 2-methylidenedecanamide Chemical compound CCCCCCCCC(=C)C(N)=O ZKYCLDTVJCJYIB-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
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- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
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- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
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- SCQOZUUUCTYPPY-UHFFFAOYSA-N dimethyl-[(prop-2-enoylamino)methyl]-propylazanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)CNC(=O)C=C SCQOZUUUCTYPPY-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 99
- 239000000123 paper Substances 0.000 description 24
- 239000000835 fiber Substances 0.000 description 18
- 239000002655 kraft paper Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
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- 239000007857 degradation product Substances 0.000 description 12
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- 230000008569 process Effects 0.000 description 11
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- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- 229920002554 vinyl polymer Polymers 0.000 description 6
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- 229920001131 Pulp (paper) Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 238000010008 shearing Methods 0.000 description 5
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- 150000001412 amines Chemical group 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NBTXFNJPFOORGI-UHFFFAOYSA-N 2-ethenoxyethyl prop-2-enoate Chemical compound C=COCCOC(=O)C=C NBTXFNJPFOORGI-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000447437 Gerreidae Species 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
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- 229920002873 Polyethylenimine Polymers 0.000 description 3
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- ZLSJVVLETDAEQY-UHFFFAOYSA-N n,n-dihexylprop-2-enamide Chemical compound CCCCCCN(C(=O)C=C)CCCCCC ZLSJVVLETDAEQY-UHFFFAOYSA-N 0.000 description 3
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- VZTGWJFIMGVKSN-UHFFFAOYSA-O trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium Chemical compound CC(=C)C(=O)NCCC[N+](C)(C)C VZTGWJFIMGVKSN-UHFFFAOYSA-O 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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
- 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
-
- 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
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
-
- 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
-
- 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
- D21H17/45—Nitrogen-containing groups
-
- 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
Definitions
- the invention relates to a process for the production of paper and paperboard having improved retention and drainage properties. More specifically, the subject of the invention is a manufacturing method using at least two retention and dewatering agents, respectively a main agent and a secondary agent. It also relates to paper or paperboard obtained by this method.
- retention systems are well known in papermaking processes. Their function is to improve the retention (ie the amount of fillers in the paper) and the drainage (ie the water drainage rate) during the manufacture of the leaf.
- the patent EP 1 328 161 discloses a system for improving retention and dewatering in the manufacture of paper or board using three retention agents.
- the first is a cationic flocculant IV of intrinsic viscosity greater than 4 dl / g
- the second is a siliceous material
- the third a water-soluble anionic polymer of IV greater than or equal to 4 dl / g.
- Hofmann degradation on a (co) polymer base is a known reaction to change from an amide to a primary amine having one carbon atom less.
- Hofmann degradation products are well known for their use as a dry strength agent.
- the molecular weight of the degradation product is of the order of less than 1 million g / mol, and therefore much less than the molecular weight of the cationic polymers used as dripping and retention agent (greater than 2 million g / mol ).
- As a toughener in papermaking processes they are associated with low molecular weight anionic resins.
- Such a system is for example that described in the document WO2006 / 075115 of the Applicant. It is in fact a question of a cationic polymer obtained by Hofmann degradation reaction produced at a concentration greater than 3.5% combined with an anionic resin whose highest viscosity is 9000 cps (15% solution). which corresponds to a maximum IV of about 2.0 dl / g.
- a similar system is also described in the document WO2008 / 107620 , still Applicant, which differs from the previous in that the base copolymer on which the degradation is carried out is branched, and in that the degradation is carried out in the presence of calcium hypochlorite.
- the maximum viscosity described of the anionic resin is 2500 cps, which corresponds to a maximum IV of 1.6 dl / g.
- Requirement WO2009 / 013423 again from the Applicant, differs from the previous ones in that the polymer obtained at the end of the Hofmann degradation reaction is branched after said reaction.
- the IV of the anionic resin used is at most 1.6 dl / g.
- retention properties is meant the ability to retain the suspended matter of the paper pulp (fibers, fines, fillers (calcium carbonate, titanium oxide), ...) on the training fabric, therefore in the mattress fibrous which will constitute the final leaf.
- the mode of action of the retention agents is based on flocculation of these suspended solids in water. Indeed, the formed flocs are more easily retained on the training web.
- the fibrous mattress it is the ability of the fibrous mattress to evacuate or drain the maximum amount of water so that the sheet dries as quickly as possible.
- polymers of high molecular weight at least 1 million g / mol
- weakly cationic These polymers are generally introduced at a level of 50 to 800 g / t of dry polymer relative to the dry paper.
- dry strength is the ability of the sheet to withstand mechanical stresses and degradations such as puncture, tearing, pulling, delamination and various forms of compression. These are the final properties of the sheet.
- the dry strength resins are generally polymers of average molecular weight (between 10,000 and 1.000000 g / mol), and the usual dosages applied are of the order of 1.5 to 2 kg / t (dry polymer relative to the paper dry), ie 5 to 10 times higher than the retention and dripping dosages, even though a wide range of 100 to 20,000 g / t is disclosed in the application WO2009 / 013423 .
- these dry strength resins in particular for the cationic polymer, are generally located in thick paste, otherwise called Thick Stock, whose dry matter concentration is generally greater than 1% and most often greater than 2%, so before the mixing pump (or Fan Pump) and therefore the dilution with white water.
- the Claimant further specifies that the examples of the application WO2009 / 13423 mention pulp concentrations in the order of 0.3 to 0.5%, which corresponds to the values required to perform the standard laboratory tests, but which do not correspond to the pulp concentrations in the industrial processes in which these resistance agents are used dry, and which are generally greater than 2% dry matter.
- Dry-strength polymers bind to the fibers by hydrogen and / or ionic bonding to, once the sheet is dried, improve the strength of the paper.
- the dry strength of the paper is by definition the strength of the normally dry sheet. Burst and tensile strength values traditionally provide a measure of the dry strength of the paper.
- the invention thus has the advantage of using a cationic polymer of low molecular weight without the need for shearing steps that are difficult to control and without heavy equipment for implementation (simulates in-line or tangential dilution instead of a complex unit). preparation) to improve retention and drainage.
- the main retention agent is introduced into the fibrous suspension at a rate of 200 to 500 g / t of dry pulp.
- the secondary retention agent is introduced into the fibrous suspension advantageously from 80 to 500 g / t, preferably from 100 to 350 g / t.
- the use of low molecular weight product makes it possible to put the retention system in place, possibly, without intermediate shear, or even after the last shear point (centriscreen), which has the consequence of limiting the dosages of each ingredient while maintaining a high level of performance.
- the introduction of the retention agents is separated, if necessary, by a shearing step.
- This system with at least two components can be used successfully for the manufacture of paper and cardboard packaging, paper coating media, any type of paper, cardboard or the like requiring improved retention and drainage properties, with increased formation, at main retention agent dosages ranging from 100 to 800 g / t dry pulp, which is impossible for conventional high molecular weight cationic polyacrylamide retention agents.
- the cationic flocculant conventionally used could be substituted with a cationic (co) polymer obtained by reaction.
- Hofmann degradation method on an acrylamide (co) polymer when used in combination with a high molecular weight water soluble or hydrogenation anionic polymer.
- IV means the intrinsic viscosity expressed in dl / g.
- main retention agent a very low molecular weight compound based on acrylamide, particularly unsuitable for flocculating the fibers, especially when the process is carried out in closed circuits, when it uses recycled fibers and when it is driven at increased paper machine speeds.
- One of the merits of the invention is to have developed a papermaking process which uses as main retention agent an aqueous solution that does not require a constraining step of preparation.
- the cationic (co) polymer of the invention can easily be introduced into the system with a simple tangential or in-line dilution permitting its instantaneous incorporation into the wet part of the machine.
- a tertiary retention agent may also be added, either between the two agents mentioned above, or after the secondary agent.
- They are derivatives of silica, for example silica particles, including bentonites, montmorillonites or derivatives of aluminosilicate or borosilicate type, zeolites, kaolinites, or colloidal silicas modified or not.
- the method of the invention makes it possible to obtain a significantly improved retention.
- An additional feature of this improvement is also improved the dewatering properties without deteriorating the quality of sheet formation, even at main retention agent dosages ranging from 100 to 800 g of material. active per tonne of dry pulp.
- This process achieves a level of performance unmatched until now in the paper application for total retention and charge, and dripping, including for pulp containing high levels of recycled fibers.
- the main retention agent is chosen from cationic or amphoteric copolymers characterized in that they are obtained by so-called Hofmann degradation on an acrylamide base precursor (base polymer) in the presence of an alkali hydroxide and / or alkaline earth (preferably sodium hydroxide), and an alkaline and / or alkaline earth hypochlorite (preferably sodium hypochlorite).
- the base copolymer is a synthetic water-soluble polymer based on acrylamide containing at least one nonionic monomer such as for example acrylamide, and optionally other monomers such as for example one or more monomers, or cationic, such as for example the dimethyldiallylammonium chloride (DADMAC), either anionic such as for example acrylic acid or hydrophobic character.
- nonionic monomer such as for example acrylamide
- cationic such as for example the dimethyldiallylammonium chloride (DADMAC), either anionic such as for example acrylic acid or hydrophobic character.
- DADMAC dimethyldiallylammonium chloride
- water-insoluble monomers such as acrylic, allylic or vinyl monomers having a hydrophobic group.
- these monomers will be used in very small quantities, less than 10 mol%, preferably less than 5 mol%, even less than 1%, and they will be chosen preferentially from the group comprising acrylamide derivatives such as N-alkylacrylamide for example N-tert-butylacrylamide, octylacrylamide and N, N-dialkylacrylamides such as N, N-dihexylacrylamide ... acrylic acid derivatives such as alkyl acrylates and methacrylates ...
- the base copolymer may be branched.
- the branching may preferably be carried out during (or possibly after) the polymerization of the "base” copolymer, in the presence of a polyfunctional branching agent and optionally of a transfer agent.
- a polyfunctional branching agent and optionally of a transfer agent.
- the following is a nonlimiting list of branching agents: methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, triallylamine, formaldehyde, glyoxal, glycidyl ether compounds such as ethylene glycol glycidyl ether, or epoxy or any other means well known to those skilled in the art for crosslinking.
- MBA methylene bisacrylamide
- ethylene glycol di-acrylate polyethylene glycol dimethacrylate
- diacrylamide diacrylamide
- cyanomethylacrylate vinyloxyethylacrylate or methacryl
- the branching agent is advantageously introduced at a rate of from five to fifty thousand (5 to 50,000) parts per million by weight relative to the active ingredient, preferably from 5 to 10,000, advantageously from 5 to 5,000.
- the branching agent is methylenebisacrylamide (MBA).
- the copolymer serving as a basis for the Hofmann degradation reaction does not require the development of a particular polymerization process.
- the main polymerization techniques well known to those skilled in the art and which can be used are: precipitation polymerization, emulsion polymerization (aqueous or inverse) followed or not by a distillation step and / or spray drying, and suspension polymerization or solution polymerization, both of which are preferred.
- This base is characterized in that it has a molecular weight advantageously greater than 5000 and without any maximum limitation, the only limiting factor being, for obvious implementation constraints, the viscosity of the polymeric solution, which is a function of the concentration of (co) polymer and its molecular weight.
- additives which are capable of reacting with the isocyanate functions of the polymer generated during degradation.
- these are molecules bearing nucleophilic chemical functions such as hydroxyl or amine functions.
- the additives in question may therefore be of the family: alcohols, polyols (eg: starch), polyamines, polyethylene imines ...
- the molar amount of total (meth) acrylamide function is determined.
- the desired Alpha degradation level (which corresponds to the desired degree of amine function) is then chosen, which makes it possible to determine the dry quantity of alkaline and / or alkaline earth hypohalide and then the beta coefficient, which allows determine the dry quantity of alkali and / or alkaline earth hydroxide.
- hypohalide and alkali and / or alkaline earth hydroxide are then prepared from the alpha and beta ratios.
- the reagents preferably used are sodium hypochlorite (bleach) and sodium hydroxide (sodium hydroxide).
- the Hofmann degradation product is obtained by reaction of an alkaline earth metal hydroxide and an alkaline earth hypohalide with a hydroxide / hypohalide molar ratio of between 2 and 6, preferably between 2 and 6. and 5.
- the Hofmann degradation product is produced at a concentration greater than 4% by weight, preferably greater than 7%, advantageously greater than 8% and advantageously has a viscosity of greater than 30 cps (at a concentration of 9%, at 25 ° C., Brookfield LV1, 60 rpm), preferably greater than 40 cps.
- the amount of the main retention agent introduced into the suspension is between 100 and 800 grams of active polymer per tonne of dry pulp (g / t).
- the amount of main retention agent introduced is between 200 g / t and 500 g / t.
- the injection or the introduction of the main retention agent according to the invention is carried out before a possible shearing step, in the pulp more or less diluted according to the practice of the person skilled in the art, and generally in the diluted paper stock or thin stock.
- the injection of the main retention agent is advantageously carried out in the diluted pulp with a concentration of at most 2%.
- the secondary retention agent will be chosen from all types of water-soluble organic polymers or hydrogonflux of anionic charge density greater than 0.1 meq / g. These polymers have an intrinsic viscosity greater than 3 dl / g.
- the water-soluble polymers used do not require development of a particular polymerization process. They can be obtained by any of the polymerization techniques well known to those skilled in the art (solution polymerization, suspension polymerization, gel polymerization, precipitation polymerization, emulsion polymerization (aqueous or reverse), microemulsion polymerization followed or not a step of spray drying, suspension polymerization, micellar polymerization followed or not by a precipitation step).
- the polymer may have a linear, branched, crosslinked structure or a star polymer (comb polymer) comb structure.
- the secondary retention agent is introduced into the suspension, very preferably in a proportion of 50 g / t to 800 g / t by weight of active polymer per tonne of dry pulp, preferably from 80 g / t to 500 g / t, and more preferably from 100 to 350 g / t.
- These agents preferably comprise, but are not limited to, alone or in admixture: silica derivatives, for example silica particles whose bentonites come from hectorites, smectites, montmorillonites, nontronites, saponites, sauconites, of hormones, attapulgites and sepiolites, derivatives of aluminosilicates or borosilicates type, zeolites, kaolinites, or colloidal silicas modified or not.
- silica derivatives for example silica particles whose bentonites come from hectorites, smectites, montmorillonites, nontronites, saponites, sauconites, of hormones, attapulgites and sepiolites, derivatives of aluminosilicates or borosilicates type, zeolites, kaolinites, or colloidal silicas modified or not.
- This type of tertiary agent is preferably introduced just upstream of the headbox, at a rate of 300 to 3000 g / t dry weight of active ingredient per tonne of dry pulp, preferably 800 to 2000 g / t.
- the tertiary retention agent may also be chosen from water-soluble or hydrogen-floating organic polymers with anionic charge density greater than 0.1 meq / g, advantageously with IV intrinsic viscosity greater than 3 dl / g, this polymer being different from the polymer used as an agent. secondary retention.
- the dosage of the tertiary retention agent is chosen in the same range as that of the secondary retention agent, that is to say at a rate of 50 g / t to 800 g / t by weight of polymer. active per ton of dry pulp, preferably from 80 g / t to 500 g / t, and more preferably from 100 to 350 g / t.
- a coagulant is added to the fibrous suspension, prior to the addition of the main retention agent.
- this type of product makes it possible to neutralize the harmful anionic colloids which impact the performance of the cationic retention agent, at dosages (in active form) of from 0.01 to 10. kg / t and preferably between 0.03 and 3 kg / t.
- dosages in active form
- Mention may be made in particular, and by way of examples, of coagulants chosen from the group comprising inorganic coagulants such as polyaluminium chloride (PAC), alumina sulphate and polychlorosulphate.
- organic coagulants of which - polymers based on diallyldimethylammonium chloride (DADMAC), - quaternary polyamines manufactured by condensation of a primary or secondary amine on epichlorohydrin or resins of the type dicyandiamide.
- DMDMAC diallyldimethylammonium chloride
- quaternary polyamines manufactured by condensation of a primary or secondary amine on epichlorohydrin or resins of the type dicyandiamide.
- the retention system of the invention provides good performance particularly in total retention, retention of charges, drainage and clarification of white water without destroying the formation.
- the retention first passes in percentage (% FPR: First Pass Retention), corresponding to the total retention being calculated according to the following formula: % RPF VS HB - VS WW / VS HB * 100
- CSF Canadian Standard Freeness
- turbidity measurement NTU is carried out using a Hach 2100N type apparatus.
- a static form is used for the purpose of producing sheets with a pulp treated or not, beforehand with the various retention systems chosen, then this sheet is pressed and dried.
- the gains observed are between 2 and 7 points with regard to the total retention and between 0.5 and 8 points for the retention of charges. This increase in retention will allow the paper manufacturer to obtain papers with higher load rates, and this with a shorter circuit less loaded which ensures less fouling of the machine and therefore a lower frequency of breakages and machine downtime.
- the gains observed in dewatering are of the order of 80 to 100 ml, which is therefore this gain being totally unexpected for those skilled in the art, for a use of product of very low molecular weight compared to a retention agent conventionally used (P0).
- the paper manufacturer will be able to use these products with a real interest in terms of ease and cost of implementation. in use, the main retention agent being in liquid form, and thus not requiring a specific preparation unit as is necessary for conventional high molecular weight cationic polyacrylamide retention agents in the form of powder or emulsion.
- the dosage increase of the main retention agent has the effect of improving the drainage performance and clarification of white water. It should also be noted that the products of the invention remain more efficient than a retention polymer conventionally used.
- the primary retention agents of the invention being of low molecular weight, allow their use at such dosages without destruction of the formation of the sheet, thus allowing to obtain levels of retention and dewatering still never achieved by primary retention agents conventionally used.
Description
L'invention concerne un procédé pour la fabrication du papier et du carton présentant des propriétés de rétention et d'égouttage améliorées. Plus précisément, l'invention a pour objet un procédé de fabrication mettant en oeuvre au moins deux agents de rétention et d'égouttage, respectivement un agent principal et un agent secondaire. Elle a également pour objet les papiers ou cartons obtenus par ce procédé.The invention relates to a process for the production of paper and paperboard having improved retention and drainage properties. More specifically, the subject of the invention is a manufacturing method using at least two retention and dewatering agents, respectively a main agent and a secondary agent. It also relates to paper or paperboard obtained by this method.
La mise en oeuvre de systèmes de rétention est bien connue dans les procédés de fabrication de papier. Ils ont pour fonction d'améliorer la rétention (c'est à dire la quantité de charges dans le papier) et l'égouttage (c'est-à-dire la vitesse de drainage de l'eau) lors de la fabrication de la feuille.The implementation of retention systems is well known in papermaking processes. Their function is to improve the retention (ie the amount of fillers in the paper) and the drainage (ie the water drainage rate) during the manufacture of the leaf.
Le brevet
Tous les systèmes de rétention et d'égouttage connus dans l'art antérieur sont caractérisés par le fait qu'ils ont pour agent principal de rétention, des polymères hydrosolubles de haut poids moléculaire, supérieur à 1 million g/mol, généralement supérieur à 3 millions, appelés floculants. Ils sont généralement cationiques et ont la particularité, en raison de leur haut poids moléculaire de se présenter sous forme d'émulsion (inverse), de microémulsion, de poudre ou de dispersion.All the retention and dewatering systems known in the prior art are characterized in that they have, as main retention agent, water-soluble polymers with a high molecular weight of greater than 1 million g / mol, generally greater than 3 millions, called flocculants. They are generally cationic and have the particularity, because of their high molecular weight to be in the form of (inverse) emulsion, microemulsion, powder or dispersion.
La dégradation d'Hofmann sur un (co)polymère base est une réaction connue permettant de passer d'un amide à une amine primaire possédant un atome de carbone en moins.Hofmann degradation on a (co) polymer base is a known reaction to change from an amide to a primary amine having one carbon atom less.
Les produits de dégradation d'Hofmann sont bien connus pour leur utilisation comme agent de résistance à sec. En pratique, le poids moléculaire du produit de dégradation est de l'ordre de moins de 1 million g/mol, donc très inférieur au poids moléculaire des polymères cationiques utilisés comme agent d'égouttage et de rétention (supérieur à 2 million g/mol). Comme agent de résistance dans des procédés de fabrication de papier, ils sont associés à des résines anioniques de bas poids moléculaire.Hofmann degradation products are well known for their use as a dry strength agent. In practice, the molecular weight of the degradation product is of the order of less than 1 million g / mol, and therefore much less than the molecular weight of the cationic polymers used as dripping and retention agent (greater than 2 million g / mol ). As a toughener in papermaking processes, they are associated with low molecular weight anionic resins.
Un tel système est par exemple celui décrit dans le document
Il est essentiel dans l'invention de bien distinguer les propriétés de rétention et d'égouttage d'une part et les propriétés de résistance à sec d'autre part.It is essential in the invention to clearly distinguish the retention and dewatering properties on the one hand and the dry strength properties on the other hand.
Par propriétés de rétention, on entend la capacité à retenir les matières en suspension de la pâte à papier (fibres, fines, charges (carbonate de calcium, oxyde de titane), ...) sur la toile de formation, donc dans le matelas fibreux qui constituera la feuille finale. Le mode d'action des agents de rétention est basé sur la floculation de ces matières en suspension dans l'eau. En effet, les flocs formés sont plus facilement retenus sur la toile de formation.By retention properties is meant the ability to retain the suspended matter of the paper pulp (fibers, fines, fillers (calcium carbonate, titanium oxide), ...) on the training fabric, therefore in the mattress fibrous which will constitute the final leaf. The mode of action of the retention agents is based on flocculation of these suspended solids in water. Indeed, the formed flocs are more easily retained on the training web.
En ce qui concerne les propriétés d'égouttage (ou drainage), il s'agit de la capacité du matelas fibreux à évacuer ou drainer le maximum d'eau afin que la feuille sèche le plus rapidement possible.Regarding the drainage properties (or drainage), it is the ability of the fibrous mattress to evacuate or drain the maximum amount of water so that the sheet dries as quickly as possible.
Ces deux propriétés (rétention et drainage) étant intimement liées, l'une dépendant de l'autre, il s'agit alors de trouver le meilleur compromis entre la rétention et l'égouttage. De manière générale l'homme du métier fait référence à un agent de rétention et d'égouttage car ce sont les mêmes types de produits qui permettent d'améliorer ces deux propriétés.These two properties (retention and drainage) being intimately linked, one dependent on the other, it is then a question of finding the best compromise between the retention and the dripping. In general, those skilled in the art refer to a retention agent and dewatering agent because it is the same types of products that make it possible to improve these two properties.
Il s'agit généralement de polymères de haut poids moléculaires (au moins 1 million de g/mol), faiblement cationiques. Ces polymères sont généralement introduits à hauteur de 50 à 800 g/t de polymère sec par rapport au papier sec.It is generally polymers of high molecular weight (at least 1 million g / mol), weakly cationic. These polymers are generally introduced at a level of 50 to 800 g / t of dry polymer relative to the dry paper.
Les points d'introduction de ces agents dans le procédé papetier sont généralement situés dans le circuit court, c'est-à-dire après la pompe de mélange (ou Fan Pump), et donc en pâte diluée (ou Thin Stock) dont la concentration est très généralement inférieure à 1% en poids de matière sèche, le plus souvent comprise entre 0.1 et 0.7%.The points of introduction of these agents into the papermaking process are generally located in the short circuit, that is to say after the mixing pump (or Fan Pump), and therefore in diluted paste (or Thin Stock) whose concentration is very generally less than 1% by weight of dry matter, most often between 0.1 and 0.7%.
Contrairement aux propriétés de rétention et de drainage, la résistance à sec représente la capacité de la feuille à résister aux contraintes et dégradations mécaniques telles que la perforation, la déchirure, la traction, la délamination et différentes formes de compression. Il s'agit des propriétés finales de la feuille.Unlike retention and drainage properties, dry strength is the ability of the sheet to withstand mechanical stresses and degradations such as puncture, tearing, pulling, delamination and various forms of compression. These are the final properties of the sheet.
Les résines de résistance à sec sont généralement des polymères de poids moléculaires moyens (entre 10.000 et 1.000000 g/mol), et les dosages usuels appliqués sont de l'ordre de 1,5 à 2 kg/t (polymère sec par rapport au papier sec), c'est-à-dire 5 à 10 fois plus élevés que les dosages appliqués à la rétention et à l'égouttage, même si une fourchette large comprise entre 100 et 20.000 g/t est divulguée dans la demande
Par ailleurs, les points d'introduction de ces résines de résistance à sec, notamment pour le polymère cationique, sont généralement situés en pâte épaisse, autrement appelée Thick Stock, dont la concentration en matière sèche est généralement supérieure à 1% et le plus souvent supérieur à 2%, donc avant la pompe de mélange (ou Fan Pump) et donc la dilution avec les eaux blanches.Moreover, the points of introduction of these dry strength resins, in particular for the cationic polymer, are generally located in thick paste, otherwise called Thick Stock, whose dry matter concentration is generally greater than 1% and most often greater than 2%, so before the mixing pump (or Fan Pump) and therefore the dilution with white water.
Le Demandeur précise en outre que les exemples de la demande
Les polymères apportant de la résistance à sec se lient aux fibres par liaison hydrogène et/ou ionique pour, une fois la feuille séchée, améliorer la résistance mécanique du papier.Dry-strength polymers bind to the fibers by hydrogen and / or ionic bonding to, once the sheet is dried, improve the strength of the paper.
Il va donc de soi que, d'une part, de bonnes propriétés de rétention et d'égouttage sont recommandées pour optimiser la fabrication du papier et donc la productivité de la machine à papier, et d'autre part, de manière totalement différente, de bonnes propriétés de résistance à sec auront pour effet une amélioration des propriétés mécaniques (et donc de la qualité) de la feuille.It goes without saying that, on the one hand, good retention and dewatering properties are recommended to optimize the papermaking and therefore the productivity of the paper machine, and on the other hand, in a completely different way, good Dry strength properties will result in improved mechanical properties (and thus quality) of the sheet.
Dans la suite de la description et dans les revendications, tous les dosages de polymère exprimés en g/t sont donnés en poids de polymère actif par tonne de pâte sèche.In the rest of the description and in the claims, all the polymer dosages expressed in g / t are given by weight of active polymer per ton of dry pulp.
La résistance à sec du papier est par définition la résistance de la feuille normalement sèche. Les valeurs de résistance à l'éclatement et à la traction donnent traditionnellement une mesure de la résistance à sec du papier.The dry strength of the paper is by definition the strength of the normally dry sheet. Burst and tensile strength values traditionally provide a measure of the dry strength of the paper.
Un effet secondaire de l'application de ces systèmes de résistance à sec, à des dosages importants, est accompagné, accessoirement, d'une amélioration de rétention, mais à des coûts prohibitifs qui ne justifient en rien leur utilisation pour ce seul but.A side effect of the application of these dry resistance systems, at large doses, is accompanied, incidentally, by an improvement in retention, but at prohibitive costs which do not justify their use for this purpose alone.
Il ressort donc de ce qui précède qu'il était connu à la date de dépôt de la présente demande d'associer, pour améliorer la résistance à sec dans un procédé de fabrication de papier ou de carton, un produit de dégradation d'Hofmann cationique de bas poids moléculaire à une résine anionique également de bas poids moléculaire, les deux agents étant introduits durant le procédé à des doses de l'ordre de 1.5 à 2 kg/t.It therefore follows from the foregoing that it was known at the filing date of the present application to combine, to improve the dry strength in a paper or board manufacturing process, a cationic Hofmann degradation product. of low molecular weight to an anionic resin also of low molecular weight, the two agents being introduced during the process at doses of the order of 1.5 to 2 kg / t.
Malgré les progrès réalisés ces dernières années, l'industrie papetière rencontre encore les problématiques suivantes dans les systèmes de rétention et égouttage :
- difficulté et coût de mise en oeuvre des floculants cationiques comme agent principal de rétention. Leur haut poids moléculaire oblige à les utiliser sous des formes nécessitant des unités de préparation (inversion des émulsions, dissolution des poudres), coûteuses en main d'oeuvre, en équipement et en maintenance. Les étapes nécessaires de filtration sont aussi à l'origine de nombreux arrêts de ligne et de coûts supplémentaires ;
- un problème de filtration de particules insolubles, voire un colmatage des filtres peut occasionner des défauts majeurs sur la machine à papier : casses, défauts sur le papier tels que des clairs, des trous, ...;
- l'impact négatif sur la formation de la feuille, lors de l'utilisation de polymères de trop haut poids moléculaire ou de polymères de haut poids moléculaires à fort dosages;
- la mise en oeuvre de floculant de haut poids moléculaire rendue nécessaire par des vitesses de machines de plus en plus importantes donc des cisaillement et des taux de charges de la feuille de plus en plus élevés.
- difficulty and cost of using cationic flocculants as the main retention agent. Their high molecular weight makes it necessary to use them in forms requiring preparation units (inversion of emulsions, dissolution of powders), which are costly in terms of manpower, equipment and maintenance. The necessary filtration steps are also responsible for many line stops and additional costs;
- a problem of filtration of insoluble particles, or even clogging of the filters can cause major defects on the paper machine: breaks, defects on the paper such as clear, holes, ...;
- the negative impact on the formation of the sheet, when using too high molecular weight polymers or high molecular weight polymers with high dosages;
- the implementation of high molecular weight flocculant made necessary by machine speeds increasingly important so shear and filler rates of the sheet higher and higher.
Le Demandeur a constaté que de manière toute à fait surprenante, la mise en oeuvre d'un système similaire à celui décrit dans les documents précités, dans lequel :
- la résine anionique de bas poids moléculaire est remplacée par un polymère anionique de haut poids moléculaire,
- le dosage de chacun des deux polymères est rapporté de 1500 à 2000g/t à 100 à 800 g/t pour le polymère cationique et de 50 à 800 g/t pour le polymère anionique,
- the anionic resin of low molecular weight is replaced by a high molecular weight anionic polymer,
- the dosage of each of the two polymers is reported from 1500 to 2000 g / t at 100 to 800 g / t for the cationic polymer and from 50 to 800 g / t for the anionic polymer,
L'invention présente ainsi l'avantage de mettre en oeuvre un polymère cationique de bas poids moléculaire sans nécessaire étapes de cisaillement difficilement contrôlable et sans équipement lourd de mise en oeuvre (simule dilution en ligne ou tangentielle en lieu et place d'une unité complexe de préparation) pour améliorer la rétention et l' égouttage.The invention thus has the advantage of using a cationic polymer of low molecular weight without the need for shearing steps that are difficult to control and without heavy equipment for implementation (simulates in-line or tangential dilution instead of a complex unit). preparation) to improve retention and drainage.
En d'autres termes, l'invention a pour objet un procédé de fabrication d'une feuille de papier et/ou de carton présentant avantageusement des propriétés de rétention et d'égouttage améliorées, selon lequel, avant formation de ladite feuille et/ou de carton, on ajoute à la suspension fibreuse, en un ou plusieurs points d'injection, au moins deux agents de rétention respectivement :
- un agent principal de rétention correspondant à un (co)polymère de densité de charge cationique supérieure à 2 meq/g, obtenu par réaction de dégradation dite d'Hofmann, en solution aqueuse, en présence d'un hydroxyde d'alcalino-terreux et/ou d'alcalin et d'un hypohalogénure d'alcalino-terreux et/ou d'alcalin, sur un (co)polymère base comprenant au moins un monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylatnide) et le N,N diméthylacrylamide,
- un agent secondaire de rétention correspondant à un polymère hydrosoluble ou hydrogonflant de densité de charge anionique supérieure à 0,1 meq/g.
- a main retention agent corresponding to a cationic charge density (co) polymer of greater than 2 meq / g, obtained by the so-called Hofmann degradation reaction, in aqueous solution, in the presence of an alkaline earth hydroxide and and / or alkaline and an alkaline earth and / or alkaline hypohalide, on a (co) polymer base comprising at least one nonionic monomer chosen from the group comprising acrylamide (and / or methacrylate) ) and N, N dimethylacrylamide,
- a secondary retention agent corresponding to a water-soluble or hydrogoniferous polymer of anionic charge density greater than 0.1 meq / g.
Le procédé se caractérise en ce que :
- l'agent principal de rétention est introduit dans la suspension fibreuse à raison de 100 à 800 g/t de pâte sèche,
- l'agent secondaire de rétention est introduit dans la suspension fibreuse à raison de 50 à 800 g/t de pâte sèche et présente une viscosité intrinsèque IV supérieure à 3 dl/g.
- the main retention agent is introduced into the fibrous suspension at a rate of 100 to 800 g / t of dry pulp,
- the secondary retention agent is introduced into the fibrous suspension at a rate of 50 to 800 g / t of dry pulp and has an IV intrinsic viscosity greater than 3 dl / g.
Dans un mode de réalisation préféré, l'agent principal de rétention est introduit dans la suspension fibreuse à raison de 200 à 500 g/t de pâte sèche.In a preferred embodiment, the main retention agent is introduced into the fibrous suspension at a rate of 200 to 500 g / t of dry pulp.
De même, l'agent secondaire de rétention est introduit dans la suspension fibreuse à raison avantageusement de 80 à 500 g/t, de préférence entre 100 et 350 g/t.Similarly, the secondary retention agent is introduced into the fibrous suspension advantageously from 80 to 500 g / t, preferably from 100 to 350 g / t.
Par ailleurs, l'utilisation de produit de bas poids moléculaire permet de mettre le système de rétention en place, éventuellement, sans cisaillement intermédiaire, voire après le dernier point de cisaillement (centriscreen), ce qui a pour conséquence de limiter les dosages de chaque ingrédient tout en maintenant un haut niveau de performances.Moreover, the use of low molecular weight product makes it possible to put the retention system in place, possibly, without intermediate shear, or even after the last shear point (centriscreen), which has the consequence of limiting the dosages of each ingredient while maintaining a high level of performance.
En d'autres termes, dans un mode de réalisation particulier, l'introduction des agents de rétention est séparée le cas échéant, par une étape de cisaillement.In other words, in a particular embodiment, the introduction of the retention agents is separated, if necessary, by a shearing step.
Ce système à au moins 2 composantes peut être utilisé avec succès pour la fabrication de papiers et cartons d'emballage, de papiers supports de couchage, de tout type de papiers, cartons ou analogues nécessitant des propriétés de rétention et d'égouttage améliorées, avec une formation accrue, à des dosages d'agent principal de rétention s'étendant de 100 à 800 g/t de pâte sèche , ce qui est impossible pour les agents de rétention habituels de type polyacrylamide cationique de haut poids moléculaire.This system with at least two components can be used successfully for the manufacture of paper and cardboard packaging, paper coating media, any type of paper, cardboard or the like requiring improved retention and drainage properties, with increased formation, at main retention agent dosages ranging from 100 to 800 g / t dry pulp, which is impossible for conventional high molecular weight cationic polyacrylamide retention agents.
Comme déjà dit, selon la présente invention, il a été découvert de manière surprenante et totalement inattendue que dans un système de rétention égouttage à au moins deux composants, le floculant cationique traditionnellement utilisé pouvait être substitué par un (co)polymère cationique obtenu par réaction de dégradation d'Hofmann sur un (co)polymère d'acrylamide, lorsqu'utilisé en combinaison avec un polymère anionique hydrosoluble ou hydrogonflant de haut poids moléculaire.As already stated, according to the present invention, it has surprisingly and unexpectedly been discovered that in a two-component dewatering retention system, the cationic flocculant conventionally used could be substituted with a cationic (co) polymer obtained by reaction. Hofmann degradation method on an acrylamide (co) polymer, when used in combination with a high molecular weight water soluble or hydrogenation anionic polymer.
Le procédé de l'invention met en oeuvre au moins un agent de rétention principal qui est un (co)polymère obtenu par réaction de dégradation d'Hofmann sur un (co)polymère d'acrylamide (et/ou le méthacrylamide), et/ou de N,N diméthylacrylamide, ledit (co)polymère étant caractérisé en ce que :
- le polymère est sous forme d'une solution aqueuse ;
- son poids moléculaire est inférieur à 1 million de g/mol, préférentiellement inférieur à 500.000 g/mol, plus préférentiellement inférieur à 100.000 g/mol ;
- sa cationicité est supérieure à 2 meq/g, préférentiellement supérieure à 4 meq/g ;
- il est introduit à des dosages entre 100 et 800 g de polymère actif par tonne de pâte sèche (g/t), préférentiellement entre 200 et 500 g/t.
- the polymer is in the form of an aqueous solution;
- its molecular weight is less than 1 million g / mol, preferably less than 500,000 g / mol, more preferably less than 100,000 g / mol;
- its cationicity is greater than 2 meq / g, preferably greater than 4 meq / g;
- it is introduced at dosages between 100 and 800 g of active polymer per ton of dry pulp (g / t), preferably between 200 and 500 g / t.
Le procédé de l'invention met en oeuvre au moins un second agent de rétention qui est un polymère hydrosoluble ou hydrogonflant de densité de charge anionique supérieure à 0.1 meq/g caractérisé en ce que :
- il a une viscosité intrinsèque IV supérieure à 3dl/g.
- il est introduit à des dosages entre 50 et 800 g de polymère actif par tonne de pâte sèche (g/t), préférentiellement entre 80 et 500 g/t, plus préférentiellement entre 100 et 350 g/t.
- it has an IV intrinsic viscosity greater than 3dl / g.
- it is introduced at dosages between 50 and 800 g of active polymer per ton of dry pulp (g / t), preferably between 80 and 500 g / t, more preferably between 100 and 350 g / t.
Par IV, on entend la viscosité intrinsèque exprimée en dl/g.IV means the intrinsic viscosity expressed in dl / g.
L'homme de métier était dissuadé d'utiliser comme agent principal de rétention, un composé de très faible poids moléculaire à base d'acrylamide, particulièrement inapproprié pour floculer les fibres, notamment lorsque le procédé est mis en oeuvre dans des circuits fermés, lorsqu'il met en oeuvre des fibres recyclées et lorsqu'il est conduit à des vitesses de machine à papier accrues. Un des mérites de l'invention est d'avoir élaboré un procédé de fabrication de papier qui utilise comme agent principal de rétention une solution aqueuse ne nécessitant pas d'étape contraignante de préparation. Le (co)polymère cationique de l'invention peut facilement être introduit dans le système avec simplement une dilution tangentielle ou en ligne permettant son incorporation instantanée en partie humide de la machine.Those skilled in the art were dissuaded from using as the main retention agent, a very low molecular weight compound based on acrylamide, particularly unsuitable for flocculating the fibers, especially when the process is carried out in closed circuits, when it uses recycled fibers and when it is driven at increased paper machine speeds. One of the merits of the invention is to have developed a papermaking process which uses as main retention agent an aqueous solution that does not require a constraining step of preparation. The cationic (co) polymer of the invention can easily be introduced into the system with a simple tangential or in-line dilution permitting its instantaneous incorporation into the wet part of the machine.
Selon l'invention un agent tertiaire de rétention peut aussi être ajouté, soit entre les deux agents précédemment cités, soit après l'agent secondaire. Il s'agit de dérivés de la silice comme par exemple les particules de silice, dont les bentonites, montmorillonites ou de dérivés de type aluminosilicates ou borosilicates, les zéolites, les kaolinites, ou les silices colloïdales modifiées ou non.According to the invention a tertiary retention agent may also be added, either between the two agents mentioned above, or after the secondary agent. They are derivatives of silica, for example silica particles, including bentonites, montmorillonites or derivatives of aluminosilicate or borosilicate type, zeolites, kaolinites, or colloidal silicas modified or not.
Les additions de l'agent de rétention principal et des agents secondaires et tertiaires sont séparées ou non par une étape de cisaillement, par exemple au niveau de la pompe de mélange dite fan pump. On se référera dans ce domaine à la description du brevet
Le procédé de l'invention permet d'obtenir une rétention nettement améliorée. On améliore également, ce qui est une caractéristique supplémentaire de ce perfectionnement, les propriétés d'égouttage sans détériorer la qualité de formation de la feuille et ce, même à dosages d'agent principal de rétention s'étendant de 100 à 800 g de matière active par tonne de pâte sèche.The method of the invention makes it possible to obtain a significantly improved retention. An additional feature of this improvement is also improved the dewatering properties without deteriorating the quality of sheet formation, even at main retention agent dosages ranging from 100 to 800 g of material. active per tonne of dry pulp.
Ce procédé permet d'atteindre un niveau de performances inégalé jusqu'alors dans l'application papetière pour la rétention totale et de charges, et l'égouttage, et ce y compris pour des pâtes à papier contenant des teneurs élevées en fibres recyclées.This process achieves a level of performance unmatched until now in the paper application for total retention and charge, and dripping, including for pulp containing high levels of recycled fibers.
L'agent principal de rétention est choisi parmi les copolymères cationiques ou amphotères caractérisés en ce qu'ils sont obtenus par dégradation dite d'Hofmann sur un précurseur de base acrylamide (polymère base) en présence d'un hydroxyde d'alcalin et/ou d'alcalino-terreux (avantageusement l'hydroxyde de sodium), et d'un hypochlorite d'alcalin et/ou d'alcalino-terreux (avantageusement l'hypochlorite de sodium).The main retention agent is chosen from cationic or amphoteric copolymers characterized in that they are obtained by so-called Hofmann degradation on an acrylamide base precursor (base polymer) in the presence of an alkali hydroxide and / or alkaline earth (preferably sodium hydroxide), and an alkaline and / or alkaline earth hypochlorite (preferably sodium hypochlorite).
Le copolymère base est un polymère hydrosoluble synthétique à base d'acrylamide contenant au moins un monomère non ionique tel que par exemple l'acrylamide, et éventuellement d'autres monomères comme par exemple un ou plusieurs monomères, soit cationique, tel que par exemple le chlorure de diméthyldiallylammonium (DADMAC), soit anionique tel que par exemple l'acide acrylique, soit à caractère hydrophobe.The base copolymer is a synthetic water-soluble polymer based on acrylamide containing at least one nonionic monomer such as for example acrylamide, and optionally other monomers such as for example one or more monomers, or cationic, such as for example the dimethyldiallylammonium chloride (DADMAC), either anionic such as for example acrylic acid or hydrophobic character.
Plus précisément, le copolymère " base " utilisé contient :
- au moins un monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylamide), le N, N diméthylacrylamide,
- et éventuellement au moins :
- ∘ un monomère éthylénique cationique non saturé, choisi préférentiellement dans le groupe comprenant les monomères de type dialkylaminoalkyl (meth)acrylamide, diallylamine, methyldiallylamine et leurs sel d'ammonium quaternaire ou d'acides. On citera en particulier le chlorure de dimethyldiallylammonium (DADMAC), le chlorure d'acrylamidopropyltrimethylammonium (APTAC) et/ou le chlorure de methacrylamidopropyltrimethylammonium (MAPTAC),
- ∘ et/ou un monomère non ionique choisi préférentiellement dans le groupe comprenant le N-vinyl acetamide, N-vinyl formamide, la N-vinylpyrrolidone et/ou le vinyl acétate,
- ∘ et/ou un monomère anionique de type acide ou anhydride choisi dans le groupe comprenant l'acide (méth)acrylique, l'acide acrylamidomethylpropyl sulfonique, l'acide itaconique, l'anhydride maléique, l'acide maléique, l'acide méthallyl sulfonique, l'acide vinylsulfonique et leurs sels.
- at least one nonionic monomer selected from the group consisting of acrylamide (and / or methacrylamide), N, N dimethylacrylamide,
- and possibly at least:
- An unsaturated cationic ethylenic monomer, preferably chosen from the group comprising the dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acidic salt monomers. In particular, mention may be made of dimethyldiallylammonium chloride (DADMAC), chloride acrylamidopropyltrimethylammonium (APTAC) and / or methacrylamidopropyltrimethylammonium chloride (MAPTAC),
- And / or a nonionic monomer preferably chosen from the group comprising N-vinyl acetamide, N-vinyl formamide, N-vinylpyrrolidone and / or vinyl acetate,
- And / or an anionic monomer of the acid or anhydride type chosen from the group comprising (meth) acrylic acid, acrylamidomethylpropyl sulfonic acid, itaconic acid, maleic anhydride, maleic acid and methallyl acid. sulfonic acid, vinylsulfonic acid and their salts.
II est important de noter que, en association avec ces monomères, il est également possible d'utiliser des monomères insolubles dans l'eau tels que les monomères acryliques, allyliques ou vinyliques comportant un groupement hydrophobe. Lors de leur utilisation, ces monomères seront employés dans des quantités très faibles, inférieures à 10 moles%, de préférence inférieures à 5 moles%, voire inférieures à 1% et ils seront choisis préférentiellement dans le groupe comprenant les dérivés de l'acrylamide comme les N-alkylacrylamide par exemple le N-tert-butylacrylamide, l'octylacrylamide ainsi que les N,N-dialkylacrylamides comme le N,N-dihexylacrylamide...les dérivés d'acide acrylique comme les alkyl acrylates et méthacrylates...It is important to note that, in combination with these monomers, it is also possible to use water-insoluble monomers such as acrylic, allylic or vinyl monomers having a hydrophobic group. When they are used, these monomers will be used in very small quantities, less than 10 mol%, preferably less than 5 mol%, even less than 1%, and they will be chosen preferentially from the group comprising acrylamide derivatives such as N-alkylacrylamide for example N-tert-butylacrylamide, octylacrylamide and N, N-dialkylacrylamides such as N, N-dihexylacrylamide ... acrylic acid derivatives such as alkyl acrylates and methacrylates ...
Selon une caractéristique préférée de l'invention, le copolymère base pourra être ramifié.According to a preferred feature of the invention, the base copolymer may be branched.
On pourra effectuer la ramification de préférence durant (ou éventuellement après) la polymérisation du copolymère "base", en présence d'un agent ramifiant polyfonctionnel et éventuellement d'un agent de transfert. On trouvera ci dessous une liste non limitative des ramifiants : méthylène bisacrylamide (MBA), l'ethylene glycol di-acrylate, le polyethylene glycol dimethacrylate, le diacrylamide, le cyanomethylacrylate, le vinyloxyethylacrylate ou methacrylate, la triallylamine, le formaldehyde, le glyoxal, les composés de type glycidyléther comme l'éthylèneglycol di glycidyléther, ou des époxy ou tout autre moyen bien connu de l'homme de métier permettant la réticulation.The branching may preferably be carried out during (or possibly after) the polymerization of the "base" copolymer, in the presence of a polyfunctional branching agent and optionally of a transfer agent. The following is a nonlimiting list of branching agents: methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, triallylamine, formaldehyde, glyoxal, glycidyl ether compounds such as ethylene glycol glycidyl ether, or epoxy or any other means well known to those skilled in the art for crosslinking.
En pratique, l'agent de ramification est introduit avantageusement à raison de cinq à cinquante milles (5 à 50000) parties par million en poids par rapport à la matière active, de préférence 5 à 10000, avantageusement de 5 à 5000. Avantageusement, l'agent de ramification est le méthylène bis acrylamide (MBA).In practice, the branching agent is advantageously introduced at a rate of from five to fifty thousand (5 to 50,000) parts per million by weight relative to the active ingredient, preferably from 5 to 10,000, advantageously from 5 to 5,000. Advantageously, the branching agent is methylenebisacrylamide (MBA).
Le copolymère servant de base à la réaction de dégradation d'Hofmann ne nécessite pas le développement de procédé de polymérisation particulier. Les principales techniques de polymérisation, bien connues par l'homme de métier et pouvant être utilisées sont : la polymérisation par précipitation, la polymérisation en émulsion (aqueuse ou inverse) suivie ou non d'une étape de distillation et/ou de spray drying, et la polymérisation en suspension ou la polymérisation en solution, ces deux techniques étant préférées.The copolymer serving as a basis for the Hofmann degradation reaction does not require the development of a particular polymerization process. The main polymerization techniques, well known to those skilled in the art and which can be used are: precipitation polymerization, emulsion polymerization (aqueous or inverse) followed or not by a distillation step and / or spray drying, and suspension polymerization or solution polymerization, both of which are preferred.
Cette base est caractérisée en ce qu'elle a un poids moléculaire avantageusement supérieur à 5000 et sans limitation maximum, le seul facteur limitant étant, pour des contraintes de mise en oeuvre évidentes, la viscosité de la solution polymérique qui est fonction de la concentration en (co)polymère et de son poids moléculaire.This base is characterized in that it has a molecular weight advantageously greater than 5000 and without any maximum limitation, the only limiting factor being, for obvious implementation constraints, the viscosity of the polymeric solution, which is a function of the concentration of (co) polymer and its molecular weight.
Il est également possible d'ajouter dans la solution de copolymère base, avant ou pendant la réaction de dégradation d'Hofmann certains additifs qui sont susceptibles de réagir sur les fonctions isocyanates du polymère générées en cours de dégradation. De manière générale, il s'agit de molécules portant des fonctions chimiques nucléophiles telles que des fonctions hydroxyle, amine...A titre d'exemples, les additifs en question peuvent donc être de la famille : des alcools, des polyols (e.g. : amidon), des polyamines, des polyéthylène imines...It is also possible to add in the base copolymer solution, before or during the Hofmann degradation reaction, certain additives which are capable of reacting with the isocyanate functions of the polymer generated during degradation. In general, these are molecules bearing nucleophilic chemical functions such as hydroxyl or amine functions. By way of examples, the additives in question may therefore be of the family: alcohols, polyols (eg: starch), polyamines, polyethylene imines ...
La réaction d'Hofmann nécessite la conversion des fonctions amide en fonction aminée en faisant intervenir 2 facteurs principaux (exprimés en rapports molaires) :
- Alpha = (hypochlorite d'alcalin et/ou d'alcalino-terreux/ (meth)acrylamide)
- Beta = (hydroxyde d'alcalin et/ou alcalino-terreux / hypochlorite d'alcalin et/ou d'alcalino-terreux)
- Alpha = (alkaline and / or alkaline earth hypochlorite / (meth) acrylamide)
- Beta = (alkali and / or alkaline earth hydroxide / alkaline and / or alkaline earth hypochlorite)
A partir d'une solution de copolymère " base " précédemment décrit de concentration comprise entre 5 et 40% en poids, de préférence entre 10 et 25%, on détermine la quantité molaire de fonction (meth)acrylamide totale. On choisit alors le niveau de dégradation Alpha souhaité (qui correspond au degré de fonction amine voulue), qui permet de déterminer la quantité sèche d'hypohalogénure d'alcalin et/ou d'alcalino-terreux et ensuite le coefficient béta, qui permet de déterminer la quantité sèche d'hydroxyde d'alcalin et/ou alcalino-terreux.From a previously described "base" copolymer solution of concentration of between 5 and 40% by weight, preferably between 10 and 25%, the molar amount of total (meth) acrylamide function is determined. The desired Alpha degradation level (which corresponds to the desired degree of amine function) is then chosen, which makes it possible to determine the dry quantity of alkaline and / or alkaline earth hypohalide and then the beta coefficient, which allows determine the dry quantity of alkali and / or alkaline earth hydroxide.
On prépare alors une solution d'hypohalogénure et d'hydroxyde d'alcalin et/ou alcalino-terreux à partir des rapports alpha et béta. Selon l'invention, les réactifs préférablement utilisés sont l'hypochlorite de sodium (eau de javel) et la soude (hydroxyde de sodium).A solution of hypohalide and alkali and / or alkaline earth hydroxide is then prepared from the alpha and beta ratios. According to the invention, the reagents preferably used are sodium hypochlorite (bleach) and sodium hydroxide (sodium hydroxide).
En pratique, le produit de dégradation d'Hofmann est obtenu par réaction d'un hydroxide d'alcalino-terreux et d'un hypohalogénure d'alcalino-terreux avec un rapport molaire hydroxide/hypohalogénure compris entre 2 et 6, de préférence entre 2 et 5.In practice, the Hofmann degradation product is obtained by reaction of an alkaline earth metal hydroxide and an alkaline earth hypohalide with a hydroxide / hypohalide molar ratio of between 2 and 6, preferably between 2 and 6. and 5.
Selon une autre caractéristique, le produit de dégradation d'Hofmann est produit à une concentration supérieure à 4% en poids, de préférence supérieure à 7%, avantageusement supérieure à 8% et présente avantageusement une viscosité supérieure à 30 cps (à une concentration de 9%, à 25°C, Brookfield LV1, 60 rpm), de préférence supérieure à 40 cps.According to another characteristic, the Hofmann degradation product is produced at a concentration greater than 4% by weight, preferably greater than 7%, advantageously greater than 8% and advantageously has a viscosity of greater than 30 cps (at a concentration of 9%, at 25 ° C., Brookfield LV1, 60 rpm), preferably greater than 40 cps.
Avantageusement, la quantité de l'agent principal de rétention introduite dans la suspension est comprise entre 100 et 800 grammes de polymère actif par tonne de pâte sèche (g/t). De préférence, la quantité d'agent principal de rétention introduite est comprise entre 200 g/t et 500 g/t.Advantageously, the amount of the main retention agent introduced into the suspension is between 100 and 800 grams of active polymer per tonne of dry pulp (g / t). Preferably, the amount of main retention agent introduced is between 200 g / t and 500 g / t.
L'injection ou l'introduction de l'agent principal de rétention selon l'invention est effectuée avant une éventuelle étape de cisaillement, dans la pâte à papier plus ou moins diluée selon la pratique de l'homme de métier, et généralement dans la pâte à papier diluée ou thin stock. En d'autres termes, l'injection de l'agent principal de rétention est avantageusement effectuée dans la pâte diluée de concentration d'au plus 2%.The injection or the introduction of the main retention agent according to the invention is carried out before a possible shearing step, in the pulp more or less diluted according to the practice of the person skilled in the art, and generally in the diluted paper stock or thin stock. In other words, the injection of the main retention agent is advantageously carried out in the diluted pulp with a concentration of at most 2%.
Selon l'invention, l'agent secondaire de rétention sera choisi parmi tous les types de polymères organiques hydrosolubles ou hydrogonflant de densité de charge anionique supérieure à 0.1 meq/g. Ces polymères ont une viscosité intrinsèque supérieure à 3 dl/g.According to the invention, the secondary retention agent will be chosen from all types of water-soluble organic polymers or hydrogonflux of anionic charge density greater than 0.1 meq / g. These polymers have an intrinsic viscosity greater than 3 dl / g.
En pratique, le polymère utilisé est constitué :
- a/ d'au moins un monomère anionique possédant une fonction carboxylique (ex: acide acrylique, acide methacrylique, et leurs sels...), ou possédant une fonction acide sulfonique (ex: acide 2-acrylamido-2- méthylpropane sulfonique (AMPS), acide vinyl sulfonique, acide méthallyl sulfonique et leurs sels...), ou possédant des fonctions phosphonique (ex : l'acide vinyl phosphonique), Éventuellement associés avec :
- b/ un ou plusieurs monomères non ioniques choisi par exemple dans la liste suivante : acrylamide, methacrylamide, N,N diméthylacrylamide, N-vinyl pyrrolidone, N-vinyl acétamide, N-vinyl formamide, vinylacetate, esters acrylate, alcool allylique,
- c/ un ou plusieurs monomères cationiques choisi en particulier et de façon non limitative dans le groupe comprenant l'acrylate de dimethylaminoethyl (ADAME) quaternisés ou salifiés et/ou le methacrylate de dimethylaminoethyle (MADAME) quaternisés ou salifiés, le chlorure de dimethyldiallylammonium (DADMAC), le chlorure d'acrylamido propyltrimethyl ammonium (APTAC) et/ou le chlorure de methacrylamido propyltrimethyl ammonium (MAPTAC),
- d/ un ou plusieurs monomères à caractère hydrophobe tels que les monomères acryliques, allyliques ou vinyliques comportant un groupement hydrophobe. Ils seront choisis préférentiellement dans le groupe comprenant les dérivés de l'acrylamide comme les N-alkylacrylamide par exemple le N-tertbutylacrylamide, l'octylacrylamide ainsi que les N, N-dialkylacrylamides comme le N,N-dihexylacrylamide...les dérivés d'acide acrylique comme les alkyl acrylates et méthacrylates,
- e/ un ou plusieurs agents ramifiant/réticulants choisi préférentiellement dans le groupe comprenant le methylene bisacrylamide (MBA), l'ethylene glycol di-acrylate, le polyethylene glycol dimethacrylate, le diacrylamide, le cyanomethylacrylate, le vinyloxyethylacrylate ou methacrylate, la triallylamine, le formaldehyde, le glyoxal, les composés de type glycidyléther comme l'éthylèneglycol diglycidyléther, ou des époxy,
- f/ un ou plusieurs agents de transfert comme par exemple l'alcool isopropylique, l'hypophosphite de sodium, le mercaptoéthanol.
- a / at least one anionic monomer having a carboxylic function (eg acrylic acid, methacrylic acid, and their salts ...), or having a sulphonic acid function (eg 2-acrylamido-2-methylpropanesulphonic acid (AMPS), vinyl sulfonic acid, methallyl sulfonic acid and their salts ...), or having phosphonic functions (eg vinylphosphonic acid), optionally associated with:
- b / one or more nonionic monomers chosen for example from the following list: acrylamide, methacrylamide, N, N-dimethylacrylamide, N-vinylpyrrolidone, N-vinylacetamide, N-vinylformamide, vinylacetate, acrylate esters, allyl alcohol,
- c) one or more cationic monomers chosen in particular and without limitation in the group comprising quaternized or salified dimethylaminoethyl acrylate (ADAME) and / or dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC) ), acrylamido propyltrimethylammonium chloride (APTAC) and / or methacrylamidopropyltrimethylammonium chloride (MAPTAC),
- d / one or more hydrophobic monomers such as acrylic monomers, allylic or vinyl having a hydrophobic group. They will be chosen preferentially from the group comprising acrylamide derivatives such as N-alkylacrylamide, for example N-tertbutylacrylamide, octylacrylamide and N, N-dialkylacrylamides, such as N, N-dihexylacrylamide, and the like. acrylic acid such as alkyl acrylates and methacrylates,
- e / one or more branching / crosslinking agents preferably chosen from the group comprising methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, triallylamine, formaldehyde, glyoxal, glycidyl ether compounds such as ethylene glycol diglycidyl ether, or epoxides,
- f / one or more transfer agents such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol.
Selon l'invention, les polymères hydrosolubles utilisés ne nécessitent pas de développement de procédé de polymérisation particulier. Ils peuvent être obtenus par toutes les techniques de polymérisation bien connues par l'homme de métier (polymérisation en solution, polymérisation en suspension, polymérisation en gel, polymérisation par précipitation, polymérisation en émulsion (aqueuse ou inverse), polymérisation en microémulsion suivie ou non d'une étape de spray drying, polymérisation en suspension, polymérisation micellaire suivie ou non d'une étape de précipitation).According to the invention, the water-soluble polymers used do not require development of a particular polymerization process. They can be obtained by any of the polymerization techniques well known to those skilled in the art (solution polymerization, suspension polymerization, gel polymerization, precipitation polymerization, emulsion polymerization (aqueous or reverse), microemulsion polymerization followed or not a step of spray drying, suspension polymerization, micellar polymerization followed or not by a precipitation step).
De part la sélection de monomères et des différents additifs de polymérisation, le polymère peut présenter une structure linéaire, ramifiée, réticulée ou une architecture peigne (comb polymer), étoilée (star polymer).Due to the selection of monomers and the various polymerization additives, the polymer may have a linear, branched, crosslinked structure or a star polymer (comb polymer) comb structure.
L'agent secondaire de rétention est introduit dans la suspension, de manière tout à fait préférée à raison de 50g/t à 800g/t en poids de polymère actif par tonne de pâte sèche, préférentiellement de 80g/t à 500g/t, et plus préférentiellement de 100 à 350 g/t.The secondary retention agent is introduced into the suspension, very preferably in a proportion of 50 g / t to 800 g / t by weight of active polymer per tonne of dry pulp, preferably from 80 g / t to 500 g / t, and more preferably from 100 to 350 g / t.
Ces agents comprennent préférentiellement, mais sans caractère limitatif, seul ou en mélange: les dérivés de la silice comme par exemple les particules de silice dont les bentonites provenant d'hectorites, de smectites, de montmorillonites, de nontronites, de saponites, de sauconites, d'hormites, d'attapulgites et de sépiolites, les dérivés de type aluminosilicates ou borosilicates, les zéolites, les kaolinites, ou les silices colloïdales modifiées ou non.These agents preferably comprise, but are not limited to, alone or in admixture: silica derivatives, for example silica particles whose bentonites come from hectorites, smectites, montmorillonites, nontronites, saponites, sauconites, of hormones, attapulgites and sepiolites, derivatives of aluminosilicates or borosilicates type, zeolites, kaolinites, or colloidal silicas modified or not.
Ce type d'agent tertiaire, est, de préférence, introduit juste en amont de la caisse de tête, à raison de 300 à 3000 g/t en poids sec de matière active par tonne de pâte sèche, de préférence de 800 à 2000 g/t.This type of tertiary agent is preferably introduced just upstream of the headbox, at a rate of 300 to 3000 g / t dry weight of active ingredient per tonne of dry pulp, preferably 800 to 2000 g / t.
L'agent tertiaire de rétention peut aussi être choisi parmi les polymères organiques hydrosolubles ou hydrogonflant de densité de charges anioniques supérieure à 0.1 meq/g, avantageusement de viscosité intrinsèque IV supérieure à 3 dl/g, ce polymère étant différent du polymère utilisé comme agent secondaire de rétention. Dans cette hypothèse, le dosage de l'agent tertiaire de rétention est choisi dans la même fourchette que celle de l'agent secondaire de rétention, c'est-à-dire à raison de 50g/t à 800g/t en poids de polymère actif par tonne de pâte sèche, préférentiellement de 80g/t à 500g/t, et plus préférentiellement de 100 à 350 g/t.The tertiary retention agent may also be chosen from water-soluble or hydrogen-floating organic polymers with anionic charge density greater than 0.1 meq / g, advantageously with IV intrinsic viscosity greater than 3 dl / g, this polymer being different from the polymer used as an agent. secondary retention. In this case, the dosage of the tertiary retention agent is chosen in the same range as that of the secondary retention agent, that is to say at a rate of 50 g / t to 800 g / t by weight of polymer. active per ton of dry pulp, preferably from 80 g / t to 500 g / t, and more preferably from 100 to 350 g / t.
Dans un mode de réalisation avantageux, on ajoute à la suspension fibreuse, préalablement à l'ajout de l'agent principal de rétention, un coagulant.In an advantageous embodiment, a coagulant is added to the fibrous suspension, prior to the addition of the main retention agent.
Comme l'homme de métier le sait bien, l'utilisation de ce type de produit permet de neutraliser les colloides anioniques néfastes et impactant les performances de l'agent de rétention cationique, à des dosages (en actif) de 0,01 à 10 kg/t et préférentiellement entre 0,03 et 3 kg/t. On citera notamment, et à titre d'exemples, les coagulants choisis dans le groupe comprenant les coagulants minéraux tels que le polychlorure d'aluminium (PAC), le sulfate d'alumine, le polychlorosulfate d'aluminium..., ou les coagulants organiques dont - les polymères à base de chlorure de diallyldiméthyl ammonium (DADMAC), - les polyamines quaternaires fabriquées par condensation d'une amine primaire ou secondaire sur de l'épichlorhydrine ou les résines de type dicyandiamide. Ces coagulants peuvent être utilisés seuls ou en mélange et sont ajoutés de préférence en pâte épaisse (thick stock).As is well known to those skilled in the art, the use of this type of product makes it possible to neutralize the harmful anionic colloids which impact the performance of the cationic retention agent, at dosages (in active form) of from 0.01 to 10. kg / t and preferably between 0.03 and 3 kg / t. Mention may be made in particular, and by way of examples, of coagulants chosen from the group comprising inorganic coagulants such as polyaluminium chloride (PAC), alumina sulphate and polychlorosulphate. of aluminum ..., or organic coagulants of which - polymers based on diallyldimethylammonium chloride (DADMAC), - quaternary polyamines manufactured by condensation of a primary or secondary amine on epichlorohydrin or resins of the type dicyandiamide. These coagulants can be used alone or as a mixture and are preferably added in thick stock.
On notera que l'ajout des agents secondaires et tertiaires de rétention peut être effectué dans un quelconque ordre d'introduction, en mélange ou non.It will be noted that the addition of secondary and tertiary retention agents can be carried out in any order of introduction, mixed or not.
Les exemples suivants illustrent l'invention sans toutefois en limiter la portée.The following examples illustrate the invention without, however, limiting its scope.
Le système de rétention de l'invention apporte de bonnes performances particulièrement en rétention totale, rétention de charges, égouttage et clarification des eaux blanches et ce sans destruction de la formation.The retention system of the invention provides good performance particularly in total retention, retention of charges, drainage and clarification of white water without destroying the formation.
Les différents résultats ont été obtenus grâce à l'utilisation d'un récipient de type « Britt Jar », avec une vitesse d'agitation de 1000 tours par minute.The various results were obtained thanks to the use of a "Britt Jar" type container, with a stirring speed of 1000 rpm.
La séquence d'ajout des différents agents de rétention étant la suivante :
- T=0s : Mise en agitation de 500ml de pâte à 0,5%
- T=10s : Ajout de l'agent de rétention principal
- T=20s : Ajout éventuel de l'agent de rétention tertiaire
- T=25s : Ajout de l'agent de rétention secondaire
- T=30s : Récupération de 100ml d'eaux blanches
- T = 0s: Stirring of 500ml of paste at 0.5%
- T = 10s: Adding the main retention agent
- T = 20s: Possible addition of the tertiary retention agent
- T = 25s: Add Secondary Retention Agent
- T = 30s: Recovery of 100ml of white water
La rétention première passe en pourcentage (%FPR : First Pass Rétention), correspondant à la rétention totale étant calculée selon la formule suivante :
La rétention première passe des cendres en pourcentage (%FPAR : First Pass Ash Rétention) étant calculée selon la formule suivante :
Avec :
- CHB : Consistance de la caisse de tête
- CWW : Consistance des eaux blanches
- AHB : Consistance des cendres de la caisse de tête
- AWW : Consistance des cendres des eaux blanches
With:
- C HB : Consistency of the headbox
- C WW : Consistency of white waters
- A HB : Consistency of the ashes of the headbox
- WW : Consistency of ash from white waters
Les différents résultats ont été obtenus grâce à l'utilisation d'une formette statique pour réaliser l'agitation de la pâte, avec une vitesse d'agitation de 1000 tours par minute.The different results were obtained thanks to the use of a static form to carry out agitation of the dough, with a stirring speed of 1000 revolutions per minute.
La séquence d'ajout des différents agents de rétention étant la suivante :
- T=0s : Mise en agitation de 1000ml de pâte à 0,3%
- T=10s : Ajout de l'agent de rétention principal
- T=20s : Ajout éventuel de l'agent de rétention tertiaire
- T=25s : Ajout de l'agent de rétention secondaire
- T=30s : Arrêt de l'agitation et récupération du litre de pâte.
- T = 0s: Stirring of 1000ml of paste at 0.3%
- T = 10s: Adding the main retention agent
- T = 20s: Possible addition of the tertiary retention agent
- T = 25s: Add Secondary Retention Agent
- T = 30s: Stopping the agitation and recovery of the liter of dough.
On utilise ensuite un appareil de type « Canadian Standard Freeness » (CSF) selon la norme TAPPI T227OM-94 dans le but de mesurer l'égouttage de la pâte traitée par le système de rétention et d'égouttage.A Canadian Standard Freeness (CSF) apparatus according to TAPPI T227OM-94 is then used to measure the dewatering of the pulp treated by the retention and dewatering system.
Pour évaluer la clarification des eaux, on récupère ensuite les eaux blanches correspondantes et on réalise une mesure de turbidité (NTU) grâce à un appareil de type Hach 2100N.To evaluate the water clarification, the corresponding white waters are then recovered and a turbidity measurement (NTU) is carried out using a Hach 2100N type apparatus.
Les valeurs les plus élevées obtenues pour la %FPR, la %FPAR et le CSF correspondent aux meilleures performances. En revanche, Les turbidités (NTU) les plus faibles correspondent à une clarification des eaux accrue.The highest values obtained for the% FPR, the% FPAR and the CSF correspond to the best performances. In contrast, the lowest turbidities (NTU) correspond to increased water clarification.
On utilise une formette statique dans le but de fabriquer des feuilles avec une pâte traitée, ou non, préalablement avec les différents systèmes de rétention choisis, puis cette feuille est pressée et séchée.A static form is used for the purpose of producing sheets with a pulp treated or not, beforehand with the various retention systems chosen, then this sheet is pressed and dried.
Après séchage, nous évaluons visuellement l'homogénéité de la feuille pour en déterminer un index de formation comparatif au sein d'une même série de tests.After drying, we visually evaluate the homogeneity of the sheet to determine a comparative training index within the same series of tests.
L'échelle de l'index de formation est définie comme suit :
- 1 : Excellent, homogène,
- 2 : Bon, fondu,
- 3 : Moyen, nuageux,
- 4 : Mauvais, moutonneux,
- 5 : Désastreux, hétérogène.
- 1: Excellent, homogeneous,
- 2: Good, melted,
- 3: Medium, cloudy,
- 4: Bad, sheepish,
- 5: Disastrous, heterogeneous.
Les tests suivants sont effectués sur une pâte consistant en un mélange de :
- 70% de fibres de kraft de feuillus blanchis,
- 10% de fibres de kraft de résineux blanchis
- 20% de fibres de pâte mécanique à base de pin
- 30% de carbonate de calcium naturel
- 70% bleached hardwood kraft fibers,
- 10% bleached softwood kraft fiber
- 20% pinewood mechanical pulp fibers
- 30% natural calcium carbonate
On constate dans les essais précédents que l'utilisation d'un produit de dégradation d'Hofmann en tant qu'agent primaire de rétention, en l'absence d'un agent secondaire de rétention anionique, de haut poids moléculaire, n'apporte pas de bénéfices en terme de performances de rétention et d'égouttage face à l'utilisation d'un agent de rétention classique de haut poids moléculaire.It has been found in previous tests that the use of a Hofmann degradation product as a primary retention agent, in the absence of a high molecular weight anionic retention agent, does not contribute benefits in terms of retention and drainage performance against the use of a conventional high molecular weight retention agent.
Les tests suivants sont effectués sur une pâte consistant en un mélange de :
- 70% de fibres de kraft de feuillus blanchis,
- 10% de fibres de kraft de résineux blanchis
- 20% de fibres de pâte mécanique à base de pin
- 30% de carbonate de calcium naturel
- 70% bleached hardwood kraft fibers,
- 10% bleached softwood kraft fiber
- 20% pinewood mechanical pulp fibers
- 30% natural calcium carbonate
Dans ces cas de figure on constate très clairement, tant au niveau des performances de rétention, de rétention de charges ainsi que d'égouttage, que l'utilisation d'un produit de dégradation de Hofmann sur une base polyacrylamide est bénéfique par rapport à l'utilisation d'un agent de rétention primaire classique tel qu'un polyacrylamide cationique de haut poids moléculaire.In these cases, it can be clearly seen that the use of a Hofmann degradation product on a polyacrylamide base is beneficial in terms of retention, retention and drainage performance. use of a conventional primary retention agent such as high molecular weight cationic polyacrylamide.
En effet, les gains observés sont compris entre 2 et 7 points en ce qui concerne la rétention totale et entre 0,5 et 8 points pour la rétention de charges. Cette augmentation de rétention permettra au papetier d'obtenir des papiers avec des taux de charges plus élevés, et ceci avec un circuit court moins chargé qui garantit un encrassement moindre de la machine et donc une fréquence moins élevée de casses et d'arrêts machines.Indeed, the gains observed are between 2 and 7 points with regard to the total retention and between 0.5 and 8 points for the retention of charges. This increase in retention will allow the paper manufacturer to obtain papers with higher load rates, and this with a shorter circuit less loaded which ensures less fouling of the machine and therefore a lower frequency of breakages and machine downtime.
De même les gains observés en égouttage sont de l'ordre de 80 à 100 ml, ce qui est conséquent, ce gain étant totalement inattendu pour l'homme de l'art, pour une utilisation de produit de très bas poids moléculaire par rapport à un agent de rétention classiquement utilisé (P0).Similarly, the gains observed in dewatering are of the order of 80 to 100 ml, which is therefore this gain being totally unexpected for those skilled in the art, for a use of product of very low molecular weight compared to a retention agent conventionally used (P0).
Ceci permettra au papetier d'accélérer sa machine, et donc d'augmenter sa productivité. De plus un égouttage plus rapide garantira une siccité de feuille plus élevée et donc une réduction de la dépense énergétique lors de l'étape de séchage.This will allow the paper manufacturer to accelerate his machine, and thus increase its productivity. Moreover a faster draining will guarantee a higher dryness of leaf and thus a reduction of the energy expenditure during the drying step.
Nous confirmons finalement la tendance à obtenir des eaux blanches mieux clarifiées grâce aux résultats de turbidité (NTU) réalisés sur les eaux sous toiles correspondantes. Cela se traduit sur machine par une réduction des dépôts et moins de développements bactériens (slime) susceptibles de causer des casses machines.Finally, we confirm the tendency to obtain better clarified white water thanks to the turbidity results (NTU) achieved on the corresponding underwater waters. This translates into a reduction in deposits and fewer bacterial (slime) developments that can cause breakage.
Il faut également noter que, les performances liées aux système de rétention de l'invention étant supérieures à dosages équivalents (avec tous les avantages cités précédemment), le papetier pourra utiliser ces produits avec un réel intérêt en terme de facilité et de coût de mise en oeuvre, l'agent principal de rétention étant sous forme liquide, et ne nécessitant donc pas d'unité de préparation spécifique comme cela est nécessaire pour les agents de rétention classiques de type polyacrylamide cationique de haut poids moléculaire sous forme de poudre ou d'émulsion.It should also be noted that, as the performances linked to the retention systems of the invention are greater than equivalent dosages (with all the advantages mentioned above), the paper manufacturer will be able to use these products with a real interest in terms of ease and cost of implementation. in use, the main retention agent being in liquid form, and thus not requiring a specific preparation unit as is necessary for conventional high molecular weight cationic polyacrylamide retention agents in the form of powder or emulsion.
Les tests suivants sont effectués sur une pâte de fibres recyclées industrielle.
Les résultats, de performances en égouttage et en clarification des eaux sous toiles, de ce tableau montrent très clairement l'intérêt d'utiliser le produit de dégradation d'Hofmann, en tant qu'agent principal de rétention en combinaison avec un polymère anionique, amphotère ou associatif de haut poids moléculaire, en lieu et place d'un agent de rétention classique de type polyacrylamide cationique de haut poids moléculaire.The results, of dewatering performance and clarification of the water under canvas, of this table clearly show the interest of using the Hofmann degradation product, as main retention agent in combination with an anionic polymer, amphoteric or associative high molecular weight, instead of a conventional retention agent cationic polyacrylamide high molecular weight.
En effet, l'augmentation de dosage de l'agent principal de rétention a pour effet d'améliorer les performances d'égouttage et de clarification des eaux blanches. Il est à noter également que les produits de l'invention restent plus performants qu'un polymère de rétention classiquement utilisé.Indeed, the dosage increase of the main retention agent has the effect of improving the drainage performance and clarification of white water. It should also be noted that the products of the invention remain more efficient than a retention polymer conventionally used.
De plus, il est important de mentionner qu'une application d'un agent de rétention primaire classique à de tels dosages (500g/t) provoque une surfloculation et donc une destruction de la formation de la feuille rendant cette option irréalisable sur le terrain et affecte les caractéristiques physiques du papier.In addition, it is important to mention that an application of a conventional primary retention agent at such dosages (500g / t) causes an overflocculation and thus a destruction of the formation of the sheet making this option impracticable in the field and affects the physical characteristics of the paper.
En revanche, les agents primaires de rétention de l'invention, étant de faible poids moléculaire, permettent leur utilisation à de tels dosages sans destruction de la formation de la feuille, permettant en conséquence d'obtenir des niveaux de rétention et d'égouttage encore jamais atteints par des agents primaires de rétention classiquement utilisés.In contrast, the primary retention agents of the invention, being of low molecular weight, allow their use at such dosages without destruction of the formation of the sheet, thus allowing to obtain levels of retention and dewatering still never achieved by primary retention agents conventionally used.
Les tests suivants sont effectués sur une pâte consistant en un mélange de :
- 70% de fibres de kraft de feuillus blanchis,
- 10% de fibres de kraft de résineux blanchis
- 20% de fibres de pâte mécanique à base de pin
- 20% de carbonate de calcium naturel
- 70% bleached hardwood kraft fibers,
- 10% bleached softwood kraft fiber
- 20% pinewood mechanical pulp fibers
- 20% natural calcium carbonate
On observe au regard des essais précédents que, en combinaison avec un polymère anionique de haut poids moléculaire, l'utiliser comme agent primaire de rétention d'un produit de l'invention est très nettement bénéfique en terme de performances de rétention et de rétention de charges par rapport à tout autre agent primaire de rétention.It can be seen from the preceding tests that, in combination with a high molecular weight anionic polymer, using it as the primary retention agent of a product of the invention is very clearly beneficial in terms of retention and retention performance. loads compared to any other primary retention agent.
Les tests suivants sont effectués sur une pâte consistant en un mélange de :
- 70% de fibres de kraft de feuillus blanchis,
- 10% de fibres de kraft de résineux blanchis
- 20% de fibres de pâte mécanique à base de pin
- 30% de carbonate de calcium naturel
- 70% bleached hardwood kraft fibers,
- 10% bleached softwood kraft fiber
- 20% pinewood mechanical pulp fibers
- 30% natural calcium carbonate
Les résultats obtenus dans cette série de tests montrent que l'utilisation d'un polymère anionique de bas poids moléculaire en tant qu'agent secondaire de rétention, lorsque combiné avec un produit de dégradation d'hofmann en tant qu'agent principal de rétention, n'apporte pas des performances de rétention totale et de rétention de charges aussi bonnes qu'un polymère anionique de haut poids moléculaire et ceci même à des dosages très élevés. Par ailleurs, l'utilisation de polymères anioniques de bas poids moléculaire tels que préconisés dans les documents
De plus, l'utilisation concomitante de forts dosages de produit de dégradation d'Hofmann et de polymère anionique de bas poids moléculaire, si effectivement elle améliore les rétentions totale et de charges, n'a néanmoins aucun effet sur l'égouttage. Les effets positifs sur la rétention totale et la rétention de charges sont équivalents à ceux de l'invention mais à des dosages 6 à 10 fois supérieurs et donc à des coûts tout aussi accrus (essai 41 par rapport à l'essai 39)In addition, the concomitant use of high dosages of Hofmann degradation product and low molecular weight anionic polymer, if indeed it improves the total retentions and charges, nevertheless has no effect on the dripping. The positive effects on the total retention and the retention of charges are equivalent to those of the invention but in dosages 6 to 10 times higher and therefore to equally increased costs (test 41 compared to test 39)
Claims (12)
- A method for manufacturing a sheet of paper and/or board, according to which, before the formation of the said sheet and/or board, at least two retention aids are added to the fibrous suspension, at one or more injection points, respectively:- a main retention aid corresponding to a (co)polymer having a cationic charge density above 2 meq/g, obtained by the Hofmann degradation reaction, in aqueous solution, in the presence of an alkaline-earth and/or alkali hydroxide and of an alkaline-earth and/or alkali hypohalide, on a base (co)polymer comprising at least one non-ionic monomer selected from the group comprising acrylamide (and/or methacrylamide), N,N dimethylacrylamide,- a secondary retention aid corresponding to a water-soluble or water-swellable polymer having an anionic charge density above 0.1 meq/g,characterised in that:- the main retention aid is introduced into the fibrous suspension in a proportion of 100 to 800 g/t of dry pulp,- the secondary retention aid is introduced into the fibrous suspension in a proportion of 50 to 800 g/t of dry pulp and has an intrinsic viscosity IV above 3 dl/g.
- A method according to claim 1, characterised in that the main retention aid is introduced into the fibrous suspension in a proportion of 200 to 500 g/t of dry pulp.
- A method according to Claim 1, characterised in that the secondary retention aid is introduced into the fibrous suspension in a proportion of 80 to 500 g/t, preferably between 100 and 350 g/t of dry pulp.
- A method according to Claim 1, characterised in that the molecular weight of the main retention aid is lower than 1 million g/mol, advantageously lower than 500,000 g/mol.
- A method according to Claim 1, characterised in that the main retention aid has a cationic charge density above 4 meq/g.
- A method according to Claim 1, characterised in that the main retention aid is introduced into the thin stock in a concentration not exceeding 2%.
- A method according to Claim 1, characterised in that the secondary retention aid consists of:a. at least one anionic monomer having a carboxyl function, or possessing a sulphonic acid function or possessing phosphonic functions, Optionally combined withb. one or more non-ionic monomers selected from the group comprising acrylamide, methacrylamide, N,N dimethylacrylamide, N-vinyl pyrrolidone, N-vinyl acetamide, N-vinyl formamide, vinylacetate, acrylate esters, allyl alcohol,c. one or more cationic monomers selected from the group comprising quaternized or salified dimethylaminoethyl acrylate (ADAME) and/or quaternized or salified dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamido propyltrimethyl ammonium chloride (APTAC) and/or methacrylamido propyltrimethyl ammonium chloride (MAPTAC),d. one or more hydrophobic monomers selected from the group comprising N-tertbutylacrylamide, octylacrylamide, N,N-dihexylacrylamide alkyl acrylates and methacrylates.
- A method according to Claim 1, characterised in that a tertiary retention aid is added to the fibrous suspension, selected from the group comprising bentonites derived from hectorites, smectites, montmorillonites, nontronites, saponites, sauconites, hormites, attapulgites and sepiolites, aluminosilicate or borosilicate derivatives, zeolites, kaolinites, or colloidal silices, modified or not.
- A method according to Claim 8, characterised in that the tertiary retention aid is introduced in a proportion of 300 to 3000 g/t, preferably 800 to 2000 g/t, by weight of active matter per tonne of dry pulp.
- A method according to Claim 1, characterised in that a tertiary retention aid is added to the fibrous suspension, selected from water-soluble or water-swellable organic polymers having an anionic charge density above 0.1 meq/g, advantageously having an intrinsic viscosity IV above 3 dl/g, the said polymer being different from the secondary retention aid.
- A method according to Claim 10, characterised in that the tertiary retention aid is introduced in a proportion of 50 g/t to 800 g/t, advantageously 80 g/t to 500 g/t, and preferably 100 to 350 g/t, by weight of active polymer per tonne of dry pulp.
- A method according to Claim 1, characterised in that the introduction of the main and secondary retention aids is separated if necessary by a shear step.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1056367A FR2963364B1 (en) | 2010-08-02 | 2010-08-02 | METHOD FOR MANUFACTURING PAPER AND CARDBOARD HAVING IMPROVED RETENTION AND DRIPPING PROPERTIES |
PCT/FR2011/051801 WO2012017172A1 (en) | 2010-08-02 | 2011-07-26 | Process for manufacturing paper and board having improved retention and drainage properties |
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EP2601346A1 EP2601346A1 (en) | 2013-06-12 |
EP2601346B1 true EP2601346B1 (en) | 2015-09-09 |
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EP11752300.1A Active EP2601346B1 (en) | 2010-08-02 | 2011-07-26 | Manufacturing process of paper or cardboard having improved retention and draining properties |
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US (1) | US8999112B2 (en) |
EP (1) | EP2601346B1 (en) |
KR (1) | KR101904358B1 (en) |
CN (1) | CN103003491B (en) |
BR (1) | BR112013002371B1 (en) |
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EP2865807A4 (en) * | 2012-06-25 | 2016-02-17 | Katayama Chemical Works Co | Process for manufacturing paperboard |
FR2992981B1 (en) * | 2012-07-09 | 2014-07-04 | Snf Sas | IMPROVED PAPER MANUFACTURING METHOD USING POLYMER OBTAINED BY HOFMANN DEGRADATION |
US9051687B2 (en) * | 2012-08-22 | 2015-06-09 | Basf Se | Production of paper, card and board |
FR3009830B1 (en) | 2013-08-22 | 2015-08-14 | Snf Sas | NOVEL WATER-SOLUBLE POLYMER COMPLEXES AND USES THEREOF |
CN105107484B (en) * | 2015-09-18 | 2017-10-03 | 内江师范学院 | A kind of preparation method of industrial gelatine base retention and drainage aid agent |
JP2018044273A (en) * | 2016-09-16 | 2018-03-22 | 栗田工業株式会社 | Manufacturing method of paper, manufacturing device of additive for making paper and manufacturing device of paper |
AU2019209164B2 (en) * | 2018-01-16 | 2022-12-08 | Solenis Technologies, L.P. | Process for making paper with improved filler retention and opacity while maintaining wet tensile strength |
CN109667193A (en) * | 2019-01-28 | 2019-04-23 | 常州麒通国际贸易有限公司 | A kind of preparation method of composite papermaking retention agent |
CN111139683A (en) * | 2020-01-03 | 2020-05-12 | 王丹丹 | Preparation method of high-adsorption porous retention aid for papermaking |
FR3113069B1 (en) * | 2020-07-30 | 2022-10-14 | Snf Sa | PAPER AND CARDBOARD MANUFACTURING PROCESS |
FR3118072B1 (en) * | 2020-12-22 | 2022-12-09 | Snf Sa | METHOD FOR MANUFACTURING PAPER OR CARDBOARD |
FR3127507B1 (en) * | 2021-09-27 | 2023-10-27 | Snf Sa | PROCESS FOR MANUFACTURING PAPER AND CARDBOARD |
CN114351494A (en) * | 2021-12-17 | 2022-04-15 | 杨介思 | Paper made buffer package |
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US3052595A (en) | 1955-05-11 | 1962-09-04 | Dow Chemical Co | Method for increasing filler retention in paper |
SE432951B (en) | 1980-05-28 | 1984-04-30 | Eka Ab | PAPER PRODUCT CONTAINING CELLULOSA FIBERS AND A BINDING SYSTEM CONTAINING COLOIDAL MILIC ACID AND COTIONIC STARCH AND PROCEDURE FOR PREPARING THE PAPER PRODUCT |
GB8602121D0 (en) | 1986-01-29 | 1986-03-05 | Allied Colloids Ltd | Paper & paper board |
US5167766A (en) * | 1990-06-18 | 1992-12-01 | American Cyanamid Company | Charged organic polymer microbeads in paper making process |
GB9301451D0 (en) * | 1993-01-26 | 1993-03-17 | Allied Colloids Ltd | Production of filled paper |
US5286806C1 (en) * | 1993-05-14 | 2001-01-30 | Cytec Tech Corp | Methods of making and using high molecular weight acrylamide polymers |
CN1155269A (en) * | 1994-08-12 | 1997-07-23 | 矿业技术有限公司 | Synthetic mineral microparticles for retention aid system |
US5708071A (en) * | 1994-12-15 | 1998-01-13 | Hymo Corporation | Aqueous dispersion of an amphoteric water-soluble polymer, a method of manufacturing the same, and a treating agent comprising the same |
CN1204301A (en) * | 1995-11-08 | 1999-01-06 | 矿业技术有限公司 | Synthetic mineral microparticles and retention aid and water treatment system and method using such particles |
US6103065A (en) * | 1999-03-30 | 2000-08-15 | Basf Corporation | Method for reducing the polymer and bentonite requirement in papermaking |
GB0011675D0 (en) | 2000-05-15 | 2000-07-05 | Unilever Plc | Ambient stable beverage |
EP1451234B1 (en) | 2001-12-07 | 2006-07-26 | Hercules Incorporated | Composition comprising cellulose fiber and a water-soluble anionic copolymer as well as method of making said composition |
FR2869626A3 (en) * | 2004-04-29 | 2005-11-04 | Snf Sas Soc Par Actions Simpli | METHOD FOR MANUFACTURING PAPER AND CARDBOARD, NEW CORRESPONDING RETENTION AND DRAINING AGENTS, AND PAPERS AND CARTONS THUS OBTAINED |
US20060142431A1 (en) * | 2004-12-29 | 2006-06-29 | Sutman Frank J | Retention and drainage in the manufacture of paper |
FR2880901B1 (en) | 2005-01-17 | 2008-06-20 | Snf Sas Soc Par Actions Simpli | METHOD FOR MANUFACTURING PAPER AND CARDBOARD OF HIGH RESISTANCE BY DRY AND PAPERS AND CARTONS THUS OBTAINED |
US7981250B2 (en) * | 2006-09-14 | 2011-07-19 | Kemira Oyj | Method for paper processing |
FR2912749B1 (en) * | 2007-02-19 | 2009-04-24 | Snf Soc Par Actions Simplifiee | CATIONIC COPOLYMERS DERIVED FROM ACRYLAMIDE AND THEIR USES |
FR2918989B1 (en) * | 2007-07-18 | 2010-08-27 | Snf Sas | WATER-SOLUBLE, WATER-SOLUBLE CATIONIC ACRYLAMIDE POLYMERS AND THEIR ACHIEVEMENTS |
FR2929963B1 (en) * | 2008-04-10 | 2010-04-23 | Snf Sas | PROCESS FOR PRODUCING PAPER AND CARDBOARD |
FR2938842B1 (en) * | 2008-11-27 | 2012-09-21 | Snf Sas | NOVEL PROCESS FOR THE PREPARATION OF ACRYLAMIDE COPOLYMERS BY HOFMANN DEGRADATION REACTION |
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CN103003491A (en) | 2013-03-27 |
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FR2963364B1 (en) | 2014-12-26 |
ES2549432T3 (en) | 2015-10-28 |
FR2963364A1 (en) | 2012-02-03 |
BR112013002371B1 (en) | 2020-11-10 |
CA2807010C (en) | 2017-11-07 |
US20130139986A1 (en) | 2013-06-06 |
CN103003491B (en) | 2015-10-07 |
WO2012017172A1 (en) | 2012-02-09 |
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