EP1092064B1 - Method for making paper and cardboard and retention and dewatering agents - Google Patents
Method for making paper and cardboard and retention and dewatering agents Download PDFInfo
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- EP1092064B1 EP1092064B1 EP99923647A EP99923647A EP1092064B1 EP 1092064 B1 EP1092064 B1 EP 1092064B1 EP 99923647 A EP99923647 A EP 99923647A EP 99923647 A EP99923647 A EP 99923647A EP 1092064 B1 EP1092064 B1 EP 1092064B1
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- Prior art keywords
- emulsion
- polymer
- branched
- process according
- paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
- D21H23/06—Controlling the addition
- D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
- D21H23/765—Addition of all compounds to the pulp
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Definitions
- the present invention relates to the technical sector of manufacture of paper and polymers used in this context.
- the invention relates to a method for the production of a paper or a retention cardboard, and other properties, improved.
- EP-A-0 235 893 it has been proposed to use cationic polyacrylamides with a molecular weight greater than thirty million and more, essentially linear. In this way we obtain an effect certainly satisfactory, but still considered insufficient in the application paper, because the use of bentonite causes difficulties during the further treatment of the effluents at the output of the machine, the users select this system only in case of significant benefits.
- EP 0 574 335 has achieved an important improvement in proposing the use of polymers (in particular polyacrylamides) branched under the shape of a powder.
- the invention overcomes the disadvantages mentioned above.
- Branched polyacrylamide (or more generally (co) polymer branched) is introduced into the suspension, very preferably, under the water-in-oil inverse emulsion form, at the rate of 0.03 to one per thousand (0.03 to 1% o, ie 30 to 1000 g / t) by weight of active ingredient (polymer) per relative to the dry weight of the fibrous suspension, preferably from 0.15 to 0.5 per thousand, ie 150 to 500 g / t.
- the inverse emulsion of polymer is diluted with water and inverted (solubilized) by this dilution before its introduction, as described above.
- the polymer is prepared by water-in-oil inverse emulsion polymerization.
- this polymer can then be used (ie injected or introduced into the mass or paste to be flocculated) either in the form - preferably - of this emulsion inverse after its dissolution in water, either in the form of a powder obtained by drying (in particular by spray drying or spray-drying ")
- a powder obtained by drying in particular by spray drying or spray-drying
- redissolution of this powder in water for example at a concentration of about 5 g of active polymer / liter, the solution thus obtained being then injected into the dough substantially at the same polymer dosages.
- the branched (co) polyacrylamide is a cationic copolymer of acrylamide and a cationic ethylenic monomer unsaturated, selected from the group consisting of dimethylaminoethyl acrylate (ADAME), dimethylaminoethyl methacrylate (MADAME), quaternized or salified by different acids and quaternizing agents, benzyl chloride, methyl chloride, alkyl- or aryl chlorides, dimethylsulfate, chloride dimethyldiallylammonium (DADMAC), chloride acrylamidopropyltrimethylammonium (APTAC), and the chloride of methacrylamidopropyltrimethylammonium (MAPTAC),
- ADAME dimethylaminoethyl acrylate
- MADAME dimethylaminoethyl methacrylate
- benzyl chloride methyl chloride, alkyl- or aryl chlorides, dimethylsulfate
- this copolymer is branched by a branching constituted by a compound having at least two groups reactants selected from the group consisting of double bonds, aldehydes or epoxy bonds.
- branching constituted by a compound having at least two groups reactants selected from the group consisting of double bonds, aldehydes or epoxy bonds.
- a branched polymer is a polymer which present on the chain branches, groups or ramifications arranged globally in one plane and not in the three directions, unlike a cross-linked polymer; such polymers branched, high molecular weight, are well known as flocculating agents.
- These branched polyacrylamides are distinguished from crosslinked polyacrylamides by the fact that in the latter groups are arranged three-dimensionally to lead to practically insoluble products and of infinite molecular weight.
- Branching polymerization preferably during (or optionally after) the polymerization, for example by reaction of two soluble polymers having counterions, or by reaction on formaldehyde or a polyvalent metal compound. Often, the branching takes place during the polymerisation by addition of an agent ramifiantt, and this solution will be clearly preferred according to the invention.
- Branching polymerization methods are well known.
- Branching agents that can be incorporated include ionic branching agents such as polyvalent metal salts, formaldehyde, glyoxal, or, preferably, covalent crosslinking which will copolymerize with the monomers, diethylenically unsaturated monomers (such as family of diacrylate esters such as polyethylene diacrylates PEG glycols) or polyethylene, of the type that is conventionally used for the crosslinking of polymers soluble in water, and in particular the Methylenebisacrylamide (MBA) or any of the other known acrylic branching agents.
- ionic branching agents such as polyvalent metal salts, formaldehyde, glyoxal, or, preferably, covalent crosslinking which will copolymerize with the monomers, diethylenically unsaturated monomers (such as family of diacrylate esters such as polyethylene diacrylates PEG glycols) or polyethylene, of the type that is conventionally used for the crosslinking of polymers soluble in water, and in particular
- crosslinking agents are often identical to the crosslinking agents, but the crosslinking can be avoided, when one wishes to obtain a branched and not cross-linked polymer, by optimizing the conditions such as concentration during polymerisation, type and amount of transfer agent, temperature, type and amount of initiators, and like.
- the branching agent is methylenebisacrylamide (MBA), introduced at the rate of five to two hundred (5 to 200) moles per million moles of monomers, preferably 5 to 50.
- MBA methylenebisacrylamide
- the amount of branched polyacrylamide introduced into the suspension to flocculate is between thirty and thousand grams of active polymer / tonne of dry pulp (30 and 1000 g / t), ie between 0.03 per thousand and one per thousand, preferably 150 to 500 g / t; it has been observed that if amount is less than 0.03% o (0.03 per thousand), we do not get any significant retention; likewise, if this quantity exceeds 1% o (1 per thousand), no proportional improvement is observed; however, unlike linear cationic polyacrylamides, as described in documents EP-A-0 017 353 and EP 0 235 893 referred to in the preamble, does not observe an inverse effect of dispersion by recirculation in the circuits closed excess polymer not retained on the sheet.
- the amount of branched polyacrylamide introduced is between 0.15 and 0.5 per thousand (0.15% and 0.5%) of the quantity of the dry pulp, ie between 150 g / t and 500 g /
- the branched polymer is prepared under inverse emulsion form (water-in-oil) to achieve perfection of the invention.
- inverse emulsion form water-in-oil
- Such emulsions and their preparation process are well known to those skilled in the art.
- the invention was all the more difficult to realize that it is important to stay in the field of branched polymers and not to go into the crosslinked polymers. Now, we know that technically, especially scale of industrial production, the border between the two areas is very easily crossed, so irreversibly. As the zone of branching is very narrow, we measure the difficulty of developing the invention, and it is the Claimant's merit that he attacked the use of this technology in the field of paper making, which poses particular problems and has very stringent quality requirements.
- a “moderately branched" polymer for example at 10 ppm branching compared to the active ingredient.
- the polymer can be used either under the form of its inverse synthesis emulsion, dissolved or "inverted" in water, either in the form of the solution in the water of the powder obtained by drying said synthetic emulsion, in particular by drying by spray.
- Spray drying is a method also known of the skilled person. We will refer to the tests below to verify that the results are comparable.
- Bentonite also called “swelling smectic clay”, from the montmorillonite family, is well known and there is no need to describe it here in detail; these compounds, formed of microcrystallites, have on the surface sites with a high cation exchange capacity likely to retain water (see, for example, US-A-4,305,781, which corresponds to EP-A-0 017 353, mentioned above, and FR-A-2 283 102).
- a semi-sodium bentonite is preferably used, which is introduced just upstream of the headbox at 0.1 to 0.5 per cent (0.1 to 0.5%) of the dry weight of the fibrous suspension.
- filler we can use the kaolins, the "GCC” or ground CaCO3, precipitated CaCO3 or "PCC”, and the like.
- Injection or introduction of the branched polymer in emulsion inverse according to the invention is carried out before a shearing step in the pulp (or fibrous mass to flocculate) more or less diluted according to the practice of those skilled in the art, and generally in the thin stock or thin stock, ie a paste diluted 0.7 - 1.5% solids such as cellulose fibers, fillers possible, and the various usual additives of papermaking.
- a portion of the branched polymer emulsion, according to the invention at the stage of preparing the thick paste or "thick stock »at approx. 5% or more solids, or even at the level of the preparation of the thick paste before a shearing step.
- the UL viscosity results are as follows:
- the paste used is diluted to a consistency of 1.5%. 2.24 g is taken 150 g of 150% pulp and then diluted to 0.4% with clear waters.
- the crosslinked polymers 1, 4, 9, 12 are not of interest as regards the flocculation and retention of fines and fillers despite the high rate of shear applied during the process on the fibrous mass (and not not applied to the polymer itself), here 1500 rpm., which is characteristic of this type of microparticulate retention system. They show a low capture of charges and colloidal materials because no reduction in turbidity is observed.
- the coagulation power is higher for a branched polymer in emulsion, which results in an excellent reduction of turbidity at 30 '(30 min.).
- test R 52 and the test R 102 show that the invention allows to obtain branched products with higher UL viscosities than those accessible by a gel polymerization as described in patent EP 0 574 335 (FO 4198). Any attempt to achieve such very advantageous values of UL viscosity by a route of gel polymerization with powder drying would lead to a product totally insoluble and therefore totally unusable in the industry.
- the SD 102 test shows that the polymer used in the form of a solution in the water of the powder obtained by drying the the inverse emulsion of the polymer synthesis behaves like the polymer used in the form of the solution in the water of said reverse synthesis emulsion. In particular, we do not observe degradation of the polymer during the spray drying step.
- R 52 can be usefully compared to FO 4198 (powder) because polymers have the same chemistry, so the same cationicity, and the same% MBA, while the R 52 of the invention is much higher than the powder in terms of dewatering and retention (96.3 to bring closer to 83.6); NTU turbidity will also be compared after min. , of 32 compared to 75 NTU units.
- the invention thus also relates to a novel retention agent for the manufacture of a sheet of paper, cardboard or the like, which consists of a (co) acrylic polymer as described above, branched, in inverse emulsion, and which is characterized in that its UL viscosity is> 3, or> 3.5 or> 4.
- Said agent may be used either in inverted emulsion with water or in solution powder obtained by drying the emulsion, as described above.
- the contents of B are mixed in A with stirring. After mixing of the phases, the emulsion is sheared for 1 minute in order to create the inverse emulsion. The emulsion is then degassed by bubbling of nitrogen and then after 20 minutes, the gradual addition of metabisulphite entails the initiation then the polymerization.
- the emulsion is then incorporated with its reversing surfactant in order to subsequently release the polymer in the aqueous phase.
- the invention also relates to new retention agents described above, characterized in that they consist of, or include, the at least one (co) polymer of the type described, branched, prepared in inverse emulsion, intended to cooperate with a secondary retention agent after a step intermediate shearing of pulp, as well as the processes of manufacture of sheets of paper, cardboard or the like, using the agents according to the invention or the method according to the invention, and the sheets of paper, cardboard and analogs thus obtained.
- Said agent may be used either in inversion emulsion with water, or in solution of the powder obtained by drying the emulsion, as described above.
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Abstract
Description
La présente invention concerne le secteur technique de la fabrication du papier et des polymères utilisés dans ce cadre.The present invention relates to the technical sector of manufacture of paper and polymers used in this context.
L'invention concerne un procédé pour la fabrication d'un papier ou d'un carton à rétention, et autres propriétés, améliorées.The invention relates to a method for the production of a paper or a retention cardboard, and other properties, improved.
Lors de la fabrication du papier, du carton ou analogue, il est bien connu d'introduire dans la pâte des agents de rétention dont la fonction est de retenir un maximum de fines et de charges dans la feuille. Les effets bénéfiques qui découlent de l'utilisation d'un agent de rétention sont essentiellement :
- l'augmentation de la production et la diminution des coûts de fabrication : économie énergétique, marche plus régulière de la machine, rendement plus élevé en fibres, fines, charges et de produits d'ennoblissement anioniques, plus faible acidité dans le circuit liée a une diminution de l'utilisation de sulfate d'alumine et donc amoindrissement des problèmes de corrosion ;
- l'amélioration de la qualité : meilleure formation et meilleur épair ; amélioration du taux d'humidité de la feuille, de l'opacité, du lisse, du pouvoir absorbant et diminution de la porosité du papier.
- increased production and lower manufacturing costs: energy saving, more regular machine operation, higher yield of fibers, fines, fillers and anionic finishing products, lower acidity in the circuit related to reduction in the use of alumina sulphate and thus lessening of corrosion problems;
- quality improvement: better training and better looking; improvement of the leaf moisture content, opacity, smoothness, absorbency and decrease of paper porosity.
Depuis longtemps, on a proposé d'ajouter a la pâte de la bentonite, celle-ci pouvant être éventuellement additionnée à d'autres produits minéraux, tels que des sulfates d'aluminium, voire des polymères synthétiques, notamment du polyéthylène-imine (voir par exemple documents DE-A-2 262 906 et US-A-2 368 635).For a long time, it has been proposed to add to the paste of bentonite, this can possibly be added to other mineral products, such as aluminum sulphates, or even synthetic polymers, especially polyethyleneimine (see for example DE-A-2,262 906 and US-A-2,368,635).
Dans le document US-A-3 052 595, on a proposé d'associer de la bentonite a un polyacrylamide de caractéristique linéaire essentielle. Ce procédé s'est trouvé en concurrence avec des systèmes plus faciles a mettre en oeuvre tout en étant aussi performants. En outre, même avec les polyacrylamides linéaires actuels, le pouvoir de rétention reste encore insuffisant.In US-A-3,052,595 it has been proposed to associate the bentonite has a polyacrylamide of essential linear characteristic. This process has competed with systems that are easier to implement while still performing well. In addition, even with current linear polyacrylamides, the retention power still remains insufficient.
Dans le document EP-A-0 017 353, on a proposé, pour la rétention des pâtes peu chargées (au plus 5 % de charges) d'associer à la bentonite un copolyacrylamide linéaire non ionique à faiblement anionique. Ce procédé ne s'est guère développé, car ces polymères sont relativement peu performants en matière de rétention, notamment de pâtes chargées, sans doute par suite d'une synergie insuffisante entre ces copolymères et la bentonite qui a peu tendance à recoaguler.In EP-A-0017353, it was proposed, for the retention of slightly loaded pastes (at most 5% fillers) to associate with the bentonite a nonionic linear copolyacrylamide weakly anionic. This process has hardly developed, because these polymers are relatively poor in retention, especially filled pasta, probably as a result of insufficient synergy between these copolymers and bentonite which has little tendency to recoaguler.
Dans le document EP-A-0 235 893, on a proposé de faire appel à des polyacrylamides cationiques de poids moléculaire supérieur à un million, de trente millions et plus, essentiellement linéaires. On obtient de la sorte un effet de rétention certes satisfaisant, mais encore jugé insuffisant dans l'application papetière, car, l'utilisation de bentonite entraínant des difficultés lors du traitement ultérieur des effluents en sortie de machine, les utilisateurs ne sélectionnent ce système qu'en cas d'avantages significatifs.In EP-A-0 235 893, it has been proposed to use cationic polyacrylamides with a molecular weight greater than thirty million and more, essentially linear. In this way we obtain an effect certainly satisfactory, but still considered insufficient in the application paper, because the use of bentonite causes difficulties during the further treatment of the effluents at the output of the machine, the users select this system only in case of significant benefits.
Dans les notes présentées à l'occasion de cours à Seattle, 11-13 octobre 1989, et publiées sous le titre "Supercoagulation in the control of wet end chemistry by synthetic polymer and activated bentonite", R. Kajasvirta a décrit le mécanisme de la supercoagulation de la bentonite activée en présence d'un copolyacrylamide cationique, sans en préciser la nature exacte. Ce procédé présente les mêmes inconvénients que précédemment.In the notes presented at the course in Seattle, 11-13 October 1989, and published under the title "Supercoagulation in the control of wet end polymeristry by polymer and activated bentonite ", R. Kajasvirta describes the mechanism of supercoagulation of activated bentonite in presence of a cationic copolyacrylamide, without specifying the exact nature thereof. This process has the same disadvantages as before.
Enfin, le EP 0 574 335 a réalisé un perfectionnement important en
proposant l'emploi de polymères (notamment polyacrylamides) ramifiés sous
la forme d'une poudre.Finally,
L'invention pallie les inconvénients rappelés ci-dessus.The invention overcomes the disadvantages mentioned above.
Elle vise un procédé perfectionné du type en question, qui consiste à ajouter, à la suspension ou masse fibreuse ou pâte à papier à floculer, comme agent de rétention principal, un agent qui consiste en, ou comprend, un polyacrylamide ramifié qui se caractérise en ce qu'il a été préparé en émulsion inverse ou eau-dans-huile, et de la bentonite comme second agent de rétention (système dit « dual », de type dit également « microparticulaire »). It is aimed at an improved process of the type in question, consisting of add, to the suspension or fibrous mass or flocculant pulp, as primary retention agent, an agent that consists of, or includes, a branched polyacrylamide which is characterized in that it has been prepared in emulsion reverse or water-in-oil, and bentonite as the second agent of retention (so-called "dual" system, also called "microparticular").
Par le vocable « se présente en émulsion inverse » ou des vocables analogues, se rapportant au polymère utilisé (cad tel qu'injecté ou introduit dans la pâte à floculer) selon l'invention, l'homme de métier comprendra que l'on désigne l'émulsion inverse eau-dans-huile qui est dissoute dans l'eau avant son injection ou son introduction dans la masse ou pâte à floculer (cette dissolution dans l'eau provoque ce que l'on nomme l'« inversion » de l'émulsion inverse eau-dans-huile initiale; ces procédés sont bien connus de l'homme de métier).By the term "is in inverse emulsion" or similar terms, referring to the polymer used (ie as injected or introduced into the flocculant paste) according to the invention, the skilled person will understand that we designate the water-in-oil inverse emulsion which is dissolved in the water before its injection or its introduction into the mass or paste to be flocculated (this dissolution in the water causes what is called the "inversion" of the initial water-in-oil emulsion, these processes are well known to those skilled in the art).
Les additions du polymère et de la bentonite sont séparées 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
USP 4, 753, 710 ainsi qu'à un très vaste art antérieur traitant du point
d'addition de l'agent de rétention par rapport aux étapes de cisaillement
existant sur la machine, notamment USP 3,052,595, Unbehend, TAPPI Vol.
59, N° 10, octobre 1976, Luner, 1984 Papermakers Conference ou Tappi, avril
1984, pp 95-99, Sharpe, Merck and Co Inc, Rahway, NJ, USA, autour de 1980,
Chapter 5 « polyelectrolyte retention aids », Britt, Tappi Vol. 56, octobre 1973,
p 46 ff. et Waech, Tappi, mars 1983, pp 137, ou encore le USP 4,388,150
(Eka Nobel).The additions of the polymer and the bentonite are separated by a
shearing step, for example at the so-called mixing pump
"Fan pump". Reference in this field to the description of the
On se référera également au brevet USP 4,753,710, pour tout ce qui concerne les généralités concernant la fabrication du papier, les additifs usuels utilisés, et détails analogues.Reference is also made to USP Patent 4,753,710, for all that generalities concerning the manufacture of paper, the additives used, and similar details.
Il est possible de remplacer la bentonite, comme agent de rétention
secondaire, par un kaolin tel que décrit dans la demande de brevet
FR 95 13051 du Demandeur, ce kaolin étant préférentiellement prétraité par
un polyélectrolyte. L'homme de métier pourra se référer à ce brevet
FR 95 13051.It is possible to replace bentonite as a retention agent
secondary, by a kaolin as described in the
Ce procédé permet d'obtenir une rétention nettement améliorée de fines et de charges et ce sans effet inverse. On améliore également, ce qui est une caractéristique supplémentaire de ce perfectionnement, les propriétés d'égouttage. This method makes it possible to obtain a markedly improved retention of fines and charges and this without any reverse effect. We also improve, which is a additional feature of this refinement, the properties drip.
Le polyacrylamide ramifié (ou plus généralement le (co)polymère
ramifié) est introduit dans la suspension, de manière tout à fait préférée, sous
la forme d'émulsion inverse eau-dans-huile , à raison de 0,03 à un pour mille
(0,03 a 1 %o, soit 30 à 1000 g/t) en poids de matière active (polymère) par
rapport au poids sec de la suspension fibreuse, de préférence de 0,15 à 0,5
pour mille, soit 150 à 500 g/t.Branched polyacrylamide (or more generally (co) polymer
branched) is introduced into the suspension, very preferably, under
the water-in-oil inverse emulsion form, at the rate of 0.03 to one per thousand
(0.03 to 1% o,
De manière connue de l'homme de métier, l'émulsion inverse de polymère est diluée à l'eau et inversée (solubilisée) par cette dilution avant son introduction, comme décrit plus haut.In a manner known to those skilled in the art, the inverse emulsion of polymer is diluted with water and inverted (solubilized) by this dilution before its introduction, as described above.
Cette sélection de la forme émulsion inverse permet, dans l'application papetière pour la rétention de charges et de fines, d'atteindre un niveau de performances inégalé jusqu'alors. L'utilisation de polymères ramifiés permet de plus de mieux retenir la bentonite sur la feuille, comme décrit dans le brevet EP 574 335 précité et de ce fait de limiter ses effets négatifs sur le traitement ultérieur des effluents de sortie machine. En outre, le choix de ce polyacrylamide ramifié augmente le pouvoir de fixation de la bentonite sur la feuille, par conséquent entraíne une synergie, donc une recoagulation qui réduit la teneur en bentonite dans les eaux blanches.This selection of the inverse emulsion form allows, in the application paper for the retention of fillers and fines, to reach a level of performance unmatched until then. The use of branched polymers allows in addition to better retain the bentonite on the sheet, as described in the patent EP 574 335 cited above and thus to limit its negative effects on the treatment subsequent effluents from the machine. In addition, the choice of this branched polyacrylamide increases the binding power of bentonite on the sheet, therefore leads to a synergy, so a recoagulation that reduces the bentonite content in white waters.
On comprendra qu'il est essentiel selon l'invention que le polymère soit préparé par une polymérisation en émulsion inverse eau-dans-huile. Par contre, ce polymère peut ensuite être utilisé (cad injecté ou introduit dans la masse ou pâte à floculer) soit sous la forme - de préférence - de cette émulsion inverse après sa dissolution dans de l'eau, soit sous la forme d'une poudre obtenue par séchage (notamment par séchage par pulvérisation ou « spray-drying ») de l'émulsion inverse de la polymérisation, puis redissolution de cette poudre dans de l'eau, par exemple à une concentration de l'ordre de 5 g de polymère actif / litre, la solution ainsi obtenue étant alors injectée dans la pâte sensiblement aux mêmes dosages de polymère.It will be understood that it is essential according to the invention that the polymer is prepared by water-in-oil inverse emulsion polymerization. By against, this polymer can then be used (ie injected or introduced into the mass or paste to be flocculated) either in the form - preferably - of this emulsion inverse after its dissolution in water, either in the form of a powder obtained by drying (in particular by spray drying or spray-drying ") Of the inverse emulsion of the polymerization, then redissolution of this powder in water, for example at a concentration of about 5 g of active polymer / liter, the solution thus obtained being then injected into the dough substantially at the same polymer dosages.
Avantageusement, en pratique, le (co)polyacrylamide ramifié est un copolymère cationique d'acrylamide et d'un monomère éthylénique cationique non saturé, choisi dans le groupe comprenant l'acrylate de dimethylaminoethyl (ADAME), le methacrylate de dimethylaminoethyle (MADAME), quaternisés ou salifiés par différents acides et agents quaternisants, benzyle chlorure, méthyle chlorure, alkyl- ou aryle chlorures, diméthylsulfate, le chlorure de dimethyldiallylammonium (DADMAC), le chlorure d'acrylamidopropyltrimethylammonium (APTAC), et le chlorure de methacrylamidopropyltrimethylammonium (MAPTAC),Advantageously, in practice, the branched (co) polyacrylamide is a cationic copolymer of acrylamide and a cationic ethylenic monomer unsaturated, selected from the group consisting of dimethylaminoethyl acrylate (ADAME), dimethylaminoethyl methacrylate (MADAME), quaternized or salified by different acids and quaternizing agents, benzyl chloride, methyl chloride, alkyl- or aryl chlorides, dimethylsulfate, chloride dimethyldiallylammonium (DADMAC), chloride acrylamidopropyltrimethylammonium (APTAC), and the chloride of methacrylamidopropyltrimethylammonium (MAPTAC),
De manière connue, ce copolymère est ramifié par un agent de ramification constitué par un composé présentant au moins deux groupements réactifs choisis dans le groupe comprenant des doubles liaisons, des liaisons aldéhydes ou des liaisons époxy. Ces composés sont bien connus et sont décrits par exemple dans le document EP-A-0 374 458 (voir aussi le document FR-A-2 589 145 du Demandeur).In a known manner, this copolymer is branched by a branching constituted by a compound having at least two groups reactants selected from the group consisting of double bonds, aldehydes or epoxy bonds. These compounds are well known and are described for example in EP-A-0 374 458 (see also document FR-A-2,589,145 to the Applicant).
Comme on le sait, un polymère ramifié, ("branched"), est un polymère qui présente sur la chaíne des branches, des groupements ou des ramifications disposées globalement dans un plan et non pas dans les trois directions, contrairement à un polymère réticulé (« cross-linked »); de tels polymères ramifiés, à haut poids moléculaire, sont bien connus comme agents floculants. Ces polyacrylamides ramifiés se distinguent des polyacrylamides réticulés par le fait que dans ces derniers, les groupements sont disposés tridimensionnellement pour conduire à des produits pratiquement insolubles et de poids moléculaire infini.As is known, a branched polymer is a polymer which present on the chain branches, groups or ramifications arranged globally in one plane and not in the three directions, unlike a cross-linked polymer; such polymers branched, high molecular weight, are well known as flocculating agents. These branched polyacrylamides are distinguished from crosslinked polyacrylamides by the fact that in the latter groups are arranged three-dimensionally to lead to practically insoluble products and of infinite molecular weight.
On pourra effectuer la ramification de préférence durant (ou éventuellement après) la polymérisation, par exemple par réaction de deux polymères solubles présentant des contre-ions, ou par réaction sur du formaldéhyde ou un composé de métal polyvalent. Souvent, la ramification s'effectue durant la polymérisation par addition d'un agent ramifiantt, et cette solution sera nettement préférée selon l'invention. Ces procédés de polymérisation avec ramification sont bien connus.We can carry out the branching preferably during (or optionally after) the polymerization, for example by reaction of two soluble polymers having counterions, or by reaction on formaldehyde or a polyvalent metal compound. Often, the branching takes place during the polymerisation by addition of an agent ramifiantt, and this solution will be clearly preferred according to the invention. These Branching polymerization methods are well known.
Les agents de ramification que l'on peut incorporer comprennent des agents de ramification ioniques comme les sels de métal polyvalent, le formaldéhyde, le glyoxal, ou encore, et de préférence, des agents de réticulation covalents qui vont copolymériser avec les monomères, de préférence des monomères à insaturation diéthylénique (comme la famille des esters de diacrylates comme les diacrylates de polyéthylène glycols PEG) ou polyéthylénique, du type que l'on utilise classiquement pour la réticulation des polymères solubles dans l'eau, et notamment le méthylènebisacrylamide (MBA) ou encore un quelconque des autres agents de ramification acryliques connus.Branching agents that can be incorporated include ionic branching agents such as polyvalent metal salts, formaldehyde, glyoxal, or, preferably, covalent crosslinking which will copolymerize with the monomers, diethylenically unsaturated monomers (such as family of diacrylate esters such as polyethylene diacrylates PEG glycols) or polyethylene, of the type that is conventionally used for the crosslinking of polymers soluble in water, and in particular the Methylenebisacrylamide (MBA) or any of the other known acrylic branching agents.
Ces agents sont souvent identiques aux agents de réticulation, mais la réticulation peut être évitée, lorsque l'on souhaite obtenir un polymère ramifié et non pas réticulé, par une optimisation des conditions de polymérisation telles que concentration lors de la polymérisation, type et quantité d'agent de transfert, température, type et quantité d'initiateurs, et analogues.These agents are often identical to the crosslinking agents, but the crosslinking can be avoided, when one wishes to obtain a branched and not cross-linked polymer, by optimizing the conditions such as concentration during polymerisation, type and amount of transfer agent, temperature, type and amount of initiators, and like.
En pratique, l'agent de ramification est le méthylène bis acrylamide (MBA), introduit a raison de cinq à deux cents (5 a 200) moles par million de moles de monomères, de préférence 5 à 50.In practice, the branching agent is methylenebisacrylamide (MBA), introduced at the rate of five to two hundred (5 to 200) moles per million moles of monomers, preferably 5 to 50.
Avantageusement, la quantité de polyacrylamide ramifié introduite dans
la suspension à floculer est comprise entre trente et mille grammes de
polymère actif / tonne de pâte sèche (30 et 1000 g / t), soit entre 0,03 pour mille
et un pour mille, de préférence de 150 à 500 g / t ; on a observé que si la
quantité est inférieure à 0,03 %o (0,03 pour mille), on n'obtient aucune
rétention significative; de même, si cette quantité excède 1 %o (1 pour mille),
on n'observe aucune amélioration proportionnelle; toutefois, contrairement
aux polyacrylamides cationiques linéaires, tels que décrits dans les
documents EP-A-0 017 353 et EP 0 235 893 visés dans le préambule, on
n'observe pas d'effet inverse de dispersion par recirculation dans les circuits
fermés de l'excès de polymère non retenu sur la feuille. De préférence, la
quantité de polyacrylamide ramifié introduite est comprise entre 0,15 et 0,5
pour mille (0,15 et 0,5%o) de la quantité de la pâte sèche, soit entre 150 g/t et
500 g/t.Advantageously, the amount of branched polyacrylamide introduced into
the suspension to flocculate is between thirty and thousand grams of
active polymer / tonne of dry pulp (30 and 1000 g / t), ie between 0.03 per thousand
and one per thousand, preferably 150 to 500 g / t; it has been observed that if
amount is less than 0.03% o (0.03 per thousand), we do not get any
significant retention; likewise, if this quantity exceeds 1% o (1 per thousand),
no proportional improvement is observed; however, unlike
linear cationic polyacrylamides, as described in
documents EP-A-0 017 353 and
Comme déjà dit, il importe que le polymère ramifié soit préparé sous forme d'émulsion inverse (eau-dans-huile) pour réaliser le perfectionnement de l'invention. De telles émulsions et leur procédé de préparation sont bien connues de l'homme de métier.As already stated, it is important that the branched polymer is prepared under inverse emulsion form (water-in-oil) to achieve perfection of the invention. Such emulsions and their preparation process are well known to those skilled in the art.
Cette approche était condamnée dans le brevet EP 0 574 335 précité,
où l'on indiquait que si l'on fait appel à un polymère ramifié en émulsion, la
présence indispensable dans ces émulsions d'agents tensio-actifs favorise la
formation de mousses lors de la fabrication du papier et l'apparition de
disparités des propriétés physiques du papier fini (modification de
l'absorbance aux endroits où une partie de la phase huile de l'émulsion est
retenue sur la feuille).This approach was condemned in the
Il n'était donc pas évident de considérer a fortiori les émulsions inverses eau dans huile dont la teneur en huile est évidemment élevée.It was therefore not obvious to consider a fortiori the inverse emulsions water in oil whose oil content is obviously high.
L'invention était d'autant plus difficile à réaliser qu'il est important de rester dans le domaine des polymères ramifiés et de ne pas passer dans le domaine des polymères réticulés. Or, on sait que techniquement, surtout à l'échelle de production industrielle, la frontière entre les deux zones est très facilement franchie, de manière d'ailleurs irréversible. Comme la zone de ramification est très étroite, on mesure la difficulté de mise au point de l'invention, et c'est le mérite du Demandeur que de s'être attaqué à l'emploi de cette technologie dans le domaine de la fabrication du papier, qui pose des problèmes particuliers et présente des exigences de qualité très sévères.The invention was all the more difficult to realize that it is important to stay in the field of branched polymers and not to go into the crosslinked polymers. Now, we know that technically, especially scale of industrial production, the border between the two areas is very easily crossed, so irreversibly. As the zone of branching is very narrow, we measure the difficulty of developing the invention, and it is the Claimant's merit that he attacked the use of this technology in the field of paper making, which poses particular problems and has very stringent quality requirements.
Le risque d'échec était d'autant plus important, ce qui explique peut être le fait que cette technologie n'ait pas été employée, que les émulsions réticulées ne sont pas connues pour procurer un avantage particulier dans le papier.The risk of failure was all the more important, which may explain why the fact that this technology has not been used, that emulsions crosslinked are not known to provide a particular advantage in the paper.
Par rapport aux polymères linéaires, les polymères ramifiés en poudre
du EP précité 0 574 335 avaient déjà apporté un progrès important en ce qui
concerne les propriétés et le process de fabrication du papier. L'amélioration
était de l'ordre de 20 à 40 % selon les propriétés.Compared with linear polymers, branched polymers in
Avec les présentes émulsions ramifiées, on atteint une amélioration de l'ordre de 50 à 60 %, ce qui n'était pas prévisible puisque l'on savait, d'autre part, que les produits réticulés ne fonctionnaient pas.With the present branched emulsions, an improvement of 50% to 60%, which was not predictable since it was known On the other hand, cross-linked products did not work.
On comparera à ce sujet les essais 11 (R52) - selon l'invention et 13 (FO 4198) - selon le brevet EP 0 574 335.In this regard, the tests 11 (R52) - according to the invention and 13 (FO 4198) - according to the
Selon l'invention, on utilisera de manière préférée, mais non limitative, un polymère « moyennement ramifié », par exemple à 10 ppm de ramifiant par rapport à la matière active. According to the invention, use will preferably, but not exclusively, a "moderately branched" polymer, for example at 10 ppm branching compared to the active ingredient.
Comme déjà indiqué plus haut, on pourra utiliser le polymère soit sous la forme de son émulsion inverse de synthèse, dissoute ou « inversée » dans l'eau, soit sous la forme de la solution dans l'eau de la poudre obtenue par séchage de ladite émulsion de synthèse, notamment par séchage par pulvérisation. Le séchage par pulvérisation est un procédé également connu de l'homme de métier. On se référera aux essais ci-dessous pour vérifier que les résultats sont comparables.As already indicated above, the polymer can be used either under the form of its inverse synthesis emulsion, dissolved or "inverted" in water, either in the form of the solution in the water of the powder obtained by drying said synthetic emulsion, in particular by drying by spray. Spray drying is a method also known of the skilled person. We will refer to the tests below to verify that the results are comparable.
La bentonite, dénommée également "argile smectique gonflante", de la famille des montmorillonites, est bien connue et il n'y a pas lieu de la décrire ici en détail ; ces composés, formés de microcristallites, comportent en surface des sites présentant une forte capacité d'échange cationique susceptible de retenir l'eau (voir par exemple document US-A-4 305 781, qui correspond au document EP-A-0 017 353, mentionné ci-dessus, et le brevet FR-A-2 283 102).Bentonite, also called "swelling smectic clay", from the montmorillonite family, is well known and there is no need to describe it here in detail; these compounds, formed of microcrystallites, have on the surface sites with a high cation exchange capacity likely to retain water (see, for example, US-A-4,305,781, which corresponds to EP-A-0 017 353, mentioned above, and FR-A-2 283 102).
On utilise de préférence une bentonite semi-sodique, que l'on introduit juste en amont de la caisse de tête, à raison de 0,1 à 0,5 pour cent (0,1 à 0,5%) du poids sec de la suspension fibreuse.A semi-sodium bentonite is preferably used, which is introduced just upstream of the headbox at 0.1 to 0.5 per cent (0.1 to 0.5%) of the dry weight of the fibrous suspension.
Comme charge (« filler »), on pourra utiliser les kaolins, le « GCC » ou CaCO3 broyé, le CaCO3 précipité ou « PCC », et analogues.As load ("filler"), we can use the kaolins, the "GCC" or ground CaCO3, precipitated CaCO3 or "PCC", and the like.
L'injection ou introduction du polymère ramifié en émulsion inverse selon l'invention est effectuée avant une étape de cisaillement dans la pâte à papier (ou masse fibreuse à flocculer) plus ou moins diluée selon la pratique de l'homme du métier, et généralement dans la pâte à papier diluée ou « thin stock », cad une pâte diluée à environ 0,7 - 1,5% de matières solides telles que fibres de cellulose, charges éventuelles, et les divers additifs usuels de la fabrication du papier.Injection or introduction of the branched polymer in emulsion inverse according to the invention is carried out before a shearing step in the pulp (or fibrous mass to flocculate) more or less diluted according to the practice of those skilled in the art, and generally in the thin stock or thin stock, ie a paste diluted 0.7 - 1.5% solids such as cellulose fibers, fillers possible, and the various usual additives of papermaking.
Selon une variante de l'invention, à introduction fractionnée, on introduira une partie du polymère ramifié en émulsion, selon l'invention, au niveau de l'étape de préparation de la pâte épaisse ou « thick stock » à env. 5 % ou plus de matières solides, ou même au niveau de la préparation de la pâte épaisse avant une étape de cisaillement. According to a variant of the invention, with a fractional introduction, introduce a portion of the branched polymer emulsion, according to the invention, at the stage of preparing the thick paste or "thick stock »at approx. 5% or more solids, or even at the level of the preparation of the thick paste before a shearing step.
Les exemples suivants illustrent l'invention sans toutefois en limiter la portée.The following examples illustrate the invention without, however, limit the scope.
Dans un réacteur A, on mélange à température ambiante les constituants
de la phase organique de l'émulsion à synthétiser.
- 252 g d'Exxsol D100
- 18
g de Span 80 - 4 g d'Hypermer 2296
- 385 g d'acrylamide à 50 %
- 73 g de chlorure d'acrylate éthyl triméthyl
ammonium 80 % - 268 g d'eau
- 0,5 g de méthylène bis acrylamide à 0,25 %
- 0,75 ml du bromate de sodium à 50 g l-1
- 20 ppm d'hypophosphite de sodium par rapport à la matière active
- 0,29 ml de Versenex à 200 g l-1
La réaction terminée, on effectue un « burn out » (traitement au métabisulfite) afin de diminuer la teneur en monomère libre.
L'émulsion est alors incorporée avec son tensio-actif inverse afin de libérer par la suite le polymère en phase aqueuse. Il sera nécessaire d'introduire de 2 à 2,4 % d'alcool éthoxylé. La viscosité Brookfield standard dudit polymère sera de 4,36 cps (viscosité prise à 0,1 % dans une solution 1 M NaCl à 25°C à soixante tours par minute)In a reactor A, the constituents of the organic phase of the emulsion to be synthesized are mixed at ambient temperature.
- 252 g of Exxsol D100
- 18 g of
Span 80 - 4 g of Hypermer 2296
- 385 g of 50% acrylamide
- 73 g of acrylate ethyl trimethyl
ammonium chloride 80% - 268 g of water
- 0.5 g of 0.25% methylenebisacrylamide
- 0.75 ml of sodium bromate at 50 gl -1
- 20 ppm sodium hypophosphite relative to the active ingredient
- 0.29 ml of Versenex at 200 gl -1
When the reaction is complete, a "burn out" (metabisulphite treatment) is performed in order to reduce the content of free monomer.
The emulsion is then incorporated with its inverse surfactant in order subsequently to release the polymer in the aqueous phase. It will be necessary to introduce 2 to 2.4% ethoxylated alcohol. The standard Brookfield viscosity of said polymer will be 4.36 cps (viscosity taken at 0.1% in a 1M NaCl solution at 25 ° C. at sixty revolutions per minute).
Selon une variation de la teneur en MBA de 5 à 20 ppm, les résultats en viscosité UL sont les suivants :According to a variation of the MBA content of 5 to 20 ppm, the UL viscosity results are as follows:
On note que les produits linéaires ne développent pas de regain ioniqueRI et voient leur viscosité intrinsèque IV diminuer sous l'effet d'un fort cisaillement (deux des valeurs de IV sont négatives); les produits ramifiés en émulsion développent du regain ionique RI, mais pas de IV ( valeurs < = 0); les produits réticulés développent un fort regain ionique et un très fort regain de IV.We note that linear products do not develop a revival ionicRI and see their intrinsic viscosity IV decrease under the effect high shear (two of IV values are negative); the branched emulsion products develop ionic RI growth, but no IV (values <= 0); cross-linked products develop a strong Ionic regain and a very strong IV rush.
- avec X :with X:
- ionicité après cisaillement en meq/g.ionicity after shearing in meq / g.
- Y :Y:
- ionicité avant cisaillement en meq/g.ionicity before shearing in meq / g.
- avec V1 :with V1:
- viscosité intrinsèque après cisaillement en dl/gintrinsic viscosity after shear in dl / g
- V2 :V2:
- viscosité intrinsèque avant cisaillement en dl/gintrinsic viscosity before shear in dl / g
Une partie des émulsions citées ci-dessus feront l'objet d'une étude d'efficacité en rétention égouttage sur une « formette automatique de rétention » du Centre Technique du Papier.Some of the emulsions mentioned above will be the subject of a study efficiency in draining retention on an "automatic form of retention "of the Technical Paper Center.
Collage en milieu neutre avec 2 % d'une émulsion d'alkyle cétène dimère.Bonding in a neutral medium with 2% of an alkyl emulsion ketene dimer.
La pâte utilisée est diluée à une consistance de 1,5 %. On prélève 2,24 g sec de pâte, soit 149 g de pâte à150% puis l'on dilue à 0,4 % avec des eaux claires.The paste used is diluted to a consistency of 1.5%. 2.24 g is taken 150 g of 150% pulp and then diluted to 0.4% with clear waters.
Le volume de 560 ml est introduit dans le cylindre en plexiglas de la formette automatisée et l'on démarre la séquence.
- t = 0 s, démarrage agitation à 1500 rpm.
- t = 10 s, addition du polymère.
- t = 60 s, réduction automatique à 1000 rpm et addition si nécessaire de la bentonite.
- t = 75 s, arrêt de l'agitation, formation de la feuille avec le vide sous toile puis récupération des eaux blanches.
- t = 0 s, starting agitation at 1500 rpm.
- t = 10 s, addition of the polymer.
- t = 60 s, automatic reduction to 1000 rpm and addition of bentonite if necessary.
- t = 75 s, stopping the agitation, forming the sheet with the vacuum under canvas then recovery of white water.
On effectue alors les opérations suivantes :
- mesure de la turbidité des eaux sans toile.
- dilution d'un bêcher de pâte épaisse pour une nouvelle feuille avec les eaux sous toiles recueillies.
- séchage de la feuille dite 1 ère passe.
- démarrage d'une nouvelle séquence afin de réaliser la feuille dite 2nde passe.
- measurement of the turbidity of water without canvas.
- dilution of a beaker of thick paste for a new leaf with the collected underwater.
- drying of the so-called first pass sheet.
- starting a new sequence in order to make the sheet known as the 2nd pass.
Après 3 passes, l'on change de produits à tester.After 3 passes, we change products to test.
Les analyses suivantes sont alors réalisées :
- mesure des matières en suspension des eaux sous toile (Norme TAPPI : T 656 cm / 83 )
- mesure des cendres des feuilles, (Norme TAPPI : T 211 om - 93 )
- mesure de la turbidité 30' après que les fibres soient déposées afin de connaítre l'état du milieu ionique.
- mesure du degré d'égouttabilité de la pâte avec un Canadian Standard Freeness (CSF; Norme TAPPI T 227 om - 94).
- measurement of suspended solids under canvas (TAPPI standard: T 656 cm / 83)
- measurement of leaf ash, (TAPPI standard: T 211 om - 93)
- measurement of the turbidity 30 'after the fibers are deposited in order to know the state of the ionic medium.
- measuring the degree of drainability of the pulp with a Canadian Standard Freeness (CSF TAPPI Standard T 227 om - 94).
Notes pour les Tableaux ( I ) et ( II ) ci-après:Notes for Tables (I) and (II) below:
- X =X =
- mesure dite à la première passe.measure said to the first pass.
- R1 =R1 =
- mesure dite à la seconde passe (1 er recyclage)measured in the second pass (1st recycling)
- R2 =R2 =
- mesure dite à la troisième passe (2ème recyclage)measure said to the third pass (2nd recycling)
Les polymères réticulés 1, 4, 9, 12 ne présentent pas d'intérêt quant à la
floculation et la rétention des fines et des charges malgré le fort taux de
cisaillement appliqué en cours de process sur la masse fibreuse (et non
pas appliqué sur le polymère lui-même), ici 1500 tr/min., qui est
caractéristique de ce type de système de rétention microparticulaire. Ils
montrent une faible capture des charges et matières colloidales car
aucune réduction de turbidité n'est observée.The
La combinaison avec la bentonite n'améliore pas de manière significative l'efficacité en rétention et améliore seulement légèrement l'efficacité en égouttage.The combination with bentonite does not improve so significant efficiency in retention and only slightly improves efficiency in draining.
Pour le polymère linéaire, son comportement suit la tendance, amélioration des rétentions de charges et de fines.For the linear polymer, its behavior follows the trend, improved retentions of charges and fines.
La combinaison selon l'invention d'un polymère ramifié en émulsion inverse et de bentonite apporte un gain net en rétention de charge et en rétention totale, et se révèle être supérieure au système connu polymère linéaire / bentonite. The combination according to the invention of a branched polymer in inverse emulsion and bentonite brings a net gain in retention of load and in full retention, and proves to be superior to the system known linear polymer / bentonite.
Le pouvoir de coagulation est supérieur pour un polymère ramifié en émulsion, ce qui se traduit par une excellente réduction de la turbidité à 30' (30 min.).The coagulation power is higher for a branched polymer in emulsion, which results in an excellent reduction of turbidity at 30 '(30 min.).
L'essai R 52 et l'essai R 102 montrent que l'invention permet
d'obtenir des produits ramifiés présentant des viscosités UL plus élevées
que celles accessibles par une polymérisation en gel telle que décrite
dans le brevet EP 0 574 335 (FO 4198). Toute tentative pour atteindre de telles
valeurs très avantageuses de viscosité UL par une voie de
polymérisation en gel avec séchage en poudre conduirait à un produit
totalement insoluble et donc totalement inutilisable dans l'industrie.The test R 52 and the test R 102 show that the invention allows
to obtain branched products with higher UL viscosities
than those accessible by a gel polymerization as described
in
L'essai SD 102 montre que le polymère utilisé sous la forme d'une solution dans l'eau de la poudre obtenue par séchage de l'émulsion inverse de la synthèse du polymère se comporte comme le polymère utilisé sous la forme de la solution dans l'eau de ladite émulsion inverse de synthèse. Notamment, on n'observe pas de dégradation du polymère durant l'étape de séchage par pulvérisation.The SD 102 test shows that the polymer used in the form of a solution in the water of the powder obtained by drying the the inverse emulsion of the polymer synthesis behaves like the polymer used in the form of the solution in the water of said reverse synthesis emulsion. In particular, we do not observe degradation of the polymer during the spray drying step.
L'essai R 52 peut être utilement comparé à l'essai FO 4198 (poudre) car les polymères présentent la même chimie, donc la même cationicité, et le même % de MBA, tandis que le R 52 de l'invention est très supérieur à la poudre en termes d'égouttage et de rétention (96,3 à rapprocher de 83,6); on comparera également la turbidité NTU après 30 min. , de 32 par rapport à 75 unités NTU.R 52 can be usefully compared to FO 4198 (powder) because polymers have the same chemistry, so the same cationicity, and the same% MBA, while the R 52 of the invention is much higher than the powder in terms of dewatering and retention (96.3 to bring closer to 83.6); NTU turbidity will also be compared after min. , of 32 compared to 75 NTU units.
De telles valeurs de viscosité UL conduisent notamment à un égouttage très amélioré.Such values of UL viscosity lead in particular to a drainage very improved.
L'invention concerne donc également un nouvel agent de rétention pour la fabrication d'une feuille de papier, carton ou analogue, qui consiste en un (co)polymère acrylique tel que décrit ci-dessus, ramifié, en émulsion inverse, et qui est caractérisé en ce que sa viscosité UL est > 3, ou > 3,5 ou > 4. Ledit agent peut être utilisé soit en émulsion inversée à l'eau, soit en solution de la poudre obtenue par séchage de l'émulsion, comme décrit ci-dessus. The invention thus also relates to a novel retention agent for the manufacture of a sheet of paper, cardboard or the like, which consists of a (co) acrylic polymer as described above, branched, in inverse emulsion, and which is characterized in that its UL viscosity is> 3, or> 3.5 or> 4. Said agent may be used either in inverted emulsion with water or in solution powder obtained by drying the emulsion, as described above.
Dans un réacteur A, on mélange à température ambiante les constituants
de la phase organique de l'émulsion à synthétiser.
- 252 g d'exxsol D100
- 18
g de Span 80 - 4 g d'Hypermer 2296.
- 378 g d'acrylamide à 50 %
- 102,2 g de chlorure d'acrylamido-propyl triméthyl ammonium (60 %)
- 245,7 g d'eau
- 0,5 g de méthylène bis acrylamide à 0,25 %
- 0,75 ml de bromate de sodium à 50 g/l
- 20 ppm d'hypophosphite de sodium par rapport à la matière active
- 0,29 ml de Versenex à 200 g/l
- 252 g of exxsol D100
- 18 g of
Span 80 - 4 g of Hypermer 2296.
- 378 g of 50% acrylamide
- 102.2 g of acrylamido-propyltrimethylammonium chloride (60%)
- 245.7 g of water
- 0.5 g of 0.25% methylenebisacrylamide
- 0.75 ml of sodium bromate at 50 g / l
- 20 ppm sodium hypophosphite relative to the active ingredient
- 0.29 ml of Versenex at 200 g / l
On mélange le contenu de B dans A sous agitation. Après le mélange des phases, on cisaille l'émulsion au mixer pendant 1 minute afin de créer l'émulsion inverse. L'émulsion est alors dégazée par un bullage d'azote puis après 20 minutes, l'addition progressive du métabisulfite entraíne l'initiation puis la polymérisation.The contents of B are mixed in A with stirring. After mixing of the phases, the emulsion is sheared for 1 minute in order to create the inverse emulsion. The emulsion is then degassed by bubbling of nitrogen and then after 20 minutes, the gradual addition of metabisulphite entails the initiation then the polymerization.
La réaction terminée, on effectue un « burn out » afin de diminuer la teneur en monomère libre.When the reaction is complete, a burn-out is made to reduce the free monomer content.
L'émulsion est alors incorporée avec son tensio-actif inverseur afin de libérer par la suite le polymère en phase aqueuse. The emulsion is then incorporated with its reversing surfactant in order to subsequently release the polymer in the aqueous phase.
Les résultats appellent les mêmes commentaires que ceux de l'exemple 1 et confirment le grand intérêt de la présente invention.The results call for the same comments as in the example 1 and confirm the great interest of the present invention.
L'invention concerne également les nouveaux agents de rétention décrits ci-dessus, caractérisés en ce qu'ils consistent en, ou comprennent, au moins un (co)polymère du type décrit, ramifié, préparé en émulsion inverse, destiné à coopérer avec un agent secondaire de rétention après une étape intermédiaire de cisaillement de la pâte à papier, ainsi que les procédés de fabrication de feuilles de papier, carton ou analogue, utilisant les agents selon l'invention ou le procédé selon l'invention, et les feuilles de papier, carton et analogues ainsi obtenues.The invention also relates to new retention agents described above, characterized in that they consist of, or include, the at least one (co) polymer of the type described, branched, prepared in inverse emulsion, intended to cooperate with a secondary retention agent after a step intermediate shearing of pulp, as well as the processes of manufacture of sheets of paper, cardboard or the like, using the agents according to the invention or the method according to the invention, and the sheets of paper, cardboard and analogs thus obtained.
Ledit agent peut être utilisé soit en émulsion inversée à l'eau, soit en solution de la poudre obtenue par séchage de l'émulsion, comme décrit ci-dessus. Said agent may be used either in inversion emulsion with water, or in solution of the powder obtained by drying the emulsion, as described above.
Claims (20)
- Process for manufacturing a sheet of paper or cardboard or the like having improved retention and dewatering characteristics, which consists in using a dual system of branched acrylic polymer as primary retention agent and bentonite or an optionally treated kaolin as secondary retention agent, of which the introduction is separated by a stage of shearing the fibrous suspension or mass or wood pulp, characterised in that said polymer is a branched acrylic (co)polymer prepared in the form of an invert water-in-oil emulsion and used either as an emulsion inverted with water or as a solution of the powder obtained by drying the emulsion, and in that its viscosity (UL) is > 3, preferably > than 3.5 and preferably > 4.
- Process according to claim 1, characterised in that the branched acrylic (co)polymer prepared as an invert emulsion is introduced into the wood pulp in a concentration from 0.03 to one per thousand (0.03 to 1‰) by weight, that is from 30 to 1000 g/t, of the dry weight of the fibrous wood pulp suspension, preferably from 0.15 to 0.5 per thousand (0.15 to 0.5‰), that is from 150 to 500 g/t.
- Process according to claim 1 or 2, characterised in that the branched acrylic (co)polymer prepared as an invert emulsion is a cationic (co)polymer of acrylamide and of an unsaturated cationic ethylenic monomer, selected from the group comprising dimethylaminoethyl acrylate (ADAME), dimethylaminoethyl methacrylate (MADAME), which are quaternised or salified by various acids and quaternising agents, benzyl chloride, methyl chloride, alkyl or aryl chlorides, dimethyl sulphate, dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) and methacrylamidopropyltrimethylammonium chloride (MAPTAC).
- Process according to any of claims 1 to 3, characterised in that the branched acrylic (co)polymer as an invert emulsion is branched by a branching agent formed by a polyfunctional compound containing at least two reactive groups selected from the group comprising double bonds, aldehyde bonds or epoxy bonds.
- Process according to any of claims 1 to 4, characterised in that the branched acrylic (co)polymer as an invert emulsion is branched by a branching agent formed by methylenebisacrylamide (MBA).
- Process according to claim 5, characterised in that the (MBA) is introduced in a concentration of 5 to 200 moles per million moles of monomers.
- Process according to claim 5 or 6, characterised in that the bentonite is a semi-sodium bentonite used in a proportion of 0.1 to 0 . 5 per cent (0.1 to 0.5%) of the dry weight of the fibrous suspension.
- Process according to claim 5, 6 or 7, characterised in that the filler-containing pulp used is diluted, then the polymer is added as main retention agent, a shearing stage is carried out, for example in the mixing pump or fan pump, then the bentonite is added as secondary retention agent.
- Process according to claim 8, characterised in that the amount of branched polyacrylamide (or more generally of branched acrylic (co)polymer) introduced either as an invert water-in-oil emulsion inverted with water, or as a solution of the powder obtained by drying the emulsion is between 0.03 and 1‰, that is between thirty and a thousand grammes/tonne (30 and 1000 g/t) of dry pulp.
- Process according to claim 8 or 9, characterised in that the amount of branched polyacrylamide (or more generally of branched acrylic (co)polymer) introduced either as an invert water-in-oil emulsion inverted with water, or as a solution of the powder obtained by drying the emulsion is between 0.15 and 0.5‰ (that is between 150 and 500 g/t).
- Process according to claim 8, 9 or 10, characterised in that the bentonite is replaced by kaolin, optionally pretreated with a polyelectrolyte as secondary retention agent.
- Process according to any of claims 1 to 11, characterised in that the branched polymer prepared as an invert emulsion is injected or introduced (either as an emulsion inverted with water or as a solution of the powder obtained by drying the emulsion) prior to a shearing stage into the more or less dilute wood pulp (or fibrous mass to be flocculated) according to the practice of the person skilled in the art, and generally into the dilute wood pulp or thin stock, in other words a pulp diluted to approx 0.7 to 1.5% of solids such as cellulose fibres, possible fillers and the various additives conventional in paper manufacture.
- Process according to any of claims 1 to 11, characterised in that a portion of the branched polymer is introduced as an emulsion during the stage of preparation of the thick pulp or thick stock containing approx 5% or more of solids, or even during preparation of the thick pulp prior to a shearing stage.
- Retention agent for. the manufacture of a sheet of paper, cardboard or the like, characterised in that it comprises a branched polyacrylamide (or more generally a branched acrylic (co)polymer) as an invert (or water-in-oil) emulsion (either an invert emulsion dissolved or inverted with water, or as a solution of the powder obtained by drying the invert emulsion, in particular by spray drying), and in that its viscosity (UL) is > 3.
- Retention agent for manufacturing a sheet of paper, cardboard or the like, according to claim 14, characterised in that the branching agent is a branching agent formed by a polyfunctional compound containing at least two reactive groups selected from the group comprising double bonds, aldehyde bonds or epoxy bonds, in particular methylenebisacrylamide (MBA).
- Retention agent for manufacturing a sheet of paper, cardboard or the like, according to claim 15, characterised in that the branching agent is introduced in a proportion of five to two hundred (5 to 200) moles per million moles of monomers, preferably 5 to 50.
- Retention agent for manufacturing a sheet of paper, cardboard or the like, according to claim 14, 15 or 16, characterised in that the branched polyacrylamide is a cationic (co)polymer of acrylamide and of an unsaturated cationic ethylenic monomer selected from the group comprising dimethylaminoethyl acrylate (ADAME), dimethylaminoethyl methacrylate (MADAME), which are quaternised or salified by various acids and quaternising agents, benzyl chloride, methyl chloride, alkyl or aryl chlorides, dimethyl sulphate, dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) and methacrylamidopropyltrimethylammonium chloride (MAPTAC).
- Retention agent for manufacturing a sheet of paper, cardboard or the like, according to any of claims 14 to 17, characterised in that its viscosity (UL) is > 3.5.
- Retention agent for manufacturing a sheet of paper, cardboard or the like, according to any of claims 14 to 18, characterised in that its viscosity (UL) is > 4.
- Retention agent for manufacturing a sheet of paper, cardboard or the like, according to any of claims 14 to 19, characterised in that it is "averagely branched", for example with 10 ppm of branching agent based on the active substance.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9807144A FR2779452B1 (en) | 1998-06-04 | 1998-06-04 | PROCESS FOR PRODUCING PAPER AND CARDBOARD AND NOVEL RETENTION AND DRIPPING AGENTS THEREOF, AND PAPER AND CARDBOARD THUS OBTAINED |
FR9807144 | 1998-06-04 | ||
PCT/FR1999/001278 WO1999063159A1 (en) | 1998-06-04 | 1999-06-01 | Method for making paper and cardboard and retention and dewatering agents |
Publications (4)
Publication Number | Publication Date |
---|---|
EP1092064A1 EP1092064A1 (en) | 2001-04-18 |
EP1092064B1 true EP1092064B1 (en) | 2003-11-19 |
EP1092064B2 EP1092064B2 (en) | 2009-04-22 |
EP1092064B9 EP1092064B9 (en) | 2009-10-21 |
Family
ID=9527102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99923647A Expired - Lifetime EP1092064B9 (en) | 1998-06-04 | 1999-06-01 | Method for making paper and cardboard |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1092064B9 (en) |
JP (1) | JP4699608B2 (en) |
KR (1) | KR100685533B1 (en) |
AT (1) | ATE254693T1 (en) |
AU (1) | AU4043999A (en) |
CA (1) | CA2334196C (en) |
DE (1) | DE69912954T3 (en) |
FR (1) | FR2779452B1 (en) |
WO (1) | WO1999063159A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2779752B1 (en) * | 1998-06-12 | 2000-08-11 | Snf Sa | PROCESS FOR PRODUCING PAPER AND CARDBOARD AND NOVEL RETENTION AGENTS THEREOF, AND PAPER AND CARDBOARD THUS OBTAINED |
DE20220979U1 (en) | 2002-08-07 | 2004-10-14 | Basf Ag | Preparation of paper, pasteboard, or cardboard involving cutting of the paper pulp, addition of microparticles of cationic polymer, e.g. cationic polyamide, and a finely divided inorganic component after the last cutting step |
MXPA04003942A (en) * | 2003-05-05 | 2007-06-29 | German Vergara Lopez | Retention and drainage system for the manufacturing of paper, paperboard and similar cellulosic products. |
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 |
DE102004044379B4 (en) | 2004-09-10 | 2008-01-10 | Basf Ag | Process for the production of paper, paperboard and cardboard and use of a retention agent combination |
DE102004063005A1 (en) | 2004-12-22 | 2006-07-13 | Basf Ag | Process for the production of paper, cardboard and cardboard |
DE102008000811A1 (en) | 2007-03-29 | 2008-10-09 | Basf Se | Preparing paper, paperboard and cardboard, comprises shearing the paper material, adding ultrasound treated microparticle system and fine-particle inorganic component to the paper material and dewatering the paper material to form sheets |
BRPI0917678B1 (en) | 2008-09-02 | 2019-09-10 | Basf Se | process for the production of paper, cardboard and cardboard |
US9909070B2 (en) | 2009-09-15 | 2018-03-06 | Suncor Energy Inc. | Process for flocculating and dewatering oil sand mature fine tailings |
PL3199218T3 (en) | 2009-09-15 | 2020-04-30 | Suncor Energy Inc. | Process for drying oil sand mature fine tailings |
US9068776B2 (en) | 2009-10-30 | 2015-06-30 | Suncor Energy Inc. | Depositing and farming methods for drying oil sand mature fine tailings |
ES2720487T3 (en) * | 2012-02-01 | 2019-07-22 | Basf Se | Paper and cardboard manufacturing process |
GB2567456B (en) | 2017-10-12 | 2021-08-11 | Si Group Switzerland Chaa Gmbh | Antidegradant blend |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4617362A (en) * | 1984-12-31 | 1986-10-14 | Allied Corporation | Inverse emulsion polymers with improved incorporation of diallyldimethylammonium chloride |
DE3666690D1 (en) † | 1985-04-25 | 1989-12-07 | Allied Colloids Ltd | Flocculation processes |
FR2589145A1 (en) * | 1985-10-25 | 1987-04-30 | Snf Sa | Flocculating agent for the treatment of sludges based on branched water-soluble addition polymers |
GB8602121D0 (en) † | 1986-01-29 | 1986-03-05 | Allied Colloids Ltd | Paper & paper board |
US5354481A (en) † | 1988-12-19 | 1994-10-11 | Cytec Technology Corp. | Water-soluble highly branched polymeric microparticles |
ATE118224T1 (en) * | 1988-12-19 | 1995-02-15 | Cytec Tech Corp | HIGH PERFORMANCE POLYMER FLOCCULATING AGENT. |
US5405554A (en) † | 1990-02-08 | 1995-04-11 | Cytec Technology Corp. | High performance dewatering aids |
US5234548A (en) * | 1992-01-02 | 1993-08-10 | Vinings Industries Inc. | Production of paper and paperboard |
FR2692292B1 (en) * | 1992-06-11 | 1994-12-02 | Snf Sa | Method for manufacturing paper or cardboard with improved retention. |
GB9313956D0 (en) * | 1993-07-06 | 1993-08-18 | Allied Colloids Ltd | Production of paper |
GB9410920D0 (en) † | 1994-06-01 | 1994-07-20 | Allied Colloids Ltd | Manufacture of paper |
FR2740482B1 (en) * | 1995-10-30 | 1997-11-21 | Snf Sa | PROCESS FOR IMPROVING RETENTION IN A PAPER, CARDBOARD AND THE LIKE PROCESS |
SE9504081D0 (en) * | 1995-11-15 | 1995-11-15 | Eka Nobel Ab | A process for the production of paper |
JP3614609B2 (en) * | 1996-09-10 | 2005-01-26 | ハイモ株式会社 | Papermaking chemicals, papermaking methods and methods for producing papermaking chemicals |
-
1998
- 1998-06-04 FR FR9807144A patent/FR2779452B1/en not_active Expired - Lifetime
-
1999
- 1999-06-01 AT AT99923647T patent/ATE254693T1/en active
- 1999-06-01 WO PCT/FR1999/001278 patent/WO1999063159A1/en active IP Right Grant
- 1999-06-01 EP EP99923647A patent/EP1092064B9/en not_active Expired - Lifetime
- 1999-06-01 KR KR1020007013706A patent/KR100685533B1/en not_active IP Right Cessation
- 1999-06-01 DE DE69912954T patent/DE69912954T3/en not_active Expired - Lifetime
- 1999-06-01 CA CA002334196A patent/CA2334196C/en not_active Expired - Lifetime
- 1999-06-01 AU AU40439/99A patent/AU4043999A/en not_active Abandoned
- 1999-06-01 JP JP2000552347A patent/JP4699608B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
AU4043999A (en) | 1999-12-20 |
CA2334196A1 (en) | 1999-12-09 |
DE69912954T3 (en) | 2010-01-28 |
FR2779452A1 (en) | 1999-12-10 |
FR2779452B1 (en) | 2000-08-11 |
KR20010052553A (en) | 2001-06-25 |
KR100685533B1 (en) | 2007-02-22 |
DE69912954T2 (en) | 2004-11-11 |
ATE254693T1 (en) | 2003-12-15 |
DE69912954D1 (en) | 2003-12-24 |
CA2334196C (en) | 2008-07-15 |
EP1092064A1 (en) | 2001-04-18 |
JP2002517626A (en) | 2002-06-18 |
JP4699608B2 (en) | 2011-06-15 |
EP1092064B2 (en) | 2009-04-22 |
EP1092064B9 (en) | 2009-10-21 |
WO1999063159A1 (en) | 1999-12-09 |
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