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    • 专利摘要:
    The present invention relates to a method for preparing an aqueous polymeric solution of viscosity V3 containing at least one cationic or amphoteric (co) polymer, comprising the following steps: Hofmann degradation reaction on a (co) polymer base of at least one nonionic monomer selected from the group consisting of acrylamide, methacrylamide, N, N-dimethylacrylamide, and acrylonitrile; after-treatment of the resulting aqueous polymeric solution of viscosity V1; characterized in that the post-treatment comprises the following successive steps: a) increasing the viscosity V1 to a value V2 corresponding to at least 1.5 times the value V1 while being less than 100,000 cps, by adjusting the pH of the polymeric solution has a value greater than or equal to 5.5; b) lowering the pH of the polymeric solution to a value of between 2 and 5; c) obtaining a polymeric solution whose viscosity V3 is greater than V1 and less than V2. The invention also relates to the use of this polymeric solution as a flocculation agent, retention and / or drainage, and dry strength in the paper industry.
    公开号:FR3016363A1
    申请号:FR1450301
    申请日:2014-01-15
    公开日:2015-07-17
    发明作者:Rene Hund；Christophe Auriant
    申请人:SNF SA；
    IPC主号:
    专利说明:

    [0001] The invention relates to an aqueous solution of cationic or amphoteric (co) polymers obtained by so-called Hofmann degradation carried out on a (co) polymer base of at least a nonionic monomer selected from the group consisting of acrylamide, methacrylamide, N, N dimethylacrylamide, and acrylonitrile. The process for the preparation of this polymeric solution is characterized in that a specific post-treatment on the solution of (co) polymers obtained after the Hofmann degradation is carried out.
    [0002] The invention also relates to the use of this solution of (co) polymers as an additive in a process for producing paper, paperboard or the like, and more particularly as flocculation agents, retention and / or drainage, and dry strength.
    [0003] Hofmann's degradation This reaction, discovered by Hofmann at the end of the nineteenth century, makes it possible to convert an amide function into a primary amine function having one carbon atom less. The reaction mechanism is detailed below.
    [0004] In the presence of a base (soda), a proton is torn from the amide. The amidate ion formed then reacts with the active chlorine (C12) of the hypochlorite (eg: NaC1O which is in equilibrium: 2 NaOH + C12 <1> NaClO + NaCl + +). H2O) to give N-chloramide. The base (NaOH) tears a proton out of the chloramide to form an anion. The anion loses a chloride ion to form a nitrene which is transposed to isocyanate. R-N = C = O By reaction between the hydroxide ion and the isocyanate, a carbamate is formed.
    [0005] After decarboxylation (removal of CO2) from the carbamate, a primary amine H is obtained. RN-CO2-R-NH 2 H -CO 2 For the conversion of all or part of the amide functions of a (co) polymer comprising an amide group in the amine function, two main factors intervene (expressed in molar ratios). These are: - Alpha = (alkaline and / or alkaline earth hypohalide / amide group) and - Beta = (alkaline and / or alkaline earth hydroxide / alkaline and / or alkaline earth hypohalide).
    [0006] Although the Hofmann degradation initially relates to amide groups, it can also relate to nitrile functions (-CI I), and in particular those of (co) polymers of acrylonitrile. The polymers obtained by Hofmann degradation reaction are especially used in papermaking processes. In general, the effectiveness of these polymers as resistance agents increases with their cationicity. In other words, in order to increase their cationicity, the (co) polymers used have a high degree of degradation. Indeed, depending on the degree of degradation Alpha, it is possible to generate cationicity variations related to the amount of amine functions produced on the carbon skeleton of the (co) polymer. Furthermore, it is recognized that when the product obtained by Hofmann degradation reaction is amphoteric, it can also be used to improve the retention of charges during the paper or board manufacturing process, while maintaining the performance of dry resistance.
    [0007] The cationicity of the degraded (co) polymer can in particular come from formed amine groups that can be protonated, but also from the possible presence of a cationic monomer.
    [0008] Until recently, only very heavy processes using, in situ, a Hofmann degradation product manufacturing unit (EP 377313) or processes using another polymer (base of the (co) polymer type of N-vinylformamide followed by hydrolysis) itself relatively expensive (US 2004/118540), had been put in place. The first viable industrial solution was proposed at the beginning of 2005 in the document WO2006075115 of the Applicant. In this document, the Hofmann degradation product described is an organic polymer produced at a concentration greater than 3.5% by weight. Although the polymers described in this document can greatly improve the dry strength performance, they have a very low molecular weight giving these (co) polymers a very limited interest for applications such as drainage or flocculation.
    [0009] The documents W02008 / 107620 and WO / 2010/061082 of the Applicant had partially solved this problem of poor performance in dewatering. However, the polymers described in these documents exhibit some capping of the performance relating to dripping and retention.
    [0010] The document WO 2009/013423 of the Applicant had also made it possible to increase the dewatering performance by proposing a post-treatment of a (co) polymer resulting from the Hofmann reaction. This post-treatment consists of a post-branching carried out on the copolymer obtained by Hofmann degradation in the presence of at least one polyfunctional branching agent. However, this process had very high limits with a very complex control of post-branching (delicate industrialization), as well as performance also saturated for dosages higher than 1.5kg active / ton of paper. The document WO 2011/015783 of the Applicant proposes new polymers which have made it possible to push back the saturation limits in performance, in particular for high dosages, of the order of 2 kg active / ton. The problem to be solved by the invention is therefore to develop polymers whose dewatering properties can be further improved over the polymers of the prior art, without causing loss of physical properties.
    [0011] In addition, the present invention makes it possible to achieve, and even surpass, the properties of the polymers of the prior art, at equal or lower dosage.
    [0012] Description of the Invention The Applicant has found and developed novel water-soluble polymers having improved drainage properties, said polymers being obtainable by alkalinization followed by acidification of a cationic or amphoteric copolymer, 10 obtained by Hofmann degradation. The Applicant has found, surprisingly and unexpectedly, that the treatment thus carried out makes it possible to confer on a cationic or amphoteric polymer obtained by Hofmann degradation an improvement in the dewatering performance with respect to the same untreated polymer. In other words, the subject of the invention is a process for the preparation of an aqueous polymeric solution of viscosity V3 containing at least one cationic or amphoteric (co) polymer, comprising the following steps: degradation reaction known as Hofmann, in aqueous solution, in the presence of an alkaline earth hydroxide and / or alkali and an alkaline earth and / or alkaline hypohalide, on a (co) polymer base of minus one nonionic monomer selected from the group consisting of acrylamide, methacrylamide, N, N dimethylacrylamide, and acrylonitrile; After-treatment of the resulting aqueous polymeric solution of viscosity V1; characterized in that the post-treatment comprises the following successive steps: a) increasing the viscosity V1 to a value V2 corresponding to at least 1.5 times the value V1 while being less than 100,000 cps, by adjusting the pH of the polymeric solution has a value greater than or equal to 5.5; b) lowering the pH of the polymeric solution to a value of between 2 and 5; c) obtaining a polymeric solution whose viscosity V3 is greater than V1 and less than V2.
    [0013] By "resulting aqueous polymeric solution" is meant the polymeric solution obtained at the end of the Hofmann degradation reaction. This solution comprises the or (co) polymers degraded by the Hofmann reaction. In addition, and according to a particular embodiment, it may be concentrated or diluted before the post-treatment steps. Hofmann degradation can be carried out on at least one (co) polymer base. Viscosities are measured with a Brookfield viscometer at 25 ° C. with an LV module. In the present application, it is considered that one skilled in the art is able to determine the modulus and the speed (Brookfield viscometer, LV module) adapted according to the viscosity range to be measured. This type of measurement is indeed part of the general knowledge of the skilled person. As already stated, in the post-treatment step a), the pH of the polymer solution is adjusted to a value greater than or equal to 5.5. According to a particular embodiment, the pH is preferably between 5.5 and 12, and more preferably between 5.5 and 10, and even more preferably between 5.5 and 8. With respect to viscosity V2, it is less than 100. 000 cps, preferentially less than 50,000 cps, and even more preferably less than 30,000 cps. In addition, the viscosity V 2 is advantageously greater than or equal to 2 times the viscosity V 1. In the post-treatment stage b), the pH of the polymer solution is lowered to a value between 2 and 5, preferably between 2 and 5. and 4, and even more preferably between 3 and 4. The post-treatment according to the invention is preferably carried out on the aqueous polymer solution directly obtained after the Hofmann degradation. As already indicated, the polymeric solution obtained after the Hofmann degradation can also be diluted or concentrated before the post-treatment according to the invention is carried out. The concentration of the aqueous polymer solution on which the post-treatment according to the invention is carried out is advantageously between 0.5% and 50% by weight of (co) polymer relative to the weight of said polymeric solution, more preferably between 2 and 30%, even more preferably between 7 and 20%.
    [0014] The viscosity V1 of the polymer solution on which the post-treatment according to the invention is carried out is advantageously between 10 cps and 5000 cps (Brookfield at 25 ° C. and an LV1 module), and even more preferably between 50 and 500 cps. .
    [0015] According to a particular embodiment, the post-treatment according to the invention is carried out on a polymer solution containing as polymer only the polymers directly derived from the Hofmann degradation. In other words, and according to this particular embodiment, the post-treated aqueous polymer solution contains only (co) polymers resulting from the Hofmann degradation of a (co) polymer base as described above. .
    [0016] According to another particular embodiment, the Hofmann degradation reaction is partially or completely completed before the post-treatment according to the invention is carried out. The post-treated aqueous polymeric solution may thus comprise the (co) polymer base but also the (co) polymer resulting from the Hofmann degradation.
    [0017] The post-treatment steps are generally carried out at a temperature of between 5 and 50 ° C, preferably between 10 and 30 ° C. Generally the pH of the polymer solution directly obtained after the Hofmann degradation is between 2 and 5, and more generally between 3 and 4. This corresponds to the pH range in which a (co) polymer from a so-called Hofmann degradation has a stability of its performances over time. In general, the pH adjustment during step a) of the process therefore consists in increasing the pH to a value greater than or equal to 5.5.
    [0018] The post-treatment according to the invention is carried out on a polymer solution having a pH advantageously between 2 and 5 and more preferably between 2.5 and 4.5, and very preferably between 3 and 4.
    [0019] The Applicant has found that the adjustment of the pH to a value greater than or equal to 5.5 of a polymeric aqueous solution containing a cationic or amphoteric (co) polymer obtained by Hofmann degradation reaction caused a gradual increase in the viscosity of this, this increase in viscosity can be interrupted at any time by a return to the initial pH, without affecting the cationicity of the (co) polymer. This increase in viscosity makes it possible, surprisingly and unexpectedly, to confer on the final cationic or amphoteric polymer significantly improved drainage performance properties compared to the same polymers which have not undergone post-treatment, ie say with respect to the Hofmann polymers of the prior art. Without being limited to any theory, the Applicant considers that this increase in viscosity could be related to either an increase in molecular weight or to a branching reaction. In this case, and contrary to the prior art, this branching would not be linked to the addition of a polyfunctional compound. The first step of the post-treatment according to the invention consists in adjusting the pH of a polymer solution containing the polymers obtained at the end of said Hofmann degradation, at a pH greater than or equal to 5.5, preferably between 5.5 and 12, thereby allowing the viscosity of said solution to increase. For this purpose any base or basic product can be used. There may be mentioned for example alkali hydroxides such as sodium hydroxide, alkaline earth hydroxides such as calcium hydroxide, or other bases such as ammonia, and quicklime. Preferably, the sodium hydroxide is used, preferably diluted in an aqueous solution having a concentration generally less than 10 mol / liter. The adjustment of the pH by addition of base can be done once or several times, in continuous casting or in complete and rapid addition. The amount of base and the manner of incorporating the base will be readily determined by those skilled in the art so as to adjust the pH of the solution to the desired pH. The addition is preferably carried out with mechanical stirring of the aqueous polymer solution.
    [0020] The rate of this increase in viscosity depends greatly on the pH, with an acceleration of the kinetics when the pH is between 8 and 9. Above pH = 10, the kinetics tends to decrease.
    [0021] This step of the post-treatment according to the invention also consists in allowing the mixture thus produced to react during a so-called maturation time so that the viscosity V2 of the aqueous polymer solution increases by at least 50% with respect to V1, preferably at least 100%, and that the viscosity of the polymeric solution is not too high.
    [0022] Indeed, a viscosity V2 too high could cause difficulty in handling the solution and perform the next acidification step. This is the reason why the maximum viscosity V2 is less than 100,000 cps, preferably less than 50,000 cps, and very preferably less than 30,000 cps.
    [0023] During this step, the increase in viscosity V2 can be controlled by regular viscosity measurements using a Brookfield viscometer at 25 ° C. The time required to reach V2 viscosity may vary according to different parameters. It is advantageously between 5 minutes and 100 hours, and even more preferably between 30 minutes and 10 hours. As with any chemical reaction, various factors may be modified in order to accelerate or slow down the viscosity setting kinetics, such as, for example, the temperature, the dilution of the mixture, the incorporation of salts, etc.
    [0024] During this step of increasing the viscosity V1 to the value V2, the mixture is preferably mechanically stirred. The second step of the post-treatment consists, after obtaining the viscosity V2, of reducing the pH of the polymer solution to a pH of between 2 and 5, preferably less than 4 and very preferably of between 3 and 4. This step makes it possible to stop the reaction, that is to say the rise in viscosity.
    [0025] The final viscosity V3 of the polymeric solution obtained at the end of the second stage of the post-treatment is generally less than V2. It is advantageously greater than 150 cps (Brookfield, 25 ° C.) when the (co) polymer concentration is 8% by weight relative to the weight of the solution. It is preferably greater than 200 cps (Brookfield, 25 ° C).
    [0026] For this purpose, any acid or acid product may be used. Non-limiting examples include hydrochloric acid, sulfuric acid, and nitric acid. The acid is advantageously added in the form of an aqueous acid solution.
    [0027] The lowering of pH by adding acid can be done once or several times, in continuous casting or in complete and rapid addition. The amount of acid used and the manner of incorporating the base will be readily determined by those skilled in the art so as to adjust the pH of the solution to the desired pH. The addition is preferably carried out with stirring.
    [0028] The cationic or amphoteric (co) polymer derived from acrylamide on which the post-treatment according to the invention II is carried out is obtained by Hofmann degradation reaction on a (co) polymer base.
    [0029] (Co) polymer "base" In practice, the (co) polymer base is prepared prior to Hofmann degradation. The (co) base polymer used contains: at least 5 mole% of at least one nonionic monomer chosen from the group comprising acrylamide, methacrylamide, N, N-dimethylacrylamide, and acrylonitrile, preferably acrylamide - optionally up to 95 mole% of at least: o an unsaturated cationic ethylenic monomer, preferably selected from the group comprising the dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine monomers, and their quaternary ammonium salts mention will in particular be made of dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) and / or methacrylamidopropyltrimethylammonium chloride (MAPTAC), and / or at least one nonionic monomer preferentially chosen from the group comprising N-vinyl acetamide, N-vinyl formamide, Nvinylpyrrolidone and / or vinyl acetate, and / or at least one anionic monomer of the selected acid or anhydride type in the group comprising (meth) acrylic acid, acrylamidomethylpropyl sulfonic acid, itaconic acid, maleic anhydride, maleic acid, methallyl sulfonic acid, vinylsulfonic acid, and their salts, and or at least one additional polyfunctional compound chosen from the group comprising polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), and polyamine amides (PAA), advantageously polyethyleneimine. 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 used, these monomers will be used in very small amounts, 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 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 ... According to a preferred feature of the invention, the (co) polymer base may be branched.
    [0030] According to a preferred embodiment of the invention, the base copolymer is a cationic copolymer. Preferably it contains at least 5 mol% of cationic monomers. The branching of the (co) polymer base may be carried out preferably during (or possibly after) the polymerization of the monomers of the (co) "base" polymer, in the presence of at least one polyfunctional branching agent and optionally at least one agent transfer. Below is a nonlimiting list of branching agents: methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, triallylamine, formaldehyde, compounds glycidyl ether type such as ethylene glycol glycidyl ether, or epoxy or any other means well known to those skilled in the art for crosslinking.
    [0031] 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).
    [0032] At least one transfer agent may also be used in the synthesis of the base polymer. The following is a non-limiting list of transfer agents: isopropyl alcohol, sodium hypophosphite, and mercaptoethanol. The skilled person will choose the best combination based on his own knowledge, the present description, as well as examples below. The (co) polymer serving as a basis for the Hofmann degradation reaction does not require the development of a particular polymerization process. The main polymerization techniques, which are well known to those skilled in the art and which can be used, include in particular: precipitation polymerization, emulsion polymerization (aqueous or inverse) followed or not by a distillation step and / or spray drying step and suspension polymerization or solution polymerization, the latter two techniques being preferred. It is also possible to add to the solution of (co) polymer base, before or during the Hofmann degradation reaction, certain additives which are capable of reacting on the isocyanate functions of the polymer, functions which are generated during degradation according to reaction scheme described above. In general, these are molecules bearing nucleophilic chemical functions such as hydroxyl or amine functions. By way of examples, the additives in question can therefore be of the family: alcohols, polyols (eg starch). ), polyamines, polyethylene imines ...
    [0033] According to another particular embodiment, the (co) polymer base contains within itself (in addition to the monomers constituting it) at least one polyfunctional compound containing at least 3 heteroatoms chosen from N, S, O, P and each having at least less a mobile hydrogen.
    [0034] In practice, the multifunctional compound is added before or during the polymerization of the (co) polymer base. This polyfunctional compound is advantageously chosen from the group comprising polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, epichloridrin polyamides and polyamines amides. It is advantageously polyethyleneimine or polyamine amide. According to this particular embodiment, the (co) polymer base contains at least 100 ppm of a polyfunctional compound. The (co) polymer base advantageously contains at most 10% by weight of a polyfunctional compound. Inclusion of polyvalent cationic ion salts, as mentioned in Applicant's patent application WO 2010/0101082, can also be carried out in order to increase the stability of products having an Alpha coefficient of less than 1. The Hofmann degradation reaction on the "base" copolymer The Hofmann reaction requires the conversion of the amide (and optionally nitrile) functions to the amine function by involving two main factors (expressed as molar ratios): = (alkali and / or alkaline earth hypochlorite / amide group - Beta = (alkali and / or alkaline earth hydroxide / alkaline and / or alkaline earth hypochlorite) From a solution of a (co) polymer "base" previously described, with a concentration of between 5 and 40% by weight, preferably between 20 and 30%, the molar quantity of total acrylamide function is determined, then the level of degradation Alpha 35 desired is selected. (which corresponds to the desired degree of amine function, that is to say to the number of amide / nitrile functions converted to amine functions), which makes it possible to determine the dry quantity of alkaline and / or alkaline earth hypohalide and then the beta coefficient, which makes it possible to determine the dry quantity of alkali and / or alkaline earth hydroxide. 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). The alpha hypohalogenide / nonionic monomer coefficient used for the preparation of the polymers is advantageously greater than 0.1, or even 0.3, more preferably greater than 0.5 and preferably less than 1. In order to stabilize the amine functions that are produced, it is optionally possible to add in the reactor containing the (co) polymer base, one (or possibly more) quaternary ammonium derivatives as described in JP 57077398. This is indeed intended to avoid the reaction between the functions amine and residual amide functions. It will be noted, in addition, that the addition of these agents can be carried out separately, simultaneously, mixed or not, in any order of introduction, and at one or more injection points.
    [0035] The increase in cationicity of the (co) polymer base occurs during the so-called Hofmann degradation, by the use / consumption, in whole or not, of an alkaline or alkaline earth hypohalide. In addition, it is also possible to use cationic or amphoteric acrylamide (co) polymers of the invention obtained by the so-called Hofmann degradation reaction, in the form of a mixture with one or more other (s) synthetic or natural polymer (s). The polymers obtained after the post-treatment according to the invention.
    [0036] The polymeric solution according to the invention advantageously has a viscosity V3 (Brookfield, 25 ° C.) greater than 150 cps, when the concentration of (co) polymer is 8% by weight relative to the weight of the solution. It is preferably greater than 200 cps. It is greater than the initial viscosity Vl.
    [0037] The polymers of the invention have a cationic charge density preferably greater than 2 meq / g, and preferably greater than 5 meq / g. Similarly, although prepared in solution, the polymers of the invention may also be provided in solid form. Under these conditions, the solid form contains not only the (co) polymer, but also a proportion of salt obtained at the end of the Hofmann degradation reaction. In practice, they are obtained inter alia by methods of drying the aforementioned solution. The main insulation techniques then used are those of spray drying (which consists of creating a cloud of fine droplets in a hot gas stream for a controlled period of time), drum drying, fluidized bed dryers, etc. The aqueous polymeric solution according to the invention can be used successfully for the manufacture of packaging paper and cardboard, of coating paper, of any type of paper, cardboard or the like requiring the use of a cationic polymer as an agent. coagulation and / or retention and / or cationic charge promoter. The polymers of the invention provide a significant improvement in drainage performance over the same untreated polymers as compared to prior art Hofmann polymers. They allow, in particular, a significant gain in productivity of paper machines in particular through the achievement of good dewatering properties and resistance to bursting and very high traction.
    [0038] The present invention also relates to the use of the aqueous polymeric solution according to the invention as flocculation agent, retention and / or drainage, and dry strength in a papermaking process.
    [0039] Because of their intrinsic properties (stabilization, cationization, complexation, etc.), the polymers of the invention may also have an interest in a wide variety of applications, the following may be mentioned in a nonlimiting manner: water treatment (drinking or wastewater), coagulation / flocculation techniques, the mining industry, the cosmetics industry, the detergent industry, and the textile industry.
    [0040] The invention and the advantages that ensue from it are apparent from the following embodiments. Examples The cationic (co) polymers derived from acrylamide Polymer A: A cationic polymer A is obtained by a Hofmann degradation reaction on a copolymer base (20% of active material) of acrylamide (70 mol%) and of chloride of dimethyldiallyl ammonium (DADMAC) (30% molar) branched (MBA: 600 ppm by weight / active ingredient) modified with a polyamineamide polymer (Kemira type Retaminol CO1), at a level of 2.5% by weight relative to the material active.
    [0041] To do this, the polyamineamide is mixed with the DADMAC monomer and the MBA in the reactor. Acrylamide is incorporated in continuous casting for 2 hours, in a reaction medium maintained at 85 ° C. Catalysis is made with sodium metabisulfite SPS and metabisulfite (MBS), catalysts well known to those skilled in the art. The base polymer thus obtained has a viscosity of 5500 cps (LV3, 12 rpm). The Hofmann degradation itself proceeds in the same manner as in Example 1 of Applicant's document WO / 2010/061082. A calcium salt in the form of calcium chloride (CaCl 2) is dissolved in the base copolymer solution at a level of 2% by weight relative to the base copolymer. The Hofmann degradation reaction is carried out on the solution thus prepared at a temperature of 25 ° C. using sodium hypochlorite and sodium hydroxide in proportions necessary to obtain a partial alpha (0.7).
    [0042] The intermediate product obtained is then decarboxylated in an excess of hydrochloric acid, and then adjusted to pH by adding sodium hydroxide (pH of the order of 3 to 4). The resulting acrylamide-derived cationic copolymer has a viscosity V1 of 72 cps (25 ° C, Brookfield LV1, 60 rpm) and a concentration of 8.5%. Postprocessing (Counterexample): The post-treatment 1 is carried out according to the process developed in the Applicant's document WO 2009/013423: the polymer A is thus post-branched by adding 1% by weight / active ingredient of polyethylene glycol. triepoxide (GrilBond G 1701). The resulting acrylamide-derived cationic copolymer has a viscosity of 324 cps (25 ° C, Brookfield LV1, 60 rpm) and a concentration of 8.0%.
    [0043] Post-treatment 2 (INVENTION): Polymer A, cooled to 15 ° C., is post-treated by basifying it to pH = 9, by adding an aqueous solution of sodium hydroxide diluted to 30% by weight, with stirring. A maturation time of 1 hour is observed, always at 15 ° C. The viscosity V2 reached is 1300 cps. The pH is then lowered to pH = 3 by addition of 30% hydrochloric acid. The resulting aqueous acrylamide derivative copolymer solution had a V3 viscosity of 938 cps (25 ° C, Brookfield LV1, 60 rpm) and a concentration of 8.0%. Post-Treatment 3 (Against Example) Polymer A, cooled to 15 ° C., is post-treated by basifying it to pH = 6, by adding a 30% by weight solution of sodium hydroxide, with stirring. A maturation time of 10 minutes is observed, always at 15 ° C. The viscosity V2 reached is 94 cps. The pH is then lowered to pH = 3 by addition of 30% hydrochloric acid. The aqueous acrylamide derivative copolymer solution thus obtained has a viscosity V3 of 86 cps (25 ° C, Brookfield LV1, 60 rpm) and a concentration of 8.0%.
    [0044] Test of the dewatering performance of the polymers resulting from the Hofmann reaction. CSF sequence at 1000 rpm (revolutions per minute): Use of a static form to stir the dough. Introduction of 1 liter of dough at 0.3 ° A. T = Os: stirring of the paste T = 10s: addition of the polymer T = 30s: stop stirring and recovery of the liter of dough. Realization of the TAPPI 10 T2270M-94 test. Performance Versus Polymers of the Prior Art: Polymer Cationic Assay CSF Value (ml)% Improvement in (kg / ton) CSF White 0 293 0 Polymer A 1 357 22 Post Treatment 1 1 366 25 Post Processing 2 1 387 32 Post Treatment 1 Table 1 - Dewatering Performance at 1 kg / ton 15 Polymer Cationic Assay CSF Value (ml)% Improvement in (kg / ton) CSF White 0 296 0 Polymer A 1.3 385 30 Post Processing 1 1.3 397 34 Post treatment 2 1.3 420 42 Post treatment 3 1.3 388 31 Table 2 - Dewatering performance at 1.3 kg / tonne Polymer Cationic determination CSF value (ml)% Improvement in (kg / ton) CSF White 0 295 0 Polymer A 1.5 410 39 Post processing 1 1.5 428 45 Post processing 2 1.5 448 52 Post processing 3 1.5 413 40 Table 3 - Drainage performance at 1.5 kg / tonne CSF: Measurement of the degree of "drainability" of CSF pulp: Canadian Standard Freeness. For each of these analyzes, the highest values correspond to the best performances. The post-treated polymer 2, according to the post-treatment of the invention, has the best drainage performance at any dosage, compared to the polymers of the prior art. In addition, the post-treated polymer 2 provides performance close to those of the polymer A, but using a lower polymer dosage. The performances of the polymer A at 1.3 kg / t are reached with a dosage of 1 kg / t of post-treated polymer 2. In addition, the performances of the polymer A at 1.5 kg / t are reached with a dosage of 1.3 kg / t of polymer post-processed 2. These dosage reductions, for equivalent performance, make it possible to offer the end customer less expensive systems, and thus to reach a market that the price of the technologies of the prior art could up to now rebuff. The polymer solution resulting from the post-treatment 3, for which the viscosity V2 is only 30% higher (1.3 times higher) than the viscosity V1, does not make it possible to obtain a significant improvement in the performances. Dry paper forms are made with an automatic dynamic form.
    [0045] The "slurry" of the dough is made by disintegrating dry pulp in order to obtain a final concentration of 3%. The necessary amount of pulp is removed so as to finally obtain a sheet having a basis weight of 60 g / m 2.
    [0046] The concentrated paste is introduced into the vat of the dynamic form and stirred there. To this paste are injected, in different tests, the polymers A, post-treated 1, post-treated 2, as well as the Xelorex RS1200 from BASF, a current reference in terms of DSR (Dry Strenght Resistance) agent. . This paste is then diluted to a concentration of 0.32%. In manual mode, the dough is pumped to the nozzle level to prime the circuit. A blotter and training cloth are placed in the bowl of the dynamic formette before starting the rotation of the bowl at 900m / min and constructing the water wall. The polymer will be injected 10 seconds before starting the production cycle of the sheet. The sheet is then made (in automatic mode) by 22 round trips of the nozzle projecting the paste into the wall of water. Once the water is drained and the automatic sequence is complete, the forming web with the formed fiber network is removed from the dynamically shaped bowl and placed on a table. A dry blotter is deposited on the side of the wet fiber mat and is pressed once with a roll. The whole is returned and the fabric is delicately separated from the fibrous mat. A second dry blotter is deposited and the sheet (between the two blotters) is pressed once under a press delivering 4 bars and is then dried on a dryer stretched for 9 min at 117 ° C. The two blotters are then removed and the sheet is stored overnight in a room with controlled humidity and temperature (50% relative humidity and 23 ° C). The dry strength properties of all the sheets obtained by this procedure are then evaluated.
    [0047] The burst index is measured with a Messmer Buchel M 405 (average of 14 measurements). Dry traction is measured in the machine direction with a Testometric AX tensile tester (average of 5 samples). The tests are made with a neutral pH paste composed of 100% recycled packaging board.
    [0048] Results obtained: Polymer Determination Polymer Burst Burst Length Index (km) - - 2.50 4.89 Polymer A 1.5 kg / t 3.20 6.10 Post treatment 1 1.5 kg / t 3.19 5.99 Post treatment 2 1.5 kg / t 3.24 6.14 Post treatment 3 1.5 kg / t 3.20 6.09 Xelorex RS1200 1.5 kg / t 3.22 6.15 Table 4 - Dry strength performance at 1.5 kg / tonne We observe that in addition to better drainage performance, the post-treated polymer 2 according to the invention has good performance. in dry strength equivalent or even better than the technologies of the prior art.
    权利要求:
    Claims (8)
    [0001]
    CLAIMS 1- A process for preparing an aqueous polymeric solution of viscosity V3 containing at least one cationic or amphoteric (co) polymer, comprising the following steps - Hofrnann degradation reaction, in aqueous solution, in the presence of a hydroxide alkaline earth and / or alkali and an alkaline earth and / or alkali hypohalide on a (co) polymer base of at least one nonionic monomer selected from the group consisting of acrylamide methacrylamide, N, N dimethylacrylamide, and acrylonitrile; after-treatment of the resulting aqueous polymeric solution of viscosity V1; characterized in that the post-treatment comprises the following successive steps: a) increasing the viscosity V1 to a value V2 corresponding to at least 1.5 times the value V1 while being less than 100,000 cps, by adjusting the pH of the polymer solution has a value greater than or equal to 5.5 b) lowering the pH of the polymer solution to a value of between 2 and 5; c) obtaining a polymeric solution whose viscosity V3 is greater than V1 and less than V2, the viscosities V1, V2, V3 being measured with a Brookfield viscometer at 25 ° C, with an LV module.
    [0002]
    2- Method according to claim 1, characterized in that in step a), the pH is adjusted between 5.5 and 12.
    [0003]
    3- Process according to claim 1, characterized in that the viscosity V2 is greater than or equal to 2 times the viscosity V1.
    [0004]
    4. Process according to claim 1, characterized in that the viscosity V2 of the aqueous polymer solution is less than 50,000 cps.
    [0005]
    5. Method according to claim 1, characterized in that in step b), the pH is lowered to a value between 3 and 4.
    [0006]
    6. Process according to claim 1, characterized in that the pH of the polymeric aqueous solution on which the post-treatment is carried out is between 2 and 5 before the post-treatment.
    [0007]
    7- Process according to claim 1, characterized in that the concentration of the polymer solution on which the post-treatment is carried out is between 0.5% and 50% by weight of (co) polymer relative to the weight of the aqueous polymer solution .
    [0008]
    8. Process according to claim 1, characterized in that the or (co) polymers contained in the post-treated polymer solution are solely and directly derived from the Hofmann degradation of a (co) polyfine base. -9- A process according to claim 1, characterized in that in step a); the pH adjustment is carried out by adding at least one compound selected from the group consisting of alkali hydroxides, alkaline earth hydroxides, ammonia, and quicklime. 10- Method according to claim 1, characterized in that in step b), the lowering of the pH is carried out by addition of at least one compound selected from the group comprising hydrochloric acid, sulfuric acid, and nitric acid. 11- The method of claim 1, characterized in that the aqueous polymer solution has a viscosity V3 greater than 150 cps when the concentration of (co) polymer is 8% by weight relative to the weight of the aqueous polymer solution. 12- Method according to claim 1, characterized in that the (co) polymer base used contains: a. at least 5 mol% of at least one nonionic monomer selected from the group consisting of acrylamide, methacrylamide, N, N-dimethylacrylamide, and acrylonitrile, optionally up to 95 mol% of at least: b. an unsaturated cationic ethylenic monomer selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium salt monomers, c. and / or at least one nonionic monomer selected from the group consisting of N-vinyl acetamide, N-vinyl formamide, N-vinylpyrrolidone and vinyl acetate, d. and / or at least one anionic monomer selected from the group consisting of (meth) acrylic acid, acrylamidomethylpropyl sulfonic acid, aciditaconic acid, maleic anhydride, maleic acid, methallyl sulfonic acid, acid vinylsulfonic acid, and their salts, e. and / or at least one polyfunctional compound selected from the group consisting of polyethyleneimine, primary polyamine, secondary polyamine, polyallylamine, polythiols, polyalcohols, epichlorohydrin polyamides (PAEs), and polyamines amides (PAAs). 13- The method of claim 1, characterized in that the (co) polymer base further contains at least one polyfunctional compound containing at least 3 heteroatoms selected from N, S, O, P and each having at least one mobile hydrogen. 14- Use of the aqueous polymeric solution obtainable according to one of claims 1 to 11, as a flocculating agent, retention and / or drainage, and dry strength in a papermaking process.
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    同族专利:
    公开号 | 公开日
    CA2933976C|2021-11-23|
    FR3016363B1|2017-05-26|
    CN106068284A|2016-11-02|
    KR102293150B1|2021-08-25|
    BR112016014566B1|2021-06-08|
    CN106068284B|2019-06-14|
    US9725532B2|2017-08-08|
    WO2015107302A1|2015-07-23|
    CA2933976A1|2015-07-23|
    US20160311940A1|2016-10-27|
    KR20160110361A|2016-09-21|
    EP3094658A1|2016-11-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3619358A|1968-06-12|1971-11-09|Seiko Kagaku Kogyo Co Ltd|Method for improving water drainage from a paper web on a wire-screen of a paper machine by using a modified polyacrylamide prepared from a water-soluble polyacrylamide by the hoffman reaction|
    WO2011015783A1|2009-08-04|2011-02-10|S.P.C.M. Sa|Acrylamide-derived cationic copolymers, and uses thereof|
    WO2014029593A1|2012-08-22|2014-02-27|Basf Se|Method for producing paper, paperboard and cardboard|
    US3250665A|1963-08-19|1966-05-10|Scott Paper Co|Process of modifying a paper web with epoxy resins by addition of polyalkyl-acrylamide degradation product in formation of the paper|
    US5039757A|1988-12-28|1991-08-13|Mitsui Toatsu Chemicals, Inc.|Method of manufacturing cationic acrylamide polymers, cationic acrylamide polymers, and the applications of these polymers|
    JP2003301398A|2002-04-08|2003-10-24|Mitsui Chemicals Inc|Method of making paper|
    US20040118540A1|2002-12-20|2004-06-24|Kimberly-Clark Worlwide, Inc.|Bicomponent strengtheninig system for paper|
    FR2880901B1|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|
    FR2912749B1|2007-02-19|2009-04-24|Snf Soc Par Actions Simplifiee|CATIONIC COPOLYMERS DERIVED FROM ACRYLAMIDE AND THEIR USES|
    FR2918989B1|2007-07-18|2010-08-27|Snf Sas|WATER-SOLUBLE, WATER-SOLUBLE CATIONIC ACRYLAMIDE POLYMERS AND THEIR ACHIEVEMENTS|
    JP2011521114A|2008-05-15|2011-07-21|ビーエーエスエフソシエタス・ヨーロピア|Method for producing paper, board and cardboard with high dry strength|
    EP2315875B1|2008-08-18|2014-03-05|Basf Se|Method for increasing the dry strength of paper, paperboard and cardboard|
    FR2938842B1|2008-11-27|2012-09-21|Snf Sas|NOVEL PROCESS FOR THE PREPARATION OF ACRYLAMIDE COPOLYMERS BY HOFMANN DEGRADATION REACTION|
    CN102174748B|2011-01-13|2012-11-14|青岛大学|Salt-free dyeing method of vinyl sulphone type reactive dye for cotton fiber|
    CN102432090B|2011-10-27|2013-06-19|常州大学|Method for preparing flocculation aid for pretreating blue algae biogas slurry|
    FR2992981B1|2012-07-09|2014-07-04|Snf Sas|IMPROVED PAPER MANUFACTURING METHOD USING POLYMER OBTAINED BY HOFMANN DEGRADATION|CA2978437A1|2015-03-04|2016-09-09|Ecolab Usa Inc.|Reverse emulsion breaker polymers|
    WO2016144613A1|2015-03-06|2016-09-15|Ecolab Usa Inc.|Reverse emulsion breaker polymers|
    CN106008798B|2016-05-12|2018-01-16|河南正佳能源环保股份有限公司|The preparation method of micro- crosslinking net hydrophobic-associatcationic cationic polyacrylamide flocculant|
    KR20190018137A|2016-06-10|2019-02-21|에코랍 유에스에이 인코퍼레이티드|Low molecular weight dry powder polymer for use as a drying enhancer for paper|
    JP2018044273A|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|
    EP3662108A1|2017-07-31|2020-06-10|Ecolab Usa Inc.|Dry polymer application method|
    法律状态:
    2015-01-30| PLFP| Fee payment|Year of fee payment: 2 |
    2016-01-15| TP| Transmission of property|Owner name: S.P.C.M. SA, FR Effective date: 20151210 |
    2016-01-29| PLFP| Fee payment|Year of fee payment: 3 |
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    2022-01-28| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1450301A|FR3016363B1|2014-01-15|2014-01-15|AQUEOUS SOLUTION OF ACRYLAMIDE-DERIVED CATIONIC COPOLYMERS, PROCESS FOR PREPARATION AND USE|FR1450301A| FR3016363B1|2014-01-15|2014-01-15|AQUEOUS SOLUTION OF ACRYLAMIDE-DERIVED CATIONIC COPOLYMERS, PROCESS FOR PREPARATION AND USE|
    CA2933976A| CA2933976C|2014-01-15|2015-01-15|Aqueous solution of cationic copolymers derived from acrylamide, preparation method and use|
    KR1020167016595A| KR102293150B1|2014-01-15|2015-01-15|Aqueous solution of cationic copolymers derived from acrylamide, preparation method and use|
    US15/104,018| US9725532B2|2014-01-15|2015-01-15|Aqueous solution of cationic copolymers derived from acrylamide, preparation method and use|
    CN201580003282.3A| CN106068284B|2014-01-15|2015-01-15|Derivative cationic copolymer aqueous solution of acrylamide and its preparation method and application|
    BR112016014566-6A| BR112016014566B1|2014-01-15|2015-01-15|process for preparing an aqueous polymer solution; and, using an aqueous polymer solution|
    PCT/FR2015/050100| WO2015107302A1|2014-01-15|2015-01-15|Aqueous solution of cationic copolymers derived from acrylamide, preparation method and use|
    EP15705638.3A| EP3094658A1|2014-01-15|2015-01-15|Aqueous solution of cationic copolymers derived from acrylamide, preparation method and use|
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