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    • 专利摘要:
    The present invention relates to a polymer complex and its use in a process for producing paper, cardboard or the like. This polymer complex is obtained by polymerization of water-soluble monomers: in the presence of a host polymer comprising vinylamine functions and a non-polymeric transfer agent, and in the absence of a branching or crosslinking agent of polyfunctional ethylenic type. It is obtained from an anionic monomer / water mass ratio greater than 0.035.
    公开号:FR3080853A1
    申请号:FR1853919
    申请日:2018-05-07
    公开日:2019-11-08
    发明作者:Gatien Faucher；Damien FOUGEROUSE；Rene Hund
    申请人:SNF SA；
    IPC主号:
    专利说明:

    POLYMER COMPLEX, PREPARATION AND USE
    FIELD OF THE INVENTION
    The present invention relates to a polymer complex resulting from the polymerization of one or more water-soluble monomers in the presence of a previously prepared polymer.
    Another aspect of the invention relates to the use of this complex as a dry resistance agent for its use in the manufacture of paper, cardboard or the like.
    PRIOR STATE OF THE ART
    We are looking for increasingly resistant paper and cardboard, especially for the packaging industry.
    The dry strength of the paper is by definition the strength of the normally dry sheet. Mechanical strength values traditionally provide a measure of the paper's dry strength. We can speak in particular of bursting, tensile, compression, delamination resistance ...
    It is well known to use cationic water-soluble polymers to improve the strength characteristics of paper. By their nature, they can attach directly to anionic cellulose and increase the number of inter-fiber hydrogen bonds to improve the mechanical strength in the dry state of the paper.
    Furthermore, they can also give it a cationic charge so that, in association with anionic polymers, there is fixation of the latter on the cellulose fibers, thereby improving the dry resistance of the sheet.
    Other polymers can also be introduced into the cellulose suspension in order to improve the properties of the paper sheet. However, the introduction of polymers of different molecular weights can be problematic.
    Indeed, it is known to those skilled in the art the difficulties associated with the preparation of a homogeneous composition containing two polymers having distinct molecular weights.
    Due to this difference in molecular weight, a phase shift may appear during the dissolution of these polymers.
    Those skilled in the art have therefore developed polymerization methods thus making it possible to alleviate the problem of phase shift.
    For example, US Patents 7,001,953 and US 8,021,516 describe water-soluble polymers that can be used in the treatment of sludge or in the manufacture of paper. These polymers are obtained by polymerization of monomers in the presence of a polymer which has been prepared beforehand and independently. As indicated in these documents, the polymer already synthesized and the polymer being synthesized, do not graft substantially.
    It is actually the formation of an intercalated polymer in the presence of a host polymer. The host polymer is not grafted during the polymerization of the monomers which can be carried out in the presence of a branching agent. This process therefore makes it possible to obtain a mixture of two distinct and intercalated polymers. This structure of intercalated polymers makes it possible to obtain properties distinct from those resulting from a mixture of non-intercalated polymers.
    US Patent 9,546,246 of the Applicant overcomes the problem of phase shift. This patent describes a complex and its use as an agent for treating mineral charges and in particular for its use in the manufacture of paper, cardboard or the like.
    On the other hand, the products described in this latter patent have the drawback of being of high viscosity (around 10,000 cps), and are therefore difficult to incorporate into solutions or dispersions of low viscosities. Furthermore, this high viscosity tends to increase over time, the product therefore has a short lifespan of only a few months.
    One of the problems which the Applicant proposes to solve is to develop a new complex of polymers which do not exhibit a phase shift, that is to say a homogeneous mixture of interconnected polymers. In addition, this new complex has the advantage of being stable in terms of viscosity over time.
    Another aspect of the invention relates to a new dry strength agent used in the manufacture of paper, cardboard or the like.
    STATEMENT OF THE INVENTION
    The present invention relates to a polymer complex comprising a water-soluble polymer (host polymer) and one or more water-soluble monomers polymerized in the presence of said water-soluble host polymer.
    By definition, a water-soluble ((co) polymer, monomer ...) compound is a compound which gives an aqueous solution when it is dissolved with stirring at 25 ° C and with a concentration of 50 g.L ' 1 in water.
    More specifically, the subject of the present invention relates to a polymer complex obtained by polymerization of water-soluble monomers in the presence of at least one water-soluble host polymer comprising vinylamine functions and of at least one non-polymeric transfer agent and to the same. absence of branching or crosslinking agent of polyfunctional ethylenic type.
    The polymer complex is obtained from an anionic monomer / water mass ratio greater than 0.035. This ratio is determined according to the following formula:
    mass of anionic monomer total mass of water
    This is the amount of the anionic monomer (s) introduced to form the polymer complex in the presence of the host polymer. These are not zwitterionic monomers or any anionic or zwitterionic monomers of the host polymer.
    The total amount of water corresponds to the amount of water initially present during the formation of the polymer complex by polymerization of monomer (s) in the presence of the host polymer, regardless of the type of polymerization used ( emulsion, gel, solution ...) and whatever the origin of the water (monomers in solution, host polymer in solution ...).
    The anionic monomer / water mass ratio is advantageously between 0.035 and 0.35, more advantageously between 0.035 and 0.25, and even more advantageously between 0.035 and 0.15.
    The total amount of water available corresponds to water from the host polymer, the different monomers and the different additives.
    In the complex thus obtained, the polymer (s) resulting from the polymerization of the monomers branch out with the host polymer. It is not a mixture of polymers but a complex in which the host polymer plays the role of crosslinker or branching agent, during the polymerization of the monomers.
    The transfer agent makes it possible in particular to limit the crosslinking linked to the host polymer and to control the length of the polymer chains formed during the polymerization of the water-soluble monomers.
    By polymer is meant a homopolymer or a copolymer resulting from the polymerization of identical or distinct monomers respectively.
    Another aspect of the invention is the use of this polymer complex as a dry strength agent in the field of the manufacture of paper, cardboard or the like.
    Host polymer
    The host polymer preferably comprises vinylamine functions, that is to say that the polymer is of the polyvinylamine type: - (CH 2 -CH (NH 2 )) -.
    The host polymer comprising vinylamine functions can be derived from various methods known to those skilled in the art. This can include:
    of a polymer resulting from the degradation of Hofmann on a "base polymer", or of a polymer resulting from the total or partial hydrolysis of a homopolymer or a copolymer of N vinylformamide.
    Polyviny laminates from the degradation of Hofmann
    The degradation of Hofmann is a reaction discovered by Hofmann at the end of the nineteenth century, which makes it possible to convert an amide (or even an acrylonitrile) into a primary amine by elimination of carbon dioxide. The reaction mechanism is detailed below.
    In the presence of a base (soda), a proton is torn away from the amide.
    he
    R-C-hr /
    Ή
    Oh o
    he
    R — C - N - H
    In the case of hypochlorite, the amidate ion formed then reacts with the active chlorine (Cl 2 ) of the hypochlorite (eg: NaCIO which is in equilibrium: 2 NaOH + Cl 2 <=> NaCIO + NaCl + H 2 O) to give an N-chloramide. The base of Bronsted (for example NaOH) tears off a proton from the chloramide to form an anion. The anion loses a chloride ion to form a nitrene which undergoes a transposition into isocyanate.
    By reaction between the hydroxide ion and the isocyanate, a carbamate is formed.
    R —N = C = 0 + OH
    R — NH —C0 2
    After decarboxylation (elimination of CO2) from the carbamate, a primary amine is obtained:
    - H +
    R — NH —COj
    -1.¾
    For the conversion of all or part of the amide functions of a polymer into amine functions, two main factors are involved (expressed in molar ratios). It is :
    Alpha = (alkaline and / or alkaline earth hypohalide / amide),
    Beta = (alkali and / or alkaline earth hydroxide / alkaline and / or alkaline earth hypohalide).
    The hypohalide (also called hypohalogenite) is advantageously NaClO.
    According to a preferred embodiment, the polymer comprising vinylamine functions results from the degradation of Hofmann carried out on a "base polymer" comprising a nonionic monomer chosen from the group comprising acrylamide or one of its derivatives.
    Among the acrylamide derivatives, there may be mentioned N-isopropylacrylamide, N, N-dimethylacrylamide, methylacrylamide. The preferred monomer is acrylamide.
    According to the invention, the proportion of acrylamide monomer or derivatives in the “base polymer” is between 30% mol and 100% mol, preferably between 50% mol and 95% mol, and even more preferably between 60% mol and 90 % mol, based on the total number of monomers in the "base polymer".
    The “base polymer” can also additionally contain cationic and / or anionic monomers.
    The cationic monomer or monomers which can be used within the framework of the invention can be chosen, in particular from quaternary ammonium salts of the monomers of the acrylamide, acrylic, vinyl, allyl or maleic type. Mention may be made, in particular and in a nonlimiting manner, of quaternized dimethylaminoethyl acrylate (ADAME), of quaternized dimethylaminoethyl methacrylate, of dimethyldiallylammonium chloride (DADMAC), of acrylamide propyltrimethyl ammonium chloride (APTAC), and methacrylamido propyltrimethyl ammonium chloride (MAPTAC). A preferred cationic monomer is DADMAC.
    According to the invention, the proportion of cationic monomer in the “base polymer” is between 0% mol and 70% mol, preferably between 5% mol and 50% mol, and even more preferably between 10% mol and 40% mol , based on the total number of monomers in the "base polymer".
    The anionic monomer (s) which can be used in the context of the invention can be chosen from a large group. These monomers can have acrylic, vinyl, maleic, fumaric, allylic functionalities and contain a carboxylate, phosphonate, phosphate, sulfate, sulfonate group, or another group with an anionic charge. The monomer can be acidic or else in the form of a salt or alkaline earth metal, alkali metal or corresponding ammonium of such a monomer. Examples of suitable monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and strong acid type monomers having for example an acid type function sulfonic or phosphonic acid such as 2-acrylamido 2methylpropane sulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, allylphosphonic acid, styrene sulfonic acid, and the salts of these soluble monomers in l water of an alkali metal, an alkaline earth metal, and ammonium. A preferred monomer is acrylic acid.
    According to the invention, the proportion of anionic monomer in the “base polymer” is between 0% mol and 70% mol, preferably between 2% mol and 50% mol, and even more preferably between 5% mol and 30% mol, based on the total number of monomers in the "base polymer".
    According to the invention, the alpha factor of the host polymer is advantageously between 0.1 and 1, preferably between 0.3 and 0.9, and even more preferably between 0.5 and 0.8.
    According to another embodiment of the invention, it is possible to use polyvinylamines obtained by Hofmann degradation carried out on a polymer comprising acrylamide or its derivatives, and at least one polyfunctional compound containing at least 3 heteroatoms from N, O, S, P each having at least one mobile hydrogen.
    The polyfunctional compound is incorporated before or during the polymerization of the constituent monomers of the "base polymer".
    Preferably, the polyfunctional compound is chosen from the group comprising polyethyleneimine, polyamine, and polyallylamine.
    Polyvinylamines resulting from the total or partial hydrolysis of a polymer of Nvinylformamide
    In a first step, an N-vinylformamide (NVF) polymer is obtained, the NVF having the following motif:
    N H — C — H
    II 0 ;
    Subsequently, this NVF motif is converted, by hydrolysis, to vinylamine:
    -CHY-CH
    ZI nh 2
    Hydrolysis can be carried out by acid action (acid hydrolysis) or base action (basic hydrolysis).
    Depending on the amount of acid or base added, the NVF polymer is partially or completely converted to vinylamine.
    Advantageously, the degree of hydrolysis is between 1 and 100%, more advantageously still between 30 and 90%. In other words, 30 to 90 NVF groups are converted to amine groups for 100 starting NVF groups.
    Preferably, the N-vinylformamide polymer (NVF) comprises at least one nonionic monomer and / or at least one cationic monomer and / or at least one anionic monomer. The monomers which can be used in the context of the invention can be chosen from the lists mentioned above.
    In addition to the vinylamine monomer, according to a preferred embodiment, the host polymer comprises at least one nonionic monomer and at least one cationic monomer. Preferably, the polymer comprises acrylamide and DADMAC.
    According to a preferred characteristic of the invention, the host polymer can be branched.
    The branching is preferably carried out during (or possibly after) the polymerization of the monomers constituting the host polymer, in the presence of a polyfunctional branching agent and optionally a transfer agent.
    The following is a non-limiting list of branching agents: methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate, vinyloxymethacrylate, triallylamine, formaldehyde, glyoxal, glycidyl ether compounds such as ethylene glycol di glycidyl ether, or epoxies. Advantageously, the branching agent is methylene bis acrylamide (MBA).
    In practice, the branching agent is advantageously introduced at a rate of five to fifty miles (5 to 50,000) parts per million by weight relative to the active material (weight of the monomers constituting the host polymer), preferably 5 to 10,000 ppm , advantageously from 5 to 5000 ppm.
    Transfer agents making it possible to limit the length of the polymer chains may also be present during the polymerization of the monomers constituting the host polymer. A non-exhaustive list of transfer agents is given below: isopropyl alcohol, sodium hypophosphite, mercaptoethanol.
    According to the invention, the host polymer has a molecular weight of at least 10,000 g / mol, preferably at least 50,000 g / mol, and even more preferably at least 100,000 g / mol. This is the weight average molecular weight.
    The polymer complex
    It comes from the polymerization of water-soluble monomers during which the preexisting host polymer acts as a crosslinking or branching agent.
    The water-soluble monomer or monomers used during the preparation of the polymer complex can in particular be a nonionic monomer and / or at least one anionic monomer and / or at least one cationic monomer.
    The amount of non-ionic monomer (s) is advantageously between 1 and 99 mol%, preferably between 10% mol and 80% mol, and even more preferably between 20% mol and 60% mol, relative to the number of water-soluble monomers.
    The amount of anionic monomer (s) is advantageously between 1 and 99 mol%, preferably between 10% mol and 80% mol, and even more preferably between 20% mol and 60% mol, relative to the number of water-soluble monomers.
    The amount of cationic monomer (s) is advantageously between 0% mol and 99% mol of cationic monomer, preferably between 0% mol and 60% mol, and even more preferably between 0% mol and 20% mol, relative to the number of water-soluble monomers.
    As already indicated, this polymerization is carried out in the presence of at least one non-polymeric transfer agent. Advantageously, the molecular weight of the non-polymeric transfer agent is less than 200 g / mol. In addition, the polymerization of the monomers is also carried out in the absence of a branching or crosslinking agent of the polyfunctional ethylenic type.
    The term “branching or crosslinking agent of the polyfunctional ethylenic type” denotes agents comprising a bifunctionalized, trifunctionalized or tetrafunctionalized polyvinyl or polyallylic group.
    At least one non-polymeric transfer agent used during the polymerization of the water-soluble monomer (s) is advantageously chosen from the group comprising isopropyl alcohol, sodium hypophosphite, and mercaptoethanol.
    Depending on the nature of the transfer agent, the quantity introduced of the latter is advantageously between 1 and 150,000 ppm, preferably between 10 and 10,000 ppm, more preferably between 100 and 5,000 ppm by weight relative to the weight of the water-soluble monomers used. artwork.
    The different monomers used can be chosen from the respective lists mentioned above in the description of the host polymer (Hofmann degradation and hydrolysis).
    According to the invention, the proportion of water-soluble monomers used is advantageously as follows, relative to the total number of water-soluble monomers used:
    99 mol% of nonionic monomer, preferably between 10% mol and 80% mol, and even more preferably between 20% mol and 60% mol; and / or 99 mol% of anionic monomer, preferably between 10% mol and 80% mol, and even more preferably between 20% mol and 60% mol; and / or mol% to 99% mol of cationic monomer, preferably between 0% mol and 60% mol, and even more preferably between 0% mol and 20% mol;
    the total number of water-soluble monomers representing 100%.
    According to a preferred embodiment, at least one nonionic monomer and at least one anionic monomer are used. They are preferably acrylamide and acrylic acid.
    The complexes of the present invention differ in particular from the prior art due to the presence of at least one non-polymeric transfer agent during the polymerization of the water-soluble monomers in the presence of the host polymer. Indeed, the presence of the transfer agent makes it possible to limit the crosslinking of the polymer resulting from the polymerization of the water-soluble monomers with the host polymer while controlling the molecular weight of the polymer chains formed.
    The mass ratio between the host polymer and the monomers is advantageously between 0.5 and 4, preferably between 0.75 and 3.5 and even more preferably between 1 and 3.
    According to the invention, the complex dissolved in 8% by weight of dry polymer has a transmittance preferably less than 70%, more preferably less than 55%, and even more preferably less than 40%. The transmittance is measured at a concentration in water of 8% by dry weight of the polymer complex.
    The transmittance values are measured using a device of the UVphotometer DR 3900 (HACH) type on an aqueous solution of 8% by weight of dry polymer. Transmittance is the percentage of light transmitted through a 1 cm thick sample in a quartz cell at a wavelength of 750 nm.
    In general, the preparation of the polymer complex of the invention does not require the development of any particular polymerization process. Indeed, this complex can be obtained according to all the polymerization techniques well known to the skilled person. This may especially be solution polymerization; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous or reverse); suspension polymerization; or micellar polymerization.
    The process for preparing the polymer complex can comprise the following steps:
    preparation of a mixture comprising at least one host polymer, at least one type of water-soluble monomer, and at least one non-polymeric transfer agent;
    obtaining of the polymer complex by polymerization of the water-soluble monomers.
    The process for preparing the polymer complex can comprise the following steps:
    preparation of a mixture comprising at least one host polymer, and at least one non-polymeric transfer agent;
    at least one type of water-soluble monomer is added in a continuous flow into the mixture;
    obtaining of the polymer complex by polymerization of the water-soluble monomers.
    The process for preparing the polymer complex can comprise the following steps:
    preparation of a mixture comprising at least one host polymer;
    at least one type of water-soluble monomer, and at least one non-polymeric transfer agent are added by continuous casting into the mixture;
    obtaining of the polymer complex by polymerization of the water-soluble monomers.
    The process for preparing the polymer complex can comprise the following steps:
    at least one host polymer, at least one type of water-soluble monomer, and at least one non-polymeric transfer agent are added by continuous casting into the reactor;
    obtaining of the polymer complex by polymerization of the water-soluble monomers.
    The polymer complex can be in powder, liquid or emulsion form. Preferably, the complex is in liquid form.
    Preferably, during the preparation of the complex, the host polymer is introduced into the reactor with the monomers and the non-polymeric chain transfer agent. The polymerization is then advantageously initiated by adding the catalysts.
    Another aspect of the invention is the use of polymer complexes as a dry strength agent in the field of paper, board or the like.
    It has been surprisingly found that the use of the complexes of the invention, as a dry resistance agent, makes it possible to greatly improve the mechanical properties of the sheet in the dry state within the framework of manufacturing. of paper, cardboard or the like.
    Without wishing to formulate any theory, it would seem that the grafting of the polymer resulting from the polymerization of the water-soluble monomers on the host polymer makes it possible to obtain products having better performances as dry resistance agent.
    The complex can be used in the form of a dilute or undiluted aqueous solution.
    The amount of complex added is advantageously between 3 g of active material / tonne of paper (dry weight of fibers, advantageously cellulosic) and 10,000 g / T, preferably between 10 g / T and 7000g / T and even more preferably between 30 g / T and 3000 g / T.
    In addition to the complex, other compounds known to those skilled in the art may be associated. Mention may be made, without limitation, of dispersants, biocides or even anti-foaming agents.
    Another aspect of the invention relates to a process for manufacturing paper, cardboard or the like, according to which, before said sheet is formed, the fibrous suspension (advantageously cellulose fibers) is added, at one or more injection points to the minus one complex according to the invention.
    This process can also include the addition of polymers distinct from the complex according to the invention. By way of example, mention may be made of coagulants, retention agents, flocculants or even starch.
    The various stages of the process for manufacturing paper, cardboard or the like are in accordance with the techniques forming part of the knowledge of a person skilled in the art.
    The examples below illustrate the invention without, however, limiting it.
    EXAMPLES OF EMBODIMENT OF THE INVENTION
    Synthesis of a complex of polymer P according to the invention
    570 g of host polymer (commercial product HF31 (SNF SAS), active ingredient) are introduced into a 1 liter reactor equipped with a mechanical stirrer, a thermometer, a condenser and a plunger rod of nitrogen gas. = 10.5%) named in the examples by XI (30mol% DADMAC / 70mol% acrylamide). 44g of acrylamide (50% by weight solution) and 25g of acrylic acid (90% by weight solution) are added, as well as 0.9g of sodium hypophosphite chain transfer agent. The temperature is adjusted to 30 ° C. and the catalysts are then injected into the reaction medium, ie 0.44 g of sodium persulfate, 0.11 g of sodium metabisulfite and 0.03 g of Mohr salt. Thanks to the reaction exotherm, the temperature of the reaction medium increases up to the temperature of 45 ° C. During the conversion of the monomers, a whitish haze appears, which becomes a precipitate, to finally form a completely white dispersion. After 45 minutes of aging at 45 ° C., 2 g of sodium bisulfite (40% by weight solution) are added to react any residual monomers. A new 45-minute aging at 45 ° C is applied before cooling.
    The complex solution obtained (product P) has a pH of 2.9, a dry extract of 26.2% and a viscosity of 450 cps. This complex polymer is stable, without phase shift, for at least 12 months.
    Synthesis of polymer X2
    In a 1 liter reactor, equipped with a mechanical stirrer, a thermometer, a condenser and a plunger rod of nitrogen gas, 555 g of deionized water, 127 g of acrylamide (solution at 50% by weight), 71 g of acrylic acid (solution at 90% by weight), 71 g of sodium hydroxide 50% (solution at 50% by weight). The temperature is adjusted to 35 ° C. 0.9 g of sodium hypophosphite, 0.17 g of VAO44 (2,2'-azobis [2- (2-imidazolin-2yl) propane] dihydrochloride) and 0.08 g of V50 (2, 2'-azobis (2methylpropionamidine) dihydrochloride). Thanks to the reaction exotherm, the temperature of the reaction medium increases up to the temperature of 75 ° C. After 45 minutes of aging at 45 ° C., 2 g of 40% sodium bisulfite (40% by weight solution) are added to react any residual monomers. A new 45-minute aging at 45 ° C is applied before dilution with 1173g of water for cooling to 25-30 ° C.
    An anionic polymer having a pH of 6.3, a dry extract of 7.4% and a viscosity of 250 cps is obtained by this process.
    Evaluation test procedures
    Transmittance measurement:
    Aqueous solutions comprising 8% by weight of dry polymer are prepared. The transmittance values are measured at a wavelength of 750 nm using a device of the UV-photometer DR 3900 (HACH) type. Transmittance corresponds to the percentage of light transmitted through a 1 cm thick sample.
    Dry strength performance:
    The paper closers are made with an automatic dynamic closer. First of all, the paper pulp is prepared by disintegrating, for 25 minutes, 90g of recycled cardboard fibers in 2 liters of hot water. The paste obtained is then diluted in water to a volume of 6 liters. Once the consistency has been precisely measured, the necessary quantity of this paste is removed so as to obtain a sheet with a grammage of 90g / m 2 in the end .
    The dough is then introduced into the vat of the dynamic form, diluted to a consistency of 0.5% and stirred moderately with a mechanical stirrer in order to homogenize the aqueous suspension.
    A blotter and the training cloth are placed in the bowl of the dynamic formette before starting the rotation of the bowl at 1000 rpm and building the wall of water. The various dry resistance agents are then introduced into the agitated fibrous suspension with a contact time of 30 seconds for each polymer. The sheet is then produced by 23 round trips of the nozzle projecting the dough into the water wall. Once the water is drained and the automatic sequence is completed, the training cloth with the network of fibers formed is removed from the bowl of the dynamic form and placed on a table. A dry blotter is placed on the side of the damp fiber mattress and is pressed once with a roller. The assembly is turned over and the fabric is delicately separated from the fibrous mattress. A second dry blotter is deposited and the sheet (between the two blotters) is pressed under a press delivering 4 bars, then is dried on a tensioned dryer for 9 minutes 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 sheets obtained by this procedure are evaluated.
    Burst Index is measured with a Messmer Buchel M 405 eclatometer (Average over 12 measurements).
    In all of the examples which follow, and unless otherwise indicated, the sheets of paper are produced according to the above procedure by introducing the dry resistance agent at a dosage of 1.5 kg / t (dry polymer / dry fibers).
    No.Trial Product dosage(Kg / t) Improvement of the burst index (%) transmittance(%) Anionic monomer / water mass ratio 0 White 0 Reference N / A N / A 1 XI 1.5 6.3 98.4 N / A 2 X2 1.5 3.7 99.2 N / A 3 Mix X1 / X2 (57.5 / 42.5% dry weight) 1.5 N / A N / A 0.0163 4 P (INVENTION) 1.5 21.7 0.1 0.0458 5 X3 1.5 5.1 82.4 0.0150 6 X4 1.5 1.4 99.8 0 7 NOT 1.5 6.7 99.5 0.0169 8 M 1.5 N / A N / A 0.0169 9 Q 1.5 6.5 99.4 0.0177
    Table 1: Comparison of DSR and transmittance performances (The dosages expressed are in quantity of dry polymer compared to the dry paste)
    XI: Copolymer resulting from the degradation of Hofmann of a DADMAC / AM 5 copolymer (30/70 mol%) with an alpha factor = 0.7 (Corresponds to the host polymer of the product
    P)
    X2: AA / AM copolymer (50/50% by mole).
    P: Complex of polymers according to the invention (570 g XI / 44.5 g monomers).
    X3: Mixture of polymers: polyamine / X2 (15/85% by dry weight), the polyamine being branched and of the dimethylamine / ethylenediamine / epichlorohydrin type according to
    US 7,001,953 (WSP).
    X4: PVAm type polymer grafted PAM (PVAm / PAM: 30mol / 70mol) according to US 5,753,759 (BASF).
    N: Polymer complex according to US Patent 9,546,246 B2 (SNF SAS) (% Dry Extract: 15 35.2%; Viscosity: 9600 cps).
    Μ: Product synthesized as the polymer complex N, but without the use of transfer agent.
    Q: Product synthesized as the polymer complex P, but with an anionic monomer / water mass ratio = 0.0177.
    VAm = vinylamine
    DADMAC = dimethyldiallylammonium chloride
    AM = acrylamide
    AA = acrylic acid
    NVF = N-vinylformamide
    In tests 1 and 2 of Table 1, it can be seen that the use of the host polymer (XI), or of the secondary polymer (X2), alone does not offer any significant improvement in dry strength performance compared to l 'reference test (white).
    The best dry resistance performance is obtained with test 4, which corresponds to the use of product P of the invention, and which outperforms the products of the state of the art.
    The mixture X1 / X2 (test 3) corresponds, in terms of chemical nature as well as ionic ratios, to the product P of the invention (test 4). The mixture X1 / X2 (test 3) is in the form of a coacervate which is not stable on storage and which solidifies at room temperature after 24 hours.
    Products X3 and X4 (tests 5 and 6) as well as product N, respectively from US patents 7,001,953 (WSP) and US 5,753,759 (BASF) and from US patent 9,546,246 B2 (SPCM SA), do not provide equivalent performance in dry strength relative to the product P of the invention.
    During the synthesis of product M, a compact gel is obtained, which makes it impossible to test.
    The product Q (test 9), which corresponds to a synthesized product such as the polymer complex P, but with an anionic monomer / water mass ratio of 0.0177, is in the form of a translucent liquid with 99.4% transmittance, and develops low dry strength performance compared to the product of the invention P (test 4).
    权利要求:
    Claims (11)
    [1" id="c-fr-0001]
    1. Polymer complex obtained by polymerization of water-soluble monomers: in the presence of a host polymer comprising vinylamine functions and of a non-polymeric transfer agent, and in the absence of branching or crosslinking agent of ethylene polyfunctional type, characterized in that the polymer complex is obtained from an anionic monomer / water mass ratio greater than 0.035.
    [2" id="c-fr-0002]
    2. A polymer complex according to claim 1, characterized in that the complex has a transmittance of less than 70%, preferably less than 55%, and even more preferably less than 40%, at a concentration in water of 8%. dry weight of polymer complex.
    [3" id="c-fr-0003]
    3. Polymer complex according to claim 1 or 2, characterized in that the mass ratio between the host polymer and the monomers is advantageously between 0.75 and 3.5, and even more preferably between 1 and 3.
    [4" id="c-fr-0004]
    4. Polymer complex according to one of claims 1 to 3, characterized in that the non-polymeric transfer agent is chosen from the group comprising isopropyl alcohol, sodium hypophosphite, and mercaptoethanol.
    [5" id="c-fr-0005]
    5. Polymer complex according to one of claims 1 to 4, characterized in that the host polymer comprising vinylamine functions is derived from the hydrolysis of a homopolymer or a copolymer of N vinylformamide.
    [6" id="c-fr-0006]
    6. Polymer complex according to one of claims 1 to 4, characterized in that the host polymer comprising vinylamine functions is derived from the Hofmann degradation reaction on a "base polymer".
    [7" id="c-fr-0007]
    7. Polymer complex according to claim 6, characterized in that the "base polymer" comprises at least one nonionic monomer chosen from the group comprising acrylamide and its derivatives.
    [8" id="c-fr-0008]
    8. Polymer complex according to claim 6 or 7, characterized in that the "base polymer" comprises at least one polyfunctional compound containing at least 3 heteroatoms from N, O, S, P each having at least one mobile hydrogen.
    [9" id="c-fr-0009]
    9. Complex of polymers according to one of claims 6 to 8, characterized in that the "base polymer" comprises at least one polyfunctional compound chosen from the group comprising polyethyleneimine, polyamine, and polyallylamine.
    [10" id="c-fr-0010]
    10. Polymer complex according to one of claims 1 to 9, characterized in that the constituent monomers of the host polymer and the water-soluble monomers are chosen from the group comprising:
    acrylamide; N-isopropylacrylamide; Ν, Ν-dimethylacrylamide; N-vinylformamide;
    quaternary ammonium salts of dimethylaminoethyl acrylate (ADAME); quaternary ammonium salts of dimethylaminoethyl methacrylate (MADAME); dimethyldiallylammonium chloride (DADMAC); acrylamide propyltrimethyl ammonium chloride (APTAC); methacrylamido propyltrimethyl ammonium chloride (MAPTAC);
    acrylic acid; methacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; 2-acrylamido 2-methylpropane sulfonic acid; vinyl sulfonic acid; vinylphosphonic acid; allylsulfonic acid; allylphosphonic acid; styrene sulfonic acid; the water-soluble salts of an alkali metal, an alkaline earth metal, or ammonium of these monomers.
    [11" id="c-fr-0011]
    11. A method of manufacturing paper, cardboard or the like, according to which, before said sheet is formed, at least one complex according to one of claims 1 to 10 is added to the fibrous suspension at one or more injection points.
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    同族专利:
    公开号 | 公开日
    WO2019215413A1|2019-11-14|
    CA3097657A1|2019-11-14|
    CN112004846A|2020-11-27|
    FR3080853B1|2020-05-01|
    BR112020021260A2|2021-02-02|
    EP3790914A1|2021-03-17|
    KR20210006341A|2021-01-18|
    US20210140111A1|2021-05-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5753759A|1994-03-23|1998-05-19|Basf Aktiengesellschaft|Graft polymers containing N-vinyl units, their preparation and their use|
    US9546246B2|2013-08-22|2017-01-17|S.P.C.M. Sa|Complexes of water-soluble polymers, and uses thereof|EP3722330A1|2019-04-10|2020-10-14|S.P.C.M. Sa|New additive made of water-soluble polymers and uses thereof|
    WO2021186132A1|2020-03-20|2021-09-23|Spcm Sa|Novel water-soluble polymer complexes in the form of an inverse emulsion and uses thereof|US7001953B2|2001-04-16|2006-02-21|Wsp Chemicals & Technology, Llc|Water-soluble polymer complexes|
    法律状态:
    2019-05-27| PLFP| Fee payment|Year of fee payment: 2 |
    2019-11-08| PLSC| Search report ready|Effective date: 20191108 |
    2020-05-01| TP| Transmission of property|Owner name: S.P.C.M. SA, FR Effective date: 20200324 |
    2020-05-28| PLFP| Fee payment|Year of fee payment: 3 |
    2021-05-25| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1853919A|FR3080853B1|2018-05-07|2018-05-07|POLYMER COMPLEX, PREPARATION AND USE|
    FR1853919|2018-05-07|FR1853919A| FR3080853B1|2018-05-07|2018-05-07|POLYMER COMPLEX, PREPARATION AND USE|
    EP19730193.0A| EP3790914A1|2018-05-07|2019-05-07|Complex of polymers, preparation and use|
    US17/045,867| US20210140111A1|2018-05-07|2019-05-07|Complex of polymers, preparation and use|
    PCT/FR2019/051039| WO2019215413A1|2018-05-07|2019-05-07|Complex of polymers, preparation and use|
    BR112020021260-1A| BR112020021260A2|2018-05-07|2019-05-07|polymer complex, and method for making paper, cardboard or the like.|
    KR1020207030186A| KR20210006341A|2018-05-07|2019-05-07|Composites of polymers, preparation and use|
    CA3097657A| CA3097657A1|2018-05-07|2019-05-07|Complex of polymers, preparation and use|
    CN201980027243.5A| CN112004846A|2018-05-07|2019-05-07|Polymer composites, preparation and use|
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