• 专利附录
  • 专利说明
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    • 专利摘要:
    The present invention relates to a method for preparing mineral particles by milling a mineral material in the presence of a particular anionic polymer. The polymer used is obtained by polymerization in the presence of sodium hypophosphite, dipropionate trithiocarbonate disodium and at least one radical-generating compound. The invention also relates to an aqueous composition comprising particles of ground mineral material and such a polymer, in particular a composition of paper coating.
    公开号:FR3060419A1
    申请号:FR1662582
    申请日:2016-12-16
    公开日:2018-06-22
    发明作者:Clementine CHAMPAGNE；Christian Jacquemet；Benoit Magny；Jacques Mongoin；Jean-Marc Suau
    申请人:Coatex SAS；
    IPC主号:
    专利说明:

    DESCRIPTION
    The present invention relates to a method for preparing mineral particles by grinding a mineral material in the presence of a particular anionic polymer. The polymer used is obtained by polymerization in the presence of sodium hypophosphite, disodium dipropionate trithiocarbonate (DPTTC) and at least one radical-generating compound. The invention also relates to an aqueous composition comprising particles of ground mineral material and such a polymer, in particular a composition for paper coating sauce.
    Methods of grinding mineral material are known, in particular for grinding mineral materials used in the paper industry. In particular, methods for grinding mineral material are known which use grinding aid agents, in particular polymers derived from unsaturated monomers comprising one or more carboxylic acid functions. These grinding aid agents make it possible to control the rheology of the suspension during the grinding operation. Generally, these grinding aid agents make it possible to reduce the flow limit of the suspension of mineral filler to be ground as much as possible while maintaining a sufficient level of viscosity during the grinding operation.
    In general, the methods of grinding mineral matter must be effective and make it possible to control the particle size of the particles obtained.
    In addition, the methods of grinding mineral material must have a high efficiency in terms of grinding time for a particular particle size for a defined quantity of mineral material. Indeed, for the preparation of a defined quantity of mineral particles of particular particle size, a reduced use time of the grinding installations allows an improvement in the overall yield of the grinding method.
    Likewise, it is important to have methods of grinding mineral material which make it possible to prepare aqueous suspensions of particles of mineral material of low viscosity which are stable shortly after grinding but also several hours or several days after grinding. Viscosity drift phenomena must be controlled because they can lead to gelation of the prepared suspensions which would make handling difficult or impossible. Such viscosity differences should be as small as possible. Likewise, the phenomena of particle sedimentation must be avoided or greatly slowed down.
    In addition to the stability control, the control of the viscosity of the aqueous suspensions of ground mineral particles is also essential. In general, controlling the viscosity of the aqueous suspensions of particles of ground mineral material must make it possible to achieve a low viscosity.
    It is also important to be able to prepare aqueous suspensions of particles of mineral matter having a high dry extract. A high dry extract of these aqueous suspensions of particles of mineral matter makes it possible in particular to increase the productivity of the processes for the preparation of these suspensions.
    In addition, from an environmental point of view, it is important to be able to have grinding aid agents making it possible to prepare suspensions of particles of mineral material comprising a reduced amount of water while maintaining or improving the properties. of these suspensions.
    Furthermore, during the production of coated and surfaced papers, aqueous compositions of paper coating sauces are used to deposit a layer of particles of mineral matter and binder on the surface of the paper sheet in order to modify its surface condition. to improve its printability, its gloss or its opacity. For example, for coated paper intended for printing, the layer is obtained from an aqueous dispersion consisting mainly of binders and pigments also called mineral fillers. The most commonly used pigments for coating paper are kaolin, calcium carbonate, titanium dioxide, talc and organic pigments, especially plastic pigments. Within these compositions, the mineral filler is in the form of particles. The use of such papermaking coating sauces makes it possible in particular to improve the physical properties of paper, in particular to improve its optical properties.
    Improvements in the efficiency of paper manufacturing processes are also made possible through the use of these paper coating sauces.
    Improving the compatibility of the various compounds used during the preparation of the paper must also be sought.
    Thus, although there are methods of wet grinding of mineral material which use polymers as a grinding aid agent, the methods of the prior art do not always make it possible to provide a satisfactory solution to the problems met. There is therefore a need for improved methods of grinding mineral matter in water.
    The method according to the invention makes it possible to provide a solution to all or part of the problems of the methods of the state of the art.
    Thus, the invention provides a method for preparing particles of mineral matter comprising grinding, in the presence of water, at least one mineral matter in the presence of at least one polymer of molecular mass by weight Mw (measured by CES ) less than 8000 g / mol and a polymolecularity index IP or polydispersity index less than 3, obtained by a radical polymerization reaction in water, at a temperature above 50 ° C, of at least one monomer anionic comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function, in the presence of:
    sodium hypophosphite, disodium dipropionate trithiocarbonate (DPTTC) and at least one radical-generating compound chosen from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, hydrogen peroxide associated with an ion chosen from Fe 11 , Fe 111 , Cu 1 , Cu 11 and their mixtures.
    For the grinding method according to the invention, the mineral material used can be in different forms, in particular in the form of coarse-grained grains obtained from blocks or pieces of crushed mineral material. During the grinding according to the invention, the size of the grains, in particular coarse-sized grains, of mineral material or pieces of mineral material used is reduced until particles are obtained. The method according to the invention is particularly effective in controlling the size of the particles prepared during the grinding of the mineral matter. According to the invention, the particle size is measured by sedimentation.
    For the method according to the invention, the particle size can be defined by their median diameter dso for which half by weight of a population of particles has a size less than a given value. Thus, the particles having a size less than 50 μm are particles belonging to a population of which half by weight has a diameter less than 50 μm. Preferably, the method according to the invention relates to the preparation of particles whose size is less than 50 μm or else whose size ranges from 0.05 μm to 50 μm. More preferably, the method according to the invention relates to the preparation of particles of mineral material whose size is less than 10 μm or even less than 5 μm or 2 μm. More preferably, the size of the particles of mineral matter is less than 1 μηι or less than 0.5 μπι. Also preferably for the method according to the invention, at least 50% by weight of the particles have a size ranging from 0.5 μm to 50 μm or else a size less than 10 μm. In particular, at least 50% by weight of the particles have a size less than 5 μm or 2 μm, or even less than 1 μm.
    Advantageously for the method according to the invention, at least 60% by weight of the particles have a size ranging from 0.5 μm to 50 μm or else a size less than 10 μm. In particular, at least 60% by weight of the particles have a size less than 5 μm or 2 μm, or even less than 1 μm. Also advantageously for the method according to the invention, at least 75% by weight of the particles have a size ranging from 0.5 μm to 50 μm or else a size less than 10 μm. In particular, at least 75% by weight of the particles have a size of less than 5 μm or 2 μm, or even less than 1 μm.
    Also advantageously for the method according to the invention, at least 90% by weight of the particles have a size ranging from 0.5 μm to 50 μm or else a size less than 10 μm. In particular, at least 90% by weight of the particles have a size less than 5 μm or 2 μm, or even less than 1 μm.
    For the method according to the invention, a population of mineral particles can also be defined by an equivalent spherical diameter (esd). Preferably according to the invention, the equivalent spherical diameter of the particles having a size less than 50 μm is equal to 50% by weight. In this case, 50% by weight of the particles have a size less than 50 μm. Also preferably according to the invention, the spherical equivalent diameter of the particles ranging in size from 0.05 μm to 50 μm or less than 0.05 μm to 50 μm, is equal to 60% by weight or equal to 70% by weight or also equal to 80% by weight or also equal to 90% by weight.
    More preferably according to the invention, the spherical equivalent diameter of the particles for a size less than 10 μm is equal to 60% by weight or equal to 70% by weight or even equal to 80% by weight or even equal to 90% in weight.
    Much more preferably according to the invention, the spherical equivalent diameter of the particles for a size less than 5 μm is equal to 60% by weight or equal to 70% by weight or even equal to 80% by weight or even equal to 90 % in weight.
    Even more preferably according to the invention, the spherical equivalent diameter of the particles for a size less than 2 μm is equal to 60% by weight or equal to 70% by weight or even equal to 80% by weight or even equal to 90 % in weight.
    Very particularly preferably according to the invention, the spherical equivalent diameter of the particles for a size less than 1 μm is equal to 60% by weight or equal to 70% by weight or equal to 80% by weight or even equal to 90% in weight.
    Preferably, the method according to the invention uses at least one synthetic mineral material or of natural origin.
    Also preferably, the method according to the invention uses at least one mineral material chosen from carbonates of alkaline earth metal, preferably calcium carbonate (natural calcium carbonate or precipitated calcium carbonate), strontium carbonate, magnesium carbonate, barium carbonate, dolomite, kaolin, titanium dioxide, talc, lime, calcium sulfate, barium sulfate. More preferably, the method according to the invention uses at least one mineral material chosen from natural calcium carbonate, precipitated calcium carbonate, dolomite, kaolin, calcined kaolin, titanium dioxide, talc, lime.
    The method according to the invention can use a single mineral material or several mineral materials. Thus, the method according to the invention can use two or three mineral materials. In particular, the method according to the invention can use calcium carbonate and at least one other mineral material chosen from dolomite, kaolin, calcined kaolin, titanium dioxide, talc, lime, in particular calcium carbonate and kaolin or calcium carbonate and lime. Likewise, the method according to the invention can use titanium dioxide and at least one other mineral material chosen from calcium carbonate, dolomite, kaolin, talc, lime, in particular titanium dioxide and kaolin or carbon dioxide. titanium and lime. Also, the method according to the invention can use kaolin or calcined kaolin and at least one other mineral material chosen from dolomite, talc, lime. The method according to the invention can also use talc and lime or talc and dolomite.
    In addition to a mineral material, the method according to the invention uses at least one specific polymer resulting from a radical polymerization reaction, in the presence of sodium hypophosphite, disodium trithiocarbonate dipropionate (DPTTC) and at least one compound. radical generator chosen from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, hydrogen peroxide associated with an ion chosen from Fe 11 , Fe in , Cu 1 , Cu 11 and their mixtures.
    Preferably, the polymerization reaction is carried out in water or in a solvent mixed with water, in particular an alcoholic solvent, in particular isopropyl alcohol. In a particularly preferred manner, the polymerization reaction is carried out in water only.
    According to the invention, sodium hypophosphite (CAS No 7681-53-0 or 10039-56-2 for the monohydrate form) is a sodium salt of hypophosphorous acid.
    According to the invention, DPTTC is disodium 2,2 ’- (thiocarbonylbrsthro) -drpropanoate (CAS No 864970-33-2). Its sodium salts are used according to the invention.
    Also preferably, the polymerization reaction uses a radical-generating compound chosen from hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate and their mixtures. In a particularly preferred manner, the polymerization reaction uses a radical-generating compound chosen from hydrogen peroxide and sodium persulfate.
    Also preferably, the polymerization reaction uses, relative to the amount by weight of monomer:
    from 2% to 8% by weight, preferably from 2.5% to 7% by weight or from 2.5% to 6% by weight of sodium hypophosphite or from 0.01% to 1.5% by weight , preferably from 0.01% to 1.2% by weight or from 0.05% to 1.5% by weight, more preferably from 0.05% to 1.2% by weight or from 0.1% to 1% by weight of disodium dipropionate trithiocarbonate (DPTTC) or from 0.1% to 5% by weight of radical-generating compound or, preferably, from 0.5% to 4.5% by weight of hydrogen peroxide or from 0.1% to 4% by weight of sodium persulfate, potassium persulfate or ammonium persulfate.
    Also preferably, the polymerization reaction uses, relative to the amount by weight of monomer:
    from 2% to 8% by weight, preferably from 2.5% to 7% by weight or from 2.5% to 6% by weight of sodium hypophosphite or from 0.01% to 1.5% by weight , preferably from 0.01% to 1.2% by weight or from 0.05% to 1.5% by weight, more preferably from 0.05% to 1.2% by weight or from 0.1% to 1% by weight of disodium dipropionate trithiocarbonate (DPTTC) or from 0.5% to 4.5% by weight of hydrogen peroxide or from 0.1% to 4% by weight of sodium persulfate, potassium persulfate or ammonium persulfate.
    More preferably, the polymerization reaction uses, relative to the amount by weight of monomer:
    from 2% to 8% by weight, preferably from 2.5% to 7% by weight or from 2.5% to 6% by weight of sodium hypophosphite, from 0.01% to 1.5% by weight , preferably from 0.01% to 1.2% by weight or from 0.05% to 1.5% by weight, more preferably from 0.05% to 1.2% by weight or from 0.1% to 1% by weight of disodium dipropionate trithiocarbonate (DPTTC) and from 0.1% to 5% by weight of radical-generating compound or, preferably, from 0.5% to 4.5% by weight of hydrogen peroxide or from 0.1% to 4% by weight of sodium persulfate, potassium persulfate or ammonium persulfate.
    Also more preferably, the polymerization reaction uses, relative to the amount by weight of monomer:
    from 2% to 8% by weight, preferably from 2.5% to 7% by weight or from 2.5% to 6% by weight of sodium hypophosphite, from 0.01% to 1.5% by weight , preferably from 0.01% to 1.2% by weight or from 0.05% to 1.5% by weight, more preferably from 0.05% to 1.2% by weight or from 0.1% to 1% by weight of disodium dipropionate trithiocarbonate (DPTTC) and from 0.5% to 4.5% by weight of hydrogen peroxide or from 0.1% to 4% by weight of sodium persulfate, potassium persulfate or ammonium persulfate.
    When using hydrogen peroxide associated with an ion chosen from Fe 11 , Fe in , Cu 1 , Cu 11 , these ions can be introduced by means of different chemical compounds. As examples of chemical compounds making it possible to introduce ions Fe 11 , Fe in , Cu 1 , Cu 11 , there may be mentioned iron sulphate, hydrated iron sulphate, hemi-hydrated iron sulphate, iron sulphate heptahydrate, iron carbonate , hydrated iron carbonate, hemi-hydrated iron carbonate, iron chloride, copper carbonate, hydrated copper carbonate, hemi-hydrated copper carbonate, copper acetate, copper sulphate, copper sulphate pentahydrate, copper hydroxide, copper halide.
    The weight average molecular weight Mw (measured by CES or Steric Exclusion Chromatography) of the polymer used according to the invention is less than 8000 g / mol, it can vary quite widely. Also preferably, the polymer according to the invention has a weight average molecular weight Mw of less than 7,500 g / mol, preferably less than 6,500 g / mol, less than 6,000 g / mol, more preferably less than 5 500 g / mol.
    Also preferably, the polymer according to the invention has a weight-average molecular mass Mw greater than 1000 g / mol or greater than 1200 g / mol or greater than 1500 g / mol.
    Thus, the polymer according to the invention preferably has a weight-average molecular mass Mw ranging from 1,000 g / mol to 7,500 g / mol, 6,500 g / mol, 6,000 g / mol or 5,500 g / mol. More preferably, the polymer according to the invention has a weight average molecular weight Mw ranging from 1,200 g / mol to 7,500 g / mol, 6,500 g / mol, 6,000 g / mol or 5,500 g / mol. Even more preferably, the polymer according to the invention has a weight-average molecular mass Mw ranging from 1,500 g / mol to 7,500 g / mol, 6,500 g / mol, 6,000 g / mol or 5,500 g / mol.
    In a particularly preferred manner, the polymer according to the invention has a weight-average molecular mass Mw ranging from 3,500 g / mol to 5,500 g / mol. Also particularly preferably, the polymer according to the invention has a weight-average molecular mass Mw ranging from 4,500 g / mol to 5,500 g / mol.
    According to the invention, the polymolecularity index IP, or polydispersity index, of the polymer used is less than 3. Preferably, the polymolecularity index IP of the polymer is less than 2.8. Also preferably, the polymolecularity index IP of the polymer ranges from 1.5 to 3. More preferably, the polymolecularity index IP of the polymer ranges from 1.5 to 2.8 or from 1.5 to 2 , 5.
    An essential step in the preparation of the polymer used according to the invention is the radical polymerization reaction of at least one anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function. The polymerization reaction is known as such. Preferably, it can be carried out at a temperature above 80 ° C or above 95 ° C. It can be carried out in a solvent chosen from water, organic solvents and their mixtures, preferably in water.
    Preferably according to the invention, the anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function is chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and their mixtures.
    In a particularly preferred manner according to the invention, the anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function is acrylic acid. More particularly preferably according to the invention, the radical polymerization reaction uses only acrylic acid.
    However, in addition to the anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function, the radical polymerization reaction can use at least one other monomer. Preferably, the polymerization reaction can then also use at least one monomer chosen from:
    another anionic monomer comprising at least one different olefinic unsaturation chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, their salts and mixtures thereof, a nonionic monomer comprising at least one polymerizable olefinic unsaturation, preferably at least one unsaturation polymerizable ethylenic and in particular a polymerizable vinyl function, more preferably a nonionic monomer chosen from esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid chosen from acrylic acid, methacrylic acid, and their mixtures, for example styrene, vinylcaprolactam, alkyl acrylate, in particular Ci-Cio-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, acrylate isobutyl, n-butyl acrylate, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferred ely Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, aryl acrylate, preferably phenylacrylate, benzylacrylate, phenoxyethylacrylate aryl, preferably phenylmethacrylate, benzylmethacrylate, phenoxyethylmethacrylate, a compound of formula (I):
    ^ - (Lbm-CLVR 2 (I) in which:
    o R 1 represents a polymerizable acrylate group or a polymerizable methacrylate group, o R 2 represents an OH group or an OCH3 group,
    L 1 and L 2 , identical or different, independently represent an ethyloxy group or a propyloxy group and m and n, identical or different and at least one of which is different from 0, represent a number less than or equal to 150 and their sum m + n is less than 150 and sulfonic, a sulfonic, an acid salt acid acid 2-acrylamido-2-methylpropane 2-acrylamido-2-methylpropane 2- (methacryloyloxy) ethanesulfonic acid,
    2- (methacryloyloxy) ethanesulfonic (CAS No 010595-80-9), sodium methallyl sulfonate, styrene sulfonate and their mixtures.
    During the polymerization reaction, the amounts of anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function can vary quite widely. Preferably, the polymerization reaction uses 100% by weight of this anionic monomer.
    Similarly, the amounts of other monomers can also vary quite widely. Preferably, the polymerization reaction can then use from 70% to 99.5% by weight of anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function and from 0.5% to 30% by weight of '' at least one monomer chosen from:
    another different anionic monomer chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, their salts and mixtures thereof, a nonionic monomer comprising at least one polymerizable olefinic unsaturation, preferably at least one polymerizable ethylenic unsaturation and in particular a function polymerizable vinyl, more preferably a nonionic monomer chosen from esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid chosen from acrylic acid, methacrylic acid, and mixtures thereof, for example styrene, vinylcaprolactam, alkyl acrylate, in particular Ci-Cio-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n- acrylate butyl, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferred mainly methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, aryl acrylate, preferably phenylacrylate, benzylacrylate, phenoxyethylacrylate, aryl methacrylate, preferably phenylmethacrylate, phenylmethacrylate , a compound of formula (I):
    R ^ CLbm-CL ^ nR 2 (I) in which:
    o R 1 represents a polymerizable acrylate group or a polymerizable methacrylate group, o R 2 represents an OH group or an OCH3 group, o L 1 and L 2 , identical or different, independently represent an ethyloxy group or a propyloxy group and om and n , identical or different and at least one of which is different from 0, represent a number less than or equal to 150 and their sum m + n is less than 150 and
    2-acrylamido-2-methylpropane sulfonic, a salt of sulfonic acid, a salt of acidic acid
    2-acrylamido-2-methylpropane 2- (methacryloyloxy) ethanesulfonic
    2- (methacryloyloxy) ethanesulfonic, sodium methallyl sulfonate, styrene sulfonate and their mixtures.
    Preferably, the grinding method according to the invention uses a totally or partially neutralized polymer. According to the invention, the neutralization of the polymer used is carried out by neutralizing or salifying all or part of the carboxylic acid functions present within the polymer.
    Preferably, the neutralization is carried out by means of a base, for example by means of an alkali metal derivative or of an alkaline earth metal derivative. The preferred bases are chosen from NaOH, KOH, NH4OH, Ca (OH) 2, Mg (OH) 2, monoisopropylamine, triethanolamine, triisopropylamine, 2-amino-2-methyl-1-propanol (AMP), triethylamine, diethylamine, monoethylamine . In a particularly preferred manner, the neutralization is carried out by means of NaOH, Ca (OH) 2, Mg (OH) 2, alone or in combination.
    During the preparation of the polymer according to the invention, a separation step can also be implemented. According to the invention, the separation can be carried out after the total or partial neutralization of the polymer used according to the invention. It can also be implemented before neutralization of the polymer.
    The aqueous solution of the polymer, totally or partially neutralized, can be treated according to static or dynamic fractionation methods known as such. One or more polar solvents are then used, belonging in particular to the group consisting of methanol, ethanol, n-propanol, isopropanol, butanols, acetone, tetrahydrofuran, thus producing a separation into two phases. During separation, the least dense phase comprises the major fraction of the polar solvent and the fraction of low molecular weight polymers, the densest aqueous phase comprises the fraction of polymers of higher molecular weight. The temperature at which the polymer fraction selection treatment is carried out can influence the partition coefficient. It is generally between 10 ° C and 80 ° C, preferably between 20 ° C and 60 ° C. During separation, it is important to control the ratio of the quantities of dilution water and polar solvents. When implementing a dynamic separation method, for example by centrifugation, the ratios of the extracted fractions generally depend on the centrifugation conditions. The selection of the polymer fraction can also be improved by re-treating the densest aqueous phase with a new amount of polar solvent, which may be different. It can also be a mixture of polar solvents. Finally, the liquid phase obtained after treatment can be subjected to distillation to remove the solvent (s) used for the treatment.
    In addition to a method of grinding, the invention also relates to a method of preparing an aqueous suspension of particles of mineral matter comprising the implementation of the method of grinding according to the invention.
    Preferably, the preparation method according to the invention makes it possible to prepare an aqueous suspension in which the dry extract in mineral matter is greater than 60% by weight. More preferably, the preparation method according to the invention makes it possible to prepare an aqueous suspension in which the dry extract in mineral matter is greater than 70% by weight. More preferably, the preparation method according to the invention makes it possible to prepare an aqueous suspension in which the dry extract in mineral matter is greater than 75% by weight or 80% by weight of the suspension.
    The particular, advantageous or preferred characteristics of the grinding method according to the invention define methods for preparing an aqueous suspension according to the invention which are also particular, advantageous or preferred.
    The invention also provides an aqueous composition comprising particles of ground mineral material and at least one polymer defined for the method of grinding according to the invention.
    Advantageously, the composition according to the invention can also comprise at least one adjuvant, in particular at least one adjuvant chosen from dispersing agents, anti-foaming agents, biocidal agents, coloring agents, lubricating agents and optical brighteners.
    Advantageously, the composition according to the invention can also comprise at least one binding agent, in particular a natural binding agent such as starch or a synthetic binding agent such as a latex.
    The invention also provides a method for preparing a papermaking coating sauce comprising grinding, in the presence of water, at least one mineral material in the presence of at least one polymer obtained by a radical polymerization reaction in l water, at a temperature above 50 ° C., of at least one anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function, in the presence of:
    sodium hypophosphite, disodium dipropionate trithiocarbonate (DPTTC) and at least one radical-generating compound chosen from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, hydrogen peroxide associated with an ion chosen from Le 11 , Le 111 , Cu 1 , Cu 11 and their mixtures.
    The invention also relates to the use as a grinding aid agent of at least one mineral material, of at least one polymer obtained by a radical polymerization reaction in water, at a temperature above 50 ° C., at least one anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function, in the presence of:
    sodium hypophosphite, disodium dipropionate trithiocarbonate (DPTTC) and at least one radical-generating compound chosen from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, hydrogen peroxide associated with an ion chosen from Le 11 , Le 111 , Cu 1 , Cu 11 and their mixtures.
    Preferably for use as a grinding aid agent according to the invention, the polymer used is the anionic polymer of the grinding method according to the invention.
    The invention also provides a method of preparing paper comprising the use of an aqueous composition according to the invention.
    The particular, advantageous or preferred characteristics of the grinding method according to the invention define aqueous compositions, uses and preparation methods according to the invention which are also particular, advantageous or preferred.
    The following examples illustrate the various aspects of the invention. The methods or techniques used are known or described.
    EXAMPLES
    Molecular mass by size exclusion chromatography (CES}
    The molecular weights and polymolecularity indices of the polymers obtained by a radical polymerization reaction in water, at a temperature above 50 ° C., of at least one monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function are determined by size exclusion chromatography.
    A test sample of the polymer solution corresponding to 90 mg of dry matter is introduced into a 10 mL bottle. Mobile phase, added with 0.04% dimethylformamide (DMF), is added to a total mass of 10 g. The composition of this mobile phase is as follows: NaHCCU: 0.05 mol / L, NaNCU: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaN3 0.03% by mass.
    The CES chain is composed of an Waters 510 type isocratic pump, the flow rate of which is set at 0.8 mL / min, a Waters 717+ sampler, an oven containing a Guard type guard column. Column Ultrahydrogel Waters 6 cm long and 40 mm internal diameter, followed by a linear column type Ultrahydrogel Waters 30 cm long and 7.8 mm internal diameter.
    Detection is ensured by means of a RI Waters 410 type refractometer. The oven is brought to the temperature of 60 ° C and the refractometer is brought to the temperature of 45 ° C.
    The CES device is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standard Service with molecular weight at the peak peak between 1000 g / mol and 1.10 6 g / mol and with a polydispersity index between 1, 4 and 1.7, as well as with a sodium polyacrylate of molecular weight equal to 5600 g / mol and of polymolecularity index equal to 2.4. The calibration curve is linear and takes into account the correction obtained with the flow marker: dimethylformamide (DMF). The acquisition and processing of the chromatogram is carried out by the PSS WinGPC Scientific v 4.02 software utrlisatron. The chromatogram obtained is integrated into the zone corresponding to molecular weights greater than 65 g / mol.
    Grinding technique and particle size measurement
    Using a peristaltic pump, suspensions of coarse grains of mineral matter prepared in the presence of a polymer according to the invention or of a comparative polymer are introduced into a Dyno Mill grinder of the pilot KDL type 1.4 L containing 2,850 g of ceramic balls of ER 120 S type from 0.6 mm to 1.0 mm in diameter from the company ZirPro. The grinding conditions are adjusted so as to obtain a suspension of particles of mineral material of desired particle size. The necessary quantity of polymer introduced into the system is adjusted in order to achieve the desired particle size. This suspension is then characterized by a particle size measurement, a Brookfield viscosity measurement followed by a stability test. This stability test consists in measuring the Brookfield viscosity of the crushed suspension after a standing time of 8 days at a temperature of 25 ° C ± 1 ° C.
    The particle size characteristics relating to the preparation of particles of mineral matter are determined using a SediGraph III5120 device (Micromeritics, USA). In known manner, this method and this measuring instrument make it possible to measure the particle size distribution of the suspensions of particles of mineral matter. They make it possible in particular to determine the mass fraction as a percentage of a population of mineral particles whose equivalent spherical diameter is less than 1 μm or else less than 2 μm (esd <lpm or else esd <2 pm, both expressed in%) . These measurements are carried out using a suspension of particles of mineral material diluted to a concentration of approximately 33 g of dry matter per liter of solution of a sodium polyacrylate of molecular weight equal to 4,000 g / mol and of concentration equal to 1.6 g of dry sodium polyacrylate per liter of solution. This sample is dispersed and sonicated before measurement.
    Brookfield viscosity measurement
    The Brookfield viscosities (mPa.s) of the suspensions of particles of mineral matter prepared according to the method of the invention are measured after the grinding operation (VB0) and after 8 days of rest (VB8), at 25 ° C ± 1 ° C and at a speed of rotation of 100 rpm using a Brookfield DVIII viscometer equipped with a suitable module, for example 2 to 5.
    Example 1: Preparation of co-neutralized polymers according to the invention
    A mixture (R) of water and sodium hypophosphite is introduced into a stirred reactor. Then, mixture 1 (Ml), mixture 2 (M2) and mixture 3 (M3) are prepared from water, acrylic acid (AA), hydrogen peroxide or sodium persulfate, d sodium hypophosphite and DPTTC. The reactor is then heated so as to reach the polymerization temperature (T in ° C.) and mixtures 1, 2 and 3 are introduced in parallel into the reactor. Finally, the reactor is cooled and the polymer is neutralized by injecting the previously prepared neutralization mixture (MN). The quantities (in g) of reagents, the reaction conditions as well as the characteristics of the polymers (dry extract ES, molecular mass Mw and polymolecularity index IP) prepared are presented in Tables 1, 2 and 3.
    Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 R water 282.8 282.8 198 198 198 277.2 277.2 282.8 NaH 2 PO 2 .H 2 O 2.61 2.47 15 13 9 12 12 2.72 Miss AA 439.8 439.8 208.6 208.6 208.6 205.6 205.6 439.8 DPTTC at 20% 0 0 13.41 13.41 13.41 4.26 4.26 0 water 48.8 48.8 0 0 0 0 0 48.8 M2 H 2 O 2 at 35% 0 0 7.1 7.1 7.1 3.5 4.5 0 Na persulfate 6.96 6.56 0 0 0 0 0 1.85 water 97.1 97.1 130 130 130 27.2 27.2 97.1 M3 NaH 2 PO 2 .H 2 O 23.45 22.21 0 0 0 0 0 24.44 DPTTC at 20% 0.23 2.2 0 0 0 0 0 0.23 water 81.2 81.2 0 0 0 0 0 81.2 MN water 471.9 471.9 185 185 185 185 185 489.4 50% NaOH 238.1 241.1 113.6 113.6 115.9 104.3 104.3 239.5 Ca (OH) 2 to 97% 116.1 117.2 55.31 55.31 56.44 62.08 62.08 117.9 T (° C) 97 + 1 97 + 1 90 + 2 90 + 2 90 + 2 90 + 2 90 + 2 97 + 1 ES (%) 36 35.2 33.16 32.62 32.67 34.11 33.98 35.1 Mw (g / mol) 4,845 4,915 4,205 4,910 6,375 5,780 5,890 4,915 IP 2.2 2.2 2.2 2.3 2.5 2.4 2.3 2.1
    Table 1
    Example 2-1 2-2 2-3 2-4 2-5 2-6 R Water 198 198 198 198 198 198 NaH 2 PO 2 .H 2 O 11 11.5 12 13 14 15 Miss AA 208.65 208.65 208.65 208.65 208.65 208.65 DPTTC at 20% 13.41 13.41 13.41 13.41 13.41 13.41 Water 23.18 0 23.18 23.18 23.18 23.18 M2 H 2 O 2 at 35% 7.1 7.1 7.1 7.1 7.1 7.1 Na persulfate 0 0 0 0 0 0 Water 130 130 130 130 130 130 M3 NaH 2 PO 2 .H 2 O 0 0 0 0 0 0 DPTTC at 20% 0 0 0 0 0 0 Water 0 0 0 0 0 0 MN Water 170 170 170 170 170 170 50% NaOH 160.66 159.85 160.66 159.03 159.85 159.85 Ca (OH) 2 to 97% 33.52 33.35 33.52 33.18 33.35 33.35 T (° C) 90 + 2 90 + 2 90 + 2 90 + 2 90 + 2 90 + 2 ES (%) 31.69 32.5 31.69 31.68 31.38 31.5 Mw (g / mol) 6,165 5,465 5,640 5,225 5,145 4,590 IP 2.4 2.5 2.3 2.3 2.3 2.2
    Table 2
    Example 3-1 3-2 3-3 3-4 R Water 198 198 198 198 NaH 2 PO 2 .H 2 O 14 13 12 15 Miss AA 208.65 208.65 208.65 231.83 DPTTC at 20% 13.41 13.41 13.41 13.41 Water 23.18 23.18 23.18 23.18 M2 H 2 O 2 at 35% 7.1 7.1 7.1 7.1 Na persulfate 0 0 0 0 Water 130 130 130 130 M3 NaH 2 PO 2 .H 2 O 0 0 0 0 DPTTC at 20% 0 0 0 0 Water 0 0 0 0 MN Water 0 0 0 0 50% NaOH 228 228 228 228 Ca (OH) 2 to 97% 0 0 0 0 T (° C) 90 + 2 90 + 2 90 + 2 90 + 2 ES (%) 36.13 36.73 36.65 36.63 Mw (g / mol) 5,010 4,830 5,325 4,445 IP 2.2 2.2 2.3 2.2
    Table 3
    Example 2 Preparation of Comparative Co-Neutralized Polymers
    Analogously to Example 1, comparative polymers are prepared. The quantities (in g) of reagents, the reaction conditions as well as the characteristics of the polymers prepared are presented in Table 4.
    Example Cl C2 C3 C4 R Water 282.8 244.40 224.93 262.71 CuSO 4 .5H 2 O 0 0.32 0.30 0.35 FeSO 4 .7H 2 O 0 0.28 0.25 0.30 NaH 2 PO 2 .H 2 O 2.74 0 0 0 Miss AA 439.82 279.82 257.91 301.8 DPTTC at 20% 0 0 0 0 Water 48.8 0 0 0 M2 H 2 O 2 at 35% 0 35.33 32.57 38.11 Na persulfate 7.33 0 0 0 Water 97.1 9.34 8.62 10.07 M3 NaH 2 PO 2 .H 2 O 24.68 0 0 0 DPTTC at 20% 0 3.47 3.55 3.74 Water 81.2 31.15 28.71 25.52 MN Water 357.37 127.99 226.73 27.86 50% NaOH 248.91 144.99 80.35 323.53 Ca (OH) 2 to 97% 118.63 42.41 60.18 0 T (° C) 97 + 1 93 + 1 93 + 1 93 + 1 ES (%) 35.3 38 35 41.2 Mw (g / mol) 4,710 5,700 5,700 5,700 IP 2.1 2.6 2.5 2.6
    Table 4
    Example 3: Grinding of calcium carbonate with an esd of less than 1 μm equal to 80% by weight
    The polymers according to the invention and a comparative polymer are used as a grinding aid agent for natural calcium carbonate. The different polymers are used at the same doses and under the same operating conditions.
    Aqueous suspensions of natural calcium carbonate having a solid content by weight of 76% ± 1% are prepared. They are prepared in the presence of an amount of 1.07% by dry weight of an aqueous solution of polymer, as a grinding aid agent, relative to the dry amount of calcium carbonate used in this operation grinding in order to reach the targeted particle size. The polymer solutions have a concentration of 35% ± 1% of active material and a pH of 8.5 ± 0.5. The raw material for preparing these aqueous suspensions is an aqueous suspension of coarse-grained calcium carbonate at 75% ± 1% by weight of solid. Calcium carbonate is a coarse marble (commercial product Omyacarb 10 AV Omya) from the region of Carrara (Italy). The grinding conditions are adjusted so as to obtain a suspension of mineral particles of which 80.0% ± 0.5% by weight of its population has an equivalent spherical diameter less than 1 pm (esd <lpm = 80.0% ± 0 , 5%).
    The suspensions according to the invention and the comparative suspension are then analyzed and characterized by Brookfield viscosity measurements after the grinding operation and then after 8 days of rest at 25 ° C. The results are presented in Table 5.
    Suspension Polymer VB0 VB8 Sl-1 1-1 291 650 S1-2 1-2 299 645 Sl-3 1-3 232 750 SCI Cl 310 983 Your island 5
    The use of grinding aid agents according to the invention makes it possible to prepare suspensions of ground calcium carbonate of low viscosity. The viscosities of these suspensions change over time over a period of 8 days in a lower manner than that of the suspension prepared in the presence of the comparative polymer. The suspensions prepared according to the invention therefore have lower viscosities than those of the suspension of the comparative test. They are more stable.
    Example 4 Grinding of Esd Calcium Carbonate Less Than 1 Pm Equal to 80% by Weight
    The polymers according to the invention and a comparative polymer are used as a grinding aid agent for natural calcium carbonate. The different polymers are used at the same doses and under the same operating conditions.
    Aqueous suspensions of natural calcium carbonate having a solid content by weight of 76% ± 1% are thus prepared. They are prepared in the presence of an effective amount (QE - expressed as% dry / dry) by dry weight of an aqueous solution of polymer based on 100 g of dry calcium carbonate, as a grinding aid agent. , in order to reach the targeted particle size. The polymer solutions have a concentration of 35% ± 1% of active material and a pH of 8.5 ± 0.5. The raw material for preparing these aqueous suspensions is an aqueous suspension of coarse-grained calcium carbonate at 75% ± 1% by weight of solid. Calcium carbonate is a coarse calcite (commercial product BL 200 Omya) from the region of Orgon (Lrance). The grinding conditions are adjusted so as to obtain a suspension of mineral particles of which 80.0% ± 0.5% by weight of its population has an equivalent spherical diameter less than 1 pm (esd <lpm = 80.0% ± 0 , 5%).
    The calcium carbonate suspensions are then analyzed and characterized by Brookfield viscosity measurements after the grinding operation and then after 8 days of rest at 25 ° C. The effective quantity (QE) of dry polymer to reach the targeted particle size is also measured. The results are presented in Table 6.
    Suspension Polymer QE VB0 VB8 S2-1 2-1 0.93 679 1,356 S2-2 2-2 0.99 508 1,406 S2-3 2-3 0.96 670 1,352 S2-4 2-4 0.95 547 1,226 S2-5 2-5 0.95 580 1,326 SC2 C2 1.05 1,019 1,786
    Table 6
    The use of the polymers according to the invention allows a reduction in the effective amount of grinding aid agent. Again, the use of the grinding aid agents according to the invention makes it possible to prepare suspensions of ground calcium carbonate of low viscosity. The viscosities of these suspensions change over time over a period of 8 days in a lower manner than that of the suspension prepared in the presence of the comparative polymer. The suspensions prepared according to the invention therefore have lower viscosities than those of the suspension of the comparative test. They are more stable.
    EXAMPLE 5 Grinding of Esd Calcium Carbonate Less Than 2 pm Equal to 60% by Weight
    The polymers according to the invention and a comparative polymer are used as a grinding aid agent for natural calcium carbonate. The different polymers are used at the same doses and under the same operating conditions.
    Aqueous suspensions of natural calcium carbonate are thus prepared having a solid content by weight of 74% ± 1%. They are prepared in the presence of an amount of 0.26% by dry weight of an aqueous solution of polymer, as a grinding aid agent, relative to the dry amount of calcium carbonate used in this operation grinding in order to reach the targeted particle size. The polymer solutions have a concentration of 35% ± 1% of active material and a pH of 8.5 ± 0.5. The raw material for preparing these aqueous suspensions is an aqueous suspension of coarse-grained calcium carbonate at 75% ± 1% by weight of solid. Calcium carbonate is a coarse marble (commercial product Omyacarb 10 AV Omya) from the region of Carrara (Italy). The grinding conditions are adjusted so as to obtain a suspension of mineral particles of which 60.0% ± 0.5% by weight of its population has an equivalent spherical diameter less than 2 pm (esd <2pm = 60% ± 0.5 %).
    The calcium carbonate suspensions are then analyzed and characterized by Brookfield viscosity measurements after the grinding operation and then after 8 days of rest at 25 ° C. The results are presented in Table 7.
    Suspension Polymer VB0 VB8 S3-1 3-1 98 276 S3-2 3-2 105 304 SC3 C3 123 450
    Table 7
    Again, the use of the grinding aid agents according to the invention makes it possible to prepare suspensions of ground calcium carbonate of low viscosity. The viscosities of these suspensions change over time over a period of 8 days in a lower manner than that of the suspension prepared in the presence of the comparative polymer. The suspensions prepared according to the invention therefore have lower viscosities than those of the suspension of the comparative test. They are more stable.
    权利要求:
    Claims (17)
    [1" id="c-fr-0001]
    1. Method for preparing particles of mineral matter comprising grinding, in the presence of water, at least one mineral matter in the presence of at least one polymer of molecular mass by weight Mw (measured by CES) of less than 8000 g / mol and of polymolecularity index IP less than 3, obtained by a radical polymerization reaction in water, at a temperature above 50 ° C., of at least one anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function, in the presence:
    sodium hypophosphite,
    disodium trithiocarbonate dipropionate (DPTTC) and at least one radical-generating compound chosen from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, hydrogen peroxide associated with an ion chosen from Fe 11 , Fe ni , Cu 1 , Cu 11 and their mixtures.
    [2" id="c-fr-0002]
    2. Method according to claim 1 for which:
    the particles have a size less than 50 μm or else a size ranging from 0.05 μm to 50 μm or else a size less than 10 μm, preferably less than 5 μm or 2 μm, more preferably less than 1 μm or less than 0.5 µm or the equivalent spherical diameter of the particles for a size ranging from 0.05 µm to 50 µm or less than 0.05 µm to 50 µm, preferably for a size less than 10 µm, more preferably less than 5 pm or 2 pm, even more preferably less than 1 pm or less than 0.5 pm, is equal to 60% by weight or equal to 70% by weight or even equal to 80% by weight or even equal to 90 % in weight.
    [3" id="c-fr-0003]
    3. Method according to one of claims 1 and 2 for which:
    only one mineral material or two or three mineral materials are used or for which:
    the mineral material is synthetic or of natural origin, preferably chosen from alkaline earth metal carbonate, preferably calcium carbonate (natural calcium carbonate or precipitated calcium carbonate), strontium carbonate, magnesium carbonate, barium carbonate , dolomite, kaolin, titanium dioxide, talc, lime, calcium sulfate, barium sulfate.
    [4" id="c-fr-0004]
    4. Method according to one of claims 1 to 3 for which the polymerization reaction is carried out in water or in a solvent mixed with water, in particular an alcoholic solvent, in particular isopropyl alcohol, preferably in l 'water.
    [5" id="c-fr-0005]
    5. Method according to one of claims 1 to 4 for which the polymer:
    has a weight average molecular weight Mw of less than 7,500 g / mol, preferably less than 6,500 g / mol, less than 6,000 g / mol, more preferably less than 5,500 g / mol or has a mean molecular weight of weight Mw greater than 1,000 g / mol or greater than 1,200 g / mol or greater than 1,500 g / mol or has a polymolecularity index IP less than 2.8 or a polymolecularity index IP ranging from 1.5 to 3 , from 1.5 to 2.8 or ranging from 1.5 to 2.5.
    [6" id="c-fr-0006]
    6. Method according to one of claims 1 to 5 for which the anionic monomer is chosen from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid and their mixtures, preferably acrylic acid.
    [7" id="c-fr-0007]
    7. Method according to one of claims 1 to 6 for which the polymerization reaction also implements at least one monomer chosen from:
    another different anionic monomer chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, their salts and mixtures thereof, a nonionic monomer comprising at least one polymerizable olefinic unsaturation, preferably at least one polymerizable ethylenic unsaturation and in particular a function polymerizable vinyl, more preferably a nonionic monomer chosen from esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid chosen from acrylic acid, methacrylic acid, and mixtures thereof, for example styrene, vinylcaprolactam, alkyl acrylate, in particular Ci-Cio-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n- acrylate butyl, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferred mainly methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, aryl acrylate, preferably phenylacrylate, benzylacrylate, phenoxyethylacrylate, aryl methacrylate, preferably phenylmethacrylate, phenylmethacrylate , a compound of formula (I):
    R'-fL'MLjn-R 2 (I) in which:
    o R 1 represents a polymerizable acrylate group or a polymerizable methacrylate group, o R 2 represents an OH group or an OCH3 group, o L 1 and L 2 , identical or different, independently represent an ethyloxy group or a propyloxy group and om and n , identical or different and at least one of which is different from 0, represent a number less than or equal to 150 and their sum m + n is less than 150 and
    2-acrylamido-2-methylpropane acid sulfonic, an acid salt 2-acrylamido-2-methylpropane sulfonic, the acid 2- (methacryloyloxy) ethanesulfonic, a acid salt 2- (methacryloyloxy) ethanesulfonic, methallyl sulfonate sodium, styrene sulfonate and mixtures thereof.
    [8" id="c-fr-0008]
    8. Method according to one of claims 1 to 6 for which the polymerization reaction implements:
    100% by weight of anionic monomer or from 70% to 99.5% by weight of anionic monomer and from 0.5% to 30% by weight of at least one monomer chosen from:
    o another different anionic monomer chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, their salts and their mixtures, a nonionic monomer comprising at least one polymerizable olefinic unsaturation, preferably at least one polymerizable ethylenic unsaturation and in particular a polymerizable vinyl function, more preferably a nonionic monomer chosen from esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid chosen from acrylic acid, methacrylic acid, and mixtures thereof, for example styrene , vinylcaprolactam, alkyl acrylate, in particular Ci-Cio-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n acrylate -butyl, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, aryl acrylate, preferably phenylacrylate, benzylacrylate, phenoxyethylacrylate, aryl methacrylate, phenylmethacrylate, phenylmethacrylate , a compound of formula (I):
    ^ - (l'mlVr 2 (I) in which:
    o R 1 represents a polymerizable acrylate group or a polymerizable methacrylate group, o R 2 represents an OH group or an OCH3 group, o L 1 and L 2 , identical or different, independently represent an ethyloxy group or a propyloxy group and om and n , identical or different and at least one of which is different from 0, represent a number less than or equal to 150 and their sum m + n is less than 150 and
    2-acrylamido-2-methylpropane sulfonic, an acidic salt
    2-acrylamido-2-methylpropane
    2- (methacryloyloxy) ethanesulfonic, sulfonic, a salt acid acid
    2- (methacryloyloxy) ethanesulfonic, sodium methallyl sulfonate, styrene sulfonate and their mixtures.
    [9" id="c-fr-0009]
    9. Method according to one of claims 1 to 8 for which the radical-generating compound is chosen from hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate and their mixtures.
    [10" id="c-fr-0010]
    10. Method according to one of claims 1 to 9 for which the polymerization reaction uses, relative to the amount by weight of monomer:
    from 2% to 8% by weight, preferably from 2.5% to 7% by weight or from 2.5% to 6% by weight of sodium hypophosphite or from 0.01% to 1.5% by weight , preferably from 0.01% to 1.2% by weight or from 0.05% to 1.5% by weight, more preferably from 0.05% to 1.2% by weight or from 0.1% to 1% by weight of disodium trithiocarbonate dipropionate (DPTTC) or
    - from 0.1% to 5% by weight of radical-generating compound or, preferably, from 0.5% to 4.5% by weight of hydrogen peroxide or 0.1% to 4% by weight of persulfate sodium, potassium persulfate or ammonium persulfate.
    [11" id="c-fr-0011]
    11. A method of preparing an aqueous suspension of particles of mineral material comprising the implementation of the grinding method according to one of claims 1 to 10, preferably an aqueous suspension in which the dry extract of mineral material is greater to 60% by weight, preferably greater than 70% by weight, more preferably greater than 75% by weight or 80% by weight of the suspension.
    [12" id="c-fr-0012]
    12. An aqueous composition comprising particles of ground mineral material and at least one polymer defined according to one of claims 1 to 10.
    [13" id="c-fr-0013]
    13. Composition according to claim 12 also comprising at least one adjuvant, in particular at least one adjuvant chosen from dispersing agents, anti-foaming agents, biocidal agents, coloring agents, lubricating agents and optical brighteners or at least one binding agent, in particular a natural binding agent such as starch or a synthetic binding agent such as a latex.
    [14" id="c-fr-0014]
    14. Method for preparing a paper coating sauce comprising grinding, in the presence of water, at least one mineral matter in the presence of at least one polymer obtained by a radical polymerization reaction in water, to a temperature above 50 ° C., of at least one anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function, in the presence of:
    sodium hypophosphite,
    disodium trithiocarbonate dipropionate (DPTTC) and at least one radical-generating compound chosen from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, hydrogen peroxide associated with an ion chosen from Fe 11 , Fe In , Cu 1 , Cu 11 and their mixtures.
    [15" id="c-fr-0015]
    15. Use as a grinding aid agent of at least one mineral material, of at least one polymer obtained by a radical polymerization reaction in water, at a temperature above 50 ° C., of at least one anionic monomer comprising at least one polymerizable olefinic unsaturation and a carboxylic acid function, in the presence of:
    sodium hypophosphite, disodium dipropionate trithiocarbonate (DPTTC) and
    - at least one radical-generating compound chosen from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, hydrogen peroxide associated with an ion chosen from Fe 11 , Fe In , Cu 1 , Cu 11 and their mixtures.
    [16" id="c-fr-0016]
    16. Use according to claim 15 for which the polymer is defined according to one of claims 1 to 10.
    [17" id="c-fr-0017]
    17. A method of preparing paper comprising the use of an aqueous composition according to one of claims 12 and 13.
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    同族专利:
    公开号 | 公开日
    MX2019006583A|2019-08-14|
    WO2018109400A1|2018-06-21|
    FR3060419B1|2018-11-30|
    EP3555152A1|2019-10-23|
    PT3555152T|2021-05-25|
    SI3555152T1|2021-08-31|
    KR20190097150A|2019-08-20|
    US20200255669A1|2020-08-13|
    BR112019010836A2|2019-10-01|
    ES2871553T3|2021-10-29|
    EP3555152B1|2021-02-24|
    CN110088151A|2019-08-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2900708A1|2012-09-26|2015-08-05|Coatex|Method for polymerising acrylic acid in solution, polymer solutions obtained and uses thereof|
    EP3074436A1|2013-11-26|2016-10-05|Coatex S.a.S|Method for polymerising meth acid in a solution, polymer solutions obtained and uses thereof|
    FR2873047B1|2004-07-13|2007-10-05|Coatex Soc Par Actions Simplif|PROCESS FOR MILLING MINERAL MATERIALS IN THE PRESENCE OF BINDERS, AQUEOUS SUSPENSIONS OBTAINED AND USES THEREOF|FR3088645B1|2018-11-16|2020-11-20|Coatex Sas|OSIDIC DISPERSING AGENT|
    FR3093012B1|2019-02-26|2021-01-22|Coatex Sas|REDUCTION OF HYGROSCOPICITY OF A MINERAL MATERIAL|
    FR3093011B1|2019-02-26|2021-02-19|Coatex Sas|REDUCTION OF HYGROSCOPICITY OF A MINERAL MATERIAL|
    CN111440259A|2020-04-23|2020-07-24|济宁明升新材料有限公司|Multi-branch type dispersing agent and preparation method thereof|
    法律状态:
    2017-11-13| PLFP| Fee payment|Year of fee payment: 2 |
    2018-06-22| PLSC| Publication of the preliminary search report|Effective date: 20180622 |
    2019-11-13| PLFP| Fee payment|Year of fee payment: 4 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 5 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1662582A|FR3060419B1|2016-12-16|2016-12-16|METHOD FOR GRINDING MINERAL MATERIAL|
    FR1662582|2016-12-16|FR1662582A| FR3060419B1|2016-12-16|2016-12-16|METHOD FOR GRINDING MINERAL MATERIAL|
    SI201730761T| SI3555152T1|2016-12-16|2017-12-14|Method for grinding mineral material|
    MX2019006583A| MX2019006583A|2016-12-16|2017-12-14|Method for grinding mineral material.|
    EP17822421.8A| EP3555152B1|2016-12-16|2017-12-14|Method for grinding mineral material|
    KR1020197020433A| KR20190097150A|2016-12-16|2017-12-14|Method for grinding minerals|
    US16/466,385| US20200255669A1|2016-12-16|2017-12-14|Method for grinding mineral material|
    PCT/FR2017/053571| WO2018109400A1|2016-12-16|2017-12-14|Method for grinding mineral material|
    BR112019010836A| BR112019010836A2|2016-12-16|2017-12-14|methods for preparing mineral matter particles, for preparing an aqueous suspension of mineral matter particles, aqueous composition, method for preparing a paper coating, use and method of preparing paper|
    CN201780077758.7A| CN110088151A|2016-12-16|2017-12-14|The method of grinding mineral materials|
    PT178224218T| PT3555152T|2016-12-16|2017-12-14|Method for grinding mineral material|
    ES17822421T| ES2871553T3|2016-12-16|2017-12-14|Procedure for grinding mineral material|
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