Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F11/00—Compounds of calcium, strontium, or barium
  • C01F11/18—Carbonates
  • C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
  • C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2/00—Lime, magnesia or dolomite
  • C04B2/02—Lime
  • C04B2/04—Slaking
  • C04B2/06—Slaking with addition of substances, e.g. hydrophobic agents ; Slaking in the presence of other compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
  • C08F222/08—Maleic anhydride with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/02—Compounds of alkaline earth metals or magnesium
  • C09C1/021—Calcium carbonates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

• the present invention relates to the use of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, to prepare an aqueous suspension of Precipitated Calcium Carbonate (PCC), said copolymers being optionally used in combination with at least one additive extinction.
• PCC Precipitated Calcium Carbonate
• CCN Natural Calcium Carbonate
• PCC Precipitated Calcium Carbonate
• Scalenohedral Precipitated Calcium Carbonate is, in particular, used as a mineral filler in combination with cellulose fibers in mass-load applications in paper.
• the methods of producing PCC include the steps of quenching a calcium oxide-containing material (commonly referred to as "quicklime") with water to produce a suspension of calcium hydroxide ( generally referred to as "lime milk”), followed by the subsequent synthesis of calcium carbonate by circulating carbon dioxide through said resultant calcium hydroxide slurry.
• Such methods produce PCC suspensions having a low solids content. Therefore, these methods generally include an additional concentration step to obtain a CCP slurry having a higher solids content, which is of interest in transporting the PCC slurry.
• additional steps of concentration are energy consuming, expensive and require the use of specific equipment (eg a centrifuge, requiring significant maintenance).
• the use of such equipment can lead to destroy the structure of the CCP formed, this is particularly the case, for example, the CCP-S prepared in the form of clusters.
• WO 2005/000742 A1 relates to a process for the preparation of lamellar PCC comprising the steps of providing a suspension of calcium hydroxide, carbonating said suspension, and adding a polyacrylate to the suspension before the end of the carbonation to precipitate lamellar calcium carbonate.
• the unpublished patent application FR 15 51690 filed in the name of the present applicants relates to the use of a cationic polymer, optionally in the presence of an extinguishing additive, in a process for producing an aqueous suspension of calcium carbonate. precipitate.
• the invention described in this document makes it possible to prepare suspensions of CCP having cationic surface charges, even at alkaline pH.
• patent application WO 2007/067146 A1 describes a process for preparing PCC in the presence of starch or carboxymethylcellulose (CMC).
• CMC carboxymethylcellulose
• the unpublished patent application FR 15 56789 filed in the name of the present applicants relates to the use of a depolymerized carboxylated cellulose solution to prepare an aqueous suspension of Precipitated Calcium Carbonate (PCC), said depolymerized carboxylated cellulose solution having an extract dry matter of between 25% and 40% by weight relative to the total weight of the solution and said depolymerized carboxylated cellulose having a molecular weight of between 10 000 g / mol and 40 000 g / mol, in a process for producing a suspension aqueous precipitated calcium carbonate.
• PCC Precipitated Calcium Carbonate
• Document FR 3017872 describes a process for the preparation of particles by dry grinding of natural calcium carbonate and not of PCC.
• WO 99/51691 discloses a method for preparing PCC which comprises a step of removing water to increase the concentration.
• EP 0467287 describes the preparation of a PCC dispersion which uses a maleic anhydride copolymer but does not disclose the use of such a polymer during the preparation of the PCC as such.
• An object of the present invention is to provide a solution for the production of CCP suspensions having, for example, a high solids content, without resorting to an additional step of thermal or mechanical concentration.
• Another object of the present invention is to provide a solution for the production of CCP suspensions with a high dry matter content having easily manageable viscosities, that is to say a solution for increasing the solids content of the solids. CCP suspensions, while preventing the increase of the viscosity of the suspensions. It is also desirable that said solution does not adversely affect the kinetics of the carbonation step and / or does not alter the crystallographic structure of the PCC.
• Another object of the present invention is to provide a solution for the preparation of PCC slurries for direct use as a mineral filler in a papermaking process.
• the present invention relates to the use of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, to prepare an aqueous suspension of Precipitated Calcium Carbonate (PCC) by extinguishing a material containing calcium oxide. in water and then carbonation of the milk of lime thus obtained.
• PCC Precipitated Calcium Carbonate
• the present invention further relates to the use of a combination of at least one copolymer obtained by polymerization of maleic anhydride and styrene, functionalized or not, and at least one extinguishing additive in a process of production of an aqueous suspension of precipitated calcium carbonate.
• the present invention also relates to the use of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, to prepare dry Calcium Calcium Carbonate (PCC) by extinguishing an oxide-containing material. of calcium in water, carbonation of the milk of lime thus obtained and at least drying of the suspension of CCP.
• PCC Calcium Calcium Carbonate
• Calcium oxide-containing material means a mineral or synthetic material having a calcium oxide content of not less than 50% by weight, for example not less than 75% by weight, or at least less than 90% by weight or at least 95% by weight relative to the total weight of the material containing calcium oxide.
• Mineral material means a solid substance having a defined inorganic chemical composition and a crystalline and / or amorphous characteristic structure.
• Natural Calcium Carbonate means calcium carbonate obtained from natural sources such as limestone, marble or chalk and subjected to a wet and / or dry treatment such as grinding sieving and / or fractionation, for example using a cyclone or a sorter.
• Precipitated Calcium Carbonate is meant a synthetic material generally obtained by precipitation following the reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous medium or by precipitation of a source of calcium and a source of carbonate in the water.
• the precipitated calcium carbonate may also be the product for introducing calcium and carbonate salts, calcium chloride and sodium carbonate, for example in an aqueous medium.
• the PCC can be in the form of vaterite, calcite or aragonite. The PCCs are described, for example, in EP 2447213 A1, EP 2524898 A1 and EP 2371766 A1.
• the "dry matter content” or “dry extract” of a liquid composition is a measure of the amount of material remaining after evaporation of all solvents or water.
• the value d x represents the diameter for which x% by weight of the particles have a diameter less than d x .
• the value dm is also called “top cut”.
• the dso value is referred to as the median particle size by weight, i.e. 50% by weight of the particles have a diameter smaller or larger than this particle size.
• the particle size is indicated as the median particle size by weight dso unless otherwise indicated.
• a Sedigraph 5100 or 5120 device from Micromeritics, USA, can be used.
• a "specific surface according to the BET (SS) method” within the meaning of the present invention, is defined as being the surface of the particles of precipitated calcium carbonate divided by the mass of the PCC particles.
• the specific surface area is measured by N 2 adsorption using BET isotherms (ISO 9277: 1995) and is reported in m 2 / g.
• stable in an aqueous suspension having a pH of 12 and a temperature of 90 ° C means that the polymeric additive retains its physical properties and its chemical structure when it is added to an aqueous suspension having a pH of 12 and a temperature of 90 ° C.
• the polymeric additive retains its dispersion qualities and is not depolymerized or degraded under said conditions.
• viscosity or “Brookfield viscosity” refers to Brookfield viscosity. Brookfield viscosity is measured using a Brookfield viscometer (RVT type) at 25 ° C. ⁇ 1 ° C. at 100 rpm using a suitable motive and is indicated in mPa.s.
• the "water-soluble” materials are defined as materials which, when mixed with deionized water and filtered on a filter having a pore size of 0.2 ⁇ at 20 ° C to recover the liquid filtrate, lead to a mass less than or equal to 0.1 g of solid material recovered after evaporation between 95 ° C and 100 ° C of 100 g of said liquid filtrate.
• “Water-soluble” materials are defined as materials leading to a mass greater than 0.1 g of solid material recovered after evaporation between 95 ° C and 100 ° C of 100 g of said liquid filtrate.
• a “suspension”, within the meaning of the present invention, comprises insoluble solids and water, and possibly other additives. It is likely to contain large amounts of solids and therefore to be more viscous and to have a higher density than the liquid of which it is formed.
• copolymers referred to in the context of the present invention result from the polymerization of monomers of maleic anhydride and styrene monomers. Mention may be made, by way of illustration, of low molecular weight copolymers of maleic anhydride and styrene and their derivatives.
• copolymer derivatives of maleic anhydride and styrene having:
• the units x, y and z are arranged in blocks, randomly, alternately or statistically, - x is non-zero and at least one of y or z is also non-zero, the sum of x + y + z being less than or equal to 150,
• R 1 represents H or a sulphonated group
• P 2 represents a heteroatom, optionally substituted by an alkyl chain, an alkenyl chain, a heteroalkyl chain and / or a polyalkoxylated chain
• R 3 and R 4 independently of each other, represent OH, (O ⁇ , M + ), an O-alkyl chain comprising between 1 and 20 carbon atoms, an N-alkyl chain comprising between 1 and 20 carbon atoms and / or a polyalkoxylated chain
• M + represents a monovalent, divalent or trivalent cation.
• sulfonated group means a group -SO3H or - (SO3 " , M + ), the term” heteroatom "means an atom of oxygen, sulfur, nitrogen, silicon or phosphorus,
• alkyl a linear, branched or cyclic, saturated, optionally substituted, carbon radical comprising from 1 to 20 carbon atoms,
• alkenyl a linear, branched or cyclic carbon radical containing one or more unsaturations, optionally substituted, comprising from 2 to 20 carbon atoms,
• heteroalkyl an alkyl radical as defined above, said alkyl system comprising at least one heteroatom, in particular chosen from the group comprising sulfur, oxygen, nitrogen, phosphorus and silicon and
• polyalkoxylated chain means a chain of type [(EO) n (PO) n '(BO) n "] -Z, consisting of alkoxylated units, randomly, alternately or statistically distributed, in blocks; of the ethoxylated units EO, the propoxylated units PO and the butoxylated units BO, n, n ', n "representing, independently of each other, 0 or an integer ranging from 1 to 150, the sum of n, n' and n '' not being zero and Z represents an alkyl chain comprising between 1 and 20 carbon atoms, for example 1 or 2 carbon atom (s).
• copolymers according to the invention are obtained by polymerization of at least two different monomers, according to methods known and described.
• the units x in formula (I) are derived from polymerizable monomers of the styrene type, optionally modified before or after polymerization.
• the units may in particular be subjected to total or partial sulfonation, after polymerization.
• the copolymer according to the invention may comprise styrene units as such and / or styrene units substituted with a sulphonated group.
• the units y and z are derived from maleic anhydride monomers, optionally modified before or after polymerization.
• the copolymer consists of units x and units y.
• the copolymer consists of units x and units z.
• the copolymer consists of units x and units y and units z.
• the copolymer consists of styrene type x units, as well as sulfonated styrene type x units and y and z units.
• the molar ratio between the units x on the one hand, and the units y and / or z on the other hand, within the copolymer can vary between 10: 1 and 1: 2 or between 5: 1 and 1: 2.
• the molar ratio between the units x on the one hand, and the units y and / or z on the other hand, within the copolymer is 1: 1, 2: 1 or 3: 1.
• Said copolymers or derivatives used in the context of the present invention are in acid form or in neutralized form.
• the copolymers according to the invention are wholly or partially.
• M + is, for example, selected from calcium (Ca 2+ ), magnesium (Mg 2+ ), lithium (Li + ), sodium (Na + ), potassium (K + ) and ammonium (NH 4 + ). M + may also be ammonium.
• the degree of neutralization and the concentration of the polymer can be adapted so that the polymer remains soluble.
• a copolymer of the following formula (II) is used:
• the units x and y are arranged in blocks, randomly, alternately or statistically, x and y are non-zero, the sum of x + y being less than or equal to 150,
• R 1 represents H or a sulphonated group
• P 2 represents a heteroatom, optionally substituted by an alkyl chain, an alkenyl chain, a heteroalkyl chain and / or a polyalkoxylated chain.
• the units x and z are arranged in blocks, randomly, alternately or statistically, x and z are non-zero, the sum of x + z being less than or equal to 150,
• R 1 represents H or a sulphonated group
• P 3 represents OH, (O ⁇ , M + ), an O-alkyl chain comprising between 1 and 20 carbon atoms, an N-alkyl chain comprising between 1 and 20 carbon atoms and / or a polyalkoxylated chain and
• M + represents a monovalent, divalent or trivalent cation.
• the group R 2 represents a heteroatom, optionally substituted with an alkyl chain, an alkenyl chain, a heteroalkyl chain and / or a polyalkoxylated chain.
• the group R 2 represents an atom of O.
• the group R 2 represents an N atom substituted by an alkyl chain, an alkenyl chain, a heteroalkyl chain and / or a chain polyalkoxylated.
• the N atom can in particular be substituted with an alkyl chain bearing a primary, secondary or tertiary ammonium function.
• the group R 2 represents N-CH 2 -CH 2 -N (CH 3) 2 .
• the groups R 3 and R 4 independently of each other, represent OH, (O " , M + ), an O-alkyl chain comprising between 1 and 20 carbon atoms. , an N-alkyl chain comprising between 1 and 20 carbon atoms and / or a polyalkoxylated chain.
• the groups R 3 and R 4 represent (O " , M + ), for example (O " , NH 4 + ).
• the groups R 3 and R 4 represent for one OH and the other an O-alkyl chain comprising between 1 and 20 carbon atoms.
• the groups R 3 and R 4 represent, for one (O " , M + ), for example (O " , NH 4 + ), and for the other, an O-alkyl chain comprising between 1 and 20 carbon atoms.
• the copolymer is such that it comprises two different types of z units.
• part of the units z of the copolymer according to the invention is such that the groups R 3 and R 4 represent (O " , M + ), for example (O " , NH 4 + ).
• Another part of the units z of the copolymer is such that the groups R 3 and R 4 represent for one (O " , M + ), for example (O " , NH 4 + ), and for the other, a chain O-alkyl comprising between 1 and 20 carbon atoms.
• the groups R 3 and R 4 represent for one (O " , M + ), for example (O " , NH 4 + ), and for the other a polyalkoxylated chain, for example -C 4 H 8 -O-CH 2 -CH 3 .
• the copolymer according to the invention is in the form of a solution, in the form of a powder, in the form of a resin or in the form of flakes ("flakes" in English).
• the copolymers have a molecular weight of less than 100,000 g / mol, for example less than 50,000 g / mol or less than 15,000 g / mol or 12,000 g / mol.
• the copolymers have a molecular weight greater than 1000 g / mol.
• the molecular weight of the copolymers according to the invention is determined by Steric Exclusion Chromatography (CES) or in English “Gel Permeation Chromatography” (GPC). Material containing calcium oxide
• the aqueous suspension of PCC is prepared by extinguishing a material containing CaO calcium oxide.
• a calcium oxide-containing material is provided in the process for producing an aqueous suspension of precipitated calcium carbonate.
• Said material containing calcium oxide can be obtained by calcining a material containing calcium carbonate. Calcination is a heat treatment process applied to the calcium carbonate containing material to cause thermal decomposition leading to the formation of calcium oxide and gaseous carbon dioxide.
• the calcium carbonate-containing materials that can be used in such a calcination process are those selected from the group consisting of precipitated calcium carbonates, natural calcium carbonate-containing minerals such as marble, limestone and chalk, and minerals containing a mixture of alkaline earth carbonates including calcium carbonate such as dolomite or calcium carbonate rich fractions from other sources. It is also possible to subject a residual material containing calcium carbonate to a calcination process to obtain a material containing calcium oxide.
• calcination step can be performed under conditions and using equipment well known to those skilled in the art. In general, calcination may be carried out in furnaces or reactors (sometimes referred to as furnaces) of various designs, including shaft furnaces, rotary kilns, multi-furnace furnaces and fluidized bed reactors.
• the end of the calcination reaction can be determined, for example, by monitoring the change in density, the residual carbonate content, for example by X-ray diffraction, or the extinction reactivity by common methods.
• the material containing calcium oxide is obtained by calcining a material containing calcium carbonate, for example selected from the group consisting of precipitated calcium carbonate, natural minerals containing calcium carbonate such as marble, limestone and chalk; minerals containing a mixture of alkaline earth carbonates including calcium carbonate such as dolomite or mixtures thereof.
• a material containing calcium carbonate for example selected from the group consisting of precipitated calcium carbonate, natural minerals containing calcium carbonate such as marble, limestone and chalk; minerals containing a mixture of alkaline earth carbonates including calcium carbonate such as dolomite or mixtures thereof.
• the calcium oxide-containing material has a minimum calcium oxide content of at least 75% by weight, preferably at least 90% by weight, and preferably at least 90% by weight. most preferred of 95% by weight in relation to the total weight of the material containing calcium oxide.
• the material containing calcium oxide consists of calcium oxide.
• the material containing calcium oxide may consist of a single type of material containing calcium oxide.
• the calcium oxide-containing material may consist of a mixture of at least two types of calcium oxide-containing materials.
• the material containing calcium oxide can be used in the process of the invention in its original form, that is to say in the form of raw material, for example more or less large pieces.
• the calcium oxide-containing material can be milled before use.
• the material containing calcium oxide is in the form of particles having a median particle size by weight dso ranging from 0.1 ⁇ to 1000 ⁇ and, for example, from 1 ⁇ to 500 ⁇ .
• the present invention relates to the use of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, to prepare a Precipitated Calcium Carbonate (PCC).
• PCC Precipitated Calcium Carbonate
• the present invention relates to the use of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, to prepare a Precipitated Calcium Carbonate (PCC) in dry form or in the form of an aqueous solution or suspension aqueous.
• PCC Precipitated Calcium Carbonate
• the processes for producing an aqueous suspension of PCC generally include the steps of (i) preparing a lime milk by mixing water and the calcium oxide containing material, and optionally the at least one additive of quenching, and (ii) carbonating the lime milk obtained in step (i) to form an aqueous suspension of precipitated calcium carbonate.
• carbonate is meant to circulate carbon dioxide in the suspension of calcium hydroxide Ca (OH) 2 , so as to form calcium carbonate CaCO 3 precipitated.
• at least one copolymer obtained by polymerization of maleic anhydride and styrene, functionalized or not, is used to prepare an aqueous suspension of Precipitated Calcium Carbonate (PCC) by extinguishing an oxide-containing material. of calcium in water then carbonation of the milk of lime thus obtained.
• PCC Precipitated Calcium Carbonate
• a lime milk is prepared by mixing water, the material containing calcium oxide, copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, and optionally the at least one extinguishing additive.
• said copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, are present in the extinguishing water of the material containing calcium oxide.
• the temperature of the water, which is used in the quenching step is adjusted to be in the range of 0 ° C to 100 ° C, for example 1 ° C to 70 ° C or 2 ° C to 50 ° C or ° C to 50 ° C or 35 ° C to 45 ° C.
• the initial temperature of the water is not necessarily the same as the temperature of the mixture prepared in the quenching step because of the highly exothermic nature of the quenching reaction and or the mixture of substances having different temperatures.
• the process extinction step comprises the steps of:
• step a1) is carried out at a temperature of between 0 ° C. and 99 ° C., for example between 1 ° C. and 70 ° C. or between 2 ° C. and 50 ° C. or between 30 ° C. and 50 ° C or between 35 ° C and 45 ° C.
• the step of quenching the process comprises the steps of:
• step b2) add water to the mixture of step b1).
• the material containing calcium oxide, the copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or otherwise, optionally the at least one extinguishing additive and water are mixed simultaneously.
• the at least one extinguishing additive is added before or after the quenching step of the process.
• copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, may be added to the quenching step in whole or in several parts, for example in two, three, four, five or more parts.
• the quenching step of the process can be carried out at room temperature, ie at a temperature of 20 ° C ⁇ 2 ° C or at an initial temperature of between 30 ° C and 50 ° C or between ° C and 45 ° C.
• the reaction being exothermic, the temperature generally reaches a temperature between 85 ° C and 99 ° C during step i), preferably a temperature between 90 ° C and 95 ° C.
• step i) of the process is carried out by mixing or stirring, for example with mechanical stirring. Equipment suitable for mixing or stirring the process is known to those skilled in the art.
• the progress of the quenching reaction can be observed by measuring the temperature and / or the conductivity of the reaction mixture.
• the inventors have surprisingly found that the addition of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, as defined previously and optionally of an extinguishing additive as defined above, before or during Extinguishing stage of a process for the production of CCP, may allow the preparation not only of a lime milk having a low dry matter content but also of a lime milk having a high dry matter content. Indeed, it is It is interesting to note that, according to one aspect of the invention, by carbonating said highly concentrated lime milk, it is possible to obtain an aqueous suspension of PCC which also has a high solids content. Accordingly, the process of the present invention does not require an additional concentration step to obtain a CCP slurry having a high solids content.
• the lime milk of the quenching step has a dry matter content of at least 8% by weight, for example ranging from 10% to 66% by weight or 15% by weight. % to 45% by weight or for example from 20% to 40% by weight or for example from 25% to 37% by weight relative to the total weight of the milk of lime.
• the lime milk of the quenching step has a Brookfield viscosity ranging from 1 mPa.s to 1000 mPa.s at 25 ° C, for example from 5 mPa.s to 800 mPa.s at 25 ° C or for example 10 mPa.s at 500 mPa.s at 25 ° C, as measured at 100 rpm.
• the lime milk of the quenching step has a Brookfield viscosity ranging from 1 mPa.s to 1000 mPa.s at 25 ° C, for example 5 mPa.s at 800 mPa.s at 25 ° C or, for example, from 10 mPa.s to 500 mPa.s at 25 ° C, as measured at 100 rpm, at a solids content of at least 8% by weight for example ranging from 10% to 66% by weight or from 15% to 45% by weight or for example from 20% to 40% by weight or for example from 25% to 37% by weight relative to the total weight of the milk of lime.
• additional water may be introduced during the quenching reaction to control and / or maintain and / or reach the dry matter content or Brookfield viscosity of the milk of the invention. desired lime.
• the quench step of the process can be performed as a batch, semi-continuous or continuous process.
• the calcium oxide-containing material and the water may be mixed in a weight ratio of from 1: 1 to 1: 12, for example from 1: 2 to 1:12, for example from 1: 2.5 to 1: 6.
• said copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, are used in combination with at least one extinguishing additive.
• the at least one extinguishing additive may be chosen from the group consisting of organic acids, organic acid salts, sugar alcohols, monosaccharides, disaccharides, polysaccharides, gluconates, phosphonates, lignosulfonates and mixtures thereof.
• the at least one extinguishing additive is selected from the group consisting of sodium citrate, potassium citrate, calcium citrate, magnesium citrate, monosaccharides, disaccharides, polysaccharides, sucrose, sugar alcohols, meritol, citric acid, sorbitol, sodium salt of diethylenetriamine pentaacetic acid, gluconates, phosphonates, sodium tartrate, sodium lignosulfonate, calcium lignosulfonate and their mixtures.
• the lime milk obtained at the end of the quenching step is carbonated. to form an aqueous suspension of precipitated calcium carbonate.
• Carbonation is carried out by means and under conditions well known to those skilled in the art.
• the introduction of carbon dioxide into the milk of lime rapidly increases the concentration of carbonate ions (CO3 2 ) and the calcium carbonate is formed.
• the carbonation reaction can be easily controlled taking into account the reactions involved in the carbonation process.
• the carbon dioxide dissolves, according to its partial pressure, to form carbonate ions via the formation of carbonic acid (H2CO3) and unstable hydrogen carbonate ions (HCO3) in alkaline solution.
• H2CO3 carbonic acid
• HCO3 unstable hydrogen carbonate ions
• the carbonation is carried out by incorporating pure carbon dioxide gas or technical gases containing at least 10% by volume of carbon dioxide in the milk of lime.
• the progress of the carbonation reaction can be easily observed by measuring the conductivity and / or the pH.
• the pH of the milk of lime before the addition of carbon dioxide will be greater than 10, generally between 11 and 12.5 and will decrease continuously until a pH of about 7 is reached. then be stopped.
• the conductivity decreases slowly during the carbonation reaction and then decreases rapidly to low values when the precipitation is complete.
• the Progression of carbonation can be monitored by measuring the pH and / or conductivity of the reaction mixture.
• the temperature of the lime milk obtained at the end of the quenching step, which is used in the carbonation step is adjusted to be included in the range from 20 ° C to 60 ° C and, for example, from 30 ° C to 50 ° C. It will be apparent to those skilled in the art that the initial temperature of the lime milk is not necessarily the same as the temperature of the mixture prepared in the carbonation step because of the exothermic nature of the carbonation reaction and / or mixture of substances having different temperatures.
• the carbonation step is carried out at a temperature of between 5 ° C. and 95 ° C., for example 30 ° C. to 70 ° C. and, for example, 40 ° C. C at 60 ° C.
• the carbonation stage of the process can be carried out as a batch, semi-continuous or continuous process.
• the process for producing PCC involving the quenching and carbonation steps of the process is carried out as a batch, semi-continuous or continuous process.
• the process for producing PCC does not comprise a step of concentrating the aqueous suspension of precipitated calcium carbonate obtained in the quenching and carbonation stages of the process.
• the present invention relates to the use of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, in a process for the preparation of CCP, more precisely in the step of preparing a milk of lime which must to be carbonated afterwards.
• the use of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, during the process for the preparation of PCC confers on the aqueous suspensions of PCC produced a Zeta potential lower than 4 mV, for example less than 0 mV, but higher than the potential Zeta of a PCC prepared in the presence of negatively charged polymers, for example polymers of (meth) acrylic acid, especially those described in application WO 2005/000742 A1, which remains an advantage for the application mass load .
• the aqueous suspensions of PCC obtained using the copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not are characterized in that they have a Zeta potential of less than 4 mV, for example less than 0 mV, for example between 0 mV and - 40 mV, for example between 0 mV and - 30 mV.
• the use of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, during the process for the preparation of the PCC confers on the aqueous suspensions of PCC produced a Mutek load of less than 0 ⁇ eq / g .
• the aqueous suspensions of PCC obtained using the copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not are characterized in that they have a Mutek load of less than 0 ⁇ eq / g of suspension (as it is), for example between 0 ⁇ eq / g and -1 ⁇ eq / g or between 0 ⁇ eq / g and -0.8 ⁇ eq / g.
• the copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not are added during the first step of the process of producing PCC, that is to say that the copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, are added before or during the quenching step.
• the milk of lime known to those skilled in the art, obtained by extinguishing a material containing calcium oxide with water generally has a pH of between 11 and 12.5 measured at a temperature of 25 ° C. C according to the concentration of the material containing calcium oxide in the milk of lime.
• the temperature of the milk of lime can reach a temperature above 80 ° C, for example between 80 ° C and 99 ° C.
• the copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, used in the context of the present invention are chosen so as to be stable in an aqueous suspension having a pH of 12 and a temperature of 90 ° C.
• stable in an aqueous suspension having a pH of 12 and a temperature of 90 ° C means that the polymeric additives retain their physical properties and their chemical structure when added to an aqueous suspension having a pH of 12 and a temperature of 90 ° C.
• the polymeric additives retain their dispersing qualities and are not degraded under said conditions.
• the copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not are added in an amount ranging from 0.01% by weight to 2% by weight, for example from 0 From 0.02% by weight to 1% by weight and, for example, from 0.05% by weight to 0.5% by weight relative to the total weight of the material containing calcium oxide.
• At least one extinguishing additive can be used in addition to the copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not.
• said copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, are used in combination with at least one extinguishing additive.
• the at least one extinguishing additive may be chosen from the group consisting of organic acids, organic acid salts, sugar alcohols, monosaccharides, disaccharides, polysaccharides, gluconates, phosphonates, lignosulfonates and their mixtures.
• the at least one extinguishing additive is chosen from the group consisting of sodium citrate, potassium citrate, calcium citrate, magnesium citrate, monosaccharides and disaccharides. polysaccharides, sucrose, sugar alcohols, meritol, citric acid, sorbitol, sodium salt of diethylenetriamine pentaacetic acid, gluconates, phosphonates, sodium tartrate, sodium lignosulfonate, calcium lignosulfonate and mixtures thereof.
• the at least one extinguishing additive is sodium citrate and / or sucrose.
• the at least one extinguishing additive used consists of a single type of extinguishing additive.
• the at least one extinguishing additive used may consist of a mixture of at least two types of extinguishing additives.
• the at least one extinguishing additive may be added in an amount of from 0.01% by weight to 2% by weight based on the total amount of the oxide-containing material.
• calcium for example in an amount of from 0.05% by weight to 1% by weight, for example from 0.06% by weight to 0.8% by weight or, for example, from 0.07% by weight to 0, 5% by weight.
• the addition of an extinguishing additive may be useful for controlling the size of the PCC particles and their crystalline morphology without affecting the viscosity of the aqueous suspension.
• the inventors have surprisingly found that the addition of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or otherwise, as defined above, possibly combined with the addition of a polyisocyanate additive. extinguishing before or during the quenching step of a CCP production process may allow the preparation of a PCC slurry having a high solids content. It is also believed that omitting a concentration step improves the quality of the PCC particles produced since particle surface damage, which may occur during the concentration step, is avoided.
• PCC slurry can be further concentrated to a solids content of 52% by weight with acceptable viscosities, for example Brookfield viscosities less than or equal to 1000 mPa.s at 25 ° C and at 100 rpm.
• the process for producing precipitated calcium carbonate may include additional steps.
• Lime milk can be sieved to remove oversized particles.
• a suitable sieve may comprise, for example, a sieve having a size of 100 ⁇ to 700 ⁇ , for example about 100 ⁇ or about 300 ⁇ .
• the lime milk is sieved after the quenching step and before the carbonation step, for example using a sieve having a size ranging from 100 ⁇ to 300. ⁇ .
• the process for producing precipitated calcium carbonate may further comprise an additional step of separating the precipitated calcium carbonate from the aqueous suspension obtained at the end of the carbonation step.
• separation means that the CCP is removed or isolated from the aqueous suspension obtained at the carbonation stage of the process.
• Any conventional separation means known to those skilled in the art can be used, for example a mechanical and / or thermal means.
• mechanical separation processes are filtration, for example by means of a drum filter or a filter press, nanofiltration or centrifugation.
• An example of a separation process Thermal is a concentration process by applying heat, for example in an evaporator.
• the CCP obtained can be converted, for example deagglomerated or subjected to a dry grinding step. It can also be milled wet in the form of suspension. If the PCC is subjected to dehydration, dispersion and / or milling steps, these steps can be accomplished by methods known in the art. Wet milling can be carried out in the absence or in the presence of a grinding aid agent. Dispersants may also be included to prepare dispersions where appropriate.
• the process for producing precipitated calcium carbonate may further comprise an additional step of drying the precipitated calcium carbonate, for example separated precipitated calcium carbonate obtained at the end of the separation step described above.
• drying refers to a process in which at least a portion of the water is removed from a material to be dried, so that a constant weight of the "dry” material obtained at 120 ° C is achieved.
• a “dry” material may be further defined by its total moisture content which, unless otherwise indicated, is less than or equal to 1.0% by weight, preferably less than or equal to 0.5% by weight. weight, more preferably less than or equal to 0.2% by weight and most preferably between 0.03% by weight and 0.07% by weight relative to the total weight of the dry material.
• the drying step may be carried out using any suitable drying equipment and may, for example, include thermal drying and / or drying under reduced pressure using equipment such as an evaporator, flash dryer, oven, spray dryer and / or drying in a vacuum chamber.
• the drying step results in a dry precipitated calcium carbonate having a low total moisture content which is less than or equal to 1.0% by weight based on the total weight of the dry precipitated calcium carbonate.
• the precipitated calcium carbonate obtained by the process of the invention may be post-treated, for example during and / or after a drying step, by an additional component.
• the precipitated calcium carbonate is treated with a fatty acid, for example stearic acid, a silane or phosphoric esters of fatty acid.
• the precipitated calcium carbonate obtained has a median particle size by weight dso ranging from 0.1 ⁇ to 100 ⁇ , by example of 0.25 ⁇ to 50 ⁇ , for example 0.3 ⁇ to 5 ⁇ and, for example, 0.4 ⁇ to 3.0 ⁇ .
• the precipitated calcium carbonate may have a crystalline aragonite, calcite or vaterite structure or mixtures of these structures. Another advantage of the present invention is that the crystalline structure and morphology of precipitated calcium carbonate can be controlled, for example by adding seed crystals or other structural modifying chemicals. According to a preferred embodiment, the precipitated calcium carbonate obtained by the process of the invention has a scalenohedral crystalline structure in clusters.
• the BET specific surface area of the precipitated calcium carbonate obtained by the process according to the present invention may range from 1 m 2 / g to 100 m 2 / g, for example from 2 m 2 / g to 70 m 2 / g, for example from 3 m 2 / g to 50 m 2 / g, for example from 4 m 2 / g to 30 m 2 / g, measured using nitrogen and the BET method according to ISO 9277.
• the BET specific surface area of Precipitated calcium carbonate obtained by the process of the present invention can be controlled using additives, for example surfactants, which involve shearing during the precipitation step or subsequently high mechanical shear rates leading to only at a small particle size but also at a high BET specific surface area.
• additives for example surfactants, which involve shearing during the precipitation step or subsequently high mechanical shear rates leading to only at a small particle size but also at a high BET specific surface area.
• the suspension of precipitated calcium carbonate obtained has a solids content of at least 10% by weight, for example ranging from 20% by weight to 50% by weight, for example 25% by weight to 45% by weight or for example from 30% by weight to 40% by weight relative to the total weight of the suspension.
• the PCC slurry has a Brookfield viscosity less than or equal to 1500 mPa.s at 25 ° C, for example less than or equal to 1000 mPa.s at 25 ° C or 800 mPa.s at 25 ° C or for example less than or equal to 600 mPa.s at 25 ° C as measured at 100 rpm.
• the PCC suspension when no extinguishing additive is used, has a Brookfield viscosity less than or equal to 2500 mPa.s at 25 ° C, for example less than or equal to 2000 mPa.s at 25 ° C or 1000 mPa.s at 25 ° C or for example less than or equal to 800 mPa.s at 25 ° C as measured at 100 rpm.
• Another aspect of the present invention relates to the use of a combination of copolymers obtained by polymerization of maleic anhydride and styrene, functionalized or not, and an extinguishing additive in a process for producing an aqueous suspension of precipitated calcium carbonate, wherein:
• the copolymer has a following formula (I):
• the units x, y and z are arranged in blocks, randomly, alternately or statistically,
• x is non-zero and at least one of y or z is also non-zero, the sum of x + y + z being less than or equal to 150,
• R 1 represents H or a sulphonated group
• R 2 represents a heteroatom, optionally substituted by an alkyl chain, an alkenyl chain, a heteroalkyl chain and / or a polyalkoxylated chain,
• R 3 and R 4 independently of each other, represent OH, (O " , M + ), an O-alkyl chain comprising between 1 and 20 carbon atoms, an N-alkyl chain comprising between 1 and 20 carbon atoms and / or a polyalkoxylated chain and
• M + represents a monovalent, divalent or trivalent cation and the extinguishing additive is selected from the group consisting of organic acids, organic acid salts, sugar alcohols, monosaccharides, disaccharides, polysaccharides, gluconates, phosphonates, lignosulfonates and mixtures thereof.
• said aqueous suspension of precipitated calcium carbonate thus obtained is used in formulations of the technical field of paper, plastic or paint.
• Such a technique implements a WATERS TM brand liquid chromatography apparatus equipped with a detector.
• This detector is a WATERS TM refractometric concentration detector.
• This liquid chromatography apparatus is provided with a steric exclusion column appropriately chosen by those skilled in the art in order to separate the different molecular weights of the polymers studied.
• the liquid elution phase is an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05M NaHCO 3, 0.1M NaNO 3, 0.02M trietanolamine and 0.03% NaN 3 .
• the copolymer is diluted to 0.9% dry in the solvent for solubilization of the CES, which corresponds to the liquid phase of elution of the CES to which 0.04% of dimethylformamide is added. which acts as a flow marker or internal standard. Then, it is filtered at 0.2 ⁇ . 100 ⁇ ⁇ are then injected into the chromatograph (eluent: an aqueous phase adjusted to pH 9.00 by N sodium hydroxide containing 0.05 M NaHC0, NaN0 0.1M, 0.02M and triétanolamine 0.03% NaN 3 ).
• the liquid chromatography apparatus contains an isocratic pump (WATERS TM 515) with a flow rate of 0.8 mL / min.
• the chromatography apparatus also comprises an oven which, itself, comprises in series the following system of columns: a precolumn GUARD COLUMN type ULTRAHYDROGEL WATERS TM 6 cm long and 40 mm internal diameter and a linear column type ULTRAHYDROGEL WATERS TM 30 cm long and 7.8 mm inside diameter.
• the detection system consists of a RI WATERS TM 410 type refractometric detector.
• the oven is heated to a temperature of 60 ° C and the refractometer is heated to a temperature of 45 ° C.
• the chromato graphie is calibrated with powdered polyacrylate standards of various molecular weights certified for the supplier: POLYMER STANDARD SERVICE or AMERICAN POLYMER STANDARDS CORPORATION. Brookfield Viscosity
• the Brookfield viscosity of the aqueous suspensions was measured after one hour of production and after one minute of stirring at 25 ° C. ⁇ 1 ° C. at 100 rpm using an RVT type Brookfield viscometer fitted with a suitable disk rotor. , for example a mobile 2 to 5.
• the pH of a slurry or solution was measured at 25 ° C using a Mettler Toledo Seven Easy pH meter and a Mettler Toledo InLab® Expert Pro pH electrode.
• a three-point calibration (according to the segmentation method) of the instrument was performed initially using commercially available buffer solutions (from Sigma-Aldrich Corp., USA) having a pH of 4.7. and 10 to 20 ° C.
• the reported pH values are the terminal values detected by the instrument (the measurement is complete when the measured signal differs by less than 0.1 mV from the average over the last 6 seconds).
• the particle size distribution of the prepared PCC particles was measured using a Sedigraph 5100 from Micromeritics, USA.
• the method and the instrument are known to those skilled in the art and are commonly used to determine the grain size of mineral fillers and pigments.
• the measurement was carried out in an aqueous solution comprising 0.1% by weight Na 2 P 2 O 7.
• the samples were dispersed using a high speed stirrer and ultrasound. For the measurement of the dispersed samples, no other dispersing agent was added. Dry matter content of an aqueous suspension
• dry matter content of the suspension (also called “dry weight”) was determined using a MJ33 Moisture Analyzer from Mettler-Toledo, Switzerland, with the following settings: drying temperature 160 ° C, stop automatically if the mass does not vary by more than 1 mg over a period of 30 seconds, standard drying of 5 g to 20 g of suspension.
• Specific Surface (SS) (SS)
• the specific surface area was measured using the BET method according to ISO 9277 using nitrogen, followed by conditioning the sample by heating at 250 ° C for a period of 30 minutes. Before proceeding with these measurements, the sample is filtered through a Buchner funnel, rinsed with deionized water and dried overnight at a temperature of between 90 ° C and 100 ° C in an oven. Then, the dry filter cake is thoroughly ground in a mortar and the resulting powder is placed in a moisture analysis scale at 130 ° C until a constant weight is obtained.
• Tf (min) is the time required to complete the carbonation of the lime milk, as determined by monitoring the conductivity
• M (g) is the weight of the lime milk introduced into the carbonation reactor and TMSLdc (%) is the dry matter content by weight of the milk of lime.
• the load measurement was carried out using a Mutek PCD 03 device equipped with a Mutek PCD titrator.
• 0.5 g to 1 g of dry PCC is weighed into the plastic measuring cell and diluted with 20 mL of deionized water. Move the displacement piston to the "on" position. As the piston oscillates in the cell, wait for the flow current between the two electrodes to stabilize. The sign of the measured value displayed on the screen indicates whether the sample load is positive (cationic) or negative (anionic).
• An oppositely charged polyelectrolyte having a known charge density is added to the sample as a titrant (either 0.001 N sodium polyoxyethylene sulphate or 0.001 N pDADMAC). The titrant loads neutralize the existing charges in the sample. The titration is interrupted as soon as the zero point of charge (0 mV) is reached.
• the consumption of the titrant in mL is used as a basis for subsequent calculations.
• the specific charge quantity q [eq / g of suspension] is calculated according to the following formula:
• V volume of titrant consumed [L]
• This suspension is introduced into the measuring cell of the Malvern Zetasizer Nano-ZS which directly displays the Zeta potential value of the CCP suspension in mV.
• a milk of lime was prepared by mixing, with mechanical stirring, water and various polymeric additives, optionally in the presence of an extinguishing additive (for example dry sodium citrate, NaCl), at an initial temperature of between 40.degree. ° C and 41 ° C (the amounts of polymeric additives and possibly extinguishing additives are shown in Table 1 below). Then, calcium oxide (raw lime from Golling, Austria) was added with stirring. The mixture obtained was stirred for 25 min and sieved through a sieve of 200 ⁇ .
• an extinguishing additive for example dry sodium citrate, NaCl
• the resulting lime milk was transferred to a stainless steel reactor in which the lime milk was cooled to 50 ° C. Then, the lime milk was carbonated by introducing an air / CC mixture (26% by volume of C0 2 and a flow rate of 23 L / min). During the step of carbonation, the reaction mixture was stirred at a speed of 1400 rpm. The kinetics of the reaction were monitored by in-line pH and conductivity measurements.
• x and z are non-zero, the sum of x + z being less than or equal to 150,
• P 3 represents (0 ⁇ , M + )
• M + represents Na +.
• the sample 3 according to the invention confirms that the viscosities of the milk of lime and of the suspension of CCP obtained are compatible with the intended use of the PCC thus obtained, that is to say suspensions of CCP having a Brookfield viscosity less than or equal to 1500 mPa.s at 25 ° C, for example less than or equal to 1000 mPa.s at 25 ° C or less than or equal to 600 mPa.s at 25 ° C, at 100 rpm min.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Geology (AREA)
• General Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Structural Engineering (AREA)
• Materials Engineering (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Paper (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=55022575

Family Applications (1)

Country Status (9)

Families Citing this family (4)

Family Cites Families (4)

• 2015
  • 2015-10-16 FR FR1559898A patent/FR3042488B1/fr not_active Expired - Fee Related
• 2016
  • 2016-10-13 US US15/763,997 patent/US20180282172A1/en not_active Abandoned
  • 2016-10-13 BR BR112018005562-0A patent/BR112018005562A2/pt not_active Application Discontinuation
  • 2016-10-13 CN CN201680060261.XA patent/CN108137336A/zh active Pending
  • 2016-10-13 WO PCT/FR2016/052645 patent/WO2017064425A1/fr active Application Filing
  • 2016-10-13 RU RU2018115919A patent/RU2018115919A/ru not_active Application Discontinuation
  • 2016-10-13 EP EP16793962.8A patent/EP3362411A1/fr not_active Withdrawn
  • 2016-10-13 JP JP2018515150A patent/JP2018535907A/ja active Pending
• 2018
  • 2018-03-13 IL IL258068A patent/IL258068A/en unknown

Also Published As

Similar Documents

Legal Events