Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
  • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
  • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
• • 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
  • C08F4/00—Polymerisation catalysts
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/14—Derivatives of phosphoric acid
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/16—Amines or polyamines

Definitions

• the present invention relates to the sector of dispersants and grinding aid agents for mineral materials, with a view to respectively improving the stability of aqueous dispersions of mineral materials, and of facilitating the grinding of said mineral materials in aqueous suspension.
• the invention relates firstly to the use, as a dispersing agent and / or aids in the grinding of pigments and / or mineral fillers in aqueous suspension, of a water-soluble polymer of controlled structure obtained by a process of controlled radical polymerization using, as a polymerization initiator, a particular alkoxyamine of general formula (A):
• - Ri and R 2 represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 5
• - I represents an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 8, and preferably a tert-butyl radical
• - R 5 represents an alkyl radical, linear or branched, having a number of atoms of carbon ranging from 1 to 8, and preferably a tert-butyl radical
• - R 6 and R 7 represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 8, and preferably an
• the invention also relates to the processes of aqueous dispersions and of grinding in aqueous suspensions of pigments and / or mineral fillers, which use this water-soluble polymer.
• the invention also relates to the aqueous dispersions and suspensions of pigments and / or mineral fillers thus obtained.
• the invention also relates to the use of aqueous suspensions of pigments and / or of mineral fillers thus obtained in the paper sectors and in particular in the coating of paper and the mass loading of paper, or also in the sectors of aqueous paints , plastics, cement, ceramics, detergents, cosmetics, and drilling muds.
• the invention also relates to paper formulations, aqueous paints, plastic compositions, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds thus obtained.
• the invention also relates to the direct use as a dispersing agent of said water-soluble polymers in paper formulations, aqueous paints, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds.
• aqueous suspensions of mineral materials are operations where the stability and viscosity of these suspensions represent a crucial problem for those skilled in the art, in order to avoid phenomena harmful such as sedimentation, solidification, pigment incompatibility or pumpability problems due to too high viscosity.
• a person skilled in the art is also often called upon to carry out a so-called grinding operation, which consists in reducing the size of the pigment particles and / or inorganic fillers through an energy supply, with a view to adapt the particle size of the particles to their final application.
• additives called “dispersants” have gradually been developed, intended to improve the stability of said suspensions, and on the other hand additives called “grinding aid agents”, used to facilitate the reduction in particle size.
• additives are generally based on acrylic and methacrylic polymers, as demonstrated by all of the documents cited in the prior art relating to this application.
• a process for obtaining a polymer with a controlled structure or architecture will therefore be designated, a process which allows a person skilled in the art to obtain a particular structure for the polymer which he wishes to produce. (such as block, comb, alternate, random, ).
• WO 01/44388 and WO 01/44376 which describe an inorganic dispersion containing water, a pigment, and a dispersant obtained by a process of controlled radical polymerization.
• the dispersant is a polymer having the structure of a comb with a hydrophobic skeleton and hydrophilic pendant groups.
• the 2 documents differ in the choice of the polymerization initiator: a compound containing a halogen group (WO 01/44388) or a compound chosen from polyethers, polyesters, or polyurethanes (WO 01/44376).
• document FR 2 797 633 describes a process for the polymerization by ATRP of acrylic and methacrylic monomers.
• “First example of the ATRP of an acidic monomer: direct synthesis of methacrylic acid copolymers in aqueous media” (Chem. Commun., 1999, 1285-1286) describes the use of this polymerization process applied to the synthesis of poly block copolymers (ethylene oxide-sodium methacrylate).
• document WO 00/40630 describes a composition containing an organic or inorganic pigment and a dispersant in the form of a block copolymer obtained by said technique.
• the ATRP process uses catalysts based on copper salts which generate undesirable pollution; copper will also be found in the synthesized products, which is not necessarily desired by those skilled in the art.
• the ATRP process also involves often undesirable amines in the final product.
• the Applicant has surprisingly found a solution to the problem of obtaining aqueous suspensions of stable mineral materials using polymers with a controlled structure, exhibiting neither the pollution problems of the polymers produced by the use of copper-based compounds or the odor problems of polymers obtained by the use of sulfur-based compounds, nor the pollution problems that the incorporation of organo-sulfur molecules can represent.
• the Applicant has surprisingly found a radical polymerization process controlled at low temperature, that is to say at a temperature below the boiling temperature of the monomers used as well as of water, making it possible to obtain water-soluble polymers with controlled structure, used very effectively as a dispersant and / or agent for grinding pigments and / or mineral fillers in aqueous suspension.
• This polymerization process uses, as a polymerization initiator, a particular alkoxyamine of general formula (A):
• - Ri and R 2 represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 5, and preferably represent the methyl radical
• - R 4 represents an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 8, and preferably a tert-butyl radical
• - R 5 represents an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 8, and preferably a tert-butyl radical
• - R 6 and R 7 represent an alkyl radical, linear or branched, having a number
• the polymers then obtained by the process have the advantage of not containing compounds based on copper salts, unlike the polymers obtained by ATRP and sulfur compounds, unlike the products obtained via the RAFT technique, while having an architecture that can be controlled through their polymerization process.
• the finished products obtained are also polymers which can be used at the end of the polymerization reaction resulting directly from this polymerization without the need to carry out post-treatment reactions after polymerization such as filtration, precipitation or other reactions which change the conformation of the resulting polymer.
• the object of the invention is therefore the use, as a dispersing agent and / or aid in grinding pigments and / or mineral fillers in aqueous suspension, of a water-soluble polymer of controlled structure obtained by a polymerization process controlled radical using, as a polymerization initiator, a particular alkoxyamine of general formula (A).
• Another object of the invention lies in the aqueous dispersions and suspensions of pigments and / or mineral fillers thus obtained.
• Another object of the invention is the use of aqueous dispersions and suspensions of pigments and / or mineral fillers thus obtained in the paper sectors such as in particular coating using a formulation of coating sauces and the loading of mass in the manufacture of paper sheets, aqueous paints, plastics, cement, ceramics, detergents, cosmetics and drilling muds.
• Another subject of the invention is the paper formulations, the aqueous paints, the plastic compositions, the cements, the ceramic compositions, the detergent compositions, the cosmetic compositions and the drilling muds thus obtained.
• Another subject of the invention is the direct use of said water-soluble homopolymers and / or copolymers in paper formulations, aqueous paints, cements, ceramic compositions, detergent compositions, cosmetic compositions, and drilling muds, as dispersing agent.
• a final object of the invention resides in paper formulations, aqueous paints, cements, ceramic compositions, detergent compositions, cosmetic compositions, and drilling muds, obtained by the direct use of said polymers as an agent. dispersant.
• water-soluble polymers therefore makes it possible to obtain stable aqueous dispersions of pigments and / or mineral fillers and finely ground aqueous suspensions of pigments and / or mineral fillers.
• aqueous dispersions and suspensions of pigments and / or mineral fillers make it possible to obtain paper formulations, aqueous paints, plastic compositions, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds which can be regulate the viscosity according to the final application envisaged.
• water-soluble polymers makes it possible to obtain paper formulations, aqueous paints, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds whose viscosity can also be regulated according to the envisaged final application.
• a water-soluble polymer which is characterized in that said polymer has a controlled structure and is obtained by a process of controlled radical polymerization using as initiator polymerization, a particular alkoxyamine of general formula (A).
• a water-soluble polymer according to the invention is also characterized in that the polymer is obtained by a controlled radical polymerization process, involving the particular alkoxyamine described above, of monomers chosen from: a) at least one ionic monomer which is either i) anionic and having a carboxylic or dicarboxylic or phosphoric or phosphonic or sulfonic function or a mixture thereof, or ii) cationic, or iii) the mixture of i) and ii)
• nonionic monomer consisting of at least one monomer of formula (I):
• m and p represent a number of alkylene oxide units less than or equal to 150
• n represents a number of ethylene oxide units less than or equal to 150
• q represents an integer at least equal to 1 and such that 5 ⁇ (m + n + p) q ⁇ 150, and preferably such that 15 ⁇ (m + n + p) q ⁇ 120
• Ri represents hydrogen or the methyl or ethyl radical
• R 2 represents l hydrogen or the methyl or ethyl radical
• R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as to the group of unsaturated urethanes such as, for example, acrylurethanes, methacrylurethanes, ⁇ - ⁇ 'dimethyl-isopropenyl-benzylurethanes, ally
• a water-soluble polymer according to the invention is also characterized in that the water-soluble polymer is obtained by controlled radical polymerization of monomers chosen from: a) at least one ionic monomer which is either i) anionic ethylenic unsaturation and with a monocarboxylic function in acid or salt form selected from monomers with ethylenic unsaturation and with a monocarboxylic function such as acrylic or methacrylic acid or the half esters of diacids such as the monoesters to C 4 acid maleic or itaconic, or chosen from ethylenically unsaturated monomers and dicarboxylic function in the acid or salified state such as crotonic, isocrotonic, cinnamic, itaconic, maleic acid, or also anhydrides of carboxylic acids, such as maleic anhydride or chosen from ethylenically unsaturated monomers with a sulfonic function at l acid or salified state
• m and p represent a number of alkylene oxide units less than or equal to 150
• n represents a number of ethylene oxide units less than or equal to 150
• q represents an integer at least equal to 1 and such that 5 ⁇ (m + n + p) q ⁇ 150, and preferably such that 15 ⁇ (m + n + ⁇ ) q ⁇ 120
• Ri represents hydrogen or the methyl or ethyl radical
• R 2 represents hydrogen or the methyl or ethyl radical
• R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic esters , vinylphthalic as well as to the group of unsaturated urethanes such as for example acrylurethane, methacrylurethane, - ⁇ 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well
• - ml, pi, m2 and p2 represent a number of alkylene oxide units less than or equal to 150
• ni and n2 represent a number of ethylene oxide units less than or equal to 150
• - ql and q2 represent an integer at least equal to 1 and such that 0 ⁇ (ml + nl + pl) ql ⁇ 150 and 0 ⁇ (m2 + n2 + p2) q2 ⁇ 150
• r represents a number such that 1 ⁇ r ⁇ 200
• R 3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as to the group of unsaturated urethanes such as for example acrylurethane, methacrylurethane , ⁇ - ⁇ 'dimethyl-isopropenyl-benzylurethane
• - R represents a radical containing an unsaturated polymerizable function, preferably belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic esters, crotonic, vinylphthalic as well as to the group of unsaturated urethanes such as for example acrylurethane, methacrylurethane, ⁇ - 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of allyl or vinyl ethers substituted or not, or also to the group ethylenically unsaturated amides or iides
• A is an optionally present group, which then represents a hydrocarbon radical having 1 to 4 carbon atoms
• B represents a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers, and optionally at least one crosslinking monomer chosen in a nonlimiting manner from the group consisting of ethylene glycol dimethacrylate, tri
• m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150
• n3 and n4 represent a number of ethylene oxide units less than or equal to 150
• q3 and q4 represent an integer at least equal to 1 and such that 0 ⁇ (m3 + n3 + p3) q3 ⁇ 150 and 0 ⁇ (m4 + n4 + p4) q4 ⁇ 150
• - r ' represents a number such that 1 ⁇ r' ⁇ 200
• - R i3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic esters, vinylphthalic as well as to the group of unsaturated urethanes such as for example acrylurethane, methacrylurethane, ⁇ - ⁇ 'dimethyl-isopropenyl-benzy
• a water-soluble polymer according to the invention is characterized in that said aforementioned polymer consists, expressed by weight: a) of 2% to 100% and even more particularly of 5% to 100% of minus an ionic monomer which is either i) an anionic ethylenically unsaturated monomer with a monocarboxylic function in the acid or salified state chosen from ethylenically unsaturated monomers with a monocarboxylic function such as acrylic or methacrylic acid or also the hemiesters of diacids such as the C 1 to C monoesters of maleic or itaconic acids, or chosen from ethylenically unsaturated monomers and dicarboxylic function in the acid or salified state such as crotonic, isocrotonic, cinnamic, itaconic, maleic acid, or else anhydrides of carboxylic acids, such as maleic anhydride or chosen from ethylenically unsaturated monomers with
• m and p represent a number of alkylene oxide units less than or equal to 150
• n represents a number of ethylene oxide units less than or equal to 150
• q represents an integer at least equal to 1 and such that 5 ⁇ (m + n + p) q ⁇ 150, and preferably such that 15 ⁇ (m + n + p) q ⁇ 120
• Ri represents hydrogen or the methyl or ethyl radical
• R 2 represents hydrogen or the methyl or ethyl radical
• R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic esters , vinylphthalic as well as to the group of unsaturated urethanes such as for example acrylurethane, methacrylurethane, ⁇ - ⁇ 'dimethyl-isopropenyl-benzylurethane, allylurethane, as
• - ml, pi, m2 and p2 represent a number of alkylene oxide units less than or equal to 150
• - ni and n2 represent a number of ethylene oxide units less than or equal to 150
• - ql and q2 represent an integer at least equal to 1 and such that 0 ⁇ (ml + nl + pl) ql ⁇ 150 and 0 ⁇ (m2 + n2 + p2) q2 ⁇ 150
• r represents a number such that 1 ⁇ r ⁇ 200
• R 3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as to the group of unsaturated urethanes such as for example acrylurethanes, methacrylurethane, ⁇ - ⁇ 'dimethyl-isopropenyl-benzylure
• R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic esters, vinylphthalic as well as to the group of unsaturated urethanes such as, for example, acrylurethanes, methacrylurethanes, ⁇ - ⁇ 'dimethyl- isopropenyl-benzylurethane, allylurethane, as well as in the group of substituted or unsubstituted allylic or vinyl ethers, or also in the group of ethylenically unsaturated amides or imides,
• A is an optionally present group, which then represents a hydrocarbon radical having 1 to 4 carbon atoms
• B represents a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several of these monomers, from 0 to 3% of at
• a water-soluble polymer according to the invention is characterized in that said polymer is a water-soluble copolymer and has a structure of the random, block, comb, grafted, or alternated type.
• This molecular weight is determined according to the GPC method (Steric Exclusion Chromatography or Gel Permeability Chromatography) using a Waters TM brand liquid chromatography device equipped with two detectors, one of which combines dynamic light scattering with viscosimetry. measured by a Niscotek TM viscometer and the other being a Waters TM brand refractometric concentration detector.
• This liquid chromatography apparatus is equipped with steric exclusion columns suitably chosen by a person skilled in the art in order to separate the different molecular weights of the polymers studied.
• the liquid elution phase is an aqueous phase.
• Another subject of the invention resides in dispersing agents and / or agents for grinding mineral materials in aqueous suspension.
• the dispersing agent for mineral materials in aqueous suspension according to the invention is characterized in that the polymer is a water-soluble polymer having a controlled structure and obtained by a controlled radical polymerization process using, as a polymerization initiator , an alkoxyamine of general formula (A) previously defined.
• the water-soluble polymer is obtained by the controlled radical polymerization of monomers chosen from the monomers mentioned above.
• the dispersing agent according to the invention is characterized in that it is a water-soluble copolymer and in that it has a structure of random type, block, comb, grafted or alternated.
• the mineral grinding aid agent according to the invention is characterized in that the polymer is a water-soluble polymer having a controlled structure and obtained by a controlled radical polymerization process using, as polymerization initiator, an alkoxyamine of general formula (A) previously defined.
• the water-soluble polymer is obtained by the controlled radical polymerization of monomers chosen from the monomers mentioned above.
• the grinding aid agent according to the invention is characterized in that it is a water-soluble copolymer and in that it has a structure of the random type, block, comb, grafted or alternately.
• Another object of the invention lies in the dispersion process and the grinding process of mineral matter in aqueous suspension.
• the process for dispersing mineral materials according to the invention is characterized in that the water-soluble polymer according to the invention is used and in particular in that 0.05% to 5% by dry weight of the said use is used polymer relative to the dry weight of pigment and / or mineral filler, and very preferably between 0.1% and 3% of said polymer relative to the dry weight of pigment and / or mineral filler.
• the mineral material grinding process according to the invention is characterized in that the water-soluble polymer according to the invention is used and in particular in that 0.05% to 5% by dry weight of the said use is used polymer relative to the dry weight of pigment and / or mineral filler, and very preferably between 0.1% and 3% of said polymer relative to the dry weight of pigment and / or mineral filler.
• Another object of the invention resides in the aqueous dispersions and suspensions of pigments and / or inorganic fillers obtained thanks to the use according to the invention of the above-mentioned water-soluble polymer.
• aqueous dispersions of mineral materials are characterized in that they contain a pigment and / or a mineral filler chosen from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement, gypsum, lime, magnesia, titanium oxide, satin white, aluminum trioxide or even aluminum trihydroxide, silicas, mica and the mixture of these charges together, such as talc-calcium carbonate mixtures, carbonate calcium-kaolin, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or mineral co-structures such as talc co-structures -carbonate of calcium or talc-titanium dioxide, or mixtures thereof.
• a pigment and / or a mineral filler chosen from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement, gypsum, lime, magnesia, titanium oxide, satin white, aluminum trioxide or even aluminum trihydroxide, silicas, mica
• aqueous suspensions of mineral materials are characterized in that they contain a pigment and / or a mineral filler chosen from carbonate of natural or synthetic calcium, dolomites, kaolin, talc, gypsum, lime, magnesia, titanium oxide, white satin, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these fillers together, such as talc-calcium carbonate, calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or even mineral co-structures such as talc-calcium carbonate or talc-titanium dioxide co-structures, or mixtures thereof.
• a pigment and / or a mineral filler chosen from carbonate of natural or synthetic calcium, dolomites, kaolin, talc, gypsum, lime, magnesia, titanium oxide, white satin, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of
• aqueous dispersions according to the invention are characterized in that they particularly contain natural or synthetic calcium carbonate and more particularly a natural calcium carbonate chosen from marble, calcite, chalk or their mixtures.
• aqueous suspensions according to the invention are characterized in that they contain in a particular way natural or synthetic calcium carbonate, and more particularly a natural calcium carbonate chosen from marble, calcite, chalk or their mixtures.
• aqueous suspensions and dispersions are characterized in that they contain from 0.05 to 5% by dry weight of the water-soluble polymer used according to the invention relative to the dry weight of the pigments and / or mineral fillers, and in that that they more particularly contain from 0.1 to 3% by dry weight of the water-soluble polymer used according to the invention relative to the dry weight of the pigments and / or mineral fillers.
• Another object of the invention is the use of aqueous dispersions and suspensions of pigments and / or mineral fillers thus obtained in the paper sectors such as in particular the coating of paper using a formulation of coating sauces and the mass load of paper in the manufacture of sheets of paper, aqueous paints, plastic, cement, ceramics, detergency and drilling muds.
• a further object of the invention is a process for dispersing mineral matter in a paper formulation, in an aqueous paint, in a cement, in a ceramic composition, in a detergent composition, in a drilling mud. This process is then characterized in that the water-soluble polymer according to the invention is used directly as a dispersing agent.
• Another subject of the invention resides in paper formulations, aqueous paints, plastic compositions, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds obtained from said aqueous dispersions and suspensions of pigments. and / or the aforementioned mineral fillers.
• Another object of the invention is the direct use of the polymer according to the invention as a dispersing agent in paper formulations, aqueous paints, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds.
• a final object of the invention resides in paper formulations, aqueous paints, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds thus obtained.
• the formulations paper mills, aqueous paints, plastic compositions, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds are characterized in that they contain from 0.01% to 5% by dry weight of said water-soluble polymer.
• This example illustrates the production of water-soluble polymers used according to the invention.
• the medium is heated to 55 ° C. and a solution consisting of 25 g of ethanol and 2.92 g of the following alkoxyamine is introduced at once:
• a clear aqueous solution containing 37% of dry matter is obtained of a polymer composed by weight of:
• the medium is heated to 65 ° C. and a solution consisting of 25 g of ethanol and 2.92 g of the following alkoxyamine is introduced at once:
• a clear aqueous solution containing 36% of dry matter is obtained of a polymer composed by weight of:
• the medium is heated to 65 ° C. and a solution consisting of 25 g of ethanol and 2.92 g of the following alkoxyamine is introduced at once:
• a clear aqueous solution containing 39% of dry matter is obtained of a polymer composed by weight of:
• This example illustrates the use of the polymers obtained according to the invention as a grinding aid agent for mineral matter and more particularly calcium carbonate. This example also illustrates the production of an aqueous suspension of calcium carbonate according to the invention.
• This test which illustrates the invention, uses 1.2% by dry weight of the polymer of test No. 1, relative to the dry weight of calcium carbonate.
• This test which illustrates the invention, uses 1.2% by dry weight of the polymer of test No. 2, relative to the dry weight of calcium carbonate.
• Test # 7 This test, which illustrates the invention, uses 1.2% by dry weight of the polymer of test # 3, relative to the dry weight of calcium carbonate.
• This test which illustrates the invention, uses 1.2% by dry weight of the polymer of test No. 4, relative to the dry weight of calcium carbonate.
• an aqueous suspension was prepared from calcium carbonate from the Orgon deposit (France), with an average diameter of the order of 50 micrometers.
• the aqueous suspension has a dry matter concentration of 78% by weight relative to the total mass.
• the grinding aid agent is introduced into this suspension in the quantities indicated, expressed in percent by dry weight relative to the mass of dry calcium carbonate to be ground.
• the suspension circulates in a mill of the Dyno-Mill TM type with fixed cylinder and rotating impeller, the grinding body of which consists of corundum balls with a diameter in the range 0.6 millimeters to 1.0 millimeters.
• the total volume occupied by the grinding body is 1,150 cubic centimeters while its mass is 2,900 g.
• the grinding chamber has a volume of 1,400 cubic centimeters.
• the circumferential speed of the mill is 10 meters per second.
• the calcium carbonate suspension is recycled at the rate of 18 liters per hour.
• the outlet of the Dyno-Mill TM mill is provided with a 200 micron mesh separator allowing the suspension resulting from the grinding to be separated from the grinding body.
• the temperature during each grinding test is maintained at approximately 60 ° C.
• a sample of the pigment suspension is recovered in a flask.
• the particle size of this suspension (% of particles smaller than 1 micrometer) is measured using a Sedigraph TM 5100 particle size analyzer from the company Micromeritics.
• the bottle is shaken then the viscosity of the suspension is measured by introducing the Brookfield TM RVT type viscometer, at a temperature of 20 ° C. and speeds, into the bottle of the appropriate mobile. rotation of 10 revolutions per minute and 100 revolutions per minute.
• Table 1 shows that it is possible to use the polymers according to the invention as a grinding aid agent for mineral materials in aqueous suspension, and in particular natural calcium carbonate, just as it is possible to obtain aqueous suspensions of natural calcium carbonate containing the polymer according to the invention.
• This example concerns the demonstration of the use of the polymers according to the invention as a cement dispersing agent. This example also illustrates the obtaining of an aqueous suspension of cement according to the invention.
• the different constituents of the standard mortar of constant real volume equal to 1 m 3 per 450 kg of cement are poured into a mortar mixer (EN 196-1) in the on position. with constant workability equal to 2 seconds measured with the PERRIER site mortar maneuverimeter defined by standard NF P 18452.
• the mixer is kept at high speed for 30 seconds then the latter is stopped for 90 seconds in order to be able to scrape the walls of the mixer.
• This test illustrates the control and uses a cement formulation without adding an additive.
• Test No. 11 This test, which illustrates the invention, uses the polymer of test No. 1.
• This test which illustrates the invention, uses the polymer of test No. 4.
• Test No. 14 This test, which illustrates the invention, uses the polymer of test No. 2.
• Reading the table makes it possible to distinguish the improvement brought by the use of the copolymers according to the invention as a cement dispersing agent.
• This example relates to the use of the polymers according to the invention in the field of ceramics. To this end, the dispersing efficiency of the polymers according to the invention contained in the aqueous clay suspensions according to the invention used in the field of ceramics is evaluated.
• the viscosity of the slip is measured by measuring the Brookfield TM viscosity RNT type at 10 revolutions per minute and 100 revolutions per minute.
• This test is a control and does not use any dispersant.
• Brookfield TM viscosities obtained are equal to 6400 mPa.s at 10 rpm and 870 mPa.s at 100 rpm.
• Brookfield TM viscosities obtained are equal to 6000 mPa.s at 10 rpm and 800 mPa.s at l00 rpm.
• Trial # 17 This test illustrates the use of polymer according to the invention and implements the polymer of test No. 4.
• Brookfield TM viscosities obtained are equal to 6000 mPa.s at 10 rpm and 800 mPa.s at l00 rpm.
• Brookfield TM viscosities obtained are equal to 6000 mPa.s at 10 rpm and 800 mPa.s at 100 rpm.
• Test n ° 19 This test illustrates the use of polymer according to the invention and implements the polymer of test n ° 3.
• Brookfield TM viscosities obtained are equal to 6000 mPa.s at 10 rpm and 800 mPa.s at l00 rpm.
• This example illustrates the production of water-soluble polymers used according to the invention.
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units.
• the medium is heated to 95 ° C. and a solution consisting of 8.8 g of the following alkoxyamine, which has been diluted in 50 g of water and 2.2, is gradually introduced over a period of 2 hours.
• g of 50% sodium hydroxide g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 30.9% of dry matter of a polymer is obtained which is composed by weight of: 5.7% methacrylic acid, - 92.8% of methoxy methacrylate polyethylene glycol of molecular mass 2000, 1, 5% butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units,
• the medium is heated to 95 ° C. and a solution consisting of 8.8 g of the following alkoxyamine, which has been diluted in 50 g of water and 2.2, is gradually introduced over a period of 2 hours.
• g of 50% sodium hydroxide g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 32.7% of dry matter of a polymer composed by weight of: - 93.6% of methacrylic acid is obtained,
• the medium is heated to 95 ° C. and a solution consisting of 8.8 g of the following alkoxyamine, which has been diluted in 50.7 g of water and 2, is gradually introduced over a period of 2 hours. , 2 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 32.1% of dry matter of a polymer is obtained which is composed by weight of: - 18.4% methacrylic acid, 79.6% methoxy methacrylate polyethylene glycol with a molecular weight of 2000, 1, 5% butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units, - 0.5% ethylene glycol dimethacrylate,
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units.
• the medium is heated to 95 ° C. and a solution consisting of 3.96 g of the following alkoxyamine, which has been diluted in 90.2 g of water and 1, is gradually introduced over a period of 2 hours. 0.02 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 34.1% of dry matter of a polymer is obtained which is composed by weight of: 18.5% of methacrylic acid, 80.0% of methoxy methacrylate polyethylene glycol of molecular mass 2000, ⁇ 1, 5% butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units,
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units.
• the medium is heated to 95 ° C. and a solution consisting of 7.90 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 2, is gradually introduced over a period of 2 hours. 0.03 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 34.4% of dry matter of a polymer is obtained which is composed by weight of: 18.5% methacrylic acid, 80.0% methoxy methacrylate polyethylene glycol of molecular weight 2000, 1.5 % of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units,
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units.
• the medium is heated to 95 ° C. and a solution consisting of 15.86 g of the following alkoxyamine, which has been diluted in 90.2 g of water and 4, is gradually introduced over a period of 2 hours. 0.03 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 34.5% of dry matter of a polymer is obtained which is composed by weight of: 18.5% of methacrylic acid, 80.0% of methoxy methacrylate polyethylene glycol of molecular mass 2000, 1.5 % of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units,
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units, - 1.5 g of a sililated monomer of formula R - A - Si (OB) 3 where R denotes the methacrylate group, A denotes the propyl radical and B denotes the methyl radical.
• the medium is heated to 95 ° C. and a solution consisting of 12.4 g of the following alkoxyamine, which has been diluted in 71.0 g of water and 3, is gradually introduced over a period of 2 hours. , 15 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 30.6% of dry matter of a polymer is obtained which is composed by weight of: 18.4% of methacrylic acid, - 79.6% of methoxy methacrylate polyethylene glycol of molecular mass 2000,
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units
• a sililated monomer of formula R - A - Si (OB) 3 where R denotes the methacrylate group, A denotes the propyl radical and B denotes the methyl radical, whose GPC analysis previously described indicates a weight average molecular weight Mw of 32,470.
• Test No 27 18.94 g of methacrylic acid, 175 g of water are introduced into a 1 liter glass reactor fitted with mechanical stirring and a heating system of the oil bath type.
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units.
• the medium is heated to 95 ° C. and a solution consisting of 6.6 g of the following alkoxyamine, which has been diluted in 75.0 g of water and 1, is gradually introduced over a period of 2 hours.
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 36.4% of dry matter of a polymer is obtained, composed by weight of: 7.5% of methacrylic acid, - 91.0% of methoxy methacrylate polyethylene glycol of molecular mass 5000, 1, 5% butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units, whose GPC analysis previously described indicates a weight average molecular weight Mw of 53070.
• Test No. 28 In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced:
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units.
• the medium is heated to 95 ° C. and a solution consisting of 6.6 g of the following alkoxyamine, which has been diluted in 75.0 g of water and 1, is gradually introduced over a period of 2 hours.
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 35.2% of dry matter is obtained of a polymer composed by weight of:
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units, whose GPC analysis previously described indicates a weight average molecular weight Mw of 51900.
• the medium is heated to 95 ° C. and a solution consisting of 15.87 g of the following alkoxyamine, which has been diluted in 90.1 g of water and 50, is gradually introduced over a period of 2 hours. , 0 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• the medium is heated to 95 ° C. and a solution consisting of 15.9 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours.
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units
• urethane methacrylate product of the reaction of ethylene glycol methacrylate and of toluene diisocyanate and of methoxy polyethylene glycol of average molecular weight by weight Mw equal to 5000, 17.2 g of ethyl methacrylate .
• the medium is heated to 95 ° C. and a solution consisting of 5.57 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 1, is gradually introduced over a period of 2 hours. , 4 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 41.1% of dry matter is obtained of a polymer composed by weight of:
• the medium is heated to 95 ° C. and a solution consisting of 15.86 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours. , 0 g of 50% sodium hydroxide:
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units
• the medium is heated to 95 ° C. and a solution consisting of 15.86 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours. 28 g of 50% sodium hydroxide:
• the medium is heated to 95 ° C. and a solution consisting of 15.86 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours. 0.08 g of 50% sodium hydroxide:
• the medium is heated to 95 ° C. and a solution consisting of 12.69 g of the following alkoxyamine, which has been diluted in 72.0 g of water and 3, is gradually introduced over a period of 2 hours. , 3 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 33.3% of dry matter is obtained of a polymer composed by weight of:
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units.
• the medium is heated to 95 ° C. and a solution consisting of 15.86 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours.
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units
• the medium is heated to 95 ° C. and a solution consisting of 16.0 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours.
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• the medium is heated to 95 ° C. and a solution consisting of 16.0 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours. , 0 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 39.1% of dry matter is obtained of a polymer composed by weight of: 80.0% methacrylic acid, - 20.0% acrylamide,
• the medium is heated to 95 ° C. and a solution consisting of 16.0 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours. , 0 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 37.3% of dry matter is obtained of a polymer composed by weight of: 80.0% methacrylic acid, 20.0% itaconic acid,
• the medium is heated to 95 ° C. and a solution consisting of 16.0 g of the following alkoxyamine, which has been diluted in 90.0 g of water and 4, is gradually introduced over a period of 2 hours. , 0 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 37.3% of dry matter of a polymer is obtained, composed by weight of: 80.0% methacrylic acid, 20.0% acrylamidomethylpropanesulfonic acid,
• the medium is heated to 95 ° C. and a solution consisting of 12.7 g of the following alkoxyamine which has been diluted in 72.0 g of water and 3 is gradually introduced over a period of 2 hours. , 4 g of 50% sodium hydroxide:
• the medium is neutralized to pH 8 with a 50% sodium hydroxide solution.
• a clear aqueous solution containing 37.3% of dry matter is obtained of a homopolymer of methacryloyloxyethyltrimethylammonium chloride, the GPC analysis of which previously described indicates a weight average molecular weight Mw of 26,000.
• This example relates to the use of grinding aid agents according to the invention for the grinding of a calcium carbonate which is chalk, the aqueous suspensions according to the invention thus obtained, their use according to the invention in the manufacture of ceramic compositions, and finally the ceramic compositions obtained according to the invention.
• the first of them is rinsed, dried and then filtered through the same sieve as that used previously. The other will later be used to formulate ceramic compositions.
• test No. 26 Two aqueous chalk suspensions are produced according to the method described above. In the first, once rinsed and dried, the percentage by weight of particles whose size is greater than 45 ⁇ m is 5.21%.
• This test illustrates the invention and uses the polymer described in test No. 26.
• the percentage by weight of particles whose size is greater than 45 ⁇ m is 5.21 %.
• ceramic compositions are produced from the aqueous suspensions of ground mineral material, but not rinsed and dried, obtained during tests No. 42 and No. 43.
• test illustrates the invention and uses the aqueous suspension, not rinsed and dried, described in test No. 42.
• Brookfield TM viscosity RNT type at 10 revolutions per minute measured for the slip obtained is then equal to 21,200 mPa.s.
• This example illustrates the direct use of dispersing agents according to the invention in a drilling mud, and the drilling mud according to the invention thus obtained.
• drilling mud is produced according to the following procedure, the composition of said mud being given in table 3.
• the mud is prepared by introducing into a bowl of Hamilton Beach TM marketed by the company of the same name:
• Viscosity measurements are then carried out with a Fann TM viscometer sold by the company of the same name.
• a viscosity reading is then carried out at 600, 200, 100, 6, and 3 revolutions / minute.
• This example illustrates the direct use of dispersing agents according to the invention in detergent formulations of scouring creams, and said creams obtained according to the invention.
• scouring creams are prepared by introducing into a planetary mill at a speed of rotation at least equal to 20,000 revolutions per minute a mineral filler which is calcium carbonate marketed by the company OMYA TM under the name of Omyacarb TM 30 AN, water, an active surfactant which is Ethylan TM 1005 sold by the company AKZO NOBEL TM, and the dispersing agent to be tested.
• a mineral filler which is calcium carbonate marketed by the company OMYA TM under the name of Omyacarb TM 30 AN
• water an active surfactant which is Ethylan TM 1005 sold by the company AKZO NOBEL TM
• Ethylan TM 1005 sold by the company AKZO NOBEL TM
• the Brookfield TM RNT type viscosity at 20 revolutions per minute is then determined for the compositions obtained according to the method previously described in the present application.
• This test illustrates the invention and uses the polymer according to test No. 25.
• Test No. 50 This test illustrates the invention and uses the polymer according to test No. 28.
• Brookfield TM viscosities type RVT The values of Brookfield TM viscosities type RVT at 20 revolutions per minute demonstrate that the dispersing agents according to the invention can be used directly in recurrent creams in the detergency field.
• This example illustrates the use of aqueous suspensions of ground mineral materials according to the invention, in detergent formulations of scouring creams, and said creams obtained according to the invention.
• scouring creams are prepared by introducing an aqueous suspension of mineral matter according to the invention which has been obtained, into a planetary grinder at a speed of rotation at least equal to 20,000 revolutions / minute. by grinding calcium carbonate with a dispersing agent according to the invention, water, a surfactant which is Ethylan TM 1005 sold by the company AKZO NOBEL TM, and the dispersing agent to be tested.
• the Brookfield TM viscosity type RVT is then determined for the compositions obtained at 20 revolutions per minute according to the method previously described in the present application.
• Test No. 52 This test illustrates the invention and uses the aqueous suspension of ground calcium carbonate according to test No. 5.
• This test illustrates the invention and uses the aqueous suspension of ground calcium carbonate according to test No. 6.
• This test illustrates the invention and uses the aqueous suspension of ground calcium carbonate according to test No. 7.
• This test illustrates the invention and uses the aqueous suspension of ground calcium carbonate according to test No. 8.
• Brookfield TM viscosities type RVT demonstrate that the aqueous suspensions of calcium carbonate ground according to the invention can be used in recurrent creams in the detergency field.
• This example illustrates the use of dispersing agents according to the invention, for dispersing mineral materials in water, as well as the aqueous dispersions of mineral materials obtained according to the invention.
• the mixture is subjected to constant stirring by means of a notched turbine of diameter 70 mm, at the speed of 1000 revolutions / minute, for 20 minutes.
• a first Brookfield TM viscosity measurement is then carried out at 10 revolutions / minute.
• One then proceeds to successive additions of product to be tested, while stirring for 5 minutes at the speed of 10O0 revolutions / minute and after performing a new measurement. Brookfield TM viscosity at 10 revolutions / minute (according to the method and with the device previously described in this document).
• Test No 56 This test illustrates the invention and uses the dispersing agent according to the invention as described in test No 26.
• Test No. 57 This test illustrates the invention and implements the dispersing agent according to the invention as described in test No. 21.
• Test No 58 This test illustrates the invention and uses the dispersing agent according to the invention as described in test No 34.
• Test No 59 This test illustrates the invention and uses the dispersing agent according to the invention as described in test No 33.
• This example illustrates the direct use of dispersing agents according to the invention in aqueous paint formulations, and the aqueous paint formulations according to the invention thus obtained.
• an aqueous paint formulation is produced according to methods well known to those skilled in the art, by adding 0.24% by dry weight of a dispersing agent according to the invention, relative to the total weight of the formulation: the compositions of these formulations are indicated in table 7.
• ICI TM viscosity is determined at 10 revolutions / minute according to the procedure described above. Its ICI TM and Stormer TM viscosities are also determined by the following methods.
• the ICI TM viscosity is determined on a cone-plane viscometer, called an ICF viscometer, sold by the company ERICHSEN TM, according to the method perfectly known to those skilled in the art. The measurement is carried out at 25 ° C.
• the Stormer TM viscosity is determined on a Stormer KU-1 viscometer marketed by the company Brookfield TM, equipped with a unique measurement system. The measurement is carried out at 25 ° C. The same measurements were carried out after 24 hours of storage of the paints at room temperature.
• Test No 60 This test illustrates the invention and uses the polymer according to test No 26.
• Test No 61 This test illustrates the invention and uses the polymer according to Test No 21.
• Coatex TM BR 100 is a thickener sold by the company COATEX TM.
• Mergal TM K.6N is a bactericide sold by the company TROY TM.
• Nopco TM NDW is an anti-foaming agent sold by the company COGNIS TM.
• Rhodopas TM 290 D is a styrene acrylic binder sold by the company RHODIA TM.
• This example illustrates the use of aqueous dispersions of mineral materials produced with dispersing agents according to the invention, in aqueous paint formulations and the aqueous paint formulations according to the invention thus obtained.
• an aqueous paint formulation is produced according to methods well known to those skilled in the art, in particular by introducing 200 grams of the aqueous dispersion of titanium dioxide according to tests No. 56 and No. 57 produced with 0 , 70% by dry weight of dispersing agent according to the invention relative to the dry weight of mineral matter.
• the corresponding formulations appear in Table 8.
• said aqueous suspensions contain 0.70% by dry weight of dispersing agent according to the invention relative to the dry weight of mineral matter.
• Coatex TM BR 100 is a thickener sold by the company COATEX TM.
• Mergal TM K6N is a bactericide sold by the company TROY TM.
• Nopco TM NDW is an anti-foaming agent sold by the company COGNIS TM.
• Rhodopas TM 290 D is a styrene acrylic binder sold by the company RHODIA TM.
• This example illustrates the use of aqueous dispersions of mineral materials according to the invention produced with dispersing agents according to the invention, in the formulation of mortars used in the cement industry, as well as said mortars obtained according to the invention.
• the various constituents of the standard mortar dosed at 450 kg / m of cement are poured into a mortar mixer (EN 196-1) in the on position.
• the amounts of the constituents are adjusted for each of the mortars of the different tests in order to work at constant compactness. After 90 seconds of mixing, the latter is stopped in order to be able to scrape the walls of the mixer.
• This test illustrates the invention and relates to a mortar according to the invention, dosed at 450 kg / m 3 with a water / cement ratio equal to 0.46 and using 10% by dry weight, relative to the dry weight of cement, of an aqueous dispersion of a calcite at 20% in dry matter with a median diameter equal to 2 micrometers measured with Sedigraph TM 5100, using 0.70%, by dry weight relative to the dry weight of calcium carbonate , of the copolymer of test No. 38.
• the aqueous dispersion of calcium carbonate is prepared by introduction of the mineral filler in the water additive with the dispersing copolymer.
• This example illustrates the use of dispersing agents according to the invention for dispersing in mineral water a material which is kaolin.
• This test illustrates the invention and uses the polymer according to test No. 25.
• Test No. 68 This test illustrates the invention and uses the polymer according to test No. 28.
• EXAMPLE 15 This example illustrates the use of grinding aid agents according to the invention for grinding calcium carbonate suspensions, the suspensions according to the invention thus obtained, their use according to the invention in the formulation of sauces of paper coatings, and the paper coatings of the invention thus produced.
• the first step is the grinding of a natural calcium carbonate sold by the company OMYA TM under the name of Omyacarb TM 10 AV.
• the grinding procedure is identical to that described in Example 2.
• This test illustrates the invention and uses 1.0% by dry weight of grinding agent according to the invention and as described in test No. 24, relative to the dry weight of calcium carbonate.
• This test illustrates the invention and uses 1.0% by dry weight of grinding agent according to the invention and as described in test No. 25, relative to the dry weight of calcium carbonate.
• Table 11 shows that it is possible to use grinding agents according to the invention to grind mineral materials in aqueous suspension, and in particular natural calcium carbonate, just as it is possible to obtain aqueous suspensions of natural calcium carbonate containing the grinding agent according to the invention.
• paper coating sauces were produced, according to methods well known to those skilled in the art, using 100 grams of aqueous suspensions of ground calcium carbonate, obtained during tests n ° 71 and n ° 72.
• This test illustrates the invention and uses 100 grams of the aqueous suspension according to the invention and as described in test No. 71. A coating sauce is then obtained, the percentage by weight of mineral matter being equal to 66.7%, and the pH being equal to 8.4.
• Test No. 74 This test illustrates the invention and uses 100 grams of the aqueous suspension according to the invention and as described in test No. 72.
• a coating sauce is then obtained, the percentage by weight of mineral matter being equal to 67.0%, and the pH being equal to 8.4.
• Table 12 demonstrate that it is possible to use aqueous suspensions of ground mineral material (such as in particular calcium carbonate) according to the invention, in the formulation of paper coating sauces according to the invention.
• ground mineral material such as in particular calcium carbonate
• This example relates to the use of the dispersing agent according to the invention, in the field of plastics.
• the aqueous marble suspension is prepared by introducing into the cake, the quantity required by dry weight of the dispersing agent according to the invention as described in test No. 27 relative to the dry weight of said cake to be suspended in order to obtain an aqueous suspension of marble, the dry matter concentration of which is equal to 68%.
• this suspension is dried at a temperature below 105 ° C. by the use of a laboratory dryer of the Niro TM type.
• the powder obtained without agglomerates is then divided into two samples, one of which will be the subject of the dispersion test in a thermoplastic resin and the other the object of the dispersion test in a thermosetting resin.
• This test represents the dispersion test of the marble powder, previously obtained, in a thermoplastic resin.
• the whole is mixed for 20 minutes at this temperature and at the speed of 42 rpm.
• the mixture thus prepared a part of it was then calendared in the form of plates which were cut into small cubes having a dimension of 2 at 3 millimeters on a side and of which the melt flow index MFI was measured at 230 ° C. under a load of 2.16 kg and 10 kg with a die of 2.09 mm in diameter.
• the MFI (Hot Flow Index or Melt Flow Index) obtained is equal to 8.0 g / 10 min under a load of 2.16 kg with a die of 2.09 mm in diameter and at a temperature of 230 ° C .
• the MFI obtained is equal to 132.0 g / 10 min under a load of 2.16 kg with a die of 2.09 mm in diameter and at a temperature of 230 ° C.
• This test represents the dispersion test of the marble powder, previously obtained, in a thermosetting resin of the unsaturated polyester type.
• the mixture is then homogenized by stirring with a spatula, then the Brookfield TM viscosity at 100 revolutions / min is measured after these 24 hours using a Brookfield TM viscometer type RVT equipped with module 7.
• dispersing agent according to the invention can be used in such a premix of polyester and calcium carbonate, which is itself usable for the manufacture of prepregs of SMC (Sheet Molding Compound) or BMC (Bulk) type. Molding Compound).

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