EP1708803A2

EP1708803A2 - Use of structured water-soluble polymers obtained by controlled radical polymerization as a dispersant and agent for assisting in the grinding of mineral materials

Info

Publication number: EP1708803A2
Application number: EP04816460A
Authority: EP
Inventors: Jean-Marc Suau; Christian Jacquemet; Yves Kensicher
Original assignee: Coatex SAS
Current assignee: Coatex SAS
Priority date: 2003-12-24
Filing date: 2004-12-22
Publication date: 2006-10-11
Also published as: US20070185258A1; FR2864455B1; WO2005063371A2; CA2548802A1; US20110160348A1; FR2864455A1; AR047572A1; WO2005063371A3; UY28696A1; TW200602120A

Abstract

The invention relates to the use, as a dispersant and/or agent for assisting in the grinding of pigments and/or mineral loads in aqueous suspension, of a water-soluble polymer having a controlled structure and obtained by a controlled radical polymerization process while using, as a polymerization initiator, a particular alkoxyamine.

Description

USE OF STRUCTURED WATER-SOLUBLE POLYMERS OBTAINED BY CONTROLLED RADICAL POLYMERIZATION AS A DISPERSANT AND AID FOR GRINDING MINERAL MATERIALS

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):

R ₂ R4

Ri - C - O -N - CH - R5

0 = CO = P - OR ₆ IIOR ₃ OR ₇

in which: - Ri and R ₂ represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 5, - R ₃ represents a hydrogen atom, an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 8, a phenyl radical, a cation such as Li ⁺ , Na ⁺ , K ⁺ , H ₄ N ⁺ , Bu ₃ HN ⁺ with Bu = butyl, - 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 ethyl radical.

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.

Finally, it relates to paper formulations, aqueous paints, cements, ceramic compositions, detergent compositions, cosmetic compositions and drilling muds thus obtained by direct use, as dispersing agent, of said water-soluble polymers.

Historically, the manufacture, handling, transport or use of 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.

Furthermore, 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.

Also, 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. . These 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.

Numerous applied research works as well as several patents quickly guided the person skilled in the art towards the choice of “controlled structure” polymers. We will detail this concept through a few examples and give a precise meaning which will be repeated throughout the rest of this request.

In addition to the specific knowledge constituted by the synthesis of particular polymers, the person skilled in the art finds in document US 5,424,364 the following general education: "polymers of controlled structure" are effective dispersants for mineral fillers. When reading this document, this expression must be interpreted as polymers of block structure AB, to the detriment of polymers with statistical architecture. This notion is found in document US 5,231,131 which teaches the skilled person that the purer these structured polymers, the more effective they are as a dispersing agent: the preferred structure here is that of block polymers, or combs , to the detriment of a random architecture. Similarly, in terms of grinding processes, it appears in the document “Wetting and dispersing agents” (Chimia, 56, 2002, 170-176) that block structure copolymers can behave like very grinding aid agents. effective for inorganic pigments used in paints and plastics.

In accordance with these documents, the term “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, ...).

By way of example, a person skilled in the art thus knows the documents 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).

As for document US 4,656,226, it relates to a dispersant for pigments obtained by the GTP (Group Transfer Polymerization) technique, having a block structure of type AB, where A is a segment made up of polymerized methacrylic monomer units and B is a segment made up of polymerized methacrylic or acrylic monomeric units.

At this stage of research, the objective of a person skilled in the art is therefore to obtain such polymers with controlled architecture.

Continuing his research in this direction, the person skilled in the art then becomes aware of the documents presenting the synthesis of polymers with controlled structure, obtained by the ATRP process (Atom Transfer Radical Polymerization). This technique was widely described in the document (Controlled Radical Polymerization, K. Matyjaszewski, Am.Chem.Soα, 1998, Chaplό, pρ258).

Thus, document FR 2 797 633 describes a process for the polymerization by ATRP of acrylic and methacrylic monomers. Similarly, "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).

Finally, 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.

Nevertheless, all of these documents reveal new problems to those skilled in the art. On the one hand, 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. On the other hand, the ATRP process also involves often undesirable amines in the final product.

In view of this serious drawback, a person skilled in the art then turns to another polymerization process making it possible to obtain controlled structures: the RAFT (Reversible Addition Fragmentation chain Transfer) technique. This has been widely described in the document (Controlled / Living Radical Polymerization-Progress in ATRP, NMP, and RAFT, K. Matyjaszewski, Am.Chem.Soc, 2000, Chap20, ρρ278).

A person skilled in the art knows in this field the document WO 98/01478 which describes the synthesis of polymers of the block, graft or star type, using a transfer agent of the R-C (= S) -S-R 'type.

At the same time, he knows the document FR 2 821 620 which proposes a RAFT type polymerization process for acrylic acid, using a transfer agent of the RXC (= S) -S-R 'type. The polymer obtained can then be used as a dispersing agent or as a grinding aid in suspensions of mineral materials. But a new problem, inherent in this polymerization technique, then appears: it is the use of sulfur transfer agents. In addition to the disadvantage of being dangerous for the environment, these transfer agents give the polymers obtained a very unpleasant odor, and introduce into the final product organo-sulfur molecules which are not necessarily desired.

To overcome this new drawback, those skilled in the art finally turn to recent techniques for controlled radical polymerization, which use nitroxides or alkoxyamines as polymerization initiators.

Thus, document WO 00/71501 teaches him that particular polyalkoxyamines can be used to synthesize in particular triblock copolymers, each block being derived from monomers as different as alkyl acrylates and styrenic derivatives, with excellent control of the polymerization and of the polydispersity index. This document does not however reveal any particular use of said polymers.

Finally, the document WO 01/02345 teaches those skilled in the art that polyalkoxyamines make it possible to obtain polymers with controlled structure, such as block, comb, grafted, or even random. These polymers find numerous applications as rheology modifiers or dispersants for mineral fillers in the aqueous phase. However, this patent application reveals a major drawback in the industrial manufacture of polymers. If it is indicated in the text that the cleavage of the OC bond of the selected alkoxyamine takes place between 50 and 160 ° C (page 35), it is clear in the examples that it is necessary to work at temperatures much higher at 100 ° C in order to be effective.

As demonstrated in Examples C1 to C9 (pages 57 to 59) on the polymerization of butyl acrylate, the reaction must be carried out at 145 ° C for 3 hours. However, if it is desired to work in the aqueous phase, which is the wish of a person skilled in the art with respect for the environment, such temperatures make the polymerization process at atmospheric pressure impossible. Furthermore, the fact of having to work at such high temperatures constitutes a crippling disadvantage for the synthesis of dispersants and grinding aid agents from acrylic compounds; in fact, at such temperatures, one is close to, or even beyond, the boiling temperatures of the monomers used, these boiling temperatures being respectively equal to 145 ° C., 141 ° C., 161 ° C. for the butyl acrylate, acrylic acid and methacrylic acid.

In addition, at such temperatures, thermal initiation phenomena appear, thus generating uncontrolled chains and thereby degrading the controlled architecture.

Continuing its research, 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.

Thus, 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):

R ₂ R4

R, - C - O -N - CH - R ₅

O = CO = P - OR ₆

OR ₃ OR ₇

in which: - 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 ₃ represents a hydrogen atom, a radical alkyl, linear or branched, having a number of carbon atoms ranging from 1 to 8, a phenyl radical, a cation such as Li ⁺ , Na ⁺ , K ⁺ , H ₄ N, Bu ₃ HN ⁺ with Bu = butyl, and preferably represents the hydrogen atom, - 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 of carbon atoms ranging from 1 to 8, and preferably an ethyl radical.

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. Finally, 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.

The use according to the invention of said 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. These 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.

Finally, the direct use of said 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.

These aims are achieved thanks to the use, according to the invention of 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).

The use of 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)

b) and optionally at least one nonionic monomer, the nonionic monomer consisting of at least one monomer of formula (I):

in which: 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, α-α 'dimethyl-isopropenyl-benzylurethanes, allylurethanes, as well as in the group of substituted or unsubstituted allyl or vinyl ethers, or also in the group of ethylenic amides or imides hardly unsaturated, R 'represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I), c) and optionally at least one monomer of the acrylamide or methacrylamide type and their mixtures, or alternatively at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as acetate of vinyl, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or also at least one organofluorinated or organosililated monomer, or their mixtures, d) and optionally at least one monomer having at least two ethylenic unsaturations hereinafter called the crosslinking monomer application, or of the mixture of several of these monomers.

In particular, the use of 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 such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinyl sulfonic acid and styrene sulfonic acid or else chosen among the ethylenically unsaturated monomers and with phosphoric function in the acid or salified state such as vinyl phosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene acrylate phosphate glycol, propylene glycol acrylate phosphate and their ethoxylates or alternatively chosen from ethylenically unsaturated monomers with a phosphonic function in the acid or salified state such as vinyl phosphonic acid, or mixtures thereof, or ii) cationic chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate, or N- [2- (dimethylamino) ethyl] acrylate, or among quaternary ammoniums such as [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [2- (acryloyloxy) ethyl chloride or sulfate ] trimethyl ammo nium, [3- (acrylamido) propyl] trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethyl ammonium chloride or sulfate, or mixtures thereof, or iii) the mixture of the above-mentioned anionic and cationic monomers

and optionally at least one nonionic ethylenically unsaturated monomer of formula (I):

in which: 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 + ρ) 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, -α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically unsaturated amides or iides, R 'represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 atom es of carbon and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or of a mixture of several monomers of formula (I), and optionally at least one monomer of the acrylamide or methacrylamide type and their mixtures, or alternatively at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least one organofluorinated or organosililated monomer preferably chosen from molecules of formulas (Ha) or (Ilb): with formula (Ha)

in which : - 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 , α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of allylic or vinyl ethers substituted or not, or also to the group of ethylenically unsaturated amides or imides, R4, R ₅ , Rio and Ru, represent hydrogen or the meth radical yl or ethyl, R ₆ , R ₇ , R ₈ and R, represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture, R ₁₂ represents a hydrocarbon radical having 1 to 40 carbon atoms, A and B are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms,

with formula (Ilb) R- A - Si (OB) ₃

in which: - 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, α- '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, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide , methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers obtained from p olyols such as pentaerythritol, sorbitol, sucrose or others, or chosen from the molecules of formula (III):

in which 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, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, - Rι ₄ , R ₁₅ , R ₂ o and R ₂ ι, represent hydrogen or the methyl or ethyl radical, Rie, Rπ, Ris and R _i , represent linear or branched alkyl groups, or aryl, or alkylaryl, or arylalkyl having 1 to 20 carbon atoms, or their mixture, D and E are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers.

More particularly, the use of 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 a functional group acidic or salified ulfonic such as acid acrylamido-methyl-propane-sulfonic, sodium methallylsulfonate, vinyl sulfonic acid and styrene sulfonic acid or alternatively chosen from ethylenically unsaturated monomers with phosphoric function in the acid or salified state such as acid vinyl phosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate and their ethoxylates or alternatively chosen from unsaturated monomers ethylenic and with a phosphonic function in the acid or salified state such as vinyl phosphonic acid, or mixtures thereof, or ii) a cationic monomer chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3 - (dimethylamino) propyl] methacrylamide, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate, or N- [2- (dimethylamino) ethyl] acrylate, or among ammonium quaterna ires such as [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [2- (acryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [3- (acrylamido) propyl chloride or sulfate ] trimethyl ammonium, dimethyl diallyl ammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethyl ammonium chloride or sulfate, or mixtures thereof, or iii) a mixture of the above anionic and cationic monomers,

b) from 0 to 98% and even more particularly from 0% to 96% of at least one nonionic ethylenically unsaturated monomer of formula (I):

in which: 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, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group ethylenically unsaturated amides or imides, R 'represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 ato mes of carbon and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or of a mixture of several monomers of formula (I), from 0 to 50% of at least one monomer of the acrylamide or methacrylamide type and their mixtures, or moreover at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or also at least one organofluorinated or organosililated monomer preferably chosen from the molecules of formulas (Ha) or (Ilb): with formula (Ha)

in which : - 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, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or to the group of ethylenically unsaturated amides or imides, R ₄ , R ₅ , Rio and Rπ , represent hydrogen or the radical methyl or ethyl, R ₆ , R ₇ , R ₈ and R ₉ , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture, Rι ₂ represents a hydrocarbon radical having 1 to 40 carbon atoms, A and B are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms,

with formula (Ilb) R - A - Si (OB) ₃ in which: 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, α-α '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 least one crosslinking monomer chosen in a nonlimiting manner from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose or others, or chosen from the molecules of formula (III):

(III) in which: - 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 a 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, Rι ₃ represents a radical containing an 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, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or to the group of ethylenically unsaturated amides or imides, Rι ₄ , R ₁₅ , R ₂ o and R ₂ ι, represent hydrogen or the methyl or ethyl radical, R _IO , Ri ₇ , Ris and R _{] 9} , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 atoms of carbon, or their mixture, D and E are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several of these monomers.

Finally, the use of 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.

Depending on its use, those skilled in the art will be able to adapt the molecular weight of the polymer used according to the invention.

This molecular weight is determined according to the GPC method (Steric Exclusion Chromatography or Gel Permeability Chromatography) using a Waters ™ brand liquid chromatography device equipped with two detectors, one of which combines dynamic light scattering with viscosimetry. measured by a Niscotek ™ viscometer and the other being a Waters ™ 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.

Thus 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.

It is preferably characterized in that the water-soluble polymer is obtained by the controlled radical polymerization of monomers chosen from the monomers mentioned above. Another particular way consists in that 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.

Likewise, 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.

It is preferably characterized in that the water-soluble polymer is obtained by the controlled radical polymerization of monomers chosen from the monomers mentioned above.

Another particular way consists in that 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.

Finally, 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.

These 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.

These 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.

The 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.

The 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.

Finally, the abovementioned 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.

Whatever their mode of production (using aqueous dispersions and / or suspensions of mineral matter produced with said polymer and / or said copolymer, or by direct introduction of said polymer and / or said copolymer into the formulations concerned) 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.

The scope and the interest of the invention will be better perceived thanks to the following examples which cannot be limiting. EXAMPLE 1:

This example illustrates the production of water-soluble polymers used according to the invention.

Test # 1

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced:

- 10.56 g of methacrylic acid - 200 g of water

- 490 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 5000.

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:

Then cooked for 2 hours with stirring at 60 ° C and the ethanol is distilled. The medium is neutralized to pH 7 with a 50% sodium hydroxide solution.

A clear aqueous solution containing 37% of dry matter is obtained of a polymer composed by weight of:

- 4.13% methacrylic acid,

- 95.87% methoxy polyethylene glycol methacrylate of molecular weight 5000

whose GPC analysis previously described indicates a weight average molecular weight Mw of 169,000. Test # 2

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced: - 10.56 g of methacrylic acid, - 200 g of water,

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:

Then cooked for 2 hours with stirring at 70 ° C and the ethanol is distilled. The medium is neutralized to pH 7 with a 50% sodium hydroxide solution.

A clear aqueous solution containing 36% of dry matter is obtained of a polymer composed by weight of:

- 4.13% methacrylic acid,

- 95.87% methoxy polyethylene glycol methacrylate of molecular weight 5000

whose GPC analysis previously described indicates a weight average molecular weight Mw of 103,000.

Test # 3

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath heating system, the following are introduced: - 16.9 g of methacrylic acid - 200 g of water

- 490 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000.

A clear aqueous solution containing 39% of dry matter is obtained of a polymer composed by weight of:

- 6.45% methacrylic acid, 93.55% methoxy polyethylene glycol methacrylate of molecular weight 2000,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 85,000.

Test # 4

10.56 g of methacrylic acid are introduced into a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system.

- 200 g of water,

- 490 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 1100. 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 40% dry matter of a polymer composed by weight of:

- 4.13% methacrylic acid,

- 95.87% methoxy methacrylate polyethylene glycol with molecular weight 1100

whose GPC analysis previously described indicates a weight average molecular weight Mw of 129,000.

EXAMPLE 2:

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.

It should also be noted that these calcium carbonate suspensions according to the invention are refined, highly concentrated in mineral matter and easily handled by the end user, that is to say easily usable both for coating the paper and for the mass charge of the paper. Test # 5

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.

Test # 6

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.

Trial # 8

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.

For each test, 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 ™ 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 ™ 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.

At the end of the grinding (T ₀ ), 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 ™ 5100 particle size analyzer from the company Micromeritics.

The Brookfield ™ viscosity of the suspension is measured using a Brookfield ™ viscometer type RNT, at a temperature of 20 ° C. and rotational speeds of 10 rpm and 100 rpm with the appropriate mobile. The results constitute the viscosity values at t = 0.

After a standing time of 8 days in the bottle, the bottle is shaken then the viscosity of the suspension is measured by introducing the Brookfield ™ 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.

These viscosity measurements constitute the results of APAG viscosity at t = 8 d after stirring.

All these experimental results are recorded in the following table 1, which moreover indicate the consumption in percentage by weight of grinding aid agent used to obtain the particle size indicated. TABLE 1

Reading the results in 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.

EXAMPLE 3:

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.

For this purpose, for each of the tests in the example, 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.

To do this, we weigh in the mixing bowl

- 450 g of CCB 42.5R HES cement from Gaurain in accordance with standard NF P 15-301 - the amount of water required;

- and 0.5% by dry weight, relative to the weight of cement, of the dispersant to be tested;

- a variable quantity in grams of standardized Leucate sand (EN 196-1). This amount of sand being added according to standard EN 196-1 for 30 seconds and after 30 seconds of slow stirring of the mixture of the constituents previously added.

After the addition of these various constituents, 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.

Once the scraping of the adhesive mortar on the walls is finished, the mixing is repeated for 1 minute at high speed.

Respecting these times allows us to obtain a mixing cycle which lasts 4 minutes and complies with standard EN 196-1.

Test # 9

This test illustrates the control and uses a cement formulation without adding an additive.

Test # 10

This test illustrates the prior art and uses a naphthalene sulfonate sold by the company SCHEPPENS.

Test No. 11 This test, which illustrates the invention, uses the polymer of test No. 1.

Trial # 12

This test, which illustrates the invention, uses the polymer of test No. 3. Test # 13

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.

The quantities of the constituents being adjusted for each of the mortars of the different tests in order to work at constant real volume (1 m ³ for 450 kg of cement) and constant workability (2 seconds), the polymer used is all the more effective as the reduction of water is important and the addition of sand more important.

The results obtained for the various tests are collated in Table 2 below. TABLE 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.

EXAMPLE 4:

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.

To do this and for each of the tests n ° 16 to 19, 250 grams of raw water and 0.65 grams are weighed, in a plastic beaker of 500 milliliters provided with a stirring blade of 60 mm in diameter. dispersant to be tested.

After stirring the mixture contained in the beaker, 217.3 g of FUCHS-TON clay for slip are poured in rain so as to obtain a dry matter concentration equal to 46.5% and a dispersant content to be tested equal at 0.3% by dry weight relative to the dry weight of clay.

After 20 minutes of stirring at a speed of 750 revolutions per minute, the viscosity of the slip is measured by measuring the Brookfield ™ viscosity RNT type at 10 revolutions per minute and 100 revolutions per minute.

The various tests are as follows:

Trial # 15

This test is a control and does not use any dispersant.

The Brookfield ™ viscosities obtained are equal to 6400 mPa.s at 10 rpm and 870 mPa.s at 100 rpm.

Trial # 16

This test illustrates the use of polymer according to the invention and implements the polymer of test No. 1.

The Brookfield ™ 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.

Trial # 18

This test illustrates the use of polymer according to the invention and implements the polymer of test No. 2.

The Brookfield ™ 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.

Reading the results of the various tests shows that the use of polymers in the ceramic field is possible.

EXAMPLE 5:

Test No. 20: 13.03 g of methacrylic acid are introduced into a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, - 233 g of water,

425.46 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000,

- 3.3 g of 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:

Then cooked for 1 hour with stirring at 95 ° C. 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,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 22,870.

Trial # 21

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced: - 206.3 g of methacrylic acid,

- 233 g of water,

- 22.4 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000, - 3.3 g of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 d units oxypropylene.

Then cooked for 1 hour with stirring at 95 ° C.

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,

- 4.9% of methoxy polyethylene glycol methacrylate of molecular mass 2000, 1.5% 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 39,130.

Trial # 22

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced: - 30.0 g of methacrylic acid,

- 233 g of water,

- 363.9 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000, - 3.3 g of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 d units oxypropylene,

- 1.1 g of ethylene glycol dimethacrylate.

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:

Then cooked for 1 hour with stirring at 95 ° C.

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,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 40,000.

Trial # 23 In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced:

- 54.0 g of methacrylic acid,

- 270 g of water, - 655 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000,

- 5.9 g of 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:

Then cooked for 1 hour with stirring at 95 ° C.

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,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 162,400. Trial # 24

- 54.0 g of methacrylic acid,

- 270 g of water,

- 655 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000,

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:

Then cooked for 1 hour with stirring at 95 ° C.

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,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 66 100. Trial # 25

- 54.0 g of methacrylic acid,

- 270 g of water,

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:

Then cooked for 1 hour with stirring at 95 ° C.

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,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 33,300. Trial # 26

- 42.0 g of methacrylic acid, - 326 g of water,

- 509.5 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000,

- 4.6 g of 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:

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,

- 1.5% butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units,

0.5% 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, 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.

609.9 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol with molecular mass 5000,

- 4.9 g of 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. 81 g of 50% sodium hydroxide:

Then cooked for 1 hour with stirring at 95 ° C.

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:

- 20.66 g of methacrylic acid,

- 175 g of water,

Then cooked for 1 hour with stirring at 95 ° C.

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:

- 7.5% methacrylic acid,

- 91.0% methoxy polyethylene glycol methacrylate of molecular weight 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 51900.

Test No. 29 In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced:

- 20.66 g of methacrylic acid,

- 270 g of water, 572.8 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000, 5.9 g of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 units of oxyethylene and 11 oxypropylene units,

- 79.6 g of tristyrylphenol methacrylate with 25 ethylene oxide units.

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:

Then cooked for 1 hour with stirring at 95 ° C.

The medium is neutralized to pH 8 with a 50% sodium hydroxide solution.

A clear aqueous solution containing 34.2% of dry matter of a polymer composed by weight of: 18.5% of methacrylic acid, - 70.0% of methoxy methacrylate polyethylene glycol of molecular weight 2000, is obtained, - 1.5% butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units,

- 10% tristyrylphenol methacrylate with 25 ethylene oxide units,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 52,700.

Trial # 30

16.65 g of methacrylic acid are introduced into a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system.

- 270 g of water,

- 572.8 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000, - 5.9 g of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 d units oxypropylene, 79.6 g of nonylphenol methacrylate with 50 units of ethylene oxide.

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. 0.05 g of 50% sodium hydroxide:

Then cooked for 1 hour with stirring at 95 ° C.

The medium is neutralized to pH 8 with a 50% sodium hydroxide solution.

A clear aqueous solution containing 34.0% dry matter of a polymer composed by weight of: - 18.5% methacrylic acid,

- 70.0% methoxy polyethylene glycol methacrylate of molecular weight 2000,

- 10% nonylphenol methacrylate with 50 ethylene oxide units,

Trial # 31

- 54.0 g of methacrylic acid, - 270 g of water,

- 246.8 g of 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:

Then cooked for 1 hour with stirring at 95 ° C.

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:

- 17.0% methacrylic acid,

- 77.6% of 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,

- 5.4% ethyl methacrylate,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 105,730.

Trial # 32

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced: - 54.0 g of methacrylic acid,

- 270 g of water, 655 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000, 5.9 g of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene patterns.

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:

Then cooked for 1 hour with stirring at 95 ° C. The medium is neutralized to pH 8 with a 50% sodium hydroxide solution. A clear aqueous solution containing 34.6% dry matter of a polymer composed by weight of:

- 18.5% methacrylic acid,

- 80.0% methoxy polyethylene glycol methacrylate of molecular weight 2000,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 27,630.

Trial # 33

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced: - 11.9 g of methacrylic acid,

- 270 g of water,

- 736.4 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular weight 2000, 5.9 g of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 units of oxypropylene.

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:

Then cooked for 1 hour with stirring at 95 ° C. The medium is neutralized to pH 8 with a 50% sodium hydroxide solution. A clear aqueous solution containing 33.7% of dry matter is obtained of a polymer composed by weight of:

- 8.5% methacrylic acid,

- 90.0% methoxy polyethylene glycol methacrylate of molecular weight 2000, 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 25,830.

Essay # 34

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced: - 96.35 g of methacrylic acid,

- 270 g of water, 572.8 g of an aqueous solution at 50% by mass concentration of methoxy methacrylate polyethylene glycol of molecular mass 2000, 5.9 g of butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 units of oxyethylene 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. 0.08 g of 50% sodium hydroxide:

Then cooked for 1 hour with stirring at 95 ° C. The medium is neutralized to pH 8 with a 50% sodium hydroxide solution. A clear aqueous solution containing 35.4% of dry matter is obtained of a polymer composed by weight of:

- 28.5% methacrylic acid,

- 70.0% methoxy polyethylene glycol methacrylate of molecular weight 2000, 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 24,950.

Trial # 35

The following are introduced into a 1 liter glass reactor fitted with mechanical stirring and an oil bath heating system: - 316.7 g of methacrylic acid, 216 g of water, 4.72 g butoxypoly methacrylate (oxyethylene oxypropylene) comprising 10 oxyethylene units and 11 oxypropylene units.

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:

Then cooked for 1 hour with stirring at 95 ° C.

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:

- 98.5% methacrylic acid,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 22,400.

Essay # 36

163.0 g of methacrylic acid, 198.5 g of methoxy polyethylene glycol methacrylate are introduced into a 1 liter glass reactor fitted with mechanical stirring and an oil bath heating system. molecular weight 2000,

- 270 g of water, 5.9 g of 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. 0.05 g of 50% sodium hydroxide:

Then cooked for 1 hour with stirring at 95 ° C.

The medium is neutralized to pH 8 with a 50% sodium hydroxide solution. A clear aqueous solution containing 38.1% of dry matter of a polymer composed by weight of:

- 49.0% methacrylic acid,

- 49.5% methoxy polyethylene glycol methacrylate of molecular weight 2000,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 25,430.

Essay # 37

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced: - 358.2 g of methacrylic acid,

- 39.8 g of ethylene glycol methacrylate phosphate,

- 270 g of water.

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 sodium hydroxide at 50%:

Then cooked for 1 hour with stirring at 95 ° C.

The medium is neutralized to pH 8 with a 50% sodium hydroxide solution.

A clear aqueous solution containing 34.6% dry matter of a polymer composed by weight of: - 90.0% methacrylic acid,

- 10.0% of ethylene glycol methacrylate phosphate,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 25,400.

Essay # 38

In a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system, the following are introduced: - 318.4 g of methacrylic acid, 79.6 g of acrylamide,

- 270 g of water.

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:

Then cooked for 1 hour with stirring at 95 ° C.

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,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 25,200. Trial # 39

- 318.4 g of methacrylic acid, - 79.6 g of itaconic acid,

- 250 g of water.

Then cooked for 1 hour with stirring at 95 ° C.

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,

whose GPC analysis previously described indicates a weight average molecular weight Mw of 26,000.

Trial 40

- 318.4 g of methacrylic acid, - 79.6 g of acrylamidomethylpropanesulfonic acid, - 250 g of water.

Then cooked for 1 hour with stirring at 95 ° C.

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,

Trial # 41

318.5 g of methacryloyloxyethyltrimethylammonium chloride are introduced into a 1 liter glass reactor fitted with mechanical stirring and an oil bath type heating system.

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:

Then cooked for 1 hour with stirring at 95 ° C.

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.

EXAMPLE 6

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.

First, we begin by grinding the mineral filler, according to the following procedure.

In a planetary mixer whose rotational speed is at least equal to 20,000 revolutions / minute, 300 grams of grinding substance which are aluminum oxide balls, 200 grams of calcium carbonate which is chalk, are introduced, 117 grams of water and 1.6 grams of polymer to be tested. On the other hand, this calcium carbonate is initially filtered through a sieve whose mesh is equal to 45 μm; the percentage by weight of particles whose size is greater than 45 μm is thus determined: this value is equal to 95%. The mixture is ground for 10 minutes at 20,000 rpm. For each polymer to be tested, two identical suspensions are produced according to the method described above.

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.

Trial # 42

This test illustrates the invention and uses the polymer described in 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 μm is 5.21%.

Trial # 43

This test illustrates the invention and uses the polymer described in test No. 26. In the first, once rinsed and dried, the percentage by weight of particles whose size is greater than 45 μm is 5.21 %.

These results demonstrate that the polymers can be used according to the invention as agents for grinding the chalk.

In a second step, 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.

To do this, weigh in a plastic beaker of 500 milliliters fitted with a 60 mm diameter stirring blade, 162 grams of raw water and, after stirring at a speed of 1300 rpm, the suspension of mineral material to be tested is poured.

After 20 minutes of stirring at a speed of 1300 revolutions per minute, the viscosity of the slip obtained is measured by determination of the Brookfield ™ viscosity RNT type at 10 revolutions per minute according to the method previously described in the present application. Trial n ° 44

This test illustrates the invention and uses the aqueous suspension, not rinsed and dried, described in test No. 42.

The Brookfield ™ viscosity RNT type at 10 revolutions per minute measured for the slip obtained is then equal to 21,200 mPa.s.

Trial # 45

This test illustrates the invention and uses the aqueous suspension, not rinsed and dried, described in test No. 43. The Brookfield ™ RNT type viscosity at 10 revolutions per minute measured for the slip obtained is then equal to 7,900 mPa.s.

The viscosity values obtained during tests No. 44 and No. 45 demonstrate that the use of aqueous suspensions of mineral materials according to the invention, obtained by using the grinding agents according to the invention, is possible in the field of ceramic.

EXAMPLE 7:

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.

For tests No. 46 and No. 47, 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 ™ marketed by the company of the same name:

- 375.9 g of synthetic sea water (deionized water added with 44.05 g / 1 of ΝaCl, 0.67 g / 1 of KC1, 1.36 g / 1 of CaCl ₂ , 2H ₂ O, 4, 66 g / 1 of MgCl ₂ , 6H ₂ O, 6.29 g / 1 of MgSO ₄ , 7H ₂ O, 0.18 g / 1 of ΝaHCO ₃ ), - 17.655g (i.e. 48.77 g / 1) of Zéogel ™ which is a clay marketed by the company BAROID ™ while maintaining stirring in the "low" position for 10 minutes, - 10.088 g of Aquagel ™ which is a clay sold by the company BAROID ™ while maintaining the stirring in the "low" position for 10 minutes, - 277.5 g of barium sulfate while maintaining the stirring for 15 minutes , - 5.35 g of Thermacheck ™ which is a filtrate reducer sold by the company BAROID ™, while maintaining stirring for 15 minutes, then the pH is adjusted to 10.5 using sodium hydroxide .

686.5 g of mud are then removed from the bowl and 5.0 grams of polymer to be tested are then optionally introduced. The pH is maintained at 10.5 by adding sodium hydroxide.

Viscosity measurements are then carried out with a Fann ™ 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.

We then calculate:

- Apparent viscosity (Va): reading at 600 rpm Va (mPa.s) = 2 - Plastic viscosity (Np): Np (mPa.s) = reading at 600 rpm - reading at 300 rpm

- The flow limit: Yv = 2 x (Va-Np)

The corresponding results are shown in Table 3. Trial # 46

This test illustrates the prior art and uses the drilling mud described above, without adding polymer.

Trial # 47

This test illustrates the invention and uses according to the invention the polymer described in test No. 26.

TABLE 3

The values of the apparent viscosity and the flow limit in Table 3 demonstrate that the use of the dispersing agents according to the invention is possible in drilling muds. EXAMPLE 8:

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.

For tests n ° 48 to n ° 51, 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 ™ under the name of Omyacarb ™ 30 AN, water, an active surfactant which is Ethylan ™ 1005 sold by the company AKZO NOBEL ™, and the dispersing agent to be tested. The corresponding quantities are shown in Table 4.

Sodium hydroxide is then added so as to obtain a pH equal to 8.

These products are mixed for 5 minutes in the planetary mill at a speed of 20,000 revolutions / minute.

The Brookfield ™ 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.

Trial # 48

This test illustrates the invention and uses the polymer according to test No. 24.

Essay # 49

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.

Essay # 51

This test illustrates the invention and uses the polymer according to test No. 29. The composition of the recurrent formulations and the values of Brookfield ™ viscosities type RNT at 20 revolutions per minute obtained for tests No. 41 to No. 44 are indicated in Table 4.

TABLE 4

The values of Brookfield ™ 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.

EXAMPLE 9:

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.

For tests no. 52 to no. 55, 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 ™ 1005 sold by the company AKZO NOBEL ™, and the dispersing agent to be tested.

Sodium hydroxide is then added so as to obtain a pH equal to 8.

The Brookfield ™ 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.

Essay # 53

This test illustrates the invention and uses the aqueous suspension of ground calcium carbonate according to test No. 6.

Essay # 54

This test illustrates the invention and uses the aqueous suspension of ground calcium carbonate according to test No. 7.

Trial 55

This test illustrates the invention and uses the aqueous suspension of ground calcium carbonate according to test No. 8.

The composition of the recurring formulations and the values of Brookfield ™ viscosities type RVT at 20 revolutions per minute obtained for tests No. 52 to No. 55 are indicated in Table 5. TABLE 5

The values of Brookfield ™ viscosities type RVT at 20 revolutions per minute demonstrate that the aqueous suspensions of calcium carbonate ground according to the invention can be used in recurrent creams in the detergency field.

EXAMPLE 10:

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.

To do this, are introduced into a 1 liter beaker 321 grams of water, 0.2 grams of an anti-foaming agent sold by the company BYK ™ under the name Byk ™ 034, 1000 grams of titanium dioxide sold by the company TIOXIDE ™ under the name RHD2, and a given quantity of product to be tested.

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 ™ 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 ™ viscosity at 10 revolutions / minute (according to the method and with the device previously described in this document).

For tests No. 56 to No. 59 which use dispersing agents according to the invention, the values of the Brookfield ™ viscosities (in mPa.s) obtained are listed in Table 6, as a function of the percentage by dry weight d dispersing agent tested relative to the dry weight of mineral matter.

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.

TABLE 6

Reading the values of the Brookfield ™ viscosity at 20 revolutions / minute demonstrates that the dispersing agents of the invention can be used to disperse titanium dioxide in water.

EXAMPLE 11

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.

To do this, 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.

For each of the paints thus formulated, its Brookfield ™ viscosity is determined at 10 revolutions / minute according to the procedure described above. Its ICI ™ and Stormer ™ viscosities are also determined by the following methods. The ICI ™ viscosity is determined on a cone-plane viscometer, called an ICF viscometer, sold by the company ERICHSEN ™, according to the method perfectly known to those skilled in the art. The measurement is carried out at 25 ° C. The Stormer ™ viscosity is determined on a Stormer KU-1 viscometer marketed by the company Brookfield ™, 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.

The results corresponding to the Brookfield ™, ICI ™ and Stormer ™ viscosities, measured for tests # 60 and # 61 are shown in Table 7.

TABLE 7

Coatex ™ BR 100 is a thickener sold by the company COATEX ™.

Mergal ™ K.6N is a bactericide sold by the company TROY ™.

Nopco ™ NDW is an anti-foaming agent sold by the company COGNIS ™. Rhodopas ™ 290 D is a styrene acrylic binder sold by the company RHODIA ™.

The values of the various viscosities obtained in Table 7 demonstrate that the direct use of dispersing agents according to the invention is possible in the field of aqueous paints.

EXAMPLE 12:

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.

To do this, 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.

Essay # 62

This test illustrates the invention and uses the aqueous suspension according to the invention described in Example No. 56.

Trial # 63

This test illustrates the invention and uses the aqueous suspension according to the invention described in Example No. 57.

As in Example 11, the viscosities ICF ^M , Stormer ™ and Brookfield ™ of the aqueous paints thus produced are determined immediately after formulation, then after a storage time of 24 hours at room temperature. The corresponding results appear in Table 8. 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 ™ BR 100 is a thickener sold by the company COATEX ™.

Mergal ™ K6N is a bactericide sold by the company TROY ™. Nopco ™ NDW is an anti-foaming agent sold by the company COGNIS ™.

Rhodopas ™ 290 D is a styrene acrylic binder sold by the company RHODIA ™.

The values of the various viscosities obtained in Table 8 demonstrate that the use of aqueous suspensions according to the invention of mineral materials dispersed with dispersing agents according to the invention is possible in the field of aqueous paints.

EXAMPLE 13:

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.

For this purpose, for each of the tests of the example, the various constituents of the standard mortar dosed at 450 kg / m of cement, the composition of which is as follows, are poured into a mortar mixer (EN 196-1) in the on position.

450 g of Caur 142.5R CP2 cement from Gaurain in accordance with standard NF P 15-301, the amount of calcium carbonate dispersion to be tested, the amount of water required,

- a variable quantity in grams of standardized Leucate sand (EN 196-1). This quantity of sand being added for 30 seconds and after 30 seconds of rapid stirring of the mixture of the constituents previously added.

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.

Once the scraping of the adhering mortar on the walls is finished, the mixing is resumed for 1 minute at high speed. Respecting these times allows us to obtain a mixing cycle which lasts 4 minutes and complies with standard EN 196-1.

The maneuverability of the mortars thus formulated is then determined on a mortar maneuverimeter as defined by standard NF P 15-412.

Essay # 64

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 ™ 5100, using 0.70%, by dry weight relative to the dry weight of calcium carbonate , of the copolymer of test No. 38.

For this purpose, and using an electromagnetic stirrer with fins, the aqueous dispersion of calcium carbonate is prepared by introduction of the mineral filler in the water additive with the dispersing copolymer.

Test n ° 65

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 0.41 and using 30% by dry weight, relative to the dry weight of cement, of a dispersion of calcite at 45% in dry matter of equal median diameter at 2 micrometers measured with Sedigraph ™ 5100, using 0.70%, by dry weight, relative to the dry weight of calcium carbonate, of the copolymer of test No. 38.

The procedure and the equipment used for the dispersion of calcium carbonate are identical to those of test No. 64.

The results of the workability measurement are collated in Table 9. TABLE 9

The results in Table 9 demonstrate that the aqueous dispersions of mineral materials according to the invention and produced with dispersing agents according to the invention can be used to produce mortars.

EXAMPLE 14:

This example illustrates the use of dispersing agents according to the invention for dispersing in mineral water a material which is kaolin.

To do this, in a 1000 milliliter beaker, 500 grams of a mineral filler is introduced, which is a kaolin marketed by the company CADAM ™ under the name Amazon + ™, 175 grams of water, and 1 gram of hydroxide. 12.5% sodium. Using a Rayneri ™ Turbotest device, this mixture is stirred at a speed of 2000 rpm.

Successive additions of dispersing agent according to the invention are carried out, the mixture being stirred for 2 minutes at the speed of 2000 revolutions per minute, then a Brookfield ™ viscosity measurement is carried out at 100 revolutions per minute according to the method described above.

Essay # 66

This test illustrates the invention and uses the polymer according to test No. 23. Essay # 67

Test No. 68 This test illustrates the invention and uses the polymer according to test No. 28.

Essay # 69

This test illustrates the invention and uses the polymer according to test No. 32.

Trial n ° 70

This test illustrates the invention and uses the polymer according to test No. 34.

The corresponding results appear in Table 10, which indicates on the one hand the amount of product tested expressed as a percentage by dry weight of dispersing agent according to the invention relative to the dry weight of mineral matter, and on the other hand the values Brookfield ™ viscosity measured at 100 revolutions per minute and expressed in mPa.s.

TABLE 10

The results in Table 10 demonstrate that the dispersing agents according to the invention can be used to disperse kaolin in water. In addition, a person skilled in the art notes on reading the Brookfield ™ viscosities measured at 100 revolutions per minute, that these dispersions can be used in the paper industry, and in particular in the formulation of paper coating sauces.

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 ™ under the name of Omyacarb ™ 10 AV. The grinding procedure is identical to that described in Example 2.

Trial n ° 71

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.

Trial 72

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.

As in Example 1, their particle size is determined for the aqueous suspensions of ground calcium carbonate, as well as the Brookfield ™ viscosities type RVT, measured at a temperature of 20 ° C. and at rotational speeds of 10 revolutions per minute and 100 revolutions per minute, at t = 0 and t = 8 days after shaking (the measurement methods and notations are identical to those used in example D-

The corresponding measures are shown in Table 11.

TABLE 11

Reading the results in 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.

In a second step, 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.

They also contain 11 grams of a binder sold by the company DOW ™ under the name DL966, 0.4 grams of 2 coliants which are Mowiol 6/98 and Finnfix 10 sold respectively by the companies CLARIANT ™ and METS A SERLA ™, and 0.6 grams of an optical brightener which is Blancophor ™ P sold by the company CLARIANT ™.

Trial # 73

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.

According to the methods described above, the Brookfield ™ RVT type viscosities were then measured at 10 and 100 revolutions per minute for each of the coating sauces obtained; the results are shown in Table 12.

TABLE 12

The results obtained in 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.

EXAMPLE 16:

This example relates to the use of the dispersing agent according to the invention, in the field of plastics.

To do this, we first filter an aqueous suspension of calcium carbonate which is marble, obtained after flocculation, to end up with a cake of marble filtration medium diameter equal to 2 microns as measured using a digraph S _é ™ 5100 sold by the company Micromeritics ™.

From this cake, 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%.

Once this suspension has been produced, it is dried at a temperature below 105 ° C. by the use of a laboratory dryer of the Niro ™ 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.

Trial # 75

This test, illustrating the invention, represents the dispersion test of the marble powder, previously obtained, in a thermoplastic resin.

To do this, 300 grams of powdered marble previously prepared and with an equal average diameter are introduced into a Guittard mixer with a Z-arm with a capacity of 1.5 liters and having a tank electrically heated to 240 ° C. at 2 μm.

After 15 minutes of preheating to 240 ° C. of the feed, 3 grams of commercially available zinc stearate and 125.5 grams of polypropylene homopolymer sold by the company Appryl under the name of PPH 3120MN are introduced.

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.

These results show that the use of the dispersing agent according to the invention is possible in plastic compositions, and in particular thermoplastic compositions.

Essay # 76

This test, illustrating the invention, represents the dispersion test of the marble powder, previously obtained, in a thermosetting resin of the unsaturated polyester type.

To do this, in a 500 ml metal box, we weigh 90 grams of unsaturated polyester resin reference Palapreg ™ PI 8 from BASF, 60 grams of an additive called "Low Profile" and available under the reference LP40A by UNION CARBIDE ™ as well as 300 grams of the marble powder obtained.

After 24 hours of storage at rest, there is a presence of settling or sedimentation before homogenization.

The mixture is then homogenized by stirring with a spatula, then the Brookfield ™ viscosity at 100 revolutions / min is measured after these 24 hours using a Brookfield ™ viscometer type RVT equipped with module 7.

It is equal to 32,000 mPa.s.

This value demonstrates that the 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).

Claims

1 - Use, as a dispersing agent and / or aid for grinding pigments and / or mineral fillers in aqueous suspension, of a water-soluble polymer, characterized in that said water-soluble polymer has a controlled structure and is obtained by a process controlled radical polymerization using, as a polymerization initiator, a particular alkoxyamine of general formula (A):

R ₂ R4

II 0 = CO≈P - O Rô I i OR ₃ OR ₇ in which: - Ri and R represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 5, - R ₃ represents a hydrogen atom, an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 8, a phenyl radical, a cation such as Li ⁺ , Na ⁺ , K ⁺ , H ₄ N, Bu ₃ HN ⁺ with Bu = butyl,

- 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 atoms 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 ethyl radical. 2 - Use, as a dispersing agent and or for grinding aid of pigments and / or mineral fillers in aqueous suspension, of a water-soluble polymer according to claim 1, characterized in that Ri and R ₂ represent the methyl radical and R ₃ represents the hydrogen atom.

3- 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 according to any one of claims 1 or 2, characterized in that said polymer is a water-soluble copolymer and has a structure of the random, block, comb, grafted, or alternating type.

4 - 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 according to any one of claims 1 to 3, characterized in that said polymer and / or water-soluble copolymer is obtained by the controlled radical polymerization 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) b) and optionally at least one nonionic monomer, the nonionic monomer consisting of at least one monomer of formula (I):

(I) in which :

- 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, R _\ 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, vinylphthalic esters as well as to the group of unsaturated urethanes such as acrylurethanes, methacrylurethanes, α-α 'dimethyl-isopropenylbenzylurethanes, allylurethanes, as well as in the group of substituted or unsubstituted allyl or vinyl ethers, or in the group of ethylenically unsaturated amides or imides, R '' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I),

c) and optionally at least one monomer of the acrylamide or methacrylamide type and their mixtures, or alternatively at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or alternatively at least one organofluorinated or organosililated monomer, or their mixtures,

d) and optionally at least one crosslinking monomer, or a mixture of several of these monomers.

5 - Use, as a dispersing agent and / or aid for grinding pigments and / or mineral fillers in aqueous suspension, of a water-soluble polymer according to any one of claims 1 to 4, characterized in that said polymer and / or the water-soluble copolymer is obtained by the controlled radical polymerization of monomers chosen more particularly from: a) at least one ionic monomer which is either i) anionic with ethylenic unsaturation and with a monocarboxylic function in the acid or salified state chosen from the monomers with ethylenic unsaturation and 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 state acid or salified such as crotonic, isocrotonic, cinnamic, itaconic, maleic, or anhydrous ides of carboxylic acids, such as maleic anhydride or chosen from ethylenically unsaturated monomers with a sulfonic function in the acid or salified state such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, l vinyl sulfonic acid and styrene sulfonic acid or alternatively chosen from ethylenically unsaturated monomers with a phosphoric function in the acid or salified state such as vinyl phosphoric acid, ethylene glycol methacrylate phosphate, phosphate propylene glycol methacrylate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate and their ethoxylates or alternatively chosen from ethylenically unsaturated monomers with phosphonic function in the acid or salified state such as vinyl phosphonic acid, or mixtures thereof, or ii) cationic chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propy l] methacrylamide, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate, or N- [2- (dimethylamino) ethyl] acrylate, or among quaternary ammoniums such as chloride or [2- (methacryloyloxy) ethyl] trimethyl ammonium sulfate, [2- (acryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [3- (acrylamido) propyl] trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethyl ammonium chloride or sulfate, or mixtures thereof, either iii) mixing at least one of the above anionic monomers with at least one of the above cationic monomers

in which: 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenylbenzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically insidious amides or imides tured, - R 'represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I), and optionally at least one monomer of the acrylamide or methacrylamide type and their mixtures, or alternatively at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as acetate of vinyl, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least one organofluorinated or organosililated monomer preferably chosen from the molecules of formulas (Ha) or (Ilb): with formula (Ha)

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 a number 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl- benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, - R, R ₅ , Rio and Ru, represent hydrogen or the methyl radical or ethyl, - R ₆ , R ₇ , R ₈ and R ₉ , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture, Rι ₂ represents a hydrocarbon radical having 1 to 40 carbon atoms, A and B are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms,

with formula (Ilb) R- A - Si (OB) ₃

in which: 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 acrylurethanes, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or to 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 a mixture of several of these monomers,

and optionally at least one crosslinking monomer chosen from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, the tetrallyloxyethane, triallylcyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose, or chosen from the molecules of formula (III):

(III) in which: m3, ρ3, 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, Ri 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, Rι ₄ , R _{) 5} , R ₂₀ and R _2] , represent hydrogen e or the methyl or ethyl radical, Rι ₆ , Rπ, R ₁₈ and Rι ₉ , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or a mixture thereof, - D and E are groups possibly present, which represent then a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers,

6 - Use as dispersing agent and / or aid for grinding pigments and / or mineral fillers of a water-soluble polymer according to one of claims 1 to 5, characterized in that said polymer consists, expressed by weight: a) from 2% to 100% and even more particularly from 5% to 100% of at least one ionic monomer, which is either i) anionic with ethylenic unsaturation and with a monocarboxylic function in the acid or salified state chosen from the monomers containing ethylenic unsaturation and having a monocarboxylic function such as acrylic or methacrylic acid or alternatively diacid hemi esters such as the C 1 to C ₄ monoesters of maleic or itaconic acids, or chosen from monomers containing ethylenic unsaturation and having a dicarboxylic function acidic or salified state such as crotonic, isocro tonic, cinnamic, itaconic, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride or chosen pa rmi the monomers with ethylenic unsaturation and with sulfonic function in the acid or salified state such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinyl sulfonic acid and styrene sulfonic acid or else chosen among the ethylenically unsaturated monomers and with phosphoric function in the acid or salified state such as vinyl phosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene acrylate phosphate glycol, propylene glycol acrylate phosphate and their ethoxylates or alternatively chosen from ethylenically unsaturated monomers with a phosphonic function in the acid or salified state such as vinyl phosphonic acid, or mixtures thereof, or ii) cationic chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, unsaturated esters such as methacrylate N- [2- (dimethylamino) ethyl], or N- [2- (dimethylamino) ethyl] acrylate, or among quaternary ammonium such as [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulfate , [2- (acryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [3- (acrylamido) propyl] trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethyl ammonium chloride or sulfate, or mixtures thereof, or iii) mixing at least one of the above anionic monomers with at least one of the above cationic monomers

from 0 to 98% and even more particularly from 0% to 96% of at least one nonionic ethylenically unsaturated monomer of formula (I):

in which: 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 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or even to the group of ethylenically unsaturated amides or imides Rees R 'represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I), from 0 to 50% of at least one monomer of the acrylamide or methacrylamide type and their mixtures, or alternatively of at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or also at least one organofluorinated or organosililated monomer preferably chosen from the molecules of formulas (Ha) or (Ilb): with formula (lia)

in which: 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 that acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, - ₄ , R ₅ , Rio and Ru, represent hydrogen or the methyl or ethyl radical, - R ₆ , R ₇ , R ₈ and R ₉ , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 atoms of carbon, or their mixture, - R ₁₂ represents a hydrocarbon radical having 1 to 40 carbon atoms, A and B are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, with formula (Ilb)

R - A - Si (OB) ₃ in which: 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 group of unsaturated urethanes such as acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to 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 a mixture of several of these monomers,

from 0 to 3% of at least one crosslinking monomer chosen from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose, or chosen from the molecules of formula (III):

(III) in which: 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 + ρ3) q3 ≤ 150 and 0 <(m4 + n4 + p4) q4 <150, r 'represents a number such that 1 < r '<200, Ri 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, Rι ₄ , R15, R ₂ o and R ₂ ι, represent the hydrogen ne or the methyl or ethyl radical, Ri 6, Ri 7, is and R _J9 , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or a mixture thereof, D and E are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several of these monomers,

7 - Agent dispersing pigments and / or mineral fillers in aqueous suspension, characterized in that it is a water-soluble polymer, having a controlled structure and obtained by a controlled radical polymerization process using, as a polymerization initiator , a particular alkoxyamine of general formula (A): R ₂ R ₄ IIR, - C - O -N - CH -R5

O = CO = P - OR _Ô

OR ₃ OR ₇

in which: - Ri and R ₂ represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 5, - R ₃ represents a hydrogen atom, an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 8, a phenyl radical, a cation such as Li ⁺ , Na ⁺ , K ⁺ , H ₄ N, Bu ₃ HN ⁺ with Bu = butyl,

- Ri 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 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 ethyl radical.

8 - Agent dispersing pigments and / or mineral charges in aqueous suspension according to claim 7, characterized in that Ri and R ₂ represent the methyl radical and R ₃ represents the hydrogen atom.

9- Dispersing agent for pigments and / or mineral fillers in aqueous suspension according to any one of claims 7 or 8, characterized in that said polymer is a water-soluble copolymer and has a structure of random type, block, comb, grafted, or alternating.

10- dispersing agent for pigments and / or mineral fillers in aqueous suspension according to any one of claims 7 to 9, characterized in that said water-soluble polymer is obtained by controlled radical polymerization 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 sulphonic function or a mixture thereof, either ii) cationic or iii) the mixture of i) and ii) b) and optionally at least one nonionic monomer , the nonionic monomer consisting of at least one monomer of formula (I):

(D in which: 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, vinylphthalic esters as well as to the group of unsaturated urethanes such as acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or to the group of ethylenically unsaturated amides or imides, R' re has hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I),

d) and optionally at least one crosslinking monomer, or of the mixture of several of these monomers. 11 - Agent dispersing pigments and / or mineral fillers in aqueous suspension according to any one of claims 7 to 10, characterized in that said water-soluble polymer is obtained by controlled radical polymerization of monomers chosen more particularly from: a) at least one ionic monomer, which is either i) anionically ethylenically unsaturated and having a monocarboxylic function in the acid or salified state chosen from ethylenically unsaturated monomers having a monocarboxylic function such as acrylic or methacrylic acid or alternatively hemi esters 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 monomers with ethylenic unsaturation and with a sulfonic function in the acid or salified state such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinyl sulfonic acid and styrene sulfonic acid or alternatively chosen from monomers ethylenically unsaturated and with phosphoric function in the acid or salified state such as vinyl phosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate and their ethoxylates or alternatively chosen from ethylenically unsaturated monomers with a phosphonic function in the acid or salified state such as vinyl phosphonic acid, or mixtures thereof, or ii) cationic chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, unsaturated esters such as N- [2- methacrylate (dimethylamin o) ethyl], or N- [2- (dimethylamino) ethyl] acrylate, or among quaternary ammoniums such as [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, chromium or sulfate [2- (acryloyloxy) ethyl] trimethyl ammonium, [3- (acrylamido) propyl] trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, chromium or [3- (methacrylamido) propyl] trimethyl ammonium sulfate, or mixtures thereof, or iii) the mixture of at least one of the above anionic monomers with at least one of the above cationic monomers

in which: 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 + ρ) q ≤ 150, and preferably such that 15 <(m + n + p) q <120, Ri represents hydrogen or the methyl or ethyl radical, R2 represents hydrogen or the radical methyl or ethyl, 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 acrylurethanes , methacrylurethane, α-α 'dimethyl -isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or to the group of ethylenically unsaturated amides or imides, - R' re has hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I), and optionally at least one monomer of the acrylamide or methacrylamide type and their mixtures, or alternatively at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or alternatively at least one organofluorinated or organosililated monomer chosen from preferentially among the molecules of formulas (Ha) or (Ilb): with formula (Ha)

in which: 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of ethers allyl or vinyl, substituted or unsubstituted, or alternatively from the group of ethylenically unsaturated amides or imides, R, R ₅ , Rio and Ru, represent hydrogen or the methyl or ethyl radical, - R ₆ , R ₇ , R ₈ and R ₉ , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture, Rι ₂ represents a hydrocarbon radical having 1 to 40 carbon atoms, A and B are groups optionally present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, with formula (Ilb) R - A - Si (OB) ₃

in which :

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 acrylurethane, methacrylurethane, α -α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or to 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 a mixture of several of these monomers,

(III) in which: 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-f-n3 + p3) q3 <150 and 0 <(m4 + n4 + p4) q4 <150, r 'represents a number such that 1 <r '<200, Rι 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of allyl or vinyl ethers substituted or not, or also to the group of ethylenically unsaturated amides or imides, Rι ₄ , Rι ₅ , R ₂₀ and R ₂ ι, represent the hydrog ene or the methyl or ethyl radical, RIO, RΠ, R] ₈ and Rι ₉ , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or a mixture thereof, D and E are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several of these monomers,

12 - Agent dispersing pigments and / or mineral fillers according to one of claims 7 to 11, characterized in that said water-soluble polymer consists, expressed by weight: a) of 2% to 100% and even more particularly of 5 % to 100% of at least one ionic monomer, which is either i) anionically ethylenically unsaturated and with a monocarboxylic function in the acid or salified state chosen from ethylenically unsaturated monomers with a monocarboxylic function such as acrylic acid or methacrylic or else 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 acid, itaconic, maleic, or also anhydrides of carboxylic acids, such as maleic anhydride or chosen from ethylenically unsaturated and functional monomers sulfonic ion in the acid or salified state such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinyl sulfonic acid and styrene sulfonic acid or alternatively chosen from monomers containing ethylenic unsaturation and phosphoric function in the acid or salified state such as vinyl phosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, acrylate phosphate propylene glycol and their ethoxylates or alternatively chosen from ethylenically unsaturated monomers with a phosphonic function in the acid or salified state such as vinyl phosphonic acid, or their mixtures, or ii) cationic chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate, or N- [2- (acrylate) dime thylamino) ethyl], or among quaternary ammoniums such as [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [2- (acryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [3- (acrylamido) propyl] trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethyl ammonium chloride or sulfate, or mixtures thereof, or iii) the mixture of at least one of the above anionic monomers with at least one of the aforementioned cationic monomers

0 ⁾ in which: 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 at least an integer 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, vinylphthalic esters as well as to the group unsaturated urethanes such as acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl- benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, R ′ represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferentially a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I), c) from 0 to 50% of at least one acrylamide or methacrylamide type monomer and mixtures thereof, or alternatively at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or alternatively of at least one organofluorinated or organosililated monomer preferably chosen from the molecules of formulas (Ha) or (Ilb): with form ule (Ha)

in which: - 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or to the group of ethylenically unsaturated amides or imides, R ^ R ₅ , Rio and Ru, represent l 'hydrogen or the methyl or ethyl radical, R ₆ , R ₇ , R ₈ and R, represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture, Rι ₂ represents a hydrocarbon radical having 1 to 40 carbon atoms, A and B are groups possibly present, which then represent a hydrocarbon radical ay ant 1 to 4 carbon atoms,

with formula (Ilb) R -A - Si (OB) ₃

in which: 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 acrylurethanes, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or to 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 a mixture of several of these monomers,

from 0 to 3% of at least one crosslinking monomer chosen from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene -bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose, or chosen from the molecules of formula (III):

(III) in which: 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, Ri 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, - Rι ₄ , Rι ₅ , R ₂ o and R _2Î , represent hydrogen or the methyl or ethyl radical, - Rie, R ₁₇ , Ris and Rι ₉ , represent linear or branched alkyl, or aryl, or alkylaryl groups, or arylalkyl having 1 to 20 carbon atoms, or their mixture, D and E are optionally present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several of these monomers,

13 - Agent for grinding pigments and / or mineral fillers in aqueous suspension, characterized in that it is a water-soluble polymer, having a controlled stracture and obtained by a controlled radical polymerization process using as polymerization initiator, a particular alkoxyamine of general formula (A): R ₂ R ₄ II Ri - C - O -N - CH - R ₅ II 0 = CO = P - OR ₆ | | OR ₃ OR ₇ in which: - Ri and R ₂ represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 5, - R ₃ represents a hydrogen atom, an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 8, a phenyl radical, a cation such as Li ⁺ , Na ⁺ , K ⁺ , H ₄ N ⁺ , Bu ₃ HN ⁺ with Bu = butyl,

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 of carbon atoms ranging from 1 to 8, and preferably an ethyl radical.

14 - Agent for grinding pigments and or mineral fillers in aqueous suspension according to claim 13, characterized in that Ri and R ₂ represent the methyl radical and R ₃ represents the hydrogen atom.

15- Agent for grinding pigments and / or mineral fillers in aqueous suspension according to any one of claims 13 or 14, characterized in that said polymer is a water-soluble copolymer and has a structure of random type, block, comb, grafted, or alternated.

16 - Agent for grinding pigments and / or mineral fillers in aqueous suspension according to any one of claims 13 to 15, characterized in that said water-soluble polymer is obtained by controlled radical polymerization 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) b) and optionally at at least one nonionic monomer, the nonionic monomer consisting of at least one monomer of formula (I):

in which: 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of amide or ethylenically imide i nsaturated, R 'represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several monomers of formula (I),

d) and optionally at least one crosslinking monomer, or of the mixture of several of these monomers. 17 - Agent for grinding pigments and / or mineral fillers in aqueous suspension according to any one of Claims 13 to 16, characterized in that the said water-soluble polymer is obtained by the controlled radical polymerization of monomers chosen more particularly from : a) at least one ionic monomer, which is either i) anionic with ethylenic unsaturation and with monocarboxylic function in the acid or salified state chosen from the monomers with ethylenic saturation and with monocarboxylic function such as acrylic or methacrylic acid or also the hemiesters of diacids such as 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, isocro tonic, cinnamic, itaconic acid, maleic, or also anhydrides of carboxylic acids, such as maleic anhydride or chosen from mon omers with ethylenic saturation and with sulfonic function in the acid or salified state such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinyl sulfonic acid and styrene sulfonic acid or alternatively chosen from monomers with ethylenic unsaturation and with phosphoric function in the acid or salified state such as vinyl phosphoric acid, phosphate of ethylene glycol methacrylate, phosphate of propylene glycol methacrylate, phosphate of ethylene glycol acrylate, propylene glycol acrylate phosphate and their ethoxylates or alternatively chosen from ethylenically unsaturated monomers with a phosphonic function in the acid or salified state such as vinyl phosphonic acid, or their mixtures, or ii) cationic chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, unsaturated esters such as N- [2- methacrylate (dimeth ylamino) ethyl], or N- [2- (dimethylamino) ethyl] acrylate, or from quaternary ammonium such as [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, chloride or sulfate [2- (acryloyloxy) ethyl] trimethyl ammonium, [3- (acrylamido) propyl] trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, chloride or [3- (methacrylamido) propyl] trimethyl ammonium sulfate, or mixtures thereof, or iii) the mixture of at least one of the above anionic monomers with at least one of the above cationic monomers

in which: 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenylbenzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically insidious amides or imides Tureas, R 'represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I), and optionally at least one monomer of the acrylamide or methacrylamide type and their mixtures, or alternatively at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or alternatively at least one organofluorinated or organosililated monomer chosen from preferentially among the molecules of formulas (Ha) or (Ilb): with formula (Ha)

in which: 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 esters , maleic, itaconic, crotonic, vinylphthalic as well as to the group of unsaturated urethanes such as acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of ethers allylic or vinyl substituted or not, or also to the group of ethylenically unsaturated amides or imides, - R _A , R ₅ , Rio and Ru, represent hydrogen or the methyl or ethyl radical, - R ₆ , R ₇ , R ₈ and R, represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or a mixture thereof, Rι ₂ represents a hydrocarbon radical having 1 to 40 carbon atoms, A and B are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms,

with formula (Ilb) R - A - Si (OB) ₃

in which :

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 acrylurethane, methacrylurethane , α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or to the group of ethylenically unsaturated amides or imides, - A is an optionally present group, which represents then a hydrocarbon radical having 1 to 4 carbon atoms, B represents a hydrocarbon radical having 1 to 4 carbon atoms, or of a mixture of several of these monomers,

and optionally at least one crosslinking monomer chosen from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose, or chosen from molecules of formula (III):

(III) in which: m3, p3, tn4 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, Rι 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, Rι, R15, R ₂₀ and R ₂ ι, represent hydrogen o u the methyl or ethyl radical, RIO, Rπ, Ris and Rj ₉ , represent linear or branched groups of alkyl, or aryl, or alkylaryl, or arylalkyl having 1 to 20 carbon atoms, or a mixture thereof, D and E are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several of these monomers,

18 - Agent for grinding pigments and / or mineral fillers in aqueous suspension according to one of claims 13 to 17, characterized in that said water-soluble polymer consists, expressed by weight: a) of 2% to 100 % and even more particularly from 5% to 100% of at least one ionic monomer, which is either i) anionic with ethylenic unsaturation and with monocarboxylic function in the acid or salified state chosen from ethylenically unsaturated monomers and with monocarboxylic function such as acrylic or methacrylic acid or also the hemiesters of diacids such as the C1 to C monoesters of maleic or itaconic acids, or chosen from monomers with ethylenic unsaturation and dicarboxylic function in the acid or salified state such as crotonic, isocrotonic, cinnamic, itaconic, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride or chosen from unsaturated monomers ethylenic ation and sulfonic function in the acid or salified state such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinyl sulfonic acid and styrene sulfonic acid or alternatively chosen from monomers with ethylenic unsaturation and with phosphoric function in the acid or salified state such as vinyl phosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, phosphate of propylene glycol acrylate and their ethoxylates or alternatively chosen from ethylenically unsaturated monomers with a phosphonic function in the acid or salified state such as vinyl phosphonic acid, or their mixtures, or ii) cationic chosen from N - [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, unsaturated esters such as N- [2- (dimethylamino) ethyl methacrylate), or N- [2- (dimethylamino) ethyl] acrylate, or among quaternary ammoniums such as [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [2- (acryloyloxy) ethyl] trimethyl ammonium chloride or sulfate, [3- (acrylamido) propyl] trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethyl ammonium chloride or sulfate, or mixtures thereof, or iii) the mixture of at least one of the above anionic monomers with at least one of the aforementioned cationic monomers

in which: 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 acrylurethanes, methacrylurethanes, α-α 'dimethyl-isopropenylbenzylurethanes, allylurethanes, as well as in the group of ethers allyl or vinyl substituted or not, or also to the group of ethylenically unsaturated amides or imides, R 'represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I), from 0 to 50% of at least one monomer of the acrylamide or methacrylamide type and their mixtures, or alternatively d '' at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or alternatively at least one organofluorine monomer or organosililum chosen preferably from the molecules of formulas (Ha) or (Ilb): with formula (Ha)

in which: 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 group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as the group of unsaturated urethanes such as acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenylbenzylurethane, allylurethane, as well as the group of allyl ethers or vinyl substituted or unsubstituted, or also to the group of ethylenically unsaturated amides or imides, - Rφ, R ₅ , Rio and Ru, represent hydrogen or the methyl or ethyl radical, - R ₆ , R ₇ , R ₈ and R ₉ , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture, Rι ₂ represents a hydrocarbon radical having 1 to 40 carbon atoms, A and B are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms,

with formula (Ilb)

R- A - If (OB) ₃

in which: 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 acrylurethanes, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or to 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 a mixture of several of these monomers, d) from 0 to 3% of at least one crosslinking monomer chosen from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose, or chosen from the molecules of formula (III):

(in) in which: 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, Ri 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 acrylurethane, methacrylurethane, α-α 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allyl or vinyl ethers, or also to the group of ethylenically unsaturated amides or imides, Rι ₄ , R15, R ₂₀ and R ₂ ι, represent hydrogen or the methyl or ethyl radical, - RI _O , Rπ, Ris and Rι ₉ , represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture, - D and E are groups possibly present, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers,

19 - Process for dispersing pigments and / or mineral fillers in aqueous suspension, characterized in that the water-soluble polymer according to one of claims 1 to 6 is used.

20 - Process for dispersing pigments and / or mineral fillers in aqueous suspension according to claim 19, characterized in that 0.05 to 5% by dry weight of said polymer is used, and more particularly in that which is used from 0.1 to 3% by dry weight of said polymer, relative to the dry weight of pigments and / or mineral fillers.

21 - Process for dispersing pigments and / or mineral fillers according to one of claims 19 or 20, characterized in that the pigments and / or mineral fillers are chosen from natural or synthetic calcium carbonate, dolomites, kaolin , talc, cement, gypsum, lime, magnesia, titanium oxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these fillers between them, 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 still the mineral co-structures such as talc-calcium carbonate or talc-titanium dioxide co-structures, or their mixtures, and more particularly among natural calcium carbonate, synthetic calcium carbonate, and cement and very pa particularly among marble, calcite, chalk or their mixtures.

22 - Process for grinding pigments and / or mineral fillers characterized in that the water-soluble polymer according to one of claims 1 to 6 is used. 23 - Process for grinding pigments and or mineral fillers according to one of claims 21 or 22, characterized in that 0.05 to 5% by dry weight of said polymer is used, and more particularly in that uses 0.1 to 3% by dry weight of said polymer, relative to the dry weight of pigments and / or mineral fillers.

24 - Process for grinding pigments and / or mineral fillers according to claims 22 or 23 characterized in that the pigments and / or mineral fillers are chosen from natural or synthetic calcium carbonate, dolomites, kaolin, talc, gypsum, lime, magnesia, titanium oxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these charges together, such as talc mixtures - calcium carbonate, calcium carbonate-kaolin, 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, and more particularly from natural calcium carbonate and synthetic calcium carbonate, and very particularly from marble, calcite, chalk or their mixtures.

25 - Aqueous dispersion of pigments and / or mineral fillers characterized in that it contains the water-soluble polymer according to one of claims 1 to 6, and more particularly in that it contains from 0.05 to 5% by weight dryness of said polymer, and more particularly in that it contains 0.1 to 3% by dry weight of said polymer, relative to the dry weight of pigments and / or mineral fillers.

26 - Aqueous dispersion of pigments and / or mineral fillers according to claim 25, characterized in that the pigments and / or mineral fillers are chosen from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement , gypsum, lime, magnesia, titanium oxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these charges together, such as mixtures talc-calcium carbonate, calcium carbonate-kaolin, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or the co-structures of minerals like talc-calcium carbonate or talc-titanium dioxide co-structures, or mixtures thereof, and more particularly from natural calcium carbonate and synthetic calcium carbonate, and very particularly from marble, calcite, chalk or their mixtures.

27 - Aqueous suspension of pigments and / or ground mineral charges characterized in that it contains the water-soluble polymer according to one of claims 1 to 6, and more particularly in that it contains from 0.05 to 5% in dry weight of said polymer, and more particularly in that it contains from 0.1 to 3% by dry weight of said polymer, relative to the dry weight of pigments and / or mineral fillers.

28 - Aqueous suspension of pigments and / or ground mineral charges according to claim 27, characterized in that the pigments and / or mineral charges are chosen from natural or synthetic calcium carbonate, dolomites, kaolin, talc, gypsum, lime, magnesia, titanium oxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these charges together, such as talc mixtures calcium carbonate, calcium carbonate-kaolin, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or co-structures of minerals such as talc-calcium carbonate or talc-titanium dioxide co-structures, or mixtures thereof, and more particularly from natural calcium carbonate and synthetic calcium carbonate, and very particularly from marble , calcite, chalk or their mixtures.

29 - Use of aqueous dispersions of pigments and / or mineral fillers according to one of claims 25 or 26 in the paper sectors such as coating and mass loading of paper, aqueous paints, plastic, cement, ceramic and detergency.

30 - Use of aqueous suspensions of pigments and / or ground mineral charges according to one of claims 27 or 28 in the paper sectors such as coating and mass loading of paper, aqueous paints, plastic, cement, ceramic and detergency.

31 - 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, characterized in that the water-soluble polymer according to l 'one of claims 1 to 6.

32- Use, directly as a dispersing agent, of the water-soluble polymer used in the process for dispersing mineral materials in paper formulations, aqueous paints, cements, ceramic compositions, detergent compositions, cosmetic compositions, and sludges drilling according to claim 31.

33 - Paper formulation containing from 0.01 to 5% by dry weight of the water-soluble polymer used according to any one of claims 1 to 6 and 32.

34 - Aqueous paint containing from 0.01 to 5% by dry weight of the water-soluble polymer used according to any one of claims 1 to 6 and 32.

35 - Plastic composition containing from 0.01 to 5% by dry weight of the water-soluble polymer used according to any one of claims 1 to 6 and 32.

36 - Cement containing from 0.01 to 5% by dry weight of the water-soluble polymer used according to any one of claims 1 to 6 and 32.

37 - Ceramic composition containing from 0.01 to 5% by dry weight of the water-soluble polymer used according to any one of claims 1 to 6 and 32.

38 - Detergent composition containing from 0.01 to 5% by dry weight of the water-soluble polymer used according to any one of claims 1 to 6 and 32. 39 - Cosmetic composition containing from 0.01 to 5% by dry weight of the water-soluble polymer used according to any one of claims 1 to 6 and 32.

40 - Composition of drilling muds containing from 0.01 to 5% by dry weight of the water-soluble polymer used according to any one of claims 1 to 6 and 32.