CA2243847C - Graft copolymers, method for preparing same, compositions containing said copolymers, and use thereof for preparing pigment dispersions in aqueous and/or organic media - Google Patents

Abstract

The invention relates to graft copolymers comprising at least three sequences of a distinct chemical nature, among which one or more anchoring sequence (s) on solid particles, one or several hydrophobic sequence (s) and one or more sequence (s) of hydrophilic nature. The invention also relates to preparation process, the compositions containing them, their use as a dispersing agent, solid particle stabilizer and / or emulsifier in an aqueous and / or organic medium, as well as their use for the preparation of pigment dispersions in medium aqueous and / or organic.

Description

Graft copolymers, process for their preparation, compositions containing and their use for the preparation of pigment dispersions in aqueous and / or organic medium The invention relates to graft copolymers comprising at least three sequences of a distinct chemical nature, including one or more sequence (s) anchoring on solid particles, one or more sequence (s) at hydrophobic character and one or more hydrophilic sequence (s).
The invention also relates to a process for their preparation, compositions containing them, their use as dispersing agents, stabilizing solid particles and / or emulsifier in an aqueous and / or organic medium, as well as their use for the preparation of pigment dispersions in middle aqueous and / or organic.
At the end of their manufacturing process, the solid particles used in the ink and paint industry, pigments and fillers essentially, present in the form of aggregates or agglomerates. Their incorporation in a fluid, in order to obtain a stable suspension, therefore first requires step of dispersion, a step during which these assemblages are dissociated into elementary particles under the effect of important mechanical constraints.
The action of these mechanical forces, however, can not be effective in the absence of a dispersing agent.
These copolymers, used in solution by adsorption on the surface solid, or by coating the particle prior to its incorporation into the liquid, occur at each stage of dispersion.
At first, they ensure a good wetting of the particle by the continuous phase, replacing the air film surrounding the surface of the solid by molecules of liquid. Then, they significantly improve the return of the dissolver / grinder during the phase of disaggregation of associations. Finally, these dispersants, adsorbed on the surface of the solid, constitute a layer of solvated polymer, at the origin of steric repulsion forces, and in the case of polyelectrolytes in aqueous medium, repulsion forces electrostatic, opposing the attractive forces of Van der Waals, thus ensuring stability of dispersion.
To be effective, a copolymer usable as a dispersant must therefore include an anchoring sequence, having a good affinity for the

2 particle surface and one or more compatible sequence (s) with the continuous phase in which these solids are incorporated.
In the absence of one of these constituents, or in case of desorption of dispersant, there is a flocculation of the system, a phenomenon that manifests itself by the reagglomeration of the particles, and an increase in the viscosity of the dispersion. In the particular case of a painting, a bad dispersion of the pigments within the binder results in color differences and loss of brilliant gloss on the final film.
To overcome these problems, dispersants have been proposed, which make it possible to formulate paints specifically in the middle aqueous (EP 018 099) or in organic medium (US 4, 032, 698, GB 1 393 401 and 1,393,402). These products, however, offer only a partial solution, in the as the mixture of different pigments, minerals and organic, or interactions between the dispersant and the continuous phase, as can be the case in lacquers, cause a loss of stability of the suspension.
The synthesis of new additives, containing several sequences, based on the use of polyisocyanates, as described in US patents 4,647,647 or EP 0 520 586 makes it possible to overcome these difficulties. Nevertheless, the setting polyisocyanates, molecules with high toxicity and high poorly defined functionality, leads to obtaining a product consisting of a mixture of various structures, including the adsorption and dispersion does not are not optimal. In addition, this method prohibits the presence in the copolymer of polar functions containing a reactive hydrogen atom, functions chemical appreciated when used in an aqueous medium, or to promote the compatibility with resins.
In addition, monografted copolymers obtained by the technique "Macromonomer" and / or Grafting of Polyether Type Telomeres on a Chain preformed consisting of one or more unsaturated ethylenic monomer (s) and comprising nitrogenous units are the subject of patent EP 0 311 157.
The copolymers of the present invention contain a allowing them to be anchored to solid particles, in particular pigments and charges as well as at least 2 sequences of respectively hydrophilic and hydrophobic, allowing their use in aqueous compositions and or organic. The presence of an insoluble sequence in a selective medium increases by surprisingly the amount of dispersant adsorbed on the surface of particles thus avoiding the phenomenon of flocculation when mixing different pigments.

3 On the other hand, the plurality of chemical functions within the same copolymer, as well as the possibility of formulating pigment concentrates without elongation resin, improve compatibility with the resins, allowing so the formulation of paints from a wide range of binders.
In addition, the synthesis process makes it possible to obtain structural products homogeneous, whose performance is not limited by the presence of contaminants.
The subject of the invention is therefore a graft copolymer or salt of the copolymer graft comprising at least three sequences of a different chemical nature, which one or more anchoring sequence (s) on solid particles, which solid particles are chosen from pigments, fillers, solid fibers and combinations thereof, one or more sequence (s) with hydrophobic and one or more hydrophilic sequence (s) constituted from:
1/1 to 80% by weight of one or more anchoring sequence (s) on the solid particles, constituted by a hydrocarbon chain, linear or branched cycloalkyl or aromatic, comprising basic nitrogenous monomers, which comprise basic nitrogen groups selected from groups :
heterocyclic, -NH2, -NH-, -NHR, -NR2, -CONH2, -CONHR, and -CONR2 (where R
is a (C1-C6) alkyl radical, optionally substituted with one or more group (s) -OH, -COO-, -CO-, -O-, or -SO3H), which may comprise -COO- groups, and whose molecular mass is between 150 and 10 the mass content of basic nitrogenous monomers in the anchor chain being at minimum of 5%, and 2/10 to 90% by mass of one or more sequence (s) with character hydrophobic, constituted (s) by a hydrocarbon chain, linear or branched, cycloalkyl or aromatic, which can contain -COO-, -S-, -F groups, or -If (OR ') n (R ") 2_õ (where R' and R" represent alkyl or aryl radicals, similar or different, in C 1 -C 10, and n = 0 to 2), formed (s) of monomeric units whose solubility parameter is less than or equal to 21.5 Jl / 2 / cm3 / 2 and whose mass molecular weight is between 250 and 10,000, and

4 3/10 to 90% by mass of one or more sequence (s) with character hydrophilic, constituted by a hydrocarbon chain, linear or branched having -O-, -OH, -NCO-, -COO-, -COOH, -CONH2 - groups CONHR "'(where R"' is a (C1-C3) alkyl), -NH-, -S-, or -SO3H radical, formed of monomer units whose solubility parameter is greater than 22 JI / 2 / cm3 / 2 and whose molecular mass is between 250 and 10,000.
It will be noted that, advantageously, there are three ways different from combining the three types of sequences: anchoring, hydrophobic and hydrophilic. The graft copolymers according to the invention can therefore have alternatively the following structures:
- anchor main chain + at least 2 grafts respectively hydrophilic (s) and hydrophobic (s) - hydrophobic main chain + at least 2 grafts respectively hydrophilic (s) and anchor - hydrophilic main chain + at least 2 grafts respectively hydrophobic (s) and anchor.
The graft copolymers comprising a main anchor chain and at least 2 hydrophilic (s) and hydrophobic (s) respectively are preferred compounds according to the invention.
According to a preferred aspect, the invention relates to a graft copolymer such as as defined above comprising at least three sequences of a chemical nature distinct, in which the main chain is an anchor sequence on the solid particles consisting of a hydrocarbon chain, linear or branched cycloalkyl or aromatic, comprising basic nitrogenous groups of type :
heterocyclic, -NH2, -NH-, -NHR, -NR2, -CONH2, -CONHR, -CONR2 (where R
is a (C1-C6) alkyl radical, optionally substituted by one or more group (s) -OH, -COO-, -CO-, -O-, -SO3H), which may comprise -COO- groups, and whose molecular mass is between 150 and 10 000, preferably between 300 and 3000, the mass content of nitrogenous monomers in the anchor chain being at least 5%, and preferably 30 %.
Advantageously, the invention also relates to a copolymer graft as defined above, wherein the main chain is a sequence to hydrophobic character consisting of a hydrocarbon chain, linear or WO 9'7128200 PCT / FR97 / 00185 branched, cycloalkyl or aromatic, which may contain -COO- groups, -S-, -F, -Si (OR ') n (R ") 2-n- (where R' and R" represent alkyl radicals or aryl, similar or different, in C 1 -C 10, and n = 0 to 2), formed of monomer units whose solubility parameter is less than or equal to 21.5 J 1/2 / cm3 / 2, of

Preferably less than 19 J1 / 2 / cm3 / 2, and whose molecular weight is range between 250 and 10,000, preferably between 500 and 3,500.
Other preferred graft copolymers are products as defined above, in which the main chain is a character sequence hydrophilic, consisting of a linear or branched hydrocarbon chain, having -O-, -OH, -NCO-, -COO-, -COOH, -CONH2 groups, -CONHR "'(where R"' is a radical (Cl-C3) alkyl), -SO3H, formed of units monomer whose solubility parameter is greater than 22 J1 / 2 / cm3 / 2, preferably greater than 22.5 J1 / 2 / cm3 / 2, and whose molecular mass is range between 250 and 10,000, preferably between 300 and 3,000.
The solubility parameters expressed in Jl / 2 / em3 / 2, were calculated by the method of incrementation of Hoftyzer-Van Krevelen or measured experimentally (case of polydimethylsiloxane). Molar volumes necessary when calculating the solubility parameters are calculated from of the Feedor data. These calculation methods and experimental values are exhibited in the book: DW VAN KREVELEN, "Properties of polymers.
correlation with chemical structure; their numerical estimation and prediction from additive group contributions ", Third edition, Elsevier, 1990, pp. 189-225.
The invention also relates to said copolymer in the form of one of its salts, obtained by quaternization or neutralization of basic functions.
The invention also relates to the processes for the preparation of graft copolymers defined above.
The synthesis of the graft copolymers according to the invention is based on the use of the "macromonomer" technique and / or the telomere grafting functionalized on a preformed linear or grafted chain.
Thus these dispersants can be prepared by copolymerization radical of one or more hydrophilic macromonomer (s) and one or more many hydrophobic macromonomer (s) with one or more nitrogen comonomer (s) and optionally with one or more ethylenic comonomer (s) unsaturated (s) and / or unsaturated ethylenic comonomer (s) reagent (s).
These syntheses are carried out under an inert atmosphere in the presence of a solvent or an appropriate solvent mixture, that is to say in which the

6 reagents, macromonomers, comonomers are completely soluble and the end products are totally or at least partially soluble. These solvents will be selected among aromatic hydrocarbons such as toluene or xylene; ethers such as dioxane or tetrahydrofuran; of the ketones such as acetone or methyl ethyl ketone; esters such as acetate ethyl or butyl acetate. It is preferable to use dioxane or tetrahydrofuran during the preparation of the graft copolymers.
The synthesis starts with the preparation of the macromonomers, by telomerisation then fixation of a double bond at the end of the chain, stage followed by copolymerization of said macromonomers with the comonomers.
The graft copolymers according to the invention can also be prepared in fixing one or more functionalized molecule (s), one of two types of hydrophilic or hydrophobic grafts, or both types of grafts, on a polymer preformed with reactive monomers, this chain can already contain one or more hydrophilic (s) or hydrophobic (s) graft (s) incorporated by radical way. In this case the course of the reaction imposes the use of at at least two separate reactors, the first one serving to prepare the chain principal, the second for the preparation of the telomere.
The grafting of these side chains onto the preformed polymer can then be achieved by adding the contents of the reactor (s) containing the telomeres at first. It may be advantageous to make this addition in several steps, so to better adjust the properties of the final copolymer.
The invention also relates to compositions containing one or several graft copolymer (s) as defined above, particles solids selected from pigments and / or fillers and / or fibrous solids, and optionally an organic solvent and / or water.
The subject of the invention is also a pigment or a filler or a fibrous solid coated with compositions containing one or more copolymer (s) graft (s) as (s) defined (s) above.
The invention finally relates to the use of said copolymer (s) as dispersants, stabilizers of solid particles or emulsifiers in a aqueous and / or organic medium, their use for the preparation of dispersions pigments in an aqueous and / or organic medium, as well as paints and inks containing them.

7 Description of the anchoring sequence on solid particles The graft copolymers according to the invention have, distributed along their anchoring sequence of the basic nitrogenous groups arranged in a manner statistic and chosen for their affinity with the surface of many pigments and loads, both organic and mineral.
Said basic groups can be defined by their pKa, understood between 2 and 14, preferably between 5 and 14, in particular between 5 and 12.
measures pKa are carried out at 25 C in water at a concentration of 0.01 molar.
The invention therefore relates in particular to one of its aspects a graft copolymer as defined above wherein the sequence (s) anchor comprises or comprise basic nitrogen groups introduced to from one or more compound (s) chosen for example from:
a) - vinylpyridines, such as 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine or 2-methyl-5-vinylpyridine, vinylimidazole, 2-methyl-N-vinylimidazole, vinylcarbazole, N-vinylpyrrolidone, 3-methyl-N-vinylpyrazole, 4-methyl-5-vinylthiazole, the N-vinylcaprolactam, ethylimidazolidone methacrylate, (meth) acrylamides such as (meth) acrylamide, N-methylacrylamide, N-isopropylacrylamide and N, N-dimethylacrylamide, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, diacetone acrylamide, methyl-2-acrylamido-2-methoxyacetate, N-tris (hydroxymethyl) methylacrylamide, the aminoalkyl (meth) acrylates of the following formula:
~ RI

CH2 = CH2 CH2 N ~
~~

-O R 1 is a hydrogen atom or a (C 1 -C 4) alkyl radical; R2 and R3 identical or different each represent a (C 1 -C 6) alkyl radical, n = 0 at 6, said nitrogenous groups being in this first case introduced by radical copolymerization of one or more ethylenic monomer (s) = unsaturated (s) cited above, and (b) NN-diethyl-1,4-butanediamine, 1- (2-aminoethyl) piperazine, 2- (1-pyrrolidyl) ethylamine, 4-amino-2-methoxy-pyrimidine, 2-

8 dimethylaminoethanol, 1- (2-hydroxyethyl) -piperazine, 4- (2-hydroxyethyl) -morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, N, N-dimethyl-1,3-propanediamine, 4- (2-aminoethyl) -pyridine ,. NN-diallyl-melamine, 3-amino-1,2,4-triazole, 1- (3-aminopropyl) imidazole, 4- (2-hydroxyethyl) -pyridine, 1- (2-hydroxyethyl) imidazole, 3-mercapto-1,2,4-triazole, said nitrogenous groups being in this second case fixed on a copolymer, linear or grafted, taking advantage of the reactive functions introduced on along the preformed chain.
Among the compounds a), the monomers of the following type vinylpyridine, vinylimidazole, (meth) acrylamide N, N-dimethylacrylamide and 2-dimethylaminoethyl methacrylate.
The compounds b) mentioned above are preferably grafted directly on the copolymer from reactive chemical functions incorporated by radical copolymerization of one or more ethylenic monomer (s) unsaturated reagent (s) containing one or more group (s) containing at least one least one reactive hydrogen atom with respect to functions such as epoxy group, selected from -OH, -SH, -COOH, -NH2, -NHR (where R is a alkyl radical having 1 to 3 carbon atoms).
For example, we can use:
hydroxyl compounds: 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, carboxylated compounds: (meth) acrylic acid, maleic acid, acid fumaric, itaconic acid, crotonic acid, maleic anhydride, monomers bearing an epoxy function: glycidyl methacrylate.
Monomers bearing hydroxyl functions will preferably be used.
and epoxy, and more particularly the hydroxyl (meth) acrylates, hydroxypropyl (meth) acrylates and glycidyl methacrylate.
The proportion of the reactive monomers contained in the copolymer is is between 0 and 80% by weight, advantageously between 0 and 40% by weight and preferably between 5 and 40% by weight.

It is often interesting also to copolymerize one or more unsaturated ethylenic monomer (s) neutral with the monomer (s) nitrogen (s) a) cited above and / or the reactive monomer (s) allowing the grafting of the compounds b) mentioned above.
Indeed, these monomers, if they do not directly influence the capacities dispersants and stabilizers of the copolymer, make it possible to modify favorably

9 some of its properties, such as its transition temperature vitreous, its stability or its mechanical properties.
These monomers will be, for example, esters of acrylic acid or methacrylic acid, vinyl esters, styrenics or alkylstyrenics.
The content of neutral unsaturated ethylenic monomers in the final copolymer may vary from 0 to 76% by weight and in particular from 0 to 28%
Mass.
The unsaturated ethylenic monomers introducing the compounds a), the reactive unsaturated ethylenic monomers used to graft compounds b) and the neutral unsaturated ethylenic monomers described above as well as the Hydrophilic and hydrophobic macromonomers are copolymerized by from the initiators usually used, for example organic peroxides, redox systems, or preferably the compounds azo.
Description of the sequence with character h, dr, o-phobe The sequence (s) with a hydrophobic nature are chosen in such a way their solubility properties are complementary to those of the of the hydrophilic sequence (s) mentioned below, in order to confer on the copolymer is its universal dispersant character with respect to solvents and binders.
Organosoluble polymers formed from monomeric units whose solubility parameter less than or equal to 21.5 JI / 2 / cm3 / 2, preferably inferior at 19 J1 / 2 / cm3 / 2 constitute these hydrophobic and allow to disperse the particles in an apolar medium. The incorporation of this (s) sequence (s) or graft (s) in the copolymer can be carried out by copolymerizing with way radical one or more organosoluble macromonomer (s) with one or several unsaturated ethylenic comonomer (s) mentioned earlier in the description of the anchoring sequence, namely one or more monomer (s) N-ethylenic (s), optionally one or more monomer (s) neutral unsaturated ethylenic (s) and at least one macromonomer with hydrophilic described below (from the initiators usually used, by organic peroxides, redox systems, or preferably azo compounds), and will lead to the formation of a blended copolymer.
These hydrophobic grafts can also be fixed by grafting on a linear or branched copolymer consisting of one or more unsaturated ethylenic unsaturated monomer (es) cited earlier in the description of the anchoring sequence, namely one or more monomer (s) a) and / or one or many unsaturated ethylenic monomer (s) reagent (s) used for grafting the compounds b) on the copolymer and / or one or more ethylenic monomer (s) neutral unsaturated (s) and / or one or more macromonomer (s) of a Hydrophilic described below and / or hydrophobic, from one or several telomeres with hydrophobic character.
Telomeres with a hydrophobic nature can be grafted directly on the copolymer with the aid of the reactive groups according to the process described more high for the anchor sequence.

According to the invention, the monomeric units constituting the macromonomers and telomeres used to prepare the character sequence (s) hydrophobic for example, will be introduced from the following compounds:
(meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate ethylhexyl, octyl (meth) acrylate, nonyl (meth) acrylate, (Meth) acrylate isodecyl, lauryl (meth) acrylate, stearyl (meth) acrylate, (Meth) acrylate pentadecyl, cetyl (meth) acrylate, behenyl (meth) acrylate, 3- (trimethoxysilyl) propyl (meth) acrylate, vinyl esters such as vinyl acetate, vinyl propionate, butyrate vinyl, vinyl sorbate, vinyl hexanoate, vinyl ethylhexanoate, laurate vinyl, vinyl stearate, styrene and alkylstyrenes such as α-methylstyrene, vinyltoluene, tertiobutylstyrene, dienes, such as butadiene and isoprene, which can be hydrogenated after polymerization, alkylenes such as ethylene, propylene, siloxanes such as dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, fluorinated compounds such as trifluoroethyl (meth) acrylate), (Meth) acrylate pentafluoropropyl, heptafluorobutyl (meth) acrylate, (meth) acrylate octafluoropentyl, pentadecafluorooctyl (meth) acrylate, (meth) acrylate eicosafluoroundecyl, vinyl fluoride, tetrafluoroethylene.

Polycondensation products, polyesters or polyamides, such as those prepared from either diacids and long-chain alkyl diols, or hydroxy acids with long alkyl chains (for polyesters), or from is diacids and diamines with long alkyl chains, from amino acids to

11 long alkyl chains (for polyamides) may also constitute the telomers and macromonomers used.
Preferably, the graft copolymers according to the invention will be prepared by radical copolymerization from one or more macromonomers, of which the constitutive units are preferably chosen from acid esters (meth) acrylic or vinyl esters having at least 8 carbon atoms, as well as styrenics and alkylstyrenics such as styrene and tert-butylstyrene, and fluorinated monomers, in particular methacrylate of trifluoroethyl, and synthesized by telomerization from a transfer of chain, then condensation on a (meth) acrylic, vinylic or allylic, preferably (meth) acrylic.
The molecular weight of the hydrophobic grafts obtained by this between 250 and 10 000, and will advantageously be included between 500 and 3,500.
On the other hand, the mass content of hydrophobic grafts in the final mixed-graft copolymer is between 10 and 90%, and preferably between 25 and 80%.
Description of the SequenceH character, Ydrophile The sequence (s) of hydrophilic nature, distributed in a manner statistics along the main chain of the copolymer, are at the origin of the solubility of copolymers in water. These are the sequences that stabilize the dispersions of particles in an aqueous medium.
The solubility parameter of the monomeric units constituting these grafts is greater than or equal to 22 J1 / 2 / cm3 / 2, preferably greater than 22.5 J1 / 2 / em3 / 2.
The introduction of these side chains into the copolymer can be carried out using one or more macromonomers (s) of hydrophilic nature.
A
macromonomer of this type consists of a water-soluble polymer terminated at one of its ends by a polymerizable group of radical.
This group may be, for example, of (meth) acrylic, vinylic or allylic, preferably (meth) acrylic.
The copolymerization of one or more of these macromonomers with a or more unsaturated ethylenic comonomer (s) mentioned above in the description of the anchoring sequence, namely one or more compound (s) a) one or more neutral unsaturated ethylenic monomer (s), and less a hydrophobic macromonomer described above (from the initiators usually used, for example organic peroxides,

12 redox systems, or preferably azo compounds) will lead to the training of a graft copolymer according to the invention.
These hydrophilic grafts can also be fixed by grafting on a linear or branched copolymer consisting of one or more Unsaturated ethylenic monomer (s) cited earlier in the description of the anchoring sequence, namely one or more ethylenic monomer (s) unsaturated nitrogen (s) a) and / or one or more ethylenic monomer (s) unsaturated reagent (s) used to graft compounds (b) onto the copolymer and / or one or more neutral unsaturated ethylenic monomer (s) and / or one or several macromonomers (s) with hydrophobic nature described above and / or hydrophilic, from one or more telomeres (s) of hydrophilic nature.
These telomeres consist of a functionalized water-soluble polymer at the end of the chain by a group containing a reactive hydrogen atom, -OH, -NH2, -NHR (where R is an alkyl radical having from 1 to 3 carbon atoms carbon), -COOH, -SH.
Telomeres can be grafted directly onto the copolymer from reactive groups.
According to the invention, the monomeric units constituting the macromonomers and telomeres, used to prepare the sequence (s) of character hydrophilic will for example be chosen from:
- ethylene oxide, - (meth) acrylic acids, maleic acid, fumaric acid, acid itaconic acid, acrylamide derivatives such as (meth) acrylamide, N-methylacrylamide, the N-isopropyl acrylamide, ethyleneimine, - vinyl alcohol, vinylpyrrolidone, vinylmethyloxazolidone, vinylsulphonate, sodium methallyl sulphonate, - Glycerol methacrylate.
Preferably, the graft copolymers according to the invention are prepared by radical pathway ("macromonomer" technique), from macromonomers such as poly (ethylene glycol) (meth) acrylates, the products HEMA-5 and HEMA-10, marketed by Bimax Chemicals Ltd. The molecular mass of grafts

13 hydrophilicity is chosen between 250 and 10,000, and preferably between 300 and 3,000.
On the other hand, the mass content represented by these grafts water-soluble in the final copolymer is from 10 to 90%, and in particular from 15 to 70%.
In a further aspect, the invention also relates to a method of preparation of the graft copolymers according to the invention.
As mentioned above, said copolymers can be prepared by radical copolymerization from macromonomers and / or by grafting of functionalized polymers on a preformed chain, and thereby a well controlled structure.
This synthesis mode also offers the possibility of adjusting the mass of the anchoring sequence, in order to increase the adsorption rate of the copolymers on particles, both mineral and organic, as well as that side chains, improving their compatibility with the phase keep on going.
Thus, by using the graft copolymers according to the invention for preparation of pigment concentrates, a state of dispersion is achieved better than that obtained from the dispersants of the prior art. In addition the mass high molecular weight of the products according to the invention makes it possible to prepare pigment concentrates without elongation teasin.
The radical copolymerization is preferably carried out at a temperature between 50 C and 140 C, and the grafting reaction to a temperature preferably between 20 C and 150 C.
Advantageously, the order of addition of the monomers during the Radical copolymerization is as follows:
macromonomers, which have a high molecular mass and are therefore less reactants, are incorporated from the outset in the reactor, with the solvent;
- the comonomer or comonomers constituting the main chain, more reactive, are introduced continuously over time, so that their concentration is always low compared to that of macromonomers.

Preparation of a copolymer in which the main chain is The Sequence of Registration on Solid Substances The invention thus relates, according to a first variant, to a method of preparation of a graft copolymer as defined above comprising at least less three sequences of a distinct chemical nature, including a sequence

14 anchoring to the solid particles, one or more sequence (s) to character hydrophobic and one or more hydrophilic sequence (s) in which the main chain is an anchoring sequence on solid particles, characterized in that one carries out:
1) radical copolymerization of:
i) 0 to 80% by weight, preferably. 0 to 40% by weight, of one or more monomer (s) comprising at least one basic nitrogen-type group heterocyclic, -NH2, -NHR, -NR2, -CONH2, -CONHR, -CONR2 (where R is a (C 1 -C 6) alkyl radical, optionally substituted with one or more group (s) -COO-, -CO-, -O-, -OH, -SO3H), and ii) 0 to 90% by weight, preferably 0 to 80% by weight, of one or more macromonomer (s) represented by the formula:

CC

where R4, R5, R6, identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl radical, R7 is a hydrophobic sequence consisting of a chain hydrocarbon, linear or branched, cycloalkyl or aromatic, have groups -COO-, -S-, -F, -Si (OR ') n (R ") 2-n- (where R' and R"
represent alkyl or aryl radicals, similar or different, in C 1 -C 10, and n = 0 to 2), formed of monomer units whose parameter of solubility is less than or equal to 21.5 J1 / 2 / cm3 / 2, preferably less than Jl / 2 / cm3 / 2, and whose molecular mass is between 250 and 10 000, preferably between 500 and 3,500, and iii) 0 to 90% by weight, preferably 0 to 70% by weight, of one or more macromonomer (s) represented by the formula C = C

where R4, R5, R6 are as defined above, and Rg is a hydrophilic sequence, consisting of a chain linear or branched hydrocarbon containing groups -O-, -OH, -NCO-, -COO-, -COOH, -CONH2, -CONHR "(where R"'is a radical (Cl-C3) alkyl), -NH-, -S-, -SO3H, formed of monomer units whose parameter of Solubility is greater than 22 J1 / 2 / cm3 / 2, preferably greater than 22.5.
J1 / 2 / cm3 / 2, and whose molecular mass is between 250 and 10 000, preferably between 300 and 3000, and iv) 0 to 80% by weight, preferably 0 to 40%, of one or more monomer (s) containing at least one group likely to be involved in a reaction 10 coupling, and, v) 0 to 76% by weight, preferably 0 to 28%, of one or more monomer (s) unsaturated ethylenic acid (s) containing up to 25 carbon atoms, except for the monomers already mentioned in i), it being understood that if one of the mass contents of the compounds defined in i), ii)

15 and / or iii) is zero, the mass content of the compounds defined in (iv) is different from 0, and 2) grafting on this preformed chain of:
vi) 0 to 80% by weight, preferably 0 to 40%, of one or more molecule (s) derived from a compound having at least one basic nitrogen moiety heterocyclic, -NH2, -NHR or -NR2 (where R is a (C1-C6) alkyl radical, and containing at least one group likely to be involved in a reaction coupling, and vii) 0 to 90% by weight, preferably 0 to 80% by weight, of one or more telomere (s) represented by the formula:

where G represents a group containing a reactive hydrogen atom, -OH, -COOH, -SH, -NH2, -NHR '(where R "' is a (C1-C3) alkyl radical), and R7 is such as defined above, and viii) 0 to 90% by weight, preferably 0 to 70%, of one or more telomere (s) represented by the formula G-R
where G and Rg are as defined above, Being heard that :

16 - the mass contents of the compounds defined in i) and vi) can not be be simultaneously equal to 0, and when one of them is equal to 0, so the other is equal to at least 1%, - the mass contents of the compounds defined in (ii) and (vii) can not be simultaneously equal to 0, and when one of them is equal to 0, so the other is equal to at least 10%, - the mass contents of the compounds defined in (iii) and (viii) can not be be simultaneously equal to 0, and when one of them is equal to 0, so the other is equal to at least 10%.
According to this first variant of the process, a copolymer is prepared graft as defined above, consisting of a main anchor chain on the solid particles and at least 2 grafts, respectively hydrophobic (s) and hydrophilic (s), said copolymers being preferred products according to the invention.

Preparation of a copol, re Lyreffé in which the principal chief is ms with hydrophobic nature The invention also relates, according to a second variant, to a method of preparation of a graft copolymer comprising at least three distinct chemical nature, including one or more sequence (s) anchoring, a hydrophobic sequence and one or more sequence (s) at hydrophilic character, in which the main chain is a sequence character hydrophobic, as defined above characterized in that the radical copolymerization of:
i) 10 to 90% by weight, preferably 25 to 80% by weight, of one or more hydrophobic monomer (s) having at least one group aromatic, -COO-, -F, or -Si (OR ') n (R ") 2- (where R and R" represent alkyl radicals or aryl radicals, identical or different, in C 1 -C 10, and n = 0 to 2) after polymerization constituting a chain formed of monomer units whose solubility parameter is less than or equal to 21.5 J1 / 2 / cm3 / 2, preference less than 19 JI / 2 / cm3 / 2, and whose molecular mass is between 250 and 10,000, preferably between 500 and 3,500, and ii) 0 to 90% by weight, preferably 0 to 70% by weight, of one or more macromonomer (s) represented by the formula

17 C = C
R6 Rg where R4, R5, R6 are as defined above, and R8 is a hydrophilic sequence consisting of a chain hydrocarbon, linear or branched, having -O-, -OH groups, -NCO-, -COO-, -COOH, -CONH2, -CONHR "(where R"'is a radical (Cl-C3) alkyl), -NH-, -S-, -SO3H, formed of monomer units whose parameter of solubility is greater than 22 Jl / 2 / cm3 / 2, preferably greater than 22.5 J1 / 2 / cm3 / 2, and whose molecular mass is between 250 and 10 000, preferably between 300 and 3000, and iii) 0 to 80% by weight, preferably 0 to 40% by weight, of one or more macromonomer (s) represented by the formula:

C = C
R6 I ~ i where R4, R5, R6 are as defined above, and Rg is an anchoring sequence, consisting of a hydrocarbon chain, linear or branched, cycloalkyl or aromatic, comprising groups basic nitrogen compounds of the type: heterocyclic, -NH2, -NH-, -NHR, -NR2, -CONH2, -CONHR, -CONR2 (where R is a (C1-C6) alkyl radical, optionally substituted with one or more group (s) -OH, -COO-, -CO-, -O-, -SO3H), which can comprise -COO- groups and whose molecular weight is between 150 and 10,000, preferably between 300 and 3000, the mass content of basic nitrogenous monomers in the chain at least 5%, and preferably 30%, and iv) 0 to 80% by weight, preferably 0 to 40%, of one or more monomer (s) containing at least one group likely to be involved in a reaction coupling, it being understood that if one of the mass contents of the compounds defined in i), ii) and / or iii) is zero, the mass content of the compounds defined in (iv) is different from 0, and

18 2) grafting on this preformed chain of:
v) 0 to 90% by weight, preferably 0 to 70%, of one or more telomere (s) represented by the formula where G represents a group containing a reactive hydrogen atom, -OH, -COOH, -SH, -NH2, -NHR '(where R "' is a (C1-C3) alkyl radical), and R8 is as defined above, and vi) 0 to 80% by weight, preferably 0 to 40%, of one or more telomere (s) represented by the formula G-R
where G and Rg are as defined above, Being heard that :
- the mass contents of the compounds defined in (ii) and (v) can not be simultaneously equal to 0, and when one of them is equal to 0, so the other is equal to at least 10%, - the mass contents of the compounds defined in (iii) and (vi) can not be be simultaneously equal to 0, and when one of them is equal to 0, so the other is equal to at least 1%.
According to this second variant of the process, a graft copolymer is prepared.
as defined above, consisting of a hydrophobic main chain and a less than 2 grafts, respectively hydrophilic (s) and anchor.

Preparation of a graft copolymer in which the main chain is a_soq.uence of hydrophilic nature According to a later aspect, the invention relates to a third variant of the process for the preparation of a graft copolymer comprising at least three sequences of a distinct chemical nature, including one or more anchoring sequence (s), one or more hydrophobic sequence (s) and a hydrophilic sequence as defined above, in which the chain principal is a hydrophilic sequence, characterized in that the radical copolymerization of:
i) 10 to 90% by weight, preferably 15 to 70% by weight, of one or more hydrophilic monomer (s) having at least one group selected from -O-, -OH-, -COOH, -NCO-, -COO-, -SO3H, -CONH2, -CONHR "
(where R "'is a radical (C 1 -C 3) alkyl), and constituting after polymerization a chain consisting of monomer units with a higher solubility parameter

19 at 22 J1 / 2 / cm3 / 2, preferably greater than 22.5 J1 / 2 / cm3 / 2, and whose mass molecular weight is between 250 and 10,000, preferably between 300 and 3 and ii) 0 to 90% by weight, preferably 0 to 80% by weight, of one or more macromonomer (s) represented by the formula:

R \ R4 C = C

where R4, R5, R6, identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl radical, R7 is a hydrophobic sequence consisting of a chain hydrocarbon, linear or branched, cycloalkyl or aromatic, have groups -COO-, -S-, -F, -Si (OR ') n (R ") 2-n- (where R' and R"
represent alkyl or aryl radicals, similar or different, in C 1 -C 10, and n = 0 to 2), formed of monomer units whose parameter of solubility is less than or equal to 21.5 Jl / 2 / cm3 / 2, preferably less than J1 / 2 / cm3 / 2, and whose molecular mass is between 250 and 10 000, preferably between 500 and 3,500, and iii) 0 to 80% by weight, preferably 0 to 40% by weight, of one or more macromonomer (s) represented by the formula:

C = C
/ \
R6 Ry where R4, R5, R6 are as defined above, and R9 is an anchoring sequence, consisting of a hydrocarbon chain, linear or branched, cycloalkyl or aromatic, comprising groups basic nitrogen compounds of the type: heterocyclic, -NH2, -NH-, -NHR, -NR2, -CONH2, -CONHR, -CONR2 (where R is a (C1-C6) alkyl radical, optionally substituted with one or more group (s) -OH, -COO-, -CO-, -O-, -SO3H), which can comprise -COO- groups and whose molecular weight is between 150 and 10,000, preferably between 300 and 3000, the mass content of basic nitrogenous monomers in the chain at least 5%, and preferably 30%, and iv) 0 to 80% by weight, preferably 0 to 40%, of one or more monomer (s) containing at least one group likely to be involved in a reaction 5 coupling, it being understood that if one of the mass contents of the compounds defined in i), ii) and / or iii) is zero, the mass content of the compounds defined in (iv) is different from 0, and 2) grafting on this preformed chain of:
V) 0 to 90 wt%, preferably 0 to 80 wt%, of one or more telomere (s) represented by the formula:

where G represents a group containing a reactive hydrogen atom, -OH, -COOH, -SH, -NH2, -NHR "'(where R"' is a (C1-C3) alkyl radical), and R7 is such 15 as defined above, and vi) 0 to 80% by weight, preferably 0 to 40%, of one or more telomere (s) represented by the formula G-Rq where G and Rg are as defined above,

It being understood that:
- the mass contents of the compounds defined in (ii) and (v) can not be simultaneously equal to 0, and when one of them is equal to 0, so the other is equal to at least 10%, - the mass contents of the compounds defined in (iii) and (vi) can not be be simultaneously equal to 0, and when one of them is equal to 0, so the other is equal to at least 1%.
According to this third variant of the process, a copolymer is prepared graft as defined above, consisting of a hydrophilic main chain and from at least 2 grafts, respectively hydrophobic (s) and anchor.
Preferred graft copolymers according to the invention are those comprising:
a main anchor chain on the solid particles comprising dialkylaminoethyl (meth) acrylate groups, 2-vinylpyridine, 4-vinylpyridine, N, N-dimethylacrylanide, alone or as a mixture, one or more hydrophilic poly (ethylene oxide) grafts, and one or more hydrophobic grafts based on alkyl (meth) acrylates, vinyl esters alone or copolymerized with styrenic derivatives and

21 alkylstyrenic, fluorinated monomers (trifluoroethyl methacrylate), or of 3- (trimethoxysilyl) propyl methacrylate.

Use of copolymers effected according to the invention The graft copolymers according to the invention are advantageously usable for the preparation of pigment concentrates. Indeed, the presence at within the hydrophilic and hydrophobic block copolymer allows the dispersion of number of solid particles in a liquid and the formulation of pigment pastes of equal performance in an aqueous and / or organic medium.
Said copolymers also advantageously make it possible to preparation of pigment concentrates without added resin, which improves the compatibility of these pastes with a wide range of binders.
For example, pigment concentrates can be prepared containing the copolymers according to the invention using the pigments, fillers and following fibrous solids:
inorganic pigments such as titanium dioxides, oxides of zinc, zinc sulphates, zinc phosphates, lithopones, blacks of carbon oxides, iron oxides, manganese phosphates, aluminum aluminates, cobalt, antimony sulphates or zinc chromates, metallic pigments, organic pigments such as oxazines, dioxazines, thiazines, phthalocyanines, xanthenes, acrydines, quinacridones where the perylenes.
The graft copolymers according to the invention will advantageously be used.
for the incorporation of fillers or fibrous solids in paints, especially for the dispersion of oxides and hydroxides of aluminum, of silicas of quartz, talcs, kaolins, micas, calcium sulphates, sulphates of barium or calcium carbonates. Painting films made using said copolymers advantageously have a reduced sensitivity to water, all in -conserving to the application a high gloss.
In order to prepare pigment concentrates, it will be preferable to use the graft copolymers according to the invention, at a ratio of a mass ratio particles solids / dispersant between 1/50 and 100/1, in particular 1/10 and 20/1.
The reaction mixture obtained at the end of the synthesis of the copolymer grafted can be used either directly or after concentration by distillation WO 97/28200 PCT / F'R97 / 00185

22 under reduced pressure or azeotropic distillation possibly adding a cosolvent.
The reaction medium can also be replaced by the addition of a solvent having a higher boiling point or forming an azeotrope with it, then removing the reaction solvent by distillation under pressure reduced or azeotropic. It is thus advantageously possible to replace the solvent reaction with water or a water-miscible liquid to formulate pasta aqueous.
Alternatively, it is possible to isolate the graft copolymer according to the invention in a selective solvent or by completely removing the solvent from reaction. The said copolymer will then be re-dissolved in a suitable liquid or used as is if its viscosity allows it.
Pigments, fillers and fibrous solids can still be processed by a solution of graft copolymer according to the invention, for example in bed fluidized or in a cyclone, the coated particles thus obtained being then redispersed in a suitable liquid or liquid mixture (s).
Dispersions of solid particles, pigments, fillers or solids in a liquid are produced by grinding processes and pasting usual in the field of paints and inks.
EX_F, MPT, RS
Unless otherwise indicated, the parties mentioned in the examples are reference to mass quantities.
1. Telomers and macromonomers used in the past, _hèses Telomeres (homopolymers or copolymers bearing at one of their extremes a reactive chemical function likely to be engaged in a coupling reaction) as well as macromonomers (homopolymers or copolymers bearing at one of their ends a double bond capable of to be involved in a radical polymerization reaction), used during the preparation of the graft copolymers were synthesized from techniques well known to those skilled in the art and described in the publications C. BONARDI et al., Makromolekulare Chemie, IM, 261 (1985), or K. ITO and coll., Macromolecules, U, 216 (1980), or more generally in 2 books of reference: A. AKELAH et al., "Functionalized polymers and their applications, Chapman & Hall, New York (1990), and Y. YAMASHITA, "Chemistry and Industry of Macromonomers, Hfithig & Wepf, New York (1993).

WO 97128200 PC'f / FR97100185

23 The characteristics of the telomeres used during the syntheses are grouped in Table 1 below.
The characteristics of macromonomers obtained by modification previous telomers are shown in Table 2 below.
2. Examples of copol, ymers Qreffés synthesized by radical way:
Example 1 In a reactor topped with a refrigerant, 2 ampoules of addition, of a nitrogen inlet, an agitator and a thermometer, 100 parts of the solution of macromonomer A, 10.9 parts of methacrylate MC
poly (ethylene glycol) of average molecular weight 500 (HEMA-10), and 170 parts of tetrahydrofuran (THF). The temperature of the solution is fixed at under an inert atmosphere of nitrogen. The addition ampoule 1 is loaded with 1.2 parts of 2-dimethylaminoethyl methacrylate (MADAME) and 40 parts of THF, while ampoule 2 contains 0.1 parts of azobisisobutyronitrile (AIBN) and parts of THF. The contents of the 2 ampoules are introduced in a drip in the reactor in 2 hours. The reaction is continued for 6 hours at temperature of polymerization, Tp, 65 C.
A yellow solution of graft copolymer, mass is then obtained number average molecular weight (Mn) 6,400 and polydispersity index (Ip) 1.94, in THF, measured by gel permeation chromatography (GPC) at MC
using a WATERS 150 ALC / GPC type device from PS standards. The Molecular weights were determined to within 100 units.
Examples 2 to 14:
Examples of grafted copolymers, synthesized, by a radical route according to the procedure described in Example 1 are listed in the table 3.
MC
Only those parts relating to commercial silicone macromonomer Ae-5 TOAGOSEI Chemicals Ltd) relate to dry macromonomer, toluene and methyl ethyl ketone (MEK) having previously been removed by distillation.
Comparative Example 15:
In a reactor similar to that described in Example 1, 80 parts of poly (ethylene glycol) molecular weight methacrylate average 300 (HEMA-5), and 1330 parts of THF. After bringing the temperature of the solution at Tp = 65 C, the contents of the contents are added simultaneously and in 2 hours.
bulbs 1 and 2, respectively loaded with 20 parts of MADAME, .100 parts of lauryl methacrylate (LMA), 225 parts of THF and 1.7 parts WO 97/28200 PCT / FR.97 / 00185

24 of AIBN, 225 parts of THF. The mixture is allowed to evolve for 6 hours at 65 oc.
A yellow solution of monografted copolymer is then obtained.
containing only one hydrophilic macromonomer (the hydrophobic monomer, LMA, being present as monomeric units, statistically distributed on along the main anchor chain), Mn = 16,400 and Ip = 2,28, in the THF.
3. Examples of graft copolymers synthesized by radical route and then gxeffaL e ,, Example 16:
In a reactor similar to that described in Example 1, 11.5 parts of poly (ethylene glycol) methacrylate of molecular weight average 500 (HEMA-10) and 170 parts of tetrahydrofuran (THF). The solution is brought to Tp = 65 C. The reactor is then introduced into intermediary the ampoule 1, 11.5 parts of N, N-dimethylacrylamide (DMAm), 5.8 parts of glycidyl methacrylate (GLMA) and 40 parts of THF, in 2 hours.
Simultaneously and during the same period, we add via the bulb 2, 1 part azobisisobutyronitrile (AIBN) and 40 parts THF.
After 5 hours of reaction, a pale yellow solution of copolymer, Mn = 21,300 and Ip = 1.74.
In a second step 100 parts of telomer solution E, 4.8 parts of triethylamine (Et3N) and 210 parts of toluene are introduced in the reactor. The temperature of the solution is then fixed at 90 ° C., after elimination residual THF by distillation. This grafting temperature, Tgr, will be maintained for 6 hours.
Finally, a yellow solution of graft copolymer of Mn =
4500 and Ip = 2.37, in tolulene.
Ex121e 17:
In a reactor, similar to that described in Example 1, introduced 39.5 parts of poly (ethylene glycol) methacrylate of molecular weight average 300 (HEMA-5) and 780 parts of THF, and then the temperature of the solution at 65 C. Under the nitrogen flow, the 2 addition bulbs allow adding, on the one hand 13.2 parts of 2-hydroxyethyl methacrylate 78.9 parts of 2-dimethylaminoethyl methacrylate (MADAME), 195 parts of THF and on the other hand 1.4 parts of AIBN, 195 parts of THF, simultaneously and WO 97/28200 PCT / F12.97 / 00185 continue in 2 hours. The polymerization will be continued for 5 hours to Tp = 65 C.
An intermediate monografted copolymer solution is recovered.
Mn = 4300 and Ip = 2.03.
The grafting step then begins with the cooling of the mixture at room temperature. We then add 100 parts of the solution of telomer D, 18.0 parts of dicyclohexylcarbodiimide (DCCI) and 3.9 parts of dimethylaminopyridine (DMAP) in the reactor. The grafting temperature Tgr is maintained at 25 C for 6 hours.
After filtration of the acylurea formed during the condensation, obtain a yellow solution of graft copolymer, Mn = 2300 and Ip =
1.99.
Examples 18 to 21:
Additional examples, made according to the operating modes described in Examples 16 and 17 are described in Table 4.
parts 15 mentioned in this table and related to telomeres refer to telomere solutions.
4. Examples of pigment concentrates prepared from graft copolymers of the invention Example 22 The copolymer solution obtained in Example 6 is concentrated to 50%.
250 parts of water are then added to the residue and the solvent is then removed.
residual by distillation to recover the graft copolymer in solution in water at 22.2%
Mass.
This aqueous copolymer solution is used during the preparation

25 of two pigment pastes, respectively containing a mineral pigment oxide yellow (yellow pigment CI 42) and a blue organic phthalocyanine pigment (blue pigment CI 15), and whose compositions are given in the table 5.
These pigment concentrates, prepared using mashing techniques conventional, known to those skilled in the art, are then submitted for 1 hour to a zirconium bead milling.
The characteristics of these pigment concentrates, evaluated after grinding, are presented in Table 6.
Exemption 23 In the same way as in Example 22, 500 parts of the copolymer solution described in Example 7, which is then transferred in

26 aqueous medium by addition of 280 parts of water and distillation, to obtain finally a dispersant solution at 16.1% by weight.
The composition and properties of pigment concentrates formulated from this dispersant are given respectively in paintings 5 and 6.
Examples 24 and 25:
500 parts of the copolymer solutions described respectively in Example 10 (Example 24) and Example 11 (Example 25) are processed according to procedure described in Example 22, using in both cases 250 parts of water.
Two aqueous solutions of dispersant of dry extract are thus obtained 18.8% by weight, which are used to formulate pigment concentrates whose compositions and properties are respectively listed in the Tables 5 and 6.
Comparative Example 26:
500 parts of the copolymer solution described in the example Comparative 15 are processed according to the procedure described in Example 22, in using 150 parts of water.
After evaporation of the residual solvent, an aqueous solution of dispersant of dry extract 35.5% by mass, which will be used during the formulation of pigment concentrates, the compositions and properties of which are given in the Tables 5 and 6.
5. Examples of paints prepared for L-reffed polymers:
In order to test the compatibility of pigment concentrates formulated in graft copolymers, with certain binders, said concentrates have summer used alone or in mixture to tint 3 types of paints whose formulas are given below:

Paint I: (vinyl acetate-ethylene-vinyl chloride terpolymer resin) water. 178 binding. 178 charging material: 460 titanium dioxide pigment: 160 dispersant charges. 9 soda solution. 8 rheological agent. 4

27 antifoaming agent: 2 biocide: 1 paint II: (styrene-acrylic resin in emulsion) water: 200 glycol: 44 binding 402 charge material: 141 titanium dioxide pigment 191 dispersant charges: 14 ammonia solution: 2 rheological agent: 2 antifoaming agent: 3 biocide 1 Painting III: (alkyd resin long in oil) white spirit Mc: 137 binding 507 titanium dioxide pigment: 330 dispersant: 5 siccatif: 13 preservative . 8 The pigment concentrates are mixed with these paints, respecting the proportions given in Table 7 below.
t =
Example 27:
Paintings I, II and III are tinted by the two pigment concentrates based on yellow oxide (CI 42 yellow pif ment) and phthalocyanine blue (pigment blue IC 15) described in Example 22, in order to test the accounting of the graft copolymer of Example 6, used as a dispersant, with different binders.
The tests used are as follows:
- Compatibility test: apply side by side on a contrast card, two samples of the same paint, taken after 3 and 10 respectively minutes stirring by means of a device of the type Red-Devil.Mc WO 97/28200 PCT (FR97 / 00185

28 - Test of the "touch or finger" (or "Rub-test"): On the wet paint film, minutes after application, slight pressure is applied to the index, way to crush the film locally. In order to express the results of these tests, adopt a Rating scale graduated from 0 to 10, such as:
0 = no flocculation, good compatibility, no difference between sample at 3 min and 10 min, and the rub-test does not show any difference between the crushed area and the rest of the film;
= flocculated system, compatibility problem, sampling at 3 and 10 min, as well as the crushed area in the rub-test and the rest of the movie present a gap of 10 important hue.
The results of the compatibility tests with each of the paintings I, II, III
are shown in Table 8.
28-30:
Three sets of 9 samples, Examples 28, 29, 30, are prepared from paints I, II, and III as well as two pigment concentrates formulated respectively in Examples 23, 24, and 25 respectively containing the graft copolymers of Examples 7, 10 and 11 as dispersant, following the method described in Example 27.
The results of the tests carried out on these paints are reported in the table 8.
Exe the comparative 31:
Three sets of samples were prepared from paintings I and III
and of the two pigment concentrates elaborated in Comparative Example 26 containing the graft copolymer of Comparative Example 15 as dispersant, according to the procedure presented in Example 27.
The results of the tests carried out on these paints are reported in the table 8.

The results in Table 8 show that with the examples 27, 28, 29 and 30 containing the pigment concentrates of Examples 22, 23, 24 and 25 respectively comprising the graft copolymers according to the invention of Examples 6, 7, 10 and 11, the compatibility of the dispersant evaluated by the tests mentioned in Example 27 is very good in all cases. On the other hand, paints of comparative example 31 containing pigment concentrates prepared in comparative example 26 comprising the copolymer of the example poor compatibility of the dispersant is obtained.

O

TABLE I
Characteristics of the telomere solutions used in the synthesis of graft copolymers.
Telomere ABCDEF
Nature of the PLMA PLMA PLMA PLMA PLMA P (LMA-s-EHMA) telomer >
Solubility parameter 17.9 and 18.0 S (in I2 / cm3 / 2) 17.9 17.9 17.9 17.9 17.9 Functional group -OH -COOH -COOH -COOH -OH -OH
Molecular weight (Mn) 3100 1000 2400 1200 2500 1900 Polydispersity index (Ip) 2.04 2.23 1.35 2.61 1.36 1.24 Telomer Solvent THF Toluene THF Toluene Toluene Toluene Dry extract (in mass%) 11.4 16.7 43.7 19.2 41.7 45.3 not H
~
~
oh ~
~
~

Characteristics of the macromonomer solutions used during the synthesis graft copolymers.
Macromonomer ABCEF HEMA-5 HEMA-10 AK-5 Nature of PLMA PLMA PLMA PLMA PMA Macronionomer (LMA-s-EHMA) POE POE PDMS
Corresponding telomere ABCEF
Solubility parameter S (in IZ / cm312) 17.9 17.9 17.9 17.9 17.9 and 18.0 22.9 22.9 10.2 - 15.8 O W
Molecular weight 3100 1000 2500 2700 1900 310 530 5000 ~ ..
Polydispersity index (Ip) 1.99 2.05 1.40 1.45 1.24 Solvent of the macromonomer THF Toluene TI-1F Toluene Toluene Toluene / MEK

Dry extract (in mass%) 10.9 14.6 36.4 36.6 22.0 100% 100% 40% ~ =

~

Examples of graft copolymers synthesized by a radical route starting from macromonomers.

Example 2 3 4 2-Dimethylaminoethyl methacrylate 5.5 16.7 Acrylamide Sequence 9.5 11.5 13.1 anchor 2-Vinylpyridine 5.5 4.6 1-Vinylimidazole 13.2 Sequence Solution of macromonomer B 100 100 hydrophobic solution of macromonomer C 100 100 E 100 H macromonomer solution Macronionomer Sequence I-IEMA-5 30.5 h dro hile Macromonomer HEMA-10 22.5 20.5 22.0 25.0 Azobisisobutyronitrile initiator 0.3 0.5 0.5 0.3 0.6 Tetrahydrofuran Solvent polymerization 310 20 220 240 550 Polymerization temperature conditions Tp (in C) 65 65 65 65 65 polymerization Polymerization time (h) 8 8 8 8 8 Molecular Weight Characteristics (Mn) 5200 8600 7200 6800 4200 copolymer Polydispersity index (Ip) 1.81 1.93 1.84 1.89 1.53 ~
~
oh r ~
~

O
TABLE 3 (continued) . ~, Example 7 8 9 10 11 12 13 14 2-Dimethylaminoethyl methacrylate 26.0 8.3 8.3 18.5 25.0 23.1 Acrylamide sequence 8.3 33.3 anchor 2-Vinylpyridine 8.3 4.6 22.2 1-Limidazole wine 16.7 Sequence hydrophobic Macromonomer solution E 100 100 100 100 100>
Macromonomer solution F 100 Macromonomer AK-5 100 100 N w Macromonomer Sequence I-IEMA-5 125.0 66.7 h drohile Macromonomer HEMA-10 36.5 25.0 25.0 25.0 27.8 46.1 Primer Azobisisobutyronitrile 0.9 0.8 0.9 0.7 0.8 2.0 1.8 1.1 Solvent of Toluene 2170 1930 polymerization Tetrahydrofuran 690 550 550 550 615 850 Polymerization temperature conditions Tp (in C) 65 65 65 65 65 70 70 65 oh polymerization Curing time (h) 8 8 8 8 8 10 8 8 Molecular Weight Characteristics (Mn) 4500 5200 2400 4100 4500 6000 5700 copolymer Polydispersity index (Ip) 1.59 1.67 1.40 1.56 1.58 1.79 1.70 1.53 ro ~
' ~
~
~

. . . , TAIiI, EAü 4 Examples of graft copolymers synthesized by radical route and grafting telomeres.
Steps Example 18 19 20 21 Monomers N, N-dimethylacrylamide 14.4 of adsorption 2-dimethylaminoethyl methacrylate 14.4 >
2-Vinylpyridine 10.0 20.0 WN
Mono-esters of glycidyl methacrylate 7.2 7.2 Coupling Synthesis 2-hydroxyethyl methacrylate 15.0 30.0 copolymer Comonomer Lauryl methacrylate 30.0 60.0 monografted sequence intermediate hydrophilic Macromonomer HEMA-10 45.0 90.0 14.4 14.4 Azobisisobutyronitrile initiator 0.9 1.7 0.3 0.4 Solvent Tetrahydrofuran 890 1770 320 320 Polymerization temperature conditions Tp (in C) 65 65 65 65 polymerization Polymerization time (h) 8 8 8 8 Characteristics Intermediate molecular weight (Mn) 2300 2300 11500 21300 of the monograft Intermediate polydispersity index (Ip) 1.27 1.27 1.77 1.74 rr ~

O
TABLE 4 (continued) Steps Example 18 19 20 21 Sequence Solution of telomer C 100 100 hydrophilic telomer solution E 100 100 Grafting Catalysts Triethylamine 12.0 6.0 of the reaction Dicyclohexylcarbodiimide 30.0 30.0 41 Coupling telomer 4-Dimethylaminopyridine 1.5 2.0 Solvent added Toluene 260 Conditions Grafting temperature Tgr (in C) 30 30 65 80 grafting Duration of the grafting reaction (in h) 8 8 10 20 Characteristics Molecular weight (Mn) 5200 6300 4700 4100 of the copolymer Final polydispersity index (Ip) 1.95 2.12 2.15 2.48 Composition of pigment concentrates formulated from copolymers grafted.

comparative example Example Blue Oxide Blue Oxide Blue Oxide Blue Oxide Blue Oxide yellow plitalo- yellow phthalo- yellow phthalo- yellow phthalo- yellow phthalo-Cyanine Pigment Cyanine Cyanine Cyanine Cyanine>
Pigment Pigment Yellow Pigment Pigment Pigment Pigment Pigment Pigment Pigment blue winter CIC1.42 blue CI yellow blue CI yellow blue CI yellow blue C.1.
C.1.42 CI42 15 CI42 15 CI42 15 Dry extract of the - Ln 22.2 solution 22.2 16.1 16.1 18.8 18.8 18.8 18.8 35.5 35.5 ~
dispersed (in %
mass) Water 77.3 18.6 40.2 5.4 61.1 8.8 72.0 9.9 106.1 101.3 Pigment 181.7 62.1 131.4 45.1 154.0 52.6 154.0 52.6 249.2 60.5 Solution of dispersant 100 100 100 100 100 100 100 100 100 100 Defoaming 1.2 1.3 0.9 0.9 1.0 1.1 1.0 1.1 1.6 1.3 Agent riological 20.3 O
TABI, EAtJ 6 Properties of pigment concentrates formulated from graft copolymers.

comparative example Example Blue Oxide Blue Oxide Blue Oxide Blue Oxide Blue Oxide yellow phthalo- yellow phthalo- yellow phthalo- yellow phthalo- phthalo- yellow cyanine cyanine cyanine cyanine cyanine Pigment Pigment Pigment Pigment Pigment Pigment Pigment Pigment Pigment Pigment yellow blue blue yellow blue blue yellow blue blue yellow blue blue yellow blue THIS
CI42 15 C.1.42 15 CI42 15 C.1.42 15 C.1.42 15 Content in w N
pigment 50.5 34.1 48.2 29.8 48.7 32.4 47.1 32.2 49.8 23.0 mass) fineness after 9 to 9.5 8 9.5 to 10 8 to 8.5 9.5 to 10 8 to 8.5 9 to 9.5 8.5 to 9 8 to 8.5 8 grinding Viscosity Brookfield after grinding (cP) 1 8,000 9,000 13,500 26,000 13,500 10,000 1 I 500 13,000 17,500 42,000 rev / min r ..
QO
ch -. R

VS

Pigment concentrate contents used to tint the different paintings.

Pigment concentrate Paint I Paint II Paint III
oxydejaune Yellow pigment CI 42 5 8 10 (in% by mass) plitalocyanine blue JW
Pigment blue CI 15 2 3 6 (in% by mass) oxydejaune Yellow pigment CI42 2,5 4,0 3,0 + + + +
phthalocyanine blue 1.0 1.5 3.0 CI Blue Pigment 15 (in% by mass) -d c's O
TABLE 8 Compatibility tests for pigment concentrates prepared from graft copolymers.

27 (eg 6) 28 (eg 7) 29 (eg 10) 30 (eg 11) 31 (ex 15) ex.
comparative Concentrate Example Peintu Peintu Peintu Peintu Peintu Peintu Peintu Peintu Peintu Peintu Peintu Peintu Peintu Peintu Pigmentary re 1st I III III I III III I I II I
Third III III
Yellow oxide Compatibility Pigment jatine l 0 0 0 0 1 1 0 0 1 0 0 2 9 CI42 Rub-test Blue of Compatibility phthalocyanine 1 0 0 0 0 0 0 0 0 1 0 0 4 10 Pigtnent blue Rub-test C.1. 15 Yellow oxide Compatibility + 1 0 1 1 0 0 1 0 0 1 0 1 3 10 Rub-test blue ro pthalocyanine

Claims (70)

1. Graft copolymer or salt of the graft copolymer comprising at least three sequences of a distinct chemical nature, including one or more sequence (s) anchor on solid particles, which solid particles are chosen from pigments, fillers, fibrous solids and combinations thereof, one or more sequence (s) to character hydrophobic and one or more hydrophilic sequence (s) constituted from:
1/1 to 80% by weight of one or more anchoring sequence (s) on the particles solids, consisting of a linear or branched hydrocarbon chain, cycloalkyl or aromatic composition, comprising basic nitrogenous monomers, which comprise basic nitrogen groups selected from groups:
heterocyclic, -NH2, -NH-, -NHR, -NR2, -CONH2, -CONHR, and -CONR2 (where R is a (C1-C6) radical) alkyl, optionally substituted with one or more group (s) -OH, -COO-, -CO-, -0-, or -SO3H), which may comprise -COO- groups, and whose molecular mass is between 150 and 10,000, the mass content of basic nitrogenous monomers in the chain anchor being at least 5%, and 2/10 to 90% by weight of one or more hydrophobic sequence (s), constituted by a hydrocarbon chain, linear or branched, cycloalkyl or aromatic, may contain -COO-, -S-, -F, or -Si (OR ') n (R ") 2-n- (where R' groups) and R "
represent alkyl or aryl radicals, similar or different, in C1-C10, and n = 0 to 2), formed of monomer units whose solubility parameter is lower or equal to 21.5 J1 / 2 / cm3 / 2and whose molecular mass is between 250 and 10 000, and 3/10 to 90% by weight of one or more hydrophilic sequence (s), constituted by a linear or branched hydrocarbon chain comprising groupings -O-, -OH, -NCO-, -COO-, -COOH, -CONH2, -CONHR "(where R"'is a radical (C1-C3) alkyl), -NH-, -S-, or -SO3H, formed of monomer units whose parameter of solubility is greater than 22 J1 / 2 / cm3 / 2 and whose molecular mass is between 250 and 10,000. 2. Graft copolymer or salt of the graft copolymer according to claim 1, in which the main chain is an anchoring sequence on solid particles constituted by a hydrocarbon chain, linear or branched, cycloalkyl or aromatic, including basic nitrogenous monomers, which contain basic nitrogen groups selected from heterocyclic groups, -NH2, -NH-, -NHR, -NR2, -CONH2, -CONHR, and -CONR2 (where R is a (C1-C6) alkyl radical, optionally substituted by one or several groups -OH, -COO-, -CO-, -O-, -SO3H), which may comprise -COO- groups, and whose molecular mass is between 150 and 10 000, the content mass of basic nitrogenous monomers in the anchor chain being at minimum of 5%. 3. graft copolymer or salt of the graft copolymer according to claim 1, in which the main chain is a hydrophobic sequence consisting of chain hydrocarbon, linear or branched, cycloalkyl or aromatic, include groups -COO-, -S-, -F, or -Si (OR ') n (R ") 2-n- (where R' and R" represent radicals C1-C10 alkyl or aryl, similar or different, and n = 0 to 2), formed units monomer whose solubility parameter is less than or equal to 21.5 J1 / 2 / cm3 / 2, and whose molecular weight is between 250 and 10,000. 4. graft copolymer or salt of the graft copolymer according to claim 1, in which the main chain is a hydrophilic sequence consisting of chain linear or branched hydrocarbon containing groups -O-, -OH, -NCO-, -COO-, -COOH, -CONH2, -CONHR "(where R"'is a (C1-C3) alkyl radical), or -SO3H, formed of monomer units whose solubility parameter is greater than 22 J1 / 2 / cm3 / 2 and whose mass molecular weight is between 250 and 10,000. 5. graft copolymer or salt of the graft copolymer according to claim 1, in which anchoring sequence (s) on solid particles represent (s) 5 to 40%
Mass. 6. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 and 2, wherein the molecular weight of the nitrogen groups basic is between 300 and 3000. 7. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 and 2, wherein the mass content of nitrogenous monomers basic in the anchor chain is at least 30%. 8. Graft copolymer or salt of the graft copolymer according to claim 1, in which one or more hydrophobic sequences represent (s) 25 to 80%
Mass. 9. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 and 3, wherein the monomeric units of the one or more sequences in character hydrophobic have a solubility parameter less than 19 J1 / 2 / cm3 / 2. 10. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 and 3, wherein the monomeric units of the one or more sequences in character hydrophobic have a molecular weight between 500 and 3500. 11. Graft copolymer or salt of the graft copolymer according to claim 1, in which one or more hydrophilic sequences represent (s) 15 to 70%
Mass. 12. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 and 4, wherein the monomeric units of the one or more sequences in character hydrophilic have a solubility parameter greater than 22.5 J1 / 2 / cm3 / 2. 13. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 and 4, wherein the monomeric units of the one or more sequences in character hydrophilic have a molecular weight of between 300 and 3000. 14. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 to 13, in the form of one of its salts, obtained by quaternization or neutralization basic functions. 15. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 to 14, characterized in that the anchoring sequence comprises (a) in the first case, basic nitrogenous groups introduced from one or several compound (s) chosen from:
2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine or 2-methyl-pyridine, vinylimidazole, 2-methyl-N-vinylimidazole, vinylcarbazole, N-vinylpyrrolidone, 3-methyl-N-vinylpyrazole, 4-methyl-5-vinylthiazole, NOT-vinylcaprolactam, ethylimidazolidone methacrylate, (meth) acrylamide, methylacrylamide, N-isopropylacrylamide and N, N-dimethylacrylamide, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, diacetone acrylamide, methyl-2-acrylamido 2-methoxyacetate, N-tris (hydroxymethyl) methylacrylamide, and the aminoalkyl (meth) acrylates of the following formula:
where R1 is a hydrogen atom or a (C1-C4) alkyl radical; R2 and R3 identical or each represents a (C1-C6) alkyl radical, n = 0 to 6, said basic nitrogen groups being in this first case introduced by radical copolymerization of one or more ethylenic monomer (s) unsaturated above, or, (b) in a second case, basic nitrogenous groups introduced from one or several compound (s) chosen from:
NN-diethyl-1,4-butanediamine, 1- (2-aminoethyl) -piperazine, 2- (1-pyrrolidyl) ethylamine, 4-amino-2-methoxy-pyrimidine, 2-dimethylamino-ethanol, 1- (2-hydroxyethyl) piperazine, 4- (2-hydroxyethyl) morpholine, mercaptopyrimidine, 2-mercaptobenzimidazole, N, N-dimethyl-1,3-propanediamine, 4- (2-aminoethyl) -pyridine, NN-diallyl-melamine, 3-amino 1,2,4-triazole, 1- (3-aminopropyl) imidazole, 4- (2-hydroxyethyl) -pyridine, 1-(2-hydroxyethyl) imidazole, and 3-mercapto-1,2,4-triazole, said basic nitrogen groups being in this second case fixed on a copolymer, linear or grafted, taking advantage of the reactive functions introduced on along a preformed chain. 16. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 to 15, characterized in that the sequence (s) with character hydrophobic are consisting of monomer units selected from:
methyl (meth) acrylate, ethyl (meth) acrylate and (meth) acrylate of propyl, the butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylate, cyclohexyl, the ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylate, nonyl, the isodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylate, stearyl, the pentadecyl (meth) acrylate, cetyl (meth) acrylate, (meth) acrylate Behenyl 3- (trimethoxysilyl) propyl (meth) acrylate, - vinyl acetate, vinyl propionate, vinyl butyrate, vinyl sorbate, vinyl hexanoate, vinyl ethylhexanoate, vinyl laurate, vinyl stearate, α-methylstyrene, vipyltoluene, tert-butylstyrene, butadiene and isoprene, which can be hydrogenated after polymerization, - ethylene, propylene, dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, trifluoroethyl (meth) acrylate, (meth) acrylate, pentafluoropropyl, the heptafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, (meth) acrylate pentadecafluorooctyl, eicosafluoroundecyl (meth) acrylate, fluoride vinyl, the tetrafluoroethylene, of polyesters prepared from diacids and long-chain diols alkyls or hydroxy acids with long alkyl chains, and polyamides prepared from of diacids and long-chain diamines or long-chain amino acids alkyls. 17. Graft copolymer or salt of the graft copolymer according to any one of Claims 1 to 16, characterized in that the sequence (s) with character hydrophilic are consisting of monomer units selected from:
- ethylene oxide, - (meth) acrylic acids, maleic acid, fumaric acid, acid itaconic acid, (meth) acrylamide, N-methylacrylamide, N-isopropylacrylamide, ethyleneimine, - vinyl alcohol, vinylpyrrolidone, vinylmethyloxazolidone, vinylsulphonate, sodium methallylsulphonate, and - Glycerol methacrylate. 18. Graft copolymer or salt of the graft copolymer according to claim 1, comprising:
a main anchor chain on the solid particles comprising identical or different groups selected from the (meth) acrylate of dialkylaminoethyl, N, N-dimethylacrylamide, 2-vinylpyridine, and 4-pyridine, one or more hydrophilic poly (ethylene oxide) grafts, and one or more hydrophobic grafts based on alkyl (meth) acrylates, esters vinyl compounds alone or copolymerized with styrenic derivatives or alkylstyrene, fluorinated monomers (trifluoroethyl methacrylate), or methacrylate 3-(Trimethoxysilyl) propyl. 19. Process for the preparation of a graft copolymer or a salt of the copolymer graft according to claim 2, wherein the main chain is a sequence anchoring, characterized in that:
1) radical copolymerization of:
i) 0 to 80% by weight of one or more monomer (s) comprising at least one basic nitrogen group selected from heterocyclic groups, NH2, -NHR, -NR 2, -CONH 2, -CONHR, and -CONR 2 (wherein R is a (C 1 -C 6) alkyl radical, optionally substituted with one or more groups -COO-, -CO-, -O-, -OH, -SO3H), and ii) 0 to 90% by weight of one or more macromonomers represented by the formula :

where R4, R5, R6, identical or different, represent a hydrogen atom or a radical (C1-C4) alkyl, R7 is a hydrophobic sequence consisting of a chain hydrocarbon, linear or branched, cycloalkyl or aromatic, which may include -COO- groups, -S-, -F, or -Si (OR ') n (R ") 2-n- (where R' and R" represent alkyl radicals or aryls, similar or different, in C1-C10, and n = 0 to 2), formed of monomer units whose solubility parameter is less than or equal to 21.5 J1 / 2 / cm3 / 2, and whose molecular mass is between 250 and 10,000, and iii) 0 to 90 wt.%, of one or more macromonomer (s) represented by the formula:

where R4, R5, R6 are as defined above, and R8 is a hydrophilic sequence consisting of a chain hydrocarbon, linear or branched having -O-, -OH, -NCO-, -COO-, -COOH groups, or -CONH2, -CONHR '''(where R "' is (C1-C3) alkyl), -NH-, -S-, or -SO3H, formed units monomer whose solubility parameter is greater than 22 J1 / 2 / cm3 / 2, and whose mass molecular weight is between 250 and 10,000, iv) 0 to 80% by weight of one or more monomer (s) containing at least one functional group capable of being engaged in a coupling reaction, and, v) 0 to 76% by weight of one or more unsaturated ethylenic monomer (s) can contain up to 25 carbon atoms, except for the monomers already mentioned in i), it being understood that if one of the mass contents of the compounds defined in i), ii) and / or iii) is zero, the mass content of the compounds defined in iv) is different from 0, and 2) grafting on this preformed chain of:
vi) 0 to 80% by weight, of one or more molecule (s) derived from a compound having at least one heterocyclic basic nitrogen moiety, -NH2, -NHR or -NR2 (where R is a (C1-C6) alkyl radical, and containing at least one group functional to be engaged in a coupling reaction with (iv), and vii) 0 to 90% by mass, of one or more telomere (s) represented by the formula :

where G represents a group containing a reactive hydrogen atom, -OH, -COOH, -SH, -NH2, or -NHR "'(where R"' is a (C1-C3) alkyl radical), and R7 is such that defined above, and viii) 0 to 90% by mass, of one or more telomere (s) represented by the formula where G and R8 are as defined above, Being heard that :
- the mass contents of the compounds defined in i) and vi) can not be simultaneously equal to 0, and when one of them equals 0, then the other is equal to minus 1%, - the mass contents of the compounds defined in (ii) and (vii) can not be simultaneously equal to 0, and when one of them equals 0, then the other is equal to minus 10%, - the mass contents of the compounds defined in (iii) and (viii) can not be to be simultaneously equal to 0, and when one of them equals 0, then the other is equal to less 10%. The process of claim 19 wherein the copolymerization radical involves 0 to 40% by weight of one or more monomer (s) i) comprising at least minus one basic nitrogen group. 21. The process according to claim 19, wherein the copolymerization radical involves from 0 to 80% by weight of one or more macromonomer (s) ii). 22. The method of claim 19, wherein the monomer units of the R7 hydrophobic sequence have a solubility parameter lower than J1 / 2 / cm3 / 2. The method of claim 19, wherein the monomer units of the hydrophobic sequence R7 have a molecular weight of between 500 and 3,500. 24. The process according to claim 19, wherein the copolymerization radical involves from 0 to 70% by weight of one or more macromonomer (s) iii). 25. The method of claim 19, wherein the monomer units of the hydrophilic sequence R8 have a solubility parameter greater than 22.5 J1 / 2 / cm3 / 2. The method of claim 19, wherein the monomer units of the hydrophilic sequence R8 have a molecular weight of between 300 and 3,000. 27. The method of claim 19, wherein the copolymerization radical involves 0 to 40% by weight of one or more monomer (s) iv). 28. The process according to claim 19, wherein the copolymerization radical involves from 0 to 28% by weight of one or more ethylenic monomer (s) unsaturated (s) v). The method of claim 19, wherein the grafting involves 0 to 40%
mass of one or more molecule (s) vi). 30. The method of claim 19, wherein the grafting involves 0 to 80%
mass of one or more telomere (s) vii). 31. The method of claim 19, wherein the grafting involves 0 to 70%
mass of one or more telomeres (viii). 32. Process for preparing a graft copolymer or a salt of the copolymer graft according to claim 3, wherein the main chain is a sequence character hydrophobic, characterized in that the radical copolymerization is carried out from:
i) 10 to 90% by weight of one or more hydrophobic monomer (s) having at least one aromatic group, -COO-, -F, or -Si (OR ') n (R ") 2-(where R 'and R "
represent identical or different alkyl or aryl radicals in C1-C10, and n = 0 to 2) after polymerization constituting a chain formed of monomer units whose parameter of solubility is less than or equal to 21.5 J1 / 2 / cm1 / 2, and whose mass molecular is included between 250 and 10,000, and ii) 0 to 90% by weight of one or more macromonomers represented by the formula :

where R4, R5, R6, which are identical or different, represent a hydrogen atom or a radical (C1-C4) alkyl, and R8 is a hydrophilic sequence consisting of a chain hydrocarbon, linear or branched having -O-, -OH, -NCO-, -COO-, -COOH, -CONH2 groups, or -CONHR "'(where R"' is (C1-C3) alkyl), -NH-, -S-, or -SO3H, formed units monomer whose solubility parameter is greater than 22 J1 / 2 / cm3 / 2, and whose mass molecular weight is between 250 and 10,000, and iii) 0 to 80% by weight of one or more macromonomer (s) represented by the formula :

where R4, R5, R6 are as defined above, and R9 is an anchoring sequence, consisting of a hydrocarbon chain, linear or branched, cycloalkyl or aromatic, comprising basic nitrogenous monomers, which behave basic nitrogen groups selected from groups heterocyclic, -NH2, -NH-, -NHR, -NR2, -CONH2, -CONHR, and -CONR2 (where R is a (C1-C6) radical) alkyl, optionally substituted with one or more group (s) -OH, -COO-, -CO-, -O-, -SO3H), which may comprise -COO- groups, and whose molecular mass is between 150 and 10,000, the mass content of basic nitrogenous monomers in the chain anchor being at least 5%, and iv) 0 to 80% by weight of one or more monomer (s) containing at least one group capable of being engaged in a coupling reaction, it being understood that if one of the mass contents of the compounds defined in i), ii) and / or iii) is zero, the mass content of the compounds defined in iv) is different from 0, and 2) grafting on this preformed chain of:
v) 0 to 90% by mass, of one or more telomere (s) represented by the formula where G represents a group containing a reactive hydrogen atom, -OH, -COOH, -SH, -NH2, or -NHR '''(where R "' is a (C1-C3) alkyl radical), and R8 is such that defined above, and vi) 0 to 80% by mass, of one or more telomere (s) represented by the formula where G and R9 are as defined above, Being heard that :
- the mass contents of the compounds defined in (ii) and (v) can not be simultaneously equal to 0, and when one of them equals 0, then the other is equal to minus 10%, - the mass contents of the compounds defined in (iii) and (vi) can not be simultaneously equal to 0, and when one of them equals 0, then the other is equal to minus 1%. 33. The process according to claim 32, wherein the copolymerization radical involves 25 to 80% by weight of one or more monomer (s) of character hydrophobic i). The method of claim 32, wherein the monomer units to character hydrophobic have a solubility parameter less than 19 J1 / 2 / cm1 / 2. The method of claim 32, wherein the monomer units to character hydrophobic have a molecular weight between 500 and 3500. The process of claim 32, wherein the copolymerization radical involves 0 to 70% by weight of one or more macromonomer (s) ii). 37. The method of claim 32, wherein the monomer units of the hydrophilic sequence R8 have a solubility parameter greater than 22.5 J1 / 2 / cm3 / 2. 38. The method of claim 32, wherein the monomer units of the hydrophilic sequence R8 have a molecular weight of between 300 and 3,000. 39. The method of claim 32, wherein the copolymerization radical involves 0 to 40% by weight of one or more macromonomer (s) iii). 40. The method of claim 32, wherein the molecular weight of groups basic nitrogen of R9 is between 300 and 3,000. 41. The method of claim 32, wherein the mass content of monomers basic nitrogen in the anchor chain R9 is at least 30%. 42. The process according to claim 32, wherein the copolymerization radical involves 0 to 40% by weight of one or more monomer (s) iv). The method of claim 32, wherein the grafting involves 0 to 70%
mass of one or more telomere (s) v). 44. The method of claim 32, wherein the grafting involves 0 to 40%
mass of one or more telomere (s) vi). 45. Process for preparing a graft copolymer or a salt of the copolymer graft according to claim 4, wherein the main chain is a sequence character hydrophilic, characterized in that the radical copolymerization is carried out of:
i) 10 to 90% by weight of one or more monomers of hydrophilic nature having at least one group -O-, -OH-, -COOH, -NCO-, -COO-, -SO3H, -CONH2, or -CONHR "'(where R"' is a radical (C1-C3) alkyl), and constituting after polymerization a chain formed of monomer units whose solubility parameter is greater at 22 J1 / 2 / cm3 / 2, and whose molecular weight is between 250 and 10,000, and ii) 0 to 90% by weight of one or more macromonomers represented by the formula:

where R4, R5, R6, identical or different, represent a hydrogen atom or a radical (C1 -C4) alkyl, R7 is a hydrophobic sequence consisting of a chain hydrocarbon, linear or branched, cycloalkyl or aromatic, which may include -COO- groups, -S-, -F, or -Si (OR ') n (R ") 2-n- (where R' and R" represent alkyl radicals or aryls, similar or different, in C1-C10, and n = 0 to 2), formed of monomer units whose solubility parameter is less than or equal to 21.5J1 / 2 / cm3 / 2, and whose molecular mass is between 250 and 10,000, and iii) 0 to 80% by weight of one or more macromonomer (s) represented by the formula:

where R4, R5, R6 are as defined above, and R9 is an anchoring sequence, consisting of a hydrocarbon chain, linear or branched, cycloalkyl or aromatic, comprising basic nitrogenous monomers, which behave basic nitrogen groups selected from groups heterocyclic, -NH2, -NH-, -NHR, -NR2, -CONH2, -CONHR, and -CONR2 (where R is a (C1-C6) radical) alkyl, optionally substituted with one or more group (s) -OH, -COO-, -CO-, -O-, or -SO3H), which may comprise -COO- groups, and whose molecular mass is between 150 and 10,000, the mass content of basic nitrogenous monomers in the chain anchor being at least 5%, and iv) 0 to 80% by weight of one or more monomer (s) containing at least one group capable of being engaged in a coupling reaction, it being understood that if one of the mass contents of the compounds defined in i), ii) and / or iii) is zero, the mass content of the compounds defined in iv) is different from 0, and 2) grafting on this preformed chain of:
v) 0 to 90% by mass, of one or more telomere (s) represented by the formula :

where G represents a group containing a reactive hydrogen atom, -OH, -COOH, -SH, -NH2, or -NHR '''(where R "' is a (C1 -C3) alkyl radical), and R7 is such that defined above, and vi) 0 to 80% by mass, of one or more telomere (s) represented by the formula where G and R9 are as defined above, Being heard that :
- the mass contents of the compounds defined in (ii) and (v) can not be simultaneously equal to 0, and when one of them equals 0, then the other is equal to minus 10%, - the mass contents of the compounds defined in (iii) and (vi) can not be simultaneously equal to 0, and when one of them equals 0, then the other is equal to minus 1%. 46. The process according to claim 45, wherein the copolymerization radical involves 15 to 70% by mass of one or more monomer (s) with character hydrophilic i). The method of claim 45, wherein the monomer units of the hydrophilic sequence have a higher solubility parameter than 22.5 J1 / 2 / cm3 / 2. 48. The method of claim 45, wherein the monomer units of the sequence to hydrophilic character have a molecular weight of between 300 and 3000. 49. The process according to claim 45, wherein the copolymerization radical implies 0 to 80% by weight of one or more macromonomer (s) ii). The method of claim 45, wherein the monomer units of the R7 hydrophobic sequence have a solubility parameter lower than J1 / 2 / cm3 / 2. The method of claim 45, wherein the monomer units of the sequence to R7 hydrophobic character have a molecular weight of between 500 and 3500. 52. The process according to claim 45, wherein the copolymerization radical involves 0 to 40% by weight of one or more macromonomer (s) iii). The method of claim 45, wherein the molecular weight of groups basic nitrogen of R9 is between 300 and 3,000. 54. The process according to claim 45, wherein the mass content in monomers basic nitrogen in the anchor chain R9 is at least 30%. The process according to claim 45, wherein the copolymerization radical involves 0 to 40% by weight of one or more monomer (s) iv). The method of claim 45, wherein the grafting involves 0 to 80%
mass of one or more telomere (s) v). The method of claim 45, wherein the grafting involves 0 to 40%
mass of one or more telomere (s) vi). 58. Process according to any one of claims 19 to 57, characterized in what the radical copolymerization is carried out at a temperature between 50 ° C and 140 ° C, and the grafting reaction at a temperature between 20 ° C and 150 ° C. 59. Process according to any one of claims 19 to 58, characterized in what the order of addition of the monomers during the radical copolymerization is the following :
macromonomers, which have a high molecular mass and are therefore less reagents, are incorporated from the outset in a reactor, with a solvent, - the comonomer or comonomers constituting the main chain, more reactive, are introduced continuously over time, so that their concentration is always weak by compared to that of macromonomers. 60. Process according to any one of claims 19 to 59, characterized in what the radical copolymerization and / or grafting of functionalized telomeres is are) carried out in the presence of a solvent or a mixture of solvents chosen from the aromatic hydrocarbons, ethers, ketones and esters. 61. Process according to claim 60, characterized in that the solvent (s) is are) selected from dioxane, tetrahydrofuran and toluene. 62. A composition containing:
a) at least one graft copolymer or salt of the graft copolymer according to one of the Claims 1 to 18, and b) solid particles chosen from pigments, mineral fillers, solid fibrous and combinations thereof, and c) at least one organic solvent and / or water. 63. A dispersion containing at least one composition according to claim 62 in wherein said solid particles are pigments selected from mineral pigments, metallic and organic. 64. A paint comprising a dispersion according to claim 63. An ink comprising a dispersion according to claim 63. 66. An emulsification comprising, as an emulsifying agent, at least one copolymer graft or salt of the graft copolymer according to one of claims 1 to 18. 67. Use of one or more graft copolymer (s) or salt (s) of copolymer (s) graft (s) according to any one of claims 1 to 18, as an agent dispersant of solid particles in an aqueous and / or organic medium, which solid particles being selected from pigments, mineral fillers, fibrous solids and combinations of these. 68. Use of one or more graft copolymer (s) or salt (s) of copolymer (s) graft (s) according to any one of claims 1 to 18, as an agent stabilizer solid particles in an aqueous and / or organic medium, which solid particles being selected from pigments, mineral fillers, fibrous solids and combinations of these. 69. Use of one or more graft copolymer (s) or salt (s) of copolymer (s) graft (s) according to any one of claims 1 to 18, as an agent emulsifier, in an aqueous and / or organic medium containing solid particles, which particles solids being selected from pigments, mineral fillers, fibrous solids and combinations of these. 70. Use according to any one of claims 67 to 69, for the preparation of pigment dispersions in aqueous and / or organic medium containing solid particles, at least one pigment selected from inorganic pigments, metallic and organic.