Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
  • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C09D131/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/04—Printing inks based on proteins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/08—Printing inks based on natural resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/54—Aqueous solutions or dispersions
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

• the invention relates to a composition for the preparation of a coating, such as a paint or a varnish, comprising a thickening acrylic acid copolymer, a binder polymer selected from a vinyl acetate homopolymer, a vinyl acetate copolymer. vinyl, vinyl versatate homopolymer, vinyl versatate copolymer and combinations thereof, and water.
• a coating such as a paint or a varnish
• the invention also relates to the use of the acrylic acid copolymer in an aqueous coating composition comprising such a binder polymer to improve the stability thereof during storage.
• the copolymer of the composition according to the invention makes it possible to improve the stability during storage of aqueous coating compositions comprising a binder chosen from a homopolymer of vinyl acetate, a copolymer of vinyl acetate, a homopolymer of vinyl versatate , a vinyl versatate copolymer, and combinations thereof.
• aqueous coating compositions based on binder based on vinyl acetate or vinyl versatate use thickeners, rheology modifiers, which allow the compositions to be given the desired rheological properties over a wide range of shear rates.
• These thickeners can be cellulose polymers such as hydroxyethylcellulose (HEC), hydroxymethylethylcellulose (HMEC) and hydrophobic modified HEC (HMHEC), associative thickeners of the HEUR type (Hydrophobically modified Urethane oxide of Ethylene, Hydrophobically modified Ethylene (URethane oxide according to the appropriate acronym), associative thickeners of the HASE type (hydrophobically modified soluble alkali emulsion).
• HEUR rheology modifiers are that they are too expensive.
• HASE thickeners are an attractive low cost alternative to HECs.
• the compatibility of the different constituents of an aqueous coating composition must also be taken into account.
• the polymeric agents used as thickening agents do not always provide a satisfactory solution to these various problems.
• aqueous coating compositions comprising a binder chosen from a homopolymer.
• a binder chosen from a homopolymer.
• compositions comprising little or no methacrylic acid, while offering performance that is maintained or improved compared to known compositions.
• methacrylic acid in particular of methacrylic acid predominantly prepared from acetone cyanohydrin which is a highly toxic compound, should be limited as much as possible.
• Document EP 2853570 describes a composition comprising a copolymer of vinyl acetate and a HASE thickener prepared with ethyl acrylate, methacrylic acid, acrylic acid and a hydrophobic macromonomer.
• Document WO 2011/161508 describes alkali-swellable thickening emulsions prepared with 2-acrylamido-2-methylpropane sulfonic acid and in the absence of surfactant.
• Document EP 1466930 discloses a cement dispersant prepared with a polycarboxylic acid and document US 6296698 describes a cement admixture comprising a copolymer obtained by polymerization of N-vinylacetamide.
• composition according to the invention makes it possible to provide a solution to all or part of the problems of the compositions of the prior art.
• composition for preparing a coating comprising:
• al-1 chosen from acrylic acid and its salts
• At least one monomer (a2) which is an ester of an acid chosen from acrylic acid, methacrylic acid, itaconic acid and their combinations;
• n identical or different, independently represent 0 or an integer or decimal number, advantageously an integer number, less than 150, the sum m + n ranging from 5 to 150,
• - OE represents a CH2CH2O group
• - OP independently represents a group chosen from CH (CH 3 ) CH 2 0 and CH 2 CH (CH) 0,
• R 1 represents a group comprising at least one polymerizable olefinic unsaturation
• R 2 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms;
• At least one monomer (a4) chosen from 2-acrylamido-2-methylpropane sulfonic acid, 2-sulfoethyl methacrylate, sodium methallyl sulfonate, styrene sulfonate, their salts and their combinations;
• binder polymer B selected from a vinyl acetate homopolymer, a vinyl acetate copolymer, a vinyl versatate homopolymer, a vinyl versatate copolymer and combinations thereof and
• Copolymer A according to the invention is prepared by polymerization of at least one monomer (al) comprising a monocarboxylic acid function which are the monomers (al-1) and (al-2).
• the monomer comprising a monocarboxylic acid function is exclusively chosen from monomers (al-1) and (al-2).
• the monomer (al-1) is selected from acrylic acid and its salts, in particular an ammonium salt, an amine salt, alkali salts, such as its sodium and potassium salts.
• the monomer (al-1) is acrylic acid.
• the polymerization reaction for the preparation of copolymer A uses less than 10%, preferably less than 6%, more preferably less than 5%, much more preferably less than 2% or less of 1.5% by weight of monomer (al-2) relative to the total weight of the monomers.
• the polymerization reaction for the preparation of copolymer A does not use monomer (al-2).
• the monomer comprising a monocarboxylic acid function is exclusively the monomer (al-1).
• the mass ratio [monomer (al-1)] / [monomer (al-1) + monomer (al-2)] is strictly greater than 0.70, preferably greater than 0.75, preferably greater than 0.80, more preferably greater than 0.90, even more preferably greater than 0.95.
• Copolymer A according to the invention is prepared by polymerization of at least one monomer (a2) which is an ester of an acid chosen from acrylic acid, methacrylic acid, itaconic acid and their combinations.
• the preferred monomer (a2) according to the invention is chosen from alkyl acrylate, in particular C1-Cio-alkyl acrylate, preferably C1-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, ethyl acrylate.
• propyl isobutyl acrylate, n-butyl acrylate, alkyl methacrylate, in particular C1-Cio-alkyl methacrylate, preferably C1-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, methyl methacrylate propyl, isobutyl methacrylate, n-butyl methacrylate, aryl acrylate, preferably phenylacrylate, benzylacrylate, phenoxyethylacrylate, aryl methacrylate, preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate and their combinations, preferably methyl acrylate, acrylate ethyl, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, more preferably methyl acrylate or ethyl acrylate.
• the more preferred monomer (a2) according to the invention is chosen from methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, more preferably methyl acrylate or ethyl acrylate.
• Copolymer A according to the invention is prepared by polymerization of at least one hydrophobic monomer (a3) which is an associative hydrophobic monomer comprising at least ethoxylene groups and a hydrophobic end group.
• the hydrophobic end group is a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms.
• the sum m + n varies from 10 to 150, advantageously from 10 to 100, more advantageously from 10 to 60.
• m represents a whole or decimal number, advantageously an integer, greater than or equal to 10.
• the value of m is strictly greater than the value of n. More preferably according to the invention, the numerical ratio m / n ranges from 100 to 0 to 70 to 30.
• n is zero and m independently represents an integer or decimal number, advantageously an integer, ranging from 10 to 100, advantageously ranging from 10 to 60, more preferably 20 to 60, even more preferably 20 to 40.
• each of n and of m is different from 0.
• m and n identical or different, independently represent an integer or decimal number, advantageously an integer, ranging from 5 to 100, the sum m + n varying from 10 to 150, advantageously from 10 to 100, more advantageously from 10 to 60.
• the value of m is strictly greater than the value of n. More preferably according to the invention, the numerical ratio m / n ranges from 90/10 to 70/30.
• n 0.
• R 1 represents a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl, isoprenyl, an unsaturated urethane group, in particular acrylurethane, methacrylurethane, a-a'- dimethyl-isopropenyl- benzylurethane, allylurethane, more preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl and isoprenyl, even more preferably a methacrylate group.
• R 2 independently represents a hydrocarbon group comprising from 6 to 40 carbon atoms, preferably from 6 to 32 carbon atoms, more preferably from 8 to 30 carbon atoms.
• the hydrocarbon group can be linear, branched or cyclic, saturated, unsaturated or aromatic.
• the hydrocarbon group R 2 advantageously represents an alkyl or alkenyl group, linear, branched or cyclic, advantageously linear or branched, comprising from 6 to 40 carbon atoms, preferably from 6 to 32 carbon atoms.
• the hydrocarbon group R 2 advantageously represents an alkyl or alkenyl group, linear, comprising from 6 to 40 carbon atoms, preferably from 6 to 32 carbon atoms, more preferably from 8 to 30 carbon atoms. .
• the hydrocarbon group R 2 advantageously represents an alkyl or alkenyl group, branched, comprising from 6 to 40 carbon atoms, preferably from 6 to 32 carbon atoms, more preferably from 8 to 30 carbon atoms.
• the hydrocarbon group R 2 represents an alkyl group derived from a Guerbet alcohol, that is to say an alkyl group of formula (II): in which R ′ represents a C 6 -C 40 -alkyl group, preferably a Cs-C 2-alkyl group.
• the hydrocarbon group R 2 advantageously represents an alkyl or alkenyl group, linear, comprising from 6 to 40 carbon atoms, such as for example a cyclohexyl group.
• R 2 can also represent an alkyl group resulting from an alcohol obtained by an oxo reaction.
• the hydrocarbon group R 2 can also represent an aromatic group comprising from 6 to 40 carbon atoms, preferably from 6 to 32 carbon atoms, more preferably from 8 to 30 carbon atoms.
• the hydrocarbon group R 2 can represent a radical of formula
• a radical of formula (III) is advantageously derived from cardanol, and thus of bio-resourced origin.
• the hydrocarbon-based group R 2 can represent a group comprising 2 to 5 phenyl groups, such as a tristyrylphenyl (TSP) group of formula:
• DSP distyrylphenyl
• R 2 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms, preferably a linear or branched C 6 -C40-alkyl group, preferably a Cx group -Chn-alkyl, linear or branched, a C6-C40-aryl group, preferably a Cs-C 3 ⁇ 4) -aryl group, preferably comprising 2 to 5 phenyl groups, for example a tristyrylphenyl group.
• the monomer (a4) is chosen from 2-acrylamido-2-methylpropane sulfonic acid, 2-sulfoethyl methacrylate, sodium methallyl sulfonate, styrene sulfonate, their salts and their combinations.
• the preferred monomer salts (a4) are the sodium salts and the ammonium salts.
• the monomer (a4) is chosen from 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl methacrylate, their salts and their combinations.
• the monomer (a4) is 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or one of its salts, preferably its sodium salt.
• AMPS 2-acrylamido-2-methylpropanesulfonic acid
• the copolymer A is prepared by polymerization reaction of the monomers (al-1), (al-2), (a-2), (a-3) and (a-4), to the exclusion of any other monomer.
• the proportions of the various monomers used during the preparation of the copolymer (A) can vary within fairly wide proportions.
• the copolymer A is prepared by polymerization reaction:
• the copolymer A is prepared by polymerization reaction:
• composition according to the invention comprises at least one binder polymer B chosen from:
• a copolymer of vinyl acetate and ethylene a copolymer of vinyl acetate and acrylate, a copolymer of vinyl acetate and methacrylate, a copolymer of vinyl acetate, ethylene and acrylate, a copolymer of vinyl acetate, ethylene and methacrylate, a copolymer of vinyl acetate, acrylate and methacrylate;
• Polymer B can therefore also be prepared by polymerization of other monomers, in particular ethylene, esters of acrylic acid, esters of methacrylic acid and their combinations.
• the acrylic acid ester is advantageously chosen from alkyl acrylate, in particular C1-Cio-alkyl acrylate, preferably C1-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate.
• the methacrylic acid ester is advantageously chosen from alkyl methacrylate, in particular C1-Cio-alkyl methacrylate, preferably C1-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate.
• vinyl acetate-ethylene copolymers alkyl (meth) acrylate-vinyl acetate copolymers, vinyl versatate (meth) acrylate copolymers, vinyl acetate copolymers. vinyl versatate and their combinations.
• Polymer B is advantageously in the form of an aqueous continuous phase emulsion.
• composition according to the invention advantageously has a pH which is greater than 7, preferably greater than 8.
• the composition according to the invention has a pH which ranges from 7 to 12, more preferably from 8 to 12.
• the composition can in particular be prepared by adding the copolymer A to an aqueous composition comprising the polymer B, for example in an emulsion in aqueous continuous phase comprising the polymer B.
• the coating according to the invention is advantageously a varnish or a paint.
• composition can also comprise, in addition to water, polymer A and polymer B:
• Pigment D can be an inorganic pigment, an organic pigment, or combinations thereof.
• inorganic pigments mention may be made in particular of titanium dioxide, iron oxide (brown, yellow, red or black), zinc oxide, zinc phosphate and their combinations.
• organic pigment mention may in particular be made of green phthalocyanine, blue phthalocyanine, blue indanthrone, beta-naphthol, benzimidazolone, pyranthrone, diketopyrrolo-pyrrole (DPP), quinacridone, azo pigments, etc.
• condensation disazos in particular condensation disazos, dioxazine carboazole, perinone, pyrazolone, carbon black, graphite, anthraquinone, benzimidazolone, arylamide, diarylide, benzimidazolone, organic metal complexes, isoindolinone, isoindoline, quinophthalone, anthrapyrimidine, flavanthrone and combinations thereof.
• filler By way of filler, mention may in particular be made of barium sulphate, natural calcium carbonate, synthetic calcium carbonate, clay, cristobalite, diatomaceous earth, dolomite, feldspar, kaolin, mica, silica (Quartz), aluminum silicate, calcium silicate, talc and their combinations.
• the composition comprises:
• Such a composition advantageously corresponds to a varnish composition.
• the composition comprises:
• Such a composition advantageously corresponds to a paint composition.
• composition according to the invention can also comprise at least one adjuvant, in particular at least one adjuvant chosen from dispersing agents, anti-foaming agents, biocidal agents, coloring agents, lubricating agents and optical brightening agents.
• the invention also provides a method for preparing a composition according to the invention.
• the method of preparation according to the invention comprises the combination of at least one polymer A, at least one polymer B and water.
• the polymer B is in the form of an emulsion in water into which the polymer A. is introduced.
• a subject of the invention is also the use of a copolymer A as defined according to the invention in an aqueous coating composition comprising at least one binder polymer B chosen from a vinyl acetate homopolymer, an acetate copolymer vinyl, vinyl versatate homopolymer, vinyl versatate copolymer, and combinations thereof, to improve storage stability.
• binder polymer B chosen from a vinyl acetate homopolymer, an acetate copolymer vinyl, vinyl versatate homopolymer, vinyl versatate copolymer, and combinations thereof, to improve storage stability.
• the invention provides a method of preparing a coating using at least one composition according to the invention.
• the method of preparing a coating of the invention comprises applying to a substrate at least one composition according to the invention.
• a subject of the invention is also the use of a copolymer A as defined according to the invention in an aqueous coating composition comprising at least one binder polymer B chosen from a vinyl acetate homopolymer, an acetate copolymer vinyl, vinyl versatate homopolymer, vinyl versatate copolymer, and combinations thereof, to improve storage stability.
• binder polymer B chosen from a vinyl acetate homopolymer, an acetate copolymer vinyl, vinyl versatate homopolymer, vinyl versatate copolymer, and combinations thereof, to improve storage stability.
• the invention also relates to some of the copolymers A as such.
• the invention provides a particular AP copolymer prepared by the polymerization reaction:
• al-1 chosen from acrylic acid and its salts
• At least one monomer (a2) which is an ester of an acid chosen from acrylic acid, methacrylic acid, itaconic acid and their combinations, preferably an ester of an acid chosen from acrylic acid and methacrylic acid;
• - m and n identical or different, independently represent 0 or an integer or decimal number, advantageously an integer number, less than 150, the sum m + n ranging from 5 to 150, - OE represents a CH2CH2O group,
• - OP independently represents a group chosen from CH (CH 3 ) CH 2 0 and CH 2 CH (CH) 0,
• R 1 represents a group comprising at least one polymerizable olefinic unsaturation
• R 2 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms;
• At least one monomer (a4) chosen from 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl methacrylate, sodium methallyl sulfonate, styrene sulfonate, their salts and their combinations.
• the AP copolymer can also be prepared with from 0.1 to less than 15% by weight of monomer (al-2) relative to the total weight of the monomers.
• the AP copolymer is prepared with from 0.1 to less than 10% by weight of monomer (al-2) relative to the total weight of the monomers.
• the AP copolymer is prepared with from 0.1 to less than 5% by weight of monomer (al-2) relative to the total weight of the monomers.
• the AP copolymer is prepared in the absence of a monomer (al-2) chosen from methacrylic acid and its salts.
• the AP copolymer is prepared by polymerization reaction:
• composition according to the invention define methods and uses according to the invention as well as AP copolymers which are also particular, advantageous or preferred, in particular the API, AP2 and AP3 copolymers according to invention.
• the invention provides an API copolymer prepared by polymerization reaction:
• al-1 chosen from acrylic acid and its salts
• (al-2) chosen from methacrylic acid and its salts, and in a mass ratio [monomer (al-!)] / [monomer (al-1) + monomer (al-2)] strictly greater than 0.65;
• - at least one monomer (a2) which is an ester of an acid chosen from acrylic acid, methacrylic acid, itaconic acid and their combinations, preferably an ester of an acid chosen from acrylic acid and methacrylic acid;
• n identical or different, independently represent 0 or an integer or decimal number, advantageously an integer number, less than 150, the sum m + n ranging from 5 to 150,
• - OE represents a CH2CH2O group
• - OP independently represents a group chosen from CH (CH 3 ) CH 2 0 and CH 2 CH (CH) 0,
• R 1 represents a group comprising at least one polymerizable olefinic unsaturation
• R 2 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 20 carbon atoms or a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 24 to 40 carbon atoms ;
• At least one monomer (a4) chosen from 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl methacrylate, sodium methallyl sulfonate, styrene sulfonate, their salts and their combinations.
• the invention also provides an AP2 copolymer prepared by the polymerization reaction:
• al-1 chosen from acrylic acid and its salts
• At least one monomer (a2) which is an ester of an acid chosen from acrylic acid, methacrylic acid, itaconic acid and their combinations, preferably an ester of an acid chosen from acrylic acid and methacrylic acid;
• : - m and n identical or different, independently represent 0 or an integer or decimal number, advantageously an integer number, less than 150, the sum m + n ranging from 5 to 150,
• - OE represents a CH2CH2O group
• - OP independently represents a group chosen from CH (CH 3 ) CH 2 0 and CH 2 CH (CH) 0,
• R 1 represents a group comprising at least one polymerizable olefinic unsaturation
• R 2 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms;
• At least one monomer (a4) chosen from 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl methacrylate, sodium methallyl sulfonate, styrene sulfonate, their salts and their combinations.
• the invention also provides an AP3 copolymer prepared by the polymerization reaction:
• al-1 chosen from acrylic acid and its salts
• At least one monomer (a2) which is an ester of an acid chosen from methacrylic acid, itaconic acid and their combinations, preferably an ester of an acid chosen from acrylic acid and methacrylic acid;
• n identical or different, independently represent 0 or an integer or decimal number, advantageously an integer number, less than 150, the sum m + n ranging from 5 to 150,
• - OE represents a CH2CH2O group
• - OP independently represents a group chosen from CHiCH dCfEO and CH 2 CH (CH 3 ) 0,
• - R 1 represents a group comprising at least one polymerizable olefinic unsaturation
• - R 2 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms;
• At least one monomer (a4) chosen from 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl methacrylate, sodium methallyl sulfonate, styrene sulfonate, their salts and their combinations.
• the solids content of the polymers synthesized is measured using a microwave balance.
• the following monomers were used:
• Example 1 preparation and characterization of copolymers A according to the invention
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (P) at 29.9% by weight of dry extract is obtained, the composition of which is detailed in Table 1.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (P2) at 30.4% by weight of dry extract is obtained, the composition of which is detailed in Table 1.
• Example 2 preparation and characterization of a comparative copolymer
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• PCI copolymer
• Example 3 Preparation and characterization of paint compositions according to the invention and of comparative paint compositions
• a paint composition comprising:
• binder B Mowilith LDM 1871 (copolymer of vinyl versatate and ethylene at 53% by weight of dry extract and pH of 4.5, Celanese ), with a solids content (130 ° C; 30 min) of 59-61% by weight.
• the final paint has a dry extract of 72% by weight.
• composition of the paint is shown in Table 3.
• a paint composition according to the invention (C1) comprising the polymer (PI) is prepared.
• a paint composition according to the invention (C2) comprising the polymer (P2) and a comparative paint composition (CCI) comprising the polymer (PCI) is prepared.
• Brookield viscosities (mPa.s) are measured at 10 rpm and at 100 rpm at 25 ° C using an analog viscometer:
• the viscosity drift is determined according to the following formula: 100
• paint compositions according to the invention comprising respectively the polymers A (PI) and (P2) are much more stable than the comparative composition (CCI) which comprises a comparative copolymer (PCI) not comprising of unit derived from acrylic acid.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (P3) at 30.4% by weight of dry extract is obtained, the composition of which is detailed in Table 5.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (P4) at 30.1% by weight of dry extract is obtained, the composition of which is detailed in Table 5.
• a third glass beaker 0.136 g of sodium metabisulphite is weighed out, which is dissolved in 5 g of deionized water.
• a fourth container of the disposable syringe type, weighed 5.29 g of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (a4) at 50% by weight in water.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (P5) at 29.5% by weight of dry extract is obtained, the composition of which is detailed in Table 5.
• an initial charge composed of 474.56 g of deionized water and 6.46 g of sodium dodecyl sulfate.
• 123.15 g of monomer (a1-1) are weighed in a first glass beaker according to the proportions shown in Table 1, 129.00 g of monomer (a2-1), 21.98 g of monomer (a3- c), 0.07 g of dodecylmercaptan, 2.26 g of sodium dodecyl sulfate and 125.94 g of deionized water.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (P6) at 28.8% by weight of dry extract is obtained, the composition of which is detailed in Table 5.
• 89.22 g of monomer (al-1) are weighed according to the proportions shown in Table 1, 20.12 g of monomer (al-2), 158.06 g of monomer (a2- l), 21.05 g of monomer (a3-d), 0.07 g of dodecylmercaptan, 2.26 g of sodium dodecyl sulfate and 138.57 g of deionized water.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (P7) at 29.5% by weight of dry extract is obtained, the composition of which is detailed in Table 5.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (P8) at 28.3% by weight of dry extract is obtained, the composition of which is detailed in Table 5.
• an initial charge composed of 474 g of deionized water, and 6.46 g of sodium dodecyl sulfate.
• 129.71 g of monomer (al-1) are weighed out according to the proportions presented in Table 1, 1.35 g of monomer (al-2), 119.9 g of monomer (a2- l), 21.04 g of monomer (a3-d), 0.07 g of dodecylmercaptan, 2.26 g of sodium dodecyl sulfate and 140.68 g of deionized water.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• an initial charge composed of 475 g of deionized water, and 6.46 g of sodium dodecyl sulfate.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• an initial charge composed of 475 g of deionized water, and 6.46 g of sodium dodecyl sulfate.
• 125.45 g of monomer (al-1) are weighed according to the proportions presented in Table 1, 1.05 g of monomer (al-2), 131.6 g of monomer (a2- l), 16.57 g of monomer (a3-d), 0.07 g of dodecylmercaptan, 2.26 g of sodium dodecyl sulfate and 140.23 g of deionized water.
• a fourth container of the disposable syringe type, 5.41 g of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (a4) at 50% by weight in water.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• an initial charge composed of 475 g of deionized water, and 6.46 g of sodium dodecyl sulfate.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C. After 2 hours and 5 minutes, 4.57 g of EDMA are introduced.
• a third glass beaker 0.136 g of sodium metabisulphite is weighed out, which is dissolved in 5 g of deionized water.
• a fourth container of the disposable syringe type, weighed 5.27 g of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (a4) at 50% by weight in water.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a first glass beaker 79.4 g of monomer (al-1) are weighed according to the proportions presented in Table 1, 16.52 g of monomer (al-2), 129 g of monomer (a2-l) , 23.6 g of monomer (a3-g), 2.26 g of sodium dodecyl sulfate and 178.38 g of deionized water.
• a second glass beaker weigh 1.365 g of ammonium persulfate and dissolve in 5 g of deionized water.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• Example 5 preparation and characterization of comparative copolymers
• an initial charge composed of 474.56 g of deionized water and 6.46 g of sodium dodecyl sulfate.
• 109.36 g of monomer (a1-2) are weighed out in a first glass beaker according to the proportions shown in Table 6, 158.06 g of monomer (a2-l), 21.05 g of monomer (a3- d), 0.07 g of dodecylmercaptan, 2.26 g of sodium dodecyl sulfate and 138.57 g of deionized water.
• a fourth container of the disposable syringe type, weighed 5.27 g of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (a4) at 50% by weight in water. The contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• a copolymer (PC2) at 30.0% by weight of dry extract is obtained, the composition of which is detailed in Table 6.
• an initial charge composed of 474.5 g of deionized water and 6.46 g of sodium dodecyl sulfate.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• an initial charge composed of 474.5 g of deionized water and 6.46 g of sodium dodecyl sulfate.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• an initial charge composed of 474.5 g of deionized water and 6.46 g of sodium dodecyl sulfate.
• 73.36 g of monomer (al-1) are weighed according to the proportions presented in Table 6, 51.16 g of monomer (al-2), 129 g of monomer (a2-l) , 21.04 g of monomer (a3-d), 2.26 g of sodium dodecyl sulfate and 140.68 g of deionized water.
• the contents of the reactor are heated to a temperature of 76 ° C ⁇ 2 ° C.
• the reagents from the 4 vessels are introduced into the polymerization reactor at a temperature of 76 ° C ⁇ 2 ° C.
• Example 6 Preparation and characterization of paint compositions according to the invention and of comparative paint compositions
• paint compositions according to the invention comprising the polymers (P8 to P12) respectively, as well as comparative paint compositions (CC2 to CC5) respectively comprising the comparative polymers, are prepared. (PC2 to PC5).
• Brookfield viscosities (mPa.s) are measured at 10 rev / min and at 100 rev / min according to the conditions of Example 3.
• paint compositions according to the invention comprising respectively the polymers A (P8 to P12) are much more stable than the comparative composition (CC2) which comprises a comparative copolymer not comprising a unit derived from acrylic acid.
• the paint compositions according to the invention are much more stable than the comparative paint compositions (CC3 to CC5) comprising respectively a comparative copolymer (PC3 to PC5) in which the mass ratio [monomer (al - l)] / [monomer (al-1) + monomer (al-2)] is less than 0.65.

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