Classifications

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  • 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
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  • 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
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of 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; Compositions of derivatives of such polymers
  • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of 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; Compositions of derivatives of such polymers
  • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8188—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bonds, and at least one being terminated by a bond to sulfur or by a hertocyclic ring containing sulfur; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
  • A61Q3/02—Nail coatings
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/16—Sulfur-containing compounds
  • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
  • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
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  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/16—Sulfur-containing compounds
  • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
  • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
  • C04B26/02—Macromolecular compounds
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  • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
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  • 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
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
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  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
  • C04B2103/0062—Cross-linked polymers
• • C—CHEMISTRY; METALLURGY
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  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
  • C04B2103/0065—Polymers characterised by their glass transition temperature (Tg)
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00482—Coating or impregnation materials
• • 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
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
  • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
• • 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
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
  • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Definitions

• the invention provides an acrylic copolymer P, sulfonated, crosslinked and prepared from at least four monomers and in the absence of methacrylic acid.
• the invention also comprises the preparation of an aqueous, viscoelastic and suspensive composition comprising this copolymer P.
• agents associating several properties.
• certain technical fields require controlling the rheology as well as the texture of a composition.
• the agents used for this purpose must also make it possible to stabilize these compositions.
• the agents used In the field of coating compositions, in particular for stain compositions, the agents used must make it possible to control the rheology but also to confer a suspensive effect on these compositions which comprise particles.
• Stain compositions usually combine a solvent, especially water, with a binder, for example an acrylic binder, an alkyd binder or an alkyd-urethane binder, and pigment particles. These compositions make it possible to protect the substrate on which they are applied, in particular a wooden or concrete substrate. The compatibility of the different constituents of a composition is therefore also essential.
• the rheology and texture control agents of a composition must have a glass transition temperature which allows them to be combined effectively with other substances present in these compositions, in particular with a binder, generally in the form of particles.
• the suspensive effect sought for a composition is the ability to maintain particles in suspension in a continuous phase, in a stable manner over time, for example during storage of the composition.
• Particles are generally solid, solid or hollow bodies. They can also be liquid entities immiscible with the continuous phase or be encapsulated or in gaseous form. Their shape, texture and structure can vary widely, in particular depending on the final properties expected.
• the suspensive performance can be evaluated by determining the value of the modulus of elasticity G', the value of the damping factor (Tan ô) and the value of the elastic resistance.
• compositions both for low or medium shear gradients and for high shear gradients.
• a composition can be subjected to numerous stresses requiring particularly complex rheological properties, in particular viscoelastic properties.
• the behavior of a linear viscoelastic material is intermediate between that of an ideal elastic solid symbolized by a spring of modulus E (or G) and that of a Newtonian viscous liquid symbolized by a viscosity damping factor.
• the elasticity of a material reflects its ability to retain and release energy after deformation.
• the viscosity of a material reflects its ability to dissipate energy.
• the viscoelasticity of a composition must therefore also be improved so that this composition exhibits both viscous and elastic characteristics when it undergoes deformation.
• the viscous component allows this composition to resist shear flow and exhibit a deformation that increases linearly with time when stress is applied.
• the elastic component allows a deformation when a stress is applied, then the return to the original state once the stress is interrupted.
• methacrylic acid in particular methacrylic acid prepared from acetone cyanohydrin which is a highly toxic compound, should be limited as much as possible.
• Documents US2017003717 and US20190315897 describe copolymers prepared with methacrylic acid.
• Document US20080193405 describes the preparation of hydraulic or alcoholic compositions comprising a combination of copolymers combined with a mixture of acrylic acid and a crosslinking compound.
• Document WO2014185381 relates to a binder composition for a lithium battery and which comprises a fluorinated copolymer.
• the invention provides a copolymer P prepared in the absence of methacrylic acid, by at least one polymerization reaction: has. at least one anionic monomer (a) chosen from acrylic acid, a salt of acrylic acid, oligomers of acrylic acid, salts of oligomers of acrylic acid and combinations thereof; b. at least one nonionic monomer (b) chosen from styrene, C 1 -C 8 esters of an acid chosen from acrylic acid, methacrylic acid and combinations thereof; vs.
• the copolymer P can be prepared from only compounds a, b, c and d.
• the monomer (a) is acrylic acid or a mixture of oligomers of acrylic acid of formula (I): in which m is an integer or decimal number ranging from 1 to 10, preferably ranging from 2 to 4. More preferably according to the invention, the monomer (a) is acrylic acid.
• the monomer (b) is chosen from:
• Ci-Cs-alkyl acrylate in particular Ci-Cs-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n- butyl, alkyl methacrylate, in particular Ci-Cs-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n- butyl, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxy ethyl acryl ate,
• aryl methacrylate preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate and
• the monomer (b) is chosen from ethyl acrylate and butyl acrylate, more preferably ethyl acrylate.
• the monomer (b) according to the invention is a non-fluorinated monomer or else the monomer (b) is different from 2,2,2-trifluoroethyl methacrylate.
• the preferred monomer (c) is chosen from 2-acrylamido-2-methylpropane sulphonic acid (AMPS) and its sodium or ammonium salts.
• the preferred compound (d) is chosen from polyunsaturated aromatic monomers such as divinylbenzene, divinyl naphthalene and trivinylbenzene, polyunsaturated alicyclic monomers, for example 1, 2, 4-trivinyl cyclohexane, difunctional phthalic acid esters such as diallyl phthalate , polyalkenyl ethers such as triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose and trimethylolpropane diallyl ether, polyunsaturated esters of polyalcohols or polyacids such as 1,6-hexanediol di(meth)acrylate, tetramethylene tri(meth)acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, trimethylolpropane tri(meth)acryl
• the dissymmetrical crosslinking compound (d) preferred according to the invention is chosen from:
• - L 1 represents CHz, monoalkoxylated CHz or polyalkoxylated CHz
• -C(CH 3 ) CH 2
• -C(H) C(H)C(O)OH
• - Q 1 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
• - Q 2 represents CH 2 , CH 2 -CH 2 , monoalkoxylated CH 2 , monoalkoxylated CH 2 -CH 2 , polyalkoxylated CH 2 or polyalkoxylated CH 2 -CH 2 ; preferably a compound of formula (II) in which:
• L 1 represents monoalkoxylated CH 2 or polyalkoxylated CH 2 ,
• - Q 1 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
• - Q 2 represents CH 2 , CH 2 -CH 2 , monoalkoxylated CH 2 , monoalkoxylated CH 2 -CH 2 , polyalkoxylated CH 2 or polyalkoxylated CH 2 -CH 2 ;
• L 2 represents CH 2 , monoalkoxylated CH 2 or polyalkoxylated CH 2 ,
• - Q 3 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
• - Q 4 represents CH2, CH2-CH2, monoalkoxylated CH2, monoalkoxylated CH2-CH2, polyalkoxylated CH2 or polyalkoxylated CH2-CH2; preferably a compound of formula (III) in which:
• - L 2 represents monoalkoxylated CH2 or polyalkoxylated CH2,
• Q 3 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
• - Q 4 represents CH2, CH2-CH2, monoalkoxylated CH2, monoalkoxylated CH2-CH2, polyalkoxylated CH2 or polyalkoxylated CH2-CH2;
• R 3 independently represents H or CH 3 ,
• - L 3 independently represents a linear or branched Ci-C2o-alkylene group
• - n independently represents 0 or an integer ranging from 1 to 30, for example from 1 to 20, in particular from 1 to 15, in particular from 1 to 10;
• di(meth)acrylates such as polyalkylene glycol di(meth)acrylate, in particular polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, di(meth)acrylate polyethylene glycol, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, ,6-hexanediol, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, but also 2,2'-bis(4-(acryloxypropyloxy)-phenyl)propane, 2 ,2'-bis(4-(acryloxydiethoxy)-phenyl)propane; tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate
• TMPTA trimethylolpropane tri(meth)acrylate
• TMPTA 3OE ethoxylated trimethylolpropane tri(meth)acrylate
• EGDCPEA ethylene glycol dicyclopentenyl ether acrylate
• TMPTA EGDCPEA and TMPTA 3OE
• - R 4 independently represents H or CEE
• the amounts of the compounds used can vary.
• the copolymer P comprises:
• the copolymer P comprises:
• the copolymer P comprises:
• the copolymer P comprises:
• the copolymer P comprises from 39.89 to 59% by weight of monomer (b) relative to the quantity by weight of monomers (a), (c) and (d).
• the copolymer P is different from a copolymer prepared without methacrylic acid but from 30.0% by weight of acrylic acid, from 58.2% by weight of ethyl acrylate, from 7, 5% by weight of 2,2,2-trifluoroethyl methacrylate, 2.5% by weight of acrylamido-2-methylpropane sulfonic acid and 0.8% by weight of ethyl enedimethacryl ate.
• the copolymer P according to the invention has many particularly advantageous properties.
• the copolymer P has a particular glass transition temperature (Tg).
• the copolymer P according to the invention has a glass transition temperature (Tg), calculated using the Flory-Fox equation, of less than 60° C., preferably less than 30° C.
• the Flory-Fox equation makes it possible to calculate the glass transition temperature of the copolymer from the parameters of the monomers used for its preparation, with the exception of any monomers (e) used.
• the copolymer P according to the invention is totally or partially neutralized, preferably by means of a compound chosen from NaOH, KOH, LiOH, ammonium derivatives, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof.
• a compound chosen from NaOH, KOH, LiOH, ammonium derivatives, ammonia, amino bases for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof.
• the copolymer P according to the invention can be prepared by a polymerization reaction which also uses at least one hydrophobic monomer (e), in particular an associative hydrophobic monomer (e).
• the monomer (e) comprises a polymerizable olefinic unsaturation, polyalkylene glycol groups and a hydrophobic terminal group.
• the hydrophobic terminal group is a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group, comprising from 6 to 40 carbon atoms.
• the monomer (e) is a compound of formula (VI):
• - q and r identical or different, independently represent 0 or an integer or decimal number, less than 150, the sum q+r ranging from 5 to 150, preferably the sum q+r varies from 10 to 150, advantageously from 10 to 100, more preferably to - OE represents a CH2CH2O group,
• - OP independently represents a group chosen from CH(CH 3 )CH 2 O and CH 2 CH(CH 3 )O,
• R 6 represents a group comprising at least one polymerizable olefinic unsaturation, preferably 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 7 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms, preferably a hydrocarbon group comprising from 6 to 32 carbon atoms, more preferably from 8 to 30 carbon atoms. carbon.
• R 7 represents a linear alkyl or alkenyl group comprising from 6 to 40 carbon atoms, in particular a cyclohexyl group. According to the invention, R 7 can also represent an alkyl group derived from an alcohol obtained by an oxo reaction.
• R 7 can represent an aromatic group comprising from 6 to 40 carbon atoms, preferentially from 6 to 32 carbon atoms, more preferentially from 6 to 30 carbon atoms.
• R 7 can represent a group of formula (VIII): in which R 10 represents a hydrocarbon group of formula C15H31-S in which s represents 0, 2, 4 or 6; R 10 can thus comprise 0, 1, 2 or 3 ethylenic unsaturations (double bond).
• R 10 represents a hydrocarbon group of formula C15H31-S in which s represents 0, 2, 4 or 6; R 10 can thus comprise 0, 1, 2 or 3 ethylenic unsaturations (double bond).
• Such a group of formula (VIII) is advantageously derived from cardanol, and thus of bio-resourced origin.
• R 7 can represent a group comprising from 2 to 5 phenyl groups, such as a tristyrylphenyl (TSP) group of formula (IX): or a distyryl phenyl (DSP) group of formula (X) or of formula (XI): or a pentastyrylcumylphenyl group.
• TSP tristyrylphenyl
• DSP distyryl phenyl
• R 7 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon-based group comprising from 6 to 40 carbon atoms, preferably a linear or branched Cô-C4o-alkyl group, preferably a Cs- Cso-alkyl, linear or branched, a Ce-C-aryl group, preferably a Cs-Cso-aryl group, preferably comprising from 2 to 5 phenyl groups, for example a tristyrylphenyl group.
• q represents an integer or decimal number, advantageously an integer, greater than or equal to 10.
• each of r and q is different from 0.
• q and r which are identical or different, independently represent an integer or decimal number, advantageously a number ranging from 5 to 100, the sum q+r varying from 10 to 150, advantageously from 10 to 100, more advantageously from 10 to 60.
• the value of q is strictly greater than the value of r.
• r represents 0.
• the copolymer P can comprise from 0.4 to 30% by weight of monomer (e) relative to the total quantity of monomers.
• the copolymer P according to the invention can be prepared according to methods known as such. Specifically, the copolymer P according to the invention is prepared by a polymerization reaction implementing the various compounds a, b, c and d, optionally the compound e, by a radical polymerization reaction, for example a polymerization reaction in emulsion, in dispersion or in solution.
• the copolymer P is prepared in water, preferably in the presence of at least one surfactant compound, for example sodium dodecyl sulphate or sodium dodecyl laurate.
• the preparation of the copolymer P according to the invention can also implement one or more compounds, in particular at least one initiator compound, alone or in combination with at least one chain transfer agent.
• initiator compounds use may be made of a compound chosen from azo initiator compounds (for example azo-bis-isobutyronitrile), a peroxide compound, preferably hydrogen peroxide, benzoyl peroxide, benzoyl hydroperoxide and mixtures thereof.
• azo initiator compounds for example azo-bis-isobutyronitrile
• peroxide compound preferably hydrogen peroxide
• benzoyl peroxide benzoyl hydroperoxide and mixtures thereof.
• alkali metal persulfates in particular sodium persulfate and potassium persulfate, ammonium persulfate, partially water-soluble peroxides, in particular succinic peracid, t-butyl hydroperoxide, hydroperoxide cumyl, persulfates associated with a cuprous ion, a ferrous ion, a sulfite ion or a bisulfite ion and mixtures thereof.
• chain transfer agents use may be made of mercaptan compounds, in particular mercaptan compounds comprising at least 4 carbon atoms such as butyl mercaptan, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, isooctyl 3-mercaptopropionate.
• the radical initiator or generator compound can therefore be associated with at least one controlled radical polymerization transfer agent, in particular a transfer agent of the RAFT type (reversible addition-fragmentation chain transfer or radical polymerization controlled by transfer of reversible chain by addition-fragmentation).
• the reaction is a free radical emulsion polymerization reaction.
• the preparation in water of the copolymer P makes it possible to obtain an aqueous polymeric composition in the form of an emulsion.
• the copolymer P according to the invention can be used to improve the viscoelastic properties and the suspensive properties of a composition, in particular of an aqueous composition, preferably of an aqueous composition comprising particles.
• the invention provides an aqueous composition C comprising at least one copolymer P according to the invention.
• the aqueous composition C according to the invention comprises at least one copolymer P according to the invention and solid, liquid or gaseous particles, and optionally a binder compound.
• composition C according to the invention comprises from 0.1 to 5% by weight of copolymer P. More preferably, composition C according to the invention comprises from 0.5 to 3% by weight of copolymer P .
• the particles are particles of a product chosen from a cosmetic product, a phytosanitary product, a fertilizer, a coating product.
• aqueous composition C is a varnish composition comprising a copolymer P, particles of a pigment and a binder compound in latex form, optionally a pigment-dispersing compound.
• the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/-10° C. as the glass transition temperature of the copolymer P.
• the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/- 5° C. as the glass transition temperature of the copolymer P.
• the preferred binder compound is an acrylic compound, an alkyd compound or an alkyd-urethane compound or a styrene-acrylic compound or a styrene-butadiene compound.
• the properties of the copolymer P according to the invention allow it to be used under conditions which can vary significantly.
• the properties of the copolymer P can be implemented at variable pH values.
• the aqueous composition C according to the invention has a pH ranging from 3 to 13, preferably a pH ranging from 5 to 13.
• the pH of the aqueous composition C ranges from 4 to 8 or from 5 to 7.
• the invention also relates to a method for preparing an aqueous composition C, viscoelastic and suspending, comprising the introduction of at least one copolymer P according to the invention and the stirring of the composition C.
• the copolymer P makes it possible to improve the properties of composition C according to the invention.
• the copolymer P makes it possible to improve the stability of this composition, in particular for a varnish composition C.
• the invention also relates to a method for stabilizing a varnish composition C comprising the introduction into an aqueous varnish base composition C of at least one copolymer P according to the invention.
• the varnish base composition C comprises a binder compound in the form of a latex, the glass transition temperature of which is the same +/-10° C.
• the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/-5°C as the glass transition temperature of the copolymer P.
• the copolymer P according to the invention has particularly advantageous properties for controlling various components of the rheology of an aqueous composition.
• the copolymer P according to the invention makes it possible to control the flow threshold of an aqueous composition.
• the yield stress corresponds to the value of the shear stress applied to an aqueous composition which causes this composition to flow. In the absence of sufficient constraint, the viscosity of this aqueous composition prevents its spontaneous flow on an acceptable time scale.
• the invention also provides a method for controlling the yield point of an aqueous composition comprising the introduction into the aqueous composition of at least one copolymer P according to the invention.
• the yield point of this aqueous composition measured according to the method described in the examples, is greater than 0.1 Pa, more preferably greater than 0.5 Pa or else greater than 2 Pa, preferably greater than 4 Pa.
• composition C according to the invention comprises from 0.1 to 5% by weight of copolymer P and has a yield point greater than 0.1 Pa, more preferably greater than 0.5 Pa, or else greater than 2 Pa, preferably greater than 4 Pa. Also more preferably, composition C according to the invention comprises from 0.5 to 3% by weight of copolymer P and has a yield point greater than 0.1 Pa, more preferably greater than 0.5 Pa, or else greater than 2 Pa, preferably greater than 4 Pa.
• the particular, advantageous or preferred characteristics of the copolymer P according to the invention define compositions according to the invention and methods according to the invention which are particular, advantageous or preferred compositions and methods according to the invention.
• Example 1 preparation and characterization of copolymers according to the invention
• - hydrophobic monomer e compound (el) of formula VI in which R 6 represents a methacrylate group, q represents 25, OE represents a CH2CH2O group, r represents 0 and R 7 represents a group of formula VII in which R 8 represents a group Linear C6-alkyl and R 9 represents a linear Cio-alkyl group.
• a third glass beaker weigh 0.100 g of sodium metabisulphite and dissolve it in 10 g of deionized water.
• a fourth container of the disposable syringe type, 5.27 g of compound (cl) at 50% by weight in water are weighed.
• the contents of the reactor are heated to a temperature of 76°C ⁇ 2°C.
• the reagents from the 4 containers are introduced into the polymerization reactor at a temperature of 76°C ⁇ 2°C.
• the pumps are flushed with deionized water.
• 0.3 g of ammonium persulfate dissolved in 20 g of deionized water are introduced into the reactor over 1 hour.
• a copolymer (PI) with 30.6% by weight of solids content (SD, measured with a microwave balance) is obtained. Its glass transition temperature (Tg) is calculated using the Flory-Fox equation. The composition and characteristics of the copolymer (PI) are shown in Table 1.
• Example 2 Preparation and characterization of the properties of aqueous compositions C1 to C3 according to the invention
• the PI copolymer prepared according to example 1 is mixed with deionized water in an amount by dry weight of 1% then an aqueous solution of sodium hydroxide (50% by weight) is added in order to completely neutralize the composition.
• the aqueous composition C1 according to the invention is obtained.
• the aqueous compositions C2 and C3 according to the invention are prepared analogously from the copolymers P2 and P3 according to the invention.
• the Brookfield viscosity is then measured at 25° C. and at 100 revolutions/min of these compositions by means of a Brookfield DV1 viscometer equipped with a rotor adapted to the viscosity range of the composition.
• the flow threshold of these compositions is also measured, which is the applied stress which causes the flow of the aqueous composition.
• a stress ramp varying from 0.01 to 1000 Pa is implemented over a period of 3000 seconds with an equilibration time of 30 seconds between each measurement.
• Yield stress was measured at 25°C using a Haake Mars III imposed stress rheometer (ThermoFisher Scientific) equipped with a CP60-1/S cone-plane type geometry (diameter of 60 mm, truncation angle of 1°) then using processing by the RheoWin Data Manager software. The results obtained are shown in Table 2.
• the viscoelasticity of the aqueous compositions Cl, Cl and C3 according to the invention is also determined as a function of the frequency at low deformations.
• the frequency co follows a logarithmic variation from high frequencies to low frequencies (from 100 to 0.01 Hz).
• the copolymers according to the invention therefore make it possible to thicken aqueous compositions significantly.
• the aqueous compositions obtained have a high flow threshold.
• the tangent value ⁇ of these aqueous compositions according to the invention is systematically between 0 and 1, thus demonstrating their viscoelastic character. These properties are obtained in the absence of methacrylic acid during the preparation of the copolymers according to the invention.

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