EP3717529A1 - Water-soluble copolymer composition with neutral ph - Google Patents

Water-soluble copolymer composition with neutral ph

Info

Publication number
EP3717529A1
EP3717529A1 EP18821721.0A EP18821721A EP3717529A1 EP 3717529 A1 EP3717529 A1 EP 3717529A1 EP 18821721 A EP18821721 A EP 18821721A EP 3717529 A1 EP3717529 A1 EP 3717529A1
Authority
EP
European Patent Office
Prior art keywords
nitroxide
composition according
tert
butyl
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18821721.0A
Other languages
German (de)
French (fr)
Inventor
Anne-Laure BROCAS
Sylvie Cazaumayou
Sylvain Bourrigaud
Guillaume DECREVOISIER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP3717529A1 publication Critical patent/EP3717529A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • 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
    • 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
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C08F220/606—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing other heteroatoms
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/30—Sulfur
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the present invention relates to the field of water-soluble or water-dispersible copolymers with a neutral or near-neutral pH, that is to say between 5.5 and 9.5, comprising at least one random copolymer comprising methacrylic acid, from butyl acrylate, styrene and a monomer selected from styrene sulfonic acid or its salts, vinyl benzoic acid or its salts, 2-acrylamido-2-methanesulfonic acid or its salts, N-vinylpyrrolidone alone or in combination.
  • copolymers have a solubilization or a faster dispersibility in water at neutral pH or close to neutral than copolymers known from the prior art.
  • This invention is appreciated in various uses of these copolymers as pigment dispersing agents, as rheology modifiers in applications as diverse as drilling muds, textile printing pastes, cosmetics, or detergents, coatings such as anti-sedimentation and / or suspending agents for coarse mineral or organic fillers for example in phytosanitary applications, but especially in the three-dimensional printing (or 3D printing) of an object and more particularly as sacrificial materials modeling by deposition of molten filaments.
  • this technology makes it possible to manufacture English: "additive manufacturing” or AM) a real object from a virtual object. It is based on the cutting of the 3D virtual object in 2D strips of very thin thickness. These thin strips are deposited one by one by fixing them on the previous ones, which reconstitutes the real object.
  • materials constituting the object are plastic materials (especially acrylonitrile butadiene styrene (or ABS) and polylactic acid (or PLA)), wax, metal or ceramics.
  • additive techniques are the deposition of fused deposition (FDM) and laser sintering (laser sintering).
  • Molten filament deposition modeling is a mechanical technique that consists in melting a filament of synthetic material (generally ABS or PLA type plastic) through an extrusion nozzle heated to a temperature of between 160 and 270 ° C. From this nozzle comes a molten filament with a diameter of about one-tenth of a millimeter. This wire is deposited online and is sticking by re-fusion on what has been filed beforehand.
  • This technique makes it possible to create parts made of good material, having mechanical, thermal and stability characteristics identical to injected thermoplastic parts.
  • This technique also has an important advantage concerning the support structure necessary for the production of the parts, since this construction support is in most cases constituted in a different material than that constituting the created object, material which is eliminated from said object. when the construction process of the latter is finished.
  • the construction support is generally a water-soluble polymeric composition or water-dispersible responding to a specific specification.
  • desired properties in addition to the mechanical strength, the glass transition temperature of the polymer, its thermal stability or its ease of implementation, the kinetics of solubilization or dispersibility in water is of primary importance.
  • EP 2447292, EP2699611 and EP 2041192 describe copolymers or soluble compositions water-dispersible in water and used in the field of 3D printing.
  • compositions consist of random copolymers comprising monomers such as maleic anhydride (EP 2699611), methacrylic acid (EP 2041192), and more generally unsaturated ⁇ -b monocarboxylic acids (EP 2447292) polymerized in a radical manner.
  • WO2015175682 A copolymer comprising neutralized carboxylic groups soluble in an aqueous alkaline solution.
  • compositions have a kinetics of solubilization or dispersibility in water still too slow, moreover at neutral pH.
  • Increasing the proportion of hydrophilic monomers could be a solution, but in this case other important characteristics such as Tg, thermal stability, melt flow or mechanical properties are degraded.
  • composition comprising a random copolymer comprising methacrylic acid, butyl acrylate, styrene and an additional hydrophilic monomer judiciously chosen has a much faster dissolution or dispersibility at neutral pH or near neutral, that is to say between 5.5 and 9.5, than the known compositions of the prior art.
  • the invention therefore relates to a composition
  • a composition comprising a random copolymer comprising the following monomers: styrene, from 1 to 45% by weight, inclusive.
  • methacrylic acid from 35 to 45% by weight, limits included.
  • butyl acrylate 15 to 35% by weight, inclusive of: a monomer selected from styrene sulphonic acid or its salts, vinyl benzoic acid or its salts, 2-acrylamido-2-methanesulphonic acid or its salts, N-vinyl pyrolidone, alone or in combination in proportions from 1 to 45% inclusive.
  • solubilization or dispersibility in water is meant solubilization or dispersibility in an aqueous phase having a pH of 5.5 to 9.5 in a temperature range of 40 to 70 ° C.
  • a polymer is said to be “dispersible” if it forms, at a concentration of 5% by weight in a solvent, at 25 ° C., a stable suspension of fine, generally spherical particles.
  • the average particle size constituting said dispersion is less than 1 ⁇ m and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm by weight. These particle sizes are measured by light scattering.
  • the solvent is water, it is called “water-dispersible" polymer.
  • copolymers of the invention can be prepared by radical polymerization or by controlled radical polymerization.
  • the Applicant states that it is preferable to use controlled radical polymerization and that the copolymer thus prepared is more rapidly solubilized or dispersed in aqueous solution.
  • the copolymers are prepared by controlled nitroxide polymerization (NMP).
  • nitroxides derived from alkoxyamines derived from the stable free radical (1) are preferred.
  • the radical R 1 has a molar mass greater than 15.0342 g / mol.
  • the radical R 1 may be a halogen atom such as chlorine, bromine or iodine, a linear hydrocarbon group, branched or cyclic, saturated or unsaturated such as an alkyl or phenyl radical, or a group -COOR ester or an alkoxyl group -OR, or a phosphonate group -PO (OR) 2, provided that it has a molar mass greater than 15.0342.
  • the radical R 1, monovalent is said in position b with respect to the nitrogen atom of the nitroxide radical.
  • the remaining valences of the carbon atom and the nitrogen atom in the formula (1) can be linked to various radicals such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aryl radical. -alkyl, comprising from 1 to 10 carbon atoms. It is not excluded that the carbon atom and the nitrogen atom in the formula (1) are connected to each other via a divalent radical, so as to form a ring. Preferably, however, the remaining valencies of the carbon atom and the nitrogen atom of the formula (1) are attached to monovalent radicals.
  • the radical R 1 has a molar mass greater than 30 g / mol.
  • the radical R 1 may, for example, have a molar mass of between 40 and 450 g / mol.
  • the radical R 1 may be a radical comprising a phosphoryl group, said radical R 1 may be represented by the formula: "
  • R and R which may be the same or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl, aralkyl, and may include from 1 to 20 carbon atoms.
  • R 1 and / or R 1 may also be a halogen atom such as a chlorine or bromine or fluorine or iodine atom.
  • the radical R 1 may also comprise at least one aromatic ring as for the phenyl radical or the naphthyl radical, the latter may be substituted, for example by an alkyl radical comprising from 1 to 4 carbon atoms.
  • alkoxyamines derived from the following stable radicals are preferred:
  • the alkoxyamines used in controlled radical polymerization must allow good control of the sequence of monomers. Thus they do not all allow good control of certain monomers.
  • the alkoxyamines derived from TEMPO make it possible to control only a limited number of monomers, the same goes for the alkoxyamines derived from 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide. (TIPNO).
  • TIPNO 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide.
  • other alkoxyamines derived from nitroxides corresponding to formula (1) particularly those derived from nitroxides corresponding to formula (2) and even more particularly those derived from N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl. nitroxide allow to expand to a large number of monomer controlled radical polymerization of these monomers.
  • alkoxyamines also influences the economic factor. The use of low temperatures will be preferred to minimize industrial difficulties.
  • the mass proportion of the monomers is chosen from the following ranges: styrene, from 1 to 45% by weight, inclusive, and preferably from 5 to 30% inclusive.
  • methacrylic acid from 35 to 45% by weight, inclusive and preferably from 35 to 40% inclusive.
  • butyl acrylate 15 to 35% by weight, inclusive and preferably 20 to 30% inclusive.
  • the preferred monomer is styrene sulphonic acid or its salts.
  • the weight-average molecular weight of the water-soluble or water-dispersible copolymers according to the invention, measured by SEC, is between 30000 g / mol and 300000 g per mole, preferably between 70000 and 17000 g / mol, and more preferably between 80000 and 130000 g / mole.
  • the dispersibility of the water-soluble or water-dispersible copolymers is less than 2.2 and preferably less than 2.
  • the glass transition temperature (Tg) measured by DMA (dynamic mechanical analysis) of the random copolymer present in the composition which is the subject of the invention is greater than 60 ° C. and preferably greater than 110 ° C.
  • the water-soluble or water-dispersible compositions that are the subject of the invention may contain impact modifiers, which they are of the random block copolymer type, or core - bark particles, alone or in combination.
  • compositions of the invention can be used as pigment dispersing agents, or as rheology modifiers in applications such as drilling muds, textile printing pastes, cosmetics, or detergents, and other compositions of the invention. coating as paint and as an anti-sedimentation and / or suspending agent for coarse mineral or organic fillers in the phytosanitary field, but also the field of three-dimensional printing (or 3D printing) of an object of the type FDM (fused deposition molding) as a sacrificial polymer.
  • the compositions of the invention can be shaped in the form of extruded filament, with or without impact modifiers, these extruded filaments also being the subject of the invention.
  • the invention also relates to the objects obtained using the compositions of the invention.
  • the reagent mixture is as follows:
  • BlocBuilder® (from Arkema).
  • Styrene (St) (provenance Aldrich)
  • AMA Methacrylic acid
  • Styrene (St) (provenance Aldrich)
  • AMA Methacrylic acid
  • composition of the three copolymers is analyzed by 1 H NMR and gives the following results in mass%, Table 2:
  • the copolymers obtained are heated at a temperature of 160 ° C. under a compression press to form a pellet of 2.5 cm in diameter and 1 mm in thickness.
  • the pellets are then placed in a beaker, with stirring, in water at pH 7 at a temperature of 60 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to the field of water-soluble or water-dispersible copolymers with neutral or near neutral pH, in other words between 5.5 and 9.5, comprising at least one statistical copolymer comprising methacrylic acid, butyl acrylate, styrene and a monomer chosen from styrene sulfonic acid or the salts thereof, vinylbenzoic acid or the salts thereof, 2-acrylamido-2-methane sulfonic acid or the salts thereof, N-vinylpyrrolidone, alone or in combination.

Description

COMPOSITION COPOLYMERIQUE HYDROSOLUBLE A PH NEUTRE  WATER SOLUBLE COPOLYMERIC COMPOSITION WITH PH NEUTRAL
DOMAINE DE L'INVENTION FIELD OF THE INVENTION
La présente invention se rapporte au domaine des copolymères hydrosolubles ou hydrodispersibles à pH neutre ou proche du neutre, c'est-à-dire entre 5,5 et 9,5 comprenant au moins un copolymère statistique comprenant de l'acide méthacrylique, de l'acrylate de butyle, du styrène et un monomère choisi parmi l'acide styrène sulfonique ou ses sels, l'acide vinyle benzoique ou ses sels, l'acide 2-acrylamido-2- methane sulfonique ou ses sels, la N-vinyle pyrolidone, seuls ou en combinaison .  The present invention relates to the field of water-soluble or water-dispersible copolymers with a neutral or near-neutral pH, that is to say between 5.5 and 9.5, comprising at least one random copolymer comprising methacrylic acid, from butyl acrylate, styrene and a monomer selected from styrene sulfonic acid or its salts, vinyl benzoic acid or its salts, 2-acrylamido-2-methanesulfonic acid or its salts, N-vinylpyrrolidone alone or in combination.
De tels copolymères présentent une solubilisation ou une dispersibilité plus rapide dans l'eau à pH neutre ou proche du neutre que des copolymères connus de l'art antérieur. Such copolymers have a solubilization or a faster dispersibility in water at neutral pH or close to neutral than copolymers known from the prior art.
Cette invention est appréciée dans diverses utilisations de ces copolymères comme agents dispersants pour pigments, comme modificateurs de rhéologie dans des applications aussi diverses que les boues de forage, les pâtes d'impression textile, la cosmétique, ou encore la détergence, les revêtements comme la peinture, les agents anti-sédimentation et/ou de mise en suspension pour des charges minérales ou organiques grossières par exemple dans des applications phytosanitaire, mais surtout dans l'impression tridimensionnelle (ou impression 3D) d'un objet et plus particulièrement comme matériaux sacrificiel du modelage par dépôt de filaments en fusion.  This invention is appreciated in various uses of these copolymers as pigment dispersing agents, as rheology modifiers in applications as diverse as drilling muds, textile printing pastes, cosmetics, or detergents, coatings such as anti-sedimentation and / or suspending agents for coarse mineral or organic fillers for example in phytosanitary applications, but especially in the three-dimensional printing (or 3D printing) of an object and more particularly as sacrificial materials modeling by deposition of molten filaments.
Concernant plus particulièrement le domaine de l'impression tridimensionnelle (ou impression 3D) , cette technologie permet de fabriquer de manière additive (en anglais : « additive manufacturing » ou AM) un objet réel à partir d'un objet virtuel. Elle est basée sur la découpe de l'objet virtuel 3D en lamelles 2D de très fine épaisseur. Ces fines lamelles sont déposées une à une en les fixant sur les précédentes, ce qui reconstitue l'objet réel. Parmi les matériaux constitutifs de l'objet, on trouve les matériaux plastiques (notamment 1 ' acrylonitrile butadiène styrène (ou ABS) et acide polylactique (ou PLA) ) , la cire, le métal ou les céramiques. Des exemples de techniques additives sont le dépôt de filaments en fusion (« fused déposition modeling » ou FDM) et le frittage par laser (en anglais « laser sintering ») . In particular, in the field of three-dimensional printing (or 3D printing), this technology makes it possible to manufacture English: "additive manufacturing" or AM) a real object from a virtual object. It is based on the cutting of the 3D virtual object in 2D strips of very thin thickness. These thin strips are deposited one by one by fixing them on the previous ones, which reconstitutes the real object. Among the materials constituting the object are plastic materials (especially acrylonitrile butadiene styrene (or ABS) and polylactic acid (or PLA)), wax, metal or ceramics. Examples of additive techniques are the deposition of fused deposition (FDM) and laser sintering (laser sintering).
Le modelage par dépôt de filaments en fusion est une technique mécanique qui consiste à faire fondre un filament de matière synthétique (généralement du plastique type ABS ou PLA) à travers une buse d'extrusion chauffée à une température variant entre 160 et 270 °C. De cette buse en sort un filament en fusion, d'un diamètre de l'ordre du dixième de millimètre. Ce fil est déposé en ligne et vient se coller par re-fusion sur ce qui a été déposé au préalable. Cette technique permet de créer des pièces en bonne matière, disposant de caractéristiques mécaniques, thermiques et d'une stabilité identiques aux pièces thermoplastiques injectées. Cette technique a également un avantage important concernant la structure de support nécessaire à la production des pièces, puisque ce support de construction est dans la plupart des cas constitué dans une autre matière que celle constitutive de l'objet créé, matière qui est éliminée dudit objet, lorsque le processus de construction de ce dernier est fini. Molten filament deposition modeling is a mechanical technique that consists in melting a filament of synthetic material (generally ABS or PLA type plastic) through an extrusion nozzle heated to a temperature of between 160 and 270 ° C. From this nozzle comes a molten filament with a diameter of about one-tenth of a millimeter. This wire is deposited online and is sticking by re-fusion on what has been filed beforehand. This technique makes it possible to create parts made of good material, having mechanical, thermal and stability characteristics identical to injected thermoplastic parts. This technique also has an important advantage concerning the support structure necessary for the production of the parts, since this construction support is in most cases constituted in a different material than that constituting the created object, material which is eliminated from said object. when the construction process of the latter is finished.
Le support de construction est généralement une composition polymérique hydrosoluble ou hydrodispers ible répondant à un cahier des charges bien précis. Parmi les propriétés recherchées, outre la résistance mécanique, la température de transition vitreuse du polymère, sa stabilité thermique ou sa facilité de mise en oeuvre, la cinétique de solubilisation ou de dispersibilité dans l'eau est de première importance . The construction support is generally a water-soluble polymeric composition or water-dispersible responding to a specific specification. Among the desired properties, in addition to the mechanical strength, the glass transition temperature of the polymer, its thermal stability or its ease of implementation, the kinetics of solubilization or dispersibility in water is of primary importance.
ARRIERE-PLAN TECHNIQUE TECHNICAL BACKGROUND
EP 2447292, EP2699611 et EP 2041192 décrivent des copolymères ou des compositions solubles hydrodispersibles dans l'eau et utilisés dans le domaine de l'impression 3D. EP 2447292, EP2699611 and EP 2041192 describe copolymers or soluble compositions water-dispersible in water and used in the field of 3D printing.
Ces compositions sont constituées de copolymères statistiques comprenant des monomères tels que l'anhydride maléique (EP 2699611), l'acide méthacrylique (EP 2041192), plus généralement des acides a-b mono-carboxyliques insaturés (EP 2447292) polymérisés de façon radicalaire. WO2015175682 un copolymère comprenant des groupes carboxyliques neutralisés soluble dans une solution aqueuse alcaline. These compositions consist of random copolymers comprising monomers such as maleic anhydride (EP 2699611), methacrylic acid (EP 2041192), and more generally unsaturated α-b monocarboxylic acids (EP 2447292) polymerized in a radical manner. WO2015175682 A copolymer comprising neutralized carboxylic groups soluble in an aqueous alkaline solution.
Cependant de telles compositions présentent une cinétique de solubilisation ou de dispersibilité dans l'eau encore trop lente qui plus est à pH neutre. Augmenter la proportion de monomères hydrophiles pourraient constituer une solution, mais dans ce cas d'autres caractéristiques importantes telles que la Tg, la stabilité thermique, la fluidité à l'état fondu ou encore les propriétés mécaniques se trouvent dégradées. However, such compositions have a kinetics of solubilization or dispersibility in water still too slow, moreover at neutral pH. Increasing the proportion of hydrophilic monomers could be a solution, but in this case other important characteristics such as Tg, thermal stability, melt flow or mechanical properties are degraded.
La demanderesse a maintenant découvert qu'une composition comprenant un copolymère statistique comprenant de l'acide méthacrylique, de l'acrylate de butyle, du styrène et un monomère supplémentaire hydrophile judicieusement choisi présente une bien plus rapide dissolution ou dispersibilité à pH neutre ou proche du neutre, c'est-à-dire entre 5,5 et 9,5, que les compositions connues de l'art antérieur. The Applicant has now discovered that a composition comprising a random copolymer comprising methacrylic acid, butyl acrylate, styrene and an additional hydrophilic monomer judiciously chosen has a much faster dissolution or dispersibility at neutral pH or near neutral, that is to say between 5.5 and 9.5, than the known compositions of the prior art.
RESUME DE L'INVENTION SUMMARY OF THE INVENTION
L'invention concerne donc une composition comprenant un copolymère statistique comprenant les monomères suivants : -styrène, de 1 à 45 % massique, bornes comprises.  The invention therefore relates to a composition comprising a random copolymer comprising the following monomers: styrene, from 1 to 45% by weight, inclusive.
-l'acide méthacrylique, de 35 à 45 % massique, bornes comprises .  methacrylic acid, from 35 to 45% by weight, limits included.
-acrylate de butyle, de 15 à 35 % massique, bornes comprises -un monomère choisi parmi l'acide styrène sulfonique ou ses sels, l'acide vinyle benzoique ou ses sels, l'acide 2- acrylamido-2- methane sulfonique ou ses sels, la N-vinyle pyrolidone, seuls ou en combinaison dans des proportions de 1 à 45 % bornes comprises.  butyl acrylate, 15 to 35% by weight, inclusive of: a monomer selected from styrene sulphonic acid or its salts, vinyl benzoic acid or its salts, 2-acrylamido-2-methanesulphonic acid or its salts, N-vinyl pyrolidone, alone or in combination in proportions from 1 to 45% inclusive.
DESCRIPTION DETAILLEE DETAILED DESCRIPTION
Par solubilisation ou une dispersibilité dans l'eau, on entend une solubilisation ou une dispersibilité dans une phase aqueuse dont le pH est compris entre 5,5 et 9,5, dans une plage de température comprise entre 40 et 70°C. By solubilization or dispersibility in water is meant solubilization or dispersibility in an aqueous phase having a pH of 5.5 to 9.5 in a temperature range of 40 to 70 ° C.
Un polymère est dit « dispersible », s'il forme à une concentration de 5% en poids dans un solvant, à 25°C, une suspension stable de fines particules, généralement sphériques. La taille moyenne des particules constituant ladite dispersion est inférieure à 1 pm et, plus généralement, varie entre 5 et 400 nm, de préférence de 10 à 250 nm en poids. Ces tailles de particules sont mesurées par diffusion de lumière. Lorsque le solvant est l'eau, on parle de polymère « hydrodispers ible ». A polymer is said to be "dispersible" if it forms, at a concentration of 5% by weight in a solvent, at 25 ° C., a stable suspension of fine, generally spherical particles. The average particle size constituting said dispersion is less than 1 μm and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm by weight. These particle sizes are measured by light scattering. When the solvent is water, it is called "water-dispersible" polymer.
Les copolymères de l'invention peuvent être préparés par polymérisation radicalaire ou par polymérisation radicalaire contrôlée. Lorsqu'il s'agit d'obtenir un copolymère hydrosoluble ou hydrodispersible, la demanderesse constate cependant qu'il est préférable d'utiliser la polymérisation radicalaire contrôlée et que le copolymère ainsi préparé est plus rapidement solubilisé ou dispersé en solution aqueuse. The copolymers of the invention can be prepared by radical polymerization or by controlled radical polymerization. When it is a question of obtaining a water-soluble or water-dispersible copolymer, the Applicant however states that it is preferable to use controlled radical polymerization and that the copolymer thus prepared is more rapidly solubilized or dispersed in aqueous solution.
A cet effet On pourra utiliser tout type de polymérisation radicalaire contrôlée dans le cadre de l'invention telle que la NMP ("Nitroxide Mediated Polymeri zation" ) , la RAFT ("Réversible Addition and Fragmentation Transfer"), l'ATRP ("Atom Transfer Radical Polymeri zation" ) , l' INIFERTER ("Initiator-Transfer-Termination") , la RITP (" Reverse Iodine Transfer Polymeri zation" ) , l'ITP ("Iodine Transfer Polymerization) . For this purpose it is possible to use any type of controlled radical polymerization in the context of the invention such as NMP ("Nitroxide Mediated Polymerization"), RAFT ("Reversible Addition and Fragmentation Transfer"), ATRP ("Atom Transfer Radical Polymerization "), INIFERTER (" Initiator-Transfer-Termination "), RITP (" Reverse Iodine Transfer Polymerization "), ITP (" Iodine Transfer Polymerization ").
Selon une forme préférée de l'invention, les copolymères sont préparés par polymérisation contrôlée par les nitroxydes (NMP) . According to a preferred form of the invention, the copolymers are prepared by controlled nitroxide polymerization (NMP).
Plus particulièrement les nitroxydes issus des alcoxyamines dérivées du radical libre stable (1) sont préférées. More particularly, the nitroxides derived from alkoxyamines derived from the stable free radical (1) are preferred.
(1) (1)
RL R L
— C— N— O* Dans laquelle le radical R^ présente une masse molaire supérieure à 15,0342 g/mole. Le radical R^ peut être un atome d'halogène tel que le chlore, le brome ou l'iode, un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé ou insaturé tel qu'un radical alkyle ou phényle, ou un groupement ester -COOR ou un groupement alcoxyle -OR, ou un groupement phosphonate -PO(OR)2^ dès lors qu'il présente une masse molaire supérieure à 15,0342. Le radical R^, monovalent, est dit en position b par rapport à l'atome d'azote du radical nitroxyde. Les valences restantes de l'atome de carbone et de l'atome d'azote dans la formule (1) peuvent être liées à des radicaux divers tels qu'un atome d'hydrogène, un radical hydrocarboné comme un radical alkyle, aryle ou aryle-alkyle, comprenant de 1 à 10 atomes de carbone. Il n'est pas exclu que l'atome de carbone et l'atome d'azote dans la formule (1) soient reliés entre eux par l'intermédiaire d'un radical bivalent, de façon à former un cycle. De préférence cependant, les valences restantes de l'atome de carbone et de l'atome d'azote de la formule (1) sont liées à des radicaux monovalents. De préférence, le radical R^ présente une masse molaire supérieure à 30 g/mole. Le radical R^ peut par exemple avoir une masse molaire comprise entre 40 et 450 g/mole. A titre d'exemple, le radical R^ peut être un radical comprenant un groupement phosphoryle, ledit radical R^ pouvant être représenté par la formule : » - C- N- O * Wherein the radical R 1 has a molar mass greater than 15.0342 g / mol. The radical R 1 may be a halogen atom such as chlorine, bromine or iodine, a linear hydrocarbon group, branched or cyclic, saturated or unsaturated such as an alkyl or phenyl radical, or a group -COOR ester or an alkoxyl group -OR, or a phosphonate group -PO (OR) 2, provided that it has a molar mass greater than 15.0342. The radical R 1, monovalent, is said in position b with respect to the nitrogen atom of the nitroxide radical. The remaining valences of the carbon atom and the nitrogen atom in the formula (1) can be linked to various radicals such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aryl radical. -alkyl, comprising from 1 to 10 carbon atoms. It is not excluded that the carbon atom and the nitrogen atom in the formula (1) are connected to each other via a divalent radical, so as to form a ring. Preferably, however, the remaining valencies of the carbon atom and the nitrogen atom of the formula (1) are attached to monovalent radicals. Preferably, the radical R 1 has a molar mass greater than 30 g / mol. The radical R 1 may, for example, have a molar mass of between 40 and 450 g / mol. By way of example, the radical R 1 may be a radical comprising a phosphoryl group, said radical R 1 may be represented by the formula: "
- p - R2 - p - R 2
O O
(2)  (2)
Dans laquelle R et R , pouvant etre identiques ou differents, peuvent être choisis parmi les radicaux alkyle, cycloalkyle, alkoxyle, aryloxyle, aryle, aralkyloxyle , perfluoroalkyle, aralkyle, et peuvent comprendre de 1 à 20 atomes de carbone.Wherein R and R, which may be the same or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl, aralkyl, and may include from 1 to 20 carbon atoms.
R^ et/ou R^ peuvent également être un atome d'halogène comme un atome de chlore ou de brome ou de fluor ou d'iode. Le radical R^ peut également comprendre au moins un cycle aromatique comme pour le radical phényle ou le radical naphtyle, ce dernier pouvant être substitué, par exemple par un radical alkyle comprenant de 1 à 4 atomes de carbone. R 1 and / or R 1 may also be a halogen atom such as a chlorine or bromine or fluorine or iodine atom. The radical R 1 may also comprise at least one aromatic ring as for the phenyl radical or the naphthyl radical, the latter may be substituted, for example by an alkyl radical comprising from 1 to 4 carbon atoms.
Plus particulièrement les alcoxyamines dérivées des radicaux stables suivants sont préférées : More particularly alkoxyamines derived from the following stable radicals are preferred:
- N-tertiobutyl-l-phényl-2 méthyl propyl nitroxyde, N-tert-butyl-1-phenyl-2-methylpropyl nitroxide,
- N-tertiobutyl-1- (2-naphtyl) -2-méthyl propyl nitroxyde,N-tert-butyl-1- (2-naphthyl) -2-methylpropyl nitroxide,
- N-tertiobutyl-l-dibenzylphosphono-2 , 2 -diméthyl propyl nitroxyde , N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide,
N-phényl-l-diéthyl phosphono-2 , 2-diméthyl propyl nitroxyde ,  N-phenyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide,
- N-phényl-l-diéthyl phosphono-l-méthyl éthyl nitroxyde, N-phenyl-1-diethyl phosphono-1-methyl ethyl nitroxide,
N-(l-phényl 2-méthyl propyl ) -1-diéthylphosphono-1- méthyl éthyl nitroxyde, N- (1-phenyl-2-methylpropyl) -1-diethylphosphono-1-methylethyl nitroxide,
- 4-oxo-2, 2, 6, 6-tétraméthyl-l-piperidinyloxy,  4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy
- 2 , 4 , 6-tri-tert-butylphenoxy nitroxyde. N-tertiobutyl-l-diéthylphosphono-2 , 2-diméthyl propyl nitroxyde . 2,4,6-tri-tert-butylphenoxy nitroxide. N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide.
Les alkoxyamines utilisées en polymérisation radicalaire contrôlée doivent permettre un bon contrôle de l'enchaînement des monomères. Ainsi elles ne permettent pas toutes un bon contrôle de certains monomères. Par exemples les alcoxyamines dérivées du TEMPO ne permettent de contrôler qu'un nombre limité de monomères, il en va de même pour les alcoxyamines dérivées du 2 , 2 , 5-tri-methyl-4-phenyl-3-azahexane-3-nitroxyde (TIPNO) . En revanche d'autres alcoxyamines dérivées des nitroxydes répondant à la formule (1), particulièrement celles dérivées des nitroxydes répondant à la formule (2) et encore plus particulièrement celles dérivées du N-tertiobutyl-1- diéthylphosphono-2 , 2 -diméthyl propyl nitroxyde permettent d'élargir à un grand nombre de monomère la polymérisation radicalaire contrôlée de ces monomères. The alkoxyamines used in controlled radical polymerization must allow good control of the sequence of monomers. Thus they do not all allow good control of certain monomers. For example, the alkoxyamines derived from TEMPO make it possible to control only a limited number of monomers, the same goes for the alkoxyamines derived from 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide. (TIPNO). On the other hand, other alkoxyamines derived from nitroxides corresponding to formula (1), particularly those derived from nitroxides corresponding to formula (2) and even more particularly those derived from N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl. nitroxide allow to expand to a large number of monomer controlled radical polymerization of these monomers.
En outre la température d'ouverture des alcoxyamines influe également sur le facteur économique. L'utilisation de basses températures sera préférée pour minimiser les difficultés industrielles. On préférera donc les alkoxyamines dérivées des nitroxydes répondant à la formule (1), particulièrement celles dérivées des nitroxydes répondant à la formule (2) et encore plus particulièrement celles dérivées du N-tertiobutyl-1- diéthylphosphono-2 , 2 -diméthyl propyl nitroxyde à celles dérivées du TEMPO ou 2 , 2 , 5-tri-methyl-4-phenyl-3-azahexane-3- nitroxyde (TIPNO) .  In addition, the opening temperature of the alkoxyamines also influences the economic factor. The use of low temperatures will be preferred to minimize industrial difficulties. Alkoxyamines derived from nitroxides corresponding to formula (1), particularly those derived from nitroxides corresponding to formula (2) and even more particularly those derived from N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, will thus be preferred. those derived from TEMPO or 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO).
La proportion massique des monomères est choisie dans les gammes suivantes : -styrène, de 1 à 45 % massique, bornes comprises, et de préférence de 5 à 30 % bornes comprises. The mass proportion of the monomers is chosen from the following ranges: styrene, from 1 to 45% by weight, inclusive, and preferably from 5 to 30% inclusive.
-l'acide méthacrylique, de 35 à 45 % massique, bornes comprises et de préférence de 35 à 40 % bornes comprises.  methacrylic acid, from 35 to 45% by weight, inclusive and preferably from 35 to 40% inclusive.
-acrylate de butyle, de 15 à 35 % massique, bornes comprises et de préférence de 20 à 30 % bornes comprises.  butyl acrylate, 15 to 35% by weight, inclusive and preferably 20 to 30% inclusive.
-un monomère choisi parmi l'acide styrène sulfonique ou ses sels, l'acide vinylique benzoique ou ses sels ou l'acide 2- acrylamido-2- methane sulfonique ou ses sels ou la N-vinyle pyrolidone, seuls ou en combinaison dans des proportions de 1 à 45 % bornes comprises et de préférence de 15 à 45% bornes comprises .  a monomer chosen from styrene sulphonic acid or its salts, benzoic vinyl acid or its salts or 2-acrylamido-2-methanesulphonic acid or its salts or N-vinylpyrrolidone, alone or in combination in proportions from 1 to 45% inclusive and preferably from 15 to 45% inclusive.
De façon préférée, le monomère préféré est le l'acide styrène sulfonique ou ses sels.  Preferably, the preferred monomer is styrene sulphonic acid or its salts.
La masse moléculaire en poids des copolymères hydrosoluble ou hydrodispersibles objet de l'invention, mesurée par SEC est comprise entre 30000 g/mole et 300000 g par mole, de préférence entre 70000 et 170000 g/mole, et de façon encore préférée entre 80000 et 130000 g/mole. The weight-average molecular weight of the water-soluble or water-dispersible copolymers according to the invention, measured by SEC, is between 30000 g / mol and 300000 g per mole, preferably between 70000 and 17000 g / mol, and more preferably between 80000 and 130000 g / mole.
La dispersité des copolymères hydrosolubles ou hydrodispersibles est inférieure à 2,2 et de préférence inférieure à 2. The dispersibility of the water-soluble or water-dispersible copolymers is less than 2.2 and preferably less than 2.
La température de transition vitreuse (Tg) mesurée par DMA (dynamic mechanical analysis) du copolymère statistique présent dans la composition objet de l'invention est supérieure à 60°C et de préférence supérieure à 110 °C. The glass transition temperature (Tg) measured by DMA (dynamic mechanical analysis) of the random copolymer present in the composition which is the subject of the invention is greater than 60 ° C. and preferably greater than 110 ° C.
Les compositions hydrosolubles ou hydrodispersibles objet de l'invention peuvent contenir des modifiants chocs, qu'ils soient du type copolymères statistiques, à blocs, ou encore des particules cœur - écorce, seuls ou en combinaison. The water-soluble or water-dispersible compositions that are the subject of the invention may contain impact modifiers, which they are of the random block copolymer type, or core - bark particles, alone or in combination.
Les compositions de l'inventions peuvent être utilisées comme agents dispersants pour pigments, ou encore comme modificateurs de rhéologie dans des applications telles que les boues de forage, les pâtes d'impression textile, la cosmétique, ou encore la détergence, et autres compositions de revêtement comme la peinture et comme agent anti-sédimentation et/ou de mise en suspension pour des charges minérales ou organiques grossières dans le domaine du phytosanitaire, mais également le domaine de l'impression tridimensionnelle (ou impression 3D) d'un objet du type FDM (fused déposition molding) en tant que polymère sacrificiel. A ce titre, les compositions de l'invention peuvent être mises en forme sous forme de filament extrudé, avec ou sans modifiants chocs, ces filaments extrudés étant également objet de l'invention The compositions of the invention can be used as pigment dispersing agents, or as rheology modifiers in applications such as drilling muds, textile printing pastes, cosmetics, or detergents, and other compositions of the invention. coating as paint and as an anti-sedimentation and / or suspending agent for coarse mineral or organic fillers in the phytosanitary field, but also the field of three-dimensional printing (or 3D printing) of an object of the type FDM (fused deposition molding) as a sacrificial polymer. As such, the compositions of the invention can be shaped in the form of extruded filament, with or without impact modifiers, these extruded filaments also being the subject of the invention.
L'invention porte également sur les objets obtenus à l'aide des compositions de l'invention. The invention also relates to the objects obtained using the compositions of the invention.
Exemples : Examples:
Le mélange de réactifs est le suivant :  The reagent mixture is as follows:
Amorceur : BlocBuilder® (provenance Arkema) .  Primer: BlocBuilder® (from Arkema).
Styrène (St) (provenance Aldrich)  Styrene (St) (provenance Aldrich)
Acide méthacrylique (AMA) (provenance Aldrich)  Methacrylic acid (AMA) (provenance Aldrich)
Styrène sulfonate de sodium (provenance Aldrich)  Styrene sodium sulfonate (provenance Aldrich)
Acrylate de Butyle (ABu) (provenance Aldrich)  Butyl Acrylate (ABu) (from Aldrich)
Ethanol (provenance Aldrich) Amorceur : BlocBuilder® (provenance Arkema) . Ethanol (from Aldrich) Primer: BlocBuilder® (from Arkema).
Styrène (St) (provenance Aldrich)  Styrene (St) (provenance Aldrich)
Acide méthacrylique (AMA) (provenance Aldrich)  Methacrylic acid (AMA) (provenance Aldrich)
Styrène sulfonate de sodium (provenance Aldrich)  Styrene sodium sulfonate (provenance Aldrich)
- Acrylate de Butyle (ABu) (provenance Aldrich)  - Butyl acrylate (ABu) (provenance Aldrich)
Ethanol (provenance Aldrich)  Ethanol (from Aldrich)
Toluène (provenance Aldrich)  Toluene (from Aldrich)
DMSO (diméthyle sulfoxyde) , (provenance Aldrich)  DMSO (Dimethylsulfoxide), (Aldrich sourced)
La totalité des réactifs et des solvants est introduite dans un réacteur inox fermé de 2L, sous atmosphère d'azote. Le mélange est chauffé pendant 180 minutes, sous une agitation de 200tr/min . La conversion finale est de 71%. Le copolymère de l'invention est récupéré par précipitation dans de l'acétone. Pour le copolymère témoin, les solvants et monomères résiduels sont éliminés dans une étuve sous vide à 100°C. Dans les 2 cas le résidu obtenu est séché puis broyé dans un mortier pour être utilisé sous forme de poudre. All the reagents and solvents are introduced into a closed stainless steel reactor of 2L under a nitrogen atmosphere. The mixture is heated for 180 minutes, with stirring of 200 rpm. The final conversion is 71%. The copolymer of the invention is recovered by precipitation in acetone. For the control copolymer, residual solvents and monomers are removed in a vacuum oven at 100 ° C. In both cases the residue obtained is dried and then ground in a mortar to be used in powder form.
La composition des trois copolymères est analysée par RMN 1H et donne les résultats suivants en % massique, tableau 2 : The composition of the three copolymers is analyzed by 1 H NMR and gives the following results in mass%, Table 2:
Tests de dissolution Dissolution tests
Les copolymères obtenus sont chauffés à une température de 160°C sous une presse à compression pour former une pastille de 2.5cm de diamètre et 1mm d'épaisseur. Les pastilles sont ensuite placées dans un bêcher, sous agitation, dans de l'eau à pH 7 à une température de 60 °C.  The copolymers obtained are heated at a temperature of 160 ° C. under a compression press to form a pellet of 2.5 cm in diameter and 1 mm in thickness. The pellets are then placed in a beaker, with stirring, in water at pH 7 at a temperature of 60 ° C.
Les échantillons sont sortis périodiquement et pesés pour évaluer la perte de poids liée à la dissolution du polymère. Les tests sont réalisés à un pH de 7 à 60°C ; tableau 1 : Tableau 1 : The samples are periodically taken out and weighed to evaluate the weight loss related to the dissolution of the polymer. The tests are carried out at a pH of 7 to 60 ° C; table 1: Table 1:
En figure 1 est visualisée la dissolution des copolymères témoin et de l'invention (essai 1) à pH=7 et 60°C. On constate que les copolymères préparés à l'aide des quatre monomères Abu/STY/AMA/styrene sulfonate de sodium (Invention) se dissolvent plus rapidement que ceux préparés sans styrène sulfonate de sodium. In Figure 1 is shown the dissolution of the control copolymers and the invention (test 1) at pH = 7 and 60 ° C. It is found that the copolymers prepared using the four monomers Abu / STY / AMA / sodium styrene sulfonate (Invention) dissolve more rapidly than those prepared without sodium styrene sulfonate.

Claims

REVENDICATIONS 1 Composition comprenant un copolymère statistique comprenant les monomères suivants : -styrène, de 1 à 45 % massique, bornes comprises. -l'acide méthacrylique, de 35 à 45 % massique, bornes comprises . -acrylate de butyle, de 15 à 35 % massique, bornes comprises -un monomère choisi parmi l'acide styrène sulfonique ou ses sels, l'acide vinyle benzoique ou ses sels, l'acide 2- acrylamido-2- méthane sulfonique ou ses sels, la N-vinyle pyrolidone, seuls ou en combinaison dans des proportions de 1 à 45 % bornes comprises. 2 Composition selon la revendication 1 dans laquelle le copolymère statistique est préparé par polymérisation radicalaire contrôlée 3 Composition selon une des revendications 1 à 2 dans laquelle la masse moléculaire en poids du ou des copolymères est comprise entre 30000 et 300000 g/mole. 4 Composition selon une des revendications 1 à 3 dans laquelle la température de transition vitreuse du copolymère, mesurée par DMA est supérieure à 60 °C. 5 Composition selon une des revendications 2 à 4 selon laquelle la polymérisation est conduite par polymérisation radicalaire contrôlée de type RAFT . 6 Composition selon une des revendications 2 à 4 selon dans laquelle la polymérisation est conduite par polymérisation radicalaire contrôlée de type ATRP. 7 Composition selon une des revendications 1 à 4 selon dans laquelle la polymérisation est conduite par polymérisation radicalaire contrôlée de type NMP. 8 Composition selon la revendication 7 dans laquelle le nitroxyde est issu des alcoxyamines dérivées du radical stable 1 composition comprising a random copolymer comprising the following monomers: -styrene, from 1 to 45% by weight, inclusive. methacrylic acid, from 35 to 45% by weight, limits included. butyl acrylate, 15 to 35% by weight, inclusive of: a monomer selected from styrene sulfonic acid or its salts, vinyl benzoic acid or its salts, 2-acrylamido-2-methanesulfonic acid or its salts, N-vinyl pyrolidone, alone or in combination in proportions from 1 to 45% inclusive. 2 Composition according to claim 1 wherein the random copolymer is prepared by controlled radical polymerization Composition according to one of claims 1 to 2 wherein the molecular weight of the copolymer or copolymers is between 30000 and 300000 g / mol. 4 Composition according to one of claims 1 to 3 wherein the glass transition temperature of the copolymer, measured by DMA is greater than 60 ° C. 5. Composition according to one of claims 2 to 4 according to which the polymerization is carried out by controlled radical polymerization of RAFT type. 6. Composition according to one of claims 2 to 4 according to which the polymerization is carried out by controlled radical polymerization of ATRP type. 7 Composition according to one of claims 1 to 4 according to which the polymerization is conducted by controlled radical polymerization of NMP type. 8 Composition according to Claim 7, in which the nitroxide is derived from alkoxyamines derived from the stable radical
(1) (1)
RL R L
— C— N— O* - C- N- O *
dans laquelle le radical présente une masse molaire supérieure à 15,0342 g/mole. in which the radical has a molar mass greater than 15.0342 g / mol.
9 Composition selon la revendication 8 dans laquelle les alcoxyamines sont dérivées des radicaux stables suivants : The composition of claim 8 wherein the alkoxyamines are derived from the following stable radicals:
- N-tertiobutyl-l-phényl-2 méthyl propyl nitroxyde,N-tert-butyl-1-phenyl-2-methylpropyl nitroxide,
- N-tertiobutyl-1- (2-naphtyl) -2-méthyl propyl nitroxyde,N-tert-butyl-1- (2-naphthyl) -2-methylpropyl nitroxide,
- N-tertiobutyl-l-dibenzylphosphono-2 , 2-diméthyl propyl nitroxyde , N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide,
N-phényl-l-diéthyl phosphono-2 , 2-diméthyl propyl nitroxyde ,  N-phenyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide,
- N-phényl-l-diéthyl phosphono-l-méthyl éthyl nitroxyde, N-phenyl-1-diethyl phosphono-1-methyl ethyl nitroxide,
N-(l-phényl 2-méthyl propyl ) -1-diéthylphosphono-1- méthyl éthyl nitroxyde, - 4-oxo-2, 2, 6, 6-tétraméthyl-l-piperidinyloxy,N- (1-phenyl-2-methylpropyl) -1-diethylphosphono-1-methylethyl nitroxide, 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy
- 2 , 4 , 6-tri-tert-butylphenoxy nitroxyde . 2,4,6-tri-tert-butylphenoxy nitroxide.
N-tertiobutyl-l-diéthylphosphono-2 , 2-diméthyl propyl nitroxyde .  N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide.
10 Composition selon la revendication 9 dans laquelleles alcoxyamines sont dérivées du N-tertiobutyl-1- diéthylphosphono-2 , 2 -diméthyl propyl nitroxyde. The composition of claim 9 wherein the alkoxyamines are derived from N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide.
11 Utilisation d'une composition selon l'une des revendications 1 à 10 comme agents dispersants pour pigments, ou encore comme modificateurs de rhéologie dans des applications telles que les boues de forage, les pâtes d'impression textile, la cosmétique, ou encore la détergence, et autres compositions de revêtement comme la peinture et comme agent anti-sédimentation et/ou de mise en suspension pour des charges minérales ou organiques grossières dans le domaine du phytosanitaire, mais également le domaine de l'impression tridimensionnelle (ou impression 3D) d'un objet du type FDM (fused déposition molding) en tant que polymère sacrificiel. 11 Use of a composition according to one of claims 1 to 10 as dispersing agents for pigments, or as rheology modifiers in applications such as drilling muds, textile printing pastes, cosmetics, or the detergency, and other coating compositions such as paint and as an anti-sedimentation and / or suspending agent for coarse mineral or organic fillers in the phytosanitary field, but also the field of three-dimensional printing (or 3D printing) an FDM type object (fused deposition molding) as a sacrificial polymer.
12 Filament extrudé à partir d'une composition de l'une des revendications 1 à 10. Extruded filament from a composition of one of claims 1 to 10.
EP18821721.0A 2017-11-28 2018-11-23 Water-soluble copolymer composition with neutral ph Pending EP3717529A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1761283A FR3074181B1 (en) 2017-11-28 2017-11-28 HYDROSOLUBLE COPOLYMERIC COMPOSITION WITH NEUTRAL PH
PCT/FR2018/052966 WO2019106265A1 (en) 2017-11-28 2018-11-23 Water-soluble copolymer composition with neutral ph

Publications (1)

Publication Number Publication Date
EP3717529A1 true EP3717529A1 (en) 2020-10-07

Family

ID=61873400

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18821721.0A Pending EP3717529A1 (en) 2017-11-28 2018-11-23 Water-soluble copolymer composition with neutral ph

Country Status (7)

Country Link
US (1) US11453735B2 (en)
EP (1) EP3717529A1 (en)
JP (1) JP7177164B2 (en)
KR (1) KR102496407B1 (en)
CN (1) CN111417661A (en)
FR (1) FR3074181B1 (en)
WO (1) WO2019106265A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3088327B1 (en) * 2018-11-08 2021-11-05 Arkema France WATER-SOLUBLE COPOLYMERIC COMPOSITION

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928273A (en) * 1974-06-03 1975-12-23 Ford Motor Co Method of making organic solvent free aqueous coating compositions of acrylic polymer latex, water soluble emulsion-polymerized acrylic polymer, and aminoplast
JPS5950056A (en) * 1982-09-17 1984-03-22 Daicel Chem Ind Ltd Bundling agent for glass fiber
JP3315523B2 (en) * 1994-04-19 2002-08-19 日本化薬株式会社 Dispersant for inorganic hydraulic composition, hydraulic composition and cured product thereof
DE19640208A1 (en) * 1996-09-30 1998-04-02 Agfa Gevaert Ag Photographic material useful for colour photographic paper
JP3944890B2 (en) * 1997-12-30 2007-07-18 荒川化学工業株式会社 Undercoat agent for release paper
DE102006032225A1 (en) 2006-07-07 2008-01-10 Belland Ag Anhydrified copolymer
WO2008038857A1 (en) * 2006-09-28 2008-04-03 Korea Kumho Petrochemical Co., Ltd Maleimide-alpha-alkylstyrene-based tetrapolymer with low molten viscosity and continuous bulk process for producing it
EP2447292B1 (en) 2010-10-29 2017-03-29 BellandTechnology AG Water soluble copolymer which disintegrates in water
EP2514775A1 (en) 2011-04-20 2012-10-24 Evonik Röhm GmbH Maleic anhydride copolymers as soluble support material for fused deposition modelling (FDM) printer
FR2983773B1 (en) * 2011-12-09 2014-10-24 Arkema France PROCESS FOR PREPARING SURFACES
US10675853B2 (en) * 2014-05-16 2020-06-09 Stratasys, Inc. High-temperature soluble support material for additive manufacturing
WO2019081370A1 (en) * 2017-10-27 2019-05-02 Basf Se Aqueous binder formulation

Also Published As

Publication number Publication date
CN111417661A (en) 2020-07-14
US11453735B2 (en) 2022-09-27
US20200369808A1 (en) 2020-11-26
JP7177164B2 (en) 2022-11-22
KR20200079342A (en) 2020-07-02
WO2019106265A1 (en) 2019-06-06
FR3074181B1 (en) 2020-11-06
KR102496407B1 (en) 2023-02-06
JP2021504558A (en) 2021-02-15
FR3074181A1 (en) 2019-05-31

Similar Documents

Publication Publication Date Title
CA2320426C (en) Compositions based on semicrystalline thermoplastic resins and block copolymers, resulting materials and methods for obtaining same
EP3237473B1 (en) 3d-printing process using a water soluble block copolymer as support material
US6875808B2 (en) Multiple polymeric additive systems: compositions, processes, and products thereof
EP1616907B1 (en) Masterbatch composition based on fluoropolymer and its use for the extrusion of polyolefins
JP2011506653A (en) Molded body with matte and structured surface properties
EP3717529A1 (en) Water-soluble copolymer composition with neutral ph
EP3877181B1 (en) Water-soluble copolymer composition
FR3053348A1 (en) COMPOSITION COMPRISING A MULTI-PHASE POLYMER AND TWO DIFFERENT (METH) ACRYLIC POLYMERS, METHOD FOR PREPARING THE SAME AND ARTICLE THEREOF
WO2012058256A1 (en) A thermoplastic composition, method of producing the same, and articles made therefrom
WO2009153506A1 (en) Composition containing (meth)acrylic polymer and copolymer having associative groups
CA2739504A1 (en) Macromonomers improving the thermal stability of (meth)acrylic comb polymers, use of said polymers in charged plastic compositions
US20020052429A1 (en) Functional liquid-solid additive systems: compositions, processes, and products thereof
FR3019549A1 (en)
EP3344697A1 (en) Vinylidene chloride polymer compositions and articles comprising the same
FR3061717A1 (en) POLYMER COMPOSITION WITH CHARGE, PROCESS FOR PREPARING SAME AND USE THEREOF
WO2022269167A1 (en) Use of multiblock copolymers as sacrificial material in a 3d printing process
FR2736922A1 (en) PROCESS FOR THE PREPARATION OF AQUEOUS DISPERSION OF COMPOSITE PARTICLES COMPRISING LATEX PARTICLES AND INORGANIC PARTICLES
Lopes Brito Film formation of multiphase latex particles.
EP3097129B1 (en) Latex of spherical particles having improved thermal ageing properties
JP2004323708A (en) Method for producing coloring agent
Arunyagasemsuke et al. Reactive Blends of Poly (butylene adipate-co-terephthalate) and Thermoplastic Starch
Raj Scientia Research Library
JPS59210964A (en) Polyvinyl halide polymer composition
FR3038611A1 (en)
FR3038612A1 (en)

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200609

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20231010