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.

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• Chemical & Material Sciences (AREA)
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• Medicinal Chemistry (AREA)
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• 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)

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• 2017
  • 2017-11-28 FR FR1761283A patent/FR3074181B1/fr active Active
• 2018
  • 2018-11-23 JP JP2020545891A patent/JP7177164B2/ja active Active
  • 2018-11-23 EP EP18821721.0A patent/EP3717529A1/de active Pending
  • 2018-11-23 US US16/766,926 patent/US11453735B2/en active Active
  • 2018-11-23 KR KR1020207017804A patent/KR102496407B1/ko active IP Right Grant
  • 2018-11-23 CN CN201880077092.XA patent/CN111417661A/zh active Pending
  • 2018-11-23 WO PCT/FR2018/052966 patent/WO2019106265A1/fr unknown

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