WO2021043820A1 - Particules nanocomposites électriquement conductrices possédant un cœur de polyacrylate d'alkyle et une écorce de polymère conducteur - Google Patents
Particules nanocomposites électriquement conductrices possédant un cœur de polyacrylate d'alkyle et une écorce de polymère conducteur Download PDFInfo
- Publication number
- WO2021043820A1 WO2021043820A1 PCT/EP2020/074462 EP2020074462W WO2021043820A1 WO 2021043820 A1 WO2021043820 A1 WO 2021043820A1 EP 2020074462 W EP2020074462 W EP 2020074462W WO 2021043820 A1 WO2021043820 A1 WO 2021043820A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- monomers
- pedot
- polyelectrolyte
- alkyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L41/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/12—Processes in which the treating agent is incorporated in microcapsules
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/96—Applications coating of particles
- C08G2261/962—Applications coating of particles coating of organic particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
Definitions
- Electrically conductive nanocomposite particles having a polyalkrylate core and a conductive polymer shell
- the present invention relates to the technical field of stretchable conductive materials, in particular for the fields of printed electronics requiring elasticity.
- the IoE can be implemented thanks to the latest technological advancements, and mainly to the advancements acquired in the world of printed electronics.
- Printed electronics allow the production of flexible components and on large surfaces, in particular as a complement to traditional electronics on silica.
- the main differences in the devices obtained with traditional semiconductor technologies are in their thickness, weight, robustness and cost. These qualities have enabled the emergence of new markets and products, and have contributed to the development of innovative concepts such as portable electronics and smart labels.
- stretchable and flexible substrates especially for “wearables”, such as connected clothing.
- the nanocomposites take advantage of the inclusion of conductive fillers in insulating elastomeric matrices. Materials like carbon nanotubes, silver nanowires or metallic nanoparticles are used as conductive materials. Despite the versatility and the large number of material choices, percolation dependent conductivity is highly sensitive to voltage and remains an obstacle for miniaturization in the case of a device, and stability under cyclic strain.
- An inherently stretchable and conductive material capable of being deposited in solution and capable of printing a pattern is further desirable.
- Conductive polymers are good candidates due to their flexibility and their electrical and mechanical properties. Unfortunately, to date, high conductivity and high stretchability could not be achieved simultaneously for conductive polymers.
- Poly (3,4-ethylenedioxythiophene): sodium poly (styrene sulfonate) (PEDOT: PSS) is a conductive polymer which can be deposited from solution and exhibits high conductivity, but it exhibits deformation fracture around by 5%.
- Patent EP3221404 describes a conductive polymer coating comprising in particular a conductive polymer such as PEDOT and a polymer improving the flexibility of the coating, such as a copolymer of acrylamide and acrylic acid.
- This coating is indicated as particularly suitable for flexible surfaces and allows the maintenance of the conductivity of the coating even after several stretching cycles.
- the two polymers being in simple mixture, this coating can present risks of phase segregation and / or of diffusion harmful to the conduction properties.
- Application WO2007012736 describes electrically conductive particles comprising a core of n-butyl polyacrylate, a polyaniline shell and a nonionic surfactant. These particles combine an elastomeric core and a shell providing electrical conduction properties to the particles.
- application WO2007012736 does not describe the behavior of such particles during their stretching, and in particular it does not describe whether the electrical conduction is retained by the particles when they are stretched.
- polyaniline is a conductive polymer, its conductivity is significantly lower than that of PEDOT: PSS.
- the particle synthesis process is specific for polyaniline.
- the present invention relates to electrically conductive nanocomposite particles comprising:
- a core consisting of a homopolymer of C1-C6 alkyl polyacrylate or of a copolymer of C1-C6 alkyl acrylate and of an a, b-unsaturated amide comonomer;
- a shell comprising a conductive polymer chosen from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT), derivatives of PEDOT and poly (3-hexylthiophene) (P3HT); and
- PEDOT poly (3,4-ethylenedioxythiophene)
- P3HT poly (3-hexylthiophene)
- the present invention also relates to a process for preparing a dispersion of particles comprising:
- a core consisting of a homopolymer of C1-C6 alkyl polyacrylate or of a copolymer of C1-C6 alkyl acrylate and of an a, b-unsaturated amide comonomer;
- a shell comprising a conductive polymer chosen from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT), derivatives of PEDOT and poly (3-hexylthiophene) (P3HT);
- PEDOT poly (3,4-ethylenedioxythiophene)
- P3HT poly (3-hexylthiophene)
- a nonionic surfactant comprising the steps of: a) polymerization of C1-C6 alkyl acrylate monomers, and optionally of a, b-unsaturated amide monomers, in the presence of a nonionic surfactant and a polymerization catalyst in a dispersing medium to obtain a latex in aqueous solution; b) solubilizing a polyelectrolyte stabilizing the conductive polymer in an aqueous solution to obtain an aqueous solution comprising said polyelectrolyte; c) addition of 3,4-ethylenedioxythiophene (EDOT) monomers, EDOT derivatives, or 3-hexylthiophene in the aqueous solution comprising the polyelectrolyte obtained in step (b); d) adding a polymerization initiator and the latex obtained in step (a) to the solution comprising the polyelectrolyte and the monomers obtained in step (c); and e
- the present invention also relates to the use of electrically conductive nanocomposite particles according to the invention for printing on a stretchable medium.
- the present invention relates to a printed stretchable support, in which the printing comprises at least one particle according to the invention.
- Figure 1 is a graph showing the development of the strength of the printed thermoplastic polyurethane specimen during the tensile test as a function of the stretch.
- FIG. 2 is a graph showing the evolution of the resistance (upper part) and the stretch (lower part) of the thermoplastic polyurethane specimen printed during a pull / release cycle with a stretch of 120%.
- FIG. 3 is a graph showing the evolution of the resistance (upper part) and the stretch (lower part) of the thermoplastic polyurethane specimen printed during a pull / release cycle with a stretch of 150%.
- FIG. 4 is a graph showing the evolution of the resistance of the Lycra test piece printed during the tensile test as a function of the stretching.
- FIG. 5 is a graph showing the evolution of the resistance of the printed stretchable yarn test piece during the tensile test as a function of time for a stretch of 110%.
- Figure 6 is a graph showing the development of the resistance of the printed stretchable yarn test piece during the tensile test as a function of time for a stretch of 125%.
- FIG. 7 is a graph showing the change in the resistance of the printed stretchable yarn test piece during the tensile test as a function of time for a stretch of 150%.
- the present invention relates to electrically conductive nanocomposite particles comprising:
- a core consisting of a homopolymer of C1-C6 alkyl polyacrylate or of a copolymer of C1-C6 alkyl acrylate and of an a, b-unsaturated amide comonomer;
- a shell comprising a conductive polymer chosen from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT), derivatives of PEDOT and poly (3-hexylthiophene) (P3HT); and
- PEDOT poly (3,4-ethylenedioxythiophene)
- P3HT poly (3-hexylthiophene)
- nanocomposites is understood to mean composite particles of size less than one micrometer.
- the size (diameter) of the core is generally in the range of 20 nm to 700 nm and the shell size (thickness) is generally in the range of a few nm to 100 nm.
- the diameter of the core of the particles is less than 200 nm.
- particles with a core diameter of less than 200 nm have advantages in terms of processing (deposition in the form of a film or easier impregnation), material savings ( less conductive polymer needed to achieve percolation rates similar to those of the prior art) and conductivity.
- processing deposition in the form of a film or easier impregnation
- material savings less conductive polymer needed to achieve percolation rates similar to those of the prior art
- conductivity conductivity
- the size of the core and / or the shell of the particles can be measured by any suitable technique known in the art. It can in particular be measured by dynamic light scattering.
- PEDOT poly (3,4-ethylenedioxythiophene)
- EDOT 3,4-ethylenedioxythiophene
- PEDOT derivative is meant a polymer obtained by polymerization of monomers of EDOT derivatives chosen from the group consisting of hydroxymethyl-EDOT, vinyl-EDOT, EDOT allyl ether, EDOT-COOH, EDOT-MeOH; EDOT-silane, EDOT-acrylate, EDOT-sulfonate, EDOT-amine and EDOT-amide or a mixture of such monomers.
- poly (3-hexylthiophene) (P3HT) is meant a polymer obtained by polymerization of 3-hexylthiophene monomers.
- the conductive polymer is PEDOT or one of its derivatives, in particular it is PEDOT.
- the term “shell comprising a conductive polymer” is understood to mean a continuous or discontinuous deposit of conductive polymer bound physically (ie adsorbed) and / or chemically (ie grafted) to the surface of the polyalkylacrylate core. Preferably, this deposit is discontinuous. Preferably, the bark is adsorbed on the surface of the heart.
- the conductive polymer in particular PEDOT, can be mixed with at least one stabilizer and / or at least one dopant.
- PEDOT can be present as a mixture with a polyelectrolyte stabilizer, such as poly (sodium styrene sulfonate) (PSS).
- PSS poly (sodium styrene sulfonate)
- PSS poly (sodium styrene sulfonate)
- PSS poly (sodium styrene sulfonate)
- PSS poly (sodium styrene s
- a “polyalkyl acrylate homopolymer” means a polymer resulting from the linking of several identical alkyl acrylate monomer units.
- polyalkylacrylate embraces polymethacrylates of alkyl.
- C1-C6 alkyl polyacrylates are in particular polymethyl methacrylate, polyethylacrylate, polyethylacrylate, polymethyl methacrylate, polyacrylate of n-propyl or of isopropyl, polymethacrylate of n -propyl or isopropyl, polyacrylate of n-, sec- or tert-butyl and polymethacrylate of n-, sec- or tert-butyl.
- the poly (C1-C6) alkyl is n-butyl polyacrylate.
- the latter advantageously has a glass transition temperature of -54 ° C., which makes it possible to obtain film-forming properties at room temperature.
- the polyalkylacrylate is crosslinked.
- particularly suitable crosslinking agents are in particular the diacrylate compounds, preferably 1,6 hexanediol diacrylate. The latter is available in particular under the trade name SR238 (R) (Cray Valley).
- R trade name
- alkyl polyacrylate makes it possible to modulate the mechanical properties of the conductive composite and in particular to reduce its elasticity.
- a crosslinking agent is distinguished from a comonomer in particular in that it has a functionality at least equal to two, when a comonomer generally has a functionality of 1.
- the polyalkylacrylate or the copolymer of C1-C6 alkyl acrylate and of an a, b-unsaturated amide comonomer which constitutes the core of the particles is not crosslinked, or at least not sufficiently crosslinked to harden the core of the particle.
- the absence of crosslinking helps maintain the mobility of the polymer chains and the percolation, the two phases formed by the particles (core and shell) being able to appear as two continuous phases one inside the other.
- the absence of crosslinking of the core contributes in particular to greater stretchability of the particles according to the invention.
- the core consists of a copolymer of C1-C6 alkyl acrylate and of an a, b- unsaturated amide comonomer.
- the weight ratio of polyalkylacrylate / conductive polymer in particular PEDOT, varies from 45/55 to 98/2 and is preferably between 50/50 and 95/5.
- the weight ratio of polyalkylacrylate / conductive polymer, in particular PEDOT varies from 70/30 to 95/5, in particular it is equal to approximately 75/25, in particular it is equal to 75/25.
- the particles according to the invention can be obtained by polymerization of PEDOT in a dispersion of polyalkylacrylate stabilized by the presence of a surfactant.
- the surfactant can be nonionic or ionic, in particular cationic. It is preferably nonionic because ionic surfactants can undesirably interfere with the polymerization reactions, in particular during the polymerization of PEDOT.
- nonionic surfactant is meant a surfactant which is uncharged under the operating conditions.
- the nonionic surfactant can be physically adsorbed on the surface of the polyalkylacrylate particles (i.e. physically bound) or incorporated into the polyalkylacrylate (i.e. chemically bound).
- the nonionic surfactant is physically bonded to the polyalkylacrylate. This can be achieved by carrying out the polymerization of the polyalkylacrylate in the presence of the nonionic surfactant.
- the nonionic surfactant can be chosen from a wide variety of compounds including in particular alkylphenol alkoxylates, alcohol alkoxylates, alkyl alkoxylates, amine alkoxylates, alkyl amine oxides, in particular from ethoxylates. of alkylphenols, alcohol ethoxylates, alkyl ethoxylates, or EO / PO block copolymers (ethylene oxide / propylene oxide), amine ethoxylates or polyethoxylates.
- the nonionic surfactant preferably has a hydrophilic / lipophilic balance (HLB) of between 12 and 20, in particular between 17 and 19, limits included.
- HLB hydrophilic / lipophilic balance
- it may be the surfactant known under the name Brij TM S100, of formula I:
- the amount of nonionic surfactant used is not critical and can vary to a large extent. Thus, dispersions of small particles generally require a higher amount of stabilizing surfactant than dispersions of larger particles. However, this amount must be sufficient to make it possible to stabilize the polyalkylacrylate particles and must not be too large so as not to alter the mechanical and conductive properties of the particles.
- the nonionic surfactant present in the particles according to the invention generally represents 1% to 20% by mass, and more preferably from 1 to 10% by mass, the values by mass being expressed relative to the total dry mass of the bark and from the heart.
- the particles further comprise a second nonionic surfactant having chemical functions capable of improving the conductivity of the composite.
- a second nonionic surfactant having chemical functions capable of improving the conductivity of the composite.
- nonionic surfactants comprising at least one amide function, such as the compounds of formula II:
- Alk2 denotes a C1-C20, preferably C1-C15, alkyl group, and m represents an integer from 1 to 100.
- a compound corresponding to formula II, in which Alk2 is used is a C11 alkyl group and m represents an average number of 6. This is commercially available under the name Ninol® (Stepan).
- Ninol® Ninol®
- this second nonionic surfactant represents 1% to 20% by mass relative to the dry mass of the bark and of the heart.
- the particles used according to the invention may alternatively comprise a second ionic surfactant, in particular a second cationic surfactant so as not to create charge incompatibility between the conductive polymer and the second ionic surfactant.
- the cationic surfactant can be chosen from surfactants of the family of alkyltrimethylammoniums, in particular C4 to C20 alkyltrimethylammoniums. In particular, it may be dodecyltrimethylammonium bromide (DTAB).
- this second ionic surfactant represents 1% to 20% by mass relative to the dry mass of the bark and of the heart.
- the mass ratio between the first nonionic surfactant and the second nonionic or ionic surfactant is preferably between 50/50 and 30/70 , terminals included.
- the present invention also relates to a process for preparing a dispersion of particles comprising:
- a core consisting of a homopolymer of C1-C6 alkyl polyacrylate or of a copolymer of C1-C6 alkyl acrylate and of an a, b-unsaturated amide comonomer;
- a shell comprising a conductive polymer chosen from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT), derivatives of PEDOT and poly (3-hexylthiophene) (P3HT);
- PEDOT poly (3,4-ethylenedioxythiophene)
- P3HT poly (3-hexylthiophene)
- a nonionic surfactant comprising the steps of: a) polymerization of C1-C6 alkyl acrylate monomers, and optionally of a, b-unsaturated amide monomers, in the presence of a nonionic surfactant and a polymerization catalyst in a dispersing medium to obtain a latex in aqueous solution; b) solubilization of a polyelectrolyte stabilizing the conductive polymer, in particular poly (3,4-ethylenedioxythiophene) (PEDOT), in an aqueous solution to obtain an aqueous solution comprising said polyelectrolyte; c) addition of 3,4-ethylenedioxythiophene (EDOT) monomers, EDOT or 3-hexylthiophene derivatives in the aqueous solution comprising the polyelectrolyte obtained in step (b); d) adding a polymerization initiator and the latex obtained in step (a) to the solution comprising
- Step (a) of polymerization of the alkyl acrylate monomers can be carried out by any suitable technique accessible to those skilled in the art.
- this step can be carried out by the method described in application WO2007012736.
- Step (b) of solubilizing the electrolyte in aqueous solution can be carried out by any suitable technique accessible to a person skilled in the art.
- concentration of the polyelectrolyte in the aqueous solution can be adjusted by a person skilled in the art depending on the nature of the polyelectrolyte and the amount of EDOT monomers, EDOT derivatives or 3-hexylthiophene subsequently introduced.
- concentration of the polyelectrolyte may be such that the molar ratio of repeating units of the polyelectrolyte: monomers of EDOT, of EDOT derivatives or of 3-hexylthiophene is between 1: 2 and 2: 1, preferably approximately equal to 1: 1.
- the polyelectrolyte stabilizing the conductive polymer when the latter is poly (3,4-ethylenedioxythiophene) (PEDOT), in an aqueous solution is poly (sodium styrene sulfonate) (PSS).
- PEDOT poly (3,4-ethylenedioxythiophene)
- PSS poly (sodium styrene sulfonate)
- the aqueous solution in which the polyelectrolyte is solubilized in step (b) comprises water and sulfuric acid.
- sulfuric acid has a solubility parameter close to that of EDOT which probably promotes the compatibilization of EDOT monomers or EDOT derivatives in water.
- the sulfuric acid: EDOT in water mass ratio is preferably between 2: 1 and 1: 2, in particular it is about 1: 1.
- the aqueous solution comprising the polyelectrolyte obtained in step (b) does not include ethanol, methanol or chloroform.
- the aqueous solution comprising the polyelectrolyte obtained in step (b) comprises water as the sole solvent, or optionally a mixture of water and dimethyl sulfoxide (DMSO).
- Step (c) of adding the monomers can be carried out by simply adding the monomers to the solution.
- the monomers can be added in a solvent, for example water, DMSO or a mixture of water and DMSO. The addition can be carried out with stirring.
- Step (d) of adding a polymerization initiator and the latex can be performed by simultaneously adding the initiator and the latex.
- the polymerization initiator can be added first, then the latex.
- the initiator can be chosen from conventional polymerization initiators known to those skilled in the art. This may include, in particular, ammonium persulfate (APS).
- APS ammonium persulfate
- the addition can be made with stirring.
- Step (e) of polymerization of the monomers can be carried out under conventional conditions known to those skilled in the art for polymerizing said monomers.
- the polymerization of the monomers, in particular the EDOT monomers, in step (e) is carried out in the presence of a co-solvent.
- the co-sovant is dimethylsulfoxide (DMSO).
- DMSO dimethylsulfoxide
- DMSO makes it possible not to destabilize the suspension.
- DMSO can in particular be added during step (c), the addition of the monomers being in the form of adding a solution of monomers in a solvent comprising DMSO.
- DMSO is both water miscible and capable of solubilizing monomers, especially EDOT monomers.
- the polymerization of the monomers in step (e) is carried out in an aqueous medium comprising as the sole solvent water or a mixture of water and dimethyl sulfoxide.
- the aqueous medium in which step (e) is carried out does not include methanol, ethanol or chloroform.
- the method according to the invention further comprises, after step (e), a step (f) of adding a dopant.
- a dopant suitable for increasing the conductivity of the conductive polymer or of the mixture of the conductive polymer with the polyelectrolyte stabilizing it, such as the PEDOT: PSS mixture, can be used.
- the dopant can be selected from the group consisting of sulfuric acid and para-toluenesulfonic acid (APTS).
- step (e) of polymerizing the monomers at their surface since the process according to the invention is carried out in an aqueous dispersed medium, it is not useful to crosslink the core of the particles before carrying out step (e) of polymerizing the monomers at their surface. Indeed, in the case where the shell is synthesized in the presence of an organic co-solvent, it would be necessary to crosslink the core of the particles so that the latter is not dissolved in the solvent. On the contrary, in the process according to the present invention, crosslinking is not necessary. The absence of crosslinking of the core of the particles makes it possible to maintain the mobility of the polymer chains and the possibility of percolation of the two phases into one another, which contributes to a better stretchability of the particles and to a better conductivity of the latter.
- the present invention also relates to the use of electrically conductive nanocomposite particles according to the invention or obtained by a method according to the invention for printing on a stretchable support.
- the particles can be used in the form of a dispersion, in particular a dispersion in an aqueous medium, in particular in water.
- the solid content of the dispersion of particles is generally between 1 and 60% by weight of the dispersion, preferably 10 to 40% by weight.
- stretchable support denotes a material capable of withstanding an elongation of at least 120% in at least one direction without breaking, and on which the nanocomposite particles according to the invention, or a film formed from such particles, can be printed. .
- the stretchable material can withstand elongation in at least one direction of at least 150%, at least 200%, at least 250%, at least 300% or at least 500%.
- the stretchable backing may include a greater degree of stretchability in a first direction than in a second direction of the same plane.
- stretchable supports which can be used according to the invention, mention may be made of thermoplastic polymers, such as polypropylene, polyurethane, poly (ethylene terephthalate) or polyethylene. Elastomeric fibers and fabrics comprising such fibers can also be mentioned. Elastomeric fibers are known to be able to be stretched by at least 400% and then be able to recover their original shape. As examples of elastomeric fibers, mention may be made of elastane fibers (for example Lycra), natural or synthetic rubber fibers, olefins, polyesters, polyethers or their combinations, in particular elastic yarns comprising elastane and polyester. Stretchable supports comprising at least one of the examples of supports mentioned above, even if they do not consist thereof, can also be used according to the invention.
- thermoplastic polymers such as polypropylene, polyurethane, poly (ethylene terephthalate) or polyethylene.
- Elastomeric fibers and fabrics comprising such fibers can also be mentioned. Elastomeric fiber
- the printed stretchable support is selected from the group consisting of polypropylene, polyurethane, poly (ethylene terephthalate), polyethylene, elastane fibers, natural or synthetic rubber fibers, d olefins, polyesters, polyethers or combinations thereof.
- the term “printing” with a nanocomposite on a support is understood to mean depositing the nanocomposite on the substrate, for example by depositing a film of the nanocomposite or by impregnating the fibers of the substrate with the particles. nanocomposites, or with a dispersion of the nanocomposite particles in a solvent, preferably with the nanocomposite particles in their synthesis medium.
- the deposition can be carried out by any suitable technique known to those skilled in the art. For the deposition of a film, mention may in particular be made of the deposition of drops (drop casting), screen printing or deposition with equipment of the “Doctor Blade” type.
- the printing is carried out by depositing the nanocomposite particles on the support in the form of a film, or by impregnating all or part of the fibers of the support with a solution or suspension comprising the nanocomposite particles and at least a solvent.
- the Applicant has demonstrated that, unexpectedly, the use of the particles described above or of a dispersion containing them to print on a stretchable support makes it possible to obtain a print that is both stretchable and conductive, ie. that is, its conduction properties are retained even when the stretchable support is stretched, especially up to an elongation of 200%.
- the conduction properties are also maintained upon reverting to the unstretched state of the stretchable carrier, as well as after several cycles of elongation / reverting to the unstretched state.
- the present invention relates to a printed stretchable support, in which the printing comprises at least one particle according to the invention or obtained by a process according to the invention.
- the stretchable support printed according to the invention can obviously have each of the characteristics and preferred embodiments described in the section relating to the use of nanocomposite particles for printing on a stretchable support.
- the stretchable medium printed according to the invention can be used as such as a stretchable conductive material. It can also in some cases be used to form stretchable electrodes.
- the printed conductive substrate according to the invention can be used in a wide variety of fields such as wearable technologies (clothing or accessories comprising advanced computer and electronic elements, designated under the term “wearables” in English), printed electronics, but also coatings for housing or development.
- wearable technologies clothing or accessories comprising advanced computer and electronic elements, designated under the term “wearables” in English
- printed electronics but also coatings for housing or development.
- devices such as presence detectors and step sensors have been obtained according to the invention.
- a stretchable support printed according to the invention in particular in the case of Lycra, has a sensitivity to movement or to pressure which is markedly greater, in particular at least 10 times greater, than that observed with a similar support printed with a composite comprising core / shell particles having the same core as those of the present invention and a polyaniline shell as described in application WO2007012736.
- a stretchable support printed according to the invention is therefore particularly suitable for forming devices such as presence detectors or step sensors.
- a final object of the invention is a detection device sensitive to movement or to pressure, in particular a presence detector device, movement sensor or step sensor comprising a stretchable support printed according to the invention.
- v1 denotes a value lying in a range between 0.9 x v1 and 1.1 x v1, that is to say v1 ⁇ 10%, of preferably v1 ⁇ 5%, in particular v1 ⁇ 1%.
- the intervals of values denote the open intervals not including their limits.
- the terms “greater than” and “less than” refer to strict inequalities.
- test 1 of Table 1 The particles of test 1 of Table 1 are obtained according to the conditions of application WO2007012736.
- This synthesis is carried out from a latex of particles (core) with a diameter of 260 nm, stabilized with NP40 and Ninol L5 according to test 1 of Table 1 above.
- PSS is dissolved in water, then EDOT monomer is added with stirring to the resulting suspension.
- the EDOT: repeating units of PSS molar ratio is 1: 1.
- the polyalkylbutoxide latex obtained according to test 1 of Table 1 above is added, as well as the ammonium persulfate initiator.
- the polybutylate latex: EDOT weight ratio is 70:30. A stable dispersion with a conductivity of less than 0.001 S / cm is obtained.
- Post-doping of the particles obtained is carried out by adding 10% by mass of sulfuric acid or paratoluene sulfonic acid.
- the conductivities obtained are 8S / cm for sulfuric acid, and 2S / cm for paratoluene sulfonic acid.
- the PSS is first dissolved in a water / sulfuric acid mixture, then the EDOT is added to this solution. After stabilization, the alkyl polybutoxide latex with a diameter of 120 nm, stabilized with DTAB and BrijS100 according to test 4 of Table 1, is added with stirring. Finally, the ammonium persulfate initiator (APS) is introduced into the reaction system and the polymerization is continued at room temperature for 3 days.
- the EDOT: PSS: sulfuric acid molar ratio used is 1: 1: 1.
- the synthesis was carried out for four different latex polybutoxide: EDOT ratios different, 70:30, 75:25, 80:20 and 85:15. The conductivities are respectively 9 S / c, 20 S / cm, 3 S / cm and 0.5 S / cm.
- Example 2 Measurement of the resistance to stretching of composite films and substrates on which the composites are deposited
- thermoplastic polyurethane TPU
- thermoplastic polyurethane TPU
- a composite film of particles according to the invention with a PBuA: PEDOT ratio of 75:25, a core diameter of about 120 nm, stabilized with DTAB and BrijS100 according to test 4 of Table 1, and a conductivity of 20 S / cm was deposited on a polyurethane substrate by drop casting.
- the test piece is placed between two jaws of a motorized bench of the Versatest brand. The lower jaw is fixed and the upper jaw is mobile. The electrical contact is provided by gold needles which are in contact with the film inside the jaw while the resistance measurement is made by a keithley.
- the traction arm and keithley are connected to acquisition software that allows for stretch control. Thus, tensile cycles can be performed while measuring resistance.
- This test consists in determining the value of the resistance under stretching. Two phases of stretching are studied, the first during stretching (50 mm / min), the period during which the traction arm is in motion, and the second once the test piece has been stretched.
- the resistance of a sample is proportional to the ratio between the length (distance between the electrodes) of the test piece and its section (product of the width and the thickness).
- stretching the length increases and the section decreases, which leads to an increase in the value of resistance.
- relaxation takes place, leading to a decrease in the resistance value.
- FIG. 1 shows the evolution of the resistance of the substrate on which is deposited the composite according to the stretch. Stretch cycles were then performed with 120 and 150% stretches. The graphs showing the evolution of resistance and stretch as a function of time for these two tests are presented respectively in Fig. 2 and Fig. 3. An increase in resistance is observed when stretching, and a decrease in resistance is observed when relaxing. Whatever stretch is applied to the test piece, electrical continuity is maintained, and the resistance value when the substrate is relaxed returns to its initial value.
- a composite of particles according to the invention with a PBuA: PEDOT ratio of 75:25, a core diameter of approximately 120 nm, stabilized by DTAB and BrijS100 according to test 4 of Table 1, and a conductivity of 20 S / cm was deposited on a stretched Lycra substrate, which allows good impregnation of the fibers.
- the value of the resistance varies very quickly when the material undergoes movement. However, it is possible to measure resistance after stabilization. As shown in Fig. 4, the resistance value increases with stretching.
- the high sensitivity to movement of this composite / Lycra pair makes it a good candidate for all applications with high sensitivity, such as for example touch or presence sensors. After relaxation of the stretch, resistance returns to its original value.
- the aforementioned conductive composite has been coated on an elastic yarn composed of 60% elastane and 40% polyester. To do this, and in order to wet all the air-wire interface possible, the wire is first stretched to its maximum, then covered by the conductive composite and kept stretched for the time of drying. Once dry, tests similar to those carried out on thermoplastic polyurethane film or on textile were carried out, namely the monitoring of resistance as a function of stretching. The behavior observed is identical to that observed previously, the resistance increases during stretching and decreases during relaxation. Thus, cycles were performed at different stretch rates.
- Figs. 5 to 7 show that the test piece is neither damaged nor degraded by the stretching cycles undergone, and that the conductivity is retained during stretching and relaxation. The results were obtained for stretches of 110% (Fig. 5), 125% (Fig. 6), and 150% (Fig.7).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Physics & Mathematics (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymerisation Methods In General (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA3149591A CA3149591A1 (fr) | 2019-09-04 | 2020-09-02 | Particules nanocomposites electriquement conductrices possedant un coeur de polyacrylate d'alkyle et une ecorce de polymere conducteur |
US17/638,584 US20220289962A1 (en) | 2019-09-04 | 2020-09-02 | Electrically conductive nanocomposite particles with a poly alkylacrylate core and a conductive polymer shell |
EP20764389.1A EP4025650A1 (fr) | 2019-09-04 | 2020-09-02 | Particules nanocomposites électriquement conductrices possédant un coeur de polyacrylate d'alkyle et une écorce de polymère conducteur |
JP2022513837A JP2022546996A (ja) | 2019-09-04 | 2020-09-02 | ポリアルキルアクリレート・コア及び導電性ポリマー・シェルを有する導電性ナノコンポジット粒子 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FRFR1909720 | 2019-09-04 | ||
FR1909720A FR3100250B1 (fr) | 2019-09-04 | 2019-09-04 | Particules nanocomposites électriquement conductrices possédant un cœur de polyacrylate d’alkyle et une écorce de polymère conducteur |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021043820A1 true WO2021043820A1 (fr) | 2021-03-11 |
Family
ID=68138583
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2020/074462 WO2021043820A1 (fr) | 2019-09-04 | 2020-09-02 | Particules nanocomposites électriquement conductrices possédant un cœur de polyacrylate d'alkyle et une écorce de polymère conducteur |
Country Status (6)
Country | Link |
---|---|
US (1) | US20220289962A1 (fr) |
EP (1) | EP4025650A1 (fr) |
JP (1) | JP2022546996A (fr) |
CA (1) | CA3149591A1 (fr) |
FR (1) | FR3100250B1 (fr) |
WO (1) | WO2021043820A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114437603B (zh) * | 2022-03-10 | 2023-03-24 | 山东鑫纳超疏新材料有限公司 | 一种基于导电纳米粒子的耐久型超疏微液滴自清洁涂层的制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001092377A1 (fr) * | 2000-05-27 | 2001-12-06 | Q-Sys Co., Ltd. | Microgel electriquement conducteur et procede permettant de preparer ce microgel |
KR100481665B1 (ko) * | 2001-07-09 | 2005-04-08 | 주식회사 큐시스 | 전기전도성 폴리(싸이오펜) 비-수계 분산액, 이의제조방법 및 이의용도 |
DE102005030489A1 (de) * | 2005-06-30 | 2007-01-04 | Chemetall Gmbh | Verfahren zum Beschichten von feinen Partikeln mit leitfähigen Polymeren |
WO2007012736A2 (fr) | 2005-07-29 | 2007-02-01 | Uppa - Université De Pau Et Des Pays De L'adour | Particules nanocomposites electriquement conductrices possedant un coeur de polyacrylate d'alkyle et une ecorce de polyaniline |
WO2007111996A2 (fr) * | 2006-03-24 | 2007-10-04 | Clemson University | Encre polymère conductrice |
EP3221404A2 (fr) | 2014-11-19 | 2017-09-27 | Biotectix LLC | Revêtements polymères conducteurs pour substrats tridimensionnels |
WO2018061374A1 (fr) * | 2016-09-30 | 2018-04-05 | 積水化成品工業株式会社 | Particules de résine conductrice et utilisation desdites particules |
-
2019
- 2019-09-04 FR FR1909720A patent/FR3100250B1/fr active Active
-
2020
- 2020-09-02 US US17/638,584 patent/US20220289962A1/en active Pending
- 2020-09-02 WO PCT/EP2020/074462 patent/WO2021043820A1/fr unknown
- 2020-09-02 JP JP2022513837A patent/JP2022546996A/ja active Pending
- 2020-09-02 CA CA3149591A patent/CA3149591A1/fr active Pending
- 2020-09-02 EP EP20764389.1A patent/EP4025650A1/fr active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001092377A1 (fr) * | 2000-05-27 | 2001-12-06 | Q-Sys Co., Ltd. | Microgel electriquement conducteur et procede permettant de preparer ce microgel |
KR100481665B1 (ko) * | 2001-07-09 | 2005-04-08 | 주식회사 큐시스 | 전기전도성 폴리(싸이오펜) 비-수계 분산액, 이의제조방법 및 이의용도 |
DE102005030489A1 (de) * | 2005-06-30 | 2007-01-04 | Chemetall Gmbh | Verfahren zum Beschichten von feinen Partikeln mit leitfähigen Polymeren |
WO2007012736A2 (fr) | 2005-07-29 | 2007-02-01 | Uppa - Université De Pau Et Des Pays De L'adour | Particules nanocomposites electriquement conductrices possedant un coeur de polyacrylate d'alkyle et une ecorce de polyaniline |
WO2007111996A2 (fr) * | 2006-03-24 | 2007-10-04 | Clemson University | Encre polymère conductrice |
EP3221404A2 (fr) | 2014-11-19 | 2017-09-27 | Biotectix LLC | Revêtements polymères conducteurs pour substrats tridimensionnels |
WO2018061374A1 (fr) * | 2016-09-30 | 2018-04-05 | 積水化成品工業株式会社 | Particules de résine conductrice et utilisation desdites particules |
Non-Patent Citations (4)
Title |
---|
CHIEH-HAN WU ET AL: "Conductive composite particles synthesized via pickering emulsion polymerization using conductive latex of poly(3,4-ethylenedioxythiophene) (PEDOT) as stabilizer", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 53, no. 5, 5 January 2012 (2012-01-05), pages 1086 - 1092, XP028457032, ISSN: 0032-3861, [retrieved on 20120109], DOI: 10.1016/J.POLYMER.2012.01.005 * |
HSUEH-YUNG CHEN ET AL: "Core-shell composite latexes derived from PEDOT:PSS dispersion and the preparation of conductive, flexible and transparent films", JOURNAL OF MATERIALS CHEMISTRY C, vol. 1, no. 34, 26 June 2013 (2013-06-26), GB, pages 5351, XP055697105, ISSN: 2050-7526, DOI: 10.1039/c3tc30907j * |
HUI-EN YIN ET AL: "Innovative elastic and flexible conductive PEDOT:PSS composite films prepared by introducing soft latexes", JOURNAL OF MATERIALS CHEMISTRY, vol. 22, no. 9, 20 January 2012 (2012-01-20), GB, pages 3800, XP055697456, ISSN: 0959-9428, DOI: 10.1039/c2jm15689j * |
SEUNG MO LEE ET AL: "Morphological and spectroscopic analyses of poly(alkyl methacrylate)/poly(thiophene) composite nanoparticles prepared by dual initiation system", COLLOID AND POLYMER SCIENCE ; KOLLOID-ZEITSCHRIFT UND ZEITSCHRIFT FÜR POLYMERE, SPRINGER, BERLIN, DE, vol. 291, no. 1, 12 September 2012 (2012-09-12), pages 33 - 44, XP035160730, ISSN: 1435-1536, DOI: 10.1007/S00396-012-2791-Y * |
Also Published As
Publication number | Publication date |
---|---|
EP4025650A1 (fr) | 2022-07-13 |
FR3100250B1 (fr) | 2022-06-03 |
JP2022546996A (ja) | 2022-11-10 |
CA3149591A1 (fr) | 2021-03-11 |
FR3100250A1 (fr) | 2021-03-05 |
US20220289962A1 (en) | 2022-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ruckenstein et al. | Processable conductive polypyrrole/poly (alkyl methacrylate) composites prepared by an emulsion pathway | |
JP5139088B2 (ja) | 分散液及びその製造方法 | |
EP2392550B1 (fr) | Nouvelles dispersions aqueuses stables de nanoparticules de polymères thermoplastiques haute performance et leurs utilisations comme agents filmifiants | |
US8709292B2 (en) | Polymer composites having highly dispersed carbon nanotubes | |
JP5310985B2 (ja) | 帯電防止剥離層を形成するための塗料及び帯電防止剥離フィルム | |
EP3963015A1 (fr) | Particules nanocomposites conductrices étirables | |
EP1954869B1 (fr) | Preparation de substrats fibreux superhydrophobes | |
CA2616341C (fr) | Particules nanocomposites electriquement conductrices possedant un coeur de polyacrylate d'alkyle et une ecorce de polyaniline | |
US20140364574A1 (en) | Surface-Selective Carbon Nanotube Deposition via Polymer-Mediated Assembly | |
EP2834305B1 (fr) | Copolymeres a bloc dispersants de nanocharges dans l' eau | |
WO2021043820A1 (fr) | Particules nanocomposites électriquement conductrices possédant un cœur de polyacrylate d'alkyle et une écorce de polymère conducteur | |
EP2291228B1 (fr) | Materiau polyhipe a haute tenue mecanique, son procede de preparation, emulsion utile pour sa preparation et article constitue d'un tel materiau | |
Visakh | Polyaniline-based blends, composites, and nanocomposites: state of the art, new challenges, and opportunities | |
CA2717375C (fr) | Procede de preparation de films de polyaniline et films hautement auto-orientes obtenus | |
EP0550349B1 (fr) | Compositions électroconductrices de polymères contenant des composés amphiphiles polymérisables dérivés du pyrrole, leur obtention et leur utilisation | |
EP4263620A1 (fr) | Acide hyaluronique modifié comme dopant de polymères de type pedot et/ou pprodot | |
FR3063501A1 (fr) | Synthese de fibres et textiles electroniques a base de polymeres conducteurs | |
EP1305806A1 (fr) | Preparation de materiaux composites conducteurs par depot d'un polymere conducteur dans un substrat poreux isolant et solution utile pour cette preparation | |
Jorge et al. | Oxetanes as polymerizable additives to PEDOT: PSS for water-resistant and transparent electrodes | |
EP4324789A1 (fr) | Procédé de production d'une dispersion de nanotubes monofeuillets semi-conducteurs | |
FR2936722A1 (fr) | Materiaux nanocomposites et procede de fabrication par nanoprecipitation. | |
WO2010097561A2 (fr) | Nouveaux copolymères amphiphiles comprenant un groupe colorant, leur procédé de préparation et leurs utilisations comme pigments |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20764389 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 3149591 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref document number: 2022513837 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2020764389 Country of ref document: EP Effective date: 20220404 |