Classifications

• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
  • C08J3/246—Intercrosslinking of at least two polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B64—AIRCRAFT; AVIATION; COSMONAUTICS
  • B64G—COSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
  • B64G1/00—Cosmonautic vehicles
  • B64G1/22—Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
  • B64G1/42—Arrangements or adaptations of power supply systems
  • B64G1/44—Arrangements or adaptations of power supply systems using radiation, e.g. deployable solar arrays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B64—AIRCRAFT; AVIATION; COSMONAUTICS
  • B64G—COSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
  • B64G1/00—Cosmonautic vehicles
  • B64G1/22—Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
  • B64G1/46—Arrangements or adaptations of devices for control of environment or living conditions
  • B64G1/50—Arrangements or adaptations of devices for control of environment or living conditions for temperature control
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
  • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
  • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
  • G02F1/15165—Polymers
• • 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
• • 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
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F2203/00—Function characteristic
  • G02F2203/11—Function characteristic involving infrared radiation

Definitions

• the present invention relates to materials in the form of a semi-interpenetrating network of polymers (semi-RIP) or interpenetrating polymer network (RIP) of symmetrical structure BAB wherein A is an ion-conductive polymer network (or RIP) under the form of a layer and B is an electronically conductive polymer and is interpenetrated in the polymer network layer (or RIP) A.
• the invention also relates to a method of preparing these materials, as well as to a device electrically modulatable emissivity (or reflectivity) based on these materials.
• the invention furthermore relates to the use of a material according to the invention as a stealth material, a material for improving the thermal insulation, a material for the replacement of the venetian shutters of the panels of the artificial satellites, and / or material to control the temperature according to the solar exposure or the outside temperature.
• references in brackets [] refer to the list of references at the end of the text.
• Emissivity can be defined as the property of the surface of a body to emit heat by radiation, expressed by the ratio between the radiation emitted by that surface and that emitted by a body that absorbs and transmits the entire radiation that reaches it (called black body); both bodies being at the same temperature. Emissivity therefore represents the ability of a material to absorb or emit heat.
• a device capable of modulating its emissivity can be used in various fields such as infrared camouflage or energy savings. Of the variable emissivity systems, electro-emissive devices are of great interest because of the ease of applying electrical voltage.
• electro-emissive devices Only one of the components of the electro-emissive devices is capable of modulating its emissivity: it is the active layer.
• the composition of electro-emissive systems is not however limited to this active layer: they usually consist of several stacked layers (between 5 and 7) all having a very specific role and essential to electro-emissive systems.
• their development is both expensive and complex.
• the present invention is specifically intended to meet these needs and disadvantages of the art by providing a material in the form of semi-interpenetrating network of polymers (semi-RIP) or interpenetrating network of polymers (RIP) of symmetrical structure BAB in which :
• A is an ion-conductive polymer network (or RIP) in the form of a layer
• Polymer B is an electronically conductive polymer and is interpenetrated in the polymer (or RIP) network layer A; and • Polymer B is present at a content of 0.5 to 2.5% by weight relative to the total weight of the material.
• Electron-conductive Polymer Interpenetrated Networks have a gradient-like structure: the surface is rich in electronically conductive polymer, whereas the core is completely devoid of it.
• the inventors have succeeded in designing a suitable material especially for the development of an electro-emissive device.
• the material according to the invention has all the layers necessary for an electro-emissive device (variable emissivity layer, ion reserve, mechanical support, current collectors) and, moreover, is in the form of a single block which simplifies the architecture of this type of device and, therefore, its development. Furthermore, the material of the invention has the advantage of having the ability to modulate its emissivity.
• the polymer network (or the RIP) A may be a copolymer network or an interpenetrating network of (co) polymers.
• interpenetrating network of polymers within the meaning of the present invention means a matrix or assembly consisting of at least two polymers crosslinked one inside the other thus forming two or several networks. This polymer assembly thus combines the properties of the polymers that make it up.
• a matrix or an assembly consisting of at least one crosslinked polymer, forming a network, and at least one non-crosslinked polymer, entangled in the first network and not forming a second network.
• polymer in the sense of the present invention denotes a macromolecule consisting of linear or branched chains whose structure essentially results from the repetition of constitutive units derived from monomers.
• copolymer in the sense of the present invention denotes a polymer whose constituent units are derived from more than one kind of monomer.
• polymer network is intended to mean a network consisting of one or more crosslinked polymers (or copolymers), that is to say of one or more polymers whose chains are connected to each other by covalent bonds.
• an "electronically conductive polymer” is a polymer having delocalized bonds, in particular a ⁇ -conjugated polymer.
• electronically conductive polymers that may be used, mention may be made, for example, of polypyrroles, polyparaphenylenes, polythiophenes, polyanilines, polycarbazoles and polyacetylenes, these various polymers being optionally substituted, for example by non-polar groups (aliphatic chain, alkoxy group). , fluorine-based substituent, etc.) or polar (aliphatic chain terminated by a sulfonate or carboxylate function, etc.)
• the term "ionic conductive polymer” means a polymer that can be easily complexed with organic and inorganic salts and possibly having polar groups, for example ether, amine, alcohol or other groups.
• the term "suspending branch” means a polymer chain connected to the polymer network by a single point.
• the terms "polyethylene glycol” (PEG) or “polyethylene oxide” (POE) are indifferently used to designate ethylene oxide polymers with molecular weights of 300 g / mol to 10,000000 g / mol.
• alkyl means a linear, branched or cyclic, optionally substituted and / or unsaturated carbon radical comprising 1 to 18 carbon atoms, for example 1 to 6 carbon atoms, for example 1 to 6 carbon atoms. 4 carbon atoms. Mention may be made, for example, of methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, cyclohexyl and the like.
• heteroalkyl in the sense of the present invention, an alkyl radical as defined above, said alkyl system comprising at least one heteroatom, especially selected from the group consisting of sulfur, oxygen, nitrogen, boron. Examples that may be mentioned are alkoxy groups, ether groups, and the like.
• aryl means an aromatic system comprising at least one ring which satisfies Hekel's aromaticity rule. Said aryl is optionally substituted and may comprise from 6 to 22 carbon atoms, for example 6 to 10 carbon atoms. Mention may be made, for example, of phenyl, naphthyl, indolyl, anthracyl and the like.
• heteroaryl means a system comprising at least one aromatic ring of at least 5 members, of which at least one ring of the aromatic ring is connected to a heteroatom, in particular chosen from the group comprising sulfur, oxygen, nitrogen, boron.
• Said heteroaryl is optionally substituted and may comprise from 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms. Examples that may be mentioned include pyridyl, pyrimidyl, thienyl, furanyl, pyrrolyl, furyl, quinolyl, indolyl, pyrazinyl and the like.
• substituted for example means the replacement of a hydrogen atom in a given structure by a radical selected from the group consisting of alkyl, heteroalkyl, aryl, heteroaryl, a polar group, halogen, halogenated alkyl, etc. When more than one position may be substituted, the substituents may be the same or different at each position.
• polar groups denotes, for example, the ester, ether, amine, alcohol, -CN, -COOH, -OH, -NH 2 , -SO 3 H, etc. groups.
• ambient temperature in the sense of the present invention can be a temperature ranging from 15 to 30 ° C., preferably from 20 to 25 ° C.
• swelling can be defined as following. When a network of a polymer (crosslinked polymer or simple network) or a RIP (mixture of at least two networks) are put in contact with a liquid, they are incapable of dissolving by nature (the solvent can not break connections and interactions to lead to dissolution). By cons, it can penetrate more or less in the material causing a mechanical effect of swelling.
• the polymer network (or RIP) A may have polar chemical groups selected from the group consisting of -CN, -COOCH 3 , -COOH, -OH, -NH 2 and ether groups.
• polar chemical groups selected from the group consisting of -CN, -COOCH 3 , -COOH, -OH, -NH 2 and ether groups. The presence of the polar chemical groups allows the penetration of an electrolyte into the polymer network (or the RIP) A.
• the polymer network (or RIP) A may be chosen from the group comprising polyethylene oxide (POE), nitrile butadiene rubber (NBR), poly-tetrahydrofuran (PTHF), polycarbonate, derivatives cellulose, poly (meth) acrylates C1-C4 alkyl, or a mixture thereof forming an interpenetrating network of (co) polymers.
• the cellulose derivatives may be, for example, methyl cellulose or cellulose acetate butyrate.
• alkyl poly (meth) acrylates there may be mentioned more particularly polymethyl methacrylate (PMMA).
• PMMA polymethyl methacrylate
• the use of other polymers in the constitution of the materials of the present invention further improves the flexibility and stability of semi-RIPs.
• the POE in the materials of the invention, is partially or even completely replaced by a derivative of rubber or an elastomer, for example nitrile butadiene rubber (NBR).
• NBR nitrile butadiene rubber
• This type of polymer may have mechanical properties much higher than those of POE and a much greater stability for a temperature above ambient.
• monobloc devices electro-emissive in the infrared comprising this type of material, can have very competitive performance compared to competing systems based on organic materials and / or inorganic
• the polymer network (or the RIP) A can be densified into polar chemical groups by branching the networks.
• the densification in polar chemical groups by branching of the networks allows a better penetration of an electrolyte into the polymer network (or the RIP) A.
• the polymer network (or the RIP) A can comprise a branching rate by pattern from 1 to 99% by number of monomer constituting the pendent branch, preferably from 35 to 83% by number.
• the polymer network (or RlP) A is polyethylene oxide (POE) having a content of pendant branches of 50% by weight relative to the total mass of POE.
• POE polyethylene oxide
• (or the RIP) A can have a thickness of between 10 and 500 micrometers.
• B is an electronically conductive polymer (ECP).
• ECP electronically conductive polymer
• the polymer content B gives the material of the present invention improved optical properties.
• the polymer content B may be 0.5 to 3%, for example from 0.8 to 2%, for example from 0.8 to 1.6, for example from 0.9 to 1.2, by weight relative to the total weight of the material.
• the polymer content B is advantageously from 0.8 to 2% by weight relative to the total weight of the material.
• the polymer B may be chosen from the group comprising poly (3,4-ethylenedioxythiophene) (PEDOT), poly (3,4-propylenedioxythiophene), polypyrrole (PPy), polyaniline (PANI) or one of these polymers substituted with an aliphatic chain, a C1-C18 alkoxy group or a polar group such as carboxylate (-R-COOX), sulphonate (-RSO3X), alcoholate (-R-OX).
• PEDOT poly (3,4-ethylenedioxythiophene)
• Py polypyrrole
• PANI polyaniline
• R can be chosen from the group comprising alkyls, heteroalkyls, aryls, heteroaryls, and X can be chosen from the group comprising a hydrogen, an alkaline cation such as for example Li +, Na +, K +, etc.
• Polymer B is advantageously poly (3,4-ethylenedioxythiophene) (PEDOT).
• PEDOT poly (3,4-ethylenedioxythiophene)
• the polymer B is interpenetrated into the polymer network layer (or RIP) A so that the B content decreases from the outer surface of the BAB material to the center of the material where only A is present.
• polymer B may be interpenetrated in the polymer network layer (or RIP) A to a thickness of 0.5 to 30% with respect to the thickness of the polymer network layer (or RIP). AT.
• the present invention also relates to a method for preparing a material according to the invention comprising the following successive steps:
• the monomer MB can be chosen from the group comprising (3,4-ethylenedioxythiophene (EDOT), 3-4 propylenedioxythiophene (PRODOT), pyrrole, aniline or one of these monomers substituted with an aliphatic chain, a alkoxy group or a polar group such as carboxylate, sulfonate, alcoholate.
• the monomer MB is, more particularly, (3,4-ethylenedioxythiophene (EDOT)).
• the formation of the polymer-impregnated polymer network layer A MB may include a step of crosslinking a precursor polymer A, this precursor being a crosslinkable polymer, optionally presence of MB monomer. During this step:
• the precursor may be chosen from the group comprising nitrile butadiene rubber (NBR), methylcellulose and cellulose acetate butyrate; and / or the crosslinking of the polymer A precursor can be carried out by reaction with a chemical compound selected from the group consisting of sulfur, peroxides, polyisocyanates and aldehydes.
• NBR nitrile butadiene rubber
• methylcellulose and cellulose acetate butyrate methylcellulose and cellulose acetate butyrate
• crosslinking of the polymer A precursor can be carried out by reaction with a chemical compound selected from the group consisting of sulfur, peroxides, polyisocyanates and aldehydes.
• the formation of the MB monomer impregnated polymer (or RIP) network layer may comprise a step of polymerizing a precursor MA monomer or monomer mixture (s). ) of the polymer (or RIP) A, optionally in the presence of the monomer MB.
• the formation of the monomer impregnated polymer network layer (or RIP) MB may further comprise a step of impregnating the polymer network layer A with the monomer MB.
• the polymerization may be a radical polymerization.
• the radical polymerization can be carried out according to one or more of the following conditions:
• the monomer or monomer mixture MA is selected from the group consisting of poly (ethylene glycol) methacrylate (MSL), poly (ethylene glycol) dimethacrylate (PEGDM) 1 polymethyl methacrylate, polyacrylonitrile or a mixture thereof;
• the monomer or monomer mixture MA is in the form of a mixture of two monomers in May and MA2;
• the monomer or monomer mixture MA is in the form of an equimolar mixture of two monomers MAI and MA2;
• MA2 are respectively polyethylene glycol) methacrylate (MSL) and poly (ethylene glycol) dimethacrylate (PEGDM);
• the MB monomer is present initially at a concentration of 1 to 20% by total weight of monomer or monomer mixture MA, preferably at a concentration of 5%;
• radical polymerization is conducted in the presence of a radical initiator
• the radical initiator is present initially at a concentration of 1 to 5% by total weight of the monomer or monomer mixture MA.
• the radical initiator may be, for example, chosen from the group comprising 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2-amidinopropane) hydrochloride (AAPH), 2,2'-azobis-isobutyronitrile azobis (2,4-dimethylvaleronitrile) (AMVN), dicyclohexyl peroxycarbonate (PCDH), benzoyl peroxide.
• AIBN 2,2'-azobisisobutyronitrile
• AAPH 2,2'-azobis (2-amidinopropane) hydrochloride
• AMVN 2,2'-azobis-isobutyronitrile azobis (2,4-dimethylvaleronitrile)
• PCDH dicyclohexyl peroxycarbonate
• benzoyl peroxide benzoyl peroxide.
• Step (i) can be performed according to one or more of the following conditions: • by heat treatment or light curing
• step (ii) can be carried out according to one or more of the following conditions:
• the oxidant is chosen from the group comprising FeCb, ferric tosylate; ferric sulphate or cerium and ammonium nitrate;
• Contacting is performed by immersing the layer of the polymer network A impregnated with monomer M 8 in a solution comprising the oxidant;
• the solution comprising the oxidant has an oxidizing concentration of 0.1 to 2 mol / liter
• the solution comprising the oxidant comprises a solvent chosen from water, chloroform, dichloromethane, acetonitrile, C 1 to C 4 alcohols,
• the contacting is carried out at a temperature of -10 to 80 ° C .;
• the contacting is carried out for a period of 10 minutes to 24 hours.
• the setting of contact is carried out for example by immersion in an oxidizing solution of concentration 1M, for example- at the following temperature and time conditions: 50 0 C +/- 2 ° C for 60 min +/- 1 min, 25 ° C +/- 2 ° C for 24h +/- 1h or 35 ° C +/- 2 0 C for 5h +/- 1h.
• concentration 1M 3,4-ethylenedioxythiophene
• the material of the invention may also be prepared by an electrochemical synthesis process in which the monomer MB precursor of the polymer B is electropolymerized in the polymer network (or RIP) A.
• the process for preparing a material according to the invention may comprise the following successive steps:
• a washing step may optionally be carried out after steps (ii) and / or (iv).
• the electrochemical synthesis of semi-RIP pyrrole / poly (vinyl alcohol) has already been described [2].
• Steps (i), (ii), (iii) and (iv) can be carried out according to one or both of the following conditions:
• the electrolyte consists of a solvent chosen from acetonitrile, propylene carbonate, water, dichloromethane and an electrolyte with a concentration of 0.1 to 1 mole / liter chosen from salts containing a cation. lithium, sodium, potassium or tetraalkylammonium and anion perchlorate, hexafluorophosphate, tetrafluoroborate.
• the electrolyte may also be an ionic liquid having a melting point below 0 ° C.
• the electrolytic medium comprises a solvent in which is dissolved a salt and the monomer M B has a monomer concentration of 0.1 to 1 mole / liter.
• the process steps (ii) and (v) can be carried out in an electrochemical cell according to one or more of the following conditions:
• the electrochemical cell (FIG. 15) having a thickness of between 2 and 6 mm, uses a conventional assembly with three electrodes.
• the cell consists of a working electrode chosen from a glass of ITO (Indium Tin Oxide), a platinum plate, a stainless steel plate, a counter electrode chosen from a platinum-plated titanium grid, a grid or a fabric of stainless steel (or other metal or metal alloy, preferably unalterable) to allow the species present in the medium to easily access the reaction site and a reference electrode such as a silver wire.
• the electrolyte and MB monomer impregnated polymer (or RIP) network layer is disposed between the working electrode and the counter electrode.
• a separating membrane is interposed between the network layer of electrolyte-impregnated polymers A and monomer M B and the counter electrode in order to avoid any short-circuit between the electrodes and for a better circulation of the electrolytic species.
• the separating membrane is chosen from filter paper, PVC.
• the bringing into contact is carried out at a temperature of -10 ° C. to 80 ° C. • The bringing into contact is carried out for a period of 30 minutes at
• Steps (ii) and (iv) can be performed at controlled potential or potentiostatic mode with a potential ranging from 1.0V to 1.4V.
• the solvent is selected from methanol, acetonitrile, propylene carbonate, dichloromethane, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran.
• the material of the invention may be prepared by a process comprising the following successive steps:
• a washing step may optionally be carried out after steps (ii) and / or (iv).
• step (iv) can be carried out according to one or more of the following conditions:
• the oxidant is chosen from the group comprising ferric chloride, ferric tosylate, ferric sulphate or cerium nitrate and ammonium.
• the contacting is performed by immersing the side 2 of the polymer network layer A impregnated with MB monomer in an oxidizing solution.
• the contacting is performed by protecting the face 1 of the polymer network layer A of the oxidant with a protective film selected from a Teflon film, glass, filter paper.
• the solution comprising the oxidant has an oxidant concentration of 0.1 to 2 mol / liter. • The solution comprising the oxidant comprises a solvent selected from water, chloroform, dichloromethane, acetonitrile.
• the contacting is carried out at a temperature of -10 ° C. to 80 ° C.
• the contacting is carried out for a period of 30 minutes to 24 hours.
• the material of the invention may be prepared by a process comprising the following successive steps:
• a washing step may optionally be carried out after steps (ii) and / or (iv).
• Press assembly in step (v) can be performed in one or more of the following conditions:
• the assembly in press is carried out under a pressure of 2 tons. • Assembly in press is carried out at a temperature between 150 0 C and 185 ° C.
• the present invention also relates to an electro-emissive device (DEE) comprising a material according to the invention.
• DEE electro-emissive device
• the device of the invention has the advantage of not requiring a layer of gold to function.
• ECPs electronically conductive polymers
• ITO glass interfering a layer of conductive glass
• reflective gold a thin layer of reflective gold without which the system works poorly or not at all.
• the material plays both the role of current collector and reflective layer with a flexible reflectivity.
• the device also contains an electrolyte.
• the electrolyte may for example be a liquid electrolyte combining an organic solvent and a soluble salt in this solvent or an ionic liquid having a melting point below 0 ° C.
• the electrolyte may be present at a concentration of between 20 and 150% by weight relative to the total weight of the material.
• the electrolyte may be chosen from organic salts or inorganic salts.
• the electrolyte may, for example, be chosen from imidazolium, pyrrolidium, quaternary ammonium and phosphonium salts, lithium and sodium salts, in a solvent.
• the electrolyte may also be chosen, for example, from imidazolium, pyrrolidium, quaternary ammonium or phosphonium salts, used without a solvent, because of their ionic liquid character at a temperature below 0 ° C.
• the device is inflated to saturation electrolyte. This has the advantage of reducing the response time of the electrolyte.
• the invention also relates to the use of the material according to the invention in one of the following applications:
• thermo insulation for example in the building, and / or
• FIG. 1 schematically represents the interpenetrating structure of the polymer B in a polymer network A inside an electroemissive monobloc device in the infrared.
• the surface consists mainly of PEDOT 1 while the core of the material consists only of the EPS.
• the PEDOT in black
• FIG 1 (a) is a schematic representation of the devices developed by the inventors. These devices consist on the one hand of an electrolyte carrier polymer (EPS) based on a 3D network of poly (ethylene oxide) (POE). This EPS is in the form of a flexible thin film, whose constituents are sufficiently polar so that the EPS is inflated by an electrolyte.
• An electronically conductive polymer (ECP), poly (3,4 (ethylene dioxythiophene) (PEDOT), is interpenetrated into the surface of both sides of the EPS, as shown schematically in Figure 1 (b).
• ECP electronically conductive polymer
• PEDOT poly (3,4 (ethylene dioxythiophene)
• FIG. 2 shows the reflection spectra of electro-emissive monoblock devices the infrared as a function of the doping state of the active layer
• the wavelength, expressed in ⁇ m, is represented as abscissa and the reflection as ordinate
• Figure 2 represents the "extreme" spectra in reflection of the layer
• the material has been subjected to a potential difference of ⁇ 1, 2 V.
• FIG. 3 represents photographs taken from a video filmed in band III of a prototype of electro-emissive monoblock devices.
• the color change of the material corresponds to a variation of the reflection of 30%.
• the color variation corresponds to a change of 25 ° C in the apparent temperature, the actual temperature being of the order of 60 ° C.
• the response time time required for the device to switch from 'one extreme optical state to another
• the response time is a property that depends on several factors, in particular temperature. Spectro-electrochemical coupling made it possible to measure a response time which is of the order of one minute at approximately 25 ° C.
• the video whose images were extracted in Figure 3, was filmed at 60 0 C. The answer to this temperature time is ten seconds.
• the speed of change of state in other words the "speed of camouflage" is a crucial factor, and the semi-RIPs designed have a good speed of execution.
• FIG. 4 represents the evolution of the reflection spectra in the Near Infrared of the active surface of monobloc electro-emissive devices in open circuit.
• the wavelength, expressed in ⁇ m, is represented as abscissa and the percentage of reflection as ordinate.
• the memory effect is the ability of the device to remain in an optical state when the electrical circuit is open.
• the reflection spectra of the reduced state are shown in FIG. 4 and were measured as a function of time. Only the evolution of the% R of the reduced state is reported here. Indeed, he This is the least stable state, which is the limiting factor of device stability. After 5 hours, the reflectivity increased by 3%. After 19 hours, the% R varied by 7%. The system therefore has good optical stability, and the energy inputs so that the system remains in an optical state are very limited.
• FIG. 5 represents the charge density of electro-emissive monoblock devices during a reflection state change.
• the extreme curves represent respectively the 100th and the 30,000th cycle.
• a characterization, conducted on electro-emissive monobloc devices in the infrared, is the determination of their cyclability. The latter represents the number of consecutive optical state changes that the material can undergo before presenting a decrease in its performance.
• Figure 5 shows the evolution of the charge density of a RIP subjected to ⁇ 1, 2V cycles with a duration of 1 minute. For 30 seconds, a voltage of 1.2V is applied to the material. After this time, the voltage is reversed for another 30 seconds, and so on. This measurement was carried out at room temperature and under ambient atmosphere.
• FIG. 6 represents a summary diagram of the synthesis of the semi-RIPs POE / PEDOT.
• FIG. 7 schematically represents the formation of a POE network with pendant branches.
• FIG. 8 schematically represents the measurement support used to characterize the infrared reflection properties of the semi-RIPs.
• FIG. 9 represents the evolution of contrast in reflection at 2.5 ⁇ m of semi-RIP POE / PEDOT as a function of the PEDOT content.
• the mass content in PEDOT is represented on the abscissa and the contrast in reflection at 2.5 ⁇ m of semi-RIP POE / PEDOT on the ordinate.
• FIG. 10 represents in (a) spectroelectrochemistry in the
• Figure 11 shows the reflection spectra of a semi-RIP.
• the shaded areas represent bands II (3-5 ⁇ m) and bands III (8-12 ⁇ m).
• the spectra between 0.8 ⁇ m and 2.5 ⁇ m are measured using a Jasco
• V570 Beyond 2.5 ⁇ m, the measurements are performed using a SOC 100.
• Figure 12 shows the evolution of the response time as a function of the electrolyte content for the reflective / absorbent transition
• the swelling rate expressed as mass (% w) and the response time as 90% of the contrast, expressed in seconds, as ordinate.
• FIG. 13 represents the evolution of the response time for the absorbent / reflector transition as a function of the operating temperature of the DEE whose swelling ratio in EMImTFSI is 20% by mass.
• the actual temperature, expressed in 0 C, is represented on the abscissa and the response time at 90% of the contrast, expressed in seconds, as ordinate.
• Figure 14 (a) shows the reflection spectra in the IR of a DEE over time in open circuit. The wavelength, expressed in ⁇ m, is indicated on the abscissa and the percentage of reflection on the ordinate.
• Figure 15 shows the mounting of an electropolymerization cell.
• PEGM Poly (ethylene glycol) methacrylate methyl ether
• Lithium bis (trifluoromethylsulfonyl) imide LiTFSI, 99.95%, (Aldrich)
• semi-RIP POE / PEDOT materials are referred to as semi-RIP POE / PEDOT, or simply semi-RIP.
• the synthesis of thin films of conductive semi-RIPs having electro-emissivity properties is carried out in two main steps as described below.
• the first step in the synthesis is the development of a poly (ethylene oxide) (POE) based network containing the 3,4-ethylenedioxythiophene (EDOT) monomer used as a solvent and which will lead to PEDOT.
• POE poly (ethylene oxide)
• EDOT 3,4-ethylenedioxythiophene
• the host matrix (or POE network) is composed of a three-dimensional network in which are present dangling chains. These provide a plasticizing effect to the system and promote the mobility of ionic species.
• DMA analyzes and ionic conductivity measurements, it was decided to use materials whose content of pendant branches is 50% by mass relative to the total mass of POE. Indeed this is the best compromise between the ionic conductivity and the mechanical strength of the material.
• the copolymerization of PEGM and PEGDM is carried out in the presence of a radical initiator: 2,2 'azobis-isobutyronitrile (or AIBN) whose mass represents 1% of the total mass of monomers
• the semi-RIPs are prepared from the solution (PEGM / PEGDM / AIBN) which has just been described, to which is added 5% by weight of EDOT monomer.
• the second step in the preparation of POE / PEDOT semi-RIPs is to form the Electronic Conductive Polymer (or PEDOT).
• PEDOT Electronic Conductive Polymer
• POE 50/50 networks containing 5% by weight of EDOT are immersed in 100 ml of an oxidizing solution, the concentration of FeCl3 is 0.23 mol / l.
• the polymerization of the EDOT is carried out at 50 ° C. for 1 hour. At the end of this polymerization, the materials are successively immersed in several baths of methanol in order to remove the excess of FeCl 3 and the EDOT which has not polymerized. The edges of the sample are cut to eliminate short circuits.
• the resulting materials of this synthesis have a heterogeneous distribution of PEDOT in the thickness of the matrix ( Figure 1).
• This heterogeneous distribution represents all the originality of the architecture of the semi-RIPs since it allows to find the configuration (Anode / Electrolyte / Cathode) of the Electro-Emissive Devices in the form of a single block.
• the synthesis of semi-RIPs has been studied in order to obtain materials whose PEDOT content is close to 1% by mass.
• the study of the influence of the I 1 EDOT polymerization parameters presented here is based on the PEDOT mass contents of the systems obtained, the determination of which was carried out by elemental analysis on the S element.
• Table 1 summarizes the PEDOT mass contents of POE / PEDOT networks whose only differences in the synthesis conditions are the duration and / or the polymerization temperature of the EDOT.
• the POE / PEDOT semi-RIPs whose synthesis has just been described, can be directly used as an Electro-Emissive Device (or EEM) once they are inflated with an electrolyte.
• Their optical performances are characterized by means of a measurement support, shown schematically in FIG. 8. It is composed of two epoxy plates metallized with gold by a PVD (Physical Phase Vapor Deposition) process. The DEEs are inserted between these two epoxy plates. A window is cut in one of the faces of the support in order to be able to characterize the changes of optical properties of the considered surface, named "active surface", or "active layer” in the rest of this presentation.
• This support designed to adapt to the different spectrophotometers used, makes it possible to apply a given potential difference between the two faces of the DEE and to measure the reflection, the emissivity, or the apparent temperature, (depending on the nature of the experiment) of the active surface.
• Oxidized PEDOT has high reflectivity. Conversely, it is poorly reflective (and therefore very absorbent) when it is reduced. In terms of DEE, this translates into an emissivity variation of the active surface: the oxidized PEDOT is less emissive than the reduced PEDOT. The application of a positive potential difference has the effect of reducing the emissivity of the active surface, and vice versa.
• the characterizations of the DEEs carried out relate electrochemistry and optical concepts. The relationships between these relationships are summarized in Table 2 to assist in understanding future descriptions.
• the PEDOT content of semi-RIPs is the parameter that has the most importance on their optical properties.
• the appearance of the spectra in reflection in the PIR as a function of the voltage applied across the DEEs is shown in FIG. 10.
• the 3-dimensional representation makes it possible to better appreciate the variation of the spectra between 1000 nm and 1500 nm.
• each applied voltage corresponds a spectrum in reflection and a reflection value at 2.5 .mu.m. This means that it is possible to choose which reflection value should display the semi-RIP, highlighting the adaptability of these materials.
• the reflection spectra of a semi-RIP containing 1.1% by weight of PEDOT are shown in FIG. 11 between 0.8 ⁇ m and 25 ⁇ m.
• the Strips II and III (respectively 3-5 ⁇ m and 8-12 ⁇ m) are represented by the shaded areas in this figure.
• This figure illustrates the continuity of the spectra characterized by the two different measuring instruments.
• the spectrum of the top in the oxidized state (at 1, 2V) and the spectrum of the bottom corresponds to the reduced state (at -1, 2V).
• the continuity between the two measurements makes it possible to validate the studies carried out in the PIR.
• the response time is the time required for a device to switch from one optical state to another. It is measured at 90% of the maximum contrast% R m a ⁇ - Indeed, we estimate that it is not possible for the human eye to make the difference between 100% and 90% of the contrast. However, the literature shows response times measured at 95% of the maximum contrast. Several factors influence the rate at which EEDs change their emissivity state. The electrolyte content, the initial oxidation state of the semi-RIP and the operating temperature are all factors that are studied in this section.
• Figure 12 (a) shows the response time for the reflector / absorber transition as a function of the electrolyte content of the DEEs
• Figure 12 (b) represents the evolution of the absorbing / reflective transition. The same trend is observed for both evolutions: the change of state is slow when the electrolyte content is low (2-
• the ionic liquid saturation of the semi-RIPs at 1.1% PEDOT is reached after immersion for 20 hours.
• the swelling time strongly depends on the total area of the sample. Indeed, the ionic liquid penetrates only by the edges (that is to say by the thickness) of the semi-RIPs, where there is no PEDOT. The swelling is much longer for films whose surface is extended if it is desired that it is homogeneous.
• the response time decreases drastically as the temperature increases. It is of the order of 3 seconds at a temperature of 80 ° C.
• the electrolyte content of the semi-RIP characterized in this study is 20% by weight.
• the response time at 80 0 C is lower: of the order of one second.
• the memory effect is the time during which the DEE retains a given emissivity after opening of the electric circuit.
• the evolution of the memory effect has also been followed in the infrared.
• Bands II and III are the preferred spectral domains for the use of semi-RIPs based EEDs. It is therefore from the evolution of the memory effect in these bands that will be determined the energy needs of DEEs required by the DEEs to remain in an optical state.
• the evolution of the state of the less stable electronic conductive polymer of the active surface that is to say the reduced state, has been followed. This state is, in fact, that which evolves more quickly, it is also the one that requires the most energy to stay stable.
• Figure 14 shows the reflection spectra in the IR of a DEE over open circuit time.
• the reflection of the material increases with time. Indeed, the spectra evolve towards higher and higher reflection values over time.
• the temperature of use of the DEE is likely to be higher than the ambient temperature. Their cyclability has therefore been studied at temperatures of 60 ° C and 100 ° C. Table 4 summarizes the number of cycles at the end of which a certain loss of the electroactivity of the DEEs is measured, according to their temperature of use.
• DEEs are capable of cycling at room temperature about 13000 times before their properties deteriorate by 10%. By increasing the temperature, this decrease occurs more rapidly: at the temperature 60 ° C., after 12,000 cycles, the properties of the DEEs decrease by 25%. At 100 ° C., the evolution of the properties of DEEs occurs even more quickly: their stability is still satisfactory for 1000 cycles at this temperature of use.
• Table 5 summarizes the energy performance of DEEs. These quantities depend on the initial oxidation state of the PEDOT of the active surface and the value of the applied voltage. The materials are inflated to saturation in EMImTFSI and their operating temperature is the ambient temperature.
• Table 5 Summary table of response times ( ⁇ r), reflection efficiencies ( ⁇ R), energy consumption (E) and the number of switches that semi-RIPs can perform.
• the electrical energy consumed per m 2 makes it possible to realize the needs of the systems.
• the memory effect of DEEs is high. It is not necessary to provide them with a large amount of energy so that their optical state remains constant. It has been shown that a 10-year autonomy would be predictable to maintain a DEE in its optical state if it is powered by a lithium battery.

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