WO2017136598A1 - Films polymères conjugués transparents - Google Patents

Films polymères conjugués transparents Download PDF

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Publication number
WO2017136598A1
WO2017136598A1 PCT/US2017/016289 US2017016289W WO2017136598A1 WO 2017136598 A1 WO2017136598 A1 WO 2017136598A1 US 2017016289 W US2017016289 W US 2017016289W WO 2017136598 A1 WO2017136598 A1 WO 2017136598A1
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WO
WIPO (PCT)
Prior art keywords
substrate
film
conjugated polymer
polymer
composition
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Application number
PCT/US2017/016289
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English (en)
Inventor
Leah A. THOMPKINS
Volha HRECHKA
Lilo D. POZZO
Brett A.E. COURTRIGHT
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Polydrop, Llc
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Publication of WO2017136598A1 publication Critical patent/WO2017136598A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • 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
    • C09D5/004—Reflecting paints; Signal 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • 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
    • C08G2261/3221—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 nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • 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
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants

Definitions

  • the present invention generally relates to thin film modifications of windows to improve energy efficiency.
  • an intrinsically conductive polymer is dispersed into a solvent to create a spray-on application of a UV and IR opaque film on transparent substrates.
  • the polymer has been complexed with an appropriate molecule to promote good adhesion to the window surface.
  • Windows are complex structures which provide protection to occupants from various environmental effects such as wind and cold while also providing a through view.
  • conventional windows provide poor protection against invisible long wavelength radiation such as infrared radiation (IR).
  • IR infrared radiation
  • high amounts of IR produced from the sun during the summer months penetrate windows and increase housing temperatures.
  • high amounts of IR loss from the inside of a home to the outside environment can cause excessive cooling and low energy efficiency.
  • the failure of conventional windows is due to the materials being unable to block the transport of certain invisible radiation.
  • the present invention is directed towards materials used as spray polymer coating as a means for employing an optically transparent, though ultraviolet and infrared absorbing and reflecting film.
  • embodiments of the invention describe the methods of synthesis and application of the polymers.
  • the spray polymer coating exhibits desirable physical properties that would be suitable in industrial, automotive, and home applications.
  • the spray coating material may comprise a suitable combination of polymers, oxidizing agents, solvents, and/or dopants.
  • One embodiment comprises a polymer comprising a monomer, counter ion, oxidizing agent and a dopant.
  • Another embodiment comprises a polymer comprising a monomer, counter ion, oxidizing agent and two or more dopants.
  • the invention comprises a composition comprising a polymer described herein and a carrier fluid.
  • the spray polymer coating may contain potassium persulfate.
  • the spray polymer coating may be dispersed in acetone or ethanol.
  • a transparent or semi- transparent substrate such as a window
  • a film on a surface thereof comprising:
  • a visual transparency ranging between 0.7 and 1 when measured at a film thickness of 200 nm.
  • the invention is directed to a conjugated polymer comprising monomer subunits, a counter ion, oxidizing agent and a dopant.
  • the conjugated polymer may be used in preparation of a film for adhering to the surface of a transparent or semi-transparent substrate, and such films are provided in various embodiments. Accordingly, in some embodiments a composition comprising the conjugated polymer and a carrier fluid for application to a transparent or semi- transparent substrate is provided.
  • Methods for reducing the UV or IR transmission, or both, of a transparent or semi-transparent substrate comprise applying a film comprising the conjugated polymer, and optionally a counter ion, oxidizing agent, surfactant and/or a dopant, on a surface of the substrate.
  • the spray polymer material may also be tailored to optimize adhesion to different transparent surfaces.
  • the polymer is functionalized with a silane derivative.
  • a polymeric film comprising a polymer is provided.
  • a transparent or semi- transparent substrate comprising the polymeric film on the surface thereof is provided.
  • the addition of the spray polymer coating on the exterior surface of the window reflects and absorbs IR and UV light that would otherwise enter and warm the interior space.
  • the benefit of the spray polymer coating can be measured through the direct measurement of radiation absorption and reflection.
  • the spray polymer materials is capable of absorbing and reflecting >90% of incoming IR and UV.
  • a method for reducing the UV or IR transmission, or both, of a transparent or semi-transparent substrate is provided.
  • the method comprises applying a polymeric film on the surface of a transparent or semi-transparent substrate.
  • Fig. 1 shows the operation of the conjugated polymer-based coating applied to the interior surface of a window in the winter. HVAC-produced IR radiation is reflected or absorbed by the coating while only a small amount is able to escape through the window.
  • Fig. 2 shows the operation of the conjugated polymer-based coating applied to the exterior surface of a window in the summer. IR and UV solar irradiation is reflected and absorbed by the window while transmission of visible light is only slightly affected.
  • Fig. 3 is a process flow diagram depicting the procedure by which PEDOT is synthesized and prepared as an aqueous dispersion.
  • Fig. 4 shows the transmission (T), absorption (A), and reflection (R) of two exemplary window films.
  • “Spray polymer” refers to a composition comprising a polymer and a carrier fluid.
  • the term “spray” does not limit the substance to undergo spraying for application.
  • the substance may be applied to a surface through altemative, non-spray techniques such as spin coating and cloth transfer.
  • PEDOT refers to a polymer comprising poly(3,4- ethylenedioxythiophene). Alternate varieties of PEDOT may be achieved through modification using dopants.
  • Polymer refers to a macromolecule comprising one or more structural repeating units.
  • “Monomer” is a molecule that can be combined with itself or other molecules to form a polymer.
  • Dopant is an element, molecule or compound that is inserted into a substance to purposefully modify physical, chemical, or performance characteristics.
  • binding molecule is a chemical or compound that strongly attaches to another chemical or compound.
  • EDOT refers to the compound 3,4-Ethylenedioxythiophene.
  • PEDOT:PSS refers to the polymer PEDOT, namely poly(3,4- Ethylenedioxythiophene), that is associated to the binding polymer molecule polystyrene-sulfonate (PSS).
  • a “salt” is a neutral molecule or compound comprising a positively charged molecular segment and a negatively charged molecular segment.
  • Oxide refers to a molecule or compound comprising an element or molecule that is bound to oxygen.
  • Silane is a saturated chemical compounds comprising one or multiple silicon atoms linked to each other and/or to one or multiple atoms of other chemical elements.
  • Sulfates are molecules or compounds comprising an element or molecule that is bound to one or more SO4 groups.
  • Sulfonates are molecules or compounds comprising an element or molecule that is bound to one or more SO 3 groups.
  • An “amide” refers to a molecule or compound comprising an element or molecule that is bound to one or more groups containing a nitrogen atom (N) that is also bound to one or more carbon atoms.
  • esters refers to molecule or compound comprising an element or molecule that is bound to one or more carbon atoms (C) that are bound with a double bond to oxygen.
  • Chlorate refers to a molecule or compound comprising one or more chlorine atoms bound to three oxygen atoms.
  • Chlorite refers to a molecule or compound comprising one or more chlorine atoms.
  • an “acid” is a molecule or compound capable of donating a proton to another molecule or compound.
  • the definition can also include molecules or compounds capable of accepting a pair of electrons from another chemical or compound.
  • “Functional groups” are specific groups (moieties) of atoms or bonds within molecules that impart characteristic properties to those molecules.
  • Hydroxyl is a type of functional group comprising of an oxygen atom bonded to a hydrogen atom.
  • Frctionality refers to the specific functional group present on a molecule or compound.
  • solvent refers to a substance which dissolves, disperses or suspends materials. The materials may or may not undergo further reaction within the solvent.
  • the present disclosure uses solvents both for the synthesis of the polymer material as well as the dispersion of the polymer for application as a film (i.e. as a carrier fluid).
  • Example solvents include, but are not limited to, acetone, ethanol, water, methanol, isopropanol, toluene, xylene, methyl ethyl ketone and benzene.
  • Preferred Carrier Fluid or “PCF” or “carrier fluid” refers to the chosen solvent for the application of the spray polymer material (i.e. a composition comprising a polymer and a carrier fluid).
  • the polymer is dispersed within the solvent.
  • “Film” or “coating” is a thin layer of material layered onto the surface of another. The material may or may not be chemically adhered to the surface of another.
  • Substrate is a surface to which a coating is applied.
  • the substrate can be modified prior to coating to increase mechanical properties such as adhesion.
  • Dispossion is a mixture comprising a solid or polymer material within a solvent.
  • the solvent can be aqueous or non-aqueous.
  • An “amine” is a compound comprising a nitrogen atom with a lone pair of electrons, such as -NH 2 .
  • an “alcohol” is a compound comprising a -OH moiety.
  • ether is a compound wherein an oxygen atom is bonded to either two alkyl, two aryl, or one of both alkyl and aryl groups.
  • Aliphatic is a family of compounds which contain open carbon chains, either straight or branched, rather than containing a benzene ring. Examples include alkanes, alkenes, and alkynes.
  • phenyl is a compound comprising a cyclic group of carbon atoms with alternating single and double bonds, with the chemical formula CeH 5 . Examples include chlorobenzene and biphenyl. Unless otherwise stated in the specifically in the specification, phenyl groups are optionally substituted.
  • Anionic refers to a chemical species which has either gained an electron (or pair of electrons) or lost a proton to form a negatively charged ion.
  • a “surfactant” is a substance that reduces the surface tension between two materials and thus allows them to interact more intimately.
  • fluoride is a molecule or compound comprising an element or molecule that is bound to fluorine.
  • imide is a molecule or compound comprising two acyl functional groups bound to nitrogen.
  • An “ionic liquid” is a salt wherein the ions are poorly packed and thus the material is a liquid below 100 °C.
  • “Monovalent” refers to an atom or ion that is capable of forming just one chemical bond.
  • a “nitrile” or “cyano group” is a molecule or compound comprising a carbon atom triple bonded to a nitrogen atom (i.e. C ⁇ N).
  • a "nitro compound” is a molecule or compound comprising a nitrogen atom double bonded to two oxygen atoms (i.e. -N0 2 ).
  • polyol is a molecule or compound comprising more than one hydroxyl group available for reaction; these materials often serve as the precursor monomer of polyol polymers.
  • a “sulfoxide” is a molecule or compound comprising an element or molecule that contains a sulfur atom single bonded to an oxygen atom (i.e. sulfinyl group).
  • organic solvent is a compound that contains at least one carbon and is liquid at room temperature (i.e. approximately 25°C).
  • Example organic solvents include, but are not limited to, acetic acid, acetone, acetonitrile, benzene, chloroform, ethanol, methanol, N-methyl-2-pyrrolidinone, pentane, toluene, xylene, and butanol.
  • Organic solvents may be used as either a solvent for spray polymer dispersion or for film removal.
  • An “acidic solution” is solution which has a pH less than 7.
  • a “basic solution” is a solution which has a pH greater than 7.
  • D(50) or “Dv50” or “average particle size” refers to the size of a particle as measured through methods known in the art, such as laser diffraction, wherein 50% of the volume of particles has a smaller particle size.
  • Neutralizing agent is a substance which modifies the pH of a material or solution towards 7. In the instance of a material or solution that is acidic, the substance is basic. In the instance of a material or solution that is basic, the substance is acidic.
  • Haze is defined as the percentage of incident light that is scattered away from a normally incident beam by the window.
  • Color rendering index is a measurement of the degree to which light is the same color before and after passing through a medium.
  • U-factor is a measurement of the rate of heat loss through the center of a transparent material. It is not relevant to non-transparent portions of windows, such as sashes and frames.
  • Center of glass refers to the middle of a transparent material.
  • the material does not need to be glass in composition and may include non- glass substances such as polymers.
  • UV ultraviolet
  • the source of ultraviolet radiation may be natural (i.e. sunlight) or synthetically generated (i.e. artificial light source).
  • Infrared refers to radiation with a wavelength greater than 750 nm.
  • the source of infrared radiation may be natural (i.e. sunlight) or synthetically generated (i.e. artificial light source).
  • Visible or “visible light” refers to radiation with a wavelength ranging from 350 nm to 750 nm.
  • the source of infrared radiation may be natural (i.e. sunlight) or synthetically generated (i.e. artificial light source).
  • a “semi-transparent" substrate is one which allows for the transmission of at least 5% of incoming visible light. It only refers to radiation in the visible spectrum.
  • a “transparent” substrate is one which allows for the transmission of at least 50% of incoming visible light. It only refers to radiation in the visible spectrum.
  • “Glaze” refers to a thin film applied to a substrate, for example a transparent substrate such as a window.
  • the current disclosure is directed towards materials used as spray polymer coating and the methods for employing an optically transparent film.
  • the disclosed materials represent a significant advancement over currently known methods for protective window coatings or glazes.
  • Current methods for protecting windows from UV and IR transmission include solid films in which the user cuts the appropriate shape and applies to the window directly.
  • high area windows, curved or bubble windows, or large number of windows the process can be tedious and may require professional installation.
  • high-energy efficiency windows and glass can be purchased and installed upon building construction. While effective for new construction, replacement windows are not a viable solution for all existing structures.
  • the present invention overcomes limitations of previously described, existing solutions, and provides a number of other improvements.
  • the described spray polymer has a relatively low viscosity allowing the solution to be applied to windows using common household spray bottles.
  • the film is more effective than present materials at reducing the overall UV and IR transmission while keeping optical transmission high, as it can be applied as a thin uniform coating.
  • Figure 1 and Figure 2 demonstrate how the coating can work to increase window efficiency.
  • the spray polymer can be designed to increase adhesion and scratch resistance to a wide range of transparent substrates. Certain aspects of the disclosed materials and methods are described in more detail in the following sections.
  • the invention provides a transparent or semi- transparent substrate comprising a film on a surface thereof, the film comprising:
  • a visual transparency ranging between 0.7 and 1 when measured at a film thickness of 200 nm.
  • the conjugated polymer can be any of those described herein and/or known in the art. In certain embodiment the conjugated polymer is fully conjugated, while in other embodiments the conjugated polymer is partially conjugated.
  • the film can be optimized according to the desired end use of the substrate.
  • the film has an FOM T of greater than 0.7, greater than 1 , greater than 10 or between 0.25 and 0.9.
  • the film has an average transmission of visible light of between 80 and 100% or the film has an average UV radiation absorption of between 35% and 80%.
  • the film has an FOMA of between 8 and 12.
  • the film has an FOMR of between 5 and 12.
  • the film has a TAR of between 70 and 100.
  • the film has an R/A of between 0.1 and 0.4, or the film has a [/-factor is between 0.3 and 0.8.
  • the film has an average transmission of IR of less than 50% and/or the film has an average reflection of IR of greater than 50%.
  • the polymer included within the film can be any of those described herein or known in the art.
  • the conjugated polymer is made by admixing monomer subunits, a counter ion, and an oxidizing agent.
  • the conjugated polymer comprises monomer subunits and optionally one or more counter ions.
  • the conjugated polymer may optionally further comprise an oxidizing agent and/or a dopant and/or a surfactant.
  • these optional components i.e., counter ion, oxidizing agent, dopant and/or surfactant
  • these optional components are present in the film (or the composition from which the film is prepared), but are not part of the polymer itself.
  • the conjugated polymer or the film comprises a dopant.
  • the sum of the concentration of all dopants is between 0.1 and 5% by weight of the conjugated polymer.
  • the conjugated polymer comprises a polymer of 3,4-ethylenedioxythiophene, a polymer of pyrrole or a polymer of fluorene.
  • the conjugated polymer or the film comprises a surfactant.
  • the surfactant comprises dodecylbenzene sulfonate.
  • the conjugated polymer or the film comprises a counter ion.
  • the counter ion comprises a carboxylic acid or an amine.
  • the weight ratio between the monomer subunits in the conjugated polymer and the counter ion ranges from 1 to 1000.
  • the conjugated polymer or the film comprises an oxidizing agent, for example a persulfate, a chlorate, an oxide or a chloride.
  • the oxidizing agent comprises a material in its elemental form.
  • the conjugated polymer or the film comprises a dopant.
  • the dopant comprises ferric chloride or methyl sulfonic acid.
  • the pH of the conjugated polymer ranges from 6 to 8. In different embodiments, the electronic conductivity of the conjugated polymer ranges from 0.001 to 1000 S/cm.
  • Embodiments of the invention also include a conjugated polymer as described above, films comprising the conjugated polymer and/or compositions comprising the conjugated polymer for application to a substrate, for example a transparent or semi-transparent substrate. Further aspects of such embodiments are described in more detail below.
  • the disclosed spray polymer material is made from a polymer comprising or consisting of a conjugated polymer base.
  • the conjugated polymer comprises a monomer (Component 1), a counter ion (Component 2) and an oxidizing agent (Component 3).
  • the conjugated polymer can be synthesized by mixing a monomer (Component 1), a counter-ion (Component 2) and an oxidizing agent (Component 3).
  • the polymer comprises a monomer, counter ion, oxidizing agent, and a dopant.
  • the polymer comprises a monomer, counter ion, oxidizing agent and two or more dopants.
  • Figure 3 depicts the general steps that are followed and described herein.
  • the conjugated polymer can be purchased from common commercial agencies and further modified.
  • the monomer (Component 1), used to synthesize the conjugated polymer can be chosen from a range of materials known in the art. Not wishing to be bound by theory, the monomer can be important to tailoring the optically transparent properties of the spray on film.
  • the initial monomer used to synthesize the conjugated polymer is 3, 4-ethylenedioxy thiophene (EDOT), aniline, pyrrole, fluorene, thiophene, or combinations thereof.
  • the monomer can contain EDOT.
  • the monomer can contain pyrrole.
  • Component 1 can be uniquely characterized through independent polymerization and measurement of molecular weight.
  • the molecular weight of Component 1 after polymerization is above 1,000 g/mol, above 2,000 g/mol, above 5,000 g/mol, above 10,000 g/mol, above 20,000 g/mol, above 50,000 g/mol, above 150,000 g/mol, above 400,000 g/mol, above 1,000,000 g/mol, or above 2,000,000 g/mol.
  • the molecular weight of Component 1 after polymerization is below 5,000,000 g/mol.
  • the counter ion (Component 2), or dopant, can be tailored for increased adhesion.
  • the counter ion itself it made up of two functionalities, Functionality A and Functionality B.
  • Functionality A acts as an acidic functional group that complexes strongly with Component 1 while Functionality B is a glass-interactive functional group.
  • Functionality A is sulfonic acid and Functionality B is maleic acid.
  • the sum of the concentrations of all dopants ranges from 0.01 to 5 wt%.
  • the counter ion comprises a carboxylic acid.
  • the counter ion comprises an amine.
  • at least one dopant comprises ferric chloride, methyl sulfonic acid, or combinations thereof.
  • Component 2 comprises polystyrene sulfonic acid-co-maleic acid. In other embodiments, Component 2 comprises polyacrylic acid, polymaleic acid, polystyrene sulfonate, polyacrylic-co-maleic acid, polystyrene sulfonic acid-co-maleic acid, polyacrylic acid-co-polystyrene, polystyrene sulfonate-co- polyethylene oxide, polystyrene sulfonate-co-polypropylene oxide or any combination thereof.
  • Component 1 will complex with Component 2.
  • the weight ratio between Component 1 and Component 2 has been found to impact the final performance properties of the polymer in addition to altering the reaction kinetics.
  • the weight ratio of Component 1 to Component 2 ranges from 2: 1 to 1 : 1000.
  • the weight ratio of monomer to counter ion ranges from 1 to 1000.
  • the weight ratio of Component 1 to Component 2 ranges from 1 : 1 to 1 :500, 1 :2 to 1 : 100, 1 :3 to 1 :20, or 1 :4 to 1 : 10.
  • the weight ratio of Component 1 to Component 2 ranges from 2: 1 to 1 : 1, 1.8: 1 to 1.1 : 1, or 1 :7 to 1.5: 1. In yet still another embodiment the weight ratio of Component 1 to Component 2 is 1 :4.
  • the solvent for the reaction can be altered for safety for both the user and the environment.
  • the solvent for synthesis comprises water.
  • the solvents comprise non-aqueous fluids, such as ethanol, acetone, methanol, toluene, isopropanol, benzene, or combinations thereof.
  • the concentration of Component 1 when mixed with Component 2 in solution is chosen to facilitate the reaction with Component 3.
  • the concentration of Component 1 when mixed with Component 2 in solution ranges from 0.05M to 5M.
  • the concentration of Component 1 when mixed with Component 2 in solution ranges from 0.05M to 1M, 0.1M to 0.9M, 0.5M to 0.9M, 1M to 4M, or 2M to 3M.
  • the concentration of Component 1 when mixed with Component 2 in solution is less than 0.05M or greater than 5M.
  • the concentration of Component 1 when mixed with Component 2 in solution is 0.08M.
  • an oxidization agent (Component 3) may be used.
  • the oxidizing agent comprises a persulfate, a chlorate, an oxide, a chloride, or combinations thereof.
  • the oxidizing agent comprises a material in its elemental form.
  • the oxidizing agent comprises potassium persulfate, ferric chloride, sodium persulfate, or combinations thereof.
  • Oxidizing agents refer to a large class of materials, some of which are listed in Table 2. Table 2 is illustrative list for exemplary purposes and not exhaustive. Oxidizing agents will be apparent to those skilled in the art.
  • the oxidizing agent may be chosen based on its reaction rate, solubility, and cost. In an additional embodiment, no oxidizing agent is used. able 2.
  • Oxides Barium peroxide, dibenzoyl peroxide, hydrogen peroxide, magnesium peroxide, nitrogen trioxide, potassium peroxide, sodium peroxide, perchloric acid
  • the ratio between Component 1 and Component 3 directly impacts the rate and extent of reaction.
  • the molar ratio of Component 1 to Component 3 ranges from 5: 1 to 1 :5, 1 : 1 to 5: 1, 2: 1 to 3: 1, 1 : 1 to 1 :5, or 1 :2 to 1 :3.
  • the molar ratio of Component 1 to Component 3 is about 1 : 1.
  • the combination of Component 1, Component 2 and Component 3 can be heated or cooled to directly impact the rate of reaction.
  • the polymerization temperature of Mixture 1 is increased above 30 °C, above 40 °C, above 50 °C, above 60 °C, above 70 °C, above 100 °C, above 150 °C, above 200 °C, or above 300 °C
  • the polymerization temperature of Mixture 1 is decreased below 30 °C, below 20 °C, below 10°C, or below 0 °C
  • the temperature is held constant throughout the polymerization process.
  • the temperature of Mixture 1 is dynamic.
  • the time allowed for polymerization of Mixture 1 can be controlled to obtain ideal particle size.
  • the time allowed for polymerization of Mixture 1 ranges from 5 minutes to 48 hours.
  • the polymerization time for Mixture 1 ranges from 5 minutes to 10 hours, 30 minutes to 8 hours, 1 hour to 5 hours, or 2 hours to 4 hours.
  • the polymerization time for Mixture 1 is approximately 3 hours.
  • the polymerization time for Mixture 1 ranges from 10 hours to 48 hours, 12 hours to 24 hours, or 16 hours to 20 hours. In still another embodiment the polymerization time for Mixture 1 is greater than 48 hours.
  • Dopant 1 can be included in Mixture 1 prior to or after polymerization in order to supplement the performance characteristics and mechanical properties (e.g. adhesion).
  • Dopant 1 is a material with suitable electron withdrawing capacity such as ferric chloride, methyl sulfonic acid, tosylate, or combinations thereof.
  • suitable electron withdrawing capacity such as ferric chloride, methyl sulfonic acid, tosylate, or combinations thereof.
  • Table 3 is illustrative list for exemplary purposes and not exhaustive. Dopants will be apparent to those skilled in the art. able 3.
  • Dopant 1 is typically added into solution after the combination of Component 1, Component 2 and Component 3, though it can also be added after the combination and the polymerization of Component 1, Component 2, and Component 3.
  • the concentration of Dopant 1 as a measurement of the total mass of Component 1, Component 2, Component 3, and solvent ranges from 0.001 to 1 wt%, 0.01 to 0.1 wt%, or 0.05 to 0.1 wt%. In other embodiments the concentration of Dopant 1 ranges from 0.1 to 5 wt%, 1 to 10 wt%, 5 to 20 wt%, or 10 to 30 wt%.
  • the total concentration of dopants, as defined by the sum of the mass of all dopants, in Mixture 1 ranges from 0.001 to 1 wt%, 0.01 to 0.1 wt%, or 0.05 to 0.1 wt%. In other embodiments the concentration of Dopant 1 ranges from 0.1 to 5 wt%, 1 to 10 wt%, 5 to 20 wt%, 10 to 30 wt%.
  • the polymerized product after the reaction is acidic.
  • the pH of the polymer ranges from 1 to 6, 2 to 5, 2 to 4, or 6 to 8.
  • a neutral or basic product may be desired.
  • Additive 1 can be used to alter the pH of the final product without harm to the performance characteristics of the polymeric film.
  • Additive 1 can be a strong base comprising sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, or combinations thereof.
  • Additive 1 can be a weak base comprising ammonia, ammonium hydroxide, pyridine, trimethyl ammonia, or combinations thereof.
  • the intermediate product may be dried.
  • the intermediate product is dried using vacuum filtration, centrifuged, air dried, oven dried, or freeze dried.
  • the intermediate product may never undergo a drying phase.
  • the polymer composition may undergo a continuous solvent exchange.
  • the polymer complex can be commercially purchased or synthesized using methods known to those in the art.
  • the commercially available materials used as the polymer complex are PEDOT:PSS, poly(p-phenylene vinylene), poly(3-hexylthiophene), poly(pyrrole), poly(fluorene), poly(aniline), poly(acetylene), or combinations thereof.
  • the commercially available polymer complexes are further modified using Dopant 1 or Additive 1 to yield a novel material.
  • the dried polymer complex can be mixed with a preferred carrier fluid (PCF) for the creation of the Spray Polymer material.
  • a composition comprising a polymer and carrier fluid is provided.
  • the preferred carrier fluid is an organic solvent.
  • the PCF comprises acetone, ethanol, water, methanol, isopropanol, toluene, xylene, methyl ethyl ketone, benzene or some combination thereof.
  • the carrier fluid comprises water.
  • PCF may include a surfactant or wetting agent.
  • the composition may comprise a surfactant.
  • the surfactant may be Span 20, Span 40, Span 60, Span 80, Span 83, Span 85, Span 120, Tween 20, Tween 21, Tween 40, Tween 60, Tween 61, Tween 65, Tween 80.
  • the surfactant is nonionic, zwitterionic, containing cationic head groups, anionic.
  • the composition comprises a concentration of the surfactant that ranges from 0.05 to 5 wt%, 0.01 to 50 wt%, 0.01 to 25 wt%, 0.01 to 10 wt%, 0.1 to 5 wt%, 0.1 to 2 wt%, or 0.5 to 2 wt%.
  • concentration of the polymer in the composition can impact the film thickness and the ease of application to windows. If the concentration is too high, the composition may be difficult to use in a spray bottle or may apply a film that is undesirably thick.
  • a composition wherein the concentration of the polymer in the carrier fluid ranges from 0.5 to 30 wt%, 0.1 to 10 wt%, 0.5 to 5 wt%, 1 to 2 wt%, 5 to 9 wt%, and 6 to 8 wt% is provided.
  • the composition provides the concentration of polymer in the carrier fluid is approximately 1.5 wt%. In yet another embodiment the concentration of the polymer in carrier fluid is greater than 10 wt%.
  • the concentration of the composition can be linked to the viscosity.
  • the viscosity of the composition ranges from 0.5 to 100 cP, 1 to 10 cP, 1 to 5 cP, and 1 to 2 cP. In other embodiments the viscosity of the composition ranges from 10 to 100 cP, 10 to 50 cP, and 20 to 30 cP. In one embodiment the viscosity of the composition is 1.2 cP.
  • the pH of the dispersion can impact both the adhesion and the safety of the spray polymer.
  • the pH is approximately 7.
  • the pH of the spray polymer ranges from 2 to 11 , 2 to 7, 3 to 6, 4 to 5, 6 to 8, 7 to 11 , or 8 to 10.
  • the diameter of the complex particle, dispersed in the PCF, will influence the minimum coating thickness allowed. Additionally, the diameter of the complex particle will play a role in the diffraction of light which is directly related to haze.
  • the diameter of a complex particle can be measured using methods known in the art, such as laser scattering techniques.
  • the D(50) of the dried complex particle ranges from 10 to 1000 nm, 10 to 500 nm, 20 to 300 nm, 20 to 50 nm, 50 to 200 nm, or 100 to 150 nm. In another embodiment the D(50) of the dried complex particle is approximately 200 nm.
  • the D(50) of the dried complex particle ranges from 200 to 1000 nm, 200 to 500 nm, 200 to 400 nm, or 250 to 300 nm. In still another embodiments the D(50) of the complex particle is less than 10 nm or greater than 1000 nm.
  • composition comprising polymer in carrier fluid, may be purposefully functionalized in order to preferentially bond to various substrates.
  • the polymer functionality determines the physical and chemical adhesion and reaction to substrate surfaces.
  • the polymer can be optimized to bind with specific substrate materials.
  • the functionality of the polymer can be identified using infrared spectroscopy, or any other methods known to those of skill in the art.
  • the functional group comprises silicon, such as silyl and disilanyl.
  • Component 2, Component 3) could negatively affect the optical and mechanical properties of the final polymer substance.
  • concentration of impurities can be determined with thermal gravimetric analysis, or any other methods known by those skilled in the art.
  • the concentration of impurities ranges from 0 to 1 wt%, 0 to 2 wt%, 0 to 3 wt%, 0 to 4 wt%, or 0 to 5 wt%.
  • the concentration of impurities is approximately 0.5 wt%.
  • the concentration of impurities ranges from 1 to 5 wt%, 2 to 4 wt%, or 2 to 3 wt%.
  • concentration of impurities is less than 1 wt% or greater than 5 wt%.
  • the concentration of impurities ranges from 5 to 30%, 5 to 20%, or 10 to 15%.
  • photospectrometry or any method known by those skilled in the art, may be used.
  • a completed reaction will be evidenced by absorption peaks in the precise location expected for the polymer.
  • a peak shift of greater than 10 nm suggests that the reaction was not allowed to reach completion and greater time or temperature should be employed.
  • the electronic conductivity may range between 10 "4 to 10 3 S/cm. In one embodiment the electronic conductivity of the polymer in the absence of the carrier fluid ranges from 0.001 to 1000 S/cm, 1 to 10 3 S/cm, 1 to 10 2 S/cm, or 50 to 100 S/cm. In some embodiments the electronic conductivity ranges from 10 "4 to 10 S/cm, 10 "3 to 1 S/cm, or 10 "2 to 1 S/cm.
  • the polymer material can be applied to any transparent or semi- transparent surface or substrate.
  • the invention provides a method for applying the compositions described herein.
  • the invention provides a transparent or semi-transparent substrate comprising the polymeric film described herein.
  • Transparent or semi-transparent substrates comprise silicon- containing glass, plastics, transparent ceramics, polymers, or combinations therein.
  • transparent surfaces or substrates include windows, single pane windows, double pane windows, triple pane windows, quadruple pane windows, argon or nitrogen filled windows, vacuum filled windows, car windows, residential windows, commercial windows, water bottles, light bulbs, computer screens, and watch or phone faces.
  • the invention provides a method for reducing the UV or IR transmission, or both, of a transparent or semi-transparent substrate, the method comprising applying a polymeric film described herein on a surface of the substrate.
  • the polymer material may be applied directly or indirectly to a transparent or semi- transparent surface or substrate.
  • An embodiment for application of the polymer to a surface or substrate is through mechanical spraying.
  • the polymer composition is sprayed using an aerosol canister.
  • the polymer composition is sprayed using a non-aerosol spray bottle.
  • Spray bottles are common household objects used for various cleaning supplies.
  • the spray polymer would be filled into a spray bottle.
  • the bottle material would be chosen as to prevent chemical reactions between the spray polymer and bottle.
  • Example bottle materials comprise polypropylene and silicon-containing glasses.
  • the user mechanically wipes the polymer composition across the transparent or semi-transparent surface or substrate, either after a spray application or in place of a spray application. In yet another embodiment no additional wiping or spreading is required.
  • the spray polymer is applied directly to a rag, cloth, or brush and applied through mechanical transfer.
  • the polymer composition is applied through a doctor blade, painting method, mechanical spreading technique, or extrusion process.
  • the polymer composition is applied using a dip coating process. In another embodiment, at manufacturing scale, windows may be dip coated.
  • the spray polymer film may need to undergo additional processing steps in order to reach desired performance properties.
  • the spray polymer may need to dry to remove excess carrier fluid.
  • the method of applying the polymer composition further comprises a drying step.
  • the carrier fluid is removed through ambient temperature air dry.
  • the carrier fluid is removed through forced air or elevated temperature drying.
  • the spray polymer may also require additional curing for proper adhesion and flexibility. Curing may occur before or after carrier fluid removal.
  • the spray polymer is cured using thermal assistance or UV assistance.
  • the spray polymer is designed to be removed using common solvents and removal techniques.
  • the film can be removed when exposed to an acidic solution, a basic solution, organic solvents, or water.
  • the film can be removed by common commercially available cleaning supplies, such as Windex® or bleach.
  • the film is removed through mechanical wiping of the film using a rag or cloth containing the appropriate solvent.
  • Embodiments of the present invention provide a polymeric film comprising the polymer according to the composition or methods described herein. Once applied to a window or semi-transparent surface the spray polymer substance can be further characterized as a thin film. For all measurements the film thickness is assumed to be uniform and constant at 200 nm thick. All values of performance are normalized to the semi-transparent to transparent substrate. For example, the transmission in the visible spectra is at 80% indicates a 20% reduction in visible light through the substrate.
  • the goal for an effective coating is to allow for the highest percentage of visible light to be transmitted through the film, known to those in the art as visual transparency (VT).
  • the wavelength of visible light is defined to fall between the ranges of 350 and 750 nm, as known in the art.
  • the average transmission of visible light through the film is between 70 and 100%, also referred to as a VT between 0.7 and 1.
  • the average transmission of visible light through the film ranges from 80 to 100%, 80 to 90%, 90 to 95%, or 70 to 80%, also referred to as a VT between 0.8 and 1, 0.8 and 0.9, 0.9 and 0.95, and 0.7 and 0.8.
  • the polymeric film wherein the transmission of visible light through the polymeric film ranges from 80 to 100% when the polymeric film is measured at 200 nm thick, is provided.
  • the average transmission of visible light is below 70%, also referred to as a VT below 0.7.
  • the average reflection of visible light by the film is between 0% and 100%. In another embodiment the average reflection of visible light by the film is between 1% and 80%, 5% and 70%, 5% and 60%, 5% and 50%, 5% and 40%, 5% and 30%, 5% and 20%, 5% and 10%, 2% and 8%,. In yet another embodiment the average reflection of visible light by the film is 30%.
  • UV radiation ultraviolet
  • the wavelength of UV radiation is defined as below 350 nm.
  • the average absorption of UV radiation by the polymeric film ranges from 25 to 100%.
  • the average absorption of UV radiation by the polymeric film ranges from 30 to 90%, 35 to 80%, 40 to 60%, or 45 to 55%.
  • the average absorption of UV radiation by the film is 50% or below 25%.
  • UV radiation ultraviolet
  • the wavelength of UV radiation is defined as below 350 nm.
  • the average reflection of UV radiation by the film is between 25 and 100%.
  • the average reflection of UV radiation by the film is between 30 and 90%, 35 and 80%, 40 and 60%, 45 and 55%.
  • the average reflection of UV radiation by the film is 50% or below 25%.
  • the wavelength of IR radiation is defined as above 750 nm and below 10,000 nm.
  • the average absorption of IR radiation by the film is between 25 and 100%.
  • the average absorption of IR radiation by the film is between 30 and 90%, 35 and 80%, 35 and 60%, 35 and 50%.
  • the average absorption of IR radiation by the film is 40%.
  • IR radiation infrared
  • the average reflection of IR radiation by the film is between 20 and 100%.
  • the average reflection of IR radiation by the film is between 20 and 90%, 20 and 80%, 20 and 60%, 20 and 50%.
  • the average reflection of IR radiation by the film is 30%.
  • IR radiation infrared
  • the average transmission of IR radiation by the film is between 0% and 100%.
  • the transmission reflection of IR radiation by the film is between 1% and 80%, 5% and 70%, 5% and 60%, 5% and 50%, 5% and 40%, 5% and 30%, 5% and 20%, 5% and 10%, 2% and 8%,.
  • the average transmission of IR radiation by the film is 30%.
  • the transmission figure of merit is defined as the integral of the transmission spectrum from 350 to 750 nm (visible) divided by the integral of the transmission spectrum from 750 to 2500 nm (infrared). A larger transmission figure of merit corresponds to better performance. Tr ansmis sion
  • the polymeric film has a FOMT ranging from 0.1 to 1, 0.2 to 1, 0.5 to 1, 0.8 to 0.9, or 0.25 to 0.9.
  • the FOM T is between 0.2 and 0.3, 0.25 and 0.29.
  • the FOMT ranges from 0.7 to 0.95, 0.75 to 0.9, or 0.8 to 0.85.
  • the FOM T is between 1 and 100, between 1 and 10, between 1 and 8, between 1 and 5, between 2 and 4, between 5 and 50, between 15 and 25, between 50 and 100, between 50 and 75, between 75 and 100.
  • the FOMT is between 100 and 10,000, for cases wherein the film exhibits both superior VT and superior IR opacity.
  • the absorption figure of merit is defined as the integral of the absorption spectrum from 750 to 2500 nm divided by the integral of the absorption spectrum from
  • the polymeric film has a FOMA ranging from 1 to
  • the polymeric film has a FOM A ranging from 10 to 12, 10 to 15, or 10 to 20.
  • the reflection figure of merit is defined as the integral of the reflection spectrum from 750 to 2500 nm divided by the integral of the reflection spectrum from
  • the polymeric film has a FOMR ranging from 1 to 20, 2 to 15, 5 to 10, 8 to 9, 5 to 12, or 9 and 10. In another embodiment the polymeric film has a FOMR ranging from 10 to 12, 10 to 15, or 10 to 20.
  • the complete transmission, absorption and reflection of the film can be assessed through the product of the three components.
  • One embodiment provides a polymeric film having a TAR ranging from 5 to 280.
  • the polymeric film has a TAR ranging from 5 to 20, 20 to 50, 50 to 70, 70 to 100, 100 to 150, 150 to 200, 200 to 280.
  • the TAR is approximately 75.
  • a material may have a high TAR value, wherein the absorption value is low due to a high reflection.
  • the polymeric film has an R/A ranging from 0 to 5. In other embodiments the R/A ranges from 0.01 to 0.5, 0.1 to 0.4, or 0.2 to 0.3. In yet another embodiment the polymeric film has an R/A greater than 0.5. In still another embodiment the polymeric film has an R/A that is approximately 0.
  • a material may have a high TAR value, wherein the transmission value is high and the absorption value is low.
  • the ratio between transmission and the absorption can be defined using the following equation:
  • the transmission and absorption of the film are similar.
  • the T/A is greater than zero, the absorption of the film is greater than the transmission.
  • the T/A is less than zero, the transmission of the film is greater than the absorption of the film.
  • the R/A is between 0 and 5. In another embodiment the R/A is between 0.01 and 0.5, 0.1 and 0.4, 0.2 and 0.3. In yet another embodiment the R/A is greater than 0.5. In still another embodiment the R/A is approximately 0.
  • Haze is an important measurement of the film's diffractive qualities and is known to those familiar with the art. An undesired high value for haze will make images blurry or deformed. A low value for haze is preferred in some embodiments for optimal coatings.
  • the haze of the film is between 0 and 5%. In another embodiment the haze of the film is between 0 and 4%, 0 and 3%, 0 and 2%, 0 and 1%, 0 and 0.5%. In yet another embodiment the haze of the film is approximately
  • the haze is high, purposefully distorting the transmission of light. In one embodiment the haze of the film is higher than 5% but lower than 20%.
  • the color rendering index of the film is between 0.5 and 1. In another embodiment the color rendering index of the film is between 0.6 and
  • the color rendering index of the film is greater than 0.9. In yet another embodiment the color rendering index of the film is approximately 0.95.
  • the film will also provide thermal insulating effects.
  • the thermal impacts can be measured using metrics known to those in the art.
  • the [/-factor describes the ability for the window or film to prevent heat from escaping. It is a measurement of the rate of heat transfer.
  • the polymeric film can be designed to allow for high heat transfer (high [/-factor) or high heat retention and low transfer (low [/-factor).
  • the polymeric film has a [/-factor of the film ranging from 0.05 to 1.5 BTU/sf/hr/°F.
  • the polymeric film has a [/-factor ranging from 0.1 to 0.8 BTU/sf/hr/°F, 0.1 to 0.5 BTU/sf/hr/°F, 0.2 to 0.6 BTU/sf/hr/°F, 0.3 to 0.8 BTU/sf/hr/°F, or 0.3 to 0.5 BTU/sf/hr/°F.
  • the polymeric film has a [/-factor that is approximately 0.4 BTU/sf/hr/°F.
  • the polymeric film has a [/-factor that allows for high heat transfer and ranges from 0.8 to 1.5 BTU/sf/hr/°F, 1 to 1.4 BTU/sf/hr/°F, or 1.2 to 1.3 BTU/sf/hr/°F.
  • Solar heat gain coefficient is a non-dimensional number which represents the amount of solar heat transmitted through a window glaze.
  • the film, or glaze can have a SHGC between 0 and 1, wherein 1 indicates fully transparent to solar heat while 0 indicates fully opaque to solar heat.
  • the SHGC of the film is between 0 and 0.5, between 0.1 and 0.4, between 0.1 and 0.3, between 0.2 and 0.25.
  • the SHGC of the film is between 0.5 and 1, between 0.5 and 0.9, between 0.6 and 0.8, between 0.7 and 0.75.
  • the SHGC is approximately 0.5.
  • the threshold exterior temperature for interior condensation is typically desired to be as low as possible, allowing for windows to be more effective in cold climates.
  • the threshold exterior temperature for interior condensation is between -30 to 20 °C.
  • the threshold exterior temperature for interior condensation is between -20 to 10 °C, -10 to 0 °C.
  • the threshold exterior temperature for interior condensation is approximately -5 °C.
  • Thin coatings and films can be further characterized by the adhesion testing using ASTM D3359 method for measuring adhesion by scoring and tape test.
  • ASTM D3359 The methods and classification using ASTM D3359 is well known to those in the art.
  • the film is classified as 5B (0% removed), 4B (less than 5% removed), 3B (between 5 and 15% removed), 2B (between 15 and 35% removed), IB (between 35 and 65% removed), or 0B (greater than 65% removed).
  • the end user may choose to apply the coating to the exterior of a window to block UV and IR energy from entering conditioned spaces.
  • Extreme outdoor conditions may contribute to the degradation of the film and result in decreased performance.
  • accelerated environmental stability tests may be conducted according to ISO 4892. After subjecting films to these accelerated stresses, the above characterizations may be repeated to determine the effect on performance. In one embodiment, performance of the film is decreased by 10%, in another by 15% and in another by 30%. In yet still another embodiment, the performance after simulated environmental stress fell by 8%.
  • the coating may be applied to transparent surfaces, such as windows in high traffic areas, there is the chance that the coating may be inadvertently scratched.
  • the scratch/abrasion resistance of the coating can be evaluated with a scratch apparatus as described in ISO 1518. Not wanting to be bound by theory, from this test, the minimum force to penetrate the coating through to the underlying substrate is determined. In one embodiment, the minimum load to scratch the coating is 2 N, in another it is 10 N and in another it is 20 N. In yet still another embodiment, the minimum load to penetrate the coating through to the substrate is 12 N.
  • the coating may be exposed to extreme condition, such as elevated temperatures.
  • the film needs to undergo minimal degradation or material loss when exposed to high temperature.
  • the thermal degradation onset is defined as the temperature at which 5% of the film is removed by thermo gravimetric analysis in nitrogen.
  • the thermal degradation onset temperature of the film is between 100 °C and 500 °C.
  • the thermal degradation onset temperature of the film is between 100 °C and 400 °C, 125 °C and 400 °C, 150 °C and 350 °C, 200 °C and 300 °C.
  • the thermal degradation onset temperature of the film is between 250 °C and 350 °C, 275 °C and 350 °C, 300 °C and 325 °C. In yet another embodiment the thermal degradation onset temperature of the film is between 400 °C and 500 °C.
  • the material can also be designed to be safe for children and pets in the case of inadvertent ingestion.
  • Lethal Dose, 50% is a measurement of the amount of a substance required to skill 50% of a test population.
  • the test population is adult rats.
  • the LD50 for the spray polymer material is between 0.0001 g/kg and 1000 g/kg.
  • the LD50 for the spray polymer material is between 0.01 g/kg and 50 g/kg, 0.1 g/kg and 5 g/kg, 0.5 g/kg and 2 g/kg.
  • the LD50 for the spray polymer material is between 5 g/kg and 1000 g/kg, 10 g/kg and 100 g/kg, 10 and 50 g/kg, 20 and 40 g/kg.
  • the polymeric film has an electronic conductivity ranging from 10 "4 to 10 3 S/cm. In one embodiment the polymeric film has an electronic conductivity ranging from 0.001 to 1000 S/cm, 1 to 10 3 S/cm, 1 to 10 2 S/cm, or 50 to 100 S/cm. In another embodiment the polymeric film has an electronic conductivity ranging from 10 " 4 to 10 S/cm, 10 "3 to 1 S/cm, or 10 "2 to 1 S/cm.
  • the conjugated polymer dispersion was synthesized by mixing poly(4- styrenesulfonic acid-co-maleic acid), PSSA-co-MA, and water to create a 4.8 wt% solution.
  • EDOT 3,4-ethylenedioxythiophene monomer
  • PSSA-co-MA:EDOT weight ratio of 4: 1
  • KPS Potassium persulfate
  • the mixture was heated to 50 °C and allowed to polymerize to completion (approximately 3-24 hours). The polymerization was deemed complete by a drastic change in color to dark blue.
  • Table 4 shows various combinations of Component 1, Component 2 and Component 3 to prepare the conjugated polymer.
  • the PEDOT dispersion can be further modified through additional dopants.
  • Ferric chloride FeCl 3
  • the dispersion and dopant were allowed to mix for 4 hours.
  • the pH of the dispersion from Example 2 was measured, typically falling between 2 and 4. To raise the pH of the dispersion for safe handling and application, aqueous sodium hydroxide was slowly titrated into the dispersion while constantly stirring until the pH is between 6 and 8. Alternatively, other strong and weak bases can be used to achieve a similar outcome.
  • the dispersion from Examples 1-3 was further post-processed into the spray polymer solution product.
  • 500 mL of dispersion was poured onto a vacuum filtration system using Whatman 602 H paper. The vacuum filtration was allowed to continue until complete solvent removal. Further drying was performed in air on a hot plate or oven at 50 °C.
  • the powder was then dispersed in ethanol at 1.5 wt% using a mechanical mixer. Alternatively, the dispersion was filtered with a Whatman syringe filter of appropriate pore size.
  • Example pore sizes included 220 nm and 450 nm.
  • the spray polymer solution was prepared through a solvent exchange.
  • the water was exchanged with ethanol using a centrifugal extractor. Additional ethanol was added to the dispersion in order to reach the target concentration of l .5 wt%.
  • the spray polymer solution was prepared through the manipulation of a commercially available polymer product.
  • An aqueous dispersion of PEDOT:PSS was obtained from Heraeus and modified as in Examples 2-4.
  • a transparent substrate 3 inches by 3 inches, was cut from commercially available 1/8" thick glass, obtained from Gardner Glass Products.
  • the substrate was mounted into a spin coater.
  • the spin speed was set to 1000 rpm and lmL of spray polymer dispersion was dropped into the center of the substrate. With the dispersion on the substrate, rotation was begun and allowed to continue for 30 seconds. Once the rotation was complete, the substrate was removed from the spin coater and allowed to dry.
  • the spray polymer was applied to a transparent surface by means of a spray bottle or a wipe.
  • the spray bottle was held approximately 12" from a glass surface and sprayed 2-3 times across the surface until wet.
  • a rag or towel was optionally used to spread the liquid evenly across the surface.
  • the film was allowed to air dry for at least 2 hours at room temperature.
  • Figure 4 presents data for trials 5 and 6 in graphical form.
  • Polymers prepared according to Example 1 are modified with IR and UV active agents to further limit IR transparency and improve UV stability.
  • An organometallic dopant is added below 10 wt% to the monomer and allowed to polymerize, following preparation according to Example 1.
  • the polymer is then dispersed into a PCF and coated onto a glass surface by spray, wiping, or any of the methods described herein. After drying, the film exhibits high visual transparency (average transmission of visible light > 70%) and low average transmission of infrared ( ⁇ 50%), with a FOM T > 0.7.
  • Example 6 The film from Example 6 was removed using mechanical wiping and ethanol as a solvent. The film was also removed with bleach.
  • Exemplary embodiments of the invention include, but are not limited to:
  • Embodiment 1 A transparent or semi-transparent substrate comprising a film on a surface thereof, the film comprising:
  • a conjugated polymer a conjugated polymer
  • a visual transparency ranging between 0.7 and 1 when measured at a film thickness of 200 nm.
  • Embodiment 2 The substrate of embodiment 1, wherein the conjugated polymer is fully conjugated.
  • Embodiment s The substrate of embodiment 1, wherein the conjugated polymer is partially conjugated.
  • Embodiment 4 The substrate of any one of embodiments 1-3, wherein the film has an FOM T of greater than 0.7
  • Embodiment 5 The substrate of any one of embodiments 1-3, wherein the film has an FOM T of greater than 1
  • Embodiment 6 The substrate of any one of embodiments 1-3, wherein the film has an FOM T of greater than 10
  • Embodiment 7 The substrate of any one of embodiments 1-6, wherein the film has an average transmission of visible light of between 80 and 100%
  • Embodiment 8 The substrate of any one of embodiments 1-7, wherein the film has an average UV radiation absorption of between 35% and 80%
  • Embodiment 9 The substrate of any one of embodiments 1-3, wherein the film has an FOM T of between 0.25 and 0.9
  • Embodiment 10 The substrate of any one of embodiments 1-3, wherein the film has an FOM A of between 8 and 12
  • Embodiment 11 The substrate of any one of embodiments 1-3, wherein the film has an FOM R of between 5 and 12
  • Embodiment 12 The substrate of any one of embodiments 1-11, wherein the film has a TAR of between 70 and 100
  • Embodiment 13 The substrate of any one of embodiments 1-11, wherein the film has an R/A of between 0.1 and 0.4
  • Embodiment 14 The substrate of any one of embodiments 1-11, wherein the film has a [/-factor is between 0.3 and 0.8
  • Embodiment 15 The substrate of any one of embodiments 1-14, wherein the film has an average transmission of IR of less than 50% Embodiment 16.
  • Embodiment 17 The substrate of any one of embodiments 1 -16, wherein the conjugated polymer is made from monomer subunits, a counter ion, and an oxidizing agent.
  • Embodiment 18 The substrate of any one of embodiments 1 -17, wherein the conjugated polymer comprises monomer subunits and one or more counter ions.
  • Embodiment 19 The substrate of embodiment 18, wherein the conjugated polymer further comprises an oxidizing agent.
  • Embodiment 20 The substrate of any one of embodiments 1 -19, wherein the conjugated polymer comprises a dopant
  • Embodiment 21 The substrate of any one of embodiments 1 -20, wherein the conjugated polymer comprises a polymer of 3,4-ethylenedioxythiophene.
  • Embodiment 22 The substrate of any one of embodiments 1 -20, wherein the conjugated polymer comprises a polymer of pyrrole
  • Embodiment 23 The substrate of any one of embodiments 1 -20, wherein the conjugated polymer comprises a polymer of fluorene
  • Embodiment 24 The substrate of any one of embodiments 1 -21 , wherein the polymer comprises dodecylbenzene sulfonate.
  • Embodiment 25 The substrate of any one of embodiments 20-24, wherein the sum of the concentration of all dopants is between 0.1 and 5% by weight of the conjugated polymer.
  • Embodiment 26 The substrate of any one of embodiments 17-25, wherein the counter ion comprises a carboxylic acid.
  • Embodiment 27 The substrate of any one of embodiments 17-25, wherein the counter ion comprises an amine.
  • Embodiment 28 The substrate of any one of embodiments 17-27, wherein the weight ratio between the monomer subunits and the counter ion ranges from 1 to 1000.
  • Embodiment 29 The substrate of any one of embodiments 17 or 19-28, wherein the oxidizing agent comprises a persulfate.
  • Embodiment 30 The substrate of any one of embodiments 17 or 19-28, wherein the oxidizing agent comprises a chlorate.
  • Embodiment 31 The substrate of any one of embodiments 17 or
  • the oxidizing agent comprises an oxide
  • Embodiment 32 The substrate of any one of embodiments 17 or 19-28, wherein the oxidizing agent comprises a chloride.
  • Embodiment 33 The substrate of any one of embodiments 17 or 19-28, wherein the oxidizing agent comprises a material in its elemental form.
  • Embodiment 34 The substrate of any one of embodiments 20-33, wherein at least one dopant comprises ferric chloride.
  • Embodiment 35 The substrate of any one of embodiments 20-33, wherein at least one dopant comprises methyl sulfonic acid.
  • Embodiment 36 The substrate of any one of embodiments 1-35, wherein the pH of the conjugated polymer ranges from 6 to 8.
  • Embodiment 37 The substrate of any one of embodiments 1-36, wherein the electronic conductivity of the conjugated polymer ranges from 0.001 to 1000 S/cm.
  • Embodiment 38 The substrate of any one of embodiments 1-37, wherein the substrate is a window.
  • Embodiment 39 A conjugated polymer comprising monomer subunits, a counter ion, oxidizing agent and a dopant.
  • Embodiment 40 The conjugated polymer of embodiment 39, wherein the conjugated polymer comprises a polymer of 3,4-ethylenedioxythiophene, a polymer of pyrrole or a polymer of fluorene.
  • Embodiment 41 The conjugated polymer of any one of embodiments 39 or 40, having a total dopant concentration ranging from 0.01 to 5% by weight of the conjugated polymer.
  • Embodiment 42 The conjugated polymer of any one of embodiments 39-41, wherein the counter ion comprises a carboxylic acid or an amine.
  • Embodiment 43 The conjugated polymer of any one of embodiments 39-42, having a weight ratio between the monomer subunits and the counter ion ranging from 1 to 1000.
  • Embodiment 44 The conjugated polymer of any one of embodiments 39-43, wherein the oxidizing agent comprises a persulfate, a chlorate, and oxide or a chloride.
  • Embodiment 45 The conjugated polymer of any one of embodiments 39-44, wherein the oxidizing agent is in its elemental form.
  • Embodiment 46 The conjugated polymer of any one of embodiments 39-45, wherein the dopant comprises ferric chloride or methyl sulfonic acid or both.
  • Embodiment 47 The conjugated polymer of any one of embodiments 39-46, wherein the pH of the conjugated polymer ranges from 6 to 8.
  • Embodiment 48 The conjugated polymer of any one of embodiments 39-46, wherein the electronic conductivity of the conjugated polymer ranges from 0.001 to 1000 S/cm.
  • Embodiment 49 A composition comprising the conjugated polymer according to any one of embodiments 39-48 and a carrier fluid for application to a transparent or semi-transparent substrate.
  • Embodiment 50 The composition of embodiment 49, wherein the carrier fluid comprises an organic solvent.
  • Embodiment 51 The composition of embodiment 50, wherein the organic solvent comprises toluene, acetone, xylene, methanol, isopropanol or ethanol, or combinations thereof.
  • Embodiment 52 The composition of embodiment 49, wherein the carrier fluid comprises water.
  • Embodiment 53 The composition of any one of embodiments 49- 52, further comprising a surfactant.
  • Embodiment 55 The composition of any one of embodiments 49-
  • concentration of the conjugated polymer in the composition ranges from 0.5 to 30 weight %.
  • Embodiment 56 The composition of any one of embodiments 49-
  • composition comprises dodecylbenzene sulfonate.
  • Embodiment 57 A polymeric film comprising the conjugated polymer according to any one of embodiments 39-48.
  • Embodiment 58 The polymeric film of embodiment 57, wherein the transmission of visible light through the polymeric film ranges from 80 to 100%, when the polymeric film is measured at 200 nm thick.
  • Embodiment 59 The polymeric film of any one of embodiments 57 or 58, having a UV radiation absorption ranging from 35% to 80%.
  • Embodiment 60 The polymeric film of any one of embodiments.
  • Embodiment 61 The polymeric film of any one of embodiments 57-60, having a FOM A ranging from 8 to 12.
  • Embodiment 62 The polymeric film of any one of embodiments 57-61, having a FOM R ranging from 5 to 12.
  • Embodiment 63 The polymeric film of any one of embodiments 57-62, having a TAR ranging from 70 to 100.
  • Embodiment 64 The polymeric film of any one of embodiments 57-63, having an R/A ranging from 0.1 to 0.4.
  • Embodiment 65 The polymeric film of any one of embodiments.
  • Embodiment 66 The polymeric film of any one of embodiments 57-65, having a conductivity ranging from 0.001 to 1000 S/cm.
  • Embodiment 67 A method for reducing the UV or IR transmission, or both, of a transparent or semi-transparent substrate, the method comprising applying the polymeric film of any one of embodiments 57-66 on a surface of the substrate.
  • Embodiment 68 The method of embodiment 67, wherein the polymeric film is applied in the form of the composition of any one of embodiments 49- 56.
  • Embodiment 69 The method of embodiment 68 wherein the composition is mechanically sprayed onto a surface of the substrate.
  • Embodiment 70 The method of embodiment 69, wherein the composition is sprayed using an aerosol canister.
  • Embodiment 71 The method of embodiment 69, wherein the composition is sprayed using a non-aerosol spray bottle.
  • Embodiment 72 The method of embodiment 68, wherein the composition is mechanically wiped across a surface of the substrate.
  • Embodiment 73 The method of any one of embodiments 67 or 68, wherein the polymeric film is applied using a dip coating process.
  • Embodiment 74 The method of embodiment 67, wherein the polymeric film is applied using a doctor blade or painting method.
  • Embodiment 75 The method of any one of embodiments 67-74, further comprising a drying step.
  • Embodiment 76 The method of embodiment 75, wherein drying comprises use of elevated temperature.

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Abstract

L'invention concerne des polymères et des films polymères pour modifications de fenêtres et autres substrats, par exemple pour améliorer l'efficacité énergétique.
PCT/US2017/016289 2016-02-02 2017-02-02 Films polymères conjugués transparents WO2017136598A1 (fr)

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US20080146744A1 (en) * 1999-04-06 2008-06-19 Cambridge Display Technology Limited Method For Doping A Polymer
US20130135750A1 (en) * 2010-08-05 2013-05-30 3M Innovative Properties Company Multilayer film comprising matte surface layer and articles
US20150028322A1 (en) * 2008-04-11 2015-01-29 Solvay Usa, Inc. Doped conjugated polymers, devices, and methods of making devices
US20150072159A1 (en) * 2012-04-09 2015-03-12 Konica Minolta, Inc. Conductive film and organic electroluminescent element

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US20080146744A1 (en) * 1999-04-06 2008-06-19 Cambridge Display Technology Limited Method For Doping A Polymer
US20150028322A1 (en) * 2008-04-11 2015-01-29 Solvay Usa, Inc. Doped conjugated polymers, devices, and methods of making devices
US20130135750A1 (en) * 2010-08-05 2013-05-30 3M Innovative Properties Company Multilayer film comprising matte surface layer and articles
US20150072159A1 (en) * 2012-04-09 2015-03-12 Konica Minolta, Inc. Conductive film and organic electroluminescent element

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10087320B2 (en) 2017-02-17 2018-10-02 Polydrop, Llc Conductive polymer-matrix compositions and uses thereof

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