COMPOSITIONS COMPRISING CONJUGATED POLYMERS AND USES

THEREOF

BACKGROUND

Technical Field

Embodiments of the present invention generally relate to compositions comprising conductive polymers and methods of manufacturing and use of the same.

Description of the Related Art

Inherently, plastics and paints are insulators that require additives in order to create electrical conductivity. Applications such as electrostatic dissipation and electrically charging paints for spray coating need to include conductive materials for proper use. Metals have been the most common additives to create electrical conductivity, however, due to regulation, weight and health and safety, nano-particle metals are being phased out of various applications. Metal additives are being replaced with intrinsically conductive, metal-free, materials such as poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). Unfortunately, for applications such as touch screens and panels, the inherent electrical conductivity of PEDOT:PSS is unable to match that of indium tin oxide (ITO) films. Accordingly, there is a need in the art for improved electrically conducting, metal-free polymers and compositions comprising the same, for use in various applications. The present invention fulfills this need and provides related advantages.

BRIEF SUMMARY

Embodiments of the present invention are directed to compositions comprising conductive polymers and their use in various applications, such as for conductive films and use in electrostatic discharge applications. Accordingly, in some embodiments is provided a composition comprising a conjugated polymer and one or more compounds of structure (I) or (II):

(I) (Π)

or a salt or stereoisomer thereof, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ , a, b and n are as defined herein, provided at least two of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are not H and provided that b is 1 for at least one integral value of n. Polymeric films comprising the disclosed composition, and uses of the same in various applications are also provided.

BRIEF DESCRIPTION OF THE DRAWINGS

In the figures, identical reference numbers identify similar elements. The sizes and relative positions of elements in the figures are not necessarily drawn to scale and some of these elements are arbitrarily enlarged and positioned to improve figure legibility. Further, the particular shapes of the elements as drawn are not intended to convey any information regarding the actual shape of the particular elements, and have been solely selected for ease of recognition in the figures.

Fig. 1 shows an SEM particle size image for PEDOT:PMVEMA powder.

Fig. 2 provides conductivity data for PEDOT:PMVEMA in water.

Fig. 3 shows 1H NMR spectra for PEDOT:PMVEMA in methanol.

DETAILED DESCRIPTION

In the following description, certain specific details are set forth in order to provide a thorough understanding of various embodiments. However, one skilled in the art will understand that the invention may be practiced without these details. In other instances, well-known structures have not been shown or described in detail to avoid unnecessarily obscuring descriptions of the embodiments. Unless the context requires otherwise, throughout the specification and claims which follow, the word "comprise" and variations thereof, such as, "comprises" and "comprising" are to be construed in an open, inclusive sense, that is, as "including, but not limited to." Further, headings provided herein are for convenience only and do not interpret the scope or meaning of the claimed invention.

Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Also, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. It should also be noted that the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.

As used herein, and unless the context dictates otherwise, the following terms have the meanings as specified below.

"Aldehyde" refers to a substituent of the formula -C(=0)H.

"Amide" refers to a substituent of the formula -C(=0)N(R)2 - RC(=0)R, where each R is independently H, alkyl or aryl as defined herein.

"Amine" refers to a substituent of the formula -N(R) ₂ , where each R is independently H, alkyl or aryl as defined herein.

"Carbonate" refers to a substituent of the formula -OC(=0)OR, where R is alkyl or aryl as defined herein.

"Carbonyl" or "oxo" refers to the (=0) substituent.

"Carboxylate" refers to a substituent of the formula -C(=0)0 ^" .

"Carboxylic acid" refers to a substituent of the formula -C(=0)OH.

"Chlorate" refers to the C10 ₃ ^" anion.

"Chlorate" refers to the C10 ₂ ^" anion.

"Ester" refers to a substituent of the formula -OC(=0)R or -C(=0)OR, where R is alkyl or aryl as defined herein.

"Ether" refers to a compound of the formula ROR, where each R is independently H, alkyl or aryl as defined herein. A "fluoride" is a compound comprising at least one fluorine atom.

"Hydroxyl" refers to the -OH substituent.

"Imide" refers to substituent of the formula -C(=0) RC(=0)R' substituent, where R is H, alkyl or aryl, and R' is alkyl or aryl as defined herein.

"Imine" refers to the (=NR) substituent, wherein R is H, alkyl or aryl as defined herein.

"Ketone" refers to the -C(=0)R substituent, where R is alkyl or aryl as defined herein.

"Nitrile" refers to the -CN substituent.

"Nitro" refers to the -N0 ₂ substituent.

"Sulfate" refers to the -OSO ₃ H substituent.

"Sulfonate" refers to the -SO ₃ H substituent.

"Sulfoxide" refers to the -S(=0)R substituent, where R is alkyl or aryl as defined herein.

"Alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, which is saturated or unsaturated (i.e., contains one or more double and/or triple bonds), having from one to twelve carbon atoms (Ci-Ci ₂ alkyl), preferably one to eight carbon atoms (Ci-C ₈ alkyl) or one to six carbon atoms (Ci-C ₆ alkyl), and which is attached to the rest of the molecule by a single bond, e.g., methyl, ethyl, ^-propyl, 1-methylethyl (z ^' so-propyl), «-butyl, «-pentyl, 1, 1-dimethylethyl (t-butyl), 3-methylhexyl, 2-methylhexyl, ethenyl, prop-l-enyl, but-l-enyl, pent-l-enyl, penta-l,4-dienyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, and the like. Alkyl includes alkenyls (one or more carbon-carbon double bonds) and alkynyls (one or more carbon-carbon triple bonds such as ethynyl and the like). "Fluoroalkyl" refers to an alkyl group comprising at least one fluoro substituent. "Aliphatic" refers to an alkyl group optionally containing one or more carbon-carbon double bond or carbon-carbon triple bond. Unless stated otherwise specifically in the specification, an alkyl and/or fluoroalkyl group is optionally substituted.

"Alkylene" or "alkylene chain" refers to a straight or branched divalent hydrocarbon chain linking the rest of the molecule to a radical group, consisting solely of carbon and hydrogen, which is saturated or unsaturated (i.e., contains one or more double and/or triple bonds), and having from one to twelve carbon atoms, e.g., methylene, ethylene, propylene, «-butylene, ethenylene, propenylene, «-butenylene, propynylene, «-butynylene, and the like. The alkylene chain is attached to the rest of the molecule through a single or double bond and to the radical group through a single or double bond. The points of attachment of the alkylene chain to the rest of the molecule and to the radical group can be through one carbon or any two carbons within the chain. Unless stated otherwise specifically in the specification, an alkylene chain is optionally substituted.

"Alkoxy" refers to a radical of the formula -OR _a where R _a is an alkyl radical as defined above containing one to twelve carbon atoms. Unless stated otherwise specifically in the specification, an alkoxy group is optionally substituted.

"Aryl" refers to a carbocyclic ring system radical comprising hydrogen, 6 to 18 carbon atoms and at least one aromatic ring. For purposes of this invention, the aryl radical is a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which may include fused or bridged ring systems. Aryl radicals include, but are not limited to, aryl radicals derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, fluoranthene, fluorene, as-indacene, s-indacene, indane, indene, naphthalene, phenalene, phenanthrene, pleiadene, pyrene, and triphenylene. Unless stated otherwise specifically in the specification, the term "aryl" or the prefix "ar-" (such as in "aralkyl") is meant to include aryl radicals that are optionally substituted.

"Spray polymer" refers to a composition as disclosed herein 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 alternative, non-spray techniques such as spin coating and cloth transfer.

The term "substituted" used herein means any of the above groups (e.g.., alkyl, alkylene, alkoxy and/or aryl) wherein at least one hydrogen atom (e.g., 1, 2, 3 or all hydrogen atoms) is replaced by a bond to a non-hydrogen atom such as, but not limited to: a halogen atom such as F, CI, Br, and I; an oxygen atom in groups such as hydroxyl groups, alkoxy groups, and ester groups; a sulfur atom in groups such as thiol groups, thioalkyl groups, sulfone groups, sulfonyl groups, and sulfoxide groups; a nitrogen atom in groups such as amines, amides, alkylamines, dialkylamines, arylamines, alkylarylamines, diarylamines, N-oxides, imides, and enamines; a silicon atom in groups such as trialkylsilyl groups, dialkylarylsilyl groups, alkyldiarylsilyl groups, and triarylsilyl groups; and other heteroatoms in various other groups. In some embodiments, "substituted" means that at least one hydrogen atom is replaced with a bond to -OH, -SH, -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H or -C(=N)OH. "Substituted" also means any of the above groups in which one or more hydrogen atoms are replaced by a higher-order bond (e.g., a double- or triple-bond) to a heteroatom such as oxygen in oxo, carbonyl, carboxyl, and ester groups; and nitrogen in groups such as imines, oximes, hydrazones, and nitriles. For example, "substituted" includes any of the above groups in which one or more hydrogen atoms are replaced with - RgR _h , - R _g C(=0)R _h , - R _g C(=0) R _g R _h , - R _g C(=0)OR _h , - R _g S0 ₂ R _h ,

-OC(=0) R _g R _h , -ORg, -SR _g , -SOR _g , -S0 ₂ R _g , -OS0 ₂ R _g , -S0 ₂ OR _g , =NS0 ₂ R _g , and -S0 ₂ R _g R _h . "Substituted also means any of the above groups in which one or more hydrogen atoms are replaced with -C(=0)R _g , -C(=0)OR _g , -C(=0) R _g R _h , -CH ₂ S0 ₂ R _g , -CH ₂ S0 ₂ R _g R _h . In the foregoing, R _g and R _h are the same or different and independently hydrogen, alkyl, alkoxy, alkylaminyl, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, heteroaryl, N-heteroaryl and/or heteroarylalkyl. "Substituted" further means any of the above groups in which one or more hydrogen atoms are replaced by a bond to an aminyl, cyano, hydroxyl, imino, nitro, oxo, thioxo, halo, alkyl, alkoxy, alkylaminyl, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, heteroaryl, N-heteroaryl and/or heteroarylalkyl group. In addition, each of the foregoing substituents may also be optionally substituted with one or more of the above substituents.

"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 (i.e., monomers). A "polymer terminating group" is any moiety that terminates the polymerization of monomers when reacted with a growing polymer chain. For example, a polymer terminating group may be any moiety that reacts with a polymer free radical to terminate the polymerization reaction.

"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.

A "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.

An "oxide" refers to a molecule or compound comprising an element or molecule that is bound to oxygen.

"Silane" is an alkyl or alkoxy group, wherein at least one hydrogen atom has been replaced with a silicon atom, e.g. Si(CH ₃ ) ₄ . A "disilane" is a silane dimer comprising a Si-Si bond.

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.

"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. "Carrier Fluid" or "CF" 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.

"Dispersion" is a mixture comprising a solid or polymer material within a solvent. The solvent can be aqueous or non-aqueous.

"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.

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 "polyol" is a molecule or compound comprising more than one hydroxyl group; these materials often serve as the precursor monomer of polyol polymers.

An "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" or "COG" 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.

"Ultraviolet" refers to radiation with a wavelength less than 350 nm. 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.

In some embodiments, the current disclosure is directed towards materials useful as coatings to optimize electrical conductivity or electrostatic discharge. For example, the disclosed materials can be used to coat electrical components and other devices requiring an electrically conductive coating. The electrical conductivity of the disclosed compositions may range between 10 ^"4 S/cm to 10 ⁸ S/cm. In one embodiment the electronic conductivity of the composition is between 1 S/cm and 10 ³ S/cm, 1 S/cm and 10 ² S/cm, 50 S/cm and 100 S/cm. In another embodiment the electronic conductivity of the composition is between 10 ^"4 S/cm and 10 S/cm, 10 ^"3 S/cm and 1 S/cm, 10 ^"2 S/cm and 1 S/cm. In one embodiment the electronic conductivity of the composition 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.

When used to coat substrates, such as electrical components, the composition may be combined with a carrier fluid and applied using any number of art recognized techniques, such as spray or spin coating and the like.

Other embodiments of the present invention include the use of the disclosed composition in an electronic device. In some embodiments, the electronic device is a CPU or motherboard. In other embodiments, the electronic device is an airplane, automobile, bicycle, or motorcycle. In still other embodiments, the electronic device is a computer, tablet, or faceplate.

In other embodiments, the composition is used as a spray polymer coating and an optically transparent film. The disclosed materials represent a significant advancement over currently known methods for protective window coatings. 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. For high area windows, curved or bubble windows, or large number of windows, the process can be tedious and may require professional installation. In addition, 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.

In still other embodiments, the composition is used for anti-corrosion. The disclosed material can be used either as a direct-to-metal layer, or integrated into primers, paints, and topcoats to prevent metal oxidation. In some embodiments, the present invention overcomes limitations of previously described, existing solutions, and provides a number of other improvements. For example, the described composition has a relatively low viscosity when dissolved in a carrier fluid allowing the solution to be applied to windows using common household spray bottles. Furthermore, 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. Furthermore, by altering the functionality of the polymer, the spray polymer or polymer film can be designed to increase adhesion and scratch resistance to a wide range of substrates. Certain aspects of the disclosed materials and methods are described in more detail in the following sections.

Advantageously, certain embodiments of the compositions and polymer films described herein provide a metal-free composition, which eliminates the need for chromium-based additives. Furthermore, compositions may be added at any step during the coating process, allowing for versatility of materials and methods.

Accordingly, in one embodiment is provided a composition comprising a conjugated polymer (Component 1) and one or more second components (Component 2). In certain more specific embodiments, Component 2 is a compound of structure (I) or (II) as described herein below. In some embodiments, the composition further comprises an oxidizing agent (Component 3). In some embodiments, the composition comprises a one type of Component 2. In some embodiments, the composition comprises more than one unique Component 2, for example two different compounds of structure (I), two different compounds of structure(II) or a compound of structure (I) and a compound of structure (II).

In some embodiments, the Component 1 is positively charged and

Component 2 is negatively charged. In other embodiments, the composition comprises a physical mixture of Component 1 and Component 2. In still another embodiment, the composition comprises a coordinated complex of Component 1 and Component 2. In yet another embodiment, the Component 1 and Component 2 are covalently bound.

The conjugated polymer can be chosen from a range of novel materials and those known in the art, for example those disclosed in U.S. Patent No. 7,361,728, the full disclosure of which is hereby incorporated by reference in its entirety. In some embodiments the conjugated polymer comprises a polymer of 3,4- ethylenedioxythiophene (EDOT), carbazole, indole, azepine, p-phenylsulfide, aniline, pyrrole, fluorene, thiophene, or combinations thereof. In certain embodiments, the conjugated polymer is a polymer comprising EDOT monomers. In other embodiments, the conjugated polymer comprises polypyrrole. In some embodiments, the molecular weight of the conjugated polymer 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. In another example the molecular weight of the conjugated polymer after polymerization is below 5,000,000 g/mol.

Component 2 can be tailored for increased adhesion, electrical conductivity or other desired properties of the composition. Accordingly, in some embodiments Component 2 comprises at least one compound of structure (I) or (II). In certain embodiments, Component 2 comprises a plurality of compounds that are each independently a compound of structure (I) or (II), for example, each compound comprising the same or different functionalities. In some embodiments, Component 2 comprises two functionalities, Functionality A and Functionality B. Not to be bound by theory, in some embodiments Functionality A is a functional group that complexes with Component 1 while Functionality B is a functional group that interacts with a substrate to which the composition is applied (e.g., a glass-interactive functional group). In some embodiments, Functionality A and B are both independently polar functional groups, optionally capable of hydrogen bonding. For example, in some embodiments, Functionality A and B are independently selected from -OH, -SH, -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H and -C(=N)OH. In an embodiment, Functionality A is -SO ₃ H and Functionality B is a carboxylic acid, such as maleic acid. In some embodiments, the sum of the concentrations of Component 2 in the compositions ranges from 0.01 to 5 wt%. In some embodiments Component 2 comprises a carboxylic acid functional group. In some embodiments, the Component 2 comprises an amine.

In some embodiments, the composition further comprises a doping agent selected from ferric chloride and methyl sulfonic acid, and combinations thereof. Combinations of Functionality A and Functionality B are listed in Table 1. Table 1 is illustrative list for exemplary purposes and not exhaustive. Desirable combinations of functionalities will be apparent to those skilled in the art.

Table 1. Illustrative functionality of combinations of Component 2

In some embodiments, 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.

In other embodiments, the composition comprises a conjugated polymer and one or more compounds of structure (I) or (II):

(I) (Π)

or a salt or stereoisomer thereof wherein: R ¹ is, at each occurrence, -OH, -SH, -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H, -C(=N)OH, alkoxy or aryl substituted with one or more substituent selected from -OH, -SH, -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H and -C(=N)OH;

R ² and R ³ are, at each occurrence, independently -OH, -SH, -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H or -C(=N)OH;

R ⁴ and R ⁵ are independently H or a polymer terminating group;

R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently H, -OH, -SH, -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H or -C(=N)OH, provided at least two of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are not H;

L ¹ , L ² , L ³ , L ⁴ and L ⁵ are, at each occurrence, independently a direct bond or an optionally substituted alkylene linker;

a and b are each independently 0 or 1 for each integral value of n, provided that b is 1 for at least one integral value of n; and

n is an integer of 1 or greater.

In some embodiments, the composition comprises a compound of structure (I). For example, in some embodiments a and b are each independently 1 for at least one integral value of n. In other embodiments, L ⁴ and L ⁵ are each independently methylene or ethylene. In more embodiments, L ² and L ³ are absent. In some other different embodiments, L ¹ is absent.

In different embodiments the composition comprises a compound of structure (I), and R ² and R ³ are each independently -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO3H or -C(=N)OH. In some of these embodiments R ² and R ³ are each -C0 ₂ H. In other embodiments, R ¹ is alkoxy, such as methoxy.

In other embodiments, the compositions comprise a compound of structure (I), and R ¹ is aryl substituted with one or more substituent selected from -OH, -SH, -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H and -C(=N)OH. For example, in some embodiments R ¹ is phenyl substituted with one or more substituent selected from -OH, -SH, -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H and -C(=N)OH. In other embodiments, R ¹ is phenyl substituted with one or more substituent selected from -C0 ₂ H, -OPO ₃ H, -PO ₃ H, -OSO ₃ H, -SO ₃ H and -C(=N)OH. For example, in some more specific embodiments R ¹ has the following structure:

In still other embodiments, the compositions comprise a compound of structure (I) having one of the following structures:

In some embodiments, component 2 comprises both of the following compounds:

In still other embodiments, the compositions comprise a compound of structure (II). For example, in some of these embodiments at least three of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are not H. In other embodiments, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently H, -OH, -CO ₂ H or -SO ₃ H. For example, in some embodiments the compound of structure (II) has th :

In other embodiments of the foregoing composition, the conjugated polymer comprises heteroatoms. For example, in some embodiments the conjugated polymer is a polypyrrole, polycarbazole, polyindole, polyazepine, polyaniline, polythiophene or poly(p-phenylsulfide). In other embodiments, the conjugated polymer is poly(3,4-ethylenedioxythiophene. In still different embodiments, the conjugated polymer is a carbocyclic conjugated polymer. In yet more embodiments, the conjugated polymer is a polyfluorine, polyphenylene, polypyrene, polyazulene, polynaphthalene, polyacetylene or polypheneylene vinylene. In certain embodiments, the composition further comprises a doping agent, such as ferric chloride.

In some embodiments, the composition is used as a spray polymer solution for coating substrates. Accordingly, in some embodiments the composition further comprises a carrier fluid. In some embodiments, the carrier fluid comprises an organic solvent, such as toluene, acetone, xylene, methanol, ethanol or isopropanol. In different embodiments, the carrier fluid comprises water.

In some other embodiments, the composition further comprises a surfactant, for example the concentration of the surfactant in some embodiments ranges from 0.05 to 5 wt%.

In various of the foregoing embodiments, the concentration of the conjugated polymer ranges from 0.5 to 30 percent by weight of the composition.

In some embodiments, Component 1 will complex with Component 2. The weight ratio between Component 1 and Component 2 may impact the final performance properties of the polymer in addition to altering the reaction kinetics. In one embodiment the weight ratio of Component 1 to Component 2 ranges from 2: 1 to 1 : 1000. In certain specific embodiments, the weight ratio of Component 1 to Component 2 ranges from 1 to 1000. In other embodiments 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. In other embodiments 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 molar ratios between Component 1 and Component 2 can be measured using NMR (e.g., 1H MR ), known to those in the art. In one embodiment, the molar ratio between Component 1 and Component 2 ranges between 100: 1 and 1 : 100. In another embodiment, the molar ratio between Component 1 and Component 2 ranges from 100: 1 to 10: 1, from 20: 1 to 5: 1, from 10: 1 to 2: 1, or from 5: 1 to 1 : 1. In still another embodiment, the molar ratio between Component 1 and Component 2 ranges from 1 : 100 to 1 : 10, from 1 :20 to 1 :5, from 1 : 10 to 1 :2, or from 1 : 5 to 1 : 1. In yet another embodiment, the molar ratio between Component 1 and Component 2 as measured by ^X H NMR is around 1 : 1. The solvent for the reaction can be altered for safety for both the user and the environment. In some embodiments the solvent for synthesis comprises water. In some embodiments 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 optional Component 3. In one embodiment the concentration of Component 1 when mixed with Component 2 in solution ranges from 0.05 M to 5M. In other embodiments the concentration of Component 1 when mixed with Component 2 in solution ranges from 0.05 M to 1 M, 0.1 M to 0.9 M, 0.5 M to 0.9 M, 1 M to 4 M, or 2 M to 3 M. In certain embodiments the concentration of Component 1 when mixed with Component 2 in solution is less than 0.05 M or greater than 5 M. In still yet another embodiment, the concentration of Component 1 when mixed with Component 2 in solution is 0.08 M.

To facilitate the synthesis of the composition, an oxidization agent (Component 3) may be used. In some embodiments, the oxidizing agent comprises a persulfate, a chlorate, an oxide, a chloride, or combinations thereof. In some embodiments, the oxidizing agent comprises a material in its elemental form. In one embodiment, 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.

Table 2. Illustrative listing of Component 3

Component 3 Groups Example agents

Oxides Barium peroxide, dibenzoyl peroxide, hydrogen peroxide, magnesium peroxide, nitrogen trioxide, potassium peroxide, sodium peroxide, perchloric acid

Elemental Oxygen, fluorine, bromine

The ratio between Component 1 and Component 3 may impact the rate and extent of reaction. For example, in some embodiments 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. In another embodiment the molar ratio of Component 1 to Component 3 is about 1 : 1.

For preparation of the composition, the combination of Component 1, Component 2 and optional Component 3 (Mixture 1), can be heated or cooled to directly impact the rate of reaction. In some embodiments the 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. In other embodiments the temperature of Mixture 1 is decreased below 30 °C, below 20 °C, below 10°C, or below 0 °C. In still another embodiment, the temperature is held constant throughout the polymerization process. In yet another embodiment the temperature of Mixture 1 is dynamic.

The time allowed for polymerization of Mixture 1 can be controlled to obtain ideal particle size. For example, in some embodiments the time allowed for polymerization of Mixture 1 ranges from 5 minutes to 48 hours. In some embodiments, 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. In another embodiment the polymerization time for Mixture 1 is approximately 3 hours. In other embodiments, 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.

In addition to Component 1, Component 2 and Component 3, one or more dopants (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) of the composition. In one embodiment, Dopant 1 is a material with suitable electron withdrawing capacity such as ferric chloride, methyl sulfonic acid, tosylate, or combinations thereof. A listing of possible dopants is provided in Table 3. Table 3 is illustrative list for exemplary purposes and not exhaustive. Dopants will be apparent to those skilled in the art.

Table 3. Illustrative list of dopants

In another embodiment, Dopant 1 comprises a powder. In yet another embodiment, Dopant 1 is carbon, such as carbon black, carbon nanotubes, activated carbon, graphite, graphene. In still another embodiment, the dopant comprises a metal oxide, such as zinc oxide, nickel (II) oxide, copper (IV) oxide, or molybdenum (III) oxide. In some embodiments, the composition further comprises a particulate, for example, Laponite, Laponite RDS, Laponite EP, or combinations thereof. In more specific embodiments, the composition comprises Laponite RDS.

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. In some embodiments, 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%.

Multiple dopants may be used to create unique physical and chemical properties of the material. In some embodiments, 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%.

Typically the polymerized product after the reaction is acidic. In one embodiment the pH of the composition ranges froml to 6, 2 to 5, 2 to 4, or 6 to 8. Depending on the application (e.g. corrosion) a neutral or basic product may be desired. It has been found that the addition of a neutralizing agent (Additive 1) can be used to alter the pH of the final product without harm to the performance characteristics of the polymeric film. For example, Additive 1 can be a strong base comprising sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, or combinations thereof. In yet another example, Additive 1 can be a weak base comprising ammonia, ammonium hydroxide, pyridine, trimethyl ammonia, or combinations thereof.

After polymerization of Mixture 1 and neutralization using Additive 1, the intermediate product may be dried. In some embodiments, the intermediate product is dried using vacuum filtration, centrifuged, air dried, oven dried, or freeze dried. In another embodiment the intermediate product may never undergo a drying phase. In certain embodiments, the polymer composition may undergo a continuous solvent exchange.

Alternatively, the conjugated polymer can be commercially purchased or synthesized using methods known to those in the art. In some embodiments, the commercially available materials used as the conjugated polymer are PEDOT:PSS, poly(p-phenylene vinylene), poly(3-hexylthiophene), poly(pyrrole), poly(fluorene), poly(aniline), poly(acetylene), or combinations thereof. In certain embodiments, the commercially available conjugated polymers are further modified using Dopant 1 or Additive 1 to yield a novel material.

The composition can be mixed with a carrier fluid (CF) for the creation of the Spray Polymer material. In certain embodiments, a composition comprising the foregoing composition and a carrier fluid is provided. In one embodiment the carrier fluid is an organic solvent. In some embodiments, the CF comprises acetone, ethanol, methanol, isopropanol, toluene, xylene, methyl ethyl ketone, benzene or some combination thereof. In some embodiments, the carrier fluid comprises water.

To promote spray-ability and coverage of the composition on substrates, the dried composition or the CF may include a surfactant or wetting agent. In one embodiment, the composition may comprise a surfactant. In one embodiment 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. In still another embodiment the surfactant is nonionic, zwitterionic, containing cationic head groups, anionic. In some embodiments 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%.

In some embodiments, the mass percent of Component 2 as a percentage of the total mass of the composition can be varied from 0.01% to 99.9%. In other embodiments, the mass percent of Component 2 as a percentage of the total mass of the composition ranges from 0.1% to 50%, from 0.1% to 10%, from 1% to 10%, from 1% to 5%) or 1%) to 3%). In still other embodiments, the mass percent of Component 2 as a percentage of the total mass of the composition ranges from 50% to 99.9%, from 90% to 99.9% or from 90% to 99%. In another embodiment, the mass percent of Component 2 as a percentage of the total mass of the composition is approximately 50%.

The complex skeletal density of the composition may be assessed using helium pycnometry, as known to those skilled in the art. The complex skeletal density of the composition in some embodiments may range from 0.1 g/cc to 10 g/cc. In certain embodiments, the skeletal density of the composition is below 0.2 g/cc, below 0.3 g/cc, below 0.4 g/cc, below 0.5 g/cc, below 0.6 g/cc, below 0.7 g/cc, below 0.8 g/cc, below 0.9 g/cc, below 1.0 g/cc, below 1.1 g/cc, below 1.2 g/cc, below 1.3 g/cc, below 1.4 g/cc, below 1.5 g/cc, below 1.6 g/cc, below 1.7 g/cc, below 1.8 g/cc, below 1.9 g/cc, below 2.0 g/cc, below 2.1 g/cc, below 2.2 g/cc. In still other embodiments the skeletal density of the composition is below 2.5 g/cc, below 3.0 g/cc, below 3.5 g/cc, below 4.0 g/cc, below 5.0 g/cc, below 7 g/cc, below 10 g/cc.

Not wanting to be bound by theory, the surface area of the composition may be tailored in order to provide increased conductivity. Accordingly, in one embodiment the composition comprises a BET surface area of at least 1 m ² /g, at least 2

2 2 2 2 2 2 m /g, at least 3 m /g, at least 4 m /g, at least 5 m /g, at least 6 m /g, at least 7 m /g, at least 8 m ² /g, at least 9 m ² /g, or at least 10 m ² /g. In other embodiments, the composition comprises a BET surface area of at least 50 m ² /g, at least 100 m ² /g, at least 150 m ² /g, at least 200 m ² /g, at least 250 m ² /g, at least 300 m ² /g, at least 350 m ² /g, at least 400 m ² /g, at least 450 m ² /g, or at least 500 m ² /g. In yet another embodiment, the composition comprises a BET surface area of at least 1000 m ² /g.

The concentration of the conjugated 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. In one embodiment, a composition, wherein the concentration of the conjugated 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. In an embodiment, the concentration of the conjugated polymer in the carrier fluid is approximately 1.5 wt%. In yet another embodiment the concentration of the conjugated polymer in carrier fluid is greater than 10 wt%. The concentration of the composition can be linked to the viscosity. In some embodiments 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.

Not wanting to be bound by theory, the pH of the composition can impact both the adhesion and the safety of the polymer. In one embodiment the pH is approximately 7. However, there may be substrates or environments which require significantly acidic or basic solutions. In other embodiments the pH of the 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, which may or may not be dispersed in the CF, 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. In some embodiments 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. In other embodiments 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.

The composition may be purposefully functionalized in order to preferentially bond to various substrates. Not wanting to be bound by theory, the conjugated polymer and/or Component 2 functionality may determine, at least in part, the physical and chemical adhesion and reaction to substrate surfaces. The functionality of the conjugated polymer and/or Component 2 can be identified using infrared spectroscopy, or any other methods known to those of skill in the art. In one embodiment, the conjugated polymer and/or Component 2 comprises a substituent selected from hydroxyl, carbonyl, aldehyde, carbonate, carboxylate, carboxylic acid, ester, amide, amine, imine and fluoroalkyl, and any combination thereof. In another embodiment the substituent comprises silicon, such as a silyl or disilanyl substituent.

The inclusion of impurities or unreacted precursors could negatively affect the optical and mechanical properties of the final composition. The presence and concentration of such impurities can be determined with thermal gravimetric analysis, or any other methods known by those skilled in the art. In some embodiments the concentration of impurities in the composition ranges from 0 to 1 wt%, 0 to 2 wt%, 0 to 3 wt%, 0 to 4 wt%, or 0 to 5 wt%. In another embodiment the concentration of impurities is approximately 0.5 wt%. In other embodiments the concentration of impurities ranges from 1 to 5 wt%, 2 to 4 wt%, or 2 to 3 wt%. In still another embodiment the concentration of impurities is less than 1 wt% or greater than 5 wt%. In still other embodiments the concentration of impurities ranges from 5 to 30%, 5 to 20%, or 10 to 15%.

In some embodiments, the amount of individual trace elements can be determined using inductively coupled plasma optical emission spectrometry (ICP- OES), as known to those skilled in the art. In some embodiments, the level of scandium present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of titanium present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of vanadium present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of chromium present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of manganese present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of iron present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of cobalt present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of nickel present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of copper present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of zinc present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of silver present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of molybdenum present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of platinum present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In some embodiments, the level of cadmium present in the composition is less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm. In yet other embodiments, the sum of all ICP- OES impurities, excluding dopants, present in the composition is less than 100,000 ppm, less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 1,000 ppm, less than 500 ppm, less than 100 ppm, or less than 10 ppm.

To ensure that the polymerization has reached completion, 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 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 spray polymer material can be applied to any substrate, including transparent, semi-transparent, and non-transparent surfaces or substrates. In some embodiments, the invention provides a method for applying the compositions described herein. Other embodiments of the present invention include the use of the disclosed composition in an electronic device. In some embodiments, the electronic device is a CPU or motherboard. In other embodiments, the electronic device is an airplane, automobile, bicycle, or motorcycle. In still other embodiments, the electronic device is a computer, tablet, or faceplate.

In some embodiments, 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. In some embodiments, transparent surfaces or substrates include windows, single pane windows, double pane windows, car windows, residential windows, commercial windows, water bottles, light bulbs, computer screens, and watch or phone faces.

In some embodiments, 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 composition may be applied directly or indirectly to a transparent or semi-transparent surface or substrate. An embodiment for application of the composition to a surface or substrate is through mechanical spraying. In some embodiments, the composition is sprayed using an aerosol canister. In other embodiments, the composition is sprayed using a non-aerosol spray bottle. Spray bottles are common household objects used for various cleaning supplies. In one embodiment, the spray polymer is filled into a spray bottle. The bottle material is chosen to prevent chemical reactions between the spray polymer and bottle. Example bottle materials comprise polypropylene and silicon-containing glasses. In some embodiments the user mechanically wipes the composition across the transparent or semi-transparent surface or substrate. In yet another embodiment no additional wiping or spreading is required. In still another embodiment, the spray polymer is applied directly to a rag, cloth, or brush and applied through mechanical transfer. In other embodiments, the composition is applied through a doctor blade, painting method, mechanical spreading technique, or extrusion process. In some embodiments, the composition is applied using a dip coating process.

After application, the spray polymer film may need to undergo additional processing steps in order to reach desired performance properties. For example, the spray polymer may need to dry to remove excess carrier fluid. In certain examples, the method of applying the composition further comprises a drying step. In one embodiment the carrier fluid is removed through ambient temperature air dry. In other embodiments 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. In one embodiment the spray polymer is cured using thermal assistance or UV assistance.

Users may choose to remove the polymer coating once the transparent substrate is no longer in service, repurposed, or in need of repairs. Additionally, the user may choose to seasonally apply and remove the coating as the exterior temperature dictates. The spray polymer is designed to be removed using common solvents and removal techniques. In one embodiment the film can be removed when exposed to an acidic solution, a basic solution, organic solvents, or water. In another embodiment the film can be removed by common commercially available cleaning supplies, such as Windex. In still another embodiment, the film is removed through mechanical wiping of the film using a rag or cloth containing the appropriate solvent (e.g., ethanol).

Embodiments of the present invention provides a polymeric film comprising the composition 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. The wavelength of visible light is defined to fall between the ranges of 350 and 750 nm, as known in the art. In one embodiment the transmission of visible light through the film is between 70 and 100%. In some embodiments the transmission of visible light through the film ranges from 80 to 100%, 80 to 90%, 90 to 95%, or 70 to 80%. In certain embodiments, 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. In yet another embodiment the transmission of visible light is below 70%.

Another important goal for an effective film is the ability for the film to absorb ultraviolet (UV) radiation. The wavelength of UV radiation is defined as below 350 nm. In one embodiment the absorption of UV radiation by the polymeric film ranges from 25 to 100%. In another embodiment the absorption of UV radiation by the polymeric film ranges from 30 to 90%, 35 to 80%, 40 to 60%, or 45 to 55%. In yet another embodiment the absorption of UV radiation by the film is 50% or below 25%.

Yet another important goal for an effective film is the ability for the film to absorb infrared (IR) radiation. The wavelength of IR radiation is defined as above 750 nm. In one embodiment the absorption of IR radiation by the film is between 25 and 100%). In another embodiment the absorption of IR radiation by the film is between 30 and 90%, 35 and 80%, 35 and 60%, 35 and 50%. In yet another embodiment the absorption of IR radiation by the film is 40%.

Yet another important goal for an effective film is the ability for the film to reflect infrared (IR) radiation. In one embodiment the reflection of IR radiation by the film is between 20 and 100%. In another embodiment the reflection of IR radiation by the film is between 20 and 90%, 20 and 80%, 20 and 60%, 20 and 50%. In yet another embodiment the reflection of IR radiation by the film is 30%.

To compare two films with differing transmission, absorption, and reflection spectra, figures of merit are defined. 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.

L_„ Transmission

^F0M T = - JS ₇₅ i ₀ o- Transmi—ssion

In some embodiments the polymeric film has a FOM _T 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. In another embodiment the FOM _T is between 0.2 and 0.3, 0.25 and 0.29. In other embodiments the FOM _T ranging from 0.7 to 0.95, 0.75 to 0.9, or 0.8 to 0.85. 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 350 to 750 nm. A larger absorption figure of merit corresponds to better performance.

_R 2500

L_„ Absorption

FOM _A = ^P -

J ₃₅₀ Absorption

In one embodiment the polymeric film has a FOMA ranging from 1 to 20, 2 to 15, 5 to 10, 8 to 9, 8 to 12, or 9 to 10. In another embodiment 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 350 to 750 nm. A larger reflection figure of merit corresponds to better performance.

J ₃₅₀ Reflection

In one embodiment the polymeric film has a FOM _R 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 FOM _R 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.

TAR = FOM _T x FOM _A x FOM _R

One embodiment provides a polymeric film having a TAR ranging from

5 to 280. In some embodiments 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. In another embodiment, the TAR is approximately 75.

There are cases and applications wherein the absorption and the reflection of the film should be similar to each other. For example, a material may have a high TAR value, wherein the absorption value is low due to a high reflection. The ratio between reflection and the absorption can be defined using the following equation:

FOM,

R/A = FOM _A

When the R/A is low, the reflection and absorption of the film are similar. When the R/A is high, the reflection and absorption of the film are drastically different. In one embodiment 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.

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. In one embodiment 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 0.5%. In another application, it may be preferred that 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%.

In one embodiment 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 1, 0.7 and 1, 0.8 and 1, 0.9 and 1. In still another embodiment 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.

In addition to having optical performance properties 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). In one embodiment the polymeric film has a ^/-factor of the film ranging from 0.05 to 1.5 BTU/sf/hr/°F. In other embodiments 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. In yet another embodiment the polymeric film has a ^/-factor that is approximately 0.4 BTU/sf/hr/°F. In still another embodiment 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. Yet another thermal property of the film is the temperature of the outside of the window wherein condensation is formed on the inside of the window. Not being bound by theory, 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. In one embodiment the threshold exterior temperature for interior condensation is between -30 to 20 °C. In another embodiment, the threshold exterior temperature for interior condensation is between -20 to 10 °C, -10 to 0 °C. In yet another embodiment 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. The methods and classification using ASTM D3359 is well known to those in the art. In one embodiment 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).

In the summer, 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. To replicate standard environmental stresses, including elevated temperature and humidity, 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%.

As 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. In order to remain effective, the film needs to undergo minimal degradation or material loss when exposed to high temperature. Not wanting to be bound by theory, the thermal degradation onset is defined as the temperature at which 5% of the film is removed by thermo gravimetric analysis in nitrogen. In one embodiment the thermal degradation onset temperature of the film is between 100 °C and 500 °C. In another embodiment 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. In still another embodiment 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.

In addition to high performance, the material can also be designed to be safe for children and pets in the case of inadvertent ingestion. As known by those skilled in the art, Lethal Dose, 50% (LD50) is a measurement of the amount of a substance required to skill 50% of a test population. For the LD50 values herein, the test population is adult rats. In one embodiment the LD50 for the spray polymer material is between 0.0001 g/kg and 1000 g/kg. In another embodiment 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. In yet another embodiment 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.

Another characterization is of the electronic conductivity of the film. In one embodiment, 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 composition can be used to inhibit the oxidation of metallic surfaces. Known by those in the art, the composition can be added to the surface of bare metal as a pre-treatment, it can be mixed into a primer and coated on the surface, it can be mixed into a paint or combined with pigments to achieve a desired color, or it can be mixed into a top coat. As a pre-treatment, the composition is coated either using powder coating techniques or using a diluted spray, as previous described. The coating may undergo heating or post-treatment, such as curing, in order to achieve performance. The composition may be combined with other materials or coating layers, including but not limited to primers and top-coats.

In certain embodiments, a composition as described herein further comprises a matrix material. The matrix material can have any form factor. For example, the matrix material may be a resin, paint or a liquid solvent, such as water. In some embodiments the matrix comprises a solid, such as a powder. In certain embodiments, the matrix material comprises water, benzene, xylene, toluene, ethanol, methanol, methyl-ethyl-ketone, isopropanol, acetone or combination thereof. In another embodiment the matrix material comprises a surfactant such as 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. In other embodiments, the matrix material (e.g., paint or resin) comprises phenolics (e.g., phenol, polyphenol), esters (e.g., polyesters), epoxy, polyethylene terephthalate, acrylonitrile butadiene styrene, polystyrene, polypropylene, polyethylene, polycarbonate, nylon, polyurethane, hydrocarbon resins, acrylics (e.g., acrylate polymers, polyacrylic acid), chlorinated rubbers, vinyl, thermoplastic polyester, okra gum, pitch, galbanum, amino resins or combinations thereof. In another embodiment, the matrix material is a polymer comprising a gum resin, a synthetic resin, a thermoplastic resin, or a thermoset resin. In yet other embodiments the matrix material comprises zinc, aluminum, titanium, silver, nickel, chromium, copper, tin, or combinations thereof. Alternatively, in some embodiments the matrix material comprises a combination of substances listed above.

In one embodiment the matrix material is a powder. The diameter, or D(50), of the matrix powder material can be measured using methods known in the art, such as laser scattering techniques. In one embodiment the D(50) of matrix powder material is between 10 and 1000 nm, 10 and 500 nm, 20 and 300 nm, 20 and 50 nm, 50 and 200 nm, 100 and 150 nm. In another embodiment the D(50) of matrix powder material is approximately 200 nm. In yet another embodiment the D(50) of matrix powder material is between 200 and 1000 nm, 200 and 500 nm, 200 and 400 nm, 250 and 300 nm. In still another embodiment the D(50) of matrix powder material is less than 10 nm or greater than 1000 nm.

The percentage of the composition to the matrix material may determine the performance properties of the coating, such as adhesion, transparency, color, metal oxidation rate, and hardness. The composition added ranges between 0.1 wt.% and 99 wt.%. In some embodiments the composition added ranges between 0.1 wt% and 50%, between 0.5% and 10%, between 1% and 2%, between 1% and 5%. In yet other embodiments the composition added to matrix material is greater than 50% by weight.

The electronic conductivity of the matrix material may range between 10 ^"4 S/cm to 10 ³ S/cm. In one embodiment the electronic conductivity of the matrix material is between 1 S/cm and 10 ³ S/cm, 1 S/cm and 10 ² S/cm, 50 S/cm and 100 S/cm. In another embodiment the electronic conductivity of the matrix material is between 10 ^{" 4} S/cm and 10 S/cm, 10 ^"3 S/cm and 1 S/cm, 10 ^"2 S/cm and 1 S/cm.

The matrix material may be doped with an additive to further improve the performance characteristics. This secondary or tertiary dopant may be added either during the synthesis stage or mixed post-synthesis. In certain embodiments, the level of nickel doped into the matrix material is greater than 1 wt. %, greater than 2 wt.%, greater than 5 wt.%, greater than 10 wt.%, greater than 20 wt.%, or greater than 30 wt.%). In still another embodiment, the level of nickel doped into the matrix material is between 3 wt.% and 7 wt.%. In yet another embodiment, the level of nickel doped into the matrix material is ~6 wt.%. In other embodiments, the level of aluminum doped into the matrix material is greater than 1 wt. %, greater than 2 wt.%, greater than 5 wt.%), greater than 10 wt.%, greater than 20 wt.%, or greater than 30 wt.%. In certain embodiments, the level of titanium doped into the matrix material is greater than 1 wt. %, greater than 2 wt.%, greater than 5 wt.%, greater than 10 wt.%, greater than 20 wt.%), or greater than 30 wt.%. In certain embodiments, the level of silver doped into the matrix material is greater than 1 wt. %, greater than 2 wt.%, greater than 5 wt.%, greater than 10 wt.%, greater than 20 wt.%, or greater than 30 wt.%. In still another embodiment, the level of silver doped into the matrix material is between 1 wt.% and 5 wt.%. In yet another embodiment, the level of silver doped into the matrix material is ~3 wt.%. In another embodiment, the dopant comprises a powder form. In yet another embodiment, the dopant is carbon, such as carbon black, carbon nanotubes, activated carbon, graphite, graphene, In still another embodiment, the dopant comprises a metal oxide, such as zinc oxide, nickel (II) oxide, copper (IV) oxide, or molybdenum (III) oxide.

The metal surfaces which may be protected from corrosion and oxidation using the composition include copper, aluminum, steel, silver, and brass. Other metals or mixed metals may be coated to offset corrosive behavior. In addition, the composition may be used in conjunction with other known anti-corrosive materials and additives for enhanced performance.

The anti-corrosive properties may be used in a variety of applications including, but not limited to, gas or storage tanks, ships and boat hulls and parts, shipping containers, cars, trucks, busses, airplanes and aerospace, bridges, and construction equipment and supplies. Anti-corrosion performance can be measured using ASTM D 1654-05.

EXAMPLES

The compositions disclosed herein are made according to the general methods described above the specific Examples which follow. Chemicals were obtained through commercial sources and were used without further processing unless otherwise stated. The following examples are provided for purposes of illustration and not limitation.

EXAMPLE 1

PREPARATION OF A CONJUGATED POLYMER COMPOSITION

The conjugated polymer composition is 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, is added to the PSSA-co-MA solution at a weight ratio of 4: 1 (PSSA-co-MA:EDOT) and allowed to mix for 1 hour. Potassium persulfate (KPS) is added at a molar ratio of 1 : 1 (KPS:EDOT) to the PSSA- co-MA solution. The mixture is heated to 50 °C and allowed to polymerize to completion (approximately 3-24 hours). The polymerization is 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 composition.

Table 4. Exemplary combinations of Component 1, Component 2 and Component 3

A79 water 100 Pyrrole 10 PVA 27,000 6 FeCl ₃ 23

A80 water 100 Pyrrole 10 PVA 130,000 3 FeCl ₃ 23

PSSA-co-

A103 water 100 EDOT 8.5 20,000 8 KPS 8.5

MA

EXAMPLE 2

MODIFICATION WITH DOPANTS

The PEDOT composition is further modified through additional dopants. Ferric chloride (FeCl ₃ ) is added to the PEDOT dispersion in the amount of 0.1 wt% at room temperature. The composition and dopant are allowed to mix for 4 hours.

EXAMPLE 3

NEUTRALIZATION OF COMPOSITION

The pH of the composition from Example 2 is measured, typically falling between 2 and 4. To raise the pH of the composition for safe handling and application, aqueous sodium hydroxide is slowly titrated into the composition 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.

EXAMPLE 4

PREPARATION OF SPRAY POLYMER SOLUTION

The composition from Examples 1-3 can be further post-processed into the spray polymer solution product. 500 mL of composition is poured onto a vacuum filtration system using Whatman 602 H paper. The vacuum filtration is allowed to continue until complete solvent removal. Further drying is performed in air on a hot plate or oven at 50 °C. The powder is then dispersed in ethanol at 1.5 wt% using a mechanical mixer. Alternatively, the composition is filtered with a Whatman syringe filter of appropriate pore size. Example pore sizes include 220 nm and 450 nm.

Alternatively, the spray polymer solution is prepared through a solvent exchange. The water is exchanged with ethanol using a centrifugal extractor or mix- settler. Additional ethanol is added to the composition in order to reach the target concentration of 1.5 wt%. Alternatively, the spray polymer solution can be prepared through the manipulation of a commercially available polymer product. An aqueous dispersion of PEDOT:PSS may be obtained from Heraeus and modified as in Examples 2-4.

EXAMPLE 5

APPLICATION OF SPRAY POLYMER COMPOSITION IN ETHANOL AS A FILM

A transparent substrate, 3 inches by 3 inches, is cut from commercially available 1/8" thick glass, obtained from Gardner Glass Products. The substrate is mounted into a spin coater. The spin speed is set to 1000 rpm and 1 mL of spray polymer composition is dropped into the center of the substrate. With the composition on the substrate, rotation is begun and allowed to continue for 30 seconds. Once the rotation is complete, the substrate is removed from the spin coater and allowed to dry.

EXAMPLE 6

POST-PROCESSING OF THE FILM

To remove the carrier fluid, the film is allowed to air dry for at least 2 hours. The resultant film is removed using mechanical wiping and ethanol as a solvent.

EXAMPLE 7

CHARACTERIZATION OF THE FILM

Exemplary films were prepared according to Examples 1-6 and tested to determine physical characteristics for visible wavelengths (i.e., 350-750 nm) and infrared (i.e., 750-2500 nm). The results are shown below in Table 5.

Table 5. Physical characteristics of exemplary films

EXAMPLE 8

PREPARATION OF CONJUGATED POLYMER COMPOSITIONS

A composition comprising the conjugated polymer poly(3,4- ethylenedioxythiophene) (PEDOT) and poly(methylvinyl ether-alt-maleic acid) (PMVEMA) as Component 2 (structures below, where n is an integer greater than 1) was prepared as follows:

PEDOT PMVEMA

1. A 500 mL reaction vessel was filled with 400 mL of DI water and a stir bar was added to stir at moderate speed.

2. To the water was added 24 g of PMVEMA to create a 60 mg/mL

solution. PMVEMA was allowed to completely dissolve in the water before proceeding (approximately 10 minutes).

3. To the PMVEMA aqueous solution was added 6 g of 3,4- ethylenedioxythiophene (EDOT) monomer resulting in a PMVEMA:EDOT weight ratio of 4: 1. The weight ratio can be varied from 100: 1 to 1 : 10. The EDOT does not dissolve but emulsifies in the PMVEMA solution. The emulsion was allowed to form for about 15 minutes before proceeding. The emulsion appears milky white when formed.

4. To the emulsion was added 10.05 g of sodium persulfate (NaPS) as an oxidizing agent, corresponding to a NaPS:EDOT mole ratio of 1 : 1. The mole ratio can be varied from 10: 1 to 1 :2. The reaction mixture turns further white and looks like viscous milk.

5. The reaction was allowed to proceed for 72 hours at room temperature andthe PEDOT:PMVEMA product is dark blue in color and is a perfect dispersion.

The above procedure was repeated many times with various

concentrations and weight/mole ratios. For this reaction, potassium persulfate, sodium persulfate, and ferric chloride was used as the oxidizing agent. Each synthesis was successful and produced materials of varying particle size and conductivity. A summary of each of these reactions is in Table 6 below. Table 6. Synthesis of PEDOT:PMVEMA with various weight/mole ratios

A uniform particle size (Sample A93) can be achieved, as shown in Figure 1. The small particles are porous in nature and semi -spherical. The

PEDOT:PMVEMA composition can be dried from the reaction mixture and re- dispersed very easily in water. The conductivity of these aqueous dispersions depends on concentration, as shown in Figure 2. The concentration of the reaction to produce PEDOT:PMVEMA can play a role in the resistivity (i.e. conductivity) and dispersibility of the final dried product, as evidenced in Table 7.

Further confirmation of the molar ratio of the EDOT monomer to the maleic-acid derivatives can be measured by 1H NMR. Figure 3 shows an exemplary sample, depicting approximately ratio between EDOT and PMVEMA. Table 7. Resistivity and Dispersibility of PEDOT :PMVEM A as a function of concentration

Similar reactions were performed with other monomers (i.e., conjugated polymer precursors). A summary of those reactions is below in Table 8. Table 8. Synthesis of materials with PMVEMA as Component 2 and different monomers

Using analogous procedures, a composition comprising PEDOT as the conjugated polymer and poly(styrenesulfonic acid-co-maleic acid) (PSSAMA, structure below where x and y are independently integers of 1 or greater) as Component 2 was prepared.

PSSAMA

A summary of different preparations of PEDOT:PSSAMA is provided in

Table 9 below. Table 9. Synthesis of PEDOT:PSSAMA at various concentrations and weight ratios

Different compositions comprising PEDOT as the conjugated polymer and 5-sulfosalicylic acid (5-SSA, see below) were also prepared.

5-SSA

Table 10 below summarizes successful reactions performed with 5-SSA Component 2.

Table 10. Summary of Reactions with 5-SSA as Component 2

Volume Mass 5- Mass Mass

Reaction

H ₂ 0 SSA EDOT Ox. Agent Ox.

ID

(mL) (s) (S) Agent (g)

Potassium

A3 100 5.36 1.2 2.3

Persulfate

Potassium

A5 100 5.36 1.2 2.3

Persulfate

Potassium

A6 100 5.36 1.2 2.3

Persulfate

Potassium

A7 100 5.36 1.2 2.3

Persulfate

Sodium

A13 100 9.2 6 9

Chlorate

Sodium

A15 100 5.36 1.2 0.9

Chlorate

Potassium

A42 100 3.7 1.2 2.3

Persulfate

Potassium

A43 100 5.36 1.2 2.3

Persulfate

Potassium

A44 100 5.36 1.2 2.3

Persulfate

Sodium

A57 90 5.4 1.2 2.1

Persulfate

potassium

A138 200 7.4 2.4 4.6

Persulfate

EXAMPLE 9

SAMPLES PREPARED WITH LAPONITE RDS

Different compositions using two different poly(maleic acid)-derivatives were synthesized in the presence of a nanostructured backbone, Laponite RDS. The poly(maleic acid)-derivatives were added dropwise to two premixed reaction solutions containing water, Laponite RDS, and FeCl ₃ . Reaction mixtures were allowed to stir for 2 hours prior to the addition of 3,4-ethylenedioxythiophene (EDOT). The compositions of the final reaction mixtures are provided in Table 11.

Table 11. wt% Composition of Maleic Acid-Based Formulations

After 24 hours under constant mixing, both reaction mixtures exhibited a dark blue tint, indicating successful polymerization of the EDOT monomer into poly(3,4-ethylenedioxythiophene).

EXAMPLE 10

CONDUCTIVITY OF EXEMPLARY FILMS

To evaluate conductivity, reaction mixtures described in Example 9 were coated on polyethylene terephthalate and sheet resistivity was measured. Samples were prepared by concentrating the samples and removing unreacted compounds using centrifugation and re-suspending in water. A wetting agent, AFCONA-3585, was added to provide enhanced spreading and surface leveling. Films were coated at 2 mil wet film thickness and cured at 80 °C for 2 minutes. Sheet resistivity and appearance observations are provided below in Table 12.

Table 12. Coating Maleic Acid-Based Formulations

EXAMPLE 11

ANTI-CORROSION COUPON TESTING

In order to demonstrate performance for anti-corrosion applications, mild steel and aluminum coupons were coated with a composition disclosed herein, tested, and measured in accordance to ASTM D 1654-05. A high shear mixer was used to evenly disperse select compositions into paint. Metal coupons were dip coated in the resultant paint composition (i.e., paint with 5% additive composition) as well as a control sample (paint with no additive) and allowed to dry overnight. A 1 inch scribe was cut into the face of the coated coupons. The coupons were submerged into salt water, 1 M NaCl, and a bias voltage of 2.5 V was applied for 1 to 1.5 hours while the water was agitated. The scribe failure Rating Number for the paint without additive (i.e., control sample) measured at 6, while the paint compositions with 5% additive measured between 7 and 8. Thus, the results show that compositions prepared and used according to embodiments of the present invention demonstrate improved corrosion protection.

All of the U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification or the attached Application Data Sheet are incorporated herein by reference, in their entirety to the extent not inconsistent with the present description.

U.S. provisional patent application Serial No. 62/349,472 filed June 13, 2016 is incorporated herein by reference, in its entirety.