Polyaniline composition, article thereof, and method thereof

Abstract

The present disclosure provides compositions, articles thereof, and methods for forming the compositions. In at least one embodiment, the composition comprises: (1) an epoxy; (2) an amino or amide curing agent; (3) polyaniline; (4) a dopant selected from triazolyl, thiazolyl, quinolinyl, salicylate, benzoate, glycolate, phosphate, sulfonate, oxalate, or a combination thereof; and (5) a pigment selected from titanium dioxide, silica, talc, mica, aluminum stearate, or a combination thereof. The polyaniline plus the dopant constitutes more than 6% by weight of the composition. In at least one embodiment, the method comprises introducing an acid form of polyaniline into a hydroxide to form a polyaniline hydroxide. The method comprises introducing a dopant into the polyaniline hydroxide to form a doped polyaniline.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit and priority of U.S. Patent Application No. 17 / 407,850, filed on 20 August 2021, and U.S. Provisional Patent Application No. 63 / 089,439, filed on 8 October 2020, both of which are incorporated herein by reference as fully described below and for all applicable purposes.

[0002] This disclosure provides compositions, articles thereof, and methods for forming compositions. [Background technology]

[0003] Static electricity accumulates on the surface of moving vehicles, such as aircraft. The nose of an aircraft may accumulate static electricity in a form known as precipitation static (P-static). For example, an aircraft may have one or more components located behind the nose of the aircraft that may be sensitive to static electricity.

[0004] Surface coatings can be applied to aircraft components to protect their surfaces. However, conventional surface coatings (one or more) on aircraft vehicle components are typically not highly conductive, having resistivity ranging from several hundred kiloohms to tens of megaohms. Consequently, conventional surface coatings on aircraft can lead to charge accumulation on the aircraft surface (and other components). In addition to the inability to discharge this charge accumulation, conventional coatings may not possess ideal properties. For example, durability parameters such as resistance to rain erosion, high temperature resistance, low temperature resistance, and resistance to sand and hail damage may not be ideal for conventional surface coatings on vehicle surfaces exposed to extreme conditions.

[0005] Furthermore, cold weather conditions encourage ice to accumulate on the vehicle's surface. To remove the ice, chemicals are often sprayed onto it to accelerate its melting. These chemicals are then charged to the vehicle owner.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] There is a need for novel and improved compositions, articles having the compositions, and methods of forming the compositions.

MEANS FOR SOLVING THE PROBLEMS

[0007] The present disclosure provides a composition, an article thereof, and a method of forming the composition.

[0008] In at least one aspect, the composition comprises (1) an epoxy, (2) an amino or amide curing agent, (3) polyaniline, (4) a dopant selected from triazolyl, thiazolyl, quinolinyl, salicylate, benzoate, glycolate, phosphate, or a combination thereof, and (5) a pigment selected from titanium dioxide, silica, talc, mica, aluminum stearate, or a combination thereof, wherein polyaniline + dopant constitutes more than 6% by weight of the composition based on the weight of the composition.

[0009] In at least one aspect, the substrate has the composition disposed thereon. <00001​​​​​​​​​​​​This is a diagram illustrating an exemplary series-flow reactor system in one or more embodiments. [Figure 1C] This is a diagram illustrating an exemplary parallel flow reactor system in one or more embodiments. [Modes for carrying out the invention]

[0012] For ease of understanding, the same reference numeral is used to indicate identical elements common to multiple drawings, where possible. It is intended that elements and features of one example may be usefully incorporated into other examples without further description.

[0013] This disclosure provides compositions, articles thereof, and methods for forming compositions. This disclosure relates to electrostatic discharge compositions useful for components that accumulate static electricity during use. Electrostatic discharge compositions generally include high conductivity in addition to other ideal aircraft safety properties.

[0014] The compositions of the present disclosure comprise (1) epoxy, (2) an amino or amide curing agent, (3) polyaniline, (4) a dopant selected from triazolyl, thiazolyl, quinolinyl, salicylate, benzoate, glycolate, phosphate, oxalate, sulfonate, or a combination thereof, and (5) one or more pigments selected from titanium dioxide, silica, talc, mica, aluminum stearate, or a combination thereof, wherein the polyaniline + dopant constitutes more than 6% by weight of the composition on a weight basis. The articles of the present disclosure include a substrate and a composition disposed thereon. A method for forming the compositions of the present disclosure may include treating a polyaniline base with a dopant selected from triazole, thiazole, quinoline, salicylate, benzoate, glycolic acid, phosphate, oxalate, sulfonate, or a combination thereof.

[0015] Polyanilines are conjugated polymers that have alternating single and double CC bonds along the polymer chain. The conjugation of π ("pi") electrons extends throughout the polymer backbone, making these polymers conductive and possessing switchable redox properties. The polymer backbone is positively charged in its oxidized form and can bind to negatively charged ions (e.g., negatively charged dopants). This phenomenon is also known as doping.

[0016] composition The compositions of the present disclosure comprise (1) epoxy, (2) an amino or amide curing agent, (3) polyaniline, (4) a dopant selected from triazolyl, thiazolyl, quinolinyl, salicylate, benzoate, glycolate, phosphate, oxalate, sulfonate, or a combination thereof, and (5) one or more pigments selected from titanium dioxide, silica, talc, mica, aluminum stearate, or a combination thereof, wherein the polyaniline + dopant constitutes more than 6% by weight of the composition on a weight basis.

[0017] As used herein, “composition” may include the components of the composition and / or the reaction products of two or more components of the composition (one or more).

[0018] The compositions of this disclosure may have a volatile organic compound (VOC) content of about 300 g / L or less, for example, about 100 g / L to about 300 g / L, for example, about 200 g / L to about 250 g / L, as determined by ASTM D3960-1. Compositions having a VOC content of about 300 g / L or less may give a low VOC content that makes the composition environmentally compatible (e.g., environmentally friendly).

[0019] The compositions of this disclosure may have a volume solids content of about 70% or more, for example, 80% or more, for example, about 90% or more, based on the total volume of the composition. The volume solids content is calculated for weighing the components and preparing the composition. The total solids content may be determined by evaporating the solvent. Compositions having a volume solids content of about 70% or more may give a low volatile organic matter content, which gives an environmentally friendly composition.

[0020] The compositions of this disclosure may be placed on one or more substrates. The compositions placed on the substrates (for example, as layers) may be coated with thicknesses of about 1 micrometer (μm) to about 100 μm, for example, about 1 μm to about 10 μm, for example, about 10 μm to about 80 μm, for example, about 20 μm to about 60 μm, for example, about 25 μm, about 35 μm, about 45 μm, about 50 μm. In at least one embodiment, the composition, when in contact with a 3.5% NaCl solution, is about 10 4 Ω~about 10 9 Ω, for example, about 10 6 It has an electrochemical impedance of Ω. (This is the coating's resistance to NaCl penetration. This is a measure of barrier protection. A higher value indicates better resistance.)

[0021] In at least one embodiment, the composition is about 10 4 Ohm / square (Ω / □) ~ approximately 10 8 Ω / □, for example, approximately 10 5 Ω / □~approx. 10 7 Ω / □, for example, approximately 10 6 It has a resistance value of Ω / □. Its conductivity leads to electrostatic discharge.

[0022] The substrate of this disclosure may be a vehicle component or a wind turbine component (e.g., one or more turbine blades or one or more turbine stations). The vehicle may be equipped with any suitable transport device. Examples of vehicles include, but are not limited to, aircraft, automobiles, boats, motorcycles, satellites, rockets, missiles, and therefore, manned and unmanned aerial vehicles, manned and unmanned spacecraft, manned and unmanned ground vehicles, manned and unmanned non-ground vehicles, and even manned and unmanned marine vehicles, objects, and structures.

[0023] A vehicle component may comprise one or more compositions of the present disclosure disposed on one or more surfaces of the vehicle component. Examples of vehicle components include, but are not limited to, any part of a vehicle, such as a structural component, such as a panel or joint of a vehicle. Examples of vehicle components include airfoils (e.g., rotor blades), auxiliary power units, the nose of an aircraft, fuel tanks, tail cones, panels, coated overlap joints between two or more panels, wing-fuselage assemblies, aircraft structural composites, fuselage body joints, wing rib-skin joints, and / or other internal components.

[0024] Epoxy and amino / amide curing agents The compositions of this disclosure may comprise one or more epoxys and one or more amino curing agents and / or one or more amide curing agents.

[0025] In at least one embodiment, the composition comprises an amount of ((epoxy + amino curing agent)) or (epoxy + amide curing agent) in an amount of about 40% to about 75% by weight, for example, about 45% to about 65% by weight, or about 55% to about 75% by weight, based on the total weight of the composition.

[0026] In at least one embodiment, the composition contains one or more epoxys in an amount of about 30% to about 50% by weight, for example, about 30% to about 40% by weight, or about 35% to about 45% by weight, based on the total weight of the composition. In at least one embodiment, the composition contains one or more amino curing agents in an amount of about 12% to about 22% by weight, for example, about 12% to about 18% by weight, or about 15% to about 21% by weight, based on the total weight of the composition. In at least one embodiment, the composition contains one or more amide curing agents in an amount of about 12% to about 22% by weight, for example, about 12% to about 18% by weight, or about 15% to about 21% by weight, based on the total weight of the composition.

[0027] Examples of epoxies include partially cured epoxies, two-component epoxy resins containing specific epoxy additives and catalysts (e.g., HYSOL® EA 956 epoxy resin available from Henkel Corporation in Baypoint, California), two-component systems containing the resin and curing agent of the Disclosure (e.g., EPOFIX resin available from Struers A / S in Barrelp, Denmark), triglycidyl ethers of aminophenols (e.g., Araldite MY 0500 or MY 0510 from Huntsman Advanced Materials (Monte, Switzerland)), tetrafunctional epoxies, e.g., N,N,N',N'-tetraglycidyl-m-xylenediamine (e.g., Araldite MY0720 or MY0721 from Huntsman Advanced Materials (Monte, Switzerland)), and mixtures thereof. Epoxies also include bifunctional epoxies, e.g., bisphenol A (bis-A) or bisphenol F (bis-F) based epoxies. Bisphenol A epoxy resins are commercially available as Araldite GY6010 (Huntsman Advanced Materials) or DER 331, available from Dow Chemical Company (Midland, Michigan). Bisphenol F epoxy resins are commercially available as Araldite GY281 and GY285 (Huntsman Advanced Materials). Due to their durability, epoxy resins are suitable for applications such as thermosetting resins on the exterior of aircraft. In one or more embodiments, the epoxy is a bisphenol A epoxy, which is Araldite GY 250 or GY 9090, available from Huntsman Advanced Materials.

[0028] As for amino curing agents, there are polyaminoamine curing agents (for example, Aradur 450 and Aradur 2973, commercially available from Huntsman Advanced Materials (Monte, Switzerland)). Examples include aliphatic polyamine curing agents commercially available from Materials (Montey, Switzerland), polyetheramines with a Tg of approximately 40°C to 100°C (e.g., JEFFAMINE® T-403 amine or JEFFAMINE® D-230 amine), ethyleneamines with a Tg of approximately 110°C to 125°C (e.g., diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or N-aminoethylpiperazine), alicyclic amines with a Tg of approximately 145°C to 175°C (e.g., bis-(p-aminocyclohexyl)methane, diaminocyclohexane, or bis-(dimethyldiaminocyclohexyl)methane), or aromatic amines with a Tg of approximately 160°C to 220°C (e.g., methylenedianiline, m-phenylenediamine, or diaminophenylsulfone).

[0029] Examples of amide curing agents include Aradur 360 (a polyamideamine curing agent commercially available from Huntsman Advanced Materials (Montey, Switzerland)), or polyamides or amideamines with a Tg of approximately 40°C to 100°C (for example, VERSAMID® 125 polyamide or GENAMID® 490 amideamine).

[0030] Polyaniline and dopants The compositions of the present disclosure may comprise one or more polyanilines and one or more dopants. In at least one embodiment, the composition comprises, based on the total weight of the composition, more than 6% by weight, for example, about 6.5% to about 75% by weight, for example, about 10% to about 60% by weight, for example, about 20% to about 50% by weight, for example, about 25% to about 40% by weight, for example, about 30% to about 35% by weight of polyaniline + dopant.

[0031] Examples of inorganic pigments include TiO2, talc, mica, silica, and aluminum stearate.

[0032] In at least one embodiment, the composition contains polyaniline in an amount of about 3% to about 75% by weight, for example, about 10% to about 60% by weight, for example, about 20% to about 50% by weight, for example, about 30% to about 40% by weight, based on the total weight of the composition.

[0033] In at least one embodiment, the composition contains a dopant in an amount of about 3% to about 60% by weight, for example, about 10% to about 40% by weight, for example, about 10% to about 30% by weight, for example, about 15% to about 20% by weight, based on the total weight of the composition.

[0034] The molar ratio of the dopant to the aniline units of polyaniline can range from approximately 0.1:1 to approximately 1:1, for example, approximately 0.3:1 to approximately 1:1, for example, approximately 0.5:1 to approximately 1:1, for example, approximately 1:1.

[0035] The dopant may be selected from triazolyl, thiazolyl, quinolinyl, salicylate, benzoate, glycolate, phosphate, or a combination thereof. For example, the dopant may be a phosphate that can provide temperature stability to the composition at high temperatures (e.g., one or more high curing temperatures).

[0036] In at least one embodiment, the sulfonate is selected from dinonyl naphthylene sulfonate, naphthalene sulfonate, benzene sulfonate, toluene sulfonate, or a combination thereof.

[0037] In at least one embodiment, triazolyl is selected from benzotriazole, triazolecarboxylic acid, benzotriazolesulfonic acid, or a combination thereof.

[0038] In at least one embodiment, thiazolyl is selected from one or more benzothiazoles, thiazole carboxylic acids, mercaptobenzothiazoles, or combinations thereof.

[0039] In at least one embodiment, quinolinyl is selected from 8-hydroxyquinoline, mercaptoquinoline, or a combination thereof.

[0040] In at least one embodiment, the salicylate is selected from salicylic acid, hydroxybenzoic acid, salts thereof, or combinations thereof.

[0041] In at least one embodiment, the benzoate is selected from benzoates, benzoic acid, methylbenzoic acid, salts thereof, or combinations thereof.

[0042] In at least one embodiment, the glycolate is selected from glycolate or thioglycolate.

[0043] In at least one embodiment, the phosphate is selected from phosphoric acid or a salt thereof.

[0044] The polyanilines of this disclosure may be formed using aniline and phosphoric acid, aryl sulfonic acids, such as alkyl-substituted aryl sulfonic acids (e.g., dinonylnaphthylene sulfonic acid (DNNSA)). For example, the non-sulfonated hydrocarbon content of alkyl-substituted aryl sulfonic acids may be 1% by weight or less. The non-sulfonated hydrocarbon content of conventional alkyl-substituted aryl sulfonic acids (e.g., DNNSA) is greater than 1% by weight. The non-sulfonated hydrocarbons may include branched-chain and straight-chain paraffins and / or aromatic compounds (e.g., benzene and naphthalene). For example, by using DNNSA with a non-sulfonated hydrocarbon content of 1% by weight or less, polyanilines with reduced outgassing and improved thermal stability can be obtained. Polyanilines with reduced outgassing and improved thermal stability and articles thereof may provide compositions of this disclosure that can be applied as coatings, layers, etc., for use in a wide range of articles, such as aircraft, land vehicles, wind turbines, satellites, etc. Alkyl-substituted aryl sulfonic acids (e.g., DNNSA) can be obtained from commercial sources (e.g., King Industries).

[0045] The polyanilines of this disclosure may have thermal stability above approximately 100°C, a weight-average molecular weight (Mw) of approximately 50,000 g / mol to approximately 150,000 g / mol, and / or a molecular weight distribution (MWD) of approximately 1 to approximately 5. The reduced outgassing and improved molecular weight characteristics of the polyanilines of this disclosure result in improved thermal stability compared to conventional polyanilines.

[0046] The molecular weight data (Mw, Mn, Mz, Mp, and Mw / Mn) used herein refer to neutral polyanilines (e.g., uncharged, i.e., undoped forms of polyanilines). In other words, the molecular weights of polyanilines used herein do not include the molecular weights added by the presence of dopants.

[0047] The polyanilines of this disclosure may have a weight-average molecular weight (Mw) of about 50,000 g / mol to about 150,000 g / mol, for example, about 75,000 g / mol to about 100,000 g / mol, or about 100,000 g / mol to about 130,000 g / mol. The polyanilines of this disclosure may have a number-average molecular weight (Mn) of about 50,000 g / mol to about 100,000 g / mol, for example, about 60,000 g / mol to about 80,000 g / mol, or about 80,000 g / mol to about 100,000 g / mol.

[0048] The polyanilines of this disclosure may have a molecular weight distribution (MWD) of about 1 to about 5, e.g., about 1 to about 4, e.g., about 1.2 to about 2.5, e.g., about 1.3 to about 1.7, as determined by gel permeation chromatography. The MWD is determined by dividing Mw by Mn and may be referred to herein as "Mw / Mn".

[0049] The polyanilines of this disclosure may have a z-average molecular weight (Mz) of approximately 75,000 g / mol to approximately 250,000 g / mol, for example, approximately 100,000 g / mol to approximately 250,000 g / mol, for example, approximately 150,000 g / mol to approximately 250,000 g / mol. Mz indicates the polymer content. For example, the Mz value of the polyanilines of this disclosure can be higher than that of conventional polyanilines, thereby improving processability compared to conventional polyanilines.

[0050] The polyanilines of this disclosure may have peak average molecular weights (Mp) ranging from approximately 50,000 g / mol to approximately 150,000 g / mol, for example, approximately 100,000 g / mol to approximately 150,000 g / mol, for example, approximately 110,000 g / mol to approximately 140,000 g / mol. The peak average molecular weight indicates the pattern of molecular weight distribution of the polymer.

[0051] The molecular weight properties of polyaniline (e.g., Mw, Mn, Mz, Mp) can be determined using gel permeation chromatography. The mobile phase may be a solution of N-methylpyrrolidone (NMP) in 0.02 M ammonium formate (AF). Calibration may be used to measure the molecular weight distribution using a viscosity detector and a refractive index detector. The solution may be filtered through a 0.45 micron filter before use. The polyaniline sample may be precipitated in spectroscopic quality methanol, washed four times with methanol, and recovered by vacuum filtration. The sample may be air-dried, dissolved in AF-NMP, and placed directly into a GPC vial through a 0.2 micron filter for analysis.

[0052] The hydrocarbon content of an article of the composition of this disclosure, such as a film, may be about 1% by weight or less, for example, about 0.5% by weight or less, for example, about 0.1% by weight or less, based on the total weight of the sample. Examples of hydrocarbons include C1-C20 paraffins and aromatic hydrocarbons, such as benzene and naphthalene. In at least one embodiment, the hydrocarbon is naphthalene.

[0053] The outgassing percentage of the polyaniline (and / or composition (e.g., layer)) of the present disclosure may be about 0.5% or less, e.g., about 0.3% or less, e.g., about 0.1% or less, e.g., about 0.05% or less, e.g., about 0.01% or less, according to ASTM E 595-93.

[0054] The thermal stability of the polyaniline (and / or composition (e.g., layer)) of this disclosure may be above about 100°C, e.g. above about 110°C, e.g. above about 120°C, e.g. between about 120°C and about 160°C, e.g. between about 130°C and about 160°C, e.g. between about 140°C and about 160°C, e.g. between about 150°C and about 160°C. The thermal stability may be determined by spin-coating the polyaniline (or composition) onto a microscope slide and drying the spin-coated sample at 70°C. A silver bar may be applied to the edge of the slide for electrical contacts. The sample may be exposed to a temperature (e.g., 150°C) for 24 hours in a convection oven. The resistance of the sample may then be measured to determine its thermal stability.

[0055] In at least one embodiment, the polyaniline is a PANI-acid represented by formula (I): [Chemical formula] wherein, R 1 , R 2 , R 3 , and R 4 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 aryl, substituted or unsubstituted C1-C20 alkaryl, substituted or unsubstituted C1-C20 arylalkyl, substituted or unsubstituted C1-C20 alkoxyl, and halogen (e.g., fluoro, chloro, bromo, or iodo), wherein one or more of the occurrences of R 1 , R 2 , R 3 , and R 4 are optionally substituted with a group independently selected from C1-C20 alkoxyl and halogen (e.g., fluoro, chloro, bromo, or iodo), A - is a dopant each time it occurs, n is an integer such that the weight average molecular weight (Mw) of the polyaniline is from about 55,000 g / mol to about 80,000 g / mol, such as from about 60,000 g / mol to about 75,000 g / mol, such as from about 65,000 g / mol to about 70,000 g / mol.

[0056] In at least one embodiment, R 1 , R 2 , R 3 , and R 4 are each independently selected from hydrogen and unsubstituted C1-C20 alkyl. In one or more embodiments, the C1-C20 alkyl is selected from methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, and sec-hexyl. In at least one embodiment, R 1 , R2 , R 3 , and R 4 Each instance is hydrogen.

[0057] In at least one embodiment, the C1-C20 aryl is selected from phenyl and naphthyl. In at least one embodiment, the C1-C20 alkaryl is benzyl. In at least one embodiment, the C1-C20 arylalkyl is toluyl, mesityl, or ethylbenzyl.

[0058] In at least one embodiment, A - It is a dopant that is independently selected from triazolyl, thiazolyl, quinolinyl, salicylate, benzoate, glycolate, phosphate, or sulfonate each time it appears.

[0059] Methods for preparing alkyl-substituted aryl sulfonic acids, aniline, and polyaniline A typical, non-limiting reaction scheme for forming the polyaniline of this disclosure is shown in Scheme 1 below. As shown in Scheme 1, aniline is treated with an alkyl-substituted aryl sulfonic acid and a catalyst to form the polyaniline represented by formula (I). Scheme 1 [ka]

[0060] R in equation (I) of Scheme 1 1 , R 2 , R 3 , R 4 , and A - This is as described above for equation (I).

[0061] For the aniline monomer in Scheme 1, R 1 , R 2 , R 3 , and R 4Each instance of R is independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 aryl, substituted or unsubstituted C1-C20 alkaryl, substituted or unsubstituted C1-C20 arylalkyl, substituted or unsubstituted C1-C20 alkoxyl, and halogen (e.g., fluoro, chloro, bromo, or iodine), where R 1 , R 2 , R 3 , and R 4 One or more occurrences of R are optionally substituted with a group independently selected from C1-C20 alkoxyls and halogens (e.g., fluoro, chloro, bromo, or iodine), 5 It is hydrogen.

[0062] In at least one embodiment, the R of the aniline monomer of scheme 1 1 , R 2 , R 3 , and R 4 Each occurrence is independently selected from hydrogen and unsubstituted C1-C20 alkyl groups. In one or more embodiments, the C1-C20 alkyl group is selected from methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, and sec-hexyl. In at least one embodiment, R 1 , R 2 , R 3 , and R 4 Each instance is hydrogen.

[0063] The alkyl-substituted aryl sulfonic acid (or its solution, e.g., an organic solution) of this disclosure may have a non-sulfonated hydrocarbon content of 1% by weight or less and may be a dialkyl-substituted naphthyl sulfonic acid, e.g., DNNSA. Alkyl-substituted aryl sulfonic acid, e.g., DNNSA, with a non-sulfonated hydrocarbon content of 1% by weight or less is commercially available from King Industries.

[0064] In at least one embodiment, the hydrocarbon content of the alkyl-substituted aryl sulfonic acid (e.g., DNNSA) (or a solution thereof) is about 1% by weight or less, for example about 0.5% by weight or less, for example about 0.1% by weight or less, based on the total weight of DNNSA (DNNSA does not contain any further solvent, e.g., isopropanol).

[0065] The molar ratio of dopant (e.g., alkyl-substituted aryl sulfonic acid) to aniline in the method for forming polyaniline can be about 0.2:1 to about 2:1, for example about 0.3:1 to about 1:1, for example about 0.8:1 to about 1:0.8, for example about 1:1.

[0066] Potential catalysts for forming polyaniline include any suitable ammonium catalyst or sulfate catalyst, such as ammonium persulfate.

[0067] Furthermore, the addition of additional hydrocarbon solvents may be undesirable. For example, the addition of heptane or hexane at high concentrations can prevent emulsion formation. Emulsions promote polyaniline formation. For instance, if the method is carried out using only a heptane solution of DNNSA without 2-butoxyethanol, the reaction may not proceed and a soluble product may not be obtained.

[0068] Flow reactor method for forming polyaniline This specification discloses a method for forming polyaniline (hereinafter also referred to as PANI-acid) as a solvent-soluble polymer by chemical treatment in a flow reactor using a dopant (e.g., alkyl-substituted aryl sulfonic acid (e.g., DNNSA)). The disclosed system and method provide a unique processing sequence for directly recovering the purified emeraldine salt without any post-reactoral operations. This system and method represent an improvement over known methods for synthesizing conductive polymers, particularly conductive polymer salts, e.g., PANI-acid, using extremely short reaction times that cannot be achieved by other conventional methods that require long reaction times.

[0069] For example, these systems and methods offer improvements in the efficient and controlled synthesis of polyaniline (PANI) salts as soluble, intrinsically conductive polymers. This specification describes the continuous flow synthesis of PANI-acids or "emeraldine salts" using a flow reactor. In some examples, the flow reactor includes a microfluidic (internal diameter 1 to approximately 750 μm) tubular reactor. In some examples, the microfluidic tubes consist of a fluoropolymer, e.g., TEFLON®. The tubular reactor provides a surface suitable for the deposition of the polymer during formation and the direct purification of the conductive polymer salt.

[0070] As used herein, the term “flow reactor” includes a microflow reactor. A microflow reactor is used herein as a flow reactor having a flow dimension, for example, an internal diameter (ID) of less than 1 mm (1000 microns).

[0071] As further described below, in some examples, as the polymerization reaction proceeds, the majority of the polymer product accumulates on the walls of the tube. The polymer product can be purified by washing with water to remove aqueous-soluble reactants, reagents, and by-products.

[0072] Conductive polymer salts formed in a flow reactor and deposited on the tube walls can be eluted with an organic solvent to yield soluble conductive polymer salts. The apparatus can be configured for in-situ characterization by, for example, UV-Vis spectroscopy, infrared spectroscopy, and / or mass spectrometry.

[0073] Apparatus and associated methods for polymerizing at least one reactant are described. In a particular example, the apparatus is a microfluidic apparatus comprising a mixing chamber and a microchannel. Furthermore, the reactor may further comprise an output chamber and a detection unit operably connected to the microchannel.

[0074] Using any suitable apparatus (e.g., a flow reactor), the polyanilines of this disclosure, for example, the polyanilines described in U.S. Patent No. 10,118,992, incorporated herein by reference, can be formed.

[0075] Referring to Figure 1A, a flow reactor system 100 is shown. A first reactant 10 (e.g., aniline) and a second reactant 20 (e.g., alkyl-substituted aryl sulfonic acid) are introduced into a first mixing unit 30. The reactor system 100 shown in Figure 1A can produce conductive polymer salts more efficiently (mass / unit time) than conventional macroscale or batch reactors. The flow reactor 100 can operate at a processing temperature range of room temperature to about 250°C, for example, below 100°C. In some examples, the ambient temperature is about 50°F (10°C) to about 90°F (32°C). In some examples, reactants 10 and 20 are introduced independently into the first mixing unit 30 at a predetermined flow rate and / or concentration so that they are mixed before reactants 10 and 20 in a desired molar ratio are introduced into the flow reactor. In other examples, reactants 10 and 20 are introduced together into a first mixing unit 30 so that they are mixed before reactants 10 and 20 in a desired molar ratio are introduced into the flow reactor. The first mixing unit 30 can be any suitable mixing device. In some examples, the mixing device is a high-speed or ultra-high-speed mixer capable of emulsifying one or more solutions, such as aqueous and non-aqueous solutions. In some examples, the first reactant 10 is in an aqueous solution and the second reactant 20 is in a non-aqueous solution, but the first mixing unit 30 is designed to emulsify the first reactant 10 and the second reactant 20. A third reactant 50 is joined with the first and second reactants in a second mixing unit 60. In some examples, reactant 50 is a catalyst. After mixing in the second mixing unit 60, the reactants are introduced into a tube 70 via an inlet port 65. The tube 70 has an outlet port 80 which can be monitored by an analyzer 90. The analytical apparatus 90 may include a spectrometer for examining and analyzing materials flowing from the discharge port 80, such as unreacted materials and / or reaction products. Examples of spectrometers include UV-Vis, IR (near-infrared, mid-infrared, and far-infrared), and mass spectrometry. Other analytical and investigation techniques, such as capacitance and pH, may be used.A pressure regulating unit 67 may be located at the outlet of the flow reactor 70 to monitor pressure changes during polymerization or during the recovery step of the polymerized material, and information from the pressure regulating unit 67 may be used by a controller to stop the introduction of reactants (e.g., aniline) into the flow reactor. For example, an additional pressure regulating unit 67 may be located at the inlet of the flow reactor 70 to monitor pressure changes during the process. A fluid line 69 may be fluid-coupled independently to the flow reactor 70 to introduce a purging medium 66 (e.g., water) or a recovery medium 68 (e.g., solvent) for recovering polymerization products from the flow reactor unit 70.

[0076] In some examples, the flow reactor system 100 has a single inlet port to the tube 70. In other examples, the flow reactor system 100 has an additional inlet port located between the inlet port 65 and the discharge port 80. As shown in Figure 1A, the tube 70 can be coiled to provide an elongated tubular flow reactor.

[0077] In some examples, the tube 70 is housed within a housing 40 that provides temperature control and / or support and / or protection from damage to the tube 70. In some examples, the housing 40 has an inner surface that surrounds at least a portion of the tube 70 so that the coiled tube 70 is at least partially housed within the housing 40. In some examples, the housing 40 is configured to provide temperature control to the tube 70, including heating and / or cooling.

[0078] As shown in Figure 1B, an alternative flow reactor configuration 100a is shown with a plurality of tubes 70a, 70b arranged in series in a coil configuration. The tubes 70a, 70b may be dimensionally identical or may have different lengths and / or different inner diameters. In this configuration, the housing may be divided into separate compartments 40a, 40b that can accommodate the tubes 70a and 70b and can be operated independently for heating and / or cooling the tubes. Alternatively, the flow reactor configuration 100a may have a single housing that accommodates the tubes 70a, 70b. In contrast to a parallel array configuration of tubes where the process flow is divided before entering the flow reactor, a series array maximizes the amount of time the reaction mixture is maintained under diffusion-limited conditions. While not bound by any particular theory, maintaining the reaction mixture under diffusion-limited conditions is considered to result in the improvement of the reaction of this disclosure for producing conductive polymer salts from reactants in emulsions compared to batch processing. The methods and systems disclosed herein provide such diffusion-limited conditions for emulsions of reactants.

[0079] Referring to Figure 1C, an exemplary flow reactor system 100b is shown. Multiple flow reactor units 70c, 70d, and 70e are shown in a parallel flow configuration. Each flow reactor 70c, 70d, and 70e may be independently separated by flow control valves 63 located at the inlets and outlets of the introduction of the monomer solution into each flow reactor to the corresponding flow reactor. The flow control valves 63 may be manually operated and / or solenoid-based and / or configured for computer control using a conventional control device. The flow control valves 63 may include one or more check valves to prevent backflow of the dispersion solution. One or more pressure regulating units 67 may be located at one or more outlets of the flow reactors to monitor pressure changes during polymerization or during the recovery step of the polymerized material. Further pressure regulating units 67 may be located at the inlets of each flow reactor. The flow control valve 63 may be coupled to pressure data from a controller to isolate one or more of the flow reactors 70c, 70d, and 70e in order to activate purging and / or polymer recovery. In this configuration, the flow reactor system 100b may be operated continuously by selectively isolating one or more of the flow reactor units 70c, 70d, and 70e for the recovery and / or maintenance of polymerization products, while maintaining the introduction of monomers to one or more of the remaining flow reactor units. Alternatively, the flow reactor system 100b may be operated semi-continuously, for example, by temporarily stopping the introduction of monomers to one or more of the flow reactor units 70c, 70d, and 70e. Further fluid lines 69 may be fluid-coupled independently to one or more of the flow control valves 63 to introduce a purging medium 66 (e.g., water) or a recovery medium 68 (e.g., solvent) for selectively recovering polymerization products from one or more of the flow reactor units 70c, 70d, and 70e. One or more of the flow reactor units 70c, 70d, and 70e can be physically removed from the flow reactor system 100b for transport, with or without the polymerization product recovered from the inner diameter of the tube.

[0080] The length of the tube may be selected based on the ability of the selected components of the system (pump, tube burst strength, fittings, etc.) to cope with the pressure. The maximum length of tube suitable for use in the systems of this disclosure is a function of the back pressure and the ability to transport the product over the entire length of the tube. In some examples, the system may be configured to operate with a length of tube combined with an inner diameter of tube such that the system operates at approximately 20 bar (280 psi) or less. In some examples, the length of the tube does not exceed 500 meters and the tube has an inner diameter of less than 4000 microns. In other examples, the tube is a tube (microfluidic tube) with a diameter of less than 1000 microns and a length of approximately 100 meters or less. Other combinations of tube diameter and length may be used in accordance with the operating parameters of the system and the desired reaction volume per unit time.

[0081] The molecular weight properties of polyaniline (e.g., Mw, Mn, Mz, Mp) can be determined using gel permeation chromatography. The mobile phase may be a solution of N-methylpyrrolidone (NMP) in 0.02 M ammonium formate (AF). Calibration may be used to measure the molecular weight distribution using a viscosity detector and a refractive index detector. The solution may be filtered through a 0.45 micron filter before use. The polyaniline sample may be precipitated in spectroscopic quality methanol, washed four times with methanol, and recovered by vacuum filtration. The sample may be air-dried, dissolved in AF-NMP, and placed directly into a GPC vial through a 0.2 micron filter for analysis.

[0082] Subsequently, the PANI-acid can be converted to polyaniline hydroxide (sometimes called "de-doped" polyaniline). For example, the PANI-acid can be treated with a hydroxide to form polyaniline hydroxide. For example, the PANI-acid can be treated with 1M ammonium hydroxide for about 30 minutes to about 6 hours, for example, about 2 hours. The polyaniline hydroxide product can then be filtered, washed with water, for example, and dried. The polyaniline hydroxide can then be treated with a dopant by introducing the polyaniline hydroxide into triazole, thiazole, quinoline, salicylic acid, benzoic acid, glycolic acid, phosphoric acid, or a combination thereof. Although not bound by theory, it is thought that anionic dopants (one or more) replace the hydroxide bound to polyaniline (of the polyaniline hydroxide) to form the polyaniline + dopant of this disclosure (sometimes called "re-doped" polyaniline). The re-doped polyaniline can be filtered, washed with water (e.g., deionized water), and dried (e.g., at a high temperature such as about 60°C).

[0083] pigment In at least one embodiment, the compositions of the present disclosure include pigments selected from titanium dioxide, silica, talc, mica, aluminum stearate, or combinations thereof.

[0084] The pigments of this disclosure can impart opacity to a composition. For example, a composition containing (one or more) pigments can coat a substrate and make the coated substrate opaque.

[0085] In at least one embodiment, the composition comprises titanium dioxide, talc, mica, silica, and aluminum stearate. For example, the composition may contain titanium dioxide in an amount of about 0.01% to about 10% by weight, for example, about 6% to about 10% by weight, or for example, about 7% to about 9% by weight, based on the total weight of the composition. The composition may contain talc in an amount of about 0.01% to about 10% by weight, for example, about 2% to about 8% by weight, or for example, about 3% to about 6% by weight, based on the total weight of the composition. The composition may contain mica in an amount of about 0.01% to about 10% by weight, for example, about 2% to about 8% by weight, or for example, about 3% to about 6% by weight, based on the total weight of the composition. The composition may contain silica in an amount of about 0.01% to about 10% by weight, for example, about 2% to about 8% by weight, or for example, about 3% to about 6% by weight, based on the total weight of the composition.

[0086] The composition may contain aluminum stearate in an amount of about 0.01% to about 0.5% by weight, for example, about 0.1% to about 0.4% by weight, based on the total weight of the composition.

[0087] Composition and layer of composition In at least one embodiment, a method for forming a composition comprises mixing (1) epoxy, (2) an amino or amide curing agent, (3) polyaniline, (4) a dopant selected from triazolyl, thiazolyl, quinolinyl, salicylate, benzoate, glycolate, phosphate, oxalate, sulfonate, or a combination thereof, and (5) one or more pigments selected from titanium dioxide, silica, talc, mica, aluminum stearate, or a combination thereof to form the composition. The mixing may include diffusion and / or active mixing (e.g., mixing using a stirrer). The method may include placing (e.g., depositing) the composition onto a substrate to form a layer containing the composition. The method may include curing the composition. The method may include dissolving one or more components of the composition in a solvent before mixing. The solvent may be xylene, toluene, dimethyl sulfoxide, water, or a mixture thereof.

[0088] In at least one embodiment, the substrate is a metal substrate made from aluminum, aluminum alloys, nickel, iron, iron alloys, steel, titanium, titanium alloys, copper, copper alloys, or mixtures thereof. In some embodiments, the substrate is aluminum, carbon fiber epoxy, glass fiber reinforced polymer, cellulose reinforced phenolic resin, polyimide, glass, polyether ether ketone, polyether ketone, polystyrene, polypropylene, polytetrafluoroethylene, or a combination thereof. The substrate may be a “bare” substrate without plating (e.g., unplated metal), without a chemical conversion coating, and / or without corrosion protection between the substrate and the composition. Additionally or alternatively, the substrate may include surface oxidation. Thus, the composition may be placed directly on the substrate and / or directly on a surface oxide layer on the surface of the substrate, or on a surface pre-treated with a chemical conversion coating or adhesion promoter.

[0089] In at least one embodiment, the secondary layer is disposed on (e.g., deposited on) (disposed on) the composition. The secondary layer may be an organic material (e.g., an organic composition) configured to be disposed on (e.g., adhered to) the composition. The secondary layer may include paints, topcoats, polymer coatings (e.g., epoxy coatings and / or urethane coatings), polymer materials, composite materials (e.g., filler composites and / or fiber-reinforced composites), laminating materials, or mixtures thereof. In at least one embodiment, the secondary layer includes polymers, resins, thermosetting polymers, thermoplastic polymers, epoxy, lacquers, polyurethanes, polyesters, or combinations thereof. The secondary layer may further include pigments, binders, surfactants, diluents, solvents, fine particles (e.g., mineral fillers), fibers (e.g., carbon, aramid, and / or glass fibers), or combinations thereof.

[0090] The thickness of the composition (e.g., the layer containing the composition) can be used to adjust one or more of the (1) conductivity and (2) resistance of the composition placed on the substrate. The thickness of the composition may also be used to further adjust the "aircraft safety" properties (e.g., resistance to rain erosion, as well as damage from sand and hail) of the composition and the resulting coated substrate.

[0091] The compositions of this disclosure may be applied (e.g., placed onto a surface) to a surface such as the surface of a vehicle part by any suitable method, e.g., immersion, spraying, brush coating, spin coating, roll coating, doctor blade coating, or a combination thereof. The compositions may be cured before or after application to the surface of the vehicle part. For example, the composition may be deposited onto the vehicle part. Once deposited, the composition may be heated to cure it. High temperatures may be used to accelerate the curing process. Curing facilitates the evaporation of one or more solvents in the composition (if present), e.g., xylene, toluene, and / or water.

[0092] The method may include rinsing the composition with a rinse agent (for example, in a configuration where the composition is arranged as a layer on a substrate). The rinse agent may include isopropyl alcohol, p-toluenesulfonic acid, acetone, methanol, their hydrates, their solvates, or mixtures thereof. Rinsing may include spraying the rinse agent onto the surface of the composition for about 1 second to about 10 minutes, for example, about 1 minute to about 5 minutes. Rinsing may include spraying the rinse agent onto the surface of the composition in an amount of about 1 mL to about 25 kL, for example, about 1 L to about 100 L, for example, about 1 L to about 5 L, for example, 1 L, 2 L, 3 L, 4 L, 5 L. Rinsing may include rinsing the first composition with a second rinse agent, which is different from the first rinse agent, isopropyl alcohol, p-toluenesulfonic acid, acetone, methanol, their hydrates, their solvates, or mixtures thereof. In at least one embodiment, rinsing includes immersing the composition in a rinsing agent for about 1 second to about 1 minute.

[0093] Curing the composition may involve raising the temperature of the composition to its peak curing temperature and maintaining that peak curing temperature for about 1 second to about 48 hours, for example, about 1 hour to about 10 hours. The peak curing temperature may be roughly room temperature to about 200°C, for example, about 50°C to about 90°C, for example, 50°C, 60°C, 70°C, 80°C, or 90°C.

[0094] The placement (e.g., deposition) of the composition onto the substrate can be achieved by spin-coating the composition onto the substrate, for example, the surface of a vehicle component, at speeds of approximately 100 rpm to approximately 4,000 rpm, for example, approximately 500 rpm to approximately 2,000 rpm, for example, approximately 500 rpm, approximately 1,000 rpm, approximately 1,500 rpm, and approximately 2,000 rpm.

[0095] Alternatively, the placement of the composition onto the substrate can be achieved by spraying the composition onto the substrate, for example, the surface of a vehicle component, using any suitable composition spraying apparatus.

[0096] In at least one embodiment, a method for heating a vehicle component includes applying a voltage to the surface of a composition placed on the vehicle component. Applying a voltage to the surface of the composition causes solid water (ice) placed on the surface of the vehicle component to melt at least partially. The voltage may be an alternating current (AC) voltage of about 10 Hz to about 2000 Hz, for example, about 500 Hz to about 1000 Hz, for example, about 500 Hz, about 600 Hz, about 700 Hz, about 800 Hz, or about 900 Hz. The voltage may be an alternating current (AC) voltage of about 10 volts to about 2000 volts, for example, about 100 volts to about 500 volts, for example, about 100 volts, about 200 volts, about 300 volts, about 400 volts, or about 500 volts.

[0097] The thickness of the composition, or coating thickness, can be measured using an elcometer or defelsko eddy current-based probe.

[0098] Resistance measurements can be performed using any suitable set of electrodes and measuring device, for example, a Keithley 4200 SCS. Preferably, resistance measurements are performed using the van der Pauw method. The four-point method uses parallel source-sense measurements of current and voltage across the entire surface of the sample. To test for both polarities, the current and voltage polarities are switched across each contact. The geometric shape of the sample should be kept constant to allow for direct comparison of samples. To account for differences in charge directionality, the current and voltage measurements are rotated in each of the possible arrangements, as shown in Table 1.

[0099] [Table 1]

[0100] Van der Pauw resistance measurement is performed by passing a current between two adjacent electrodes and sensing the voltage drop across the sample in a parallel arrangement of electrodes.

[0101] The sheet resistance can be calculated from the V to I ratio of the measured composition. For a sample exhibiting truly isotropic resistance, R A =R B =R C =R D In the case of isotropic resistance, for example, R A =R B In this case, the sheet resistance is determined by the average of two measured resistance values, as shown in Equation 1 below. For samples with anisotropic resistance (where the resistance values ​​differ in the x and y directions), the calculation of the sheet resistance becomes more complex, which will be discussed in the following paragraph. A ≠R C and R B ≠R DFor all samples, the measurement is invalid. Equation 2 shows how to determine the bulk resistivity ρ when the thickness d of the composition is known (typically the resistivity is reported in Ω·cm, and therefore the use of d in cm units), which is derived from the original Van der Pauw theorem. Then, the conductivity σ(S·cm⁻¹) can be calculated using the bulk resistivity ρ, which is inversely proportional to the bulk resistivity (Equation 2).

number

[0102] R A ≠R B In this case, deriving the conductivity value from Van der Pauw's equation becomes more difficult. If the conductivity is not isotropic, the conductivity becomes a tensor value in x, y, and z dimensions. For very thin compositions, an accurate conductivity value can be obtained by squaring the product of orthogonal conductivity measurements, as shown in Equation 3 below. This calculation is only valid if the direction being measured is aligned with the conductivity tensor axis. We assume that the larger of the two resistance values ​​measured by this technique is precisely aligned with the lowest conductivity tensor, and the smaller of the resistance measurements is precisely aligned with the highest conductivity tensor. If the conductivity tensor and the electrode / sample orientation are not aligned, an inaccurate conductivity value will be measured.

number

[0103] Regarding the van der Pauw measurement chip, the numbers correspond to the measurement axis, and the notation is Sigma X (σ A , σ B , and σ C The ) represents the direction of the conductivity tensor. If the sample axis and the tensor axis do not align, it will result in inaccurately measured conductivity. The van der Pauw printed electrode, along with the Keithley 4200 SCS, provides a suitable instrument test bench for measuring samples. In an attempt to control the influence of measured humidity, a small sample probe station may be used and connected solely to the Keithley 4200 SCS for accurate van der Pauw measurements on Dropsens' off-the-shelf electrodes.

[0104] Electrochemical Impedance Spectroscopy (EIS) EIS uses a variable-frequency AC source to investigate the change in impedance of a sample at different frequencies. Similar to a resistor, impedance is the lag between the applied AC and the measured voltage change. Electrical circuit components respond in a frequency-dependent manner, which can be used to identify specific properties of a coating being measured. A true ohmic resistor exhibits the same response to both direct current (DC) and alternating current (AC) sources and therefore does not exhibit a frequency-dependent resistance response. Capacitors (and more complex electrical components) have a frequency-dependent response; that is, their impedance is very high at low frequencies and low at high frequencies. In the analysis of EIS data, a predictive model known as an equivalent circuit model is constructed from true and pseudo-electrical components to closely approximate the sample system. The calculated impedance spectrum of the model is then compared to the measured spectrum.

[0105] Application of the composition Non-limiting examples of the use of the compositions of this disclosure include their use as components of thermoplastic materials and / or prepreg materials. In the case of prepreg materials, the compositions of this disclosure may be applied to and / or impregnated into fibrous materials comprising, among other things, graphite, glass fiber, nylon, Kevlar® and related materials (e.g., other aramid polymers), and polyethylene.

[0106] The compositions of this disclosure can be deposited on the surface of a substrate such as a vehicle component. Examples of vehicle components include structural components, such as panels or joints for aircraft, automobiles, ships, etc. Examples of vehicle components include airfoils (e.g., rotor blades), auxiliary power units, aircraft noses, fuel tanks, tail cones, panels, coated lap joints between two or more panels, wing-fuselage assemblies, aircraft structural composites, fuselage body joints, wing rib-skin joints, and / or other internal components.

[0107] Compared to conventional coatings, the compositions and methods of this disclosure result in a certain degree of reduction in dopant leaching over time. This is because the dopant can bind to polyaniline (e.g., polyaniline in emeraldine form).

[0108] De-icing: After one or more compositions of the Disclosure have been deposited (and possibly hardened) onto a substrate, e.g., a vehicle component, if, for example, severe weather conditions have caused ice to accumulate on one or more components, the components can be “de-iced.” Since the compositions of the Disclosure may be conductive, applying a voltage to a surface containing a composition will cause the surface temperature to rise and some of the ice accumulated on the surface to melt. In at least one embodiment, a voltage is applied to a surface containing one or more compositions of the Disclosure, thereby completely melting the ice accumulation on the surface. In at least one embodiment, a voltage is applied to a surface containing one or more compositions of the Disclosure, thereby causing partial melting of the ice accumulation on the surface, and the partially melted ice accumulation slides off the vehicle component.

[0109] In at least one embodiment, de-icing includes bringing any suitable AC / DC voltage generator into contact with a surface containing one or more compositions of the Disclosure and applying an AC voltage to the one or more compositions. By bringing the AC voltage generator into contact with a surface containing one or more compositions of the Disclosure (as resistors), resistive heating of at least this surface may be brought about, and resistive heating of one or more layers of the vehicle component may be brought about. In at least one embodiment, de-icing includes applying a voltage to a surface containing one or more compositions of the Disclosure by generating electricity in an aircraft component. For example, an aircraft engine is switched to active mode, and AC power supplied by the aircraft engine is transmitted to the surface of the aircraft, thereby de-icing one or more surfaces of the aircraft component. These embodiments result in intrinsic de-icing of the aircraft without the need to apply an external voltage generator to the surface of the aircraft component.

[0110] In at least one embodiment, the method includes applying an AC voltage to a composition in the range of about 10 Hz to about 2000 Hz, for example, about 200 Hz to about 600 Hz, for example, about 400 Hz. In at least one embodiment, the method includes applying an AC voltage to a composition in the range of 10 volts to about 2000 volts, for example, about 100 volts to about 400 volts, for example, about 200 volts. The method includes adjusting the AC voltage using one or more transformers. The method includes adjusting the AC voltage to a DC voltage using one or more rectifiers. The method includes adjusting the DC voltage to an AC voltage using one or more oscillators.

[0111] Radoms and Other Electrostatic Discharges: In aircraft, radar is located behind the nose of the aircraft. The nose often accumulates static electricity in a form known as precipitation static (P-static), which causes electrostatic interference with the radar, in addition to brush discharge events that can damage the coatings on the aircraft's exterior. Electrostatic interference with the radar results in interference with communications between the aircraft and ground control towers, as well as interference with the detection of other aircraft in the air. P-static further causes electrostatic interference with other parts of the aircraft, such as parts including (one or more) antennas. Furthermore, static charge often accumulates inside the aircraft's fuel tanks, which can affect fuel tank function.

[0112] For example, if the aircraft is a fighter jet, the canopy of the fighter jet often accumulates static charge, which causes static interference between (one or more) radars and (one or more) antennas.

[0113] After one or more compositions of the present disclosure are placed on a vehicle component (and optionally cured), the one or more compositions may discharge static electricity, such as P-static, accumulated at a location on the aircraft, for example, on the nose of the aircraft. Discharging static electricity reduces or eliminates electrostatic interference with the aircraft's radar, reduces or eliminates brush discharge events, and reduces or eliminates damage to the coating on the aircraft's exterior. The compositions of the present disclosure further reduce or eliminate electrostatic interference with other components of the aircraft, for example, components including (one or more) antennas. If the compositions of the present disclosure are coated on the inside of a fuel tank, one or more compositions reduce or eliminate electrostatic charge accumulation inside the fuel tank.

[0114] Aircraft Safety: In addition to the inability to discharge charge accumulation, the coatings of the present disclosure have further improved "aircraft safety." When applied to the surface of a vehicle, they can further improve performance with respect to, for example, durability parameters such as resistance to rain erosion, high temperature resistance, low temperature resistance, and resistance to damage from sand and hail, compared to conventional coatings applied to the surface of a vehicle. The compositions of the present disclosure may be "aircraft safe" and improve one or more parameters of aircraft safety (compared to conventional coatings), such as resistance to rain erosion, high temperature resistance, low temperature resistance, resistance to damage from sand and hail, and visibility.

[0115] The compositions and methods of this disclosure provide low-resistance compositions (which can be rinsed with various rinse agents) at least in part due to the removal of excess acid and increased electrical percolation due to the high density of the composition.

[0116] manner This disclosure provides, in particular, the following aspects, each of which may be considered to include any alternative aspects as applicable. Clause 1. A composition, Epoxy, Amino or amide curing agent, Polyaniline, Dopants selected from triazolyl, thiazolyl, quinolinyl, salicylate, benzoate, glycolate, phosphate, oxalate, sulfonate, or combinations thereof, and Contains (or consists of, or is essentially composed of) pigments selected from titanium dioxide, silica, talc, mica, aluminum stearate, or combinations thereof, A composition in which polyaniline + dopant constitutes more than 6% by weight of the composition. Clause 2. The composition according to Clause 1, wherein the polyaniline is polyaniline in the emeraldine form. Clause 3. The composition described in Clause 1 or 2, wherein the volatile organic matter content is 300 g / L or less. Clause 4. A composition according to any one of Clauses 1 to 3, having a volume solids content of about 70% or more, based on the total volume of the composition, as determined by weighing the components and preparing the composition. The total solids content may be determined by evaporating the solvent. Clause 5. A composition according to any one of Clauses 1 to 4, comprising an amount of (epoxy + amino curing agent and / or amide curing agent) in an amount of about 40% to about 75% by weight, based on the total weight of the composition. Clause 6. A composition according to any one of Clauses 1 to 5, comprising one or more epoxys in an amount of about 30% to about 50% by weight, based on the total weight of the composition. Clause 7. The composition according to any one of Clauses 1 to 6, comprising an amino curing agent in an amount of about 12% to about 22% by weight, based on the total weight of the composition. Clause 8. The composition according to any one of Clauses 1 to 7, comprising an amide curing agent in an amount of about 12% to about 22% by weight, based on the total weight of the composition. Clause 9. The composition according to any one of Clauses 1 to 8, wherein the epoxy is a bisphenol A type epoxy or a bisphenol F type epoxy. Clause 10. A composition according to any one of Clauses 1 to 9, comprising a polyaniline + dopant in an amount of about 10% to about 60% by weight, based on the total weight of the composition. Clause 11. The composition according to any one of Clauses 1 to 10, comprising polyaniline + dopant in an amount of about 30% to about 50% by weight, based on the total weight of the composition. Clause 12. A composition according to any one of Clauses 1 to 11, wherein the molar ratio of the dopant to the aniline units of the polyaniline is about 0.3:1 to about 1:1. Clause 13. The composition according to any one of Clauses 1 to 12, wherein the dopant is a triazolyl selected from benzotriazole, triazolecarboxylic acid, benzotriazolesulfonic acid, salts thereof, or combinations thereof. Clause 14. The composition according to any one of Clauses 1 to 13, wherein the dopant is a thiazolyl selected from one or more of benzothiazoles, thiazole carboxylic acids, mercaptobenzothiazoles, salts thereof, or combinations thereof. Clause 15. The composition according to any one of Clauses 1 to 14, wherein the dopant is a quinolinyl selected from 8-hydroxyquinoline, mercaptoquinoline, salts thereof, or combinations thereof. Clause 16. A composition according to any one of Clauses 1 to 15, wherein the dopant is a salicylate selected from salicylic acid, hydroxybenzoic acid, salts thereof, or combinations thereof. Clause 17. A composition according to any one of Clauses 1 to 16, wherein the dopant is a benzoate selected from benzoic acid, methylbenzoic acid, salts thereof, or combinations thereof. Clause 18. A composition according to any one of Clauses 1 to 17, wherein the dopant is a glycolate selected from glycolates, thioglycolates, salts thereof, or combinations thereof. Clause 19. The composition according to any one of Clauses 1 to 18, wherein the dopant is a phosphate selected from phosphoric acid, a salt thereof, or a combination thereof. Clause 20. A composition according to any one of Clauses 1 to 18, wherein the dopant is a sulfonate selected from dinonylnaphthylenesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, salts thereof, or combinations thereof. Clause 21. A composition according to any one of Clauses 1 to 19, comprising a pigment in an amount of about 0.01% to about 40% by weight, based on the total weight of the composition. Clause 22. A composition according to any one of Clauses 1 to 21, comprising titanium dioxide, silica, talc, mica, and aluminum stearate. Clause 23. A composition according to any one of Clauses 1 to 22, comprising titanium dioxide in an amount of about 0.01% to about 10% by weight, based on the total weight of the composition. Clause 24. A composition according to any one of Clauses 1 to 23, comprising talc in an amount of about 0.01% to about 10% by weight, based on the total weight of the composition. Clause 25. A composition according to any one of Clauses 1 to 24, comprising mica in an amount of about 0.01% to about 10% by weight, based on the total weight of the composition. Clause 26. A composition according to any one of Clauses 1 to 25, comprising silica in an amount of about 0.01% by weight to about 10% by weight, based on the total weight of the composition. Clause 27. The composition according to any one of Clauses 1 to 26, comprising aluminum stearate in an amount of about 0.01% to about 0.5% by weight, based on the total weight of the composition. Clause 28. A substrate on which a composition described in any one of Clauses 1 to 27 is disposed. Clause 29. The substrate according to Clause 28, wherein the cured composition thereon has a thickness of about 5 μm and about 100 μm. Clause 30. The cured composition is about 10 4 Ω / □~approx. 10 8 A substrate as described in Clause 28 or 29, having a resistance value of Ω / □. Clause 31. A vehicle component selected from airfoils, auxiliary power units, noses of aircraft, fuel tanks, tail cones, panels, coated overlap joints between two or more panels, wing-fuselage assemblies, aircraft structural composites, fuselage body joints, or wing rib-and-skin joints, as described in any one of Clauses 28 to 30. Clause 32. A substrate as described in any one of Clauses 28 to 31, comprising a metal substrate made from aluminum, aluminum alloys, nickel, iron, iron alloys, steel, titanium, titanium alloys, copper, copper alloys, or mixtures thereof. Clause 33. A substrate according to any one of Clauses 28 to 32, comprising aluminum, carbon fiber epoxy, glass fiber reinforced polymer, cellulose reinforced phenolic resin, polyimide, or a combination thereof.

[0117] Those familiar with the techniques of formulating paints and primers will understand that various changes in the components can result in coatings with different properties and compositions. While the examples refer to specific resin systems from well-known manufacturers, the use of similar resins from other sources is also possible within the scope of this disclosure.

[0118] Overall, this disclosure provides compositions, articles, and methods for imparting electrostatic discharge and other "aircraft safety" properties to a substrate.

[0119] As used herein, “vehicle component” includes any part of a vehicle, such as structural components, panels or joints of aircraft, automobiles, etc. Vehicle components include noses, fuel tanks, tail cones, panels, coated lap joints between two or more panels, wing-fuselage assemblies, aircraft structural composites, fuselage body joints, wing rib-and-skin joints, and / or other internal components. Vehicle components also include any suitable parts of automobiles, marine vehicles, wind turbines, housings / ground structures, drilling equipment, etc.

[0120] The compounds of this disclosure include tautomers, geometric isomers, or stereoisomers of the compounds. The compounds of this disclosure also include cationic and anionic forms of the compounds. Ester, oxime, onium, hydrate, solvate, and N-oxide forms of the compounds are also included in this disclosure. This disclosure is considered to include all such compounds, including cis- and trans-geometric isomers (Z- and E-geometric isomers), R- and S-enantiomers, diastereomers, d-isomers, l-isomers, atropisomers, epimers, conformational isomers, rotational isomers, mixtures of isomers, and racemates thereof.

[0121] While the foregoing applies to the examples provided herein, other and further examples of the disclosure may be devised without departing from its basic scope. Furthermore, while the foregoing applies to methods applicable, for example, to vehicle components in the aerospace industry, the examples provided herein may apply to other non-aircraft applications, such as those in the automotive, marine, energy, wind turbine, and satellite industries.

[0122] The various examples described herein are presented for illustrative purposes only and are not intended to be exhaustive or limit the scope of the examples disclosed. Numerous modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the examples described herein. The terminology used herein has been selected to best describe the principles, practical applications, or technological improvements over technologies found in the market, or to enable those skilled in the art to understand the examples disclosed herein. While the foregoing applies to the examples of this disclosure, other and further examples of this disclosure may be conceived without departing from their basic scope. Thus, this disclosure is not intended to be limited thereto. Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "including," it should be understood that the same composition or group of elements is also intended to be preceded by the transitional phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is," and vice versa. [Explanation of Symbols]

[0123] 10 First reactant 20 Second reactant 30 First Mixing Unit 40 Housing Sections 40a and 40b 50 Third reactant 60 Second Mixing Unit 63 Flow control valve 65 Entrance Port 66 Purge media 67 Pressure Regulating Unit 68. Recoverable media 69 Fluid lines 70, 70a, 70b tube 70c, 70d, 70e Flow Reactor Unit 80 discharge ports 90 Analyzer 100, 100b Flow Reactor System 100a Flow Reactor Configuration

Claims

1. A composition, Epoxy, Amino or amide curing agent, Doped polyaniline, wherein the dopant of the doped polyaniline is selected from benzoates, glycolates, or combinations thereof, and Contains pigments selected from titanium dioxide, silica, talc, mica, aluminum stearate, or combinations thereof. A composition in which the polyaniline + dopant constitutes more than 6% by weight of the composition, and the polyaniline is optionally polyaniline in emeraldine form.

2. The composition according to claim 1, wherein the volatile organic matter content is 300 g / L or less.

3. The composition according to claim 1, wherein, when determined by weighing the components and preparing the composition, it has a volume solids content of 70% or more based on the total volume of the composition, and the total solids content can be determined by evaporating the solvent.

4. The composition according to claim 1, comprising 40% to 75% by weight of (epoxy + amino curing agent and / or amide curing agent) based on the total weight of the composition.

5. The composition according to claim 1, comprising 30% to 50% by weight of one or more epoxys based on the total weight of the composition.

6. The composition according to claim 1, comprising an amino curing agent in an amount of 12% to 22% by weight based on the total weight of the composition, and / or comprising an amide curing agent in an amount of 12% to 22% by weight based on the total weight of the composition.

7. The composition according to claim 1, wherein the epoxy is a bisphenol A type epoxy or a bisphenol F type epoxy.

8. The composition according to claim 1, comprising 10% to 60% by weight of polyaniline + dopant based on the total weight of the composition, or alternatively comprising 30% to 50% by weight of polyaniline + dopant based on the total weight of the composition.

9. The composition according to claim 1, wherein the molar ratio of the dopant to the aniline units of the polyaniline is 0.3:1 to 1:

1.

10. The composition according to claim 1, wherein the dopant is a benzoate selected from benzoic acid, methylbenzoic acid, salts thereof, or combinations thereof, and / or the dopant is a glycolate selected from glycolate, thioglycolate, salts thereof, or combinations thereof.

11. The composition according to claim 1, comprising the pigment in an amount of 0.01% to 40% by weight, based on the total weight of the composition.

12. The composition according to claim 1, comprising titanium dioxide, silica, talc, mica, and aluminum stearate, or optionally comprising 0.01% to 10% by weight of titanium dioxide based on the total weight of the composition, and / or comprising 0.01% to 10% by weight of talc based on the total weight of the composition, and / or comprising 0.01% to 10% by weight of mica based on the total weight of the composition, and / or comprising 0.01% to 10% by weight of silica based on the total weight of the composition, and / or comprising 0.01% to 0.5% by weight of aluminum stearate based on the total weight of the composition.

13. A substrate on which the composition according to any one of claims 1 to 12 is disposed.

14. The substrate according to claim 13, wherein the cured composition on top thereof has thicknesses of 5 μm and 100 μm.

15. The cured composition is 10 4 Ω / □~10 8 A substrate according to claim 13, having a resistance value of Ω / □.

16. The substrate according to claim 13, which is a vehicle component selected from an airfoil, an auxiliary power unit, the nose of an aircraft, a fuel tank, a tail cone, a panel, a coated overlap joint between two or more panels, a wing-fuselage assembly, an aircraft structural composite, a fuselage body joint, or a joint between wing ribs and outer skin.

17. The substrate according to claim 13, comprising a metal substrate made from aluminum, aluminum alloy, nickel, iron, iron alloy, steel, titanium, titanium alloy, copper, copper alloy, or a mixture thereof, and / or comprising aluminum, carbon fiber epoxy, glass fiber reinforced polymer, cellulose reinforced phenolic resin, polyimide, or a combination thereof.

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