Continuous flow process for preparing conductive polymer

Abstract

To provide a system for providing a continuous flow process for synthesizing a conductive polymer, for example, polyaniline.SOLUTION: A system for providing a continuous flow process for controlled synthesis of a conductive polymer or its salt includes: a continuous flow reactor including at least one mixing element, an organic flow, an oxidant flow and a product flow containing a conductive polymer, whose temperature is effective for synthesizing a conductive polymer or its salt in the product flow and is controlled; one or a plurality of pumps; one or a plurality of heat exchangers; a temperature control device which is cooperative with the continuous flow reactor the temperature of which is controlled and the one or the plurality of heat exchangers; and control means for controlling one or more of concentration, a flow rate, a temperature, a pressure, and a time for the one or more flows, a fluid reaction substance, a supply source of the fluid reaction substance, the fluid or the product of the reaction.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a continuous flow process for preparing conductive polymers, such as a continuous flow process for synthesizing polyaniline. The present disclosure also relates to conductive polymers prepared by the continuous flow process, as well as to articles of manufacture comprising or prepared from the conductive polymers. [Background technology]

[0002] Although conductive polymers are of great commercial value, the scalability of processes for preparing them remains quite limited due to various issues, including solubility and reaction control requirements. For example, polyaniline is a conductive polymer that has attracted considerable attention due to its environmental stability and wide range of industrial applications. Polyaniline is unique among conductive polymers in that its conductivity can be reversibly controlled electrochemically (by oxidation / reduction) or chemically (by protonation / deprotonation). Applications of polyaniline include electrostatic dissipative coatings, anticorrosion coatings, electrochromic coatings, and chemical sensors.

[0003] Polyaniline is typically synthesized by chemical oxidative polymerization in aqueous solution. This method involves a batch reaction in which water, aniline, a protonic acid, and an oxidant are combined and allowed to react while maintaining the reaction mixture at a low temperature (typically around 5°C). Materials synthesized using this method are largely amorphous and difficult to handle, and are insoluble in most organic solvents. Organosoluble polyaniline can also be synthesized by batch emulsion polymerization in Butyl CELLOSOLVE™ / water with an organic-soluble dopant such as dinonylnaphthalene sulfonic acid. While emulsion polymerization reactions produce polymers of reasonable molecular weight, they are highly exothermic and require careful control to prevent the formation of low-molecular-weight by-products. The oxidation reaction in batch emulsion polymerization processes is problematic because it leads to exothermic temperature spikes that increase the amount of impurities, such as low-molecular-weight oligomers, and reduce the molecular weight and conductance properties of the resulting polyaniline. Furthermore, batch emulsion polymerization processes are difficult to scale for industrial applications. However, industrial processes for preparing conductive polymers have been avoided due to poor reaction performance and control problems in forming conductive polymers. Therefore, batch emulsion polymerization processes have been widely favored, especially for the preparation of polyaniline.

[0004] Therefore, there is a need to develop alternative, industrially scalable commercial processes for preparing and synthesizing various conductive polymers, including polyaniline. Summary of the Invention

[0005] The present inventors have identified alternative methods for preparing a variety of conductive polymers, including continuous flow processes.

[0006] The continuous flow process includes providing an emulsion of a polymerizable organic monomer, a protonic acid, and a free radical initiator in a temperature-controlled continuous flow reactor. The reactor can contain at least one mixing element. The temperature can be controlled to be effective for synthesizing the conductive polymer or its salt and providing a product stream comprising the conductive polymer or its salt. The continuous flow process can include a continuous flow reactor, such as a continuous flow tubular reactor, with one or more passages in fluid communication for carrying the reactants and product streams. The continuous flow process of the present invention, according to at least some examples as described herein, can provide any one or more of the following: precise variable control of reagent ratios to control the molecular weight, solubility, and thermal stability of the final product; post-polymerization dopant addition to enhance conductivity; use of increased concentrations of organic monomer; better scalability and industrial processing; and / or improved control of temperature during processing, which can prevent or reduce undesirable temperature fluctuations that contribute to the introduction of impurities or undesirable by-products into the product stream.

[0007] The continuous flow process can also include providing a continuous flow of an organic stream containing polymerizable organic monomers in an organic solvent. The organic stream can be mixed with one or more other streams to initiate polymerization of the organic monomers. For example, an oxidant stream containing a free radical initiator can be mixed with an organic stream containing aniline monomers to initiate polymerization of the aniline monomers to form polyaniline. The polymerizable organic monomers can be converted in situ to organic solvent-soluble salts during the continuous flow process prior to polymerization into conductive polymers using a free radical initiator, such as more easily processable organic-soluble conductive polymer salts.

[0008] In one aspect, a continuous flow process for the controlled synthesis of a conductive polymer or salt thereof is provided, comprising feeding an emulsion of a polymerizable organic monomer, optionally a protonic acid, and a free radical initiator into a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize the conductive polymer or salt thereof and provide a product stream comprising the conductive polymer or salt thereof.

[0009] In one example, the emulsion includes a polymerizable organic monomer, a protonic acid, and a free radical initiator. In another example, the emulsion is formed using an organic stream including the polymerizable organic monomer and an aqueous stream. In another example, the emulsion is formed using an organic stream including the polymerizable organic monomer and a protonic acid and an aqueous stream. It will be understood that the organic stream can be mixed with the aqueous stream to form the product stream. It will be understood that the aqueous stream for forming the product stream includes a free radical initiator.

[0010] The emulsion may contain either i) a polymerizable organic monomer, a protonic acid, and a free radical initiator, or ii) an organic monomer salt consisting of an organic monomer and a protonic acid, and a free radical initiator.

[0011] In another example, an emulsion is formed using an organic stream comprising a polymerizable organic monomer and an oxidant stream comprising a free radical initiator. The emulsion can be formed using an organic stream and an oxidant stream, where the oxidant stream comprises the free radical initiator and the organic stream comprises the polymerizable organic monomer and a protonic acid. It is understood that the oxidant stream is aqueous.

[0012] It has been found that the exothermic reaction and associated temperature spike that occurs in forming the product stream when the oxidant stream is initially introduced into the organic stream can be further substantially controlled in accordance with the embodiments and examples described herein. For example, a continuous flow process can further include: i) introducing an oxidant stream into an organic stream in a fluid conduit or in a continuous flow reactor in close fluid connection with a temperature-controlled continuous flow reactor; or ii) introducing the oxidant stream directly into the organic stream in a temperature-controlled continuous flow reactor; may include:

[0013] In the case of option i) above, the oxidant stream and / or the organic stream may each be cooled independently as an optional step before being introduced into the feed conduit or the continuous flow reactor. The continuous flow reactor of option i) may be equipped with at least one static mixer, for example, a continuous flow tubular reactor equipped with a static mixer element. The continuous flow reactor of option i) may also be temperature controlled, for example, equipped with a heat exchanger.

[0014] In the case of option ii) above, the oxidant stream and / or the organic stream may each be independently cooled, as an optional step, prior to introduction into the temperature-controlled continuous flow reactor.

[0015] In another example, the organic stream comprises or consists of polymerizable organic monomers, optionally one or more organic solvents, and optionally one or more protonic acids. In another example, the oxidant stream comprises or consists of a free radical initiator and optionally one or more solvents that comprise or consist of water.

[0016] In another example, the emulsion is formed from in-line mixing of a flowing organic stream and an oxidant stream by direct mixing in a temperature-controlled continuous flow reactor or by in-line mixing adjacent to a temperature-controlled continuous flow reactor. In another example, the emulsion is introduced into a temperature-controlled continuous flow reactor. In another example, the process further includes obtaining the conductive polymer or salt thereof from the product stream under continuous flow conditions.

[0017] In another example, the continuous flow process a) providing an organic stream comprising an organic solvent, a polymerizable organic monomer, and a protonic acid; b) providing an oxidant stream comprising an aqueous solvent and a free radical initiator; c) mixing the organic stream and the oxidant stream to form an emulsion stream; d) feeding the emulsion stream into a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize the conductive polymer or salt thereof to provide a product stream comprising the conductive polymer or salt thereof in a temperature-controlled continuous flow; and e) obtaining a conductive polymer or a salt thereof from the product stream under continuous flow conditions after the product stream exits the temperature-controlled continuous flow reactor. Includes:

[0018] In another example, mixing the organic stream and the oxidant stream to form the emulsion stream in step c) above may be by in-line mixing of the organic stream and the oxidant stream in a flow, either by direct mixing in a temperature-controlled continuous flow reactor or by in-line mixing in close proximity to a temperature-controlled continuous flow reactor. A continuous flow process for step c) can be, for example: i) introducing an oxidant stream into an organic stream in a fluid conduit or continuous flow reactor to form an emulsion stream, the fluid conduit or continuous flow reactor being in close fluid communication with a temperature-controlled continuous flow reactor; or ii) introducing an oxidant stream directly into the organic stream in a temperature-controlled continuous flow reactor and mixing the organic stream and the oxidant stream to form an emulsion stream; Further includes:

[0019] The temperature-controlled continuous flow reactor may be a temperature-controlled continuous flow tubular reactor.

[0020] The conductive polymer may be selected from the group consisting of polyallylamine, polyallylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), or any salt thereof. The polymerizable organic monomer may be selected from the group consisting of arylamine, arylthiol, pyrrole, carbazole, indole, azepine, thiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene monomer, or any salt thereof. Each conductive polymer and polymerizable organic monomer may be unsubstituted or substituted.

[0021] In one example, the conductive polymer is polyaniline and the polymerizable organic monomer is unsubstituted or substituted aniline. In another example, the conductive polymer is poly(3,4-ethylenedioxythiophene) and the polymerizable organic monomer is unsubstituted or substituted 3,4-ethylenedioxythiophene. In another example, the conductive polymer is poly(3,4-propylenedioxythiophene) and the polymerizable organic monomer is unsubstituted or substituted 3,4-propylenedioxythiophene monomer.

[0022] Each individual polymerized chain of the conductive polymer, or any salt thereof, may independently be composed of between about 100-1500, 300-1400, 500-1300, 600-1200, or 700-1100 individual monomer units. The weight average molecular weight of the conductive polymer produced by the present process may be between about 10,000-120,000, about 20,000-110,000, or about 60,000-100,000. In one example, each individual polymerized chain of the conductive polymer is independently composed of between about 100-1500 individual monomer units. In another example, the conductive polymer has a weight average molecular weight of between 10,000-120,000.

[0023] The temperature of the mixed stream may be set to about -10 to 10°C, -5 to 5°C, or -1 to 1°C and maintained over the axial flow length of the continuous flow tubular reactor. The temperature may be set within these ranges while providing a variation of less than about 3°C, e.g., less than about 2°C or 1°C. In one example, for step c), the temperature of the mixed stream is set to between about -5 to 5°C and maintained over the axial flow length of the continuous flow reactor while allowing a variation of 1 to 2°C or less.

[0024] In one example, a continuous flow process for the controlled synthesis of polyaniline or a salt thereof is provided, which includes feeding an emulsion of aniline, a protonic acid, and a free radical initiator into a temperature-controlled continuous flow reactor equipped with at least one mixing element at a temperature effective to synthesize a conductive polymer or a salt thereof and provide a product stream comprising the conductive polymer or salt thereof. The aniline or salt thereof can be introduced into the process in an organic stream or as a neat organic solution. The protonic acid can be selected from organic-soluble protonic acids for forming an organic-soluble aniline salt in the organic stream or organic phase of the emulsion. The protonic acid can be introduced into the process in an organic stream or as a neat organic solution.

[0025] In another example, the continuous flow process is for the controlled synthesis of polyaniline or a salt thereof, comprising the following steps: a) providing an organic stream comprising an organic solvent, an unsubstituted or substituted aniline or a salt thereof, and optionally a protonic acid; b) providing an oxidant stream comprising an aqueous solvent and a free radical initiator; c) mixing the organic stream and the oxidant stream to form an emulsion stream; d) feeding the emulsion stream into a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize polyaniline or a salt thereof and provide a product stream in the temperature-controlled continuous flow reactor comprising polyaniline or a salt thereof; e) Obtaining polyaniline or a salt thereof from the product stream under continuous flow conditions after the product stream exits the temperature-controlled continuous flow reactor. Includes:

[0026] The free radical initiator can be, for example, an oxidizing agent such as ammonium persulfate (APS).

[0027] In one example, in step b), the oxidant stream is an aqueous stream comprising an aqueous solvent, and the mixing of the organic and aqueous streams in a continuous flow in step c) provides an emulsion stream.

[0028] In one example, in step (a), the organic stream is a non-aqueous organic solution comprising an organic solvent, a polymerizable organic monomer, and a protonic acid.

[0029] The mixing element in the temperature-controlled continuous flow reactor of step (c) can be at least one of a static mixer and a dynamic mixer.

[0030] The oxidant stream and the aqueous stream may be premixed under continuous flow conditions before being introduced into the temperature-controlled continuous flow reactor of step (c).

[0031] In one example, the organic stream is a1) providing a protonic acid stream comprising an organic solvent and a protonic acid; a2) providing a monomer stream comprising a polymerizable organic monomer and, optionally, an organic solvent; and a3) combining the protonic acid stream and the monomer stream to form the organic stream of step a). Provided by.

[0032] In the case of step a2), the polymerizable organic monomer may be provided as a neat organic liquid.

[0033] In one example, the monomer stream is an aniline stream comprising unsubstituted or substituted aniline and, optionally, an organic solvent, and step a3) provides combining the protonic acid stream with the aniline stream to form the organic stream of step (a).

[0034] The protonic acid stream and the monomer stream may be premixed under continuous flow conditions prior to mixing with the oxidant stream. In at least some instances, premixing can provide further improvement to the emulsion of the product stream formed by mixing the organic stream and the oxidant stream.

[0035] In the continuous flow process, the polymerizable organic monomer may be unsubstituted aniline. The protonic acid may be dinonylnaphthalene sulfonic acid (DNNSA). The organic solvent may be selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, glycols, ethers, glycol ethers, and mixtures thereof. In one example, the organic solvent may be selected from the group consisting of alcohols, glycols, glycol ethers, and any combination thereof. In at least some examples, the selection of the organic solvent may provide further improvement of the emulsion of the product stream formed by mixing the organic stream and the oxidant stream. The free radical initiator may be an oxidant selected from the group consisting of persulfates, peroxides, dichromates, cerium (IV) salts, iron (III) salts, and any mixture thereof. In one example, the oxidant is ammonium persulfate (APS).

[0036] The concentration of aniline in the organic stream can be from about 0.1M to about 0.8M, for example, from about 0.2M to about 0.5M.

[0037] For continuous flow reactors, such as tubular reactors, the internal diameter of the passages within the reactor can enhance mixing and backpressure characteristics. For example, passages can range from small to increase shear to large to accommodate static mixer elements for industrial-scale operations. For example, the internal diameter of the passages or chambers can be at least about 2 mm, 3 mm, 4 mm, or 5 mm. The internal diameter of the reactor can be between about 5 and 20 mm, e.g., between about 5 and 10 mm. For continuous flow processes or systems, the minimum internal diameter of any part of the continuous flow system can be greater than 1 mm, e.g., at least about 2 mm or at least about 3 mm. Different internal diameters affect fluid flow within the reactor. For reactors with the same internal volume, reactors constructed with smaller diameter passages or tubes result in higher fluid flow rates at a given residence time. Therefore, reducing the diameter of the passages or tubes improves mixing performance, for example, by increasing fluid turbulence and shear forces around static mixer elements. However, reducing the diameter of the passages or tubes also increases system pressure, a consideration when determining appropriate materials of construction and reactor design. In emulsion polymerization processes, maintaining small tube diameters is beneficial, as this maximizes fluid shear forces and results in finer emulsions.

[0038] In one example, the process provides at least about 50 g of conductive polymer per hour of operation. The operational capacity can be for continuous flow reactor volumes of about 100 to 3000 ml. In at least some examples, the operational capacity can be industrial-scale. In at least some examples, the process can provide at least about 100 g of conductive polymer per liter of continuous flow reactor internal volume per hour of operation.

[0039] In another example, following step d) or step e), an additive selected from the group consisting of a secondary dopant and an additional reagent is contacted with the conductive polymer or salt thereof.

[0040] In another aspect, there is provided a conductive polymer prepared by a continuous flow process according to any aspect or example described herein.

[0041] In another aspect, there is provided a composition, coating, or material comprising a conductive polymer or a salt thereof prepared by a continuous flow process according to any aspect or example described herein. The composition can be a liquid solution comprising the conductive polymer, such as a liquid concentrate.

[0042] In another aspect, there is provided a system for a continuous flow process for the controlled synthesis of a conductive polymer or salt thereof, comprising: a) a temperature-controlled continuous flow reactor comprising at least one mixing element for forming an emulsion according to one or more embodiments or examples thereof described herein; b) one or more pumps for providing fluid flow to one or more streams passing through the temperature-controlled continuous flow reactor; c) one or more heat exchangers for controlling the temperature of the temperature-controlled continuous flow reactor; d) a temperature control device for controlling the temperature of the flow in the temperature-controlled continuous flow reactor, in cooperation with the temperature-controlled continuous flow reactor and one or more heat exchangers, useful for synthesizing the conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the streams, fluid reactants, sources of fluid reactants, fluids, or products of the reaction; A system is provided comprising:

[0043] In one example, the system further includes a continuous flow mixer (e.g., Mixer 1) for forming an organic stream, the continuous flow mixer optionally comprising at least one mixing element and in fluid communication with the temperature-controlled continuous flow reactor.

[0044] In another example, the system further includes a continuous flow mixer (e.g., Mixer 2) for forming a product stream, the continuous flow mixer optionally including at least one mixing element and in fluid communication with the temperature-controlled continuous flow reactor.

[0045] In another example, the system further includes a first mixer (e.g., Mixer 1) for forming an organic stream in fluid communication with a second continuous flow mixer (e.g., Mixer 2) for forming a product stream, the first and second continuous flow mixers each optionally including at least one mixing element, and the second continuous flow mixer in fluid communication with a temperature-controlled continuous flow reactor.

[0046] It will be appreciated that further aspects and examples are described herein that may include one or more of the features described above.

[0047] The described features, functions, and advantages may be achieved independently in various examples or may be combined in yet other examples, further details of which may be ascertained by reference to the following description and drawings.

[0048] Examples of the present disclosure will now be further described and illustrated, by way of example only, with reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0049] [Figure 1] FIG. 1 is a schematic diagram illustrating an exemplary continuous flow process and system according to one example of the present disclosure. [Figure 2] FIG. 1 is a schematic diagram illustrating a continuous flow process and system according to an example of the present disclosure. [Figure 3] FIG. 1 is a schematic diagram illustrating a continuous flow process and system according to an example of the present disclosure. [Figure 4] 1 is a reaction temperature profile versus yield for a continuous flow process according to an example of the present disclosure. [Figure 5]1 is a reaction temperature profile versus peak molecular weight for a continuous flow process according to an example of the present disclosure. [Figure 6] 1 is a reaction temperature profile versus isopropanol conductivity for a continuous flow process according to an example of the present disclosure. [Figure 7] 10A-10C are reaction temperature profiles for various continuous flow processes according to some examples of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0050] This disclosure describes the following various non-limiting examples related to research conducted to identify alternative methods for preparing various conductive polymers, such as polyaniline. Various batch processes were investigated, although it was found that poor temperature control was an issue, affecting the properties of the conductive polymers prepared from the process, including the introduction of undesirable impurities. Various batch processes were investigated, although it was unclear whether continuous flow processes would be effective for scaling up delicate and complex batch processes. Various attempts to scale up batch processes under continuous flow conditions failed. However, continued research into continuous flow processes has ultimately led to the identification of continuous flow processes that have been found to be surprisingly effective for the controlled synthesis of various conductive polymers, including polyaniline.

[0051] The continuous flow process involves providing an emulsion of a polymerizable organic monomer, a protonic acid, and a free radical initiator in a temperature-controlled continuous flow reactor. The reactor can contain at least one mixing element. The temperature can be controlled to be effective for synthesizing the conductive polymer or its salt and providing a product stream comprising the conductive polymer or its salt. The continuous flow process can include a continuous flow reactor, such as a continuous flow tubular reactor, with one or more passages in fluid communication for carrying the reactants and product streams. The continuous flow process of the present invention, according to at least some examples as described herein, can provide any one or more of the following: precise variable control of reagent ratios to control the molecular weight, solubility, and thermal stability of the final product; post-polymerization dopant addition to enhance conductivity; use of increased concentrations of organic monomer; better scalability and industrial processing; and / or improved control of temperature during processing, which can prevent or reduce undesirable temperature fluctuations that contribute to impurities or undesirable by-products in the product stream.

[0052] The continuous flow process can also include providing a continuous flow of an organic stream containing polymerizable organic monomers in an organic solvent. The organic stream can be mixed with an oxidant stream containing a free radical initiator to form a product stream that initiates polymerization of the polymerizable organic monomers. For example, an oxidant stream containing a free radical initiator can be mixed with an organic stream containing aniline monomers to initiate polymerization of the aniline monomers to form polyaniline. The polymerizable organic monomers can be converted in situ during the continuous flow process to an organic solvent-soluble salt prior to polymerization into a conductive polymer using a free radical initiator. The conductive polymer formed in situ in the product stream can be an organic-soluble conductive polymer salt, providing a more readily available conductive polymer that can be conveniently applied in other processes or materials.

[0053] References to "mixing" or "mixing" described herein with respect to continuous flow processes generally refer to in-line mixing that occurs during the continuous flow of fluids in a reactor, mixer, or conduit of the system. The emulsion or product stream may be formed by mixing within a temperature-controlled continuous flow reactor or by mixing in close proximity to the reactor. It will be appreciated from the teachings of the present disclosure that such mixing to form the emulsion or product stream in or in close proximity to a temperature-controlled continuous flow reactor can provide the additional advantage of controlling temperature fluctuations in the stream.

[0054] A continuous flow process may allow for the synthesis of conductive forms of polymers, for example, the emeraldine form of polyaniline, such as polyaniline emeraldine salt.

[0055] According to at least some examples described herein, the conductive polymer can be synthesized in a continuous flow process in its conductive form (e.g., polyaniline emerazine salt) and soluble in at least some organic solvents, which aids in the subsequent processing of the conductive polymer for use in various compositions, formulations, coatings, and materials.

[0056] According to at least some examples described herein, the continuous flow process allows for the in situ (i.e., during the flow) formation of organic-soluble polymerizable monomer salts that can themselves be polymerized into organic-soluble conductive polymeric forms that are more easily processable during the continuous flow process and allow for scalability for industrial applications.

[0057] The present continuous flow process, according to some examples, allows for improved temperature control during processing, preventing undesirable fluctuations in temperature that can introduce or increase the presence of additional impurities or undesirable by-products in the product stream and resulting materials, and allows for higher concentrations of organic monomers to be used, resulting in improved scalability and industrial preparation.

[0058] specific term As used herein, the term "polymerizable organic monomer" refers to any one or more organic monomers or comonomers that may be in the form of a protonated salt or that can form a protonated salt in the presence of a protonic acid source and that can be polymerized in the presence of a free radical initiator to form a conductive polymer. An example of a polymerizable organic monomer is aniline, including its protonated form, that can be polymerized to provide a conductive polymer of polyaniline.

[0059] The term "conductive polymer" refers to any organic polymer or copolymer that can conduct electricity and may include, for example, polymers that are semiconductors. It will be understood that conductive polymers may require subsequent processing to provide the desired conductance properties. An example of a conductive polymer is polyaniline. It will be understood that the term "conductive polymer" or "polymer" can include one or more "copolymers," and the term "monomer" can include one or more comonomers.

[0060] References to "continuous flow" will be understood, in terms of continuous flow chemistry, to mean a process in which chemical reactions occur in continuously flowing reagent streams, the reactions reach completion or near completion within a continuous reactor system, and products are produced in the stream without the need for further chemical reaction after exiting the reactor system. For example, the term "continuous flow" refers to the continuous supply of organic and oxidant streams to a temperature-controlled reactor, and polymerizable monomers exiting the reactor outlet in a fluid stream. For example, a continuous flow reactor in its most basic form consists of a series of tubes or channels, one or more pumps, and at least one mixing element.

[0061] "Element" refers to an individual unit that can be used with one or more other components in forming a continuous flow reactor system. Examples of elements include "inserts" or "modules" described herein.

[0062] "Single pass reactor" refers to a reactor used in a process or system in which a fluid component passes through the reactor a single time and is not recirculated through a reactor that the component has already passed through.

[0063] "Aspect ratio" means the ratio of the length to the diameter (L / d) of a single unit or element.

[0064] "Proximate" refers to being at, adjacent to, next to, near, or touching a point of reference.

[0065] "Organic stream" generally refers to a stream that consists essentially of one or more organic components in a fluid stream and does not contain additional aqueous solvents, such as water, unless present as an incidental impurity.

[0066] It will be understood that "incidental impurities" can refer to minor amounts of impurities, for example, less than about 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, or 0.01 (weight percent based on total weight).

[0067] It will be understood that the term "h" refers to the unit of time "hours."

[0068] As will be understood, "aryl," whether used alone or in compound words such as alkylaryl or arylalkyl, can refer to: (i) a substituted or unsubstituted monocyclic or polycyclic aromatic carbocyclic moiety of about 6 to about 20 carbon atoms, such as, for example, phenyl, naphthyl, or fluorenyl; or (ii) a substituted or unsubstituted partially saturated polycyclic carbocyclic aromatic ring system in which an aryl and a cycloalkyl or cycloalkenyl group are fused together to form a ring structure such as a tetrahydronaphthyl, indenyl, indanyl, or fluorene ring. It will be understood that polycyclic ring systems can include bicyclic and / or tricyclic ring systems. The term "unsubstituted" will also be understood to refer to the absence of one or more substituents or the presence of one or more hydrogens. A "substituted" group is a C substituted or unsubstituted group, as defined herein. 1-20 Alkyl or C 1-10 It may also be alkyl.

[0069] "Alkyl," whether used alone or in compound words such as alkylaryl or arylalkyl, refers to a straight or branched chain hydrocarbon ranging in size from 1 to about 20 or more carbon atoms. Thus, unless expressly limited to a smaller group, alkyl moieties include moieties ranging in size from, for example, 1 to about 6 carbon atoms or more, such as methyl, ethyl, n-propyl, iso-propyl, and / or butyl, pentyl, hexyl, etc., as well as higher isomers, such as those straight or branched chain hydrocarbons ranging in size from about 6 to about 20 carbon atoms or more. For example, "alkyl" can refer to "C" as described below. 1-20 Alkyl" or "C 1-10 It may contain "alkyl".

[0070] As used herein, "C 1-20 The term "alkyl" refers to a straight or branched chain saturated hydrocarbon having 1 to 20 carbon atoms. 1-20 "Alkyl" groups include, but are not limited to, -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, -n-decyl; n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl.

[0071] As used herein, "C 1-10 The term "alkyl" refers to a straight or branched chain saturated hydrocarbon having 1 to 10 carbon atoms. 1-10 "Alkyl" groups include, but are not limited to, -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl; while branched C 1-8Alkyl includes, but is not limited to, -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, -isopentyl, 2-methylbutyl, 1-hexyl, 2-hexyl, 3-hexyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethyl butyl, 2,3-dimethylbutyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 3,3-dimethylpentyl, 2,3,4-trimethylpentyl, 3-methylhexyl, 2,2-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 3,5-dimethylhexyl, 2,4-dimethylpentyl, 2-methylheptyl, 3-methylheptyl, n-heptyl, isoheptyl, n-octyl, and isooctyl.

[0072] "Alkylaryl", "C 1-20 Alkylaryl" or "C 1-10 The term "alkylaryl" refers to a compound having an alkyl group attached to an aryl group, where "alkyl," "C 1-20 Alkyl", C 1-10 The "alkyl" and "aryl" moieties are each defined above.

[0073] Unless otherwise defined, the term "substituted" generally refers to a group substituted at any available position. Substitution can be with one or more groups or moieties as described herein, for example, selected from the group consisting of halo, nitro, hydroxyl, alkyl, haloalkyl, alkyloxy, aryl, arylalkyl, and alkylaryl.

[0074] The term "unsubstituted," when used in reference to, for example, "unsubstituted aniline," refers to the absence of one or more substituents or the presence of one or more hydrogens.

[0075] "Hydroxy" refers to an --OH moiety.

[0076] "Alkyloxy" refers to an -O-alkyl group in which the alkyl group is as defined above. Examples include methoxy, ethoxy, n-propoxy, iso-propoxy, and the different butoxy, pentoxy, hexyloxy and higher isomers.

[0077] "Aryloxy" refers to an -O-aryl group, where the aryl group is as defined above. Examples include, but are not limited to, phenoxy and naphthoxy.

[0078] "Amino" refers to a -NHR moiety, where R represents hydrogen or alkyl as defined above.

[0079] "Nitro" refers to the -NO2 moiety.

[0080] "Carboxy" refers to a -C(O)R moiety, where R represents hydrogen or alkyl as defined above.

[0081] The terms "halo" or "halogen," whether used alone or in compound words such as haloalkyl, refer to fluorine, chlorine, bromine, or iodine. Additionally, when used in compound words such as haloalkyl, the alkyl can be partially halogenated or fully substituted with halogen atoms, which may independently be the same or different. Examples of haloalkyl include, but are not limited to, -CH2CH2F, -CF2CF3, and -CH2CHFCl. Examples of haloalkoxy include, but are not limited to, -OCHF2, -OCF3, -OCH2CCl3, -OCH2CF3, and -OCH2CH2CF3. Examples of haloalkylsulfonyl include, but are not limited to, -SO2CF3, -SO2CCl3, -SO2CH2CF3, and -SO2CF2CF3.

[0082] General terminology Throughout this disclosure, unless expressly stated otherwise or unless the context otherwise requires, reference to a single step, composition of matter, group of steps, or group of compositions of matter is intended to include one and the plural (i.e., one or more) thereof. Thus, as used herein, the singular forms "a," "an," and "the" include plural aspects unless the context clearly dictates otherwise. For example, reference to "a" includes two or more as well as one; reference to "an" includes two or more as well as one; reference to "the" includes two or more as well as one, etc.

[0083] Unless otherwise specified, terms such as "first," "second," etc. are used herein merely as labels, and are not intended to impose any order, position, or hierarchy on the items they refer to. Furthermore, a reference to a "second" item does not require or preclude the presence of lower-numbered items (e.g., a "first" item) and / or higher-numbered items (e.g., a "third" item).

[0084] As used herein, the phrase "at least one," when used in conjunction with a list of items, means that various combinations of one or more of the listed items can be used, and that only one of the items in the list may be required. An item may be a specific object, thing, or category. In other words, "at least one" means that any combination or number of the items in the list can be used, but not all of the items in the list are required. For example, "at least one of item A, item B, and item C" may mean item A; item A and item B; item B; item A, item B, and item C; or item B and item C. In some cases, "at least one of item A, item B, and item C" may mean, for example, but not limited to, two items A, one item B, and ten items C; and four items B and seven items C; or some other suitable combination.

[0085] Reference herein to "an example," "one example," "another example," or similar phrases means that one or more features, structures, elements, components, or characteristics described in connection with that example are included in at least one implementation or embodiment. Thus, the phrases "in one example," "by way of example," and similar phrases throughout this disclosure may, but do not necessarily, refer to the same example. Furthermore, subject matter characterizing any one example may, but does not necessarily, include subject matter characterizing any other example.

[0086] Those skilled in the art will understand that the disclosure herein is susceptible to variations and modifications other than those specifically described. The present disclosure should be understood to include all such variations and modifications. The present disclosure also includes all steps, features, compositions, and compounds referred to or indicated herein, individually or collectively, and any and all combinations of said steps or features, or any two or more thereof.

[0087] Each example of the present disclosure described herein applies mutatis mutandis to all other examples unless otherwise stated. The disclosure is not limited by the specific examples described herein, which are for illustrative purposes only. Functionally equivalent products, compositions, and methods are clearly within the scope of the disclosure described herein.

[0088] The term "and / or," e.g., "X and / or Y," shall be understood to mean either "X and Y" or "X or Y," and shall be interpreted as providing explicit support for both meanings or for either meaning.

[0089] Throughout this specification the word "comprise" or variations such as "comprising" will be understood to mean the inclusion of the stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

[0090] The term "consist of," or variations such as "consisting of," is meant to include any stated element, integer, or step, or group of elements, integers, or steps, that is listed in association with the term, and to exclude other elements, integers, or steps, or group of elements, integers, or steps, that is not listed in association with the term.

[0091] A number of prior art documents are referenced in this specification, but it will be expressly understood that this reference is not an admission that any of these documents form part of the general knowledge in the art in Australia or anywhere else.

[0092] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In case of conflict, the present specification, including definitions, will control. Additionally, the materials, methods, and examples are illustrative only and are not intended to be limiting.

[0093] Continuous Flow Process A continuous flow process in this disclosure will be understood in terms of continuous flow chemistry to mean a process in which chemical reactions occur in continuously flowing reagent streams, the reactions reach completion within a continuous reactor system, and a product is produced in the continuous fluid stream without the need for further chemical reaction after exiting the reactor system. For example, the term "continuous flow" in this disclosure can refer to a continuous flow process that has reached steady-state operation. A continuous flow process can include a continuous flow reactor with one or more passages in fluid communication for carrying reactant and product streams. For example, a continuous flow system can be a tubular reactor, which in its most basic form includes a series of passages or channels of various configurations in fluid communication.

[0094] It will be understood that the continuous flow process of the present disclosure differs from a batch, semi-batch, or semi-continuous process. For example, if a step is performed in a tubular reactor and then the product is collected in a tank to complete the chemical reaction, the entire process becomes semi-continuous. It will also be understood that periodically shutting down or interrupting the reactor to perform a cleaning cycle and collect the product is also semi-continuous. In other words, a semi-continuous process interrupts continuous flow operation before completion, preparation, or collection of the conductive polymer. It will also be understood that a reaction is continuous if the conductive polymer is chemically synthesized within the length of the flow reactor and can be obtained from the product stream present during operation without the need for further chemical synthesis. For example, the synthesis of polyaniline as a doped soluble polymer is produced in a continuous flow reactor, and no further chemical synthesis reaction is required. However, the continuous flow process of the present invention may include additional, non-continuous separation, purification, and material blending steps after the product stream containing the synthesized conductive polymer is obtained from the reactor. For example, the process of the present disclosure is still considered a "continuous process" for synthesizing conductive polymers even if a product stream containing the synthesized conductive polymer is obtained from the reactor during operation and then separated stepwise into aqueous and organic phases and washed with acidified water.

[0095] It will also be understood that various configurations and designs of continuous flow reactors can be used to achieve the continuous flow processes described herein. Continuous flow processes can include continuous flow reactors, such as continuous flow tubular reactors, that have one or more passages in fluid communication to carry reactant and product streams. The continuous flow tubular reactors described herein are not limited to design configurations requiring substantially tubular or cylindrical fluid channels or sections. The term "continuous flow tubular reactor" in its broadest general sense includes various advanced plug flow reactor designs and configurations. For example, a continuous flow tubular reactor can be a plate reactor, such as a Corning Advanced-Flow™ reactor. Plate reactor configurations can provide one or more plates, each containing one or more fluidly connected passages or channels. The fluidly connected passages or channels can have various configurations, such as flat, elongated, or elliptical. A continuous flow tubular reactor includes one or more passages in fluid communication to carry the streams. The configuration of the passages allows the streams to flow through the passages for a desired residence time. The mixing element in the continuous flow tubular reactor in step (c) can be a static mixer or a dynamic mixer. A static mixer has a static or fixed structural element disposed in a conduit or chamber capable of mixing fluids under flow, as further described in various embodiments and examples herein. In one example, the static mixing element in the continuous flow reactor can be provided by one or more passages in the reactor, including at least a section configured to enhance flow mixing (e.g., enhance radial mixing or chaotic advection). It will be understood that a dynamic mixer has a moving element capable of mixing fluids, such as a paddle, a spinning tube, a rotor, a blender, or a rotating disk.

[0096] The present disclosure provides a continuous flow process for the controlled synthesis of conductive polymers, such as polyaniline. The conductive polymer may be a salt or a copolymer. It will be appreciated that the conductive polymers prepared by the continuous flow process may be further processed or used in polymer blends or composites.

[0097] An example of a continuous flow process is shown in the schematic diagram of Figure 1a. A reaction emulsion (i.e., product stream) can be prepared containing an organic-soluble monomer salt and a water-soluble free radical initiator. The reaction emulsion can be formed or introduced into a temperature-controlled tubular reactor system containing one or more mixing elements, such as one or more static mixers or passages configured to enhance mixing. The continuous flow of reactant emulsion flowing through the continuous flow reactor synthesizes a conductive polymer within the emulsion stream flowing through the reactor, forming a product stream exiting the reactor containing the synthesized conductive polymer without the need to stop or interrupt the continuous operation of the emulsion stream (and product stream) through the reactor. The conductive polymer formed within the fluid flowing through the reactor can be converted into a conductive polymer salt without the need to stop, interrupt, or further process the product stream.

[0098] The polymerizable organic monomer may be an organic-soluble monomer salt or a precursor mixture of an organic monomer and a protonic acid. The polymerizable organic monomer salt may be introduced into the process in an organic stream or as a neat organic solution. The neat organic solution may be a concentrated liquid or may include one or more organic solvents. It will be understood that the product stream includes the polymerizable organic monomer and a free-radical initiator such that the conductive polymer can form in the flow (i.e., in-line mixing).

[0099] Figures 1 and 2 show typical examples of flow processes and reaction conditions. Various configurations can be used to obtain a product stream in a temperature-controlled continuous flow reactor, which may be provided in the form of an emulsion containing an organic-soluble polymerizable organic monomer and a water-soluble free-radical initiator. The input of the organic stream containing the organic-soluble polymerizable organic monomer or the input of the oxidant stream containing the free-radical initiator can each be varied; for example, the streams can be premixed to form an emulsion stream or combined in the reactor. In another example, the oxidant stream is introduced directly into the temperature-controlled continuous flow reactor or mixed with the organic stream adjacent to the temperature-controlled continuous flow reactor. Temperature can be established and controlled for any individual or combined streams prior to introduction into the temperature-controlled continuous flow reactor according to any temperature example or embodiment described herein. In this manner, process conditions can be further improved to reduce or prevent problematic temperature changes (i.e., spikes or exotherms) occurring in the product stream. The emulsion stream comprises a two-phase mixture of an organic phase and an aqueous phase, where the organic phase contains the polymerizable organic monomer and optional protonic acid, and the aqueous phase contains the free radical initiator. The emulsion stream can be shaped into an emulsion before or after entering a temperature-controlled continuous flow reactor. It is understood that a product stream is established when the polymerizable organic monomer (e.g., a monomer salt or a combination of monomer and protonic acid) in the organic phase is mixed with the free radical initiator in the aqueous phase. Without wishing to be bound by theory, it has been unexpectedly discovered that a highly exothermic polymerization reaction can be promoted under effectively mixed emulsion flow conditions by providing a high concentration of polymerizable organic monomer in the organic phase, which reacts with water-soluble free radicals at the interface between the aqueous and organic phases to produce the conductive polymer in situ in the organic phase. Initiating the polymerization reaction under process flow conditions can be difficult, and once initiated, problematic exothermic temperature spikes can occur. Process flow conditions can also be further controlled to enable the formation of a segmented two-phase flow product stream, which can further facilitate efficient processing of the prepared conductive polymer.

[0100] It will be understood that the emulsion or product stream is biphasic. The biphasic nature results from the mixing of an organic stream and an aqueous stream, which together form an emulsion stream. Introducing an oxidant stream or a free radical initiator into an organic or emulsion stream containing a polymerizable organic monomer (e.g., aniline and a protonic acid, or an aniline salt) results in a product stream in which a conductive polymer can be formed in the flow. As described above, once the organic-soluble conductive polymer is formed in the product stream, process conditions can be further controlled so that the emulsion in the product stream begins to form an axially segmented two-phase flow. The axially segmented two-phase flow can provide a series of aqueous axial segments separated by organic axial segments. The aqueous axial segments contain unreacted free radical initiator and / or solvent, and the organic axial segments contain the organic-soluble conductive polymer.

[0101] In another example, a continuous flow process for the controlled synthesis of a conductive polymer or any salt thereof comprises the following steps: a) providing an organic stream comprising an organic solvent, a polymerizable organic monomer, and optionally a protonic acid; b) providing an oxidant stream comprising an aqueous solvent and a free radical initiator; and d) mixing the organic stream and the oxidant stream in a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize the conductive polymer or salt thereof to provide a product stream comprising the conductive polymer or salt thereof in the tubular reactor; and d) obtaining a conductive polymer or a salt thereof from the product stream under continuous flow conditions after the product stream leaves the reactor. may include:

[0102] In step (a), the organic stream can be a non-aqueous organic solution comprising an organic solvent, a polymerizable organic monomer (e.g., as a polymerizable organic monomer salt, or a precursor mixture of an organic monomer and a protonic acid). In step (b), the oxidant stream can be an aqueous stream comprising an aqueous solvent and an oxidant such as a free radical initiator, e.g., ammonium persulfate. In step (c), the organic and aqueous streams can be combined in a continuous flow to provide a product stream in the form of an emulsion.

[0103] It will be appreciated that the reagents in the organic and oxidant streams combine in the fluid flow and react to form a product stream containing the conductive polymer or conductive polymer salt. As previously mentioned, the continuous flow process does not require a chemical synthesis reaction step to recover the conductive polymer or conductive polymer salt from the tubular reactor.

[0104] The disclosed continuous flow process, system, or reactor can be operated at a predetermined pressure and temperature. For example, the temperature of the individual or combined streams, such as the organic stream, oxidant stream, emulsion stream, or product stream within the overall process or tubular reactor, can be set between about -15°C to 15°C, -10°C to 10°C, -5°C to 5°C, or -1°C to 1°C. The temperature of the individual or combined streams within the overall process or reactor can be less than about 10°C, 9°C, 8°C, 7°C, 6°C, 5°C, 4°C, 3°C, 2°C, or 1°C. The temperature of the individual or combined streams within the overall process or reactor can be greater than about -10°C, -9°C, -8°C, -7°C, -6°C, -5°C, -4°C, -3°C, -2°C, or -1°C. The temperature can be specified within any range between these upper and lower limits. These temperatures can be maintained throughout the axial flow length of the continuous flow reactor. Additionally, the temperature may be set within these ranges while providing a variation of less than about 5° C., 4° C., 3° ​​C., 2° C., or 1° C. Improved control of temperature, including variation of axial flow length, has surprisingly been shown to provide conductive polymers from product streams having high electrical conductivity and / or reduced solids content, e.g., reduced amounts of low molecular weight product.

[0105] In one example, the continuous flow process is for the controlled synthesis of polyaniline or any salt thereof, comprising the following steps: a) providing an organic stream comprising an organic solvent, an unsubstituted or substituted aniline or a salt thereof, and optionally a protonic acid; b) providing an oxidant stream comprising an aqueous solvent and a free radical initiator; and c) mixing the organic stream and the oxidant stream in a continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize polyaniline or a salt thereof to provide in the reactor) a product stream comprising polyaniline or a salt thereof; and d) obtaining polyaniline or a salt thereof from the product stream under continuous flow conditions after the product stream leaves the reactor. Includes:

[0106] In any of the above examples, the free radical initiator may be an oxidizing agent. The free radical initiator may be an aqueous or water-soluble oxidizing agent. The free radical initiator or oxidizing agent may be ammonium persulfate. The oxidizing agent stream may be an aqueous stream comprising an aqueous solvent. The free radical initiator or oxidizing agent may be soluble in the aqueous solvent. Combining the organic stream and the aqueous stream in a continuous flow results in a product stream in the form of an emulsion. In any of the above examples, for step (a), the organic stream may be a non-aqueous organic solution comprising an organic solvent, a polymerizable organic monomer, and optionally a protonic acid. The polymerizable organic monomer may be an organic-soluble polymerizable organic monomer salt according to any one or more examples described herein.

[0107] The mixing element in the continuous flow reactor of step (c) can be a static mixer or a dynamic mixer (e.g., a rotating tube). The static mixing element can be provided by one or more passages in the reactor fluidly connected to each other to convey the streams and configured to enhance mixing of the streams (e.g., radial mixing). The oxidant stream and the aqueous stream can be premixed under continuous flow conditions before being introduced into the continuous flow tubular reactor of step (c).

[0108] In one example, the organic stream is a1) providing a protonic acid stream comprising an organic solvent and a protonic acid; a2) providing a monomer stream comprising a polymerizable organic monomer and, optionally, an organic solvent; and a3) combining the protonic acid stream and the monomer stream to form the organic stream of step a). Provided by.

[0109] The polymerizable organic monomer may be provided as a neat organic liquid, optionally with one or more organic solvents. The polymerizable organic monomer may be an organic monomer salt or a precursor mixture of an organic monomer (e.g., aniline) and a protonic acid (e.g., DNNSA). The organic stream containing the polymerizable organic monomer may be in the form of an organic liquid concentrate. For example, the organic stream may contain the polymerizable organic monomer at a concentration (wt % of the total organic stream) of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99. The organic stream may contain the organic monomer and protonic acid for forming the polymerizable organic monomer at a concentration (wt % of the combined weight of the organic monomer and protonic acid in the total organic stream) of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99. The monomer stream may contain polymerizable organic monomers in a concentration i (wt % of total monomer stream) of at least 70, 80, 85, 90, 95, 98, or 99. The protonic acid stream may contain protonic acid in a concentration i (wt % of total protonic acid stream) of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99. It will be understood that one or more organic solvents described herein can provide the remaining volume or wt % of the organic stream, in addition to impurities that may be present.

[0110] In one example, the monomer stream is an aniline stream comprising unsubstituted or substituted aniline and, optionally, an organic solvent, and step a3) provides combining the protonic acid stream with the aniline stream to form the organic stream of step (a).

[0111] The protonic acid stream and the monomer stream may be premixed under continuous flow conditions before mixing with the oxidant stream. In at least some examples, premixing can provide further improvement to the emulsion of the product stream formed by mixing the organic stream and the oxidant stream. The mixing of the streams in any one or more of the above examples may be provided by one or more static mixers under continuous flow conditions. Premixing includes ultrasonication, dynamic, or static mixing options. The premixing options can be operated within a continuous flow process or system. In one example, the premixer is a continuous flow static mixer as an in-line module in fluid communication with a continuous flow reactor, such as a continuous flow tubular reactor.

[0112] An example of a continuous flow process is shown in the schematic diagram of Figure 2. A continuous flow process can include, for example, a tubular reactor and at least first and second continuous flow mixers (i.e., Mixer 1 and Mixer 2). The continuous flow mixer can be a fluid conduit or a continuous flow reactor, e.g., a continuous flow reactor containing a mixing element. Mixer 1, Mixer 2, and the tubular reactor can each be provided in fluid communication in a series configuration. The mixing elements of Mixer 1, Mixer 2, and the tubular reactor can be any of the examples of mixing elements described above, e.g., one or more continuous flow static or dynamic mixers. A first continuous flow mixer (Mixer 1) can be provided in which the polymerizable organic monomer is introduced solely into Mixer 1 as a neat liquid or organic solution, and the protonic acid is introduced solely into the same continuous flow mixer (Mixer 1) as an organic solution, thereby forming an organic-soluble monomer ene within Mixer 1. A second continuous flow mixer (Mixer 2) can then be provided in series with the first mixer (Mixer 1). An additional aqueous stream containing a free radical initiator can then be introduced into mixer 2, thereby forming a reactant emulsion between the organic-soluble monomer salt stream and the aqueous stream containing the free radical initiator within mixer 2. The reactant emulsion stream (i.e., the product stream) can then be introduced into a temperature-controlled continuous flow reactor, such as a continuous flow tubular reactor, containing one or more static mixers (e.g., five or more static mixers) housed therein or containing one or more passages configured to enhance mixing of the streams. A conductive polymer or conductive polymer salt is then formed within the fluid flowing through the reactor during the continuous flow process, and the synthesized conductive polymer or conductive polymer salt can be recovered from the stream exiting the reactor without the need for a shutdown, interruption, or cleaning step during operation of the continuous flow process. In other words, the conductive polymer or conductive polymer salt can be synthesized within the reactor and obtained from the continuous stream exiting the reactor during normal operation of the continuous flow process.

[0113] 3 provides a schematic example illustrating the mixing of any one or more streams described herein, including the mixing of an oxidant stream and an organic stream adjacent to a temperature-controlled continuous flow reactor. For example, a continuous flow mixer including a static mixer element (C) is fluidly connected to the inlet of a temperature-controlled continuous flow reactor (D) to enable mixing of an oxidant stream and an organic stream described herein adjacent to the temperature-controlled continuous flow reactor (D). In one example, the continuous flow mixer including a static mixer element is a feed conduit to the temperature-controlled continuous flow reactor (D). Additional feed conduits or continuous flow mixers or tubular reactors (with or without static mixers) may be provided in parallel or series for optional in-line mixing of any of the streams described herein (e.g., polymerizable organic monomer salt, A3) while fluidly connected to the temperature-controlled continuous flow reactor (D).

[0114] In another example, the continuous flow process comprises the following steps: a) providing a protonic acid stream comprising an organic solvent and a protonic acid; and combining the protonic acid and the monomer stream in a continuous flow static or dynamic mixer to form an organic stream comprising protonated aniline monomer; b) providing an oxidant in an aqueous stream comprising an aqueous solvent; and optionally premixing the aqueous stream and the organic stream together to form a reactant emulsion stream; c) combining the aqueous stream and the organic stream to form a reactant emulsion stream in, or introducing into, a temperature-controlled continuous-flow tubular reactor comprising at least one static mixer at a temperature effective to synthesize a polyaniline salt and provide in the tubular reactor a product stream comprising the polyaniline salt conductive polymer; and d) Obtaining a conductive polymer of polyaniline salt from the product stream under continuous flow conditions after the product stream leaves the tubular reactor. may include:

[0115] A continuous flow process for the controlled synthesis of a conductive polymer or any salt thereof comprises the following steps: a) providing an optionally cooled organic stream comprising an organic solvent, a polymerizable organic monomer, and optionally a protonic acid; b) providing an optionally cooled oxidant stream comprising an aqueous solvent and a free radical initiator; c) directly introducing the organic stream and the oxidant stream into a temperature-controlled continuous flow reactor comprising at least one static mixer element to combine the organic stream and the oxidant stream to form an emulsion stream; and operating the temperature-controlled continuous flow reactor at a temperature effective to synthesize the conductive polymer or salt thereof to provide a product stream comprising the conductive polymer or salt thereof in a flow within the reactor; and d) Obtaining a conductive polymer or salt thereof from the product stream after it leaves the temperature-controlled continuous flow reactor under continuous flow conditions. may include:

[0116] A continuous flow process for the controlled synthesis of a conductive polymer or any salt thereof comprises the following steps: a) providing an optionally cooled organic stream comprising an organic solvent, a polymerizable organic monomer, and optionally a protonic acid; b) providing an optionally cooled oxidant stream comprising an aqueous solvent and a free radical initiator; c) introducing the organic stream and the oxidant stream into a continuous flow mixer comprising at least one static mixer element to combine the organic stream and the oxidant stream and form an emulsion stream; d) introducing the emulsion stream into a temperature-controlled continuous flow reactor in fluid communication with the continuous flow mixer of step c), wherein the temperature-controlled continuous flow reactor comprises at least one static mixer and is operated at a temperature effective to synthesize the conductive polymer or salt thereof and form a product stream comprising the conductive polymer or salt thereof in a flow within the reactor; and e) obtaining a conductive polymer or a salt thereof from the product stream after it leaves the temperature-controlled continuous flow reactor under continuous flow conditions. may include:

[0117] A continuous flow process for the controlled synthesis of a conductive polymer or any salt thereof comprises the following steps: a1) providing a protonic acid stream comprising an organic solvent and a protonic acid; a2) providing a monomer stream comprising a polymerizable organic monomer and, optionally, an organic solvent; and a3) introducing the protonic acid stream and the monomer stream into a continuous flow mixer comprising at least one static mixer element to combine the protonic acid stream and the monomer stream and form an organic stream; b) providing an optionally cooled oxidant stream comprising an aqueous solvent and a free radical initiator; c) introducing the organic stream and the oxidant stream into a continuous flow mixer comprising at least one static mixer element to combine the organic stream and the oxidant stream and form an emulsion stream; d) introducing the emulsion stream into a temperature-controlled continuous flow reactor in fluid communication with the continuous flow mixer of step c), wherein the temperature-controlled continuous flow reactor comprises at least one static mixer and is operated at a temperature effective to synthesize the conductive polymer or salt thereof and form a product stream comprising the conductive polymer or salt thereof in a flow within the reactor; and e) obtaining a conductive polymer or a salt thereof from the product stream after it leaves the temperature-controlled continuous flow reactor under continuous flow conditions. may include:

[0118] Further process steps may include subsequent treatment of the polyaniline salt conductive polymer according to any embodiment or example described herein.

[0119] conductive polymer Conductive polymers prepared by continuous flow processes can be selected from any conductive polymer that is the reaction product of a protonated polymerizable organic monomer or its salt with a free radical initiator. Many conductive polymers have well-known problems, such as reaction control issues and poor solubility that makes them difficult to handle, and batch processing solutions are commonly used, but these have become increasingly complex in recent years in order to obtain conductive polymers with suitable properties.

[0120] Each individual polymer chain of the conductive polymer, or any salt thereof, can independently be composed of between about 100 and 1500 individual monomer units. The number of individual monomer units can be at least about 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, or 1200. The number of individual monomer units can be less than about 1500, 1400, 1300, 1200, 1100, 1000, 900, 800, 700, 600, or 500. The number of individual monomer units can be between about 300 and 1400, 500 and 1300, 600 and 1200, or 700 and 1100. The number of individual monomer units in an individual polymer chain can be within a range defined by any lower and upper limits, as discussed above. It will be appreciated that lower molecular weight products may provide undesirable levels of toxicity, and higher molecular weight products may have reduced processability, in other words, it is desirable to balance reduced toxicity with practical processability properties.

[0121] The conductive polymer or salt thereof produced by the present process can have a number average molecular weight of at least 10,000. For example, the number average molecular weight can be at least about 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, or 80,000. The number average molecular weight can range from about 1,000 to 120,000, 20,000 to 115,000, 30,000 to 110,000, 40,000 to 105,000, 50,000 to 100,000, or 60,000 to 100,000. The number average molecular weight can be less than about 120,000, 110,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, or 40,000. The number average molecular weight may be in a range defined by any lower and upper limits, as discussed above. It will be appreciated that lower molecular weight products may provide undesirable levels of toxicity, while higher molecular weight products may be less processable. Again, it is desirable to balance reduced toxicity with practical processability.

[0122] The conductive polymer may be a copolymer. The conductive polymer may be selected from the group consisting of polyarylamines, polyarylthiols, polypyrroles, polycarbazoles, polyindoles, polyazepines, polythiophenes, and poly(3,4-ethylenedioxythiophene). In at least some instances, the polymer or copolymer may be selected to provide further improved processability. In at least some instances, polyaniline polymers may provide improved conductivity over aniline copolymers. It is understood that conductive polymers, including any salts thereof, may be formed by reaction with a protic acid. The conductive polymer may be the reaction product of an unsubstituted or substituted monocyclic, bicyclic, or tricyclic hetaryl monomer containing at least one cyclic heteroatom selected from N and S. The conductive polymer may be the reaction product of an unsubstituted or substituted monocyclic, bicyclic, or tricyclic aryl monomer containing at least one exocyclic heteroatom selected from N and S. It is understood that the reaction product may include the reaction of a protic acid with a free radical initiator.

[0123] Polypyrrole and polyazepine are examples of conductive polymers prepared from the reaction product of a monocyclic hetaryl containing at least one heteroatom selected from N. Polyindole is an example of a conductive polymer prepared from the reaction product of a bicyclic hetaryl containing at least one heteroatom selected from N. Polycarbazole is an example of a conductive polymer prepared from the reaction product of a tricyclic hetaryl containing at least one heteroatom selected from N. Polyarylamines such as polyaniline are examples of conductive polymers prepared from the reaction product of a monocyclic aryl monomer containing at least one exocyclic heteroatom selected from N. Polythiophene is an example of a conductive polymer prepared from the reaction product of a monocyclic hetaryl containing at least one heteroatom selected from S. Poly(3,4-ethylenedioxythiophene) is an example of a conductive polymer prepared from the reaction product of a bicyclic hetaryl containing at least one heteroatom selected from S. Polyphenylene sulfide is an example of a conductive polymer prepared from the reaction product of monocyclic aryl monomers containing at least one exocyclic heteroatom selected from S.

[0124] In one example, the conductive polymer is a polyarylamine, such as polyaniline. In another example, the conductive polymer is a polyarylthiol, such as polyphenylene sulfide. In another example, the conductive polymer is selected from the group consisting of polyaniline and poly(3,4-ethylenedioxythiophene).

[0125] The conductive polymer may be a base or salt, such as polyaniline emeraldine salt. The polyaniline base or salt may be further processed to polyaniline emeraldine base or salt. The polyaniline salt may be a sulfonate, for example, when the acid is dinonylnaphthalene sulfonic acid (DNNSA). The conductive polymer may be polyaniline-dinonylnaphthalene sulfonate (PANI-DNNSA).

[0126] Polyaniline Aniline monomers can be used in this continuous flow process and polymerized to form polyaniline. Polyaniline can exist in three oxidation states: leucoemeraldine (white), emeraldine (green), and pernigraniline (blue / purple). The repeat unit of formula 1a below provides x as half the degree of polymerization. TIFF2025138646000002.tif30170

[0127] Leucoemeraldine is the fully reduced state (e.g., n = 1, m = 0). Pernigraniline is the fully oxidized state, possessing imine bonds instead of amine bonds (n = 0, m = 1). Polyaniline can be in one of these three states or a mixture thereof. The emeraldine form of polyaniline (n = m = 0.5) is called emeraldine base (EB) when neutral, but when protonated (e.g., doped), it is called emeraldine salt (ES), with the imine nitrogen protonated by an acid. Protonation promotes delocalization of the otherwise trapped diiminoquinone-diaminobenzene state. Emeraldine base is the preferred form of polyaniline because it is typically more stable at room temperature and upon protonation to obtain the emeraldine salt form, and has a high electrical conductivity. Leucoemeraldine and pernigraniline are poor conductors, even when acid-doped.

[0128] Polyphenylene sulfide This continuous flow process can be used to form polyphenylene sulfide, which is an organic polymer containing aromatic rings linked to sulfide moieties. The repeating unit of formula 2a below provides an example of a repeating unit of polyphenylene sulfide. TIFF2025138646000003.tif27170

[0129] Polyphenylene sulfide can be converted to a semiconducting form by oxidation or the use of various dopants. Polyphenylene sulfide also offers high temperature resistance, chemical resistance, flowability, dimensional stability, and electrical properties.

[0130] Polypyrrole Polypyrrole monomers can be used in this continuous flow process and polymerized to form polypyrrole. Polypyrrole is a conductive organic polymer. The repeat unit of Formula 3a below provides an example of a polypyrrole repeat unit: TIFF2025138646000004.tif34170

[0131] Polypyrrole in its oxidized form is an excellent electrical conductor. Higher electrical conductivities can be achieved by doping polypyrrole with large anions such as tosylate.

[0132] Polycarbazole Polycarbazole monomers can be used in this continuous flow process and polymerized to form polycarbazole. Polycarbazole is a doped conductive polymer. The repeating unit of Formula 4a below provides an example of a polycarbazole repeating unit: TIFF2025138646000005.tif41170

[0133] Upon doping, the nitrogen of polycarbazole is oxidized before the backbone, which can produce high local charge and good electrical conduction properties.

[0134] Polyindole Indole monomers can be used in this continuous flow process and polymerized to form polyindole. Polyindole is a conductive polymer containing a benzene ring linked to a pyrrolic ring. The repeat unit of formula 5a below provides an example of a polyindole repeat unit. TIFF2025138646000006.tif34170

[0135] Polyazepines Azepine monomers can be used in the present continuous flow process and polymerized to form polyazepines. The repeat unit of formula 6a below provides an example of a polyazepine repeat unit: TIFF2025138646000007.tif46170

[0136] Polythiophene Thiophene monomers can be used in this continuous flow process and polymerized to form polythiophenes. Polythiophenes become conductive when oxidized (doped). The repeat unit of Formula 7a below provides an example of a polythiophene repeat unit: TIFF2025138646000008.tif34170

[0137] The electrical conductivity of polythiophenes is due to electron delocalization along the polythiophene backbone. Polythiophenes also respond to various environmental stimuli and have excellent optical properties, including color shifts in response to changes in solvent, temperature, and applied potential. Both the color change and the conductivity change are caused by twisting of the polymer backbone, which disrupts conjugation.

[0138] Poly(3,4-ethylenedioxy)thiophene 3,4-ethylenedioxythiophene monomer can be used in this continuous flow process and polymerized to form poly(3,4-ethylenedioxythiophene). Poly(3,4-ethylenedioxythiophene) is a transparent conductive polymer that can be used in liquid crystal displays (LCDs) and solar cells. The repeat unit of Formula 8a below provides an example of a repeat unit for poly(3,4-ethylenedioxythiophene): TIFF2025138646000009.tif50170

[0139] Poly(3,4-ethylenedioxythiophene) has excellent optical transparency properties in its conducting state, high stability, moderate band gap, and low redox potential.

[0140] Poly(3,4-propylenedioxy)thiophene 3,4-propylenedioxythiophene monomer can be used in this continuous flow process and polymerized to form poly(3,4-propylenedioxythiophene). Poly(3,4-propylenedioxythiophene) is a transparent conductive polymer for electrochromic devices. The repeat unit of Formula 9a below provides an example of a repeat unit of poly(3,4-propylenedioxythiophene). TIFF2025138646000010.tif54170

[0141] Poly(3,4-propylenedioxythiophene) has excellent optical and electrochromic properties, as well as good processability and solubility.

[0142] The conductive polymer and polymerizable organic monomer are described in further detail below in connection with the steps of the continuous flow process.

[0143] (A) Organic stream The organic stream can include a polymerizable organic monomer, such as unsubstituted or substituted aniline or a salt thereof. The organic stream can further include a protonic acid. The polymerizable organic monomer and / or protonic acid can be introduced into the organic stream neat or as an organic solution containing an organic solvent. It will be understood that the protonic acid can provide a reagent for converting an organic monomer, such as aniline, to a polymerizable monomer salt, such as an anilinium ion. The monomer salt can then be polymerized to form a conductive polymer or a precursor thereof, for example, when an oxidizing agent is used to initiate polymerization of the aniline or its monomer salt to form polyaniline. In one example, the polymerizable organic monomer is a polymerizable organic monomer salt. The polymerizable organic monomer salt can be selected to be soluble in an organic solvent. The polymerizable organic monomer can also be a polymerizable organic monomer salt that can be soluble in an organic solvent. As described below, the organic-soluble polymerizable organic monomer salt can contain a counterion (i.e., M ) that provides charge neutrality to the polymer. - ) with protonic acid (i.e., H + M - ), which can also enhance the solubility of the conductive polymer in organic solvents to aid in its subsequent processing.

[0144] In one example, the organic stream of step a) is a1) providing a protonic acid stream comprising an organic solvent and a protonic acid; a2) providing a monomer stream comprising an organic solvent and a polymerizable organic monomer; and a3) combining the protonic acid stream and the monomer stream to form an organic stream for use in step (a). Provided by.

[0145] In another example, the organic stream of step a) is a1) providing a protonic acid stream comprising an organic solvent and a protonic acid; a2) providing an aniline stream comprising an organic solvent and an unsubstituted or substituted aniline; and a3) combining the protonic acid stream and the aniline stream to form the organic stream in step (a). may be provided by

[0146] It will be understood that the organic stream may contain one or more organic solvents. The organic stream may be a non-aqueous organic stream, such as a non-aqueous organic solution. The organic stream may be a non-aqueous organic solution containing an organic solvent, a polymerizable organic monomer, and optionally a protonic acid. For example, the non-aqueous organic solution may contain one or more organic solvents, unsubstituted or substituted aniline or a salt thereof, and a protonic acid. The organic solvent may be selected from any one or more organic solvents described herein, for example, an alcohol such as 2-butoxyethanol. The organic stream may contain the polymerizable organic monomer as a neat organic liquid, optionally with one or more organic solvents. The polymerizable organic monomer may be an organic monomer salt or a precursor mixture of an organic monomer (e.g., aniline) and a protonic acid (e.g., DNNSA). The organic stream containing the polymerizable organic monomer may be in the form of an organic liquid concentrate. For example, the organic stream can contain a polymerizable organic monomer at a concentration of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99 (wt % of the total organic stream). The organic stream can contain an organic monomer and a protonic acid for forming the polymerizable organic monomer at a concentration of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99 (wt % of the combined weight of the organic monomer and the protonic acid in the total organic stream). The organic stream can be formed from combining a monomer stream and a protonic acid stream. The monomer stream can contain the polymerizable organic monomer at a concentration i (wt % of the total monomer stream) of at least 70, 80, 85, 90, 95, 98, or 99. In one example, the monomer stream is provided by a neat organic liquid of the polymerizable organic monomer, such as aniline. The protonic acid stream may contain protonic acids in a concentration (wt % of the total protonic acid stream) of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99. It will be understood that one or more organic solvents described herein can provide the remaining volume or wt % of the organic stream, in addition to impurities that may be present.

[0147] Polymerizable Organic Monomers As previously mentioned, the conductive polymer prepared by the present continuous flow process can be selected from any conductive polymer that is the reaction product of a protonated polymerizable organic monomer or its salt with a free radical initiator. For example, the conductive polymer can be selected from the group consisting of polyarylamines, polyarylthiols, polypyrroles, polycarbazoles, polyindoles, polyazepines, polythiophenes, poly(3,4-ethylenedioxythiophene), and poly(3,4-propylenedioxythiophene).

[0148] Thus, the polymerizable organic monomer may be an unsubstituted or substituted monocyclic, bicyclic, or tricyclic hetaryl monomer containing at least one ring heteroatom selected from N and S. The polymerizable organic monomer may be an unsubstituted or substituted monocyclic, bicyclic, or tricyclic aryl monomer containing at least one exocyclic heteroatom selected from N and S. The substitution may be selected from the group consisting of halo, hydroxy, nitro, amino, alkyloxy, alkyl, carboxy, haloalkyl, alkylaryl, and arylalkyl.

[0149] In one example, the polymerizable organic monomer is a monocyclic aryl monomer containing at least one exocyclic heteroatom selected from N, such as unsubstituted or substituted aniline. In another example, the polymerizable organic monomer is a bicyclic hetaryl containing at least one heteroatom selected from S, such as 3,4-ethylenedioxythiophene.

[0150] The polymerizable organic monomer may be provided by two or more comonomers. The polymerizable organic monomer may be a salt, for example, an aniline-sulfate salt, such as aniline-DNNSA.

[0151] The polymerizable organic monomer in step a) can be selected from the group consisting of arylamine, arylthiol, pyrrole, carbazole, indole, azepine, thiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene monomer, or derivatives thereof, or salts or combinations thereof, each of which can be independently unsubstituted or substituted. In one example, the polymerizable organic monomer is selected from the group consisting of aniline and 3,4-ethylenedioxythiophene, each of which can be unsubstituted or substituted.

[0152] Aniline Monomer The aniline monomer may be an unsubstituted or substituted aniline, according to the examples described herein.

[0153] The unsubstituted or substituted aniline monomers are represented by formula 1b: TIFF2025138646000011.tif43170[In the above formula, R 1 is hydrogen; R 2 is selected from the group consisting of hydrogen and alkyl; R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0154] In another example, R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, and carboxy, with the remaining groups being as defined above.

[0155] In another example, R 5 is hydrogen and the remaining groups are as defined above. In another example, aniline can be prepared by, for example, R 1 From R 7 is an unsubstituted aniline in which each is selected from hydrogen.

[0156] Polyphenylene Sulfide Monomer The polyphenylene sulfide monomer, according to the examples described herein, can be an unsubstituted or substituted polyphenylene sulfide monomer.

[0157] The unsubstituted or substituted polyphenylene sulfide monomers are represented by formula 2b: TIFF2025138646000012.tif42170[In the above formula, R 2 is selected from the group consisting of hydrogen and alkyl; R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0158] Pyrrole Monomer According to the examples described herein, the pyrrole monomer can be an unsubstituted or substituted pyrrole monomer.

[0159] The unsubstituted or substituted pyrrole monomers are represented by formula 3b: TIFF2025138646000013.tif45170[In the above formula, R 2 is selected from the group consisting of hydrogen and alkyl; R 3 , R 4 , R 5 and R 6are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0160] Carbazole Monomer According to the examples described herein, the carbazole monomer can be an unsubstituted or substituted carbazole monomer.

[0161] The unsubstituted or substituted carbazole monomers are represented by formula 4b: TIFF2025138646000014.tif46170[In the above formula, R 2 is selected from the group consisting of hydrogen and alkyl; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0162] Indole Monomer According to the examples described herein, the indole monomer can be an unsubstituted or substituted indole monomer.

[0163] The unsubstituted or substituted indole monomers are represented by formula 5: TIFF2025138646000015.tif45170[In the above formula, R 2 is selected from the group consisting of hydrogen and alkyl; R 3 , R 4 , R 5 , R 6 , R 7and R 8 are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0164] Azepine Monomers According to the examples described herein, the azepine monomers can be unsubstituted or substituted azepine monomers.

[0165] The unsubstituted or substituted azepine monomers are represented by formula 6b: TIFF2025138646000016.tif49170[In the above formula, R 2 is selected from the group consisting of hydrogen and alkyl; R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0166] Thiophene Monomer According to the examples described herein, the thiophene monomer can be an unsubstituted or substituted thiophene monomer.

[0167] The unsubstituted or substituted thiophene monomers are represented by formula 7b: TIFF2025138646000017.tif33170[In the above formula, R 3 , R 4 , R 5 or R 6are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0168] 3,4-ethylenedioxythiophene monomer The 3,4-ethylenedioxythiophene monomer, according to the examples described herein, can be an unsubstituted or substituted 3,4-ethylenedioxythiophene monomer.

[0169] The unsubstituted or substituted 3,4-ethylenedioxythiophene monomer has the formula 8b: TIFF2025138646000018.tif47170[In the above formula, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0170] 3,4-Propylenedioxythiophene Monomer The 3,4-propylenedioxythiophene monomer can be an unsubstituted or substituted 3,4-propylenedioxythiophene monomer, according to the examples described herein.

[0171] The unsubstituted or substituted 3,4-propylenedioxythiophene monomer has the formula 9b: TIFF2025138646000019.tif53170[In the above formula, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R10 are each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl. The compound can be selected from the following compounds:

[0172] organic solvents The organic solvent is selected to provide a carrier for the polymerizable organic monomer, e.g., aniline monomer. The organic solvent may also be selected to provide a carrier for the protonic acid in addition to the monomer.

[0173] In one example, the organic solvent is a non-aqueous organic solvent. The organic solvent can be selected from a variety of water-immiscible solvents. The non-aqueous organic solvent can form an emulsion with the aqueous stream rather than providing a single phase, and therefore is immiscible with the aqueous stream or phase.

[0174] The organic solvent can be selected from the group including aromatics, chlorinated aromatics, chlorinated aliphatic hydrocarbons, aliphatic hydrocarbons, glycols, ethers, glycol ethers, esters, alcohols, and ketones. The alcohol can be a water-immiscible alcohol with at least a medium alkyl chain or aryl group. The water-immiscible alcohol can be n-butanol or a larger alkyl chain alcohol. The ketone can be a water-immiscible ketone with at least a medium chain, such as methyl ethyl ketone or a ketone with a larger alkyl chain. In one example, the organic solvent is a glycol ether, such as 2-butoxyethanol.

[0175] The organic solvent can be selected from any one or more of an aromatic, a halogenated aromatic, a halogenated aliphatic hydrocarbon, an aliphatic hydrocarbon, a glycol, an ether, a glycol ether, an ester, an alcohol, a ketone, or a combination thereof. In another example, the organic solvent can be selected from the group consisting of a glycol, an ether, a glycol ether, and a combination thereof.

[0176] The organic solvent can also be selected to dissolve the acid dopant (i.e., the protonic acid). For example, the protonic acid DNNSA can be provided in an organic solvent such as a glycol ether (e.g., 2-butoxyethanol), a hydrocarbon (e.g., heptane), or an aromatic hydrocarbon (e.g., toluene or xylene). The protonic acid can be introduced into the process neat or in concentrated form, e.g., without dilution with an organic solvent. In at least some instances, using a more concentrated or solvent-free protonic acid can increase the reaction rate, shorten the reaction time, and improve product throughput. This can also increase the reaction exotherm, potentially resulting in a loss of control of the polymerization due to elevated temperatures, which can be compensated for in accordance with the embodiments or examples of the continuous flow process described herein. Elevated temperatures or lack of temperature control can lead to poor batch-to-batch reproducibility, reduced polymer molecular weight, and ultimately reduced polymer conductivity.

[0177] Following the reaction process, the product can be diluted using an organic solvent to achieve the desired final concentration and properties.

[0178] Other suitable exemplary liquid solvents include aromatics such as xylene, toluene, or alkylnaphthalenes; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene, or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffins (e.g., mineral oil fractions); alcohols such as butanol, isobutanol, or glycols, and their ethers and esters, for example, 2-butoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone. In one example, the organic solvent is selected from the group consisting of alcohols, glycols, ethers, glycol ethers, and any combination thereof.

[0179] Protonic Acid It will be appreciated that the protonic acid is selected to provide a source of protons that promotes the formation of a polymerizable organic monomer salt that can itself polymerize into a conductive polymer, for example, in the presence of an oxidizing agent. The protonic acid can also be selected to act as a dopant for the conductive polymer or surfactant to promote emulsion of the aqueous and organic streams.

[0180] The protonic acid can be selected from the group consisting of sulfonic acid, phosphoric acid, phosphonic acid, boronic acid, carboxylic acid, thiol, phenol, heteropolyacid (e.g., tungstosilicic acid), or any mixture thereof. The protonic acid can include a polymer functionalized with any of the above acidic groups. The protonic acid can be a hydrophobic organic acid. It will be understood that the hydrophobic organic acid can react with the base form of the polymerizable organic monomer or conductive polymer to form a salt that is at least partially soluble in at least some organic solvents. According to at least some examples described herein, the continuous flow process allows for the in situ (i.e., during the flow) formation of an organic-soluble polymerizable monomer salt that can itself be polymerized into a more easily processable organic-soluble conductive polymer form during the continuous flow process.

[0181] The protonic acid can be selected from the group consisting of dinonylnaphthalenesulfonic acid (DNNSA), dinonylnaphthalenedisulfonic acid, methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid (DBSA), p-toluenesulfonic acid, trifluoromethanesulfonic acid, fluoroboric acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorooctanoic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and phosphoric acid, or any combination thereof. The protonic acid can be selected from the group consisting of dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, and p-toluenesulfonic acid, or any mixture thereof. The protonic acid can be dinonylnaphthalenesulfonic acid (DNNSA).

[0182] An organic solvent can be used to dissolve the protonic acid, although it will be understood that in some instances the protonic acid can be introduced directly into the stream without dilution in an organic solvent. In some instances, such as when the polymerizable organic monomer salt is prepared before being introduced into the organic stream, a protonic acid may not be required.

[0183] Concentration and ratio of organic streams The concentration (mol / L) of the polymerizable organic monomer in the organic stream can be in the range of about 0.01 to 15. The concentration (mol / L) of the polymerizable organic monomer can be at least about 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. The concentration (mol / L) of the polymerizable organic monomer can be less than about 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, 0.1, or 0.05. The concentration (mol / L) of the polymerizable organic monomer in the organic stream can be in the range defined by any two of the maximum and / or minimum values ​​listed above. Increasing the concentration of organic monomer in solution increases the polymerization rate and throughput of the process, but also increases impurities and generates more detrimental exotherms that can degrade the product obtained from the process.

[0184] In a further example relating to the preparation of polyaniline, the concentration (mol / L) of aniline or its salt can be in the range of about 0.25 to 1, 0.4 to 1, or 0.6 to 1. The concentration (mol / L) of aniline or its salt in the organic stream can be at least about 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, or 0.95. The concentration (mol / L) of aniline or its salt in the organic stream can be less than about 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, or 0.6. The concentration (mol / L) of aniline or its salt in the organic stream (or emulsion stream) can be in the range defined by any two of the maximum and / or minimum values ​​listed above.

[0185] The concentration (mol / L) of the protonic acid in the organic stream can be in the range of about 0.02 to 20 mol / L. The concentration (mol / L) of the protonic acid can be at least about 0.02, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10. The concentration (mol / L) of the protonic acid can be less than about 20, 17.5, 15, 12.5, 10, 9, 8, 7, 6, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, or 0.1. The concentration (mol / L) of the protonic acid in the organic stream can be in the range defined by any two of the maximum and / or minimum values ​​listed above.

[0186] In further examples where the protonic acid is an organic-soluble protonic acid (e.g., DNNSA), the concentration (mol / L) of the organic-soluble protonic acid can be specified to be in the range of about 0.02 to 5, such as in the range of about 0.3 to 3, 0.4 to 2, or 0.5 to 1. The concentration (mol / L) of the organic-soluble protonic acid can be at least about 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, or 3. The concentration (mol / L) of the organic-soluble protonic acid can be less than about 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1. The concentration (mol / L) of the organic-soluble protonic acid in the organic stream can be within a range defined by any two of the above maximum and / or minimum values.

[0187] The molar ratio of protonic acid to polymerizable organic monomer can be at least 1:1, such as at least about 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1. The molar ratio of protonic acid to polymerizable organic monomer can range from about 1:1 to 4:1, 1.1:1 to 3:1, 1.2:1 to 2:1, or about 1.3:1 to 1.7:1. The protonic acid can, for example, simultaneously act as a surfactant (emulsifier) ​​and as a protonating agent for the resulting PANI-protonic acid complex. Varying the ratio of protonic acid to organic monomer will affect both the molecular weight and solubility of the resulting polymer.

[0188] The above concentrations and ratios may also be provided for synthesizing polyaniline, i.e., may be concentrations and ratios with respect to aniline monomer. The molar ratio of protonic acid to aniline (e.g., DNNSA) may also be as described above.

[0189] (B) Oxidant flow It will be appreciated that the oxidant stream in step (b) provides a fluid carrier for the oxidant, such as a free radical initiator, e.g., ammonium persulfate. The oxidant stream may be provided as an aqueous stream. The aqueous stream may include an aqueous solvent and a free radical initiator. The aqueous solvent may be selected so that, when the aqueous stream is mixed with the organic stream, an emulsion can be formed under certain flow and mixing parameters.

[0190] Free Radical Initiators It will be appreciated that the free radical initiator may be an oxidizing agent, such as ammonium persulfate, which provides a reagent for initiating the polymerization of polymerizable monomer salts, such as the polymerization of anilinium monomers into polyaniline.

[0191] The oxidizing agent may be selected from the group consisting of persulfates, dichromates, cerium (IV) salts, oxyhalide salts, and halide salts, iron (III) salts, or any combination thereof.

[0192] The oxidizing agent may be selected from the group consisting of APS, potassium dichromate, potassium iodate, ferric chloride, ferric tosylate, potassium permanganate, potassium bromate, potassium chlorate, ceric ammonium nitrate, and cerium sulfate.

[0193] In one example, the oxidizer is ammonium persulfate (APS), which, in at least some instances, can offer reduced overhead and ease of use in industrial-scale operations.

[0194] The concentration (mol / L) of the free radical initiator (e.g., APS) can be in the range of about 0.1 to 5. The concentration (mol / L) of the free radical initiator in the oxidant stream can be at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, or 4. The concentration (mol / L) of the free radical initiator in the oxidant stream can be less than about 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, or 0.5. The concentration (mol / L) of the free radical initiator in the oxidant stream can be in the range defined by any two of the above maximum and / or minimum values, for example, 0.4 to 4, 0.7 to 3, or 0.5 to 1.5.

[0195] In a further example, the ratio of polymerizable organic monomer to free radical initiator can range from about 1:10 to 4:1, such as 1:2 to 2:1, or 1:1 to 2:3. In a further example for preparing polyaniline, the ratio of aniline monomer or a salt thereof to free radical initiator (e.g., APS) can range from 1:1 to 1.5, such as 1:1 to 1:1.4, 1:1 to 1:3, or 1.1 to 1:4.

[0196] aqueous solvent The aqueous solvent may be provided by water, or at least an aqueous solvent system that primarily comprises water. For example, the aqueous solvent system may contain at least 50, 60, 70, 80, 90, 95, 98, or 99% water (wt. % of the total aqueous solvent system). The remainder of the aqueous solvent system may include other solvents or incidental impurities.

[0197] (C) Product logistics In one example, the emulsion stream may be formed from combining an oxidant stream and an organic stream, or from these product streams. It will be understood that the product stream is formed by combining an organic stream containing polymerizable organic monomers with an oxidant stream containing a free radical initiator.

[0198] When the oxidant stream is an aqueous stream, an aqueous stream comprising a free radical initiator and an organic stream comprising a polymerizable organic monomer can be combined in a continuous flow to provide a product stream for synthesizing the conductive polymer or salt thereof comprising an emulsion formed by combining the organic and aqueous streams.

[0199] The product stream can provide a conductive polymer synthesis as described above. The conductive polymer can be organic soluble. The conductive polymer can be in a conductive form (e.g., the emeraldine form of polyaniline). The conductive polymer can be a salt. The salt form of the conductive polymer can also be soluble in organic solvents. For example, the salt form can be prepared from a protic acid that is a hydrophobic organic acid. The hydrophobic organic acid can provide a counterion to the monomer or polymer that allows the protonated form to be neutral and soluble in at least some organic solvents. The conductive polymer can also be a copolymer or polymer blend. For example, with polyaniline, the conductive polymer can be formed from a monomer salt to provide polyaniline emeraldine salt, which can be soluble in organic solvents and more easily processable.

[0200] Regarding polyaniline emeraldine salt, also known as PANI-ES, one example is PANI-DNNSA, where the protonic acid is DNNSA (and the polymer is doped), i.e., dinonylnaphthalene sulfonic acid. PANI-DNNSA is an example of an organic-soluble conductive polymer prepared by a continuous flow process.

[0201] The concentration of the conductive polymer in the product stream can be about 15-75 wt% (based on the aforementioned suitable concentrations of the polymerizable organic monomer in the organic stream). The concentration of the conductive polymer in the product stream can be at least about 20, 30, 40, 50, 60, or 70 wt% (based on the aforementioned suitable concentrations of the polymerizable organic monomer in the organic stream). The concentration of the conductive polymer in the product stream can be in the range of about 30-75, 35-70, 40-65, or 45-60 wt% (based on the aforementioned suitable concentrations of the polymerizable organic monomer in the organic stream).

[0202] The concentration of polymerizable organic monomer in the product stream exiting the temperature-controlled continuous flow reactor may be negligible, for example, below the limit of detection (LOD) using a 400 MHz nuclear magnetic resonance (NMR) spectrometer under standard conditions as determined by NMR spectroscopy. The product stream exiting the temperature-controlled continuous flow reactor may be substantially free of unreacted polymerizable organic monomer. The conversion (or yield) of the polymerizable organic monomer to conductive polymer may be at least about 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99%, 99.5%, or 99.9%. It will be understood that some of the polymerizable organic monomer may polymerize to low molecular weight products, such as dimers or smaller oligomers. The low molecular weight products can be removed by subsequent treatment, such as an aqueous wash process. A high conversion of the polymerizable organic monomer to conductive polymer is desirable not only for process economics but also to ensure that significant amounts of known harmful monomers or low molecular weight products do not remain in the final polymer product.

[0203] The composition and components of a conductive polymer material can also be described by its dispersity value (also called polydispersity index - PDI), which indicates the distribution of various polymer molecular weights within the conductive polymer material and can be measured by determining the weight average molecular weight and dividing by the number average molecular weight. It will be appreciated that the weight average molecular weight and number average molecular weight can be determined from a sample mixture of conductive polymers by various chromatographic or spectroscopic methods, such as HPLC or NMR methods.

[0204] The polydispersity of the conductive polymer can be in the range of about 1 to 15, 1 to 10, 1 to 5, or 1 to 3. The polydispersity can be less than about 15, 13, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1.5. The dispersity can be at least about 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. The dispersity can be provided within any two of these upper and lower limits, as described above. Lower polydispersity can provide greater consistency in the properties, including solubility, of the conductive polymer.

[0205] Conductive polymers have a resistance of approximately 1x10 -6 S / cm~1x10 -2 For example, the bulk sample conductivity (untreated thin film measured at 20° C.) may be at least about 1×10 S / cm. -5 S / cm, 1x10 -4 S / cm, or 1x10 -3 S / cm.

[0206] The conductive polymer may have a bulk sample conductivity (measured at 20°C on a thin film treated with isopropanol) of between about 0.1 S / cm and 15 S / cm. The bulk sample conductivity (measured at 20°C on a thin film treated with isopropanol) may be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 S / cm. Treating a conductive polymer film with isopropanol has been shown to improve the conductivity of the film by removing excess dopant from the film and improving charge transport in the remaining polymer.

[0207] For preparing conductive polymers, a suitable molar ratio of polymerizable organic monomer (e.g., aniline), protonic acid (e.g., DNNSA), and free radical initiator (e.g., APS) can be 1.0 equivalent, 1.0-4.0 equivalents, and 0.5-2.0 equivalents of free radical initiator. For example, the ratio can be 1.0 equivalent, 1.5 equivalents, and 1.2 equivalents of free radical initiator.

[0208] The operating temperature for preparing conductive polymers in a continuous flow process can be set to operate within a narrow temperature range, for example, within a temperature variation of less than 10°C, 9°C, 8°C, 7°C, 6°C, 5°C, 4°C, 3°C, 2°C, or 1°C. In one example, the temperature of the product stream can be less than about 10°C, for example, less than about 5°C, 4°C, 3°C, 2°C, or 1°C. In one example, the reaction temperature in the product stream is maintained between about -5°C and 5°C, with a temperature variation of less than about 5°C during the reaction. In another example, the reaction temperature in the product stream is maintained between about -3°C and 3°C, with a temperature variation of less than about 3°C ​​during the reaction. In another example, the reaction temperature in the product stream is maintained at 0°C, with a temperature variation of less than about 1.0°C during the reaction. The above temperature ranges and variations may be imparted to any individual or combined stream, for example, the emulsion stream and / or the product stream. In one particular example, the temperature range and / or temperature variation may be imparted across the axial flow length of a tubular reactor containing the emulsion stream and / or the product stream. The polymerization temperature has a strong effect on both the polymerization yield and the molecular weight of the polymer. As the reaction temperature increases, both the yield and the molecular weight decrease. For the reasons stated above, it is also important to control temperature fluctuations during the reaction. Improved control of temperature, including fluctuations in axial flow length, has surprisingly been shown to provide conductive polymers from the product stream with improved electrical conductivity and / or reduced solids content, e.g., reduced amounts of low molecular weight products. It will be understood that "low molecular weight products" may include oligomers, particularly dimers, trimers, and tetramers, having up to about 20 monomer units, e.g., 10 monomer units or less. The amount of polymerizable organic monomer or low molecular weight products in the product stream may be less than 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001 (by weight of the product stream). Subsequent processing of the product stream can further reduce the low molecular weight products or other undesirable impurities from any organic-soluble conductive polymer present in the product stream.

[0209] The residence time of the reactants in the product stream is between about 0.5 h and 3.0 h (depending on the mixing efficiency). In other examples, the residence time of the product stream is between about 0.75 h and 2.0 h, 0.8 h and 1.5 h, or 0.85 h and 1.2 h. The residence time of the reactants in the product stream is less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 h. The residence time of the reactants in the product stream is at least 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, or 9 h. The residence time (h) of the reactants in the product stream may be given in a range between any two of these upper and / or lower values. The residence time is determined by the reaction rate and the continuous flow reactor geometry, and the polymerization reaction is completed before the product stream exits the continuous reactor system.

[0210] In one example, the flow rate may be in the range of approximately 1-1000, 2-500, 3-300, 4-200, or 5-100 ml / min. The flow rate may be less than 1000, 750, 500, 400, 300, 200, 100, 75, 50, or 25 ml / min. The flow rate may be greater than 1, 5, 10, 15, 20, 25, 50, or 75 ml / min. The flow rate may be within a range defined by any two of these upper and / or lower limits.

[0211] In one example, the flow rate (m / s) may be in the range of approximately 0.001-0.1, 0.005-0.5, or 0.01-0.05. The flow rate (m / s) may be less than 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, or 0.02. The flow rate (m / s) may be greater than 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, or 0.01. The flow rate may be within a range defined by any two of these upper and / or lower limits.

[0212] For continuous flow tubular reactors, the internal diameter of the tubular reactor can be at least about 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm. The internal diameter of the tubular reactor can be about 2-25 mm, 5-20 mm, or 5-10 mm. The internal diameter of the tubular reactor and the design of the static mixer affect the mixing performance of the reactor. At a given flow rate, smaller diameter tubes experience higher shear forces and more turbulence than larger diameter tubes, resulting in more efficient mixing.

[0213] For continuous flow processes or systems, the minimum internal diameter of any portion of the continuous flow system can be at least about 1 mm, 2 mm, 3 mm, 4 mm, or 5 mm. The internal diameter of any portion of the continuous flow system can be between about 1 and 25 mm, 2 and 15 mm, or 5 and 10 mm. The diameter of the portion of the continuous flow system can be varied to vary mixing performance. To enhance mixing performance and produce fine emulsions, sections of tubing containing static mixers with smaller diameters than the main tubular reactor system can be used.

[0214] The process can provide at least about 30 g of conductive polymer per hour of operation, e.g., for continuous flow reactor volumes of about 100 ml to 3000 ml. In one example, the process provides at least about 30 g, 40 g, 50 g, 60 g, 70 g, 80 g, 90 g, 100 g, 110 g, 120 g, or 130 g of conductive polymer or conductive polymer salt per liter of tubular reactor internal volume per hour of operation. It will be appreciated that higher production rates provide additional economic and supply advantages.

[0215] The space time yield (STY, in g / Lh) may be at least about 30. Space time is the time required to process one volume of fluid in the reactor given a particular set of input conditions. STY is the amount of conductive polymer in grams synthesized per liter of emulsion or product stream passing through the reactor per hour. STY can be calculated using the following formula: TIFF2025138646000020.tif46170

[0216] In one example, the STY is a conductive polymer or conductive polymer salt of at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, or 130. In another example, the STY is a conductive polymer or conductive polymer salt of less than about 130, 125, 120, 115, 110, 105, 100, 95, 90, or 85. The STY can be within a range defined by any two of these upper and / or lower limits, for example, between about 50 and 130, 60 and 125, or 70 and 115.

[0217] Synthetic Polyaniline The polyaniline emeraldine salt prepared from the continuous flow process may be provided as a solution in an organic solvent or as a solid. The polyaniline emeraldine salt has a green appearance.

[0218] The prepared polyaniline emeraldine salt can have a number-average molecular weight of at least 10,000. For example, the number-average molecular weight can be at least about 20,000, 30,000, 40,000, 50,000, 60,000, or 70,000. The number-average molecular weight can be in the range of about 1,000 to 100,000, 20,000 to 100,000, 30,000 to 100,000, 40,000 to 100,000, 50,000 to 100,000, or 60,000 to 100,000. The number-average molecular weight can be less than about 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, or 40,000. The number-average molecular weight can be within a range defined by any upper and lower limits, as described above. It will be appreciated that lower molecular weight products may provide undesirable levels of toxicity, and higher molecular weight products may be less processable.

[0219] The composition and components of a conductive polymer material can also be described by its dispersity value (also called polydispersity index - PDI), which indicates the distribution of various polymer molecular weights within the conductive polymer material and can be measured by determining the weight average molecular weight and dividing by the number average molecular weight. It will be appreciated that the weight average molecular weight and number average molecular weight can be determined from a sample mixture of conductive polymers by various chromatographic or spectroscopic methods, such as HPLC or NMR methods.

[0220] The polydispersity of the prepared polyaniline emeraldine salt can range from about 1 to 15, 1 to 10, 1 to 5, or 1 to 3. The polydispersity can be less than about 15, 13, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1.5. The dispersity can be at least about 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. The dispersity can be provided within any two of these upper and lower limits, as described above. Lower polydispersity can provide more consistency in properties, including the solubility, of the conductive polymer.

[0221] The prepared polyaniline emeraldine salt had a concentration of about 1x10 -6 S / cm~1x10 -2 For example, the bulk sample conductivity (untreated thin film measured at 20° C.) may be at least about 1×10 S / cm. -5 S / cm, 1x10 -4 S / cm, or 1x10 -3 S / cm.

[0222] The prepared polyaniline emeraldine salt can have a bulk sample conductivity (measured at 20°C on isopropanol-treated thin films) between about 0.1 S / cm and 10 S / cm. The bulk sample conductivity (measured at 20°C on isopropanol-treated thin films) can be at least about 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 S / cm. Treatment of polyaniline films with isopropanol has been shown to improve the conductivity of the thin films by removing excess dopant from the film and improving charge transport in the remaining polymer.

[0223] The concentration of polyaniline in the product stream can be about 15-75 wt% (based on the aforementioned suitable concentrations of aniline in the organic stream). The concentration of polyaniline in the product stream can be at least about 20, 30, 40, 50, 60, or 70 wt% (based on the aforementioned suitable concentrations of aniline in the organic stream). The concentration of polyaniline in the product stream can be in the range of about 30-75, 35-70, 40-65, or 45-60 wt% (based on the aforementioned suitable concentrations of aniline in the organic stream).

[0224] The concentration of aniline (unreacted aniline) in the product stream may be negligible, for example, below the limit of detection (LOD) using a 400 MHz nuclear magnetic resonance (NMR) spectrometer under standard conditions as determined by NMR spectroscopy. The product stream may be substantially free of unreacted aniline. The conversion (or yield) of aniline monomer to polyaniline may be at least about 80%, 85%, 90%, 95%, 98%, 99%, or 99.9%. It will be appreciated that some of the aniline may polymerize to dimers or smaller oligomers, which can be removed by subsequent treatment, such as an aqueous wash process. A high conversion of aniline monomer to polyaniline is desirable not only for process economics but also to ensure that significant amounts of aniline monomer or oligomers, known to be harmful, do not remain in the final polymer product.

[0225] For the preparation of polyaniline, an example of a suitable molar ratio of aniline monomer, protonic acid (e.g., DNNSA), and free radical initiator (e.g., APS) is 1.0 equivalent, 1.0 to 4.0 equivalents of DNNSA, and 0.5 to 2.0 equivalents of APS. For example, the ratio may be 1.0 equivalent, 1.5 equivalents of DNNSA, and 1.2 equivalents of APS.

[0226] It will be understood that the above examples of process conditions for conductive polymers and polymerizable organic monomers are also applicable to the process for preparing polyaniline from aniline or its salts. For example, any one or more of the operating temperatures, residence times, flow rates, yields, and pipe diameters described above may be applied to the preparation of polyaniline.

[0227] (D) Flow reactor The continuous flow process includes a temperature-controlled continuous flow reactor for facilitating the controlled synthesis of a conductive polymer or salt thereof. The temperature-controlled continuous flow reactor can be a temperature-controlled continuous flow tubular reactor. The continuous flow process can include a continuous flow reactor or a continuous flow tubular reactor with one or more passages in fluid communication for carrying reactant and product streams. At least a portion of the one or more passages can be configured to enhance flow mixing, for example, a static mixer configuration to enhance radial mixing, chaotic advection, or emulsion formation.

[0228] A continuous flow reactor (also called a continuous flow chemical reactor) can include one or more chamber sections in fluid communication with each other. At least one chamber section can include a static mixer element. The chamber sections may be referred to as modules, and each module can include one or more static mixer elements (e.g., five static mixers). The static mixer elements can be configured for insertion into the continuous flow chemical reactor and are sometimes referred to as "static mixer inserts." The static mixer elements or inserts can be provided in the form of one or more modules. It is understood that the static mixer can be provided as an integral part of the chemical reactor. The static mixer and chamber section can together form a reaction chamber and may be provided as a single unit. The chamber section can provide a housing for the static mixer. The chamber section can include a heat exchanger system that can be used to control heat removed from the reactor chamber during its operation. One or more static mixer elements or chamber sections can be configured for use in series or parallel operation. It will be understood that the static mixer or reactor thereof may include one or more reactant inlets for supplying one or more fluid reactants to the chamber section and one or more outlets in fluid communication with the static mixer for receiving an output stream comprising the product of the reaction. It will be understood that the continuous flow mixer includes at least one mixing element (e.g., a static or dynamic mixer). It will also be understood that the continuous flow mixer including a static mixer may include a static mixer or static mixer element according to any embodiment or example thereof as described herein.

[0229] The static mixer can be an integral part of the chemical reaction chamber. A static mixer element for a continuous-flow chemical reactor chamber can include an optional catalytically active scaffold defining a plurality of passages configured to disperse and mix one or more fluid reactants during flow and reaction through the mixer. The surface of the scaffold can optionally include a catalytic material, if desired. The catalytic material can be selected from at least one of a metal, a metal alloy, or a metal oxide to provide catalytic reaction sites on the surface of the scaffold.

[0230] The static mixer may be provided as one or more elements each configured for insertion into a continuous flow chemical reactor or its reactor chamber. The static mixer element may be configured as a modular insert for assembly into a continuous flow chemical reactor or its chamber. The static mixer element may be configured as an insert for an in-line continuous flow chemical reactor or its chamber.

[0231] The continuous flow process or temperature-controlled continuous flow reactor may include a recycle loop reactor or a single-pass reactor. In one example, the continuous flow process is operated as a single-pass process. In another example, the temperature-controlled continuous flow reactor is a single-pass reactor. Using a single-pass continuous flow process or a temperature-controlled continuous flow reactor as a single-pass reactor can provide additional advantages, such as efficiency and industrial-type operation.

[0232] Static mixer elements may be configured to enhance mixing (e.g., chaotic advection) and heat transfer characteristics to redistribute fluids transverse to the main flow, e.g., radially and tangentially or azimuthally relative to the central longitudinal axis of the static mixer element. Static mixer elements may be configured to enhance mixing, chaotic advection, or emulsion formation of reactant streams, or to efficiently promote heat transfer away from or to the fluids. Static mixer elements may have various geometric configurations or aspect ratios as a function of the specific application. Static mixer elements may be configured for use with turbulent flow rates, e.g., to enhance turbulence and mixing, even at or near the interior surface of the reactor chamber housing. It will also be appreciated that static mixer elements can be configured to enhance heat and mass transfer characteristics for both laminar and turbulent flow.

[0233] These configurations may also be designed to enhance efficiency, extent of chemical reaction, or other characteristics such as pressure drop (while maintaining a given or desired flow rate), residence time distribution, or heat transfer coefficient.

[0234] Static mixer elements, scaffolding, reactor chambers, or continuous flow reactors composed of these can be formed by additive manufacturing, as described in the following sections. The static mixer may be an additively manufactured static mixer. Additive manufacturing of the static mixer and optional catalyst coating can provide a static mixer configured for efficient mixing, heat transfer, and optionally catalytic reaction (of reactants in a continuous flow chemical reactor), where the static mixer can be physically tested for reliability and performance and optionally further redesigned and reconfigured using additive manufacturing (e.g., 3D printing) techniques. Additive manufacturing provides the flexibility for preliminary design and testing, followed by further redesign and reconfiguration, to facilitate the development of more commercially viable and durable static mixers.

[0235] The dimensions of the continuous flow reactor, continuous flow mixer (e.g., a continuous flow tubular reactor including a static mixer), or static mixer can vary depending on the application. The static mixer or continuous flow reactor including a static mixer may be tubular. The static mixer, continuous flow mixer, or continuous flow reactor can have a diameter (mm) ranging from 1 to 1000, 2 to 500, 3 to 250, 4 to 150, or 5 to 100, for example. The static mixer, continuous flow mixer, or continuous flow reactor can have a diameter (mm) of at least about 1, 5, 10, 25, 50, 75, 100, 250, or 500. The static mixer, continuous flow mixer, or continuous flow reactor can have a diameter (mm) of, for example, less than about 1000, 750, 500, 250, 200, 150, 100, 75, 50, 25, or 10. The aspect ratio (L / d) of a static mixer element, mixer, reactor, or reactor chamber containing a static mixer element may be provided in a range suitable for industrial-scale flow rates of a particular reaction. The aspect ratio may be, for example, in the range of about 1 to 1000, 2 to 750, 3 to 500, 4 to 250, 5 to 100, or 10 to 50. The aspect ratio may be, for example, less than about 1000, 750, 500, 250, 200, 150, 100, 75, 50, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, or 2. The aspect ratio may be, for example, greater than about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 50, 75, or 100.

[0236] Static mixer elements, continuous flow mixers or continuous flow reactors may be configured to enhance properties such as mixing (e.g., chaotic advection and emulsion formation) and heat transfer for laminar or turbulent flow rates. For a Newtonian fluid flowing inside a hollow pipe, the correlation between the Reynolds number (Re) value and laminar and turbulent flows is typically understood to provide laminar flow, where Re < 2300, transitional flow where 2300 < Re < 4000, and general turbulent flow where Re > 4000. Static mixer elements, continuous flow mixers or continuous flow reactors can be configured to match laminar or turbulent flow rates and provide enhanced properties selected from one or more of mixing, degree of reaction, heat transfer, and pressure drop.

[0237] In one example, a static mixer element, continuous flow mixer or continuous flow reactor may generally be configured to operate at a Re of at least 0.01, 0.1, 1, 5, 50, 100, 150, 200, 250, 300, 350, 400, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000. A static mixer element, continuous flow mixer or continuous flow reactor may be configured to operate in a general laminar Re range of about 0.1 - 2000, 1 - 1000, 10 - 800, or 20 - 500. A static mixer element, continuous flow mixer or continuous flow reactor may be configured to operate in a general turbulent Re range of about 1000 - 15000, 1500 - 10000, 2000 - 8000, or 2500 - 6000.

[0238] In some embodiments, static mixer elements, continuous flow mixers, or continuous flow reactors can be described by the Peclet number (Pe), another type of dimensionless number related to transport phenomena in continuums. The Peclet number provides the ratio of the rate of advection of a physical quantity by a flow to the rate of diffusion of the same quantity driven by an appropriate gradient. In the context of species or mass transfer, the Peclet number is the product of the Reynolds number (Re) and the Schmidt number (Sc). In the context of thermal fluids, the thermal Peclet number is equivalent to the product of the Reynolds number (Re) and the Prandtl number (Pr). The Peclet number is defined as Pe = advective transport rate / diffusive transport rate. In mass transfer, Pe L =Lu / D=Re L .Sc. In heat transfer, PeL=Lu / α=Re L .Pr [wherein, α=k / ρc p ] where L is the characteristic length, u is the local flow velocity, D is the mass diffusion coefficient, α is the thermal diffusivity, ρ is the density, and c p is the heat capacity. Static mixer elements can be configured to provide higher Peclet values ​​to enhance chaotic advection versus diffusion, provide a more uniform residence time distribution, and reduce dispersion. In other words, configuring static mixer elements to provide higher Peclet values ​​can provide improved performance and process control, at least according to some embodiments and examples described herein.

[0239] In one embodiment, the static mixer element has a flow rate of at least 100, 1000, 2000, 5000, 10000, 15000, 20000, 25000, 50000, 75000, 100000, 250000, 50000, 10 6 , or 10 7 The static mixer element may be configured to operate at a Peclet (Pe) value of about 10 8 , 10 7 , 10 6 , 500,000, 250,000, 100,000, 75,000, 50,000, 25,000, 20,000, 15,000, 10,000, 5,000, 2,000, or 1,000 Peclet (Pe) values. 3 ~108 , 10 3 ~10 7 , or 10 4 ~10 6 The static mixer element may be configured to operate in a Pe range between any two of the above upper and / or lower limits.

[0240] The percent volume displacement of a continuous flow reactor or static mixer relative to the reactor chamber housing the mixer can range from 1 to 40, 2 to 35, 3 to 30, 4 to 25, 5 to 20, or 10 to 15. The percent volume displacement of a continuous flow reactor or static mixer relative to the reactor chamber housing the mixer can be less than 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5%. Generally, as the volume displacement of a continuous flow reactor or static mixer relative to the reactor chamber housing the mixer increases, the pressure drop (i.e., pressure differential or backpressure) will also increase. A larger pressure drop increases the design requirements of a continuous reactor system to safely accommodate increased system pressure. Furthermore, a large volume displacement effectively narrows the fluid passages within the reactor system. This flow restriction not only contributes to the pressure drop described above, but can also increase the risk of clogging. The amount of reactor tubing required to achieve a given final reactor volume also increases due to the volume occupied by the static mixer.

[0241] A continuous flow reactor or static mixer configuration may be provided to enhance cross-sectional microscopic (CSM) turbulence. Such turbulence can result from a variety of sources, including the geometry of the CSM or microscopic surface roughness of the CSM resulting from 3D printing processes and / or surface coatings. For example, the length scale of the turbulence may be reduced to provide better mixing. The turbulence length scale may be within the microscopic length scale, for example.

[0242] A continuous flow reactor or static mixer configuration may be provided to enhance heat transfer characteristics within the reactor, such as reduced temperature differentials at the exit cross section. The heat transfer of a CSM may provide a cross-sectional or transverse temperature profile with a temperature differential of, for example, less than about 20°C / mm, 15°C / mm, 10°C / mm, 9°C / mm, 8°C / mm, 7°C / mm, 6°C / mm, 5°C / mm, 4°C / mm, 3°C / mm, 2°C / mm, or 1°C / mm.

[0243] A continuous flow reactor, static mixer, or scaffold thereof may be configured to provide a pressure drop (Pa / m) across the static mixer in use within the range of about 0.1 to 1,000,000 Pa / m (or 1 MPa / m), including any value or range of values ​​therebetween. For example, the pressure drop (Pa / m) across the continuous flow reactor or static mixer may be less than about 500,000, 250,000, 100,000, 50,000, 10,000, 5,000, 1,000, 750, 500, 250, 100, 75, 50, 25, 20, 15, 10, or 5 Pa / m. A continuous flow reactor or static mixer can be configured to provide a lower pressure drop relative to a particular flow rate. In this regard, static mixers, reactors, systems, and processes as described herein may provide parameters suitable for industrial applications. The above pressure drops can be maintained when the volumetric flow rate is at least 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 ml / min.

[0244] In one example, the continuous flow chemical reactor is a tubular or plug flow reactor.

[0245] In another example, the reactor includes a heat exchanger for controlling the temperature of the reactor, chamber section, catalytic static mixer, or any of these fluid components. The heat exchanger may be a shell-and-tube heat exchanger design or configuration. The shell-and-tube heat exchanger design may provide improved heat exchange characteristics.

[0246] The aspect ratio of the continuous flow reactor or continuous flow mixer can be similar to that described above for the static mixer, such that, for example, the static mixer elements can be configured for insertion into the reactor or mixer.

[0247] (E) System Also provided is a system for carrying out the continuous flow process described herein. The system includes a continuous flow reactor for receiving and reacting together an organic stream and an oxidant stream to synthesize a conductive polymer or any salt thereof. The continuous flow reactor can be provided according to any example described herein, such as a continuous flow tubular reactor. The organic stream includes an organic solvent, a polymerizable organic monomer, and a protonic acid. The oxidant stream includes an aqueous or organic solvent and a free-radical initiator. The oxidant and organic streams can be provided according to any example described herein. The system further includes one or more pumps for providing fluid flows to the organic stream, the oxidant stream, and the product stream through the continuous flow reactor.

[0248] The system may also include a temperature controller for the continuous flow reactor. The temperature controller may be associated with the continuous flow reactor. The system may also include one or more heat exchangers for controlling the temperatures of the streams in the continuous flow reactor effective for synthesizing the conductive polymer or any salt thereof. The temperature controller may be associated with one or more heat exchangers for controlling the temperatures of the continuous flow reactor, the organic stream, the emulsion stream, the oxidant stream, the aqueous stream, and / or the product stream, and the continuous flow reactor.

[0249] The system may also include control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the flows, fluid reactants, sources of fluid reactants, carrier fluids, or products of the reaction.

[0250] In one example, there is a system for providing a continuous flow process for the controlled synthesis of a conductive polymer or salt thereof, comprising: a) a temperature-controlled continuous flow reactor containing at least one mixing element for forming an emulsion; b) one or more pumps for providing fluid flow to one or more streams passing through the temperature-controlled continuous flow reactor; c) one or more heat exchangers for controlling the temperature of the temperature-controlled continuous flow reactor; d) a temperature control device for controlling the temperature of the flow in the temperature-controlled continuous flow reactor, in cooperation with the temperature-controlled continuous flow reactor and one or more heat exchangers, useful for synthesizing the conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the streams, fluid reactants, sources of fluid reactants, fluids, or products of the reaction; Equipped with.

[0251] Another example is a system for providing a continuous flow process for the controlled synthesis of a conductive polymer or salt thereof, comprising: a) a temperature-controlled continuous flow reactor comprising at least one mixing element for facilitating mixing of an organic stream and an oxidant stream according to any of the examples described herein at a temperature effective to synthesize a conductive polymer or salt thereof and provide a product stream comprising the conductive polymer or salt thereof to the continuous flow reactor; b) one or more pumps for providing fluid flow to the organic stream, the oxidant stream, and the product stream through the continuous flow reactor; c) one or more heat exchangers for controlling the temperature of the continuous flow reactor, the organic stream, the oxidant stream, and / or the product stream; d) a temperature control device for controlling the temperature of the stream within the continuous flow reactor useful for synthesizing the conductive polymer or any salt thereof in cooperation with the continuous flow reactor and one or more heat exchangers; and e) control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the streams, fluid reactants, sources of fluid reactants, carrier fluids, or products of the reaction; Equipped with.

[0252] The temperature-controlled continuous flow reactor (see, e.g., FIG. 3D) can include at least one mixing element to facilitate mixing of the organic stream and the oxidant stream. For example, a dynamic or static mixer. The mixing element can be provided within the continuous flow reactor and / or externally in fluid communication with it (see, e.g., FIG. 3C). The mixing element can facilitate the formation, maintenance, and / or strengthening of an emulsion from the emulsion and / or product stream. The reactor can be operated at a temperature effective to synthesize a conductive polymer or any salt thereof, and a product stream containing the conductive polymer or any salt thereof can be provided into the continuous flow reactor. In one example, the mixer element can be configured for use with turbulent flow rates, e.g., to enhance turbulence and mixing. It will also be understood that the mixer element can be configured to enhance the heat and mass transfer characteristics of the turbulent flow.

[0253] One or more pumps (see, e.g., FIG. 3) can be used to provide fluid flow for the organic, oxidant, and product streams through the continuous flow reactor. The pumps can be in-line pumps, rotary pumps, centrifugal pumps, or motor-driven pumps. In one example, the pumps are in-line pumps.

[0254] One or more heat exchangers can be used to control the temperature of the continuous flow reactor, the organic stream, the oxidant stream, and / or the product stream (see, e.g., F in Figure 3). The heat exchangers can be plate, shell, tube, or other types effective in controlling the temperature of the continuous flow reactor.

[0255] The temperature controller can cooperate with the continuous flow reactor and one or more heat exchangers to control the temperature of the stream within the continuous flow reactor useful for synthesizing the conductive polymer or any salt thereof. The temperature controller can be automatic or manual, e.g., a sensor and computer-controlled option (e.g., G in Figure 3). The temperature controller can be associated with a control means for the system. The temperature controller can control heating or cooling, e.g., to maintain a substantially constant temperature.

[0256] Control means may be provided to control one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the flows, fluid reactants, sources of fluid reactants, carrier fluids, or products of the reaction. The control means may be manual or automatic, such as a computer-controlled option (see, e.g., FIG. 3H for control of the pump of A2).

[0257] The system can include one or more mixing elements for forming or mixing the oxidant stream and the organic stream as separate or combined streams. The one or more mixing elements can be static mixers. For example, the system can include an organic stream mixing element for combining separate or combined sources of organic solvent, polymerizable organic monomer, and protonic acid.

[0258] The system may also include a combined stream mixing element for combining the organic stream with the oxidant stream to form a combined stream for introduction into the continuous flow reactor.

[0259] One or more of the reactors, reactor chambers, chamber sections, and static mixers may each be provided in a modular format due to their complementary association. The system may include multiple reactors, which may have similar or different internal and / or external configurations. The reactors may be operated in series or parallel. It will be understood that the system, reactor, or each chamber section may include one or more inlets and outlets for providing reactant feeds, obtaining products, or recycling various reactants and / or products.

[0260] One or more inlets of a continuous flow reactor (e.g., the tubular body of a continuous flow tubular reactor) can be fluidly connected to one or more feed conduits to provide input for any one or more streams as described herein (see FIG. 3). The feed conduits can fluidly connect the temperature-controlled continuous flow reactor to one or more other continuous flow reactors, such as a continuous flow mixer including mixing elements (e.g., a tubular reactor including static mixer elements). The feed conduits or continuous flow mixers can provide any one or more streams described herein to be mixed at or adjacent to one or more inlets of the temperature-controlled continuous flow reactor. In one example, the feed conduit is a tubular reactor, which can further include a static mixer.

[0261] In one example, the system further includes a continuous flow mixer (e.g., Mixer 1) for forming an organic stream, the continuous flow mixer optionally comprising at least one mixing element and in fluid connection with a temperature-controlled continuous flow reactor. In another example, the system further includes a continuous flow mixer (e.g., Mixer 2) for forming a product stream, the continuous flow mixer optionally comprising at least one mixing element and in fluid connection with a temperature-controlled continuous flow reactor.

[0262] In another example, the system further includes a first mixer (e.g., Mixer 1) for forming an organic stream in fluid communication with a second continuous flow mixer (e.g., Mixer 2) for forming a product stream, the first and second continuous flow mixers each optionally including at least one mixing element, and the second continuous flow mixer in fluid communication with a temperature-controlled continuous flow reactor.

[0263] It will be understood that one or more additional continuous flow mixers may be included in the system. It will be understood that the temperature-controlled continuous flow reactor may include at least one static mixer, for example, additional static mixer elements. The additional static mixer elements may be connected as one or more repeating units or modules. In some examples, the one or more static mixer elements may occupy at least about 50, 55, 60, 65, 70, 75, 80, or 85 percent of the length along the reactor (% of the total reactor length).

[0264] A continuous flow mixer, such as the first and second continuous flow mixers described above, can include one or more static mixer elements. In one example, the continuous flow mixer can be a tubular conduit (e.g., about 30 cm long) containing one or more static mixer elements (e.g., each about 15 cm long), such as two static mixer elements connected within the tubular conduit. In another example, the continuous flow mixer is a continuous flow static mixer containing one or more static mixer elements (e.g., up to about 15 static mixing elements, e.g., up to about 15 static mixing elements).

[0265] In one example, there is a system for providing a continuous flow process for the controlled synthesis of a conductive polymer or salt thereof, comprising: a) a temperature-controlled continuous flow reactor comprising at least one static mixer element for use in combining an organic stream and an oxidant into an emulsion to form a product stream comprising a conductive polymer or a salt thereof in a flow through the reactor; b) one or more pumps for providing fluid flow to one or more streams passing through the temperature-controlled continuous flow reactor; c) one or more heat exchangers for controlling the temperature of the temperature-controlled continuous flow reactor; d) a temperature control device for controlling the temperature of the flow in the temperature-controlled continuous flow reactor, in cooperation with the temperature-controlled continuous flow reactor and one or more heat exchangers, useful for synthesizing the conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the streams, fluid reactants, sources of fluid reactants, fluids, or products of the reaction; Equipped with.

[0266] Another example is a system for providing a continuous flow process for the controlled synthesis of a conductive polymer or salt thereof, comprising: a1) a first continuous flow reactor comprising at least one static mixer element for use in combining an optionally cooled organic stream and an optionally cooled oxidant stream to form an emulsion stream; a2) a second temperature-controlled continuous flow reactor in fluid communication with the first continuous flow reactor, the second temperature-controlled continuous flow reactor including at least one static mixer element for use in forming a product stream comprising the conductive polymer or salt thereof from the emulsion stream during flow within the reactor; b) one or more pumps for providing fluid flow to one or more streams passing through the temperature-controlled continuous flow reactor; c) one or more heat exchangers for controlling the temperature of the temperature-controlled continuous flow reactor; d) a temperature control device for controlling the temperature of the flow in the temperature-controlled continuous flow reactor, in cooperation with the temperature-controlled continuous flow reactor and one or more heat exchangers, useful for synthesizing the conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the streams, fluid reactants, sources of fluid reactants, fluids, or products of the reaction; Equipped with.

[0267] Another example is a system for providing a continuous flow process for the controlled synthesis of a conductive polymer or salt thereof, comprising: a1) a first continuous flow reactor including at least one static mixer element for use in combining a protonic acid stream and an organic monomer stream to form an organic stream; a2) a second continuous flow reactor in fluid communication with the first continuous flow reactor, the second continuous flow reactor comprising at least one static mixer element for use in combining the organic stream and the optionally cooled oxidant stream; a3) a third continuous flow reactor in fluid communication with the second continuous flow reactor, the third continuous flow reactor being temperature controlled and including at least one static mixer element for use in forming a product stream comprising a conductive polymer or a salt thereof from the emulsion stream during flow within the reactor; b) one or more pumps for providing fluid flow to one or more streams passing through the temperature-controlled continuous flow reactor; c) one or more heat exchangers for controlling the temperature of the temperature-controlled continuous flow reactor; d) a temperature control device for controlling the temperature of the flow in the temperature-controlled continuous flow reactor, in cooperation with the temperature-controlled continuous flow reactor and one or more heat exchangers, useful for synthesizing the conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the streams, fluid reactants, sources of fluid reactants, fluids, or products of the reaction; Equipped with.

[0268] (F) Post-addition of secondary dopants After the chemical synthesis reaction is complete and the conductive polymer is synthesized in the continuous flow reactor, one or more additional additives, such as secondary dopants and / or reagents, may be added at this point to enhance properties such as thermal stability, conductivity, solubility, compatibility with other polymers, etc. Additional additives, i.e., secondary dopants, may include sulfonyl diphenols, meta-cresol, thymol, polyols, and plasticizers. For example, following step c) or step d) of the continuous flow process as described according to any example herein, an additive selected from the group consisting of secondary dopants and additional reagents may be contacted, mixed, or treated with the conductive polymer or a salt thereof.

[0269] (G) Collection and further processing A method for further purifying the product obtained from the continuous flow process may include mixing the recovered product stream with an organic solvent to form a two-phase mixture comprising an organic phase and an aqueous phase, separating the aqueous phase from the organic phase, and obtaining the product from the organic phase.

[0270] A solvent such as acetone can be added to the organic phase to precipitate the conductive polymer, e.g., PANI-DNNSA can be precipitated as a fine green powder, which can be recovered by filtration and washed extensively with acetone before drying to give PANI-DNNSA in yields of, e.g., at least about 50, 60, 70, 80, or 90%.

[0271] A small portion of PANI-DNNSA can be thin-film cast from a concentrate, e.g., a 70% (w / v) solution, in toluene. The film can be dried, e.g., in an oven at 100°C overnight, then washed (e.g., with propanol) and air-dried. The resulting film can have a thickness of 5-20 μm (e.g., 8 μm). An 8.25 μm PANI-DNNSA film produced by this method was found to have a conductivity of 0.6 S / cm.

[0272] (H) Conductive polymers and materials thereof Conductive polymers can be used in compositions, formulations, coatings such as dissipative coatings, and materials such as composites. Conductive polymers can be used, for example, in or with epoxy resins to provide epoxy resin-based coatings. Conductive polymers can be used, for example, in coatings for exterior panels of aircraft.

[0273] In one example, the conductive polymer, such as the conductive polymer salt, is an organic soluble conductive polymer. For example, the conductive polymer prepared from the process of the present invention is an organic soluble polyaniline salt, such as PANI-DNNSA.

[0274] As previously described, PANI-DNNSA was obtained as a fine green powder after processing. A 70% (w / v) concentrate of PANI-DNNSA dissolved in toluene cast a thin film with a thickness of 8.25 μm and a conductivity of 10.6 S / cm.

[0275] Many variations of the examples described herein will come to mind to one skilled in the art to which this disclosure pertains having the benefit of the teachings presented in the foregoing description and the associated drawings and figures. It is understood, therefore, that the disclosure is not to be limited to the particular examples illustrated, and that modifications and other examples are intended to be included within the scope of the appended claims. Furthermore, while the foregoing description and the associated drawings and figures describe examples of the disclosure in the context of particular exemplary combinations of elements and / or functions, it should be understood that different combinations of elements and / or functions may be provided in alternative embodiments without departing from the scope of the appended claims.

[0276] Further examples of the present disclosure are provided by any of the following clauses: Clause 1. A continuous flow process for the controlled synthesis of a conductive polymer or salt thereof, comprising: feeding an emulsion of a polymerizable organic monomer, a protonic acid, and a free radical initiator into a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize the conductive polymer or salt thereof and provide a product stream comprising the conductive polymer or salt thereof. Clause 2. The continuous flow process of clause 1, further comprising obtaining the conductive polymer or salt thereof from the product stream under continuous flow conditions. Clause 3. The continuous flow process of clause 1 or 2, wherein the polymerizable organic monomer is introduced as a neat organic solution optionally containing one or more solvents. Article 4. a) providing a polymerizable organic monomer and a protonic acid in an organic stream comprising an organic solvent; b) providing a free radical initiator in an oxidant stream comprising an aqueous or organic solvent; and c) mixing the organic stream and the oxidant stream in a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize the conductive polymer or salt thereof to provide a product stream comprising the conductive polymer or salt thereof in the temperature-controlled continuous flow reactor; and d) obtaining a conductive polymer or a salt thereof from the product stream under continuous flow conditions after the product stream exits the temperature-controlled continuous flow reactor. 4. The continuous flow process of any one of clauses 1 to 3, comprising: Clause 5. The continuous flow process of any one of clauses 1 to 4, wherein the temperature-controlled continuous flow reactor is a temperature-controlled continuous flow tubular reactor. Clause 6. The continuous flow process of any one of clauses 1 to 5, wherein the conductive polymer is selected from the group consisting of polyarylamine, polyarylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), or a salt of any of these; and the polymerizable organic monomer is selected from the group consisting of arylamine, arylthiol, pyrrole, carbazole, indole, azepine, thiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene monomer, or a salt of any of these; and each conductive polymer and polymerizable organic monomer is unsubstituted or substituted. Clause 7. The continuous flow process of clause 6, wherein the conductive polymer is polyaniline and the polymerizable organic monomer is unsubstituted or substituted aniline; the conductive polymer is poly(3,4-ethylenedioxythiophene) and the polymerizable organic monomer is unsubstituted or substituted 3,4-ethylenedioxythiophene; or the conductive polymer is poly(3,4-propylenedioxythiophene) and the polymerizable organic monomer is unsubstituted or substituted 3,4-propylenedioxythiophene monomer. Clause 8. The continuous flow process of any one of clauses 1 to 7, wherein each individual polymerized chain of the conductive polymer is independently composed of between about 100 and 1500 individual monomer units. Clause 9. The continuous flow process of any one of clauses 1 to 8, wherein the conductive polymer has a weight average molecular weight between 10,000 and 120,000. Clause 10. The continuous flow process of any one of clauses 1 to 9, wherein in step c), the temperature of the mixed stream is set to between about -5 and 5°C and maintained over the axial flow length of the continuous flow reactor, with a variation of no more than 1 to 2°C. Article 11. The following steps: a) providing an unsubstituted or substituted aniline or a salt thereof and a protonic acid in an organic stream containing an organic solvent; b) providing a free radical initiator in an oxidant stream comprising an aqueous or organic solvent; and c) mixing the organic stream and the oxidant stream in a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize polyaniline or a salt thereof to provide a product stream comprising polyaniline or a salt thereof in the temperature-controlled continuous flow reactor; and d) obtaining polyaniline or a salt thereof from the product stream under continuous flow conditions after the product stream leaves the temperature-controlled continuous flow reactor. 11. The continuous flow process of any one of clauses 1 to 10 for the controlled synthesis of polyaniline or any salt thereof, comprising: Clause 12. The continuous flow process of any one of clauses 1 to 11, wherein the free radical initiator i is an oxidizing agent, such as ammonium persulfate. Clause 13. The continuous flow process of any one of clauses 1 to 12, wherein in step b), the oxidant stream is an aqueous stream comprising an aqueous solvent, and wherein mixing of the organic stream and the aqueous stream in the continuous flow of step c) provides a product stream in the form of an emulsion. Clause 14. The continuous flow process of any one of clauses 1 to 13, wherein in step (a), the organic stream is a non-aqueous organic solution comprising an organic solvent, a polymerizable organic monomer, and a protonic acid. Clause 15. The continuous flow process of any one of clauses 1 to 14, wherein the mixing element in the temperature-controlled continuous flow reactor of step (c) is at least one of a static mixer and a dynamic mixer. Clause 16. The continuous flow process of any one of clauses 1 to 15, wherein the oxidant stream and the aqueous stream are premixed under continuous flow conditions prior to introduction into the temperature-controlled continuous flow reactor of step (c). Article 17. Organic streams a1) providing a protonic acid stream comprising an organic solvent and a protonic acid; a2) providing a monomer stream comprising a polymerizable organic monomer and, optionally, an organic solvent; and a3) combining the protonic acid stream and the monomer stream to form the organic stream of step a). 17. The continuous flow process of any one of clauses 1 to 16, provided by Clause 18. The continuous flow process of clause 17, wherein in step a2), the polymerizable organic monomer is provided as a neat organic solution optionally comprising one or more solvents. Clause 19. The continuous flow process of clause 17 or 18, wherein the monomer stream is an aniline stream comprising unsubstituted or substituted aniline and, optionally, an organic solvent, and step a3) provides for combining the protonic acid stream and the aniline stream to form the organic stream of step (a). Clause 20. The continuous flow process of any one of clauses 17 to 19, wherein the protonic acid stream and the monomer stream are premixed under continuous flow conditions before mixing with the oxidant stream. Clause 21. The continuous flow process of any one of clauses 1 to 20, wherein the mixing of the streams is provided by one or more static mixers under continuous flow conditions. Article 22. a) providing an unsubstituted or substituted aniline or a salt thereof and a protonic acid in an organic stream containing an organic solvent; b) providing an oxidant in an aqueous stream comprising an aqueous solvent; c) mixing the organic stream and the oxidant stream in a temperature-controlled continuous-flow tubular reactor comprising at least one mixing element at a temperature effective to synthesize polyaniline or a salt thereof to provide a product stream comprising a conductive polymer of polyaniline or a salt thereof in the temperature-controlled continuous-flow tubular reactor; and d) Obtaining a conductive polymer of polyaniline or its salt from the product stream under continuous flow conditions after the product stream leaves the temperature-controlled continuous flow tubular reactor. 22. The continuous flow process of any one of clauses 1 to 21, comprising: Clause 23. The continuous flow process of clause 22, wherein the polymerizable organic monomer is unsubstituted aniline. Clause 24. The continuous flow process of clause 22 or 23, wherein the protic acid is dinonylnaphthalenesulfonic acid (DNNSA). Clause 25. The continuous flow process of any one of clauses 22 to 24, wherein the organic solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, glycols, ethers, glycol ethers, and mixtures thereof. Clause 26. The continuous flow process of clause 25, wherein the organic solvent is an aromatic hydrocarbon. Clause 27. The continuous flow process of any one of clauses 22 to 26, wherein the free radical initiator is selected from the group consisting of persulfates, peroxides, dichromates, cerium (IV) salts, and mixtures thereof. Clause 28. The continuous flow process of clause 27, wherein the oxidizing agent is ammonium persulfate. Clause 29. The continuous flow process of any one of clauses 1 to 28, wherein the concentration of aniline in the organic stream is from about 0.1M to about 0.8M. Clause 30. The continuous flow process of clause 29, wherein the concentration of aniline in the organic stream is from about 0.2M to about 0.5M. Clause 31. The continuous flow process of any one of clauses 1 to 30, wherein the continuous flow reactor is a continuous flow tubular reactor and the inner diameter of the tubular reactor is at least about 2 mm, e.g., about 2 to 20 mm or 5 to 10 mm. Clause 32. The continuous flow process of any one of clauses 1 to 31, providing at least about 50 g of conductive polymer per hour of operation. Clause 33. The continuous flow process of clause 32, wherein the operating capacity is for a continuous flow reactor volume of about 100 to 3000 ml. Clause 34. The continuous flow process of any one of clauses 1 to 33, wherein following step c) or step d), an additive selected from the group consisting of a secondary dopant and an additional reagent is contacted with the conductive polymer or a salt thereof. Clause 35. The continuous flow process of any one of clauses 1 to 34, providing at least about 100 g of conductive polymer per liter of internal volume of the continuous flow reactor per hour of operation. Clause 36. A conductive polymer prepared by the continuous flow process of any one of clauses 1 to 35. Clause 37. A composition, coating or material comprising the conductive polymer or salt thereof of clause 36. Clause 38. A system for providing a continuous flow process for the controlled synthesis of a conductive polymer or a salt thereof, comprising: a) a temperature-controlled continuous flow reactor comprising at least one mixing element for facilitating mixing of an organic stream and an oxidant stream according to any of the examples described herein at a temperature effective to synthesize a conductive polymer or salt thereof and provide a product stream comprising the conductive polymer or salt thereof to the temperature-controlled continuous flow reactor; b) one or more pumps for providing fluid flow to the organic stream, the oxidant stream, and the product stream through the temperature-controlled continuous flow reactor; c) a temperature-controlled continuous flow reactor, one or more heat exchangers for controlling the temperature of the organic stream, the oxidant stream, and / or the product stream; d) a temperature control device for controlling the temperature of the flow in the temperature-controlled continuous flow reactor, in cooperation with the temperature-controlled continuous flow reactor and one or more heat exchangers, useful for synthesizing the conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the streams, fluid reactants, sources of fluid reactants, carrier fluids, or products of the reaction; A system comprising: [Example]

[0277] The present disclosure is further illustrated by the following examples. It should be understood that the following descriptions are for the purpose of illustrating specific examples only and are not intended to be limiting with respect to the above descriptions.

[0278] Continuous Flow Process A continuous flow process for the controlled synthesis of polyaniline according to one embodiment of the present invention is provided, by way of example, in FIG. 3 . Continuous flow process reactor 1 includes mixing unsubstituted or substituted aniline stream A1, protonic acid stream A2, and an organic solvent (not shown), thereby forming organic stream A3. Organic stream A3 may be formed by mixing using a static mixer or any other mixing element (e.g., a static mixer or dynamic mixer within D and / or an external mixing element such as may be provided in C). Organic stream A3 is then mixed with oxidant stream B, which contains an oxidant, to form product stream C for synthesizing polyaniline. Product stream C may be formed by mixing using a static mixer or any other mixing element (e.g., a dynamic mixer). Product stream C is then introduced into temperature-controlled flow reactor D to facilitate the controlled synthesis of polyaniline. Temperature-controlled flow reactor D may optionally include one or more static mixers to facilitate mixing of product stream C. The product from controlled flow reactor D, containing the polyaniline product, is then recovered in E and, optionally, further processed.

[0279] Materials and analysis All reagents and solvents were used without further purification. Aniline (99.5%) and ammonium persulfate (98.5%) were obtained from Sigma-Aldrich, DNNSA (50% w / w in 2-butoxyethanol) from King Industries, and toluene from Merck. Molecular weight data were collected by Advanced Polymer Chromatography (APC) using a Waters ACQUITY system. The analysis was performed on two APC XT columns: an XT200 (linear range 3kJ–70kJ) and an XT450 (linear range 20kJ–400kJ). The columns were made of solid beads (trimethylsilane bonded to an ethylene-bridged hybrid (BEH) substrate). The flow rate was 0.7 ml / min at 50 °C. The RID was calibrated with freshly prepared PS standards. N-methylpyrrolidone (Acros Organics) modified with 20 mM ammonium formate (Sigma-Aldrich) was used as the mobile phase and polymer solvent. Thin films were prepared by spin-coating PANI-DNNSA solutions made in xylene or toluene (50-75% w / v, 2000 RPM, 40 seconds) onto square glass slides. The resulting films were dried overnight in an oven at 100°C before surface treatment. Resistivity measurements were recorded by averaging three readings using a Jandel RM3000 four-point probe. Film thickness was determined by averaging three surface scratches using a Veeco Dektak 6M Profilometer. UV-VIS spectra were prepared in xylene or toluene and recorded using an HP / Agilent 8453 UV / Vis spectrophotometer with Chemstation software. 1 H-NMR spectra were recorded on an AC-400 spectrometer (Bruker) in deuterated water or CDCl3 (Cambridge Isotope Laboratories). The residual solvent peak at δ = 7.26 ppm was used as the internal standard.

[0280] Example 1: Continuous controlled flow process The continuous controlled flow process for PANI synthesis consists of two stages. In the first stage, the aniline reagent and protonic acid (Figure 3, A1 and A2) are mixed at room temperature to form organic stream A3, and then this combined organic stream A3 is mixed with the oxidant stream from B to generate emulsion product stream C in the pressurized zone. This emulsion C is then fed into temperature-controlled flow reactor D downstream of the pressurized zone, where the reaction can proceed with active temperature control and reaction monitoring.

[0281] Stage 1: Reagent delivery was achieved using a three-pump configuration (Figure 3 (See TIFF2025138646000021.tif7170). Pump P-1 was used to deliver aniline solution A1, pump P-2 was used to deliver DNNSA solution A2, and pump P-3 was used to deliver ammonium persulfate solution A3. Both aniline and DNNSA were delivered by Knauer Pump 80P (pumps P-1 and P-2) capable of flow rates up to 100 mL / min and pressures up to 400 bar). Pump P-3 was an SSI PR class dual piston positive displacement pump capable of providing a maximum flow rate of 100 mL / min and pressures up to 276 bar. The reagent streams were delivered using PFA tubing (1 / 8" OD, 1 / 16" ID) obtained from VICI and mixed using an SS Swagelok T-piece. Following this initial mixing, the reagents then pass through SM-1, a 15 cm SS tubing (3 / 16" OD, 3.4 mm ID) fitted with a PP high-shear static mixer (Cambridge Reactor Design). The aniline and DNNSA solution is then combined with the APS solution from P-3 and passed through SM-2, a 30 cm SS tubing (3 / 16" OD, 3.4 mm ID) fitted with a PP high-shear static mixer (Cambridge Reactor Design). A Swagelok R3A-A pressure relief valve was used to pressurize Stage 1, allowing system pressures to be adjusted in the range of 3.4 to 24.1 bar. All other piping of the reactor lines was performed using standard Swagelok fittings.

[0282] Stage 2: A 1 L shell-and-tube continuous reactor (Cambridge Reactor Design) consists of a series of Hastelloy C276 alloy tubes (8 mm OD, 6 mm ID) connected in a serpentine configuration within the reactor shell. The reactor is equipped with static mixers along its length and has a total internal volume of 1 L. Depending on the auxiliary equipment used, the reactor can operate at temperatures ranging from -10 °C to 200 °C and up to 25 bar pressure. In this experiment, reactor temperature control was provided by a Julabo Presto A40 thermostat, capable of operating from -40 °C to 250 °C. Internal reactor tube temperature monitoring was performed using four PPT-100 temperature probes connected to positions 1, 8, 15, and 24 in a 5 x 5 array, which was recorded using a portable data acquisition and logging system. No backpressure regulator (BPR) was used in this section of the reactor.

[0283] Example 2: Preparation of comparative batch synthesis PANI-DNNSA The general preparation procedure for polyaniline dinonylnaphthalene sulfonic acid (PANI-DNNSA) using batch synthesis is shown in Scheme 1 below. TIFF2025138646000022.tif30170

[0284] Aniline (3.88 mL, 42.6 mmol) was added to deionized water (141 mL), and the resulting (0.3 M) solution was cooled to 0 °C in a constant temperature bath. Then, DNNSA (67 mL, 50% (w / w) solution in 2-butoxyethanol) was added with mechanical stirring to form a white emulsion. Then, an aqueous solution of ammonium persulfate (28 mL, 1.85 M) was added dropwise while maintaining the internal reaction temperature at 0 °C. The resulting brown mixture was stirred at 0 °C for 20 h while monitoring the internal reaction temperature. During this time, the emulsion The mixture separated into a green organic phase and a colorless aqueous phase. The biphasic product mixture was then rinsed into a separatory funnel with xylene (50 mL) and the aqueous layer was drained. The organics were then washed with water (5 x 100 mL), and the solvent was evaporated under reduced pressure to yield highly concentrated PANI-DNNSA in the remaining solvent. Acetone was added to the concentrate, resulting in the precipitation of PANI-DNNSA as a fine green powder. This was collected by filtration, washed thoroughly with acetone, and then dried to give PANI-DNNSA (12.0425 g) in 88 wt% yield.

[0285] A small portion of the PANI-DNNSA concentrate was thin-film cast in xylene to prepare a 70% (w / v) solution. The film was dried overnight in an oven at 100 °C, washed with 2-propanol, and air-dried. The resulting film had a thickness of 4.12 μm and a conductivity of 31 S / cm.

[0286] Example 3: Preparation of PANI-DNNSA using a continuous flow process After cooling the 1 L reactor system to 0 °C, aniline (1.0 equiv., neat, 99.5%) A1 was pumped at 0.56 mL / min (P-1) and DNNSA (1.5 equiv., 50% (w / w) solution in 2-butoxyethanol) A2 was pumped at 8.71 mL / min (P-2) through static mixer 1 (SM-1) for 1 min to form organic stream A3. Ammonium persulfate (1.2 equiv., 1.0 M aqueous solution) B was then introduced at 7.4 mL / min (P-3). The combined reagent streams were then sent to static mixer 2 (SM-2) to form emulsion product stream C, which then entered a pre-cooled 1 L Salamander Jacketed Flow Reactor at a total flow rate of 16.67 mL / min and remained there for a total of 1 h. Steady-state product collection at E began after 1 h 16 min. After steady-state operation, P-3 was switched to water washing, followed by P-1 and P-2 with toluene. After 3 hours and 28 minutes, collection was stopped and the crude product solution was diluted with toluene (2.45 L). The aqueous layer was then drained, and the organics were washed with 0.1 M H2SO4 (3 x 1.25 L) followed by HO (3 x 1.25 L). The washed organics were then concentrated under reduced pressure, and toluene (2.25 L) was added again to further dry the organics azeotropically. This drying process was repeated once more, after which toluene was added again to return the solution to the desired concentration (50% (w / w)).

[0287] Acetone was added to the concentrate, and the PANI-DNNSA precipitated as a fine green powder, which was collected by filtration, washed thoroughly with acetone, and then dried to give PANI-DNNSA (230.7530 g) in a yield of 88 wt%.

[0288] A small portion of the PANI-DNNSA concentrate was thin-film cast in toluene to prepare a 70% (w / v) solution. The film was dried overnight in an oven at 100 °C, washed with 2-propanol, and air-dried. The resulting film had a thickness of 8.25 μm and a conductivity of 10.6 S / cm.

[0289] Example 4: Continuous flow reaction Continuous flow reactions carried out under the same experimental conditions are shown in Table 1 below. JPEG2025138646000023.jpg29170

[0290] Table 1 shows that a continuous flow process using different formulations of monomer and protonic acid in the organic solvent stream can surprisingly obtain advantageous MP, Mn, and conductivity values ​​while enabling output significantly higher than that of the batch process.

[0291] It will be appreciated that space-time yield (STY) is a measure of the efficiency of a reactor system. It is defined as the amount of product produced in a given time frame per unit volume of reactor vessel. It provides a useful value for comparing the efficiency of processes run in batch and continuous systems.

[0292] The space-time yield (STY) of a chemical reactor is calculated by multiplying the amount of product m by the following equation: p This equation allows for a simple comparison of the efficiency of batch and flow reactors. TIFF2025138646000024.tif16170

[0293] When calculating space-time yields in a continuous scenario, TIFF2025138646000025.tif9170 is the total volumetric flow rate through the reactor, V SS is the total volume of both stock solutions, and V R is the volume of the flow reactor. An equivalent calculation is R is the total processing time, V R This can also be done for batch reactors where V is the volume of the batch reactor vessel.

[0294] Molecular Weight Range Mn = 30,000-100,000 g / mol is generally PANI with MP = 44,000 g / mol, Mn = 34,000 gmol, Mw = 53,000 gmol and polydispersity (Pd) = 1.57. -This is the scope of the flow process that generates the DNNSA.

[0295] Flow experiments in continuous reactors show fluctuations of <0.6 °C during the steady-state portion of the reaction (see Table 1 code 391-150 above and Figure 5). Here, excellent temperature control was achieved in all experiments using a cooled shell-and-tube reactor system showing a ΔT of 0.6 °C.

[0296] Example 5: Effect of temperature during flow on product quality Initially, three different temperatures were investigated in the flow (0, 9.0 °C, and 18.5 °C). Because a 100 ml flow reactor was used, mixing was not optimal. Scaling up and higher flow rates, leading to improved mixing in a 1 L flow reactor, further improved the yield. The results are shown in Figure 2. JPEG2025138646000026.jpg50170

[0297] As the reaction temperature decreased, the yield of PANI-DNNSA increased (from 391-048 to 391-050), and this comparison of yield and reaction temperature is shown in Figure 2 .

[0298] Also, the molecular weight of PANI-DNNSA increased (from 391-048 to 391-050) when the reaction temperature decreased, and this comparison of peak molecular weights is shown in Figure 3 .

[0299] Furthermore, as the reaction temperature decreased, the conductivity of PANI-DNNSA increased (from 391-048 to 391-050). This comparison of thin film conductivity after i-PrOH treatment following reactions at different temperatures is shown in Figure 4. The isopropanol treatment is used to increase the conductivity of the polymer film. In practice, any organic solvent capable of removing excess protonic acid (e.g., DNNSA in this case) may be used. An example of the isopropanol treatment procedure is as follows: A small portion of the PANI-DNNSA concentrate was used to prepare a 70% (w / v) solution in toluene for thin film casting. The film was dried overnight in an oven at 100 °C, then washed with i-PrOH and air-dried. The thickness and resistivity of the resulting thin film were then measured, from which the conductivity could be determined.

[0300] As noted above, lower reaction temperatures, such as from about −5° C. to about +5° C., can provide PANI-DNNSA products with more advantageous properties, such as conductivity (10-20 S / cm), yield (70-90 wt%), and Mw (defined as MP 30,000-100,000 g / mol), in accordance with at least some of the examples described herein.

Claims

1. 1. A continuous flow process for the controlled synthesis of a conductive polymer or salt thereof, comprising: feeding an emulsion of a polymerizable organic monomer and a free radical initiator into a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize the conductive polymer or salt thereof to provide a product stream comprising the conductive polymer or salt thereof.

2. 10. The continuous flow process of claim 1, wherein the emulsion comprises either i) a polymerizable organic monomer, a protonic acid, and a free radical initiator, or ii) an organic monomer salt of an organic monomer and a protonic acid, and a free radical initiator.

3. 3. The continuous flow process of claim 1 or claim 2, wherein the emulsion is formed from an organic stream comprising a polymerizable organic monomer.

4. 4. The continuous flow process of claim 3, wherein the organic stream further comprises a protonic acid.

5. 5. The continuous flow process of claim 1, wherein the emulsion is formed from an organic stream and an aqueous oxidant stream comprising a free radical initiator.

6. 6. The continuous flow process of claim 1, wherein the emulsion is formed from an organic stream and an oxidant stream, the organic stream comprising a polymerizable organic monomer and a protonic acid, and the oxidant stream comprising a free radical initiator.

7. A process comprising: i) by introducing an oxidant stream into an organic stream in a fluid conduit or continuous flow reactor in close fluid connection with a temperature-controlled continuous flow reactor; or ii) by introducing an oxidant stream directly into the organic stream in a temperature-controlled continuous flow reactor; 8. The process of any one of claims 1 to 7, wherein the emulsion is formed from an organic stream comprising polymerizable organic monomer and optionally a protonic acid, and an oxidant stream comprising a free radical initiator.

8. 8. The continuous flow process of claim 7, wherein at least one of the oxidant stream and the organic stream is cooled prior to introduction into each other.

9. 9. The continuous flow process of any one of claims 1 to 8, wherein the temperature-controlled continuous flow reactor is a temperature-controlled continuous flow tubular reactor.

10. 10. The continuous flow process of any one of claims 1 to 9, wherein the temperature of the emulsion in the reactor is controlled to between about -5°C and 5°C and maintained across the axial flow length of the continuous flow reactor with a variation of no more than 3 degrees Celsius.

11. a) providing an organic stream comprising an organic solvent, a polymerizable organic monomer, and a protonic acid; b) providing an oxidant stream comprising an aqueous solvent and a free radical initiator; and c) mixing the organic stream and the oxidant stream to form an emulsion stream; d) feeding the emulsion stream into a temperature-controlled continuous flow reactor comprising at least one mixing element at a temperature effective to synthesize the conductive polymer or salt thereof to provide a product stream comprising the conductive polymer or salt thereof in a temperature-controlled continuous flow; and e) obtaining a conductive polymer or a salt thereof from the product stream under continuous flow conditions after the product stream leaves the temperature-controlled continuous flow reactor.

11. The continuous flow process of claim 1, comprising:

12. 12. The continuous flow process of any one of claims 1 to 11, wherein the conductive polymer is selected from the group consisting of polyarylamine, polyarylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), or a salt of any of these; and the polymerizable organic monomer is selected from the group consisting of arylamine, arylthiol, pyrrole, carbazole, indole, azepine, thiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene monomer, or a salt of any of these; and each conductive polymer and polymerizable organic monomer is unsubstituted or substituted.

13. 13. The continuous flow process of claim 12, wherein the conductive polymer is polyaniline and the polymerizable organic monomer is unsubstituted or substituted aniline; the conductive polymer is poly(3,4-ethylenedioxythiophene) and the polymerizable organic monomer is unsubstituted or substituted 3,4-ethylenedioxythiophene; or the conductive polymer is poly(3,4-propylenedioxythiophene) and the polymerizable organic monomer is unsubstituted or substituted 3,4-propylenedioxythiophene monomer.

14. 14. The continuous flow process of any one of claims 1 to 13, wherein each individual polymerized chain of the conductive polymer is independently composed of between about 100 and 1500 individual monomer units.

15. 15. The continuous flow process of any one of claims 1 to 14, wherein the conductive polymer has a weight average molecular weight between 10,000 and 120,000.

16. 16. The continuous flow process of any one of claims 1 to 15, wherein the emulsion is formed from an oxidant stream, the oxidant stream being an aqueous stream comprising or consisting of an aqueous solvent and a free radical initiator.

17. 17. The continuous flow process of any one of claims 1 to 16, wherein the emulsion is formed from an organic stream, the organic stream being a non-aqueous organic solution comprising or consisting of an organic solvent, a polymerizable organic monomer, and a protonic acid.

18. 18. The continuous flow process of any one of claims 1 to 17, wherein the emulsion is formed from an organic stream comprising a polymerizable organic monomer and an oxidant stream comprising a free radical initiator, and the organic stream and the oxidant stream are premixed under continuous flow conditions prior to introduction into the temperature controlled continuous flow reactor.

19. a1) providing a protonic acid stream comprising an organic solvent and a protonic acid; a2) providing a monomer stream comprising an organic solvent and a polymerizable organic monomer; and a3) combining the protonic acid stream and the monomer stream to form an organic stream; 19. The continuous flow process of claim 1, wherein the organic stream is formed from

20. 20. The continuous flow process of any one of claims 1 to 19, wherein the temperature-controlled continuous flow reactor is equipped with one or more static mixers.

21. a) providing an organic stream comprising an organic solvent, an unsubstituted or substituted aniline or a salt thereof, and optionally a protonic acid; b) providing an aqueous stream comprising an aqueous solvent and a free radical initiator; c) mixing the organic stream and the aqueous stream to form an emulsion stream; d) providing the emulsion stream in a temperature-controlled continuous flow tubular reactor equipped with at least one mixing element at a temperature effective to synthesize polyaniline or a salt thereof to provide a product stream comprising a conductive polymer of polyaniline or a salt thereof in the temperature-controlled continuous flow tubular reactor; and e) Obtaining a conductive polymer of polyaniline or its salt from the product stream under continuous flow conditions after the product stream leaves the temperature-controlled continuous flow tubular reactor.

21. The continuous flow process of any one of claims 1 to 20, comprising:

22. 22. The continuous flow process of any one of claims 1 to 21, wherein the polymerizable organic monomer is an unsubstituted aniline.

23. 23. The continuous flow process of any one of claims 1 to 22, wherein the protic acid is dinonylnaphthalenesulfonic acid (DNNSA).

24. 24. The continuous flow process of any one of claims 1 to 23, wherein the organic solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, glycols, ethers, glycol ethers, and mixtures thereof.

25. 25. The continuous flow process of claim 24, wherein the organic solvent is an aromatic hydrocarbon.

26. 26. The continuous flow process of any one of claims 1 to 25, wherein the free radical initiator is selected from the group consisting of persulfates, peroxides, dichromates, cerium (IV) salts, and mixtures thereof.

27. 27. The continuous flow process of any one of claims 1 to 26, wherein the free radical initiator is ammonium persulfate.

28. 28. The continuous flow process of any one of claims 1 to 27, wherein the concentration of the polymerizable organic monomer in the organic stream is from about 0.1 M to about 0.8 M.

29. 30. The continuous flow process of claim 28, wherein the polymerizable organic monomer is aniline and the concentration of aniline in the organic stream is from about 0.2M to about 0.5M.

30. 30. The continuous flow process of any one of claims 1 to 29, wherein the continuous flow reactor is a continuous flow tubular reactor having an internal diameter of at least about 2 mm.

31. 31. The continuous flow process of any one of claims 1 to 30, providing at least about 50 g of conductive polymer per hour of operation.

32. 32. The continuous flow process of claim 31, wherein the operating capacity is for a continuous flow reactor volume of about 100 to 3000 ml.

33. 33. The continuous flow process of any one of claims 1 to 32, providing at least about 100 g of conductive polymer per liter of internal volume of the continuous flow reactor per hour of operation.

34. 34. The continuous flow process of any one of claims 1 to 33, wherein the continuous flow process is operated as a single pass process or the temperature controlled continuous flow reactor is a single pass reactor.

35. 35. A conductive polymer prepared by the continuous flow process of any one of claims 1 to 34.

36. 36. A composition, coating or material comprising the conductive polymer or salt thereof of claim 35.

37. 35. A system for providing the continuous flow process of any one of claims 1 to 34 for the controlled synthesis of a conductive polymer or salt thereof, comprising: a) a temperature-controlled continuous flow reactor equipped with at least one mixing element; b) one or more pumps for providing fluid flow to one or more streams passing through the temperature-controlled continuous flow reactor; c) one or more heat exchangers for controlling the temperature of the temperature-controlled continuous flow reactor; d) a temperature control device for controlling the temperature of the flow in the temperature-controlled continuous flow reactor, in cooperation with the temperature-controlled continuous flow reactor and the one or more heat exchangers, useful for synthesizing the conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from concentration, flow rate, temperature, pressure, and residence time of one or more of the streams, fluid reactants, sources of fluid reactants, fluids, or products of the reaction; A system comprising:

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