Continuous flow process for the preparation of conductive polymers

Abstract

To provide alternative commercial processes that are industrially scalable for preparing and synthesizing conducting polymers.SOLUTION: There is provided a method comprising: introducing a polymerizable organic monomer into a first continuous flow mixer as neat liquid or with an organic solvent; introducing protonic acid into the first continuous flow mixer separately from the polymerizable organic monomer to form an organic-soluble monomer salt; forming a mixture of reactants by introducing an aqueous stream containing the organic-soluble monomer salt and a free radical initiator into a second continuous flow mixer provided in series with the first continuous flow mixer; and introducing the mixture of reactants into a tubular reactor to form a conductive polymer or a salt thereof.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a continuous flow process for preparing conductive polymers, for example, a continuous flow process for synthesizing polyaniline. The present disclosure also relates to conductive polymers prepared by a continuous flow process, and further to products comprising or prepared from the conductive polymers.

Background Art

[0002] Conductive polymers are of high commercial value, but the scalability of the process for preparing conductive polymers is still quite limited due to various problems including solubility and reaction control requirements. For example, polyaniline is a conductive polymer and has received considerable attention due to its environmental stability and wide range of industrial applications. Polyaniline is a special member 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 dissipation coatings, anticorrosion coatings, electrochromic coatings, and chemical sensors.

[0003] The synthesis of polyaniline is generally carried out by chemical oxidative polymerization in an aqueous solution. This method involves a batch reaction that combines water, aniline, a protonic acid, and an oxidizing agent and reacts the reaction mixture while maintaining it at a low temperature (usually about 5°C). Most of the materials synthesized by this method are amorphous and difficult to handle, and are insoluble in most organic solvents. Organically soluble polyaniline can also be synthesized by a batch emulsion polymerization method in Butyl CELLOSOLVE (trademark) / water containing an organically soluble dopant such as dinonylnaphthalene sulfonic acid. Although the emulsion polymerization reaction can obtain a polymer with an appropriate molecular weight, it is highly exothermic and requires careful control to suppress the formation of low-molecular-weight by-products. The oxidation reaction in the batch emulsion polymerization process causes a heat generation temperature spike that leads to an increase in impurities such as low-molecular-weight oligomers and a decrease in the molecular weight and conductivity characteristics of the prepared polyaniline. Also, the batch emulsion polymerization process suffers from scalability for industrial applications. However, industrial processes for preparing conductive polymers have been shunned due to poor reaction performance and control problems in forming conductive polymers. Therefore, the batch emulsion polymerization process has been widely preferred, especially for the preparation of polyaniline.

[0004] Therefore, there is a need to develop an industrially scalable alternative commercial process for preparing and synthesizing various conductive polymers including polyaniline.

Summary of the Invention

[0005] The inventors have identified alternative methods for preparing various conductive polymers including a continuous flow process.

[0006] The continuous flow process involves providing an emulsion of a polymerizable organic monomer, a protonic acid, and a free radical initiator within 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 a conductive polymer or its salt to provide a product stream containing the conductive polymer or its salt. The continuous flow process can include a continuous flow reactor having one or more passageways in fluid communication for carrying reactant and product streams, such as a continuous flow tubular reactor. The continuous flow process of the present invention according to at least some examples as described herein enables precise variable control of the ratio of reagents for controlling the molecular weight, solubility, and thermal stability of the final product, addition of a post-polymerization dopant to enhance conductivity, use of increased concentrations of organic monomers, better scalability and industrial processing, and / or improved control of the temperature during processing, thereby preventing or reducing undesirable variations in temperature that can contribute to impurities or undesirable by-products being introduced into the product stream.

[0007] Also, the continuous flow process can involve supplying a continuous flow of an organic stream containing a polymerizable organic monomer in an organic solvent. The organic stream can be mixed with one or more other streams to initiate polymerization of the organic monomer. For example, an oxidizing agent stream containing a free radical initiator can be mixed with an organic stream containing an aniline monomer to initiate polymerization of the aniline monomer to form polyaniline. The polymerizable organic monomer can be converted in situ to an organic solvent-soluble salt during the continuous flow process prior to polymerization to a conductive polymer, such as an organically soluble conductive polymer salt that is more easily processable, using a free radical initiator.

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

[0009] In one example, the emulsion comprises a polymerizable organic monomer, a protonic acid, and a free radical initiator. In another example, the emulsion is formed using an organic stream and an aqueous stream comprising a polymerizable organic monomer. In another example, the emulsion is formed using an organic stream comprising a 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 a product stream. It will be understood that the aqueous stream for forming the product stream contains a free radical initiator.

[0010] The emulsion can comprise 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, the 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 the organic stream and the oxidant stream, the oxidant stream contains a free radical initiator, and the organic stream contains a polymerizable organic monomer and a protonic acid. It will be understood that the oxidant stream is aqueous.

[0012] It has been found that the exothermic reaction and the associated temperature spike occurring in forming the product stream when the oxidant stream is first introduced into the organic stream can be further substantially controlled according to the embodiments and examples described herein. For example, the continuous flow process further i) Introducing an oxidizing agent stream into an organic stream in a fluid conduit or in a continuous flow reactor with a fluid connection proximate to the temperature-controlled continuous flow reactor; or ii) Directly introducing an oxidizing agent stream into an organic stream within a temperature-controlled continuous flow reactor may be included.

[0013] In the case of option i) above, the oxidizing agent stream and / or the organic stream may each be independently cooled as an optional step prior to introduction into the supply conduit or the continuous flow reactor. The continuous flow reactor of option i) may comprise at least one static mixer, for example, it may be a continuous flow tubular reactor comprising a static mixer element. Also, the continuous flow reactor of option i) can be temperature-controlled, for example, it may comprise a heat exchanger.

[0014] In the case of option ii) above, the oxidizing agent 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 a polymerizable organic monomer, optionally one or more organic solvents, and optionally one or more protonic acids. In another example, the oxidizing agent stream comprises or consists of a free radical initiator and optionally one or more solvents comprising or consisting of water.

[0016] In another example, the emulsion is formed from in-line mixing of an organic stream and an oxidizing agent stream in the flow, by direct mixing within a temperature-controlled continuous flow reactor or by in-line mixing proximate 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 comprises obtaining a conductive polymer or a salt thereof from the product stream under continuous flow conditions.

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

[0018] In other examples, mixing the organic stream and the oxidizing agent stream in step c) above to form an emulsion stream may be by in-line mixing of the organic stream and the oxidizing agent stream in the flow, either by direct mixing within a temperature-controlled continuous flow reactor or by in-line mixing proximate to a temperature-controlled continuous flow reactor. The continuous flow process for step c) may be, for example, i) introducing the oxidizing agent stream into the organic stream within a fluid conduit or a temperature-controlled continuous flow reactor to form an emulsion stream, wherein the fluid conduit or the temperature-controlled continuous flow reactor is fluidly connected in proximity to a temperature-controlled continuous flow reactor; or ii) directly introducing the oxidizing agent stream into the organic stream within a temperature-controlled continuous flow reactor and mixing the organic stream and the oxidizing agent stream to form an emulsion stream further comprising.

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

[0020] The conductive polymer can be selected from the group consisting of polyallylamine, polyallylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), or any salts thereof. The polymerizable organic monomer can be selected from the group consisting of arylamine, arylthiol, pyrrole, carbazole, indole, azepine, thiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene monomer, or any salts thereof. Each of the conductive polymer and the 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 polymerization chain of the conductive polymer or any salt thereof can independently be composed of individual monomer units between about 100 and 1500, 300 and 1400, 500 and 1300, 600 and 1200, or 700 and 1100. The weight average molecular weight of the conductive polymer produced in this process can be between about 10,000 and 120,000, between about 20,000 and 110,000, or between about 60,000 and 100,000. In one example, each individual polymerized chain of the conductive polymer is independently composed of individual monomer units between about 100 and 1500. In another example, the conductive polymer has a weight average molecular weight between 10,000 and 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, for example less than about 2 °C or 1 °C. In one example, for step c), the temperature of the mixed stream is set between about -5 and 5 °C and maintained over the axial flow length of the continuous flow reactor, 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 comprises feeding an emulsion of aniline, 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 a conductive polymer or a salt thereof and provide a product stream comprising the conductive polymer or a salt thereof. The aniline or a 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 and comprises 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 oxidizing agent stream comprising an aqueous solvent and a free radical initiator; c) mixing the organic stream and the oxidizing agent 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 comprising polyaniline or a salt thereof in the temperature-controlled continuous flow reactor. e) After the product stream exits the temperature-controlled continuous flow reactor, obtaining polyaniline or a salt thereof from the product stream under continuous flow conditions comprises.

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

[0027] In one example, in step b), the oxidant stream is an aqueous stream comprising an aqueous solvent, and the mixing of the organic stream and the aqueous stream in the continuous flow of 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 can 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) is 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 for mixing a protonic acid stream and the aniline stream to form the organic stream of step (a).

[0034] The protonic acid stream and the monomer stream can be premixed under continuous flow conditions before mixing with the oxidizing agent stream. In at least some examples, the premixing can provide for further improvement of the emulsion of the product stream formed by mixing the organic stream and the oxidizing agent stream.

[0035] In the above continuous flow process, the polymerizable organic monomer may be unsubstituted aniline. The protonic acid may be dinonylnaphthalene sulfonic acid (DNNSA). The organic solvent can 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 can 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 can provide for further improvement of the emulsion of the product stream formed by mixing the organic stream and the oxidizing agent stream. The free radical initiator can be an oxidizing agent selected from the group consisting of persulfates, peroxides, dichromates, cerium(IV) salts, iron(III) salts, and any mixture thereof. In one example, the oxidizing agent is ammonium persulfate (APS).

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

[0037] In the case of a continuous flow reactor such as a tubular reactor, by using the inner diameter of the passage in the reactor as the inner diameter, mixing and backpressure characteristics can be promoted. For example, the passage can range from a small one for increasing shear to a large one for accommodating static mixer elements for industrial scale operation. For example, the inner diameter of the passage or chamber can be at least about 2 mm, 3 mm, 4 mm or 5 mm. The inner diameter of the reactor can be between about 5 and 20 mm, for example between about 5 and 10 mm. In the case of a continuous flow process or system, the minimum inner diameter of any part of the continuous flow system is greater than 1 mm, and can be, for example, at least about 2 mm or at least about 3 mm. Different inner diameters affect the fluid flow in the reactor. In the case of reactors with the same internal volume, a reactor composed of passages or tubes with a smaller diameter results in a faster fluid flow rate for a given residence time. Therefore, when the diameter of the passage or tube decreases, for example, the turbulent flow of the fluid increases and the shear force around the static mixer element increases, thereby improving the mixing performance. However, reducing the diameter of the passage or tube, which is a point to be considered when determining an appropriate structural material and reactor design, also increases the system pressure. In the emulsion polymerization process, it is beneficial to keep the diameter of the tube small, which maximizes the shear force of the fluid and results in a finer emulsion.

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

[0039] In another example, following step d) or step e), an additive selected from the group consisting of a secondary dopant and additional reagents is contacted with the conductive polymer or a 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 containing a conductive polymer, such as a liquid concentrate.

[0042] In another aspect, a system for a continuous flow process for the controlled synthesis of a conductive polymer or a salt thereof, 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 described herein; b) one or more pumps for providing a fluid flow to one or more flows 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 cooperating with the temperature-controlled continuous flow reactor and one or more heat exchangers to control the temperature of the flow within the temperature-controlled continuous flow reactor effective for the synthesis of a conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from the concentration, flow rate, temperature, pressure, and residence time of one or more flows, fluid reactants, sources of fluid reactants, fluids, or products of the reaction A system is provided comprising.

[0043] In one example, the system further comprises 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 being in fluid connection 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 includes at least one mixing element, and is in fluid connection with a 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, which is in fluid connection with a second continuous flow mixer (e.g., mixer 2) for forming a product stream, the first and second continuous flow mixers each optionally include at least one mixing element, and the second continuous flow mixer is in fluid connection with a temperature-controlled continuous flow reactor.

[0046] It will be understood that additional aspects and examples can be described herein that can include one or more of the above features.

[0047] The features, functions, and advantages described can be achieved independently in various examples or can be combined with further examples, and their further details can be verified by referring to the following description and drawings.

[0048] Here, examples of the present disclosure are further described and illustrated by way of example only with reference to the accompanying drawings.

Brief Description of the Drawings

[0049]

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DETAILED DESCRIPTION OF THE INVENTION

[0050] The present disclosure describes various non-limiting examples related to investigations conducted to identify alternative methods for preparing various conductive polymers, such as polyaniline. Although various batch processes were investigated, it was found that insufficient temperature control was a problem and affected the properties of conductive polymers prepared from processes involving the introduction of undesirable impurities. It was unclear whether continuous flow processes would be effective for scaling up delicate and complex batch processes, but various batch processes were investigated. Various attempts to scale up batch processes under continuous flow conditions failed. However, through continuous investigations related to continuous flow processes, a continuous flow process has finally been identified that has been 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 within 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 a conductive polymer or its salt to provide a product stream containing the conductive polymer or its salt. The continuous flow process can include a continuous flow reactor, such as a continuous flow tubular reactor, having one or more passageways in fluid communication for carrying reactant and product streams. The continuous flow process according to the present invention, according to at least some examples as described herein, provides any one or more of precise variable control of the ratio of reagents for controlling the molecular weight, solubility, and thermal stability of the final product, addition of a dopant after polymerization to enhance conductivity, use of an increased concentration of organic monomer, better scalability and industrial processing, and / or improved control of temperature during processing, thereby preventing or reducing undesirable fluctuations in temperature that contribute to impurities or undesirable by-products in the product stream.

[0052] Also, the continuous flow process can involve supplying a continuous flow of an organic stream containing a polymerizable organic monomer in an organic solvent. The organic stream can be mixed with an oxidizing agent stream containing a free radical initiator to form a product stream that initiates the polymerization of the polymerizable organic monomer. For example, an oxidizing agent stream containing a free radical initiator can be mixed with an organic stream containing an aniline monomer to initiate the polymerization of the aniline monomer to form polyaniline. The polymerizable organic monomer can be converted in situ to an organic solvent-soluble salt during the continuous flow process prior to polymerization to 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, which provides a more readily utilizable conductive polymer that can be conveniently applied in other processes or materials.

[0053] References herein to "mixing" or "mix" with respect to a continuous flow process generally refer to in-line mixing that occurs during the continuous flow of fluids within a reactor, mixer, or conduit of a system. An emulsion stream or product stream can be formed by mixing within a temperature-controlled continuous flow reactor or by mixing in proximity to the reactor. It is understood from the teachings of the present disclosure that such mixing to form an emulsion stream or product stream within or in proximity to a temperature-controlled continuous flow reactor can provide the further advantage of controlling temperature variations in the flow.

[0054] The continuous flow process can enable the synthesis of conductive forms of polymers, such as the emeraldine form of polyaniline, for example, polyaniline emeraldine salts.

[0055] According to at least some of the examples described herein, the conductive polymer can be synthesized in a continuous flow process in its conductive form (e.g., polyaniline emeraldine 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 of the examples described herein, the continuous flow process enables the in situ (i.e., in the flow) formation of an organic-soluble polymerizable monomer salt that can itself be polymerized into an organic-soluble conductive polymer form that is more easily processable and enables scalability for industrial applications during the continuous flow process.

[0057] The continuous flow process according to some examples enables improved temperature control during processing, prevents unwanted variations in temperature that can introduce or increase the presence of further impurities or undesirable by-products in the product stream and the resulting material, and enables increasing the concentration of the organic monomers used, resulting in improved scalability and industrial preparations.

[0058] Specific Terms As used herein, the term "polymerizable organic monomer" may be in the form of a protonated salt, or is capable of forming a protonated salt in the presence of a protonic acid source, and refers to any one or more organic monomers or comonomers that are capable of polymerizing in the presence of a free radical initiator to form a conductive polymer. Examples of polymerizable organic monomers include aniline, which includes a protonated form and can polymerize to provide a conductive polymer of polyaniline.

[0059] The term "conductive polymer" refers to any organic polymer or organic copolymer that is capable of conducting electricity, and may include, for example, a polymer that is a semiconductor. It will be understood that conductive polymers may require the following treatments to provide the desired conductance properties. An example of a conductive polymer is polyaniline. It will be understood that the terms "conductive polymer" or "polymer" may include one or more "copolymers", and the term "monomer" may include one or more comonomers.

[0060] Reference to "continuous flow" means a process in which a chemical reaction occurs in a continuously flowing stream of reagents, the reaction reaches completion or near completion within a continuous reactor system, and the product is produced in that flow without the need for further chemical reactions after exiting the reactor system. From the perspective of continuous flow chemistry, this will be understood. For example, the term "continuous flow" means the continuous supply of an organic stream and an oxidant stream to a temperature-controlled reactor, and the polymerizable monomer exiting as a fluid stream from the outlet of the reactor. For example, the most basic form of a continuous flow reactor 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 together with one or more other components in forming a continuous flow reactor system. Examples of elements include the "insertion" or "module" described herein.

[0062] "Single-pass reactor" refers to a reactor used in a process or system where a fluid component passes through the reactor once and is not recycled through the reactor through which the component has already passed.

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

[0064] "Proximity" refers to being at, adjacent to, next to, near, or in contact with a reference point.

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

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

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

[0068] As will be understood, "aryl", whether used alone or in a compound word such as alkylaryl or arylalkyl, can refer to the following: (i) a substituted or unsubstituted monocyclic or polycyclic aromatic carbocyclic moiety of about 6 to about 20 carbon atoms, such as phenyl, naphthyl or fluorenyl; or (ii) a substituted or unsubstituted partially saturated polycyclic carbocyclic aromatic ring system in which an aryl group is condensed together with a cycloalkyl or cycloalkenyl group to form a cyclic structure such as tetrahydronaphthyl, indenyl, indanyl or fluorene ring. It will be understood that the polycyclic ring system 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 1-20 alkyl or C 1-10 alkyl may also be.

[0069] "Alkyl", whether used alone or in a compound word such as alkylaryl or arylalkyl, represents a straight-chain or branched-chain hydrocarbon in the range of 1 to about 20 or more carbon atoms. Thus, the alkyl moiety includes, unless explicitly limited to a smaller group, moieties in the range of, for example, 1 to about 6 carbon atoms or more, methyl, ethyl, n-propyl, iso-propyl and / or butyl, pentyl, hexyl, etc., and higher order isomers, for example those straight-chain or branched-chain hydrocarbons in the range of about 6 to about 20 carbon atoms or more. For example, "alkyl" may include "C 1-20 alkyl" or "C 1-10 alkyl" as described below.

[0070] As used herein, the term "C 1-20 alkyl" refers to a straight-chain or branched saturated hydrocarbon having 1 to 20 carbon atoms. Representative "C 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, n-icosyl.

[0071] As used herein, the term "C 1-10 alkyl" refers to a straight-chain or branched saturated hydrocarbon having 1 to 10 carbon atoms. Representative "C 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 1-8Examples of alkyl include, but are 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-dimethylbutyl, 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] The term "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 the "alkyl", "C 1-20 alkyl", C 1-10 alkyl" and "aryl" moieties are as defined above, respectively.

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

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

[0075] "Hydroxy" represents the -OH moiety.

[0076] "Alkyloxy" represents an -O-alkyl group where the alkyl group is as defined above. Examples include methoxy, ethoxy, n-propoxy, iso-propoxy, and various butoxy, pentoxy, hexyloxy, and higher order isomers.

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

[0078] "Amino" represents an -NHR moiety where R represents hydrogen or alkyl as defined above.

[0079] "Nitro" represents a -NO 2 moiety.

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

[0081] The term "halo" or "halogen", whether used alone or in a compound word such as haloalkyl, represents fluorine, chlorine, bromine or iodine. Further, when used in a compound word such as haloalkyl, the alkyl may be partially halogenated or completely substituted with the same or different halogen atoms independently. Examples of haloalkyl include, but are not limited to, -CH 2 CH 2 F, -CF 2 CF 3 , and -CH 2 CHFCl. Examples of haloalkoxy include, but are not limited to, -OCHF 2 , -OCF 3 , -OCH 2 CCl 3 , -OCH 2 CF 3 , and -OCH 2 CH 2 CF 3is included. Examples of haloalkylsulfonyl include, but are not limited to, -SO 2 CF 3 -, -SO 2 CCl 3 -, -SO 2 CH 2 CF 3 -, and -SO 2 CF 2 CF 3 is included.

[0082] General terms Throughout this disclosure, unless otherwise specified and unless otherwise required by context, references to a single step, composition of matter, group of steps, or group of compositions of matter include one and more than one (i.e., one or more) of these. Thus, as used herein, the singular forms "a", "an", and "the" include plural aspects unless the context clearly indicates otherwise. For example, reference to "a" includes not only one but also two or more; reference to "an" includes not only one but also two or more; reference to "the" includes not only one but also two or more, etc.

[0083] Unless otherwise specified, terms such as "first", "second", etc. are used herein merely as labels and are not intended to impose an order, position, or hierarchical requirement on the items indicated by these terms. Further, reference to a "second" item does not require, and does not exclude, the presence of a lower numbered item (e.g., a "first" item) and / or a higher numbered item (e.g., a "third" item).

[0084] As used herein, the phrase "at least one" when used with a list of items means that various combinations of one or more of the listed items may be used and that only one of the items in the list may be needed. The items may be specific objects, things or categories. In other words, "at least one" means that any combination or number of items in the list may be used, but not all 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, 2 item As, 1 item B and 10 item Cs; as well as 4 item Bs and 7 item Cs; or some other suitable combination, but is not limited thereto.

[0085] References in this specification to "an example", "one example", "another example" or similar expressions mean that one or more features, structures, elements, components or characteristics described in connection with that example are included in at least one embodiment or implementation. Thus, throughout this disclosure, the phrases "in one example", "as an example" and similar expressions may, but do not necessarily, refer to the same example. Further, the subject matter characterizing any one example may, but does not necessarily, include the 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. It is to be understood that the disclosure includes all such variations and modifications. The disclosure also includes all steps, features, compositions and compounds individually or collectively recited or shown herein, as well as any combination or any two or more of said steps or features.

[0087] Each example of the present disclosure described herein shall apply to all other examples with necessary modifications, unless otherwise specified. The present disclosure is not limited to 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", is understood to mean either "X and Y" or "X or Y", and is construed to provide explicit support for both meanings or either meaning.

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

[0090] The term "consist of", or variations such as "consisting of", means including any stated element, integer, or step, or group of elements, integers, or steps, enumerated in relation to this term, and excluding any other element, integer, or step, or group of elements, integers, or steps, not so enumerated in relation to this term.

[0091] Although a number of prior art documents are referred to herein, it will be clearly understood that this reference does not admit that any of these documents forms part of the common general knowledge in the art in Australia or any other country.

[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. In the practice or testing of the present invention, methods and materials similar or equivalent to those described herein can be used, but the preferred methods and materials are described below. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0093] Continuous flow process The continuous flow process of the present disclosure means a process in which a chemical reaction occurs in a continuously flowing reagent stream, the reaction reaches completion within a continuous reactor system, and the product is produced in the continuous fluid stream without the need for further chemical reactions after exiting the reactor system, as would be understood from the perspective of continuous flow chemistry. For example, the term "continuous flow" in the present disclosure can refer to a continuous flow process that has reached a steady-state operation. A continuous flow process can include a continuous flow reactor having one or more passages in fluid communication for carrying reactant and product streams. For example, the continuous flow system can be a tubular reactor, and in its most basic form, it comprises 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 is different from batch, semi-batch, or semi-continuous processes. For example, after carrying out a process in a tubular reactor and collecting the product in a tank to complete a chemical reaction, the whole process becomes a semi-continuous process. Also, it will be understood that it is semi-continuous to periodically stop or interrupt the reactor to carry out a cleaning cycle and collect the product. In other words, a semi-continuous process interrupts the continuous flow operation before the completion, preparation, or recovery of the conductive polymer. Also, 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, the reaction will be understood to be continuous. 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 compounding 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 a conductive polymer even when a product stream containing the synthesized conductive polymer is obtained from the reactor during operation and then is separated stepwise into an aqueous phase and an organic phase and washed with acidified water.

[0095] To achieve a continuous flow process as described herein, it will also be understood that various configurations and designs of continuous flow reactors can be used. A continuous flow process can include a continuous flow reactor having one or more passages in fluid communication for carrying reactant and product streams, such as a continuous flow tubular reactor. The continuous flow tubular reactors described herein are not limited to design configurations that require 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 Corning's Advanced-Flow™ reactor. The configuration of a plate reactor can provide one or more plates each including one or more fluid-connected passages or channels. The fluid-connected passages or channels can be of various configurations, such as flat, elongated, or oval. A continuous flow tubular reactor includes one or more passages in fluid communication for carrying the flow. Due to the configuration of the passages, the flow can flow through the passages for the desired residence time. The mixing element within the continuous flow tubular reactor of step (c) can be a static mixer or a dynamic mixer. A static mixer has static or fixed structural elements disposed within a conduit or chamber capable of mixing fluids under flow, and is further described in various embodiments and examples herein. In one example, the static mixing element within the continuous flow reactor can be provided by one or more passages of the reactor including at least sections configured to enhance mixing of the flow (such as enhancing radial mixing or chaotic advection). A dynamic mixer will be understood to have movable elements capable of mixing fluids, such as paddles, spinning tubes, rotors, blenders, or rotating disks.

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

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

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

[0099] Figures 1 and 2 show general examples of flow processes and reaction conditions. Depending on the various configurations, a product stream can be obtained in the form of an emulsion containing an organically soluble polymerizable organic monomer and a water-soluble free radical initiator in a temperature-controlled continuous flow reactor. The introduction of the organic stream containing the organically soluble polymerizable organic monomer or the oxidizing agent stream containing the free radical initiator can each be varied, for example, these streams can be premixed to form an emulsion stream or mixed within the reactor. In another example, the oxidizing agent stream is introduced directly into the temperature-controlled continuous flow reactor or mixed with the organic stream proximate to the temperature-controlled continuous flow reactor. The temperature can be established and controlled for any individual or mixed stream prior to introduction into the temperature-controlled continuous flow reactor according to any of the temperature examples or embodiments described herein. In this way, the process conditions can be further improved to reduce or prevent temperature variations (i.e., spikes or exotherms) of problems occurring in the product stream. The emulsion stream contains a two-phase mixture of an organic phase and an aqueous phase, where the organic phase contains the polymerizable organic monomer and any protonic acid, and the aqueous phase contains the free radical initiator. The emulsion stream can be formed into an emulsion before or after entering the temperature-controlled continuous flow reactor. It will be appreciated that when the polymerizable organic monomer in the organic phase (e.g., monomer salt or combination of monomer and protonic acid) is mixed with the free radical initiator in the aqueous phase, a product stream is established. Without wishing to be bound by theory, by providing a high concentration of the polymerizable organic monomer in the organic phase that reacts with the water-soluble free radical at the interface between the aqueous and organic phases to produce an in situ conductive polymer in the organic phase, it has unexpectedly been found that a highly exothermic polymerization reaction can be promoted under effectively mixed emulsion flow conditions. Initiating the polymerization reaction under process flow conditions is difficult and, once initiated, there is a possibility of an exothermic temperature spike of concern. Also, the process flow conditions can be further controlled to enable the formation of a segmented two-phase flow product stream that can further facilitate the efficient processing of the prepared conductive polymer.

[0100] It will be appreciated that the emulsion stream or product stream is biphasic. The biphasicity results from the mixing of an organic stream and an aqueous stream, which together form an emulsion stream. When an oxidant stream or free radical initiator is introduced into the organic stream or emulsion stream containing a polymerizable organic monomer (e.g., aniline and a protonic acid, or an aniline salt), a product stream can be obtained in which a conductive polymer is formed during the flow. As described above, when an organically soluble conductive polymer is formed in the product stream, the process conditions can be further controlled such that the emulsion of the product stream begins to form an axially segmented biphasic flow. The axially segmented biphasic 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 organically 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 a salt thereof and provide a product stream containing the conductive polymer or a salt thereof in a tubular reactor; and d) obtaining the conductive polymer or a salt thereof from the product stream under continuous flow conditions after the product stream exits the reactor may be included.

[0102] In the case of step (a), the organic stream may be a non-aqueous organic solution containing 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 protic acid). In the case of step (b), the oxidant stream may be an aqueous stream containing an aqueous solvent and a free radical initiator, such as an oxidant like ammonium persulfate. In the case of step (c), mixing the organic stream and the aqueous stream in a continuous flow can provide a product stream in the form of an emulsion.

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

[0104] The continuous flow process, system or reactor of the present disclosure can be operated at a predetermined pressure and temperature. For example, the temperature of the overall process or of individual or mixed streams such as the organic stream, the oxidant stream, the emulsion stream or the product stream within the tubular reactor can be set between about -15 to 15 °C, -10 to 10 °C, -5 to 5 °C, or -1 to 1 °C. The temperature of the overall process or of individual or mixed streams within the 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 overall process or of individual or mixed streams within the reactor can exceed about -10 °C, -9 °C, -8 °C, -7 °C, -6 °C, -5 °C, -4 °C, -3 °C, -2 °C or -1 °C. The temperature may be defined in any range between these upper and lower limits. These temperatures can be maintained over the axial flow length of the continuous flow reactor. Further, 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. The improved control of the temperature, including variations in the axial flow length, has surprisingly been shown to provide a conductive polymer from a product stream having a high electrical conductivity and / or a reduced solids content, e.g., a reduced amount of low molecular weight product.

[0105] In one example, the continuous flow process is for the controlled synthesis of polyaniline or any salt thereof and comprises 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 oxidizing agent stream comprising an aqueous solvent and a free radical initiator; and c) mixing the organic stream and the oxidizing agent stream in a continuous flow reactor having at least one mixing element at a temperature effective to synthesize polyaniline or a salt thereof and to provide a product stream comprising polyaniline or a salt thereof in the reactor; and d) obtaining polyaniline or a salt thereof from the product stream under continuous flow conditions after the product stream exits the reactor comprising.

[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. Mixing the organic stream and the aqueous stream during continuous flow results in a product stream in the form of an emulsion. In any of the above examples, in case of 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 of the examples described herein.

[0107] The mixing element in the continuous flow reactor of step (c) may be a static mixer or a dynamic mixer (e.g., a rotating tube). The static mixing element may be provided by one or more passages in the reactor fluidly connected to each other for carrying the flow and configured to enhance mixing of the flow (e.g., radial mixing). The oxidizing agent 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) mixing the protonic acid stream and the monomer stream to form the organic stream of step a). is provided by.

[0109] The polymerizable organic monomer can be provided as a neat organic liquid, optionally together with one or more organic solvents. The polymerizable organic monomer can 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 can be in the form of an organic liquid concentrate. For example, the organic stream can contain the polymerizable organic monomer at a concentration of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99 wt% (weight percent of the total organic stream). The organic stream can contain the organic monomer and the 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% (weight percent of the total weight of the organic monomer and the protonic acid in the total organic stream). The monomer stream can contain the polymerizable organic monomer at a concentration of at least 70, 80, 85, 90, 95, 98, or 99 wt% i (weight percent of the total monomer stream). The protonic acid stream can contain the protonic acid at a concentration of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99 wt% (weight percent of the total protonic acid stream). It will be understood that the one or more organic solvents described herein can provide the remaining volume or weight % of the organic stream, other than 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 mixing the protonic acid stream and the aniline stream to form the organic stream of step (a).

[0111] The proton acid stream and the monomer stream can be premixed under continuous flow conditions before mixing with the oxidant stream. In at least some examples, the premixing can provide further improvement of the emulsion of the product stream formed by the mixing of 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. The premixing includes ultrasonic treatment, dynamic or static mixing options. The premixing option is operable within a continuous flow process or system. In one example, the premixing 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 FIG. 2. The continuous flow process can include, for example, at least first and second continuous flow mixers (i.e., mixer 1 and mixer 2) in addition to a tubular reactor. The continuous flow mixer is a fluid conduit or a continuous flow reactor, for example, a continuous flow reactor including mixing elements. Mixer 1, mixer 2, and the tubular reactor can each be provided in fluid communication in a series configuration. Each of the mixing elements of mixer 1, mixer 2, and the tubular reactor can be, for example, one or more of the continuous flow static or dynamic mixers described previously for mixing elements. A polymerizable organic monomer is introduced alone as a neat liquid or an organic solution into a mixer (mixer 1), and a protonic acid is introduced alone as an organic solution into the same continuous flow mixer (mixer 1), thereby providing a first continuous flow mixer (mixer 1) that forms an organosoluble monomer en in the mixer (mixer 1). Thereafter, a second continuous flow mixer (mixer 2) can be provided in series with the first mixer (mixer 1). Thereafter, a further aqueous stream containing a free radical initiator is introduced into mixer 2, whereby a reactant emulsion can be formed in mixer 2 between the organosoluble monomer salt stream and the aqueous stream containing the free radical initiator. Thereafter, the reactant emulsion stream (i.e., the product stream) can be introduced into a temperature-controlled continuous flow reactor, such as a continuous flow tubular reactor, that includes one or more static mixers (e.g., five or more static mixers) contained therein or one or more passages configured to enhance the mixing of the flow. Thereafter, a conductive polymer or a conductive polymer salt is formed in the fluid flowing through the reactor in 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 stop, interruption, or cleaning step during the operation of the continuous flow process. In other words, the conductive polymer salt can be synthesized in the reactor and obtained from the continuous stream exiting the reactor during normal operation of the continuous flow process.

[0113] Figure 3 provides a schematic example showing the mixing of any one or more of the flows described herein, including the mixing of an oxidant stream and an organic stream proximate 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) and enables the mixing of the oxidant stream and the organic stream described herein proximate to the temperature-controlled continuous flow reactor (D). In one example, the continuous flow mixer including a static mixer element is a supply conduit to the temperature-controlled continuous flow reactor (D). Additional supply conduits or continuous flow mixers or tubular reactors (with or without static mixers) may be provided in parallel or in series to optionally in-line mix any of the flows as described herein while being fluidly connected to the temperature-controlled continuous flow reactor (D) (e.g., polymerizable organic monomer salts, A3).

[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 mixing the protonic acid and a monomer stream in a continuous flow static or dynamic mixer to form an organic stream comprising a protonated aniline monomer; b) providing an oxidant in an aqueous stream comprising an aqueous solvent; and optionally pre-mixing the aqueous stream and the organic stream together to form a reactant emulsion stream; c) mixing the aqueous stream and the organic stream at a temperature effective to synthesize a polyaniline salt in a temperature-controlled continuous flow tubular reactor comprising at least one static mixer to provide a product stream comprising a conductive polymer of the polyaniline salt in the tubular reactor, or introducing the reactant emulsion stream into the reactor; and d) obtaining the conductive polymer of the polyaniline salt from the product stream under continuous flow conditions after the product stream exits the tubular reactor may be included.

[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 oxidizing agent stream comprising an aqueous solvent and a free radical initiator; c) introducing directly into a temperature-controlled continuous flow reactor comprising at least one static mixer element to mix the organic stream and the oxidizing agent stream to form an emulsion stream; and operating the temperature-controlled continuous flow reactor at a temperature effective to synthesize a conductive polymer or a salt thereof and to provide a product stream comprising the conductive polymer or a salt thereof in the flow within the reactor; and d) obtaining the conductive polymer or a salt thereof from the product stream after the product stream exits the temperature-controlled continuous flow reactor under continuous flow conditions may be included.

[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 oxidizing agent stream comprising an aqueous solvent and a free radical initiator; c) introducing the organic stream and the oxidizing agent stream into a continuous flow mixer comprising at least one static mixer element to mix the organic stream and the oxidizing agent stream to 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 a conductive polymer or a salt thereof and to form a product stream comprising the conductive polymer or a salt thereof in the flow within the reactor; and e) obtaining the conductive polymer or a salt thereof from the product stream after the product stream exits the temperature-controlled continuous flow reactor under continuous flow conditions may be included.

[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 mix the protonic acid stream and the monomer stream and form an organic stream; b) providing an optionally cooled oxidizing agent stream comprising an aqueous solvent and a free radical initiator; c) introducing the organic stream and the oxidizing agent stream into a continuous flow mixer comprising at least one static mixer element to mix the organic stream and the oxidizing agent 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 a conductive polymer or a salt thereof and form a product stream comprising the conductive polymer or a salt thereof in the flow within the reactor; and e) obtaining the conductive polymer or a salt thereof from the product stream after the product stream exits the temperature-controlled continuous flow reactor under continuous flow conditions and may include.

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

[0119] Conductive polymer The conductive polymer prepared by the continuous flow process can be selected from any conductive polymer that is a reaction product of a protonated polymerizable organic monomer or its salt and a free radical initiator. For many conductive polymers, problems such as reaction control problems and poor solubility that cause handling difficulties are well known, and batch processing solutions are generally used, but they are becoming increasingly complex in recent years in an attempt to obtain conductive polymers with appropriate properties.

[0120] Each individual polymer chain of the conductive polymer or any of its salts can independently be composed of from about 100 to 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 each individual polymer chain can be within the range defined by any lower and upper limits as described above. It will be understood 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 characteristics.

[0121] The conductive polymer or its salt produced by this 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 can be in a range defined by any lower and upper limits as described above. It will be understood that lower molecular weight products may provide undesirable levels of toxicity and higher molecular weight products may have reduced processability. Again, it is desirable to balance toxicity reduction with practical processability.

[0122] The conductive polymer may be a copolymer. The conductive polymer can be selected from the group consisting of polyarylamine, polyarylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, and poly(3,4-ethylenedioxythiophene). In at least some examples, the polymer or copolymer can be selected to provide further improved processability. In at least some examples, a polyaniline polymer can provide improved conductivity over an aniline copolymer. It will be understood that the conductive polymer includes any of its salts and can be formed by reaction with a protonic acid. The conductive polymer can be a reaction product of an unsubstituted or substituted monocyclic, bicyclic, or tricyclic heteroaryl monomer containing at least one cyclic heteroatom selected from N and S. The conductive polymer can be a 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 will be understood that the reaction product can include the reaction of a protonic acid and a free radical initiator.

[0123] Polypyrrole and polyazepine are examples of conductive polymers prepared from the reaction products of monocyclic heteroaryls containing at least one heteroatom selected from N. Polyindole is an example of a conductive polymer prepared from the reaction product of a bicyclic heteroaryl containing at least one heteroatom selected from N. Polycarbazole is an example of a conductive polymer prepared from the reaction product of a tricyclic heteroaryl containing at least one heteroatom selected from N. Polyarylamines such as polyaniline are examples of conductive polymers prepared from the reaction products of monocyclic aryl monomers 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 heteroaryl 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 heteroaryl containing at least one heteroatom selected from S. Polyphenylene sulfide is an example of a conductive polymer prepared from the reaction product of a monocyclic aryl monomer 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 a salt, such as a polyaniline emeraldine salt. The polyaniline base or salt may be further treated to a 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 / violet). The repeating unit of Equation 1a below provides x as half of the degree of polymerization. TIFF0007691483000001.tif30170

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

[0128] Polyphenylene Sulfide This continuous flow process can be used to form polyphenylene sulfide. Polyphenylene sulfide is an organic polymer containing aromatic rings bonded to sulfide moieties. The repeating unit of Equation 2a below provides an example of the repeating unit of polyphenylene sulfide. TIFF0007691483000002.tif27170

[0129] Polyphenylene sulfide can be converted into a semiconductor form by oxidation or the use of various dopants. Polyphenylene sulfide also provides high heat resistance, chemical resistance, fluidity, dimensional stability, and electrical properties.

[0130] Polypyrrole The polypyrrole monomer can be used in this continuous flow process and polymerized to form polypyrrole. Polypyrrole is a conductive organic polymer. The repeating unit of the following formula 3a provides an example of the repeating unit of polypyrrole. TIFF0007691483000003.tif34170

[0131] The oxidized form of polypyrrole is an excellent conductor. By doping polypyrrole with a large anion such as tosylate, a higher conductivity can be achieved.

[0132] Polycarbazole The polycarbazole monomer can be used in this continuous flow process and polymerized to form polycarbazole. Polycarbazole is a conductive polymer in the doped state. The repeating unit of the following formula 4a provides an example of the repeating unit of polycarbazole. TIFF0007691483000004.tif41170

[0133] When doped, the nitrogen of polycarbazole is oxidized ahead of the main chain, which can produce a high local charge and good electrical conduction properties.

[0134] Polyaniline The indole monomer can be used in this continuous flow process and polymerized to form polyaniline. Polyaniline is a conductive polymer containing a benzene ring bonded to a pyrrolitic ring. The repeating unit of the following formula 5a provides an example of the repeating unit of polyaniline. TIFF0007691483000005.tif34170

[0135] Polyazepine The azepine monomer can be used in this continuous flow process and can be polymerized to form polyazepine. The repeating unit of the following formula 6a provides an example of the repeating unit of polyazepine. TIFF0007691483000006.tif46170

[0136] Polythiophene The thiophene monomer can be used in this continuous flow process and can be polymerized to form polythiophene. Polythiophene becomes conductive when oxidized (doped). The repeating unit of the following formula 7a provides an example of the repeating unit of polythiophene. TIFF0007691483000007.tif34170

[0137] The conductivity of polythiophene is due to the delocalization of electrons along the polythiophene backbone. Also, polythiophene has excellent optical properties including color shifts in response to various environmental stimuli and changes in solvent, temperature, and applied potential. Both the change in color and the change in conductivity are caused by the twist of the polymer backbone, which disrupts conjugation.

[0138] Poly(3,4-ethylenedioxythiophene) The 3,4-ethylenedioxythiophene monomer can be used in this continuous flow process and can be 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 repeating unit of the following formula 8a provides an example of the repeating unit of poly(3,4-ethylenedioxythiophene). TIFF0007691483000008.tif50170

[0139] Poly(3,4-ethylenedioxythiophene) has excellent optically transparent properties in its conducting state, high stability, moderate bandgap, and low redox potential.

[0140] Poly(3,4-propylenedioxythiophene) The 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 repeating unit of the following formula 9a provides an example of the repeating unit of poly(3,4-propylenedioxythiophene). TIFF0007691483000009.tif54170

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

[0142] The conductive polymer and the polymerizable organic monomer are described in more detail below in relation to the steps of the continuous flow process.

[0143] (A) Organic flow 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 the protonic acid can be introduced into the organic stream as a neat or an organic solution containing an organic solvent. It will be appreciated that the protonic acid can provide a reagent for converting an organic monomer such as aniline into a polymerizable monomer salt such as anilinium ion. Thereafter, for example, when polymerization of aniline or its monomer salt is initiated using an oxidizing agent to form polyaniline, the monomer salt can be polymerized to form a conductive polymer or a precursor thereof. 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 may be a polymerizable organic monomer salt that is soluble in an organic solvent. As described below, the organically soluble polymerizable organic monomer salt can be prepared in situ as a reaction product in the organic stream by reaction with a protonic acid (i.e., H - ) having a counter ion (i.e., M + M - ) that provides charge neutrality to the polymer, and can also enhance the solubility of the conductive polymer in the organic solvent to assist 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) mixing 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 unsubstituted or substituted aniline; and a3) mixing 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 protic acid. For example, the non-aqueous organic solution may contain one or more organic solvents, an unsubstituted or substituted aniline or a salt thereof, and a protic acid. The organic solvent may be selected from any one or more of the organic solvents described herein, such as an alcohol like 2-butoxyethanol. The organic stream may optionally contain a polymerizable organic monomer as a neat organic liquid together with one or more organic solvents. The polymerizable organic monomer may be an organic monomer salt, or a precursor mixture of an organic monomer (such as aniline) and a protic acid (such as 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 the polymerizable organic monomer at a concentration of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99 (weight % of the total organic stream). The organic stream may contain the organic monomer and the protic 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 (weight % of the total weight of the organic monomer and the protic acid in the total organic stream). The organic stream can be formed by mixing a monomer stream and a protic acid stream. The monomer stream may contain the polymerizable organic monomer at a concentration of at least 70, 80, 85, 90, 95, 98, or 99 (weight % of the total monomer stream). In one example, the monomer stream is provided by a neat organic liquid of a polymerizable organic monomer such as aniline. The protic acid stream may contain the protic acid at a concentration of at least 30, 40, 50, 60, 70, 80, 85, 90, 95, 98, or 99 (weight % of the total protic acid stream). It will be understood that the one or more organic solvents described herein can provide the remaining volume or weight % of the organic stream, other than any possible impurities present.

[0147] Polymerizable organic monomer As described above, the conductive polymer prepared by the present continuous flow process can be selected from any conductive polymer that is a reaction product of a protonated polymerizable organic monomer or a salt thereof and a free radical initiator. For example, the conductive polymer can be selected from the group consisting of polyarylamine, polyarylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), and poly(3,4-propylenedioxythiophene).

[0148] Accordingly, the polymerizable organic monomer may be an unsubstituted or substituted monocyclic, bicyclic or tricyclic heteroaryl monomer containing at least one cyclic 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 can 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, for example unsubstituted or substituted aniline. In another example, the polymerizable organic monomer is a bicyclic heteroaryl containing at least one heteroatom selected from S, for example 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 aniline-sulfate such as aniline-DNNSA.

[0151] The polymerizable organic monomer of 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 may 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 may be unsubstituted or substituted.

[0152] Aniline monomer According to the examples described herein, the aniline monomer can be unsubstituted or substituted aniline.

[0153] The unsubstituted or substituted aniline monomer has the formula 1b: TIFF0007691483000010.tif43170[wherein, 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] and can be selected from the compounds of.

[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, and the remaining groups are as defined above.

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

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

[0157] The unsubstituted or substituted polyphenylene sulfide monomer has the formula 2b: TIFF0007691483000011.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] can be selected from the compounds of.

[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 monomer has the formula 3b: TIFF0007691483000012.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 6each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl] from the compounds of.

[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 monomer has the formula 4b: TIFF0007691483000013.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 each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl] from the compounds of.

[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 monomer has the formula 5: TIFF0007691483000014.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 is independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl] from the compounds of.

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

[0165] The unsubstituted or substituted azepine monomer has the formula 6b: TIFF0007691483000015.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] from the compounds of.

[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 monomer has the formula 7b: TIFF0007691483000016.tif33170[In the above formula, R 3 、R 4 、R 5 or R 6each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl] from the compounds of.

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

[0169] The unsubstituted or substituted 3,4 - ethylenedioxythiophene monomer has the formula 8b: TIFF0007691483000017.tif47170[In the above formula, R 3 R 4 R 5 R 6 R 7 and R 8 each independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl] from the compounds of.

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

[0171] The unsubstituted or substituted 3,4 - propylenedioxythiophene monomer has the formula 9b: TIFF0007691483000018.tif53170[In the above formula, R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R10 is independently selected from the group consisting of hydrogen, halo, hydroxy, nitro, amino, alkyl, haloalkyl, alkyloxy, carboxy, arylalkyl, and alkylaryl] from the compounds of.

[0172] organic solvent The organic solvent is selected to provide a carrier for the polymerizable organic monomer, such as an 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 various water-immiscible solvents. The non-aqueous organic solvent can provide an emulsion containing an aqueous stream rather than a single phase, and thus is immiscible with the aqueous stream or phase.

[0174] The organic solvent can be selected from the group including aromatic, chlorinated aromatic, chlorinated aliphatic hydrocarbon, aliphatic hydrocarbon, glycol, ether, glycol ether, ester, alcohol, and ketone. The alcohol can be a water-immiscible alcohol having at least a medium alkyl chain or aryl group. The water-immiscible alcohol can be n-butanol or an alcohol with a larger alkyl chain. The ketone can be a water-immiscible ketone having at least a medium-chain ketone 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 aromatic, halogenated aromatic, halogenated aliphatic hydrocarbon, aliphatic hydrocarbon, glycol, ether, glycol ether, ester, alcohol, ketone, or a combination thereof. In another example, the organic solvent can be selected from the group consisting of glycol, ether, glycol ether, and combinations thereof.

[0176] The organic solvent can also be selected to dissolve the acid dopant (i.e., 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, i.e., without dilution with an organic solvent, or in a concentrated form. In at least some examples, using a more concentrated or solvent-free protonic acid can increase the reaction rate, shorten the reaction time, and improve the product throughput. This can also increase the heat of reaction and potentially lead to a loss of control of polymerization due to the temperature rise, but this can be compensated for according to the embodiments or examples of the continuous flow process described herein. The temperature rise or lack of temperature control can lead to a decrease in reproducibility between batches, a decrease in the molecular weight of the polymer, and consequently a decrease in the conductivity of the polymer.

[0177] Following the reaction process, an organic solvent can be used to dilute the product to obtain the desired final concentration and properties.

[0178] Other suitable exemplary liquid solvents include aromatics such as xylene, toluene or alkylnaphthalene; chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffin (e.g., mineral oil fraction); alcohols such as butanol, isobutanol or glycol, and their ethers and esters, such as 2-butoxyethanol; and 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 understood that the protonic acid is selected to provide a proton source that promotes the formation of a polymerizable organic monomer salt that can itself polymerize, for example, onto a conductive polymer 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 the emulsion of aqueous and organic streams.

[0180] The protonic acid can be selected from the group consisting of sulfonic acid, phosphoric acid, phosphonic acid, boric 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 basic 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 of the examples described herein, the continuous flow process enables the in situ (i.e., in the flow) formation of an organic soluble polymerizable monomer salt that can itself polymerize into an organic soluble conductive polymer form that is more readily processable during the continuous flow process.

[0181] The protonic acid can be selected from the group consisting of dinonylnaphthalene sulfonic acid (DNNSA), dinonylnaphthalene disulfonic 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 dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, and p-toluenesulfonic acid, or any mixture thereof. The protonic acid can be dinonylnaphthalene sulfonic acid (DNNSA).

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

[0183] Concentration and ratio of the organic stream The concentration (mol / L) of the polymerizable organic monomer in the organic stream can range from 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 a range defined by any two of the above maximum and / or minimum values. Increasing the concentration of the organic monomer in the solution improves the polymerization rate and throughput of the process, but also increases impurities and may cause more detrimental exotherms that can degrade the product obtained from the process.

[0184] In a further example regarding the preparation of polyaniline, the concentration (mol / L) of aniline or its salt can range from 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 its emulsion stream) can be in a range defined by any two of the above maximum and / or minimum values.

[0185] The concentration (mol / L) of the protonic acid in the organic stream can range from 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 a range defined by any two of the above maximum and / or minimum values.

[0186] In a further example where the protonic acid is an organically soluble protonic acid (e.g., DNNSA), the concentration (mol / L) of the organically soluble protonic acid can be defined in a range of about 0.02 to 5, such as in a range of about 0.3 to 3, 0.4 to 2, or 0.5 to 1. The concentration (mol / L) of the organically 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 organically 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 organically soluble protonic acid in the organic stream can be in a range defined by any two of the above maximum and / or minimum values.

[0187] The molar ratio of the protonic acid to the 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 the protonic acid to the polymerizable organic monomer can be in a range of 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 act simultaneously, for example, as a surfactant (emulsifier) and as a protonating agent for the resulting PANI-protonic acid complex. Changing the ratio of the protonic acid to the organic monomer will affect both the molecular weight and solubility of the resulting polymer.

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

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

[0190] Free radical initiator It will be appreciated that the free radical initiator may be an oxidant such as ammonium persulfate. The oxidant provides a reagent for initiating the polymerization of polymerizable monomer salts, such as the polymerization of anilinium monomer to polyaniline.

[0191] The oxidant can 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 oxidant can be selected from the group consisting of APS, potassium dichromate, potassium iodate, ferric chloride, ferric tosylate, potassium permanganate, potassium bromate, potassium chlorate, ammonium cerium nitrate, cerium sulfate.

[0193] In one example, the oxidant is ammonium persulfate (APS). In at least some examples, APS can provide overhead reduction 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 a range defined by any two of the above maximum and / or minimum values, e.g., 0.4 to 4, 0.7 to 3, or 0.5 to 1.5.

[0195] In a further example, the ratio of the polymerizable organic monomer to the free radical initiator can be in the range of about 1:10 to 4:1, e.g., 1:2 to 2:1, or 1:1 to 2:3. In a further example for preparing polyaniline, the ratio of the aniline monomer or its salt to the free radical initiator (e.g., APS) can be in the range of 1:1 to 1.5, e.g., 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 mainly containing water. For example, the aqueous solvent system may contain at least 50, 60, 70, 80, 90, 95, 98, or 99 amounts of water (by weight of the total aqueous solvent system). The remainder of the aqueous solvent system may contain other solvents or incidental impurities.

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

[0198] When the acidifying agent stream is an aqueous stream, a product stream can be provided for synthesizing a conductive polymer or a salt thereof that includes an emulsion formed by mixing an aqueous stream containing a free radical initiator and an organic stream containing a polymerizable organic monomer in a continuous flow by mixing the organic stream and the aqueous stream.

[0199] The product stream can provide for the synthesis of a conductive polymer as described above. The conductive polymer can be organically 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 an organic solvent. For example, the salt form can be prepared from a protonic acid that is a hydrophobic organic acid. The hydrophobic organic acid can provide counterions to a monomer or polymer that enable solubility in at least some organic solvents in the protonated form of neutrality. The conductive polymer can be a copolymer or a polymer blend. For example, with respect to polyaniline, the conductive polymer can be formed from a monomer salt to provide a polyaniline emeraldine salt, which can be soluble in an organic solvent and more easily processable.

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

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

[0202] The concentration of the polymerizable organic monomer in the product stream exiting the temperature-controlled continuous flow reactor may be negligible and can be below the limit of detection (LOD) using a 400 MHz nuclear magnetic resonance (NMR) spectrometer under standard conditions, such 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 the conductive polymer can 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 monomers can polymerize to low molecular weight products such as dimers or smaller oligomers. The low molecular weight products can be removed by subsequent treatments such as an aqueous washing process. A high conversion of the polymerizable organic monomer to the conductive polymer is desirable not only for the economics of the process but also to ensure that no significant amount of monomers or low molecular weight products that are known to be harmful remain in the final polymer product.

[0203] The composition and components of the conductive polymer material can also be described by its dispersity value (also called the polydispersity index - PDI), which indicates the distribution of the 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 understood that the weight average molecular weight and the number average molecular weight can be determined from a sample mixture of the conductive polymer by various chromatography or spectroscopy methods such as HPLC or NMR.

[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 may be provided in the range between any two values of these upper and lower limits, as described above. A lower polydispersity can provide more consistency in properties including the solubility of the conductive polymer.

[0205] The conductive polymer can have a bulk sample conductivity (untreated thin film measured at 20 °C) between about 1×10 -6 S / cm and 1×10 -2 S / cm. For example, the conductivity of the bulk sample (untreated thin film measured at 20 °C) can be at least about 1×10 -5 S / cm, 1×10 -4 S / cm, or 1×10 -3 S / cm.

[0206] The conductive polymer can have a bulk sample conductivity (thin film treated with isopropanol measured at 20 °C) between about 0.1 S / cm and 15 S / cm. The bulk sample conductivity (thin film treated with isopropanol measured at 20 °C) can be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 S / cm. It is known that treating the conductive polymer film with isopropanol removes excess dopants from the film and improves the charge transfer of the remaining polymer, thus improving the conductivity of the thin film.

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

[0208] The operating temperature for preparing a conductive polymer in a continuous flow process can be set to operate within a narrow temperature range, e.g., 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, e.g., about 5°C, 4°C, 3°C, 2°C or less than 1°C. In one example, the reaction temperature within the product stream is maintained between about -5°C and 5°C and the temperature variation during the reaction is less than about 5°C. In another example, the reaction temperature within the product stream is maintained between about -3°C and 3°C and the temperature variation during the reaction is less than about 3°C. In another example, the reaction temperature within the product stream is maintained at 0°C and the temperature variation during the reaction is less than about 1.0°C. The above temperature ranges and variations may be applied to any individual or mixed stream, e.g., an emulsion stream and / or a product stream. In one specific example, the temperature range and / or temperature variation may be applied over the axial flow length of a tubular reactor containing an emulsion stream and / or a product stream. The polymerization temperature strongly affects 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 described above, it is also important to control the temperature fluctuations during the reaction. Surprisingly, improved control of the temperature, including fluctuations in the axial flow length, has been shown to provide conductive polymers from product streams having 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" can include oligomers up to about 20 monomer units, e.g., oligomers of 10 monomer units or less, particularly dimers, trimers, and tetramers. The amount of polymerizable organic monomer or low molecular weight product in the product stream can be less than 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001 (wt% of the product stream). Further treatment of the product stream can further reduce the low molecular weight products or other undesirable impurities from any organically 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 - 3.0 h (varies depending on the mixing efficiency). In other examples, the residence time of the product stream is between about 0.75 h - 2.0 h, 0.8 h - 1.5 h, or 0.85 - 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 the range between any two of these upper and / or lower limit values. The residence time is determined by the reaction rate and the shape of the continuous flow reactor, 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 about 1 to 1000, 2 to 500, 3 to 300, 4 to 200, or 5 to 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 exceed 1, 5, 10, 15, 20, 25, 50, or 75 (ml / min). The flow rate can be within a range defined by any two of these upper and / or lower limit values.

[0211] In one example, the flow velocity (m / s) may be in the range of about 0.001 to 0.1, 0.005 to 0.5 or 0.01 to 0.05. The flow velocity (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 velocity (m / s) may exceed 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, or 0.01. The flow velocity can be within a range defined by any two of these upper and / or lower limit values.

[0212] In the case of a continuous flow tubular reactor, the inner diameter of the tubular reactor may be at least about 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm. The inner diameter of the tubular reactor may be about 2 to 25 mm, 5 to 20 mm, or 5 to 10 mm. The inner diameter of the tubular reactor and the design of the static mixer affect the mixing performance of the reactor. At a given flow rate, a smaller diameter tube has a higher shear force and a greater turbulent flow than a larger diameter tube, resulting in a higher mixing efficiency.

[0213] For a continuous flow process or system, the minimum inner diameter of any part of the continuous flow system can be at least about 1 mm, 2 mm, 3 mm, 4 mm, or 5 mm. The inner diameter of any part of the continuous flow system may be between about 1 - 25 mm, 2 - 15 mm, or 5 - 10 mm. To vary the mixing performance, the diameter of parts of the continuous flow system can be changed. To enhance the mixing performance and generate a fine emulsion, a section of tubing containing a static mixer with a smaller diameter than the main tubular reactor system can be used.

[0214] This process can provide at least about 30 g of conductive polymer per hour of operation. For example, the operating performance is for a continuous flow reactor volume of about 100 ml - 3000 ml. In one example, this 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 hour of operation per liter of the internal volume of the tubular reactor. It will be understood that higher productivity provides further economic and supply advantages.

[0215] The space time yield (STY, unit: 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 in grams of conductive polymer synthesized per liter of the emulsion or product stream passing through the reactor per hour. STY can be calculated using the following formula. TIFF0007691483000019.tif46170

[0216] In one example, the STY is at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, or 130 of a conductive polymer or a conductive polymer salt. In another example, the STY is a conductive polymer or a conductive polymer salt of less than about 130, 125, 120, 115, 110, 105, 100, 95, 90 or 85. The STY can be in a range defined by any two of these upper and / or lower limit values, for example, between about 50 - 130, 60 - 125 or 70 - 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 may 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 - 100,000, 20,000 - 100,000, 30,000 - 100,000, 40,000 - 100,000, 50,000 - 100,000, or 60,000 - 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 in a range defined by any lower and upper limits as described above. It will be understood that lower molecular weight products may provide undesirable levels of toxicity and higher molecular weight products may have reduced processability.

[0219] The composition and components of the conductive polymer material can also be described by its dispersity value (also called the 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 it by the number average molecular weight. It will be understood that the weight average molecular weight and the number average molecular weight can be determined from a sample mixture of the conductive polymer by various chromatography or spectroscopy 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 may be provided in a range between any two values of these upper and lower limits as described above. A lower polydispersity can provide more consistency in properties including the solubility of the conductive polymer.

[0221] The prepared polyaniline emeraldine salt can have a bulk sample conductivity (untreated thin film measured at 20 °C) between about 1x10 -6 S / cm and 1x10 -2 S / cm. For example, the conductivity of the bulk sample (untreated thin film measured at 20 °C) can be at least about 1x10 -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 for a thin film treated with isopropanol) between about 0.1 S / cm and 10 S / cm. The bulk sample conductivity (measured at 20 °C for a thin film treated with isopropanol) can be at least about 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 S / cm. It is known that treating the polyaniline film with isopropanol removes excess dopant from the film and improves the charge transfer of the remaining polymer, thus improving the conductivity of the thin film.

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

[0224] The concentration of aniline (unreacted aniline) in the product stream may be negligible and can be below the detection limit (LOD) using a 400 MHz nuclear magnetic resonance (NMR) spectrometer under standard conditions as determined, for example, by NMR spectroscopy. The product stream may be substantially free of unreacted aniline. The conversion rate (or yield) of aniline monomer to polyaniline can be at least about 80%, 85%, 90%, 95%, 98%, 99%, or 99.9%. It will be understood that a portion of the aniline polymerizes to form dimers or smaller oligomers that can be removed by subsequent treatments such as an aqueous washing process. A high conversion rate of aniline monomer to polyaniline is desirable not only for the economics of the process but also to ensure that no significant amount of aniline monomer or oligomers, which are known to be harmful, remain in the final polymer product.

[0225] In the case of preparing polyaniline, examples of suitable molar ratios of aniline monomer, protonic acid (e.g., DNNSA), and free radical initiator (e.g., APS) are aniline (1.0 equivalent), DNNSA (1.0 equivalent to 4.0 equivalents), and APS (0.5 equivalent to 2.0 equivalents). For example, this ratio may be aniline (1.0 equivalent), DNNSA (1.5 equivalents), and APS (1.2 equivalents).

[0226] It will be appreciated that previous examples regarding process conditions for conductive polymers and polymerizable organic monomers are also applicable to the process of preparing polyaniline from aniline or its salts. For example, any one or more of the above operating temperatures, residence times, flow rates, yields, and pipe diameters can 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 its salt. 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 having one or more passages in fluid communication for carrying reactant and product streams. At least a portion of the one or more passages may be configured to enhance mixing of the flow, for example, a static mixer configuration enhances radial mixing or chaotic advection or emulsion formation.

[0228] A continuous flow reactor (also referred to as a continuous flow chemical reactor) can include one or more chamber sections that are 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 to be inserted into the continuous flow chemical reactor and may be referred to as "static mixer inserts". The static mixer elements or inserts can be provided in the form of one or more modules. It will be understood that the static mixer can be provided as an integral part of the chemical reactor. The static mixer and the 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 the 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 also be understood that the static mixer or its reactor can include one or more reactant inlets for supplying one or more fluid reactants to the chamber section and one or more outlets that are in fluid communication with the static mixer for receiving an output stream containing the products of the reaction. It will be understood that a continuous flow mixer includes at least one mixing element (e.g., a static or dynamic mixer). It will also be understood that a continuous flow mixer including a static mixer can comprise a static mixer or static mixer element according to any embodiment or example as described herein.

[0229] A static mixer can provide an integral element as part of a chemical reaction chamber. A static mixer element for a continuous flow chemical reactor chamber can include an optional catalytically active support defining a plurality of passages configured to disperse and mix one or more fluid reactants during flow through the mixer and during its reaction. The surface of the support can optionally include a catalytic material. 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 support.

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

[0231] A continuous flow process or a temperature-controlled continuous flow reactor can 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] The static mixer element may be configured to enhance mixing (such as chaotic advection) and heat transfer characteristics in order to redistribute fluid in a direction transverse to the main flow, for example, radially and tangentially or azimuthally with respect to the central longitudinal axis of the static mixer element. The static mixer element may be configured to enhance mixing of reactant streams, chaotic advection, or emulsion formation, or to efficiently promote heat transfer away from or to the fluid. The static mixer element may have various geometric configurations or aspect ratios for correlation with specific applications. The static mixer element may be configured for use in turbulent flow rates, for example, to enhance turbulent flow and mixing, even in or near the inner surface of the reactor chamber housing. It will also be understood that the static mixer element can be configured to improve the heat and mass transfer characteristics of both laminar and turbulent flows.

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

[0234] The static mixer element, scaffold, reactor chamber, or continuous flow reactor composed of these can be formed by additive manufacturing, as will also be described in the following sections. The static mixer may be an additively manufactured static mixer. The additive manufacturing of the static mixer and any 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 is physically tested for reliability and performance and may optionally be redesigned and reconfigured using additive manufacturing (e.g., 3D printing) techniques. Additive manufacturing provides the flexibility of pre-design and testing, and 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 be varied according to the application. The static mixer or the continuous flow reactor including the static mixer may be tubular. The static mixer, continuous flow mixer, or continuous flow reactor can have a diameter (mm) in the range of, for example, 1 to 1000, 2 to 500, 3 to 250, 4 to 150, or 5 to 100. 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 less than about 1000, 750, 500, 250, 200, 150, 100, 75, 50, 25, or 10. The aspect ratio (L / d) of the static mixer element, mixer, reactor, or reactor chamber including the static mixer element may be provided in a range suitable for the industrial scale flow rate of a particular reaction. The aspect ratio can 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 can 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 can be, for example, greater than about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 50, 75, or 100.

[0236] A static mixer element, continuous flow mixer or continuous flow reactor may be configured to enhance properties such as mixing (e.g., chaotic advection and emulsion formation) and heat transfer with respect to laminar or turbulent flow rates. In the case of a Newtonian fluid flowing within a hollow pipe, it will be understood that the correlation of Reynolds number (Re) values with laminar and turbulent flow will typically provide laminar flow, where Re < 2300, transitional flow where 2300 < Re < 4000, and general turbulent flow where Re > 4000. A static mixer element, continuous flow mixer or continuous flow reactor may 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 typical 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 typical turbulent Re range of about 1000 - 15000, 1500 - 10000, 2000 - 8000, or 2500 - 6000.

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

[0239] In one embodiment, the static mixer element may be configured to operate at a Péclet (Pe) value 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 can be configured to operate at a Péclet (Pe) value of about 10 8 , 10 7 , 10 6 , 500000, 250000, 100000, 75000, 50000, 25000, 20000, 15000, 10000, 5000, 2000, or less than 1000. The static mixer element can be about 10 3 ~108 、 10 3 ~10 7 、 or 10 4 ~10 6 It can be configured to operate within the Pe range of. The static mixer element may be configured to operate within the Pe range between any two of the above upper and / or lower limit values.

[0240] The volume displacement % of the continuous flow reactor or static mixer with respect to the reactor chamber for accommodating the mixer can be in the range of 1 to 40, 2 to 35, 3 to 30, 4 to 25, 5 to 20, or 10 to 15. The volume displacement % of the continuous flow reactor or static mixer with respect to the reactor chamber for accommodating the mixer may be less than 40%, 35%, 30%, 25%, 20%, 15%, 10% or 5%. Generally, as the volume displacement of the continuous flow reactor or static mixer with respect to the reactor chamber for accommodating the mixer increases, the pressure drop (i.e., the pressure difference or back pressure) will also increase. A larger pressure drop increases the design requirements of the continuous reactor system to safely accommodate the increased system pressure. Furthermore, a large volume displacement effectively narrows the fluid passageways within the reactor system. This flow restriction is not only the cause of the above-mentioned pressure drop but also may 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] The configuration of the continuous flow reactor or static mixer may be provided to enhance cross-sectional microscopic (CSM) turbulent flow. Such turbulent flow can result from various sources including the CSM geometry or the microscopic surface roughness of the CSM resulting from 3D printing processes and / or surface coatings. For example, the length scale of the turbulent flow may be reduced to provide better mixing. The turbulent flow length scale can be, for example, within the range of microscopic length scales.

[0242] The configuration of the continuous flow reactor or static mixer may be provided to enhance the heat transfer characteristics within the reactor, such as the reduced temperature difference at the outlet cross-section. The heat transfer of the CSM may provide a cross-sectional or lateral temperature profile having a temperature difference of less than, for example, 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] The continuous flow reactor, static mixer or its scaffold may be configured such that the pressure drop (Pa / m) across the entire static mixer during use is in 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 entire 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. The continuous flow reactor or static mixer can be configured to provide a lower pressure drop compared to a specific flow rate. In this regard, static mixers, reactors, systems and processes as described herein may provide parameters suitable for industrial applications. The above pressure drop 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 comprises a heat exchanger for controlling the temperature of the reactor, chamber section, catalytic static mixer or their fluid components. The heat exchanger may be of shell and tube heat exchanger design or configuration. The shell and tube heat exchanger design may provide improved heat transfer characteristics.

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

[0247] (E) System Also provided is a system for performing a continuous flow process as described herein. The system includes a continuous flow reactor that receives an organic stream and an oxidant stream for synthesizing a conductive polymer or any salt thereof and reacts them together. The continuous flow reactor can be provided according to any of the examples described herein, such as a continuous flow tubular reactor. The organic stream includes an organic solvent, a polymerizable organic monomer, and a protic acid. The oxidant stream includes an aqueous or organic solvent and a free radical initiator. The oxidant and the organic stream can be provided according to any of the examples described herein. The system further includes one or more pumps for providing a fluid flow to the organic stream, the oxidant stream, and the product stream passing through the continuous flow reactor.

[0248] The system may also include a temperature control device for the continuous flow reactor. The temperature control device can cooperate with the continuous flow reactor. Also, the system may include one or more heat exchangers for controlling the temperature of the flow within the continuous flow reactor so as to be effective for synthesizing a conductive polymer or any salt thereof. The temperature control device can cooperate with one or more heat exchangers for controlling the temperature of the continuous flow reactor, the organic stream, the emulsion stream, the oxidant stream, the aqueous stream, and / or the product stream, as well as the continuous flow reactor.

[0249] The present system can also include control means for controlling one or more parameters of the present system selected from the concentration, flow rate, temperature, pressure, and residence time of one or more streams, 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 a salt thereof, which a) a temperature-controlled continuous flow reactor comprising at least one mixing element for forming an emulsion; b) one or more pumps for providing a fluid flow to one or more flows 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 cooperating with the temperature-controlled continuous flow reactor and one or more heat exchangers to control the temperature of the flow within the temperature-controlled continuous flow reactor effective for the synthesis of a conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from the concentration, flow rate, temperature, pressure, and residence time of one or more flows, fluid reactants, sources of fluid reactants, fluids, or products of the reaction comprises.

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

[0252] The temperature-controlled continuous flow reactor (see, e.g., D in FIG. 3) 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 may be provided within the continuous flow reactor and / or externally in fluid communication (see, e.g., C in FIG. 3). The mixing element can facilitate the formation, maintenance and / or enhancement of emulsions and / or emulsions from the product stream. The reactor is operated at a temperature effective to synthesize the conductive polymer or any salt thereof, and a product stream containing the conductive polymer or any salt thereof can be provided within the continuous flow reactor. In one example, the mixer element may be configured for use at turbulent flow rates, such as by enhancing and mixing the turbulent flow. It will also be understood that the mixer element can be configured to improve 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 to the organic stream, oxidant stream, and product stream passing through the continuous flow reactor. The pump can be an in-line pump, rotary pump, centrifugal pump, or motor-driven pump. In one example, the pump is an in-line pump.

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

[0255] The temperature control device can cooperate with a continuous flow reactor and one or more heat exchangers to control the temperature of the flow within the continuous flow reactor effective for the synthesis of a conductive polymer or any salt thereof. The temperature control device can be automatic or manual, such as for example, a sensor and computer control options (e.g., G in Figure 3). The temperature control device can be associated with the control means of the system. The temperature control device can control heating or cooling to maintain, for example, a substantially constant temperature.

[0256] The control means can be provided to control one or more parameters of the system selected from one or more of the flow, fluid reactant, source of fluid reactant, carrier fluid, or concentration, flow rate, temperature, pressure, and residence time of the product of the reaction. The control means can be manual or automatic, such as for example, computer - control options (see H in Figure 3 with respect to the control of the pump of A2).

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

[0258] The system can 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 reactor, reactor chamber, chamber section, and static mixer may each be provided in modular form for their complementary association. The system may include a plurality of reactors that can have similar or different internal and / or external configurations. The reactors can be operated in series or in parallel. It will be appreciated that the system, reactor, or each chamber section may include one or more inlets and outlets for providing a feed of reactants, obtaining a product, 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 supply conduits to provide any one or more of the flow inputs as described herein (see FIG. 3). The supply conduit can fluidly connect a temperature controlled continuous flow reactor to one or more other continuous flow reactors such as a continuous flow mixer (e.g., a tubular reactor including a static mixer element) including a mixing element. The supply conduit or continuous flow mixer can provide any one or more of the flows described herein that are mixed at or proximate to one or more inlets of the temperature controlled continuous flow reactor. In one example, the supply conduit is a tubular reactor, which may 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 being 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 including at least one mixing element and being 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 that is in fluid connection 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 being in fluid connection with a temperature-controlled continuous flow reactor.

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

[0264] Continuous flow mixers, 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 in length) that includes one or more static mixer elements (e.g., each about 15 cm in length), for example, two static mixer elements connected within the tubular conduit. In other examples, the continuous flow mixer is a continuous flow static mixer that includes 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 a salt thereof, which a) a temperature-controlled continuous flow reactor comprising at least one static mixer element for use in mixing an organic stream and an oxidant to form an emulsion and forming a product stream comprising a conductive polymer or a salt thereof during flow within the reactor; b) one or more pumps for providing a fluid flow to one or more flows passing through a temperature-controlled continuous flow reactor; c) one or more heat exchangers for controlling the temperature of a temperature-controlled continuous flow reactor; d) a temperature control device for cooperating with a temperature-controlled continuous flow reactor and one or more heat exchangers to control the temperature of the flow within the temperature-controlled continuous flow reactor effective for the synthesis of a conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from the concentration, flow rate, temperature, pressure, and residence time of one or more flows, fluid reactants, sources of fluid reactants, fluids, or products of the reaction comprising.

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

[0267] In another example, there is a system for providing a continuous flow process for the controlled synthesis of a conductive polymer or a salt thereof, which a1) a first continuous flow reactor comprising at least one static mixer element for use in mixing 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 mixing the organic stream and optionally a 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 comprising at least one static mixer element for use in forming a product stream comprising a conductive polymer or a salt thereof from an emulsion stream during flow in the reactor; b) one or more pumps for providing a fluid flow to one or more flows 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 cooperating with the temperature controlled continuous flow reactor and one or more heat exchangers to control the temperature of the flow in the temperature controlled continuous flow reactor effective for the synthesis of a conductive polymer or any salt thereof; and e) control means for controlling one or more parameters of the system selected from the concentration, flow rate, temperature, pressure, and residence time of one or more flows, fluid reactants, sources of fluid reactants, fluids, or products of the reaction comprising.

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

[0269] (G) Recovery and next treatment 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. For example, PANI-DNNSA can be precipitated as a green fine powder. In the case of PANI-DNNSA, this can be recovered by filtration and thoroughly washed with acetone before drying to obtain PANI-DNNSA, for example, at a yield of at least about 50, 60, 70, 80, or 90%.

[0271] From a small portion of PANI-DNNSA, a concentrate, for example, a 70% (w / v) solution, can be made by thin film casting in toluene. The film is dried overnight in an oven at, for example, 100 °C, then washed (e.g., with propanol) and air dried. The resulting thin film may have a thickness of 5 - 20 μm (e.g., 8 μm). It was found that the 8.25 μm thick PANI-DNNSA film produced by this method has a conductivity of 0.6 S / cm.

[0272] (H) Conductive polymer and its materials Conductive polymers can be used in materials such as compositions, formulations, coatings such as dissipative coatings, and 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 aircraft exterior panels.

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

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

[0275] Many modifications of the examples described herein will have the advantages of the foregoing description as well as the teachings presented in the associated drawings and figures and will be apparent to those of ordinary skill in the art to which this disclosure pertains. Accordingly, it is to be understood that this disclosure is not to be limited to the specific examples illustrated and that modifications and other examples are intended to be included within the scope of the appended claims. Further, although the foregoing description and the associated drawings and figures illustrate the examples of the disclosure in the context of specific exemplary combinations of elements and / or functions, it is to be understood that different combinations of elements and / or functions can be provided by 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 a salt thereof, comprising supplying an emulsion of a polymerizable organic monomer, a protonic acid, and a free radical initiator into a temperature-controlled continuous flow reactor having at least one mixing element at a temperature effective to synthesize the conductive polymer or a salt thereof and provide a product stream containing the conductive polymer or a salt thereof. Clause 2. The continuous flow process of Clause 1, further comprising obtaining the conductive polymer or a 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. Clause 4. a) providing a polymerizable organic monomer and a protonic acid in an organic stream containing an organic solvent; b) providing a free radical initiator in an oxidizing agent stream containing an aqueous or organic solvent; and c) mixing the organic stream and the oxidizing agent stream in a temperature-controlled continuous flow reactor having at least one mixing element at a temperature effective to synthesize the conductive polymer or a salt thereof and provide a product stream containing the conductive polymer or a salt thereof in the temperature-controlled continuous flow reactor; and d) obtaining the 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 The continuous flow process according to any one of Clauses 1 to 3. Clause 5. The continuous flow process according to any one of Clauses 1 to 4, wherein the temperature-controlled continuous flow reactor is a temperature-controlled continuous flow tubular reactor. Clause 6. A continuous flow process according to 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 any salt thereof, 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 any salt thereof, and each of the conductive polymer and the polymerizable organic monomer is unsubstituted or substituted. Clause 7. A continuous flow process according to 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. A continuous flow process according to any one of Clauses 1 to 7, wherein each polymerized chain of the conductive polymer is independently composed of from about 100 to 1500 individual monomer units. Clause 9. A continuous flow process according to 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. A continuous flow process according to any one of Clauses 1 to 9, wherein in the case of step c), the temperature of the mixed stream is set between about -5 and 5 °C and is maintained with a variation of 1 to 2 °C or less over the axial flow length of the continuous flow reactor. Clause 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 oxidizing agent stream containing an aqueous or organic solvent; and c) Synthesizing polyaniline or a salt thereof and mixing an organic stream and an oxidant stream in a temperature-controlled continuous flow reactor equipped with at least one mixing element at a temperature effective to provide a product stream containing 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 exits the temperature-controlled continuous flow reactor A continuous flow process according to any one of clauses 1 to 10 for the controlled synthesis of polyaniline or any salt thereof. Clause 12. A continuous flow process according to any one of clauses 1 to 11, wherein the free radical initiator i is an oxidant, such as ammonium persulfate. Clause 13. In the case of step b), the oxidant stream is an aqueous stream containing an aqueous solvent, and the 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. A continuous flow process according to any one of clauses 1 to 12. Clause 14. In the case of step (a), the organic stream is a non-aqueous organic solution containing an organic solvent, a polymerizable organic monomer, and a protonic acid. A continuous flow process according to any one of clauses 1 to 13. Clause 15. 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. A continuous flow process according to any one of clauses 1 to 14. Clause 16. Before introducing into the temperature-controlled continuous flow reactor of step c), the oxidant stream and the aqueous stream are premixed under continuous flow conditions. A continuous flow process according to any one of clauses 1 to 15. Clause 17. The organic stream is provided by a1) providing a protonic acid stream containing an organic solvent and a protonic acid; a2) providing a monomer stream containing a polymerizable organic monomer and optionally an organic solvent; and a3) mixing the protonic acid stream and the monomer stream to form the organic stream of step a) A continuous flow process according to any one of clauses 1 to 16. Clause 18. The continuous flow process of Clause 17, wherein in the case of step a2), the polymerizable organic monomer is provided as a neat organic solution optionally containing one or more solvents. Clause 19. The continuous flow process of Clause 17 or 18, wherein the monomer stream is an aniline stream containing unsubstituted or substituted aniline and optionally an organic solvent, and step a3) provides for mixing a protonic acid stream and the aniline stream to form the organic stream of step (a). Clause 20. The continuous flow process according to any one of Clauses 17 to 19, wherein the protonic acid stream and the monomer stream are premixed under continuous flow conditions before being mixed with the oxidant stream. Clause 21. The continuous flow process according to 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. Clause 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 containing an aqueous solvent; c) Mixing the organic stream and the oxidant stream in a temperature-controlled continuous flow tubular reactor having at least one mixing element at a temperature effective to synthesize polyaniline or a salt thereof and provide a product stream containing the conductive polymer of polyaniline or a salt thereof in the temperature-controlled continuous flow tubular reactor; and d) Obtaining the conductive polymer of polyaniline or a salt thereof from the product stream under continuous flow conditions after the product stream exits the temperature-controlled continuous flow tubular reactor The continuous flow process according to 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 protonic acid is dinonylnaphthalenesulfonic acid (DNNSA). Clause 25. The continuous flow process according to 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 0.1 M to about 0.8 M. Clause 30. The continuous flow process of Clause 29, wherein the concentration of aniline in the organic stream is from about 0.2 M to about 0.5 M. 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, for example about 2 - 20 mm or 5 - 10 mm. Clause 32. The continuous flow process of any one of Clauses 1 to 31, which provides at least about 50 g of conductive polymer per hour of operation. Clause 33. The continuous flow process of Clause 32, wherein the operating performance is for a continuous flow reactor volume of about 100 - 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 secondary dopants and additional reagents is contacted with the conductive polymer or a salt thereof. Clause 35. The continuous flow process of any one of Clauses 1 to 34, which provides at least about 100 g of conductive polymer per hour of operation per liter of the internal volume of the continuous flow reactor. Clause 36. A conductive polymer prepared by the continuous flow process according to any one of Clauses 1 to 35. Clause 37. A composition, coating or material comprising the conductive polymer of Clause 36 or a salt thereof. Clause 38. A system for providing a continuous flow process for the controlled synthesis of a conductive polymer or a salt thereof, a) A temperature-controlled continuous flow reactor comprising at least one mixing element effective to promote 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 a salt thereof and provide a product stream containing the conductive polymer or a salt thereof to the temperature-controlled continuous flow reactor; b) One or more pumps for providing a fluid flow to the organic stream, the oxidant stream, and the product stream 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, the organic stream, the oxidant stream, and / or the product stream; d) A temperature control device for controlling the temperature of the flow within the temperature-controlled continuous flow reactor, in cooperation with the temperature-controlled continuous flow reactor and one or more heat exchangers, effective for the synthesis of a conductive polymer or any salt thereof; and e) Control means for controlling one or more parameters of the system selected from the concentration, flow rate, temperature, pressure, and residence time of one or more streams, fluid reactants, sources of fluid reactants, carrier fluids, or products of the reaction A system comprising the same.

Example

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

[0278] Continuous flow process A continuous flow process for the controlled synthesis of polyaniline according to one aspect of the present invention is provided as an example in FIG. 3. The continuous flow process reactor 1 includes mixing an unsubstituted or substituted aniline stream A1, a protonic acid stream A2, and an organic solvent (not shown), thereby forming an organic stream A3. The organic stream A3 can be formed by mixing using a static mixer or any other optional mixing element (e.g., a static mixer or dynamic mixer within D and / or an external mixing element as may be provided at C). Thereafter, the organic stream A3 is mixed with an oxidant stream B containing an oxidant to form a product stream C for synthesizing polyaniline. The product stream C can be formed by mixing using a static mixer or any other optional mixing element (e.g., a dynamic mixer). Thereafter, the product stream C is introduced into a temperature-controlled flow reactor D to facilitate the controlled synthesis of polyaniline. The temperature-controlled flow reactor D can optionally include one or more static mixers to facilitate mixing of the product stream C. Thereafter, the product containing the polyaniline product from the control flow reactor D is recovered at 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) was obtained from King Industries, and toluene was obtained from Merck. Molecular weight data was collected by Advanced Polymer Chromatography (APC) using a Waters ACQUITY system. Runs were performed on two APC XT columns, XT200 (linear range 3k - 70K) and XT450 (linear range 20K - 400K). The columns used solid beads (trimethylsilane bonded to an ethylene bridged hybrid (BEH) substrate). Flow rate at 50 °C was 0.7 ml / min. 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 taking PANI-DNNSA solutions made with xylene or toluene (50 - 75% w / v, 2000 RPM, 40 s) and spin-coating onto square glass slides. The resulting films were dried overnight in an oven at 100 °C before surface treatment. Resistance measurements were recorded using a Jandel RM3000 four-point probe, averaging three readings. Film thickness was determined by averaging three surface scratches using a Veeco Dektak 6M Profilometer. UV-VIS spectra were recorded using an HP / Agilent 8453 UV / Vis spectrophotometer equipped with Chemstation software, prepared with xylene or toluene. 1 The 1H-NMR spectra were recorded in deuterium water or CDCl 3 (Cambridge Isotope Laboratories) on an AC-400 spectrometer (Bruker). The residual solvent peak at δ = 7.26 ppm was used as the internal standard.

[0280] Example 1: Continuously Controlled Flow Process The configuration of the continuous controlled flow process for PANI synthesis consists of two stages. In the first stage, an aniline reagent and a protonic acid (Figure 3, A1 and A2) are mixed at room temperature to form an organic stream A3. Then, this composite organic stream A3 is mixed with an oxidant stream from B to produce an emulsion product stream C in a pressurized zone. Subsequently, this emulsion C is fed into a temperature-controlled flow reactor D downstream of the pressurized zone, where the reaction can be advanced with active temperature control and reaction monitoring.

[0281] Step 1: The supply of reagents was achieved using a three-pump configuration (refer to TIFF0007691483000020.tif, Figure 7170). Pump P-1 was used for the supply of the aniline solution A1, pump P-2 was used for the supply of the DNNSA solution A2, and pump P-3 was used for the supply of the ammonium persulfate solution A3. Both aniline and DNNSA were supplied by Knauer pump 80P (the pumps (P-1 and P-2) can be operated at a maximum flow rate of 100 mL / min and a maximum pressure of 400 bar). Pump P-3 is an SSI PR class dual-piston positive displacement pump capable of providing a maximum flow rate of 100 mL / min and a pressure of 276 bar. The reagent streams were transferred using PFA tubes (1 / 8” OD, 1 / 16” ID) obtained from VICI and mixed with an SS Swagelok T-piece. Following this initial mixing, the reagents then passed through a 15 cm SS tube (3 / 16” OD, 3.4 mm ID), SM-1, to which a PP high-shear static mixer (Cambridge Reactor Design) was attached. Subsequently, the solutions of aniline and DNNSA were combined with the APS solution from P-3 and passed through a 30 cm SS tube (3 / 16” OD, 3.4 mm ID), SM-2, to which a PP high-shear static mixer (Cambridge Reactor Design) was attached. To pressurize Step 1, a Swagelok R3A-A pressure relief valve was used. This can adjust the system pressure in the range of 3.4 - 24.1 bar. All other piping in the reactor line was carried out using standard Swagelok fittings.

[0282] Stage 2: The 1L shell and tube continuous reactor (Cambridge Reactor Design) consists of a series of Hastelloy C276 alloy tubes (8mm OD, 6mm ID) connected in a serpentine shape inside the reactor shell. The reactor is equipped with static mixers along its length and has a total internal volume of 1L. Depending on the auxiliary equipment used, the reactor can be operated in the temperature range of -10°C to 200°C and up to a pressure of 25 bar. In this experiment, the temperature control of the reactor is provided by a Julabo Presto A40 thermostat that can be operated in the range of -40°C to 250°C. Monitoring of the internal reaction tube temperature was carried out using four PPT-100 temperature probes connected to positions 1, 8, 15, and 24 of a 5×5 array recorded using a portable data collection and logging system. A back pressure regulator (BPR) was not used in this section of the reactor.

[0283] Example 2: Preparation of Comparative Batch-Synthesized PANI-DNNSA The general preparation procedure of polyaniline dinonylnaphthalenesulfonic acid (PANI-DNNSA) using batch synthesis is shown in Scheme 1 below. TIFF0007691483000021.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 thermostatic bath. Then, DNNSA (67 mL, 50% (w / w) 2-butoxyethanol solution) was added with mechanical stirring to form a white emulsion. Subsequently, 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 hours while monitoring the internal reaction temperature. During this time, the emulsion separated into a green organic phase and a colorless aqueous phase. Then, the biphasic product mixture was washed out with xylene (50 mL) in a separatory funnel, and the aqueous layer was drained. Subsequently, the organic matter was washed with water (5 x 100 mL), and the solvent was evaporated under reduced pressure to obtain a high-concentration PANI-DNNSA in the remaining solvent. Acetone was added to the concentrate to obtain a precipitate of PANI-DNNSA as a fine green powder. This was recovered by filtration, washed thoroughly with acetone, and then dried to obtain PANI-DNNSA (12.0425 g) in an 88 wt% yield.

[0285] A 70% (w / v) solution was prepared by thin-film casting in xylene from a very small portion of the PANI-DNNSA concentrate. The film was dried overnight in an oven at 100 °C, then washed with 2-propanol and air-dried. The resulting thin 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 1L reactor system to 0 °C, aniline (1.0 eq., neat, 99.5%) A1 was pumped (P-1) at 0.56 ml / min, and DNNSA (1.5 eq., 50% (w / w) in 2-butoxyethanol solution) A2 was pumped (P-2) at 8.71 ml / min through static mixer 1 (SM-1) for 1 minute to form organic stream A3. Subsequently, ammonium persulfate (1.2 eq., 1.0 M aqueous solution) B was introduced at 7.4 ml / min (P-3). Thereafter, the combined reagent stream was sent to static mixer 2 (SM-2) to form emulsion product stream C, which then entered a pre-cooled 1L Salamander Jacketed Flow Reactor at a total flow rate of 16.67 ml / min and was retained for a total of 1 hour. The steady-state product recovery at E was started after 1 hour and 16 minutes. After the steady operation was completed, P-3 was switched to water wash, followed by switching P-1 and P-2 to toluene. The recovery was stopped after 3 hours and 28 minutes, and the crude product solution was diluted with toluene (2.45 L). Thereafter, the aqueous layer was drained, and the organic matter was washed with 0.1M H 2 SO 4 (3 x 1.25 L), followed by washing with H 2 O (3 x 1.25 L). Thereafter, the washed organic matter was concentrated under reduced pressure, and toluene (2.25 L) was added again to azeotrope and further dry the organic matter. After repeating this drying process once more, toluene was added again to return the solution to the desired concentration (50% (w / w)).

[0287] Acetone was added to the concentrate to obtain a precipitate of PANI-DNNSA as a fine green powder. This was recovered by filtration, washed thoroughly with acetone, and dried to obtain PANI-DNNSA (230.7530 g) in an 88 wt% yield.

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

[0289] Example 4: Continuous Flow Reaction The continuous flow reactions carried out under the same experimental conditions are shown in Table 1 below. JPEG0007691483000022.jpg29170

[0290] Table 1 shows that a continuous flow process using different formulations of monomer and protic acid in an organic solvent stream can surprisingly achieve significantly higher outputs than those of batch processes while obtaining advantageous MP, Mn, and conductivity values.

[0291] It will be understood that the space time yield (S.T.Y.) is a measure of the efficiency of the reactor system. It is defined as the amount of product produced within a given time frame per unit volume of the reaction vessel. This provides a useful value for comparing the efficiency of processes carried out in batch and continuous systems.

[0292] The space time yield (S.T.Y.) of a chemical reactor can be calculated based on the amount of product m using the following equation. p This equation allows for easy comparison of the efficiency of batch and flow reactors. TIFF0007691483000023.tif16170

[0293] When calculating the space time yield in a continuous scenario, TIFF0007691483000024.tif9170 is the total volumetric flow rate through the reactor, V SS is the total volume of both stock solutions, V R is the volume of the flow reactor. An equivalent calculation can also be done for a batch reactor where t R is the total processing time and V R is the volume of the batch reaction vessel.

[0294] Molecular Weight Range Mn = 30,000 to 100,000 g / mol generally refers to PANI with MP = 44,000 g / mol, Mn = 34,000 g / mol, Mw = 53,000 g / mol, and polydispersity (Pd) = 1.57 - It is within the range of the flow process for generating DNNSA.

[0295] In the flow experiments in a continuous reactor, fluctuations of < 0.6 °C were observed in the steady-state part of the reaction (see Table 1 code 391-150 and Figure 5 above). Here, excellent temperature control was achieved in all experiments using a cooling shell and tube reactor system with a ΔT of 0.6 °C.

[0296] Example 5: Influence of Temperature during Flow on Product Quality First, three different temperatures were investigated during flow (0, 9.0 °C, 18.5 °C). Since a 100 ml flow reactor was used, the mixing was not optimal. Scale-up and high flow rates leading to improved mixing in a 1 L flow reactor further increased the yield. The results are shown in 2. JPEG0007691483000025.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, as the reaction temperature decreased, the molecular weight of PANI-DNNSA increased (from 391-048 to 391-050), and this comparison of peak molecular weights is shown in Figure 3.

[0299] Furthermore, as the reaction temperature decreases, the conductivity of PANI-DNNSA increases (from 391-048 to 391-050), and this comparison of the thin film conductivity after i-PrOH treatment after reaction at different temperatures is shown in Fig. 4. Isopropanol treatment is used to increase the conductivity of the polymer film. In practice, any organic solvent that can remove the excess protonic acid (e.g., DNNSA in this case) may be used. An example of the isopropanol treatment procedure is as follows. A 70% (w / v) solution was made by thin film casting in toluene from a small portion of the PANI-DNNSA concentrate. The film was dried overnight in an oven at 100 °C, then washed with i-PrOH and air dried. Thereafter, the thickness and resistance of the obtained thin film were measured, and the conductivity could be determined therefrom.

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

Claims

**Claim 1** A method for forming a conductive polymer or a salt thereof, comprising: introducing a polymerizable organic monomer into a first continuous flow mixer as a neat liquid or together with an organic solvent; introducing a protonic acid into the first continuous flow mixer separately from the polymerizable organic monomer to form an organosoluble monomer salt; forming a mixture of reactants by introducing an aqueous stream containing the organosoluble monomer salt and a free radical initiator into a second continuous flow mixer provided in series with the first continuous flow mixer; and introducing the mixture of reactants into a tubular reactor to form a conductive polymer or a salt thereof. A method comprising the above steps. **Claim 2** The method according to claim 1, wherein the first continuous flow mixer is a continuous flow mixer containing a mixing element disposed therein, and the mixing element is optionally a static mixing element. **Claim 3** The method according to claim 1, wherein the second continuous flow mixer is a continuous flow mixer containing a mixing element disposed therein, and the mixing element is optionally a static mixing element. **Claim 4** The method according to claim 1, wherein the mixture of reactants is an emulsion. **Claim 5** The method according to claim 1, wherein the tubular reactor contains a static mixing element disposed therein, or the tubular reactor is a continuous flow tubular reactor containing one or more static mixing elements disposed therein. **Claim 6** The method according to claim 1, 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), and combinations thereof. **Claim 7** The method according to claim 1, wherein 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, and combinations thereof. **Claim 8** The method according to claim 1, wherein the conductive polymer is polyaniline and the polymerizable organic monomer is aniline. **Claim 9** The method according to claim 1, wherein the conductive polymer is poly(3,4-ethylenedioxythiophene) and the polymerizable organic monomer is 3,4-ethylenedioxythiophene. **Claim 10** The method according to claim 1, wherein the conductive polymer is poly(3,4-propylenedioxythiophene) and the polymerizable organic monomer is 3,4-propylenedioxythiophene monomer. **Claim 11**: The method according to claim 1, comprising setting the temperature of the mixture of reactants in a tubular reactor to be between -5 and 5 °C with a variation of 2 °C or less. **Claim 12** The method according to claim 1, wherein the tubular reactor has an inner diameter of 2 to 20 mm. **Claim 13** The method according to claim 1, wherein the protonic acid is dinonylnaphthalenesulfonic acid (DNNSA). **Claim 14** The method according to claim 1, wherein the free radical initiator is ammonium persulfate. **Claim 15** The method according to claim 1, wherein the conductive polymer has a weight average molecular weight between 10,000 g / mol and 120,000 g / mol.

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