阅读说明：本技术 聚苯胺及其方法 (Polyaniline and method thereof ) 是由 P·J·金伦 M·A·弗莱克 E·A·布鲁顿 于 2020-04-08 设计创作，主要内容包括：本发明涉及聚苯胺及其方法。具体地,本发明提供了聚苯胺、其制品以及形成聚苯胺的方法。在至少一个方面,聚苯胺具有约100℃以上的热稳定性,约50,000g/mol～约150,000g/mol的重均分子量(Mw)和约1～约5的分子量分布(Mw/Mn)。在至少一个方面,膜包括聚苯胺,基于膜的总重量,该膜的烃含量为约1重量％以下。在至少一个方面,方法包括将苯胺水溶液和烃含量为1重量％以下的烷基取代的芳基磺酸的乳液导入流动反应器中,所述流动反应器具有一定长度的管道,该管道具有一定的内径。该方法包括使管道内的单体聚合形成聚苯胺。(The present invention relates to polyaniline and a method thereof. In particular, the present invention provides polyanilines, articles thereof, and methods of forming polyanilines. In at least one aspect, the polyaniline has a thermal stability of about 100 ℃ or greater, a weight average molecular weight (Mw) of about 50,000g/mol to about 150,000g/mol, and a molecular weight distribution (Mw/Mn) of about 1 to about 5. In at least one aspect, the film comprises polyaniline, the film having a hydrocarbon content of about 1 wt% or less, based on the total weight of the film. In at least one aspect, a method includes introducing an emulsion of an aqueous aniline solution and an alkyl-substituted aryl sulfonic acid having a hydrocarbon content of less than 1 wt% into a flow reactor having a length of tubing with an inner diameter. The method includes polymerizing monomers within the pipe to form polyaniline.)

1. A polyaniline, having:

a thermal stability of about 100 ℃ or higher,

a weight average molecular weight (Mw) of about 50,000g/mol to about 150,000g/mol as determined by gel permeation chromatography, and

a molecular weight distribution (Mw/Mn) of from about 1 to about 5 as determined by gel permeation chromatography.

2. The polyaniline of claim 1, wherein the polyaniline is substantially free of hydrocarbon content.

3. The polyaniline of claim 1, wherein the polyaniline is an acidified polyaniline having a plurality of conjugate base counterions.

4. The polyaniline of claim 1, wherein the polyaniline has a number average molecular weight (Mn) of about 50,000g/mol to about 100,000g/mol as determined by gel permeation chromatography.

5. The polyaniline of claim 1, wherein the polyaniline has a z-average molecular weight (Mz) of about 100,000g/mol to about 250,000g/mol as determined by gel permeation chromatography.

6. The polyaniline of claim 1, wherein the polyaniline has a thermal stability of about 150 ℃ to about 160 ℃.

7. The polyaniline of claim 1, wherein the polyaniline is represented by formula (I):

wherein:

R¹、R²、R³and R⁴Each independently selected from hydrogen, C1-C20 alkyl with or without substituent, C1-C20 aryl with or without substituent, C1-C20 alkylaryl with or without substituent, C1-C20 arylalkyl with or without substituent, C1-C20 alkoxy with or without substituent, and halogen, wherein R is¹、R²、R³And R⁴Is optionally substituted with a group independently selected from C1-C20 alkoxy and halogen;

A^-each is an anionic ligand; and is

n is an integer such that the polyaniline has a weight average molecular weight (Mw) of about 55,000g/mol to about 80,000 g/mol.

8. The polyaniline of claim 7, wherein A is^-Each is dinonylnaphthalenesulfonate.

9. A film comprising the polyaniline of claim 1, wherein the film has a hydrocarbon content of about 1 wt.% or less, based on the total weight of the film.

10. A method, comprising:

introducing an emulsion of an aqueous aniline solution and an organic solvent solution of an alkyl-substituted aryl sulphonic acid having a hydrocarbon content of less than 1 wt% into a flow reactor comprising a length of tubing having an internal diameter; and

polymerizing the monomers in the pipe to form polyaniline.

Technical Field

Polyaniline, articles thereof, and methods of forming polyaniline are provided.

Background

Through proper chemical structure design, conjugated polymer materials can be used as additives to provide corrosion and antistatic properties, or for electronic applications such as Organic Light Emitting Diodes (OLEDs), solar cells, semiconductors, displays, and chemical sensors. However, conjugated polymer materials often suffer from high manufacturing costs, material inconsistencies, and processing difficulties when prepared by batch processes.

Despite these advances, there are still limitations to the extended use of conductive polymers using current methods. For example, polyaniline (PANI or "aniline green") is one such conductive polymer that is not fully utilized due to high manufacturing costs, inconsistent materials, and difficult batch processing. PANI is widely used in printed board manufacturing as a final finishing process; protecting the copper and solder circuitry from corrosion. PANI is typically prepared by chemical oxidative polymerization of aniline in aqueous solution. The material obtained by this method is amorphous and insoluble in most organic solvents. Furthermore, conventional PANI products typically do not have as high thermal stability as would otherwise be desirable. Furthermore, many existing flow reactors being evaluated for the formation of PANI use microfluidic chips or miniaturized chromatography columns and specialized equipment for controlling the flow devices, which increases the cost and complexity of the process.

There is a need for new and improved polyanilines, articles containing polyanilines, and methods of forming polyanilines.

Disclosure of Invention

Polyaniline, articles thereof, and methods of forming polyaniline are provided.

In at least one aspect, a polyaniline is provided that has a thermal stability of about 100 ℃ or greater, a weight average molecular weight (Mw) of about 50,000g/mol to about 150,000g/mol, and a molecular weight distribution (Mw/Mn) of about 1 to about 5.

In at least one aspect, a membrane is provided that includes polyaniline, the membrane having a hydrocarbon content of about 1 wt% or less, based on the total weight of the membrane.

In at least one aspect, a process is provided that includes introducing an emulsion of an aqueous aniline solution and an alkyl-substituted aryl sulfonic acid having a hydrocarbon content of less than 1 wt% into a flow reactor having a length of tubing with an inner diameter. The method includes polymerizing monomers within the pipe to form polyaniline.

Drawings

So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to examples, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical examples of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective examples.

FIG. 1A is a diagram of an exemplary flow reactor system according to one or more aspects.

Fig. 1B is a diagram of an exemplary series flow reactor system, according to one or more aspects.

Fig. 1C is a diagram of an exemplary parallel flow reactor system, according to one or more aspects.

Fig. 2 is a process flow diagram of a polymerization process using systems and methods according to one or more aspects.

FIG. 3 is a cross-sectional view of an inner diameter region of a flow reactor according to one or more aspects.

Fig. 4 is a cross-sectional view of an inner diameter region of a flow reactor in which an electroconductive polymer reaction product occupies a portion of the inner diameter region, according to one or more aspects.

Fig. 5 is a process flow diagram of a polymerization process using systems and methods according to one or more aspects.

Fig. 6 is a process flow diagram of a polymerization process using PANI-DNNSA according to one or more aspects of the systems and methods.

Fig. 7A is a graph illustrating gel permeation results (refractive index versus retention volume (mL)) of polyaniline using a refractive index detector in accordance with one or more aspects.

Fig. 7B is a graph illustrating gel permeation results (viscometer differential pressure versus retention volume (mL)) of polyaniline using a viscometer in accordance with one or more aspects.

Fig. 8 is a graph illustrating thermal stability data (resistance versus temperature) for polyaniline in accordance with one or more aspects.

Fig. 9 is a graph illustrating thermal stability data (resistance versus temperature) for polyaniline in accordance with one or more aspects.

Fig. 10A is a superimposed FTIR spectrum of DNNSA according to one or more aspects.

Fig. 10B is a superimposed FTIR spectrum of DNNSA according to one or more aspects.

To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one example may be beneficially incorporated in other examples without further recitation.

Detailed Description

Polyaniline, articles thereof, and methods of forming polyaniline are provided. The polyaniline of the present invention may be substantially free of by-products, such as unsulfonated hydrocarbons, which provide reduced "outgassing" of the polyaniline as compared to conventional polyanilines. The polyaniline of the present invention may have a thermal stability of about 100 ℃ or greater, a weight average molecular weight (Mw) of about 50,000g/mol to about 150,000g/mol, and/or a Molecular Weight Distribution (MWD) of about 1 to about 5. The reduced outgassing and improved molecular weight properties of the polyaniline of the present invention provide improved thermal stability compared to conventional polyanilines.

The method of the present invention includes forming the polyaniline of the present invention by using aniline and an alkyl-substituted aryl sulfonic acid, such as dinonylnaphthalene sulfonic acid (DNNSA). The alkyl-substituted arylsulfonic acids of the process of the invention have an unsulfonated hydrocarbon content of less than 1% by weight. Conventional alkyl-substituted aryl sulfonic acids (e.g., DNNSA) have an unsulfonated hydrocarbon content of greater than 1 wt.%. Unsulfonated hydrocarbons may include branched and straight chain alkanes and/or aromatics (e.g., benzene and naphthalene). It is assumed that the unsulphonated hydrocarbon content of, for example, a conventional DNNSA sample is provided by the decomposition of sulphonic acid on storage under ultra-high vacuum. However, it has been found that unsulfonated hydrocarbons are already present in DNNSA samples and are likely production by-products of conventional DNNSA manufacturing processes. The use of DNNSAs, for example, having an unsulfonated hydrocarbon content of 1 wt% or less, can provide polyanilines with reduced outgassing and improved thermal stability. Polyaniline and its articles with reduced outgassing and improved thermal stability can provide compositions, coatings or layers, etc., for various articles (e.g., aircraft, land craft, wind turbines, or satellites, etc.).

Polyaniline (PANI)

The polyaniline of the present invention may be acidified polyaniline (hereinafter referred to as PANI-acid or "aniline green salt") or neutral polyaniline. The acidified form of polyaniline may have a conjugate-base counterion (as an anionic ligand), as described in more detail below. Neutral polyaniline can be formed by neutralizing the PANI-acid under any suitable conditions, for example, by treating the PANI-acid with a sodium hydroxide solution and washing the neutralized polymer product with water.

The molecular weight data (Mw, Mn, Mz, Mp, and Mw/Mn) herein refer to neutral polyaniline (e.g., the uncharged, undoped form of polyaniline). In other words, the molecular weight of the polyaniline herein does not include an increased molecular weight due to the presence of a dopant (e.g., an acid, such as DNNSA).

The polyaniline of the present invention can have a weight average molecular weight (Mw) of from about 50,000g/mol to about 150,000g/mol, such as from about 75,000g/mol to about 100,000g/mol, or from about 100,000g/mol to about 130,000 g/mol. The polyaniline of the present invention can have a number average molecular weight (Mn) of about 50,000g/mol to about 100,000g/mol, such as about 60,000g/mol to about 80,000g/mol, or about 80,000g/mol to about 100,000 g/mol.

The polyaniline of the present invention may have a Molecular Weight Distribution (MWD) as determined by gel permeation chromatography of from about 1 to about 5, such as from about 1 to about 4, such as from about 1 to about 3, such as from about 1.2 to about 2.5, such as from about 1.3 to about 1.7. The MWD is determined by dividing Mw by Mn, which may be referred to herein as "Mw/Mn".

The polyaniline of the present invention can have a z-average molecular weight (Mz) of from about 75,000g/mol to about 250,000g/mol, such as from about 100,000g/mol to about 250,000g/mol, such as from about 150,000g/mol to about 250,000 g/mol. Mz indicates the high molecular content of the polymer. For example, the Mz value of the polyaniline of the present invention may be higher than that of the conventional polyaniline, which may provide improved processability compared to the conventional polyaniline.

The polyaniline of the present invention can have a peak average molecular weight (Mp) of from about 50,000g/mol to about 150,000g/mol, such as from about 100,000g/mol to about 150,000g/mol, such as from about 110,000g/mol to about 140,000g/mol, such as from about 113,000g/mol to about 136,000 g/mol. The peak average molecular weight indicates a mode of molecular weight distribution of the polymer, highlighting the increased molecular weight of the polyaniline of the present invention.

Molecular weight properties (e.g., Mw, Mn, Mz, Mp) of polyaniline can be determined using gel permeation chromatography. The mobile phase may be 0.02M Ammonium Formate (AF) in N-methylpyrrolidone (NMP). General calibration techniques can be used to measure molecular weight distribution using viscosity and refractive index detectors. The solution may be filtered through a 0.45 micron filter prior to use. Polyaniline samples can be precipitated in spectrally pure methanol, washed four times with methanol, and then recovered using vacuum filtration. The sample can be air dried, dissolved in AF-NMP, and then passed directly through a 0.2 micron filter into a GPC vial for analysis.

The hydrocarbon content of the article (e.g., film) of the polyaniline film of the invention can be about 1 wt% or less, such as about 0.5 wt% or less, for example about 0.1 wt% or less, such as about 0.001 wt% to about 1 wt%, for example about 0.01 wt% to about 0.5 wt%, based on the total weight of the sample (e.g., film). For example, the hydrocarbon content of the film can be about 1 wt% or less based on the total weight of the film (e.g., the total weight of the hydrocarbon content, polyaniline, and dopant). Hydrocarbons include C1-C20 paraffins and aromatic hydrocarbons such as benzene and naphthalene. In at least one aspect, the hydrocarbon is naphthalene.

An article (e.g., a film) of the polyaniline of the present invention can have an% outgassing of about 0.5% or less, such as about 0.3% or less, such as about 0.1% or less, such as about 0.05% or less, such as about 0.01% or less, according to ASTM E595-93.

The polyaniline of the present invention can have a thermal stability of about 100 ℃ or more, such as about 110 ℃ or more, for example about 120 ℃ or more, such as from about 120 ℃ to about 160 ℃, for example from about 130 ℃ to about 160 ℃, such as from about 140 ℃ to about 160 ℃, for example from about 150 ℃ to about 160 ℃. Thermal stability can be determined by spin coating polyaniline onto a microscope slide and drying the spin-coated sample at 70 ℃. Silver strips may be coated on the edges of the slide to make electrical contact. The sample may be exposed to a temperature (e.g., 150 ℃) for 24 hours in a convection oven. The resistance of the sample can then be measured to determine thermal stability.

In at least one aspect, the polyaniline is a PANI-acid represented by formula (I):

wherein R is¹、R²、R³And R⁴Each independently selected from hydrogen, C1-C20 alkyl with or without substituent, C1-C20 aryl with or without substituent, C1-C20 alkylaryl with or without substituent, C1-C20 arylalkyl with or without substituent, C1-C20 alkoxy with or without substituent, and halogen (such as fluorine, chlorine, bromine, or iodine), wherein R is¹、R²、R³And R⁴Is optionally substituted with a group independently selected from C1-C20 alkoxy and halogen (e.g., fluorine, chlorine, bromine, or iodine);

A^-each is an anionic ligand;

n is an integer such that the polyaniline has a weight average molecular weight (Mw) of about 55,000g/mol to about 80,000g/mol, such as about 60,000g/mol to about 75,000g/mol, such as about 65,000g/mol to about 70,000 g/mol.

In at least one aspect, R¹、R²、R³And R⁴Each independently selected from hydrogen and C1-C20 alkyl having no substituents. In one or more aspects, the C1-C20 alkyl is selected from the group consisting of methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, o-pentyl,N-hexyl, isohexyl and sec-hexyl. In at least one aspect, R¹、R²、R³And R⁴Each is hydrogen.

In at least one aspect, the C1-C20 aryl group is selected from phenyl and naphthyl. In at least one aspect, the C1-C20 alkaryl is benzyl. In at least one aspect, the C1-C20 aralkyl is tolyl, podyl, or ethylbenzyl.

In at least one aspect, A^-Each is an anionic ligand independently selected from sulfonate, hydroxide and halogen (e.g., fluorine, chlorine, bromine or iodine). In one or more aspects, A^-Is a sulfonate, such as dinonylnaphthalenesulfonate.

Alkyl-substituted arylsulfonic acids, anilines and methods for producing polyanilines

A representative, non-limiting reaction scheme for forming the polyaniline of the present invention is shown below in scheme 1. As shown in scheme 1, aniline is treated with an alkyl-substituted arylsulfonic acid and a catalyst to form a polyaniline represented by formula (I).

Scheme 1

R of formula (I) of scheme 1¹、R²、R³、R⁴And A^-As described above for formula (I).

For the aniline monomer of scheme 1, R¹、R²、R³And R⁴Each independently selected from hydrogen, C1-C20 alkyl with or without substituent, C1-C20 aryl with or without substituent, C1-C20 alkylaryl with or without substituent, C1-C20 arylalkyl with or without substituent, C1-C20 alkoxy with or without substituent, and halogen (such as fluorine, chlorine, bromine, or iodine), wherein R is¹、R²、R³And R⁴Is optionally substituted with a group independently selected from C1-C20 alkoxy and halogen (e.g., fluorine, chlorine, bromine, or iodine); and is

R⁵Is hydrogen.

In at least one aspect, R of the aniline monomer of scheme 1¹、R²、R³And R⁴Each independently selected from hydrogen and C1-C20 alkyl having no substituents. In one or more aspects, the C1-C20 alkyl is selected from the group consisting of methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, and sec-hexyl. In at least one aspect, R¹、R²、R³And R⁴Each is hydrogen.

The alkyl-substituted arylsulfonic acids of the invention (or solutions thereof, e.g., organic solutions) can have an unsulfonated hydrocarbon content of less than 1 wt% and can be dialkyl-substituted naphthalene sulfonic acids, e.g., DNNSA. Alkyl substituted aryl sulfonic acids (e.g., DNNSA) having unsulfonated hydrocarbon contents of 1 wt% or less are commercially available from King Industries.

In at least one aspect, the hydrocarbon content of the alkyl-substituted arylsulfonic acid (e.g., DNNSA) (or solution thereof) is about 1 wt.% or less, such as about 0.5 wt.% or less, for example about 0.1 wt.% or less, such as about 0.001 wt.% to about 1 wt.%, such as about 0.01 wt.% to about 0.5 wt.%, based on the total weight of the acid (the acid in the absence of other solvents, such as isopropyl alcohol).

In the process of the present invention, the molar ratio of alkyl-substituted arylsulfonic acid to aniline can be from about 0.2:1 to about 2:1, for example from about 0.3:1 to about 1:1, for example from about 0.8:1 to about 1:0.8, for example about 1: 1.

The catalyst of the invention may comprise any suitable ammonium or sulfate catalyst, for example ammonium persulfate.

Furthermore, the addition of other hydrocarbon solvents may not be preferred. The addition of high levels of, for example, heptane or hexane prevents the formation of emulsions. For example, if the process is carried out by simply subjecting DNNSA to heptane without 2-butoxyethanol, the reaction may not proceed until a soluble product is formed.

Flow reactor process

Disclosed herein are methods of forming polyaniline of the present invention (hereinafter also referred to as PANI-acid) as a solvent soluble polymer by flow reactor chemical processing using alkyl substituted aryl sulfonic acids (e.g., DNNSA). The disclosed system and method provide a unique processing sequence for directly collecting purified aniline green salt without post reactor treatment. The present system and method provide an improvement over known methods of synthesizing conductive polymers, particularly conductive polymer salts, such as PANI-acids, using very short reaction times that were not otherwise available using conventional methods that require longer reaction times.

For example, the present systems and methods provide an improvement in the efficient and controlled synthesis of Polyaniline (PANI) salts as soluble, inherently conductive polymers. A flow reactor is used herein to describe the continuous flow synthesis of PANI-acids or "aniline green salts". In some examples, the flow reactor comprises a microfluidic (1 to about 750 μm internal diameter) tubular reactor. In some examples, the microfluidic tube comprises a fluoropolymer, e.g.

The tubular reactor provides a suitable surface for depositing the formed polymer and for direct purification of the conductive polymer salt.

As used herein, the phrase "flow reactor" includes a microflow reactor. A microflow reactor is used herein as a flow reactor having a certain flow dimension, for example, an internal diameter (i.d.) of the conduit of less than 1mm (1000 microns).

As described further below, in some examples, as the polymerization reaction proceeds, a majority of the polymer product is deposited on the walls of the conduit. The polymer product may be purified by washing with water to remove water soluble reactants, reagents and by-products.

The conductive polymer salt formed in the flow reactor and deposited on the walls of the channels can be eluted with an organic solvent to provide a soluble conductive polymer salt suitable for solid casting, film formation or precipitation. The apparatus may be configured for in situ characterization, for example by UV-Vis spectroscopy, infrared and/or mass spectroscopy.

An apparatus and associated method for polymerizing at least one reactant will be described. In certain examples, the device is a microfluidic device comprising a mixing chamber and a microchannel. In addition, the reactor may further comprise an output chamber and a detection unit operatively connected to the micro flow channel.

Any suitable apparatus (e.g., flow reactor) may be used to form the polyaniline of the present invention, such as those described in U.S. patent No. 10,118,992, which is incorporated herein by reference for purposes of U.S. law.

Referring to fig. 1A, a flow reactor system 100 is shown. A first reactant 10 (e.g., aniline) and a second reactant 20 (e.g., an alkyl-substituted arylsulfonic acid) are introduced into a first mixing unit 30. The reactor system 100 shown in fig. 1A can produce the conductive polymer salt (mass/unit time) more efficiently than a conventional large-scale apparatus or batch reactor. The flow reactor system 100 is capable of operating at a process temperature ranging from room temperature to about 250 ℃, for example, at a process temperature of less than 100 ℃. In some examples, the ambient temperature is about 50 ° F (10 ℃) to about 90 ° F (32 ℃). In some examples, the reactants 10, 20 are independently introduced into the first mixing unit 30 at a predetermined flow rate and/or a predetermined concentration such that the reactants 10, 20 are mixed in a desired molar ratio prior to introduction into the flow reactor. In other examples, the reactants 10, 20 are introduced together into the first mixing unit 30 such that the reactants 10, 20 are mixed in a desired molar ratio prior to introduction into the flow reactor. The first mixing unit 30 may be any suitable mixing device. In some examples, the mixing device is a high speed or ultra-high speed mixing device capable of emulsifying one or more solutions (e.g., aqueous solutions and non-aqueous solutions). In some examples, the first reactant 10 is contained in an aqueous solution, the second reactant 20 is contained in a non-aqueous solution, and the first mixing unit 30 is designed to emulsify the first reactant 10 and the second reactant 20. The third reactant 50 is added to the first reactant and the second reactant in the second mixing unit 60. In some examples, reactant 50 is a catalyst. After mixing in the second mixing unit 60, the reactants are introduced into the conduit 70 through the inlet 65. The conduit 70 includes a discharge port 80 that can be monitored by an analytical device 90. The analysis device 90 may include a spectroscopic device to monitor and analyze the material, e.g., unreacted material and/or reaction products, flowing from the discharge port 80. The spectroscopic equipment includes UV-Vis, IR (near, medium and far infrared) spectrometers and mass spectrometers. Other analysis and monitoring techniques may be used, such as capacitance, pH, and the like. A pressure regulating unit 67 may be arranged at the outlet of the flow reactor 70 to monitor pressure changes during the polymerization process or during the polymeric material collection step, and the controller may use information from the pressure regulating unit 67 to stop the introduction of the reactant (e.g. aniline) into the flow reactor. Other pressure regulating units 67 may also be arranged at the inlet of the flow reactor 70, for example for monitoring pressure changes in the process. Fluid line 69 may be independently fluidly connected to flow reactor 70 to introduce a purging medium 66 (e.g., water) or a collection medium 68 (e.g., solvent) to collect polymerization product from flow reactor unit 70.

In some examples, the flow reactor system 100 has a single inlet to the conduit 70. In other examples, the flow reactor system 100 has additional inlets disposed between the inlet 65 and the discharge 80. As shown in fig. 1A, the conduit 70 may be coiled to provide an expanded tubular flow reactor.

In some examples, the conduit 70 is housed in a housing 40, the housing 40 providing temperature control and/or support and/or protection from damage to the conduit 70. In some examples, the housing 70 has an inner surface surrounding at least a portion of the tube 70 such that the coiled tube 70 is at least partially received within the housing 40. In some examples, the housing 40 is configured to provide temperature control, including heating and/or cooling, to the conduit 70.

As shown in fig. 1B, an additional flow reactor configuration 100a is shown in which a plurality of tubes 70a, 70B are arranged in a series-connected coil configuration. The conduits 70a, 70b may be the same size or may have different lengths and/or different inner diameters. In such a configuration, the housing may be divided into separate sections 40a, 40b that house the conduits 70a and 70b, which sections may be independently manipulated to heat and/or cool the conduits. Alternatively, the flow reactor configuration 100a may have a single housing that houses the conduits 70a, 70 b. Unlike parallel array configurations of tubes, where the process streams are split before entering the flow reactor, a series array maximizes the amount of time the reaction mixture is held under diffusion-limited conditions. While not being bound by any particular theory, it is believed that maintaining the reaction mixture under diffusion-limiting conditions improves the reaction of the present invention to produce conductive polymer salts from reactants in an emulsion as compared to batch processing. The methods and systems disclosed herein provide such diffusion limiting conditions for emulsions of reactants.

Referring to fig. 1C, an exemplary flow reactor system 100b is shown. A plurality of flow reactor units 70c, 70d and 70e in a parallel flow configuration are shown. Each flow reactor 70c, 70d and 70e can independently introduce the monomer solution into the respective flow reactor via flow control valves 63 located at the inlet and outlet of each flow reactor. The flow control valve 63 may be manually operated and/or configured based on a solenoid for computer control using conventional control means. The flow control valve 63 may contain one or more check valves for preventing the dispersion from flowing backward. One or more pressure regulating units 67 may be provided at the outlet of the one or more flow reactors to monitor the pressure variations during the polymerization or during the collection step of the polymeric material. Other pressure regulating units 67 may also be provided at the inlet of the respective flow reactor. The flow control valve 63 may be coupled with pressure data from the controller to isolate one or more of the flow reactors 70c, 70d, and 70e to initiate purging and/or polymer recovery. In such a configuration, the flow reactor system 100b can be operated continuously by selectively isolating one or more of the flow reactor units 70c, 70d, and 70e to collect polymerization product and/or performing maintenance while maintaining monomer introduction to one or more of the remaining flow reactor units. Alternatively, flow reactor system 100b may be operated semi-continuously, for example, by temporarily stopping the introduction of monomer to one or more of flow reactor units 70c, 70d, and 70 e. Other fluid lines 69 may be independently fluidly connected to one or more flow control valves 63 to introduce a purification medium 66 (e.g., water) or a collection medium 68 (e.g., solvent) to selectively collect polymerization product from one or more flow reactor units 70c, 70d, and 70 e. One or more of the flow reactor units 70c, 70d, and 70e may be physically removed from the flow reactor system 100b for transport with or without recovery of the polymerization product from the inner diameter of the conduit.

Referring to fig. 2, a process flow 201 is shown as an example of the method disclosed herein. Then in block 205 it is shown to prepare an emulsion of an aqueous monomer and an acid in a non-aqueous solvent. The introduction of the emulsion and catalyst into the microreactor conduit is shown in block 210. After a predetermined time, the flow of one or more reactants may be terminated and the microreactor channels optionally flushed with water, as shown in block 215. Block 215 may be performed to remove unreacted reactants and/or low molecular weight products. In block 220, recovery of the polymer from the microreactor channels with an organic solvent is performed.

Fig. 3 and 4 are cross-sectional views of a conduit 300 having an inner surface 310 of a lumen with an inner diameter D. In some examples, the maximum diameter is less than the diameter at which the preferential reduction of the diffusion limited reaction occurs. This maximum diameter can be as high as 4000 microns, similar to the diameter of pipes used for high pressure pipes. In other examples, diameters of less than 4000 microns, less than 3000 microns, or less than 1000 microns to a minimum diameter of about 100 microns may be used to obtain optimal results. While not being bound by any particular theory, it is believed that the faster reaction rates of the reactions disclosed and described herein occur as the reactor tube inner diameter size decreases, which is as much as 10 for previously reported microfluidic systems⁴～10⁶Double, but the reaction volume per unit time is somewhat compromised. In one example, the capillary tube 300 is made of glass, metal, plastic, or glass or metal coated with a polymer, such as a fluoropolymer, on its inner surface. The tubing may be encased in another polymer or coated with metal.

The length of the tubing may be selected based on the ability of selected components of the system (pump, tubing burst strength, joints, etc.) to withstand the pressure. The maximum length of a conduit suitable for use with the system of the present invention is a function of the back pressure and the ability to transport product through the entire length of the conduit. In some examples, the system may be configured to operate with a length of tubing coupled with an inner diameter of tubing such that the system operates at a pressure of about 20 bar (280psi) or less. In some examples, the length of the tube is no more than 500 meters, wherein the inner diameter of the tube is less than 4000 micrometers. In other examples, the conduit 300 is a conduit less than 1000 microns in diameter (microfluidic conduit) having a length of about 100 meters or less. Other combinations of tube diameters and lengths may be used depending on the operating parameters of the system and the desired reaction volume per unit time.

The cross-section of the conduit may be of any shape, but is preferably circular. In some examples, polymerization occurs on the inner surface 310 of the lumen as shown in fig. 4, where the polymerization product 400 limits the inner diameter D to a reduced diameter D'. In some examples, the reduction in the inner diameter of the conduit or the inner diameter D is symmetrical about the longitudinal axis A-A, B-B. In some examples, the reduction in the inner diameter of the conduit or the inner diameter D is asymmetric with respect to the longitudinal axis A-A, B-B. This reduction in diameter D to diameter D' of the tube 300 results in a back pressure that can be measured and/or used in part to control the process herein.

This back pressure can be monitored and at the start of the polymerization the back pressure at time T1 is consistent with the viscosity and flow rate of the emulsified reaction mixture fed into line 300. During time period T2 (the convergence has caused the inner diameter of the pipe 300 to decrease), the back pressure begins to increase and approach the threshold value. In some examples, the system is designed to terminate the polymerization when the back pressure value reaches a predetermined threshold. The rate of change of back pressure shown in time period T2 may be adjusted by controlling the viscosity of the reactants, the molar concentration of the reactants and/or catalyst, the temperature, the flow rate, and combinations thereof, taking into account the burst strength of the capillary channels and other reactor parameters. Fig. 5 shows a process flow diagram 500 representing an example of the method of the present invention. Thus, block 505 illustrates pumping the reactant emulsion and catalyst into the microreactor channels. Monitoring the back pressure of the reactant emulsion during polymerization is shown in block 510. It is envisaged to use a conventional pressure monitoring device, either external to the pumping device or in electrical connection with the pumping device. Once the threshold back pressure is reached, introduction of the reactant emulsion is terminated, as shown in block 515. Recovery of the product polymer from the microreactor channels by flushing with an organic solvent is shown in block 520.

For example, the methods disclosed herein may be applied to the manufacture of polyaniline of the present invention. In at least one aspect, the polyaniline formed by the method of the present invention is polyaniline-dinonylnaphthalene sulfonate ("PANI-DNNSA"), which is a conductive polymer used in electronic applications such as Organic Light Emitting Diodes (OLEDs), solar cells, semiconductors, displays, and chemical sensors.

Thus, as an illustrative example, a continuous-flow synthesis method of PANI-DNNSA salts is provided. The flow device is designed such that the oxidizing agent is added to a pre-formed emulsion of aqueous aniline and organic soluble DNNSA. For example, emulsion polymerization of equimolar amounts of aniline and DNNSA can be carried out in the presence of ammonium persulfate as the oxidation catalyst. The reaction is shown in scheme 2 below:

scheme 2

Thus, referring to FIG. 6, a process flow diagram 600 is shown. Blocks 602 and 604 introduce an aqueous composition comprising aniline and a non-aqueous composition comprising an alkyl-substituted aryl sulfonic acid into a first mixer, respectively. A reactant emulsion is formed in a first mixer in block 610. The catalyst and reactant emulsion is introduced into a second mixer in block 615. In block 620, the fluid is introduced into the microreactor channel and a threshold back pressure is obtained. Introduction of the reactant emulsion and catalyst into the microreactor channels is terminated in block 625. Optionally, the microreactor channels may be flushed with water in block 630 to remove unreacted materials and/or low molecular weight polymers. The polyaniline polymer salt is recovered from the microreactor channels using an organic solvent at block 635.

Aspect(s)

The present invention provides, inter alia, the following aspects, each of which can be considered as optionally including any alternative aspect.

Clause 1a polyaniline having a weight average molecular weight (Mw) of about 50,000g/mol to about 150,000g/mol as determined by gel permeation chromatography and a molecular weight distribution (Mw/Mn) of about 1 to about 5 as determined by gel permeation chromatography.

Clause 2 the polyaniline of clause 1, wherein the polyaniline is substantially free of hydrocarbon content.

Clause 3 the polyaniline of clause 1 or 2, wherein the polyaniline is an acidified polyaniline having a plurality of conjugate base counterions.

Clause 4 the polyaniline of any one of clauses 1-3, wherein the polyaniline has an Mw of about 55,000 to about 80,000g/mol as determined by gel permeation chromatography.

Clause 5 the polyaniline of any one of clauses 1-4, wherein the polyaniline has a Mw of about 110,000 to about 140,000g/mol as determined by gel permeation chromatography.

Clause 6 the polyaniline of any one of clauses 1 to 5, wherein the polyaniline has a number average molecular weight (Mn) of about 50,000g/mol to about 100,000g/mol as determined by gel permeation chromatography.

Clause 7 the polyaniline of any one of clauses 1-6, wherein the polyaniline has an Mn of about 72,000g/mol to about 74,000 g/mol.

Clause 8 the polyaniline of any one of clauses 1 to 7, wherein the polyaniline has a molecular weight distribution (Mw/Mn) as determined by gel permeation chromatography of about 1 to about 5.

Clause 9 the polyaniline of any one of clauses 1 to 8, wherein the polyaniline has an Mw/Mn as determined by gel permeation chromatography of about 1.5 to about 1.9.

Clause 10 the polyaniline of any one of clauses 1-9, wherein the polyaniline has a z-average molecular weight (Mz) of from about 100,000g/mol to about 250,000g/mol as determined by gel permeation chromatography.

Clause 11 the polyaniline of any one of clauses 1-10, wherein the polyaniline has an Mz of from about 152,000g/mol to about 204,000 g/mol.

Clause 12 the polyaniline of any one of clauses 1-11, wherein the polyaniline has a peak average molecular weight (Mp) of about 50,000g/mol to about 150,000 g/mol.

Clause 13 the polyaniline of any one of clauses 1-12, wherein the polyaniline has an Mp of about 113,000g/mol to about 136,000 g/mol.

Clause 14 the polyaniline of any one of clauses 1-13, wherein the polyaniline has a thermal stability of about 100 ℃ or more.

Clause 15 the polyaniline of any one of clauses 1-14, wherein the polyaniline has a thermal stability of about 150 ℃ to about 160 ℃.

Clause 16 the polyaniline of any one of clauses 1-15, wherein the polyaniline is represented by formula (I):

wherein:

R¹、R²、R³and R⁴Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy and halogen, wherein R is¹、R²、R³And R⁴Is optionally substituted with a group independently selected from C1-C20 alkoxy and halogen;

A^-each is an anionic ligand; and is

n is an integer such that the polyaniline has a weight average molecular weight (Mw) of about 55,000g/mol to about 80,000 g/mol.

Clause 17 the polyaniline of any one of clauses 1-16, wherein the polyaniline has an Mw of about 65,000 to about 70,000 g/mol.

Clause 18 the polyaniline of any one of clauses 1-17, wherein R¹、R²、R³And R⁴Each independently selected from hydrogen and C1-C20 alkyl having no substituents.

Clause 19 the polyaniline of any one of clauses 1-18, wherein R¹、R²、R³And R⁴Each is hydrogen.

Clause 20 the polyaniline of any one of clauses 1-19, wherein a^-Each is dinonylnaphthalenesulfonate.

Clause 21 a film comprising the polyaniline of any one of clauses 1-20, wherein the film has a hydrocarbon content of about 1 wt.% or less, based on the total weight of the film.

Clause 22 the membrane of clause 21, wherein the hydrocarbon content of the membrane is about 0.5 wt.% or less, based on the total weight of the membrane.

Clause 23 the membrane of clause 21 or 22, wherein the hydrocarbon is naphthalene.

Clause 24 the film of any one of clauses 21-23, wherein the film has a% outgassing of about 0.5% or less.

Clause 25 the film of any one of clauses 21-24, wherein the film has a% outgassing of about 0.1% or less.

Clause 26 a method, comprising:

introducing an emulsion of an aqueous aniline solution and an organic solvent solution of an alkyl-substituted aryl sulfonic acid having a hydrocarbon content of less than 1 wt% into a flow reactor, the flow reactor comprising a length of tubing having an inner diameter; and

polymerizing the monomers in the pipe to form polyaniline.

Clause 27 the method of clause 26, further comprising introducing a catalyst into the emulsion.

Clause 28 the method of clause 26 or 27, further comprising introducing a catalyst into the flow reactor.

Clause 29 the method of any one of clauses 26-28, wherein the length of the tube is coiled.

Clause 30 the method of any one of clauses 26-29, wherein the flow reactor comprises a plurality of tubes arranged in a parallel flow configuration.

Clause 31 the method of any one of clauses 26-30, wherein the molar ratio of aniline to acid is about 1:1 to about 0.2: 1.

Clause 32 the method of any one of clauses 26-31, wherein the catalyst is ammonium persulfate.

Clause 33 is the method of any one of clauses 26-32, wherein the alkyl-substituted arylsulfonic acid is dinonylnaphthalenesulfonic acid.

Clause 34 the method of any one of clauses 26 to 33, wherein the organic solvent solution of the alkyl-substituted arylsulfonic acid has a hydrocarbon content of 0.5 wt.% or less.

Clause 35 the method of any one of clauses 26-34, wherein the organic solvent solution of the alkyl-substituted arylsulfonic acid has a hydrocarbon content of 0.1 wt.% or less.

Clause 36 the method of any one of clauses 26-35, wherein the organic solvent solution of the alkyl-substituted arylsulfonic acid has 0.5% by weight or less naphthalene.

Clause 37 the method of any one of clauses 26-36, further comprising recovering the polyaniline from the pipeline.

Clause 38 the method of any one of clauses 26-37, wherein the polyaniline has a Mw of about 50,000 to about 150,000g/mol as determined by gel permeation chromatography.

Clause 39 the method of any one of clauses 26-38, wherein the polyaniline has a Mw of about 65,000 to about 70,000g/mol as determined by gel permeation chromatography.

Clause 40 the method of any one of clauses 26-39, wherein the polyaniline has a Mw/Mn, as determined by gel permeation chromatography, of about 1.5 to about 1.9.

Clause 41 the method of any one of clauses 26-40, wherein the polyaniline has a thermal stability of about 100 ℃ or more.

Clause 42 the method of any one of clauses 26-42, wherein the polyaniline has a thermal stability of about 150 ℃ to about 160 ℃.