Method for producing conductive polyaniline polymer

Abstract

The present invention discloses a method for preparing a conductive polyaniline polymer, comprising: preparing a polyaniline dispersion and a protonic acid aqueous solution respectively; wherein the protonic acid aqueous solution is adjusted to have a first pH value; adding the polyaniline dispersion and the protonic acid aqueous solution to a reaction tank respectively to form a reaction mixture, which is adjusted to have a second pH value greater than the first pH value; and heating the reaction mixture to a first temperature so that the protonic acid and the polyaniline polymer undergo a mixed reaction, thereby forming a conductive polyaniline polymer. The reaction mixture undergoes a pH change during the mixed reaction. When the pH value of the reaction mixture changes from the second pH value to the third pH value, the reaction mixture is cooled to a second temperature to terminate the mixed reaction. Thus, the preparation of the conductive polyaniline polymer can be carried out under the conditions of an aqueous reaction system and has a high yield.

Description

Technical Field

[0001] The invention relates to a method for preparing polyaniline polymer, in particular to a method for preparing conductive polyaniline polymer. Background Art

[0002] Conductive polymers are a type of polymer material with electrical conductivity. When a voltage is applied to the conductive polymer, electron transfer occurs in the molecular structure of the conductive polymer, thereby becoming conductive. Among the existing conductive polymer materials, polyaniline (PANI) has the characteristics of low material price, simple synthesis method, and low surface impedance, making it potentially widely used in anti-corrosion coatings, supercapacitors, and electromagnetic wave shielding.

[0003] Unblended polyaniline is not conductive. Conductive polyaniline polymers can be prepared by blending protic acid (HA) into polyaniline to make it conductive. However, most of the existing methods for manufacturing conductive polyaniline polymers are carried out in an organic solvent system. The blending reaction of protic acid in polyaniline generally uses organic solvents such as isopropyl alcohol (IPA), ethanol (EtOH), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), m-cresol, etc. Accordingly, the existing manufacturing methods have problems such as the discharge of waste organic solvents and the presence of volatile organic compounds (VOCs) in the products.

[0004] Therefore, the inventors felt that the above defects could be improved, so they devoted themselves to research and applied scientific principles, and finally proposed the present invention which has a reasonable design and effectively improves the above defects. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a method for preparing a conductive polyaniline polymer in view of the shortcomings of the prior art.

[0006] In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a method for manufacturing a conductive polyaniline polymer, comprising: performing a batching operation, including: preparing a polyaniline dispersion and a protonic acid aqueous solution respectively; wherein the polyaniline dispersion contains polyaniline polymer and liquid water, and the protonic acid aqueous solution contains protonic acid and liquid water; and the protonic acid aqueous solution is adjusted to have a first pH value; performing a feeding operation, including: adding the polyaniline dispersion and the protonic acid aqueous solution into a reaction tank respectively to form a reaction mixture, which is adjusted to have a pH value greater than the pH value. a second pH value of the first pH value; and performing a blending operation, comprising: heating the reaction mixture in the reaction tank to a first temperature between 50° C. and 100° C., so that the proton acid and the polyaniline polymer undergo a blending reaction, thereby forming a conductive polyaniline polymer; wherein the reaction mixture undergoes a pH change during the blending reaction; when the pH change of the reaction mixture is increased from the second pH value to a third pH value, the blending operation further comprises cooling the reaction mixture to a second temperature, so as to terminate the blending reaction.

[0007] Preferably, the first pH value is between 0.20 and 0.50, the second pH value is between 0.50 and 0.80, and the third pH value is between 0.80 and 1.10; wherein a difference between the second pH value and the first pH value is not less than 0.1, and a difference between the third pH value and the second pH value is not less than 0.1.

[0008] Preferably, the second temperature is between 20°C and 40°C.

[0009] Preferably, in the feeding operation, the reaction mixture comprises the polyaniline polymer, the protonic acid, and the liquid water, the amount of the polyaniline polymer is between 50 parts by weight and 100 parts by weight, the amount of the protonic acid is between 30 parts by weight and 375 parts by weight, and the amount of the liquid water is between 450 parts by weight and 550 parts by weight; wherein the ratio between the molar equivalent of the protonic acid and the molar equivalent of the polyaniline polymer is between 0.25:1 and 1.5:1.

[0010] Preferably, after the blending operation, the manufacturing method further includes: implementing a separation operation, including: discharging the cooled reaction mixture to a separation unit to separate the solid component and the liquid component of the reaction mixture; wherein the solid component in the reaction mixture includes the crude product of the conductive polyaniline polymer, and the liquid component in the reaction mixture includes the residual protonic acid and the liquid water.

[0011] Preferably, after the separation operation, the manufacturing method further includes: performing a drying operation, including: introducing the crude product of the conductive polyaniline polymer into a drying unit to reduce the moisture content in the solid component; wherein the content of the proton acid mixed into the conductive polyaniline polymer is not less than 30wt%, and an impedance value of the conductive polyaniline polymer is not greater than 20Ω.cm.

[0012] Preferably, after the separation operation, the manufacturing method further includes: performing a reflux operation, which includes: refluxing the liquid component in the reaction mixture and mixing the liquid component with another batch of the protonic acid to form a reflux aqueous solution; wherein the reflux aqueous solution is adjusted to have a fourth pH value, the fourth pH value is between the first pH value and the second pH value, and the fourth pH value has a numerical range of 0.50 to 0.70.

[0013] Preferably, the reflux operation further comprises: quantifying the content of the protonic acid in the liquid component and calculating the required addition amount of another batch of the protonic acid, so that the reflux aqueous solution is adjusted to have the fourth pH value.

[0014] Preferably, the reflux operation further comprises: adding the reflux aqueous solution and another batch of the polyaniline dispersion into the reaction tank respectively to form another batch of the reaction mixture, which has a fifth pH value, and the fifth pH value is controlled to be between 80% and 120% of the second pH value; wherein, in the other batch of the reaction mixture, the ratio between the molar equivalent of the protonic acid and the molar equivalent of the polyaniline polymer is between 0.25:1 and 1.5:1.

[0015] Preferably, in the batching operation, the polyaniline dispersion is formed by dispersing the polyaniline polymer in the liquid water, and the protonic acid aqueous solution is formed by dissolving the protonic acid in the liquid water.

[0016] The beneficial effect of the present invention is that the method for producing a conductive polyaniline polymer provided by the present invention can be carried out by "implementing a batching operation, comprising: preparing a polyaniline dispersion and a protonic acid aqueous solution respectively; wherein the polyaniline dispersion comprises polyaniline polymer and liquid water, and the protonic acid aqueous solution comprises protonic acid and liquid water; and the protonic acid aqueous solution is adjusted to have a first pH value; implementing a feeding operation, comprising: adding the polyaniline dispersion and the protonic acid aqueous solution to a reaction tank respectively to form a reaction mixture, which is adjusted to have a second pH value greater than the first pH value; and implementing a mixing operation. The process comprises: heating the reaction mixture in the reaction tank to a first temperature so that the proton acid and the polyaniline polymer undergo a blending reaction to form a conductive polyaniline polymer; wherein the reaction mixture undergoes a pH change during the blending reaction; when the pH change of the reaction mixture is increased from the second pH to a third pH, the blending process further comprises cooling the reaction mixture to a second temperature to terminate the blending reaction. "The technical scheme is adopted to enable the preparation of conductive polyaniline polymer to be carried out under the conditions of an aqueous reaction system and with a high yield. Furthermore, the existing manufacturing method has problems such as the discharge of waste organic solvents and the presence of volatile organic compounds (VOCs) in the product, which can be effectively solved.

[0017] Furthermore, the manufacturing method of the present invention can confirm whether the mixing reaction of the proton acid into the polyaniline polymer has reached an ideal level by monitoring the pH value change of the reaction mixture during the mixing reaction. When the pH value of the reaction mixture during the mixing reaction is increased from the second pH value to the third pH value, it means that the amount of the proton acid mixed into the polyaniline polymer has reached an ideal level. According to the above technical solution, the process of manufacturing the conductive polyaniline polymer can become simpler and more efficient.

[0018] To further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only for reference and description and are not intended to limit the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a schematic flow chart showing the steps of a method for manufacturing a conductive polyaniline polymer according to an embodiment of the present invention.

[0020] Figure 2 The figure shows a chemical process flow chart of a method for producing a conductive polyaniline polymer according to an embodiment of the present invention. DETAILED DESCRIPTION

[0021] The following is an explanation of the disclosed embodiments of the present invention through specific embodiments. Those skilled in the art can understand the advantages and effects of the present invention from the contents disclosed in this specification. The present invention can be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed in various ways based on different viewpoints and applications without departing from the concept of the present invention. In addition, the drawings of the present invention are only simple schematic illustrations and are not depicted according to actual dimensions. It is stated in advance. The following embodiments will further explain the relevant technical contents of the present invention in detail, but the disclosed contents are not intended to limit the scope of protection of the present invention.

[0022] It should be understood that, although the terms "first", "second", "third", etc. may be used herein to describe various components or signals, these components or signals should not be limited by these terms. These terms are mainly used to distinguish one component from another component, or one signal from another signal. In addition, the term "or" used herein may include any one or more combinations of the associated listed items depending on the actual situation.

[0023] [Method for producing conductive polyaniline polymer]

[0024] The embodiment of the present invention provides a method for producing a conductive polyaniline polymer, which mainly uses non-conductive polyaniline (PANI·EB) through a blending reaction to obtain a conductive polyaniline polymer (PANI·A). The production method of the present invention uses water as a solvent in the process of blending protonic acid to produce polyaniline. The production method of the present invention can solve the problems of the discharge of waste organic solvents and the presence of volatile organic compounds (VOC) in the product, thereby reducing the pollution level of producing conductive polyaniline polymers.

[0025] Furthermore, the manufacturing method of the present invention introduces a mechanism for recycling process wastewater, which recycles process wastewater in an energy-saving manner. This mechanism can reduce the discharge of waste solvents, and process wastewater can be recycled without wastewater treatment. The recycling rate can reach 80%, and the number of recycling times can reach more than 5 times, which greatly reduces the generation of process waste liquid.

[0026] In order to achieve the above-mentioned purpose, the method for preparing the conductive polyaniline polymer according to the embodiment of the present invention will be described in more detail below.

[0027] See also Figure 1 and Figure 2 As shown, Figure 1 It is a schematic diagram showing the steps of the method for producing a conductive polyaniline polymer according to an embodiment of the present invention, and Figure 2 The figure shows a chemical process flow chart of a method for producing a conductive polyaniline polymer according to an embodiment of the present invention.

[0028] The method for manufacturing conductive polyaniline polymer of the embodiment of the present invention comprises step S110, step S120, step S130, step S140, step S150, and step S160. It should be noted that the order of the steps and the actual operation method of the embodiment can be adjusted according to the needs, and the present invention is not limited to the embodiment.

[0029] The step S110 is to implement a material preparation operation, which includes: preparing a polyaniline dispersion S1 in a first material preparation barrel T1, and preparing a protonic acid aqueous solution S2 in a second material preparation barrel T2. The polyaniline dispersion S1 includes unmixed polyaniline polymer (PANI·EB) and liquid water (H2O), and the protonic acid aqueous solution S2 includes protonic acid (HA) and liquid water (H2O).

[0030] Furthermore, the protonic acid aqueous solution S2 must be adjusted to have a first pH value to facilitate the efficiency of the subsequent mixing reaction. In some embodiments of the present invention, the first pH value of the protonic acid aqueous solution S2 is between 0.20 and 0.50, and preferably between 0.35 and 0.45. In other words, the protonic acid aqueous solution S2 must be formulated into a strongly acidic solution to facilitate the efficiency of the subsequent mixing reaction.

[0031] In some embodiments of the present invention, the protonic acid (HA) is at least one selected from the group consisting of camphorsulfonic acid (CSA), methanesulfonic acid (MSA), p-toluenesulfonic acid (PTSA), benzenesulfonic acid (BSA), p-aminobenzenesulfonic acid (DBSA), and dodecylbenzenesulfonic acid (DBSA). In a preferred embodiment of the present invention, the protonic acid is camphorsulfonic acid (CSA).

[0032] Specifically, the polyaniline dispersion S1 is formed by dispersing polyaniline polymer (PANI·EB) in liquid water (H 2 O), and the protonic acid aqueous solution S2 is formed by dissolving protonic acid (HA) in liquid water (H 2 O).

[0033] The polyaniline dispersion S1 can be prepared, for example, by adding 180 to 220 parts by weight of liquid water into a first batching barrel T1; then adding 50 to 100 parts by weight of polyaniline polymer into the first batching barrel T1; then stirring the mixed liquid in the first batching barrel T1 at 80 to 120 revolutions per minute (RPM) and stirring at room temperature for 20 to 60 minutes to form the polyaniline dispersion S1; and finally feeding the polyaniline dispersion S1 into a reaction tank M1.

[0034] The preparation method of the protonic acid aqueous solution S2 can be, for example: adding 80 to 120 parts by weight of liquid water to the second batching barrel T2; then adding 80 to 300 parts by weight of a protonic acid (such as CSA) to the second batching barrel T2; then stirring the mixed liquid in the second batching barrel T2 at 80 to 120 revolutions per minute (RPM) and stirring at room temperature for 20 to 60 minutes to form the protonic acid aqueous solution S2; finally, feeding the protonic acid aqueous solution S2 into the above-mentioned reaction tank M1.

[0035] It is worth mentioning that the protonic acid will dissociate after being dissolved in liquid water, so the pH value of the protonic acid aqueous solution S2 can be measured, which is different from the organic solvent system, the pH value of which cannot be measured.

[0036] In addition, it is worth mentioning that the batching operation can also selectively: prepare a liquid water fluid S3 in a third batching barrel T3. After the polyaniline dispersion S1 and the protonic acid aqueous solution S2 are fed into the reaction tank M1, the liquid water fluid S3 is prepared to wash the polyaniline polymer remaining in the first batching barrel T1 and the protonic acid (HA) remaining in the second batching barrel T2, and the liquid water fluid S3 is further fed into the above-mentioned reaction tank M1.

[0037] The amount of the liquid water fluid S3 can be, for example, between 190 parts by weight and 230 parts by weight, and the liquid water fluid S3 is stirred in the third batching barrel T3 at room temperature at 80 to 120 revolutions per minute (RPM) for 5 to 30 minutes, but the present invention is not limited thereto. Furthermore, the use of the liquid water fluid S3 also includes regulating the protonic acid concentration in the reaction tank M1.

[0038] In a preferred embodiment of the present invention, the liquid water used in step S110 is all purified water, which is referred to as clean water or pure water, that is, water without impurities or bacteria. Purified water is mainly produced by electrodialysis, ion exchange, reverse osmosis, distillation and other appropriate processing methods, but the present invention is not limited thereto.

[0039] The step S120 is to implement a feeding operation. The feeding operation includes: adding the polyaniline dispersion S1 and the protonic acid aqueous solution S2 into the reaction tank M1 to form a reaction mixture S4.

[0040] According to the above configuration, the reaction mixture S4 includes: the polyaniline polymer (PANI·EB), the protonic acid (HA), and the liquid water (H 2 O).

[0041] The reaction mixture S4 is adjusted to have a second pH value greater than the first pH value. The second pH value is between 0.50 and 0.80, and preferably between 0.50 and 0.75. Furthermore, a difference between the second pH value and the first pH value is not less than 0.1.

[0042] It is worth mentioning that the reaction mixture S4 needs to be under the above-mentioned strong acid condition to effectively improve the reaction efficiency of protonic acid (HA) mixed into polyaniline polymer (PANI·EB).

[0043] Furthermore, the amount of each component in the reaction mixture S4 has a certain degree of influence on the regulation of pH value, and also has a certain degree of influence on the reaction efficiency of protonic acid (HA) mixed with polyaniline polymer (PANI·EB).

[0044] In some embodiments of the present invention, the amount of the polyaniline polymer (PANI·EB) is between 50 parts by weight and 100 parts by weight (preferably 80 parts by weight), the amount of the protonic acid (HA) is between 30 parts by weight and 375 parts by weight (preferably between 100 parts by weight and 300 parts by weight), and the amount of the liquid water (H2O) is between 450 parts by weight and 550 parts by weight (preferably 495 parts by weight). The ratio between the molar equivalent of the protonic acid and the molar equivalent of the polyaniline polymer is between 0.25:1 and 1.5:1. That is, the molar equivalent of the protonic acid is between 0.25 and 1.5 times the molar equivalent of the polyaniline polymer, but the present invention is not limited thereto.

[0045] The step S130 is to implement a blending operation. The blending operation includes: heating the reaction mixture S4 in the reaction tank M1 from room temperature (e.g., 20-30°C) to a first temperature, so that the protonic acid (HA) and the polyaniline polymer (PANI·EB) undergo a blending reaction, thereby forming a conductive polyaniline polymer (PANI·A). The first temperature may be, for example, between 50°C and 100°C, and preferably between 60°C and 90°C.

[0046] It is worth mentioning that the inventors of the present application have finally discovered through many experiments that the above-mentioned heating temperature conditions make the polyaniline polymer have better dispersibility in the water system and greatly improve the efficiency of proton acid mixing into the polyaniline polymer.

[0047] The reaction mixture S4 generates a pH change during the mixing reaction. When the pH of the reaction mixture S4 changes from the second pH value to a third pH value, the mixing operation further includes: cooling the reaction mixture S4 from the first temperature to a second temperature to terminate the mixing reaction. The second temperature may be, for example, between 20°C and 40°C.

[0048] Furthermore, the third pH value is between 0.80 and 1.10, and a difference between the third pH value and the second pH value is not less than 0.1, but the present invention is not limited thereto.

[0049] It is worth mentioning that the manufacturing method of the present invention can confirm whether the mixing reaction of the proton acid into the polyaniline polymer has reached the ideal level by monitoring the pH value change of the reaction mixture S4 during the mixing reaction. When the pH value of the reaction mixture S4 during the mixing reaction is increased from the second pH value between 0.50 and 0.80 (also called the initial pH value of the mixing reaction) to the third pH value between 0.80 and 1.10 (also called the final pH value of the mixing reaction), it means that the amount of the proton acid mixed into the polyaniline polymer has reached the ideal level. According to the above technical solution, the process of the conductive polyaniline polymer (PANI·A) can become simpler and more efficient.

[0050] Among them, the mixing reaction mechanism of proton acid into polyaniline polymer is as follows:

[0051]

[0052] In some embodiments of the present invention, the reaction mixture S4 is heated from room temperature (e.g., 20°C to 30°C) to a first temperature (e.g., 50°C to 100°C) at a heating rate of 0.5°C to 5°C per minute, and preferably 0.5°C to 3°C per minute. The reaction mixture S4 is stirred at a rate of 30 rpm to 70 rpm in the reaction tank M1. The reaction conditions of the reaction mixture S4 in the reaction tank M1 are heating to the first temperature and reacting at a constant temperature for 0.5 to 6 hours, and preferably 1 to 3 hours, but the present invention is not limited thereto.

[0053] In addition, in some embodiments of the present invention, the cooling rate of the reaction mixture S4 from a first temperature (e.g., 50°C to 100°C) to a second temperature (e.g., 20°C to 40°C) is 0.5°C to 5°C per minute, and preferably between 0.5°C and 3°C per minute, but the present invention is not limited thereto.

[0054] After the reaction mixture S4 is cooled from the first temperature (e.g., 50°C to 100°C) to the second temperature (e.g., 20°C to 40°C), the reaction mixture S4 is discharged into a temporary storage tank M2 for subsequent separation operations. After the mixing reaction is terminated, the reaction mixture S4 contains conductive polyaniline polymer (PANI·A), residual protonic acid (HA), and liquid water.

[0055] The step S140 is to implement a separation operation, which includes: discharging the cooled reaction mixture S4 to a separation unit M3 to separate the solid component S5 and the liquid component S6 in the reaction mixture S4 from each other.

[0056] The solid component S5 in the reaction mixture S4 includes conductive polyaniline polymer (PANI·A) and liquid water (H2O). Furthermore, the liquid component S6 in the reaction mixture S4 includes protonic acid (HA) and liquid water (H2O).

[0057] In some embodiments of the present invention, the cooled reaction mixture S4 is discharged to a separation unit M3 through a temporary storage tank M2. The separation unit M3 may be, for example, a continuously fed centrifugal machine.

[0058] In some embodiments of the present invention, the separation conditions of the separation unit M3 include: a feed rate of 10 to 20 kg per minute, a centrifugal speed of between 2,000 rpm and 3,500 rpm, a centrifugal time of between 60 minutes and 120 minutes, and the solid component is centrifuged to have a water content of no more than 60%.

[0059] It should be noted that the water content in this embodiment is gravimetric water content, but the present invention is not limited thereto. Water content refers to the weight ratio of water in a material. In this embodiment, the material refers to a crude product of conductive polyaniline polymer (PANI·A).

[0060] The step S150 is to implement a drying operation. The drying operation includes: introducing the crude product S5 of the conductive polyaniline polymer (PANI·A) into a drying unit M4 to reduce the moisture content in the conductive polyaniline polymer (PANI·A), thereby obtaining the final product S7 of the conductive polyaniline polymer (PANI·A). According to the above technical solution, the content of the proton acid mixed into the conductive polyaniline polymer can be not less than 30wt%, and the impedance value of the conductive polyaniline polymer is not greater than 20Ω.cm, and preferably not greater than 15Ω.cm.

[0061] In some embodiments of the present invention, the drying unit M4 is a screw vacuum dryer. The drying conditions of the drying unit M4 include: a feeding rate of 5 to 20 kg per minute, and a drying time of 4 to 8 hours.

[0062] It is worth mentioning that the content of the protonic acid (CSA) mixed into the conductive polyaniline polymer (such as PANI.CSA) is confirmed by titration. The standard operating procedure for confirming the mixing amount of the protonic acid by titration is:

[0063] (1) Weigh about 0.5 g of PANI-CSA in a 100 ml beaker and record the weight of PANI-CSA as A (g).

[0064] (2) Add 20 ml (nominal value wN) of 0.1 N NaOH(aq) to the beaker in step (1), and record the actual weight of 0.1 N NaOH(aq) added as x (g) and the volume as x (ml).

[0065] (3) The liquid in step (2) was stirred at 25°C for 30 minutes (100 rpm). After the stirring was completed, centrifugal filtration was performed (3000 rpm, 3 min). After the centrifugation was completed, 15 g of the filtrate was weighed and the weight was recorded as Z (g).

[0066] (4) Add 4 drops of BTB indicator to the beaker in step (3), titrate with 0.1 N HCl (aq) (calibration value vN), observe the solution change from blue to yellow, and record the volume of 0.1 N HCl (aq) used as y (ml).

[0067] (5) Calculate CSA: The weight of CSA is B (g), and the weight of the total filtrate in step (3) is (X + B) (g). When calculating for the first time, B is unknown and is calculated as 0.

[0068] (6) Since step (3) involves titrating a portion of the filtrate, the denominator includes not only the added NaOH but also the CSA dissolved by the alkali. Therefore, the weight of CSA calculated in step (5) must be substituted back into the formula in step (5). Repeat this process twice to obtain an approximate value.

[0069] The proton acid anion (A) in the conductive polyaniline polymer is converted into - ) is replaced, and then acid-base titration is performed to deduce the replacement A - The consumption of strong base is used to obtain the mixing amount of proton acid, and the steps are as noted.

[0070] The step S160 is to implement a reflow operation, and the reflow operation includes: reflowing the liquid component S6 in the reaction mixture S4 to a recovery tank M5, and further introducing the liquid component S6 into a fourth batching barrel T4 to mix with another batch of protonic acid (HA) to form a reflow aqueous solution S8. In addition, a condensed liquid water S9 generated by the drying unit M4 can also be reflowed to the recovery tank M5 and further introduced into the fourth batching barrel T4.

[0071] The reflux aqueous solution S8 is adjusted to have a fourth pH value, and the fourth pH value is between the first pH value (eg, 0.20-0.50) and the second pH value (eg, 0.50-0.80).

[0072] In some embodiments of the present invention, the fourth pH value ranges from 0.50 to 0.70, and preferably ranges from 0.60 to 0.70.

[0073] In some embodiments of the present invention, the reflux operation further includes quantifying the content of the protonic acid (HA) in the liquid component S6 and calculating the required addition amount of the protonic acid of another batch, so that the reflux aqueous solution S8 is adjusted to have the fourth pH value between 0.50 and 0.70.

[0074] In some embodiments of the present invention, the reflux operation further comprises: adding the reflux aqueous solution S8 and another batch of polyaniline dispersion S1' to the reaction tank M1, respectively, to form another batch of reaction mixture S4', which has a fifth pH value, and the fifth pH value is controlled to be between 80% and 120% of the second pH value of the first batch of the reaction mixture S4. Preferably, the fifth pH value is controlled to be between 90% and 110% of the second pH value. More preferably, the fifth pH value is controlled to be the same as the second pH value, but the present invention is not limited thereto.

[0075] In another batch of the reaction mixture S4', the ratio of the molar equivalent of the protonic acid to the molar equivalent of the polyaniline polymer is between 0.25:1 and 1.5:1. Alternatively, the weight ratio of the amount of the protonic acid to the amount of the polyaniline polymer is between 0.625:1 and 3.75:1, and preferably between 1.25:1 and 3.75:1.

[0076] Since the concentration of protonic acid (HA) in the refluxed liquid component S6 is only 5-8wt%, it is impossible to achieve the initial first pH value after mixing with the initial protonic acid aqueous solution S2 (HA / H2O) and the recycling rate is 80wt%. The initial HA / H2O concentration is 50-55wt%, and the pH value is 0.20 to 0.50.

[0077] In a specific embodiment of the present invention, the reflow operation further comprises the following sub-steps:

[0078] Step S210 includes: taking the refluxed liquid component S6 (ie, process waste liquid), and evaluating the protonic acid content (eg, CSA wt %) in the liquid component S6 by titration.

[0079] Take the case where the process waste contains 8wt% CSA and the recycling rate is 80wt% as an example:

[0080] Step S220 is to implement a batching operation, which includes: adding 110 to 150 parts by weight of liquid water into a first batching barrel T1; then adding 50 to 100 parts by weight of polyaniline polymer into the first batching barrel T1; then stirring the mixed liquid in the first batching barrel T1 at 80 to 120 revolutions per minute (RPM) and stirring at room temperature for 20 to 60 minutes to form another batch of polyaniline dispersion S1'; finally, feeding the other batch of polyaniline dispersion S1' into a reaction tank M1.

[0081] The batching operation also includes: adding 350 to 450 parts by weight of the refluxed liquid component S6 (i.e., process waste liquid) to the fourth batching barrel T4; then adding 50 to 80 parts by weight of a protonic acid (such as CSA) to the fourth batching barrel T4; then stirring the mixed liquid in the fourth batching barrel T4 at a speed of 80 to 120 per minute (RPM) and stirring at room temperature for 20 to 60 minutes to form the reflux aqueous solution S8; finally, feeding the reflux aqueous solution S8 into the above-mentioned reaction tank M1.

[0082] The above-mentioned another batch of polyaniline dispersion liquid S1 ′ and the reflux aqueous solution S8 are mixed in the reaction tank M1 to form another batch of reaction mixture S4 ′.

[0083] The blending operation after the reflux operation is roughly the same as step S130 to step S160 of the above-mentioned embodiment, and will not be described in detail here. It is worth mentioning that the reflux operation of the embodiment of the present invention can be repeated at least five times, and it still has a certain efficiency for the blending reaction. It is worth mentioning that when refluxed, trace metals in the refluxed liquid component S6 will accumulate. This embodiment mainly uses ICP-AES to evaluate the changes in the content of metals (such as barium, molybdenum, tin, nickel, zinc, copper, mercury, total chromium, lead, cadmium, arsenic, cobalt, iron, and manganese) in accordance with the environmental inspection standard NIEA W311.54C. When the metal value exceeds a standard mass, the used liquid component will no longer be refluxed for use. In this embodiment, if the sum of the above-listed metal values ​​exceeds 35ppm, the used liquid component will no longer be refluxed for use.

[0084] [Influence of feed ratio]

[0085] Table 1 below shows the effect of the feed ratio of the reaction mixture S4 on the conductivity of the finally obtained conductive polyaniline polymer (PANI·A).

[0086] Other fixing conditions for preparing conductive polyaniline polymer (PANI·A) are as follows:

[0087] Reaction tank temperature: 25℃ to 60℃, heating rate 1℃ / min. Stirring rate maintained at 50±10rpm. Mixing reaction: The tank temperature is controlled at 60℃ and kept for 2 hours. Cooling and discharging: The reaction tank temperature is cooled from 60℃ to 35℃, and the cooling rate is 1℃ / min. Filtration: Discharge to a continuous centrifuge, feed rate 15kg / min, centrifugal rate 2,500-3,000rpm, centrifugal time 90 minutes, centrifugal to moisture content <60%. Drying: Introduce the crude product after centrifugation into a spiral dryer, feed rate 10kg / min, drying time 4-8 hours. Finished product confirmation: Titration confirms that the CSA content is >30wt%.

[0088] [Table 1]

[0089]

[0090]

[0091] From the test results in Table 1, it can be seen that the amount of polyaniline (PANI) is 80 parts by weight, the amount of protonic acid (CSA) is between 100 parts by weight and 300 parts by weight, and the amount of liquid water is 495 parts by weight. The weight ratio between the amount of protonic acid and the amount of polyaniline polymer is between 1.25:1 and 3.75:1. The second pH value (initial pH value) is adjusted to between 0.5 and 0.71. After the reaction, the protonic acid accounts for the product equivalent (PANI:HA) between 1:0.39 and 1:0.66. The above conditions can make the final product have better conductivity, that is, it has an impedance value between 3.86 and 9.65Ω.cm.

[0092] [Effect of temperature]

[0093] Table 2 below shows the effect of the reaction temperature of the blending reaction on the conductivity of the finally obtained conductive polyaniline polymer (PANI·A).

[0094] Other fixing conditions for preparing conductive polyaniline polymer (PANI·A) are as follows:

[0095] The feed ratio (weight ratio) is CSA:PANI:H2O=100:80:495.

[0096] Reaction tank temperature: 25℃ to 60℃ or 90℃, heating rate 1℃ / min. Stirring rate maintained at 50±10rpm. Mixing reaction: The tank temperature is controlled at 60℃ or 90℃ and the reaction is maintained for 2 hours. Cooling and discharging: The reaction tank temperature is cooled from 60℃ or 90℃ to 35℃, and the cooling rate is 1℃ / min. Filtration: Discharge to a continuous centrifuge, feed rate 15kg / min, centrifugal rate 2,500-3,000rpm, centrifugal time 90 minutes, centrifugal to moisture content <60%. Drying: The crude product after centrifugation is introduced into a spiral dryer, and the feed rate is 10kg / min, and the drying time is 4-8 hours. Finished product confirmation: Titration confirms that the CSA content is >30wt%.

[0097] [Table 2]

[0098]

[0099] From the test results in Table 2, it can be seen that the reaction temperature of 60° C. or 90° C. can make the final product have better conductivity than the preparation condition of the reaction temperature of 25° C., that is, the impedance value is between 5.57 and 9.65 Ω.cm.

[0100] [Beneficial Effects of Embodiments]

[0101] One of the beneficial effects of the present invention is that the method for producing a conductive polyaniline polymer provided by the present invention can be carried out by "implementing a batching operation, comprising: preparing a polyaniline dispersion and a protonic acid aqueous solution respectively; wherein the polyaniline dispersion comprises polyaniline polymer and liquid water, and the protonic acid aqueous solution comprises protonic acid and liquid water; and the protonic acid aqueous solution is adjusted to have a first pH value; implementing a feeding operation, comprising: adding the polyaniline dispersion and the protonic acid aqueous solution to a reaction tank respectively to form a reaction mixture, which is adjusted to have a second pH value greater than the first pH value; and implementing a mixing operation. The mixing operation comprises: heating the reaction mixture in the reaction tank to a first temperature so that the proton acid and the polyaniline polymer undergo a mixing reaction to form a conductive polyaniline polymer; wherein the reaction mixture undergoes a pH change during the mixing reaction; when the pH change of the reaction mixture is increased from the second pH to a third pH, the mixing operation further comprises cooling the reaction mixture to a second temperature to terminate the mixing reaction. "The technical scheme is provided to enable the preparation of conductive polyaniline polymer to be carried out under the conditions of an aqueous reaction system and with a high yield. Furthermore, the existing manufacturing method has problems such as the discharge of waste organic solvents and the presence of volatile organic compounds (VOCs) in the product, which can be effectively solved.

[0102] Furthermore, the manufacturing method of the present invention can confirm whether the mixing reaction of the proton acid into the polyaniline polymer has reached an ideal level by monitoring the pH value change of the reaction mixture during the mixing reaction. When the pH value of the reaction mixture during the mixing reaction is increased from the second pH value to the third pH value, it means that the amount of the proton acid mixed into the polyaniline polymer has reached an ideal level. According to the above technical solution, the process of manufacturing the conductive polyaniline polymer can become simpler and more efficient.

[0103] The contents disclosed above are only preferred feasible embodiments of the present invention, and are not intended to limit the scope of the present invention. Therefore, all equivalent technical changes made using the contents of the present invention's specification and drawings are included in the scope of the present invention.

Claims

1. A method for producing a conductive polyaniline polymer, characterized in that: The method for producing the conductive polyaniline polymer comprises: Implementing a batching operation, comprising: preparing a polyaniline dispersion and a protonic acid aqueous solution respectively; wherein the polyaniline dispersion is formed by dispersing polyaniline polymer in liquid water, and the protonic acid aqueous solution is formed by dissolving protonic acid in liquid water; and the protonic acid aqueous solution is adjusted to have a first pH value, and the first pH value is between 0.20 and 0.50; Implementing a feeding operation, comprising: adding the polyaniline dispersion and the protonic acid aqueous solution into a reaction tank respectively to form a reaction mixture, which is adjusted to have a second pH value greater than the first pH value, and the second pH value is between 0.50 and 0.80; and A mixing operation is performed, comprising: heating the reaction mixture in the reaction tank to a first temperature between 50° C. and 100° C. so that the proton acid and the polyaniline polymer undergo a mixing reaction to form a conductive polyaniline polymer; wherein the reaction mixture undergoes a pH change during the mixing reaction; when the pH change of the reaction mixture is increased from the second pH to a third pH, the mixing operation further comprises cooling the reaction mixture to a second temperature to terminate the mixing reaction; wherein the third pH is between 0.80 and 1.

10.

2. The method for producing a conductive polyaniline polymer according to claim 1, characterized in that: A difference between the second pH value and the first pH value is not less than 0.1, and a difference between the third pH value and the second pH value is not less than 0.

1.

3. The method for producing a conductive polyaniline polymer according to claim 1, characterized in that: In the feeding operation, the reaction mixture comprises the polyaniline polymer, the protonic acid, and the liquid water, the amount of the polyaniline polymer is between 50 parts by weight and 100 parts by weight, the amount of the protonic acid is between 30 parts by weight and 375 parts by weight, and the amount of the liquid water is between 450 parts by weight and 550 parts by weight; wherein the ratio between the molar equivalent of the protonic acid and the molar equivalent of the polyaniline polymer is between 0.25:1 and 1.5:

1.

4. The method for producing a conductive polyaniline polymer according to claim 1, characterized in that: After the mixing operation, the manufacturing method further comprises: A separation operation is performed, comprising: discharging the cooled reaction mixture to a separation unit to separate the solid component and the liquid component of the reaction mixture; wherein the solid component in the reaction mixture comprises the crude product of the conductive polyaniline polymer, and the liquid component in the reaction mixture comprises the residual protonic acid and the liquid water.

5. The method for producing a conductive polyaniline polymer according to claim 4, characterized in that: After the separation operation, the manufacturing method further comprises: A drying operation is performed, comprising: introducing the crude product of the conductive polyaniline polymer into a drying unit to reduce the moisture content in the solid component; wherein the content of the proton acid mixed into the conductive polyaniline polymer is not less than 30wt%, and an impedance value of the conductive polyaniline polymer is not greater than 20Ω.cm.

6. The method for producing a conductive polyaniline polymer according to claim 4, characterized in that: After the separation operation, the manufacturing method further comprises: A reflux operation is performed, which includes: refluxing the liquid component in the reaction mixture and mixing the liquid component with another batch of the protonic acid to form a reflux aqueous solution; wherein the reflux aqueous solution is adjusted to have a fourth pH value, the fourth pH value is between the first pH value and the second pH value, and the fourth pH value has a numerical range of 0.50 to 0.

70.

7. The method for producing a conductive polyaniline polymer according to claim 6, characterized in that: The reflow operation further comprises: The content of the protonic acid in the liquid component is quantified and the required amount of the protonic acid to be added in another batch is calculated, so that the reflux aqueous solution is adjusted to have the fourth pH value.

8. The method for producing a conductive polyaniline polymer according to claim 6, characterized in that: The reflow operation further comprises: The reflux aqueous solution and another batch of the polyaniline dispersion are added to the reaction tank respectively to form another batch of the reaction mixture, which has a fifth pH value, and the fifth pH value is controlled to be between 80% and 120% of the second pH value; wherein, in the another batch of the reaction mixture, the ratio between the molar equivalent of the protonic acid and the molar equivalent of the polyaniline polymer is between 0.25:1 and 1.5:

1.

9. The method for producing a conductive polyaniline polymer according to claim 1, characterized in that: In the batching operation, the polyaniline dispersion is formed by dispersing the polyaniline polymer in the liquid water, and the protonic acid aqueous solution is formed by dissolving the protonic acid in the liquid water.

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