CN110655641B - Method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ solid state polymerization - Google Patents

Method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ solid state polymerization Download PDF

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CN110655641B
CN110655641B CN201910800240.2A CN201910800240A CN110655641B CN 110655641 B CN110655641 B CN 110655641B CN 201910800240 A CN201910800240 A CN 201910800240A CN 110655641 B CN110655641 B CN 110655641B
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CN110655641A (en
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曹梅娟
李路海
李亚玲
孙志成
莫黎昕
刘儒平
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Beijing Institute of Graphic Communication
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/09—Sulfur-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/44—Electrochemical polymerisation, i.e. oxidative or reductive coupling

Abstract

The invention relates to a method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ solid state polymerization, wherein the preparation method of the conductive polythiophene comprises the following steps: s1, fully dissolving thiophene derivatives and iodine which are solid at room temperature into a volatile organic solvent, and forming a monomer film on a substrate in a spin coating or spraying mode; s2, placing the monomer film in the S1 in an atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, and obtaining the conductive polythiophene film after the polymerization is completed. The preparation of the conductive paper is similar to the method, and the difference is that the paper sheet needs to be soaked in a solution of thiophene derivatives and iodine, and then in-situ solid state polymerization under plasma is carried out. The method has the advantages that DBD plasma is used for initiating solid-phase polymerization of thiophene derivatives to generate conductive polythiophene, so that the complexity of the polymerization process is reduced, and the process is simple; and (3) carrying out solid-phase polymerization on the thiophene derivative in the paper sheet to obtain the conductive paper, wherein the prepared conductive paper has stable performance.

Description

Method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ solid state polymerization
Technical Field
The invention relates to the technical field of conductive high polymer materials, conductive paper and paper-based electronic devices, in particular to a method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ polymerization.
Background
Paper-based electronics have many advantages, such as being able to replace traditional electronics due to their biodegradable, flexible, and low cost characteristics. In addition, paper electronics are easily manufactured in various shapes to meet customer needs, from smart packaging to the use of paper batteries. They are flexible and therefore can be folded like ordinary paper to build unique electronic and optoelectronic devices.
The function of the paper can be adjusted by adding various functional materials, and the paper is used for preparing paper-based electronic devices. Conductive materials such as carbon, metals or polymers can be coated on the paper or mixed into the paper matrix to make the conductive paper. The simplest method is to print or draw the material on a piece of paper. This method has disadvantages of poor long-term stability of the substrate and low adhesion to the substrate. The service life of the conductive paper can be significantly improved if the materials in the paper are mixed to form a strong paper mixture. However, this method requires the preparation of electrically conductive paper in the paper making stage, which is usually done in a paper mill, because the electrically conductive material cannot penetrate into most types of already formed paper, except for paper with large pores.
Among conductive polymers, Polythiophene (PT) is one of the most widely used conductive polymers in the field of polymer electronics due to its high stability, high conductivity and high electrochemical activity. Applications of polythiophenes include electronics, optics, transistors, electrochromic devices, solar cells, sensors, electroluminescent devices, and the like. Since unsubstituted polythiophenes are insoluble in all common organic solvents, polythiophene-based electronics are typically prepared by printing thiophene polymers directly on the surface of a substrate. The polythiophene film is synthesized by electrochemical polymerization of thiophene in solution through chemical oxidation polymerization or plasma gas phase polymerization. Chemical oxidative polymerization of thiophene refers to the deposition of a lewis acid or oxidation catalyst on a substrate, followed by exposure of the substrate to a gaseous thiophene or thiophene derivative, which initiates oxidative polymerization on the substrate. In conventional plasma polymerization reactions, gaseous thiophene is typically used as the working plasma gas in argon, and the thiophene is plasma deposited and polymerized onto a substrate to form a thin film. Electrochemical polymerization of thiophene is carried out in solution, and in the electrochemical process, a polythiophene film is formed on the anode. However, none of these methods can be used directly for the polymerization of thiophenes in paper.
The polymerization of liquid or solid monomers, such as ultraviolet initiated vinyl monomer polymerized films, greatly reduces the complexity of the polymerization process, and can be widely applied to various substrates or papers. Unfortunately, in the absence of an oxidation catalyst, uv light cannot initiate polymerization of thiophene and thiophene derivatives on a substrate or within a sheet of paper. Therefore, there is a need for a new method for preparing conductive polythiophene and conductive paper.
Disclosure of Invention
The invention provides a method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ solid state polymerization, and aims to overcome the defects that the conductive polythiophene prepared by traditional plasma polymerization or electrochemical polymerization in solution in the prior art cannot effectively introduce a conductive polymer into paper, cannot obtain conductive paper with good long-term stability and the like.
The technical scheme for solving the technical problems is as follows: the method for preparing the conductive polythiophene by the in-situ solid state polymerization of the atmospheric pressure plasma comprises the following steps:
s1, fully dissolving thiophene derivatives and iodine which are solid at room temperature into a volatile organic solvent, and forming a monomer film on a substrate in a spin coating or spraying mode;
s2, placing the monomer film in the S1 in an atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, and obtaining the conductive polythiophene film after the polymerization is completed.
The above polymerization reaction, the polymerization is initiated by a Dielectric Barrier Discharge (DBD) plasma, which is a non-thermal plasma under ordinary environmental conditions, i.e., room temperature and atmospheric pressure, by applying a discharge between two electrodes. At least one of the two electrodes is covered by a dielectric material to avoid the flow of electrons between the tunnel and the two electrodes, so that the plasma can safely be used as a so-called "cold plasma" in contrast to a thermal plasma. The DBD device can be made as a handheld device, as convenient as a UV handheld device. The ionized air-plasma contains reactive oxygen and nitrogen species (ROS and RNS), including ozone (O3),. NO,. OH, superoxide anion (O)2-) And electrons, etc., which can effectively initiate polymerization because these species can effectively penetrate thin monomer films and any type of paper.
On the basis of the technical scheme, the invention can be further improved as follows.
Specifically, the thiophene derivative in step S1 is 2,2' -bithiophene or 3,3' -dibromo-2, 2' -bithiophene.
In addition to the above two substances, other thiophene derivatives that are solid at room temperature and are readily soluble in volatile organic solvents may be used.
Specifically, the organic solvent in step S1 is preferably ethanol or chloroform, which is volatile and can effectively dissolve the above thiophene derivative.
Specifically, the thickness of the monomer film in step S1 is 0.01-0.25mm, and the monomer film is placed in the air for 5-30min after being sprayed or spin-coated, and then is placed in the atmospheric pressure plasma of the dielectric barrier discharge device for polymerization after the solvent is properly volatilized.
It should be noted that the substrate is made of quartz or silicon material, the rotation speed during spin coating is controlled to 500-.
Specifically, the dielectric barrier discharge device in step S2 uses a variable voltage and variable voltage frequency nanosecond pulse power supply, and the preferable parameters of the dielectric barrier discharge device during operation are set as: voltage 11.2kV, resistance 75 Ω, frequency 690 Hz.
It should be noted that, the specific structure of the Dielectric barrier discharge device can refer to the device used in Oxidation of L-vapor under Non-Thermal Dielectric barrier discharge Plasma, j.phys.chem. (2014),118,1612-1620, the power source is a nanosecond pulse power source with variable voltage and variable voltage frequency, the maximum operating voltage is 20kV, and the operating frequency range is 500Hz to 1.5 kHz. The DBD electrode of the dielectric barrier discharge device was made of a 38mm x 64mm copper plate covered with a 1mm thick glass strip, the discharge gap of the plasma was <1cm, and the gap between the electrode and the lower surface and the upper surface of the monomer film was fixed at 1mm when the monomer film was processed.
Specifically, the polymerization time of the monomer film under the atmospheric pressure plasma is 5-15 min.
In addition, the invention also provides a method for preparing the conductive paper by atmospheric pressure plasma in-situ solid state polymerization, which comprises the following steps:
s1, sufficiently dissolving thiophene derivatives which are solid at room temperature and iodine in a volatile organic solvent to obtain a mixed solution;
s2, soaking the paper sheet into the mixed solution in the S1, fully soaking, taking out and drying;
and S3, placing the paper sheet soaked and dried in the S2 in an atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, and obtaining the conductive paper after polymerization is completed.
Specifically, the thiophene derivative in step S1 is 2,2' -bithiophene or 3,3' -dibromo-2, 2' -bithiophene, the organic solvent is ethanol or chloroform, the concentration of the thiophene derivative in the mixed solution is 1.5 to 2.5mol/L, and the concentration of iodine is 1 to 2 mol/L.
Specifically, the sheet in step S2 was a 70g, 80g, or 90g size a4 copy sheet.
Specifically, the step S2 is to soak the paper sheet at room temperature for more than 2 days, the step S to take out and dry the paper sheet is to take out the paper sheet from the thiophene derivative solution and dry the paper sheet in the air for more than 30min, and the step S3 is to place the paper sheet in the atmospheric pressure plasma of the dielectric barrier discharge device for in-situ solid state polymerization for 8-15 min.
Compared with the prior art, the invention has the beneficial effects that:
the atmospheric pressure plasma generated by the dielectric barrier discharge device is used for initiating the solid-phase polymerization of the thiophene derivative which is solid at room temperature to generate the conductive polythiophene, so that the complexity of the polymerization process is greatly reduced, the process is simple, the operation is convenient, and the efficiency is higher; the method comprises the steps of fully soaking paper with a mixed solution containing thiophene derivatives and iodine to enable the thiophene derivatives and the iodine to enter the paper, taking out the paper, drying the paper in the air for a period of time, and directly using atmospheric pressure plasma generated by a dielectric barrier discharge device to initiate solid-state thiophene derivatives at room temperature to perform solid-phase polymerization in the paper to obtain the conductive paper, wherein the conductive polymer is generated in the paper, the combination is firm, and the performance of the prepared conductive paper is relatively stable.
Drawings
FIG. 1 is a FT-IR chart of the Monomer film before DBD plasma treatment and the conductive Polymer formed after the treatment in example 1 (Monomer is the Monomer film and Polymer is the conductive Polymer);
FIG. 2 is a UV-VIS absorption spectrum of the monomer film of example 1 after exposure to plasma;
FIG. 3 is a reaction mechanism of radical cationic polymerization of 2,2' -bithiophene in DBD plasma;
FIG. 4 is a graphical representation of the conductivity over time of the iodine non-doped conductive polythiophene prepared in example 1;
FIG. 5 is a graphical representation of the conductivity over time of the conductive polythiophene produced following incorporation of iodine as prepared in example 2;
FIG. 6 is a schematic view of the conductive paper prepared in example 4 used as an electrode in an LED lamp device to test its conductive ability (the conductive paper is a black paper sheet);
fig. 7 is a schematic view of the conductive paper prepared in example 5 when used as an electrode of a paper-based electrophoretic device.
Detailed Description
The principles and features of this invention are described in connection with the drawings and the detailed description of the invention, which are set forth below as examples to illustrate the invention and not to limit the scope of the invention.
For the sake of brevity, the drugs used in the following examples are all commercially available drugs unless otherwise specified, and the methods used are conventional in the art unless otherwise specified.
Example 1
The method for preparing the conductive polythiophene by the in-situ solid state polymerization of the atmospheric pressure plasma comprises the following steps:
s1, fully dissolving 2,2' -bithiophene which is solid at room temperature in a volatile organic solvent, specifically dissolving 200mg of 2, 2-bithiophene in 1mL of ethanol (without iodine), centrifuging at 10000rpm for 10 minutes to fully dissolve, applying the clear solution to spin coating, spin coating 5 times on a quartz substrate at 750rpm, standing for 5-10 minutes, and forming a solid monomer film (the thickness is about 0.10mm) on the upper surface of the quartz substrate after the solvent is volatilized;
s2, placing the monomer film in the S1 in an atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, wherein the dielectric barrier discharge device (a DBD electrode is made of a copper plate with the thickness of 1mm and the thickness of 38mm multiplied by 64mm, the discharge gap of the plasma is less than 1cm) adopts a nanosecond pulse power supply with variable voltage and variable voltage frequency, and the power supply parameters are set as follows when the dielectric barrier discharge device works: voltage is 11.2kV, resistance is 75 omega, frequency is 690Hz, polymerization is carried out for 8min, and the conductive polythiophene film is obtained.
Example 2
The method for preparing the conductive polythiophene by the in-situ solid state polymerization of the atmospheric pressure plasma comprises the following steps:
s1, fully dissolving 2,2' -bithiophene which is solid at room temperature and iodine in a volatile organic solvent, specifically 200mg of 2, 2-bithiophene and 200mg of I2Dissolving in 1mL ethanol, centrifuging at 10000rpm for 10min to dissolve completely, spin coating the clear solution at 750rpm for 5 times on a quartz substrate, standing for 5-10min to evaporate the solvent, and forming a solid monomer film (with a thickness of about 0.10mm) on the upper surface of the quartz substrate;
s2, placing the monomer film in the S1 in an atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, wherein the dielectric barrier discharge device (a DBD electrode is made of a copper plate with the thickness of 1mm and the thickness of 38mm multiplied by 64mm, the discharge gap of the plasma is less than 1cm) adopts a nanosecond pulse power supply with variable voltage and variable voltage frequency, and the power supply parameters are set as follows when the dielectric barrier discharge device works: voltage is 11.2kV, resistance is 75 omega, frequency is 690Hz, polymerization is carried out for 8min, and the conductive polythiophene film is obtained.
Example 3
The method for preparing the conductive polythiophene by the in-situ solid state polymerization of the atmospheric pressure plasma comprises the following steps:
s1, fully dissolving 2,2' -bithiophene which is solid at room temperature and iodine in a volatile organic solvent, specifically dissolving 200mg of 3,3' -dibromo-2, 2' -bithiophene and 200mg of I2Dissolving in 1.5mL of chloroform, centrifuging at 10000rpm for 10 minutes to dissolve sufficiently, spin-coating the clear solution at 550rpm for 6 times on a quartz substrate, standing for 10-15min, and volatilizing the solvent to form a solid monomer film (with a thickness of about 0.20mm) on the upper surface of the quartz substrate;
s2, placing the monomer film in S1 under atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, wherein the dielectric barrier discharge device adopts a variable-voltage and variable-voltage-frequency nanosecond pulse power supply, and the power supply parameters are set when the dielectric barrier discharge device (DBD electrode is made of a 38mm x 64mm copper plate covered with a 1mm thick glass strip, and the discharge gap of the plasma is less than 1cm) works: the voltage is 11.2kV, the resistance is 75 omega, the frequency is 690Hz, and the polymerization treatment is carried out for 12min, thus obtaining the conductive polythiophene film.
Example 4
The method for preparing the conductive paper by the in-situ solid state polymerization of the atmospheric pressure plasma comprises the following steps:
s1, fully dissolving 2,2 '-bithiophene which is solid at room temperature and iodine in a volatile organic solvent to obtain a mixed solution, specifically, 3g of 2,2' -bithiophene and 3g I2Dissolved together in 9mL of chloroform at a concentration of 2,2' -bithiophene of 2mol/L, I2Has a concentration of about 1.3 mol/L;
s2, soaking A4 copy paper with the length of 2.5cm and the width of about 0.8cm in the mixed solution in the S1 for 2 days to fully soak the paper, and then taking out and drying the paper in the air for 30 min;
s3, placing the soaked and dried paper sheet in the S2 under atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, wherein the dielectric barrier discharge device (the DBD electrode is made of a copper plate which is 38mm multiplied by 64mm and covered by a glass strip with the thickness of 1mm, the discharge gap of the plasma is less than 1cm) adopts a nanosecond pulse power supply with variable voltage and variable voltage frequency, and the power supply parameters are set as follows when the dielectric barrier discharge device works: polymerizing for 8min under the atmospheric pressure plasma with the voltage of 11.2kV, the resistance of 75 omega and the frequency of 690Hz to obtain the black conductive paper.
Example 5
The method for preparing the conductive paper by the in-situ solid state polymerization of the atmospheric pressure plasma comprises the following steps:
s1, fully dissolving 3,3 '-dibromo-2, 2' -bithiophene which is solid at room temperature and iodine in a volatile organic solvent to obtain a mixed solution, specifically, 3.8g of 3,3 '-dibromo-2, 2' -bithiophene and 3.6g I2Dissolved together in 10mL of chloroform, the concentration of 3,3 '-dibromo-2, 2' -bithiophene was 1.2mol/L, I2Has a concentration of about 1.4 mol/L;
s2, soaking A4 copy paper with the length of 2.5cm and the width of about 0.8cm in the mixed solution in the S1 for 2 days to fully soak the paper, and then taking out and drying the paper in the air for 45 min;
s3, placing the soaked and dried paper sheet in the S2 under atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, wherein the dielectric barrier discharge device (the DBD electrode is made of a copper plate which is 38mm multiplied by 64mm and covered by a glass strip with the thickness of 1mm, the discharge gap of the plasma is less than 1cm) adopts a nanosecond pulse power supply with variable voltage and variable voltage frequency, and the power supply parameters are set as follows when the dielectric barrier discharge device works: polymerizing for 15min under the atmospheric pressure plasma with the voltage of 11.2kV, the resistance of 75 omega and the frequency of 690Hz to obtain the black conductive paper.
FT-IR characterization was performed on the monomer films before and after the atmospheric plasma treatment of DBD in example 1, and the IR spectra of the monomer films before and after the treatment are shown in FIG. 1, and it can be seen from the analysis that the 2,2' -bithiophene monomer film after the atmospheric plasma irradiation treatment is 1485cm-1,1421cm-1,1318cm-1,1221cm-1,1136cm-1,1034cm-1,843cm-1,797cm-1,730cm-1,700cm-1The peak is actually the same as the reported peak when the polythiophene red FT-IR obtained by oxidative polymerization and electrochemical polymerization of 2,2' -bithiophene is characterized, namely the peak is used for successfully initiating the 2,2' -bithiophene solid monomer film to generate in-situ solid polymerization when the 2,2' -bithiophene solid monomer film is treated by DBD atmospheric pressure plasma, and the conductive polythiophene is prepared.
The present inventors also tested the uv-vis spectrum of the monomer film in example 1 when exposed to the atmospheric plasma of DBD, and specifically, as shown in fig. 2, the 2,2' -bithiophene film showed a peak at 306 nm. When the film was treated with DBD, two new peaks at 398nm and 780nm were observed (fig. 2), which was attributed to the absorption of the polymer. During plasma treatment, the peak of the 2,2' -bithiophene monomer at 306nm gradually decreased and the peak of the polythiophene increased. According to the reported method, the rate of polymerization was calculated using the percent conversion of polymer, and the polymerization was known to have a second order reaction rate, indicating that the polymerization follows a free radical cation mechanism, the mechanism of polymerization being shown in FIG. 3.
The invention also takes the conductive polythiophene prepared in the example 1 and the example 2 as the object, the change of the conductivity with the time is respectively tested, and the results are respectively shown in the figure4 and 5. As can be seen from fig. 4, when no iodine is doped into the solution, the conductivity of the prepared conductive polythiophene is initially low and rapidly decreases to be stable to zero over time, which indicates that the conductive polythiophene prepared without doping is not practical due to poor conductivity and stability; as can be seen from FIG. 5, after iodine incorporation into the solution, the conductivity of the resulting conductive polythiophene was significantly increased initially compared to that without iodine incorporation, and gradually increased over time and finally stabilized at 1.8X 10-5S/cm, which is probably due to the long-lived reactive oxygen and nitrogen species (ROS and RNS) contained in the ionized air-plasma, the as yet unpolymerized bithiophene continues to undergo polymerization. Obviously, after the conductive polythiophene doped with iodine is finally stabilized, the conductive polythiophene doped with iodine meets the practical requirement better than the conductive polythiophene not doped with iodine. The conductivity of the conductive polythiophene prepared in example 3 was also tested, which is similar to the conductivity of the conductive polythiophene prepared in example, and the final stabilized conductivity was also large.
The black conductive paper prepared in examples 4 and 5 was also tested for its conductivity and ability to be used as a conductive component, as shown in fig. 6 and 7. Fig. 6a-b show that the manufactured conductive paper is conductive because the LED lamp is turned on to emit light when a voltage is applied. Figure 7 shows that conductive paper can be used as an electrode in a paper-based electrophoretic device, and when a voltage is applied, the dye chemistry moves towards the cathode, displaying a color pattern on the paper.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (3)

1. The method for preparing the conductive paper by the atmospheric pressure plasma in-situ solid state polymerization is characterized by comprising the following steps:
s1, sufficiently dissolving thiophene derivatives and iodine which are solid at room temperature into a volatile organic solvent to obtain a mixed solution;
s2, soaking the paper sheet into the mixed solution in the S1, fully soaking, taking out and drying;
s3, placing the paper sheet soaked and dried in the S2 in an atmospheric pressure plasma of a dielectric barrier discharge device for in-situ solid state polymerization, and obtaining conductive paper after polymerization is completed;
the paper sheet in the step S2 is 70g, 80g or 90g A4 copy paper;
the concentration of the thiophene derivative in the mixed solution is 1.5-2.5mol/L, and the concentration of iodine is 1-2 mol/L;
in S3, the time for polymerizing the paper sheet in the atmospheric pressure plasma of the dielectric barrier discharge device is 8-15 min.
2. The method for preparing conductive paper by atmospheric pressure plasma in-situ solid state polymerization according to claim 1, wherein the thiophene derivative in step S1 is 2,2' -bithiophene or 3,3' -dibromo-2, 2' -bithiophene, and the organic solvent is ethanol or chloroform.
3. The method for preparing conductive paper by atmospheric pressure plasma in-situ solid state polymerization according to any one of claims 1 to 2, wherein the step S2 is sufficient soaking at room temperature for more than 2 days, and the step S2 of removing and drying is to remove the paper sheet from the thiophene derivative solution and dry it in air for more than 30 min.
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