Conductive polymer and preparation method thereof
By synthesizing conductive polymers through the mixed reaction of polycarbonyl small molecules with ammonia sources and additives, the problems of limited structure and poor solubility of existing conductive polymers have been solved, achieving efficient and simple synthesis and wide application.
Patent Information
- Application Number
- CN202411001693.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-24
- Publication Date
- 2026-01-27
AI Technical Summary
Existing conductive polymers have limited structures and poor solubility, leading to difficult processing and high costs, which restricts their application in fields such as energy, optoelectronic devices, and sensors.
Conductive polymers were synthesized by mixing polycarbonyl small molecules with an ammonia source and additives, such as acetic acid and hydrochloric acid, in a simple one-pot reaction, thus broadening the structure of conductive polymers.
This method enables efficient and simple synthesis of conductive polymers, improves yield, expands the application scenarios of conductive polymers, and reduces processing difficulty and cost.
Smart Images
Figure CN121405883A_ABST
Abstract
Description
Technical Field
[0001] This application relates to a conductive polymer and its preparation method, belonging to the field of conductive polymer technology. Background Technology
[0002] In 1977, Hideki Shirakawa, Hegel, and Mark Diarmuid discovered conductive polymers and were the first to prepare polyacetylene with conductive properties, breaking the traditional view that polymers were insulators. In 2000, the three scientists were awarded the Nobel Prize in Chemistry for their discovery of conductive polymers. Since 1977, a large number of polymers with large conjugated bonds have been discovered, such as polypyrrole, polyaniline, polythiophene, and polyphenylene sulfide. Conductive polymers are materials whose main chain has a conjugated main electron system and can achieve a conductive state through doping, with conductivity levels approaching those of metallic copper.
[0003] The unique structure and excellent physicochemical properties of conductive polymers make them promising candidates for applications in secondary batteries, solar cells, solid-state batteries, supercapacitors, optoelectronic devices, transistors, ballasts, light-emitting diodes (LEDs), sensors (gas and biological), electromagnetic shielding, stealth technology, and biological probes. For example, in display materials, the conductivity of materials varies depending on the degree of doping and dedoping. Therefore, by controlling the amount of charge applied, conductive polymer materials can be altered between conductors, semiconductors, and insulators. The changes in conductivity of different types of materials correspond to different optical properties, allowing for the fabrication of display materials based on this principle. These color-changing polymer materials are also widely used in everyday life, such as coatings for energy-saving glass, display components, and instruments. In batteries, secondary batteries made from conductive polymer materials are easy to manufacture, process, form films, are flexible, small in size, lightweight, and have high energy density. In stealth technology, electromagnetic waves induce currents in conductors, generating heat and dissipating their energy. However, excessively high conductivity increases the reflection of electromagnetic waves from the material surface, hindering absorption. Because conductive polymers possess tunable conductivity, properly adjusting their conductivity can achieve a perfect stealth effect against electromagnetic waves. In the field of sensors, the conductivity of conductive polymers varies significantly with factors such as concentration, external temperature, and gas environment. Electrochemical sensors, ion concentration sensors, and temperature sensors prepared using conductive polymers have been widely applied. Summary of the Invention
[0004] According to the first aspect of this application, a conductive polymer is provided.
[0005] A conductive polymer, the general structural formula of which is as follows:
[0006]
[0007] Among them, R1, R2, R3, R 4、 R5 is independently selected from hydrogen, C6 to C6. 10 Aryl, C1-C 20 Alkyl, C2-C 20 At least one of the unsaturated alkanes.
[0008] Optionally, the molecular weight of the conductive polymer is 2,000 to 1,000,000.
[0009] According to a second aspect of this application, a method for producing a novel conductive polymer structure is provided. The method comprises: mixing a polycarbonyl small molecule (with 2 or more carbonyl groups) with various ammonia sources (such as ammonium salts, amines, ammonia, amino acids, hydrazine) in the presence of additives (such as acetic acid, hydrochloric acid, sulfuric acid, ammonium chloride proton hydrogen source, or ultraviolet light), and reacting the mixture to obtain the conductive polymer through a simple one-pot mixing and stirring process. The method provided in this application is efficient, simple, highly operable, produces a stable conductive polymer with high yield, broadens the structural range of conductive polymers, and expands their application scenarios.
[0010] This invention provides a simple and efficient method for synthesizing conductive polymers. Due to their unique properties, conductive polymers are widely used not only as conductive materials but also in energy, optoelectronic devices, sensors, and molecular wires. However, the known structures of conductive polymers are currently limited, including only polyacetylene (PAc), poly(p-phenylene) (PPP), poly(p-phenyleneacetylene) (PPV), polypyrrole (PPy), polythiophene (PT), and polyaniline (PANI). According to the generally accepted view that structure determines properties, the limited number of conductive polymer structures restricts their properties. Furthermore, the poor solubility of current conductive polymers leads to processing difficulties and high costs, thus limiting their development.
[0011] A method for preparing a conductive polymer includes the following steps:
[0012] The conductive polymer is obtained by mixing materials containing polycarbonyl small molecules, an ammonia source, and additives.
[0013] Wherein, the number of carbonyl groups in the polycarbonyl small molecule is greater than or equal to 2.
[0014] Optionally, the molar ratio of the polycarbonyl small molecule to the ammonia source is 1:1 to 10.
[0015] Optionally, the molar ratio of the polycarbonyl small molecule and the ammonia source is independently selected from any value or a range between 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, and 1:10.
[0016] Optionally, the molar ratio of the polycarbonyl small molecule to the additive is 1:0.001 to 5.
[0017] Optionally, the molar ratio of the polycarbonyl small molecule and the additive is independently selected from any value or a range between any two of 1:0.001, 1:0.005, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, and 1:10.
[0018] Optionally, the ammonia source is selected from at least one of ammonia, ammonium salts, amines, amino acids, and hydrazine.
[0019] Optionally, the number of carbon atoms in the polycarbonyl small molecule is 4 to 100.
[0020] Optionally, the number of carbon atoms in the polycarbonyl small molecule is independently selected from any value of 4, 6, 8, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or a range between any two.
[0021] Optionally, the additive is selected from a proton hydrogen source.
[0022] Optionally, the additive is selected from at least one of acetic acid, hydrochloric acid, sulfuric acid, and ammonium chloride.
[0023] Alternatively, the mixing conditions are as follows:
[0024] Temperature range: 0℃~200℃;
[0025] The time ranges from 0.1h to 36h.
[0026] Optionally, the temperature is independently selected from any value or a range between any two of 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, and 200℃.
[0027] Optionally, the time is independently selected from any value or a range between any two of 0.1h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, and 36h.
[0028] Optionally, the mixing is performed under ultraviolet light.
[0029] Optionally, the reaction is carried out with stirring at zero degrees or under heating conditions, and the product is precipitated in petroleum ether.
[0030] Optionally, the reaction is catalytic polymerization.
[0031] Optionally, the material may also contain a solvent.
[0032] Optionally, the solvent is selected from at least one of water and organic solvents.
[0033] Optionally, the organic solvent is selected from at least one of tetrahydrofuran, dichloromethane, dimethyl sulfoxide, and N,N-dimethylformamide.
[0034] According to one embodiment of this application, the technical solution included in this invention is as follows:
[0035] A method for obtaining conductive polymers by mixing polycarbonyl small molecules (carbonyl number greater than or equal to 2) with various ammonia sources (such as ammonium salts, amines, ammonia, amino acids, hydrazine, etc.) and additives (such as acetic acid, hydrochloric acid, sulfuric acid, ammonium chloride, etc. proton hydrogen sources) under the action of ultraviolet light, through simple operation.
[0036] The above synthesis mainly includes the following:
[0037] Step 1: Add polycarbonyl small molecules, ammonia, and acetic acid to a tetrahydrofuran solution;
[0038] Step 2: React at 0 degrees Celsius or under heating conditions for 0.1 h to 36 h;
[0039] Step 3: After the reaction is complete, the conductive polymer is precipitated in petroleum ether.
[0040] According to one embodiment of this application, the operation process includes the following:
[0041] (1) Take 1 equivalent (i.e. 3.73 mmol) of o-phthalaldehyde into a reaction tube;
[0042] (2) Add 0.5 equivalents of acetic acid to the reaction tube;
[0043] (3) Take 1.5 equivalents of methanol and ammonia into the reaction tube;
[0044] (3) Deoxygenate and purge the reaction tube with argon gas;
[0045] (4) When reacting at room temperature with stirring, the color of the reaction solution immediately changes from clear to black;
[0046] (4) After 24 hours, the polymer was directly precipitated in petroleum ether, rinsed three times with deionized water, and vacuum dried for 12 hours to obtain the conductive polymer.
[0047] In this application, "alkyl" refers to a group formed by losing any one hydrogen atom from an alkane compound molecule. The alkane compound includes straight-chain alkanes, branched alkanes, cycloalkanes, and branched cycloalkanes.
[0048] In this application, "aryl" is a group formed by the loss of a hydrogen atom from the aromatic ring of an aromatic compound molecule; such as p-tolyl formed by the loss of a hydrogen atom at the para position of the methyl group on the benzene ring of toluene.
[0049] In this application, "unsaturated alkane" refers to a hydrocarbon containing a double or triple bond.
[0050] In this application, the room temperature is 20℃~30℃.
[0051] The beneficial effects that this application can produce include:
[0052] This application provides a method for preparing conductive polymers. This method is simple to operate and highly feasible. It only requires mixing polycarbonyl small molecules with ammonia, amine, ammonium, etc., in the presence of additives, and then reacting. This method has a high yield. When the molar ratio of polycarbonyl small molecules to ammonia and additives is 1:1.5:0.5, the yield is >99% after 24 hours of reaction. This method is green and environmentally friendly, with minimal pollution from post-reaction treatment. This method broadens the structure of current conductive polymers. Attached Figure Description
[0053] Figure 1 This is the hydrogen NMR spectrum of the conductive polymer in Example 1 of the present invention.
[0054] Figure 2 This is the infrared spectrum of the conductive polymer in Example 1 of the present invention.
[0055] Figure 3This is the GPC spectrum of the conductive polymer in Example 1 of the present invention.
[0056] Figure 4 This is the ultraviolet-visible-near-infrared spectrum of the conductive polymer in Example 1 of the present invention.
[0057] Figure 5 This is a photograph of an LED lit up by doping a conductive polymer with ferric chloride, as described in Example 1 of this invention. Detailed Implementation
[0058] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0059] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased commercially. The phthalaldehydes, methanol, ammonia, acetic acid, and tetrahydrofuran used were of analytical grade.
[0060] The analysis method in the embodiments of this application is as follows:
[0061] Nuclear magnetic resonance (NMR) analysis was performed using a Bruker-BioSpin AVANCE III HD 400 NMR spectrometer.
[0062] Infrared analysis was performed using a Bruker infrared spectrometer.
[0063] GPC analysis was performed using an Agilent 1260 Infinity II gel permeation chromatograph.
[0064] UV-Vis-NIR analysis was performed using a PerkinElmer Lambda950 UV-Vis-NIR spectrophotometer.
[0065] The yield calculation in the embodiments of this application is as follows:
[0066] The yield of conductive polymers = separated mass / theoretical mass.
[0067] Example 1
[0068] The conductive polymer synthesized in this embodiment is shown below (molecular weight 600,000):
[0069]
[0070] This embodiment includes the following steps:
[0071] (1) Add 3.73 mmol of o-phthalaldehyde to the reaction tube, add 0.5 equivalents of acetic acid to the reaction tube, add 1.5 equivalents of methanol and ammonia to the reaction tube, and react for 24 hours at room temperature with stirring.
[0072] (2) The precipitate was placed in petroleum ether, washed three times with deionized water, and dried under vacuum for 12 hours to obtain the conductive polymer. The yield was >99%.
[0073] Figure 1 This is the hydrogen NMR spectrum of the conductive polymer in Example 1 of the present invention; Figure 2 This is the infrared spectrum of the conductive polymer of Example 1 of the present invention; Figure 3 This is the GPC spectrum of the conductive polymer of Example 1 of the present invention; Figure 4 This is the ultraviolet-visible-near-infrared spectrum of the conductive polymer of Example 1 of the present invention; Figure 5 This is a photograph of an LED lit up by doping a conductive polymer with ferric chloride, as described in Example 1 of this invention.
[0074] The conductive polymer's 1H NMR spectrum showed a bulging pattern, indicating successful polymer acquisition. Chemical shifts between 8.7 and 9.7 corresponded to hydrogen atoms on the -NH group, while those between 7.1 and 8.6 corresponded to hydrogen atoms on the benzene ring. Figure 1 Further infrared analysis revealed vibrational peaks of CN, NH, and Ar-H in the polymer. Figure 2 Gel chromatography analysis showed that the statistical molecular weight of the polymer was in the range of 600,000. Figure 3 Conductive polymers also exhibit broad UV-Vis-NIR absorption. Figure 4 Polymers doped with ferric chloride have good electrical conductivity and can be used to light up LEDs. Figure 5 ).
[0075] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A conductive polymer, characterized in that, The general structural formula of the conductive polymer is as follows: Among them, R1, R2, R3, R 4、 R5 is independently selected from hydrogen, C6 to C6. 10 Aryl, C1~C 20 Alkyl, C2-C 20 At least one of the unsaturated alkanes.
2. The conductive polymer according to claim 1, characterized in that, The molecular weight of the conductive polymer is 2,000 to 1,000,000.
3. A method for preparing a conductive polymer, characterized in that, Includes the following steps: The conductive polymer is obtained by mixing materials containing polycarbonyl small molecules, an ammonia source, and additives. Wherein, the number of carbonyl groups in the polycarbonyl small molecule is greater than or equal to 2.
4. The preparation method according to claim 3, characterized in that, The molar ratio of the polycarbonyl small molecule to the ammonia source is 1:1 to 10.
5. The preparation method according to claim 3, characterized in that, The molar ratio of the polycarbonyl small molecule to the additive is 1:0.001 to 5.
6. The preparation method according to claim 3, characterized in that, The ammonia source is selected from at least one of ammonia, ammonium salts, amines, amino acids, and hydrazine.
7. The preparation method according to claim 3, characterized in that, The number of carbon atoms in the polycarbonyl small molecules ranges from 4 to 100.
8. The preparation method according to claim 3, characterized in that, The additive is selected from a proton hydrogen source; Preferably, the additive is selected from at least one of acetic acid, hydrochloric acid, sulfuric acid, and ammonium chloride.
9. The preparation method according to claim 3, characterized in that, The mixing conditions are as follows: Temperature range: 0℃~200℃; The time ranges from 0.1 h to 36 h; Preferably, the mixing is carried out under ultraviolet light.
10. The preparation method according to claim 3, characterized in that, The material also contains solvents; Preferably, the solvent is selected from at least one of water and organic solvents; Preferably, the organic solvent is selected from at least one of tetrahydrofuran, dichloromethane, dimethyl sulfoxide, and N,N-dimethylformamide.