Hydrophilic red to transparent electrochromic polymer and preparation method thereof

Abstract

The invention provides a hydrophilic red-to-transparent electrochromic polymer and a preparation method thereof. The hydrophilic red-to-transparent electrochromic polymer is prepared from the following components in parts by weight: 1-3 parts of 5-dibromo-31, 1-3 parts of 4-ethylene disulfide thiophene, 1 part of 0.004 mmol of palladium acetate, 2 parts of 0.25 mmol of potassium carbonate, 1.2-3 parts of 0.01 mmol of pivalic acid, organic acid, weak base, a palladium catalyst and organic solvent methylbenzene. The invention provides a hydrophilic red-to-transparent electrochromic polymer and a preparation method thereof. The hydrophilic red-to-transparent electrochromic polymer is prepared from the following components in parts by weight: 1-3 parts of 5-dibromo-31, 1-3 parts of 4-ethylene disulfide thiophene, 1 part of 0.004 mmol palladium acetate, 2 parts of 0.25 mmol potassium carbonate, 1.2-3 parts of 0.01 mmol pivalic acid, organic acid, weak base, palladium catalyst, organic solvent methylbenzene, dichloromethane, chloroform concentrated solution, methanol and normal hexane. The electrochromic polymer has the characteristics of low driving voltage, high response rate, high stability and the like, and meanwhile, the organic solvents such as methylbenzene and dichloromethane have solubility, so that large-area film formation of a polymer solution is facilitated.

Description

Technical Field

[0001] This invention relates to the field of electrochromic polymers, and more particularly to a hydrophilic red to transparent electrochromic polymer and its preparation method. Background Technology

[0002] Electrochromic polymers such as polyaniline and polythiophene are difficult to dissolve due to their rigid backbone, making it challenging to achieve large-area film formation. Therefore, designing and synthesizing novel solution-processable electrochromic polymers is of great significance for the research and application of electrochromic materials.

[0003] Electrochromic polymers exhibit colors such as yellow and red, but the commonly used dioxothiophene units have low band ranges, making it difficult to realize red electrochromic materials. Some realized red-to-transparent electrochromic materials have poor hydrophilicity, which is not conducive to large-area film formation of polymer solutions, and also have problems such as insufficient stability.

[0004] Therefore, it is necessary to provide a hydrophilic red to transparent electrochromic polymer and a preparation method to solve the above-mentioned technical problems. Summary of the Invention

[0005] This invention provides a hydrophilic red-to-transparent electrochromic polymer and its preparation method, which solves the problem of poor hydrophilicity in some existing red-to-transparent electrochromic materials.

[0006] To solve the above-mentioned technical problems, the present invention provides a hydrophilic red to transparent electrochromic polymer and a preparation method thereof, comprising:

[0007] 5-Dibromo-31-3 parts, 4-ethylenedithiothiophene 1-3 parts, 0.004 mmol palladium acetate 1 part, 0.25 mmol potassium carbonate 2 parts, 0.01 mmol pentanoic acid 1.2-3 parts, organic acid, weak base, palladium catalyst, organic solvent toluene, dichloromethane, chloroform concentrate, methanol, n-hexane.

[0008] A method for preparing a hydrophilic red to transparent electrochromic polymer, used to manufacture the electrochromic polymer, wherein:

[0009] S1: Place 3 parts of 5-dibromo-31-, 1-3 parts of 4-ethylenedithiothiophene, 1 part of 0.004 mmol palladium acetate, 2 parts of 0.25 mmol potassium carbonate, and 1.2-3 parts of 0.01 mmol pentanoic acid into a 25 mL double-necked flask, evacuate the flask, inject nitrogen gas, inject 15 mL of anhydrous N,N-dimethylacetamide, evacuate the flask again to fill it with nitrogen gas, and heat it to 140 °C for 48 h.

[0010] S2: After the reaction is completed and cooled, Soxhlet extraction is performed with methanol, n-hexane and chloroform. Each extraction time is 24h. The chloroform extract is concentrated to 15mL and then added dropwise to cold methanol to precipitate a red solid.

[0011] S3: After pouring the red solid into the stirring device, add the organic solvents toluene, dichloromethane, and methanol to the stirring device, stir, and then filter.

[0012] S4: The polymer is obtained by drying the precipitate using a drying device.

[0013] Preferably, the stirring device used in step S3 is characterized in that the stirring device includes a base, a tank is provided on the top of the base, a collection box is fixedly connected to one side of the tank, a sealing plate is provided on the top of the collection box, and a guide groove is provided inside the collection box.

[0014] Preferably, a rotary motor is provided at the top of the tank, and the output end of the rotary motor is connected to a stirring rod via a coupling. Multiple stirring blades are fixedly connected to the surface of the stirring rod.

[0015] Preferably, the bottom of the stirring blade is provided with a telescopic sleeve, and a telescopic rod is slidably connected inside the telescopic sleeve. A return spring is provided at one end of the telescopic rod inside the telescopic sleeve.

[0016] Preferably, a hydraulic rod is fixedly installed at the bottom of the inner wall of the tank, a support plate is fixedly installed at one end of the hydraulic rod, a support rod is provided at the top of the support plate, a filter plate is provided at one end of the support rod, a collection groove is provided inside the filter plate, and a scraper is slidably connected inside the collection groove.

[0017] Preferably, the scraper has a vibration groove inside, and a vibration block is slidably connected inside the vibration groove.

[0018] Preferably, the surface of the tank is provided with a conveying pipe, and the surface of the conveying pipe is provided with a valve.

[0019] Preferably, a rotating plate is rotatably connected inside the collection box, a guide box is fixedly connected to one side of the collection box, and two fixing holes are opened inside the collection box.

[0020] Preferably, the rotating plate has two fixing grooves inside, and fixing pins are slidably connected inside the two fixing grooves. A fixing spring is provided at one end of the two fixing pins inside the fixing groove.

[0021] Compared with related technologies, the hydrophilic red to transparent electrochromic polymer and its preparation method provided by the present invention have the following beneficial effects:

[0022] This invention provides a hydrophilic red-to-transparent electrochromic polymer and its preparation method. The method involves using 3 parts of 5-dibromo-31-, 1-3 parts of 4-ethylenedithiothiophene, 1 part of 0.004 mmol palladium acetate, 2 parts of 0.25 mmol potassium carbonate, 1.2-3 parts of 0.01 mmol pentanoic acid, an organic acid, a weak base, a palladium catalyst, and organic solvents such as toluene, dichloromethane, concentrated chloroform, methanol, and n-hexane to achieve a contrast transition between red and transparent states. The polymer exhibits characteristics such as low driving voltage, fast response rate, and high stability. Furthermore, the organic solvents toluene and dichloromethane provide solubility, facilitating large-area film formation of the polymer solution. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the structure of a first embodiment of a hydrophilic red to transparent electrochromic polymer and its preparation method provided by the present invention.

[0024] Figure 2 for Figure 1 A cross-sectional structural schematic diagram of the entire device shown;

[0025] Figure 3 for Figure 2 The diagram shows the structure of the filter plate.

[0026] Figure 4 for Figure 2 The enlarged schematic diagram of part A shown below;

[0027] Figure 5 for Figure 2 The enlarged schematic diagram of section B is shown below;

[0028] Figure 6 This is a schematic diagram of the structure of a second embodiment of a hydrophilic red to transparent electrochromic polymer and its preparation method provided by the present invention;

[0029] Figure 7 for Figure 6 The diagram shows the structure of the rotating plate.

[0030] Figure 8 for Figure 7 The enlarged schematic diagram of section C is shown.

[0031] The following are the labels in the diagram: 1. Base, 2. Tank, 3. Collection box, 4. Sealing plate, 5. Electric rotating mechanism, 51. Stirring rod, 52. Stirring blade, 53. Telescopic sleeve, 54. Return spring, 55. Telescopic rod, 6. Hydraulic rod, 61. Support plate, 62. Filter plate, 63. Collection trough, 64. Scraper, 7. Guide trough, 8. Valve, 9. Conveying pipe, 10. Rotating plate, 11. Guide box, 12. Fixing trough, 13. Fixing pin, 14. Fixing spring, 15. Fixing hole, 16. Support rod, 17. Vibration trough, 18. Vibration block. Detailed Implementation

[0032] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0033] First Embodiment

[0034] Please refer to Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 5 ,in, Figure 1 This is a schematic diagram of the structure of a first embodiment of a hydrophilic red to transparent electrochromic polymer and its preparation method provided by the present invention.

[0035] Figure 2 for Figure 1 A cross-sectional structural schematic diagram of the entire device shown; Figure 3 for Figure 2 The diagram shows the structure of the filter plate. Figure 4 for Figure 2 The enlarged schematic diagram of part A shown below; Figure 5 for Figure 2 The enlarged schematic diagram of part B is shown. A hydrophilic red to transparent electrochromic polymer and its preparation method are disclosed, comprising:

[0036] 5-Dibromo-31-3 parts, 4-ethylenedithiothiophene 1-3 parts, 0.004 mmol palladium acetate 1 part, 0.25 mmol potassium carbonate 2 parts, 0.01 mmol pentanoic acid 1.2-3 parts, organic acid, weak base, palladium catalyst, organic solvent toluene, dichloromethane, chloroform concentrate, methanol, n-hexane.

[0037] A method for preparing a hydrophilic red to transparent electrochromic polymer, used to manufacture the electrochromic polymer, wherein:

[0038] S1: Place 3 parts of 5-dibromo-31-, 1-3 parts of 4-ethylenedithiothiophene, 1 part of 0.004 mmol palladium acetate, 2 parts of 0.25 mmol potassium carbonate, and 1.2-3 parts of 0.01 mmol pentanoic acid into a 25 mL double-necked flask, evacuate the flask, inject nitrogen gas, inject 15 mL of anhydrous N,N-dimethylacetamide, evacuate the flask again to fill it with nitrogen gas, and heat it to 140 °C for 48 h.

[0039] S2: After the reaction is completed and cooled, Soxhlet extraction is performed with methanol, n-hexane and chloroform. Each extraction time is 24h. The chloroform extract is concentrated to 15mL and then added dropwise to cold methanol to precipitate a red solid.

[0040] S3: After pouring the red solid into the stirring device, add the organic solvents toluene, dichloromethane, and methanol to the stirring device, stir, and then filter.

[0041] S4: The polymer is obtained by drying the precipitate using a drying device.

[0042] The stirring device used in step S3 is characterized in that the stirring device includes a base 1, a tank 2 is provided on the top of the base 1, a collection box 3 is fixedly connected to one side of the tank 2, a sealing plate 4 is provided on the top of the collection box 3, and a guide groove 7 is provided inside the collection box 3.

[0043] Both sides of the tank body 2 are fixed with support bases, and the bottom of each support base is fixedly connected with a connecting rod. One end of each connecting rod is fixedly connected to the top of the base 1 to increase the stability of the tank body 2.

[0044] The collection box 3 is used to collect the scraped sediment, and both the collection box 3 and the filter plate 62 have guide grooves 7 inside, which are used to guide the sediment inside the collection tank 63 into the collection box 3.

[0045] The sealing plate 4 is used to seal the top of the collection box 3.

[0046] A rotary motor 5 is installed on the top of the tank 2. The output end of the rotary motor 5 is connected to a stirring rod 51 via a coupling. Multiple stirring blades 52 are fixedly connected to the surface of the stirring rod 51.

[0047] The rotating motor 5 is a servo motor, which drives the stirring rod 51 to rotate to one side after startup, thereby driving multiple stirring blades 52 to rotate to one side, stirring and accelerating the fusion of the liquid inside the tank 2.

[0048] The bottom of the stirring blade 52 is provided with a telescopic sleeve 53, and a telescopic rod 55 is slidably connected inside the telescopic sleeve 53. A return spring 54 is provided at one end of the telescopic rod 55 and inside the telescopic sleeve 53.

[0049] Two telescopic sleeves 53 are fixedly connected to the bottom of the stirring blade 52. Telescopic rods 55 are slidably connected inside the two telescopic sleeves 53. A return spring 54 is provided at one end of the two telescopic rods 55 and inside the two telescopic sleeves 53.

[0050] A hydraulic rod 6 is fixedly installed at the bottom of the inner wall of the tank 2. A support plate 61 is fixedly installed at one end of the hydraulic rod 6. A support rod 16 is provided at the top of the support plate 61. A filter plate 62 is provided at one end of the support rod 16. A collection groove 63 is opened inside the filter plate 62. A scraper 64 is slidably connected inside the collection groove 63.

[0051] One end of each of the two telescopic rods 55 is fixedly connected to the top of the scraper 64. When the stirring blade 52 rotates to one side, it drives the telescopic sleeve 53 connected to the telescopic rod 55 to rotate to one side, thereby driving the scraper 64 to rotate to one side.

[0052] Four hydraulic rods 6 are fixedly installed on the top of the inner wall of the tank 2. One end of each of the four hydraulic rods 6 is fixedly connected to the bottom of the support plate 61. Four support rods 16 are fixedly connected to the top of the support plate 61. One end of each of the four support rods 16 is fixedly connected to the bottom of the filter plate 62.

[0053] The surface of the support plate 61 contacts the inner wall of the tank 2, and a sealing ring is provided inside the support plate 61 to seal the support plate 61 and the tank 2. At the same time, the support plate 61 can also be a piston plate, which is used to drive the support plate 61 to move up and down when the hydraulic rod 6 extends or retracts. At the same time, after the liquid enters the interior of the tank 2, the liquid will not enter the area below the support plate 61.

[0054] The top of the filter plate 62 is curved, the bottom of the scraper 64 is adapted to the top of the filter plate 62, and the bottom of the scraper 64 is fixedly connected to two scraper blocks adapted to the collection groove 63.

[0055] The scraper 64 has a vibration groove 17 inside, and a vibration block 18 is slidably connected inside the vibration groove 17.

[0056] Multiple vibrating blocks 18 are fixedly connected to the bottom of the inner wall of the collection tank 63, and two vibrating grooves 17 are opened inside the scraper 64.

[0057] When the rotating motor 5 is started, the stirring rod 51 connected to the stirring blade 52 rotates to one side, which in turn drives the telescopic sleeve 53 connected to the telescopic rod 55 to rotate to one side, thereby driving the scraper 64 to rotate to one side. When the scraper 64 rotates to a certain position, one side of the scraper 64 contacts the surface of the vibrating block 18, and the scraper 64 extends upward along the curved surface of the vibrating block 18, thereby driving the two telescopic rods 55 to move upward inside the two telescopic sleeves 53 respectively, while squeezing the two return springs 54. When the vibrating block 18 enters the vibrating groove 17, the two return springs 54 push the two telescopic rods 55 to move downward and reset inside the two telescopic sleeves 53 respectively. Thus, the scraper 64 strikes the filter plate 62 to generate vibration, thereby causing the sediment filtered down on the filter plate 62 to slide to one side more quickly and enter the collection groove 63.

[0058] The surface of the tank 2 is provided with a conveying pipe 9, and the surface of the conveying pipe 9 is provided with a valve 8.

[0059] Valve 8 can be a manual valve or an electric valve, used to control the opening or closing of the delivery pipe 9.

[0060] The working principle of the hydrophilic red to transparent electrochromic polymer and its preparation method provided by this invention is as follows:

[0061] When in use, after the liquid is poured into the tank 2, the rotating motor 5 is started to drive the stirring rod 51 connected to the stirring blade 52 to rotate to one side, thereby stirring the liquid inside the tank 2.

[0062] After stirring is complete, the liquid is discharged by activating valve 8, and the sediment in the liquid will be filtered out by filter plate 62.

[0063] When the hydraulic rod 6 is retracted, the support plate 61 moves downward. When the support plate 61 moves downward, the support rod 16 connected to the filter plate 62 moves downward to the appropriate position. At the same time, when the filter plate 62 moves downward, the two return springs 54 push the two telescopic rods 55 to move downward inside the two telescopic sleeves 53 respectively.

[0064] When the rotating motor 5 is started, the stirring rod 51 connected to the stirring blade 52 is rotated to one side, which in turn drives the telescopic sleeve 53 connected to the telescopic rod 55 to rotate to one side, thereby driving the scraper 64 to rotate to one side. The sediment filtered down from the filter plate 62 is scraped off and enters the collection tank 63. Then, it is guided into the collection box 3 through the guide groove 7 opened inside the filter plate 62 and the tank 2 for storage, thereby automatically collecting the sediment filtered down from the filter plate 62.

[0065] After the scraping is completed, the hydraulic rod 6 is activated to extend and move the support plate 61 connected to the support rod 16 upward, thereby moving the filter plate 62 upward. This causes the scraper 64 to move the two telescopic rods 55 upward inside the two telescopic sleeves 53, while simultaneously squeezing the two return springs 54.

[0066] Compared with related technologies, the hydrophilic red to transparent electrochromic polymer and its preparation method provided by the present invention have the following beneficial effects:

[0067] This invention provides a hydrophilic red-to-transparent electrochromic polymer and its preparation method. The method involves using 3 parts of 5-dibromo-31-, 1-3 parts of 4-ethylenedithiothiophene, 1 part of 0.004 mmol palladium acetate, 2 parts of 0.25 mmol potassium carbonate, 1.2-3 parts of 0.01 mmol pentanoic acid, an organic acid, a weak base, a palladium catalyst, and organic solvents such as toluene, dichloromethane, concentrated chloroform, methanol, and n-hexane to achieve a contrast transition between red and transparent states. The polymer exhibits characteristics such as low driving voltage, fast response rate, and high stability. Furthermore, the organic solvents toluene and dichloromethane provide solubility, facilitating large-area film formation of the polymer solution.

[0068] Second embodiment

[0069] Please refer to Figure 6 , Figure 7 and Figure 8 Based on the first embodiment of this application which provides a hydrophilic red to transparent electrochromic polymer and its preparation method, the second embodiment of this application proposes another hydrophilic red to transparent electrochromic polymer and its preparation method. The second embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the second embodiment will not affect the separate implementation of the first embodiment.

[0070] Specifically, the difference between the hydrophilic red to transparent electrochromic polymer and its preparation method provided in the second embodiment of this application is that, in the hydrophilic red to transparent electrochromic polymer and its preparation method, a rotating plate 10 is rotatably connected inside the collection box 3, a guide box 11 is fixedly connected to one side of the collection box 3, and two fixing holes 15 are opened inside the collection box 3.

[0071] The guide box 11 is used to guide the process when scraping out the sediment inside the collection box 3.

[0072] The rotating plate 10 has two fixing grooves 12 inside, and fixing pins 13 are slidably connected inside the two fixing grooves 12. A fixing spring 14 is provided at one end of the two fixing pins 13 inside the fixing groove 12.

[0073] Each of the two fixing pins 13 has a fixed handle fixedly connected to one side, which is used to facilitate rotating the fixing pin 13 to one side.

[0074] The working principle of the hydrophilic red to transparent electrochromic polymer and its preparation method provided by this invention is as follows:

[0075] In use, the two fixing pins 13 are moved to one side, thereby pressing the two fixing springs 14 while moving to one side inside the two fixing grooves 12 respectively. After the two fixing pins 13 separate from the two fixing holes 15, the rotating plate 10 is rotated to one side to a suitable position to scrape out the sediment inside the collection box 3.

[0076] After the rotation plate 10 is rotated to one side to reset, the two fixing pins 13 are released. The two fixing springs 14 push the two fixing pins 13 to move to one side inside the two fixing slots 12 respectively. When the two fixing pins 13 enter the two fixing holes 15 respectively, the rotation plate 10 is limited.

[0077] Compared with related technologies, the hydrophilic red to transparent electrochromic polymer and its preparation method provided by the present invention have the following beneficial effects:

[0078] This invention provides a hydrophilic red to transparent electrochromic polymer and its preparation method. After the two fixing pins 13 are moved to both sides and separated from the two fixing holes 15, the rotating plate 10 is rotated to a suitable position, which facilitates the removal of the precipitate inside the collection box 3 for subsequent work.

[0079] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A hydrophilic red to transparent electrochromic polymer and its preparation method, characterized in that, include: 5-Dibromo-31-3 parts, 4-ethylenedithiothiophene 1-3 parts, 0.004 mmol palladium acetate 1 part, 0.25 mmol potassium carbonate 2 parts, 0.01 mmol pentanoic acid 1.2-3 parts, organic acid, weak base, palladium catalyst, organic solvent toluene, dichloromethane, chloroform concentrate, methanol, n-hexane.

2. A method for preparing a hydrophilic red to transparent electrochromic polymer, used to manufacture the electrochromic polymer, characterized in that, The following is stated: S1: Place 3 parts of 5-dibromo-31-, 1-3 parts of 4-ethylenedithiothiophene, 1 part of 0.004 mmol palladium acetate, 2 parts of 0.25 mmol potassium carbonate, and 1.2-3 parts of 0.01 mmol pentanoic acid into a 25 mL double-necked flask, evacuate the flask, inject nitrogen gas, inject 15 mL of anhydrous N,N-dimethylacetamide, evacuate the flask again to fill it with nitrogen gas, and heat it to 140 °C for 48 h. S2: After the reaction is completed and cooled, Soxhlet extraction is performed with methanol, n-hexane and chloroform. Each extraction time is 24h. The chloroform extract is concentrated to 15mL and then added dropwise to cold methanol to precipitate a red solid. S3: After pouring the red solid into the stirring device, add the organic solvents toluene, dichloromethane, and methanol to the stirring device, stir, and then filter. S4: The polymer is obtained by drying the precipitate using a drying device.

3. The method for preparing a hydrophilic red to transparent electrochromic polymer according to claim 2, wherein the stirring device used in step S3 is characterized in that, The stirring device includes a base, a tank is provided on the top of the base, a collection box is fixedly connected to one side of the tank, a sealing plate is provided on the top of the collection box, and a guide groove is provided inside the collection box.

4. The method for preparing a hydrophilic red to transparent electrochromic polymer according to claim 3, characterized in that, A rotating motor is installed on the top of the tank. The output end of the rotating motor is connected to a stirring rod via a coupling. Multiple stirring blades are fixedly connected to the surface of the stirring rod.

5. The method for preparing a hydrophilic red to transparent electrochromic polymer according to claim 4, characterized in that, The bottom of the stirring blade is provided with a telescopic sleeve, and a telescopic rod is slidably connected inside the telescopic sleeve. A return spring is provided at one end of the telescopic rod inside the telescopic sleeve.

6. The method for preparing a hydrophilic red to transparent electrochromic polymer according to claim 4, characterized in that, A hydraulic rod is fixedly installed at the bottom of the inner wall of the tank. A support plate is fixedly installed at one end of the hydraulic rod. A support rod is provided at the top of the support plate. A filter plate is provided at one end of the support rod. A collection groove is opened inside the filter plate. A scraper is slidably connected inside the collection groove.

7. The method for preparing a hydrophilic red to transparent electrochromic polymer according to claim 6, characterized in that, The scraper has a vibration groove inside, and a vibration block is slidably connected inside the vibration groove.

8. The method for preparing a hydrophilic red to transparent electrochromic polymer according to claim 6, characterized in that, The surface of the tank is provided with a conveying pipe, and the surface of the conveying pipe is provided with a valve.

9. The method for preparing a hydrophilic red to transparent electrochromic polymer according to claim 3, characterized in that, The collection box is rotatably connected to a rotating plate inside, and a guide box is fixedly connected to one side of the collection box. Two fixing holes are opened inside the collection box.

10. The method for preparing a hydrophilic red to transparent electrochromic polymer according to claim 9, characterized in that, The rotating plate has two fixing slots inside, and fixing pins are slidably connected inside the two fixing slots. A fixing spring is provided at one end of the two fixing pins inside the fixing slot.

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