CN113234221A - Fluorine-containing polyarylether containing fluorene as well as preparation method and application thereof - Google Patents
Fluorine-containing polyarylether containing fluorene as well as preparation method and application thereof Download PDFInfo
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- CN113234221A CN113234221A CN202110505158.4A CN202110505158A CN113234221A CN 113234221 A CN113234221 A CN 113234221A CN 202110505158 A CN202110505158 A CN 202110505158A CN 113234221 A CN113234221 A CN 113234221A
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
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Abstract
The invention provides fluorine-containing polyarylether containing fluorene as well as a preparation method and application thereof, belonging to the technical field of triboelectric nano generator materials. The fluorine-containing polyarylether containing fluorine provided by the invention contains a large amount of fluorine and aromatic ring structures, and the existence of strong electronegative fluorine and a large amount of aromatic ring structures is favorable for generating frictional charges and stabilizing the frictional charges, so that the output performance of the frictional electricity nano generator is improved. Meanwhile, due to the existence of the aromatic ring structure, the fluorine-containing polyarylether containing fluorene has excellent thermal stability and output performance stability. The results of the examples show that the polymer film prepared by using the fluorine-containing polyarylether containing fluorene provided by the invention has excellent thermal stability and triboelectric output performance, and is suitable for being used as a triboelectric material.
Description
Technical Field
The invention relates to the technical field of triboelectric nano generator materials, in particular to fluorine-containing polyarylether containing fluorene and a preparation method and application thereof.
Background
Currently, in the face of increasing energy demand, many researchers shift the focus of research to new and green energy. In 2012, professor of Wangzhonglin (Flexible triboelectric generator, Feng-Ru Fan, Zhong-Qun Tian, ZhongLin Wang, Nano Energy (2012)1, 328-334) creatively proposed a triboelectric nanogenerator (TENG). TENG can convert weak mechanical energy in the environment into electrical energy by the basic principle of triboelectrification. Through years of research, TENG has been applied to the fields of wind energy collection, water energy collection, self-driving and the like, and the research prospect is very considerable. However, most of the research on the selection of the triboelectric materials relies on the triboelectric series, and the research on actively designing and synthesizing the triboelectric materials from the chemical perspective is few.
Disclosure of Invention
The invention aims to provide fluorine-containing polyarylether containing fluorene as well as a preparation method and application thereof, wherein the fluorine-containing polyarylether containing fluorene can be used as a triboelectric material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides fluorine-containing polyarylether containing fluorene, which has a structure shown in a formula I:
wherein n is 0 to 1 and n is not 0, and the symbol represents a connecting site.
Preferably, n is 0.3, 0.5, 0.7 or 1.
The invention provides a preparation method of fluorine-containing polyarylether containing fluorene, which comprises the following steps:
mixing hexafluorobisphenol A, bisphenol fluorene, decafluorobiphenyl, a dehydrating agent, a catalyst and an organic solvent, and carrying out polymerization reaction to obtain fluorine-containing polyarylether containing fluorene;
the molar ratio of the hexafluorobisphenol A to the bisphenol fluorene to the decafluorobiphenyl is (0.04-0.2): (0.04-0.2): (0.06-0.3).
Preferably, the dehydrating agent is one or more of benzene, toluene, xylene and cyclohexane; the volume ratio of the dehydrating agent to the organic solvent is (30-50): 100.
preferably, the catalyst is one or more of sodium carbonate, potassium carbonate, cesium carbonate, calcium hydride and potassium fluoride; the molar ratio of the catalyst to the decafluorobiphenyl is (0.9-1.2): (0.9-1.2).
Preferably, the organic solvent is one or more of dioxane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane and N-methylpyrrolidone.
Preferably, the solid content of the mixed liquid obtained by mixing the hexafluorobisphenol A, the bisphenol fluorene, the decafluorobiphenyl, the dehydrating agent, the catalyst and the organic solvent is 15-25% by mass percentage.
Preferably, the temperature of the polymerization reaction is 80-110 ℃, and the time of the polymerization reaction is 20-35 h.
The invention provides application of fluorine-containing polyarylether containing fluorene or prepared by the preparation method in the technical scheme in the field of triboelectric nano-generators.
Preferably, the method of application comprises the steps of: mixing fluorine-containing polyarylether containing fluorene with an organic solvent, and sequentially casting and curing to obtain a polyarylether film;
assembling the polyarylether film and the polyetheretherketone film into a triboelectric nano generator;
the fluorine-containing polyarylether containing fluorene is the fluorine-containing polyarylether containing fluorene in the technical scheme or the fluorine-containing polyarylether containing fluorene prepared by the preparation method in the technical scheme.
The invention provides fluorine-containing polyarylether containing fluorene, which has a structure shown in a formula I:
wherein n is 0 to 1 and n is not 0, and the symbol represents a connecting site.
The fluorine-containing polyarylether containing fluorine provided by the invention contains a large amount of fluorine and aromatic ring structures, and the existence of strong electronegative fluorine and a large amount of aromatic ring structures is favorable for generating friction charges, so that the output performance of the triboelectric nano-generator is favorably improved. Meanwhile, due to the existence of the aromatic ring structure, the fluorine-containing polyarylether containing fluorene has excellent thermal stability and output performance stability. The results of the examples show that the polymer film prepared by using the fluorine-containing polyarylether containing fluorene provided by the invention has excellent thermal stability and triboelectric output performance, and is suitable for being used as a triboelectric material.
The fluorine-containing polyarylether containing fluorine provided by the invention contains a large amount of fluorine, and strong electronegative fluorine elements easily generate strong attraction capacity to charges, so that the surface charges of a friction material are transferred, and the triboelectric output performance is further improved. Secondly, the aromatic ring structure can be used as a charge trapping point to stabilize the frictional charge in the material, so that the charge is not easy to dissipate, the material has stable frictional electricity output performance, the stability of the frictional charge is favorably improved, and the output stability is further improved. In addition, the introduction of the aromatic ring increases the rigidity of a molecular chain, so that the molecular chain of the polymer material is not easy to move, and the bond energy of the aromatic ring is higher than that of the aliphatic chain, so that the existence of the aromatic ring structure can improve the thermal stability.
The triboelectric nano generator assembled by the fluorine-containing polyarylether material containing fluorine has high triboelectric output performance and continuous and stable output performance, and the output performance is not obviously attenuated after continuous friction for 24 hours.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a fluorine-containing polyarylether prepared in examples 1-4;
FIG. 2 is a schematic structural diagram of a fluorine-containing poly (arylene ether) film triboelectric nano-generator containing fluorene in an application example;
FIG. 3 is a graph showing the output performance test results of fluorine-containing polyarylether films containing fluorene prepared in examples 1 to 4;
FIG. 4 is a graph showing the output performance stability test results of the fluorine-containing polyarylether film containing fluorene prepared in example 2.
Detailed Description
The invention provides fluorine-containing polyarylether containing fluorene, which has a structure shown in a formula I:
wherein n is 0 to 1 and n is not 0, and the symbol represents a connecting site.
In the present invention, n is preferably 0.3, 0.5, 0.7 or 1.
The invention provides a preparation method of fluorine-containing polyarylether containing fluorene, which comprises the following steps:
mixing hexafluorobisphenol A, bisphenol fluorene, decafluorobiphenyl, a dehydrating agent, a catalyst and an organic solvent, and carrying out polymerization reaction to obtain fluorine-containing polyarylether containing fluorene;
the molar ratio of the hexafluorobisphenol A to the bisphenol fluorene to the decafluorobiphenyl is (0.04-0.2): (0.04-0.2): (0.06-0.3).
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention mixes hexafluorobisphenol A, bisphenol fluorene, decafluorobiphenyl, dehydrating agent, catalyst and organic solvent. In the invention, the dehydrating agent is preferably one or more of benzene, toluene, xylene and cyclohexane; when the dehydrating agents are preferably selected from the above-mentioned groups, the ratio of the dehydrating agents of different types is not particularly limited in the present invention, and any ratio may be used. In the invention, the catalyst is preferably one or more of sodium carbonate, potassium carbonate, cesium carbonate, calcium hydride and potassium fluoride; when the catalyst is preferably selected from the above-mentioned catalysts, the proportion of the catalyst in the invention is not particularly limited, and any proportion may be used. In the invention, the organic solvent is preferably one or more of dioxane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane and N-methylpyrrolidone; when the organic solvent is preferably selected from the above-mentioned organic solvents, the ratio of the organic solvents of different types is not particularly limited, and any ratio may be used.
In the invention, the molar ratio of the hexafluorobisphenol A, the bisphenol fluorene and the decafluorobiphenyl is (0.04-0.2): (0.04-0.2): (0.06-0.3), more preferably (0.075-0.175): (0.075-0.175): (0.15 to 0.255); the molar ratio of the catalyst to the decafluorobiphenyl is preferably (0.9-1.2): (0.9-1.2), more preferably (1.0-1.1): (1.0-1.1); the volume ratio of the dehydrating agent to the organic solvent is preferably (30-50): 100, more preferably (35-45): 100, more preferably (36 to 42): 100.
in the present invention, the process of mixing hexafluorobisphenol a, bisphenol fluorene, decafluorobiphenyl, dehydrating agent, catalyst and organic solvent preferably comprises the steps of:
mixing hexafluorobisphenol A, bisphenol fluorene, a dehydrating agent, a catalyst and an organic solvent, performing azeotropic reflux, and mixing the obtained mixed material with decafluorobiphenyl to obtain a mixed solution.
In the present invention, the mixing of the hexafluorobisphenol a, the bisphenol fluorene, the dehydrating agent, the catalyst and the organic solvent is preferably performed under an argon atmosphere and under stirring, and the mixing time is preferably 0.5 to 1.5 hours, and more preferably 0.8 to 1.2 hours. The stirring process is not particularly limited in the present invention, and the materials can be uniformly mixed according to the process well known in the art.
In the invention, the temperature of the azeotropic reflux is preferably 100-150 ℃, and more preferably 120-130 ℃; the time of the azeotropic reflux is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, and further preferably 3.8 to 4.2 hours. The method removes byproduct water generated when the catalyst and the hexafluorobisphenol A are salified through azeotropic reflux so as to be beneficial to forward movement of the reaction.
After the azeotropic reflux is completed, the invention preferably performs the azeotropic operation on the obtained system to obtain a mixed material. In the invention, the azeotropic temperature is preferably 110-180 ℃, more preferably 120-150 ℃, and further preferably 130-140 ℃; the time is preferably 1 h. The invention utilizes azeotropy to remove the dehydrating agent. After the completion of the azeotropy, the present invention preferably cools the system obtained after the azeotropy to room temperature to obtain a mixed material. The cooling method of the present invention is not particularly limited, and may be performed in a manner known to those skilled in the art.
After the mixed material is obtained, the mixed material is preferably mixed with the decafluorobiphenyl to obtain a mixed solution. In the invention, the mixing is preferably carried out under stirring, and the stirring time is preferably 0.5-1.5 h, and more preferably 0.8-1.2 h. The process of cooling to room temperature is not particularly limited in the present invention, and may be performed according to a process well known in the art. The stirring rate is not particularly limited in the present invention, and the stirring may be performed at a rate well known to those skilled in the art.
The invention mixes in two steps, because the lateral fluorine atom of decafluorobiphenyl has reactivity, one-step feeding is easy to generate branching or even cross-linking, which affects the linear structure of polyarylether, the two-step feeding of the invention ensures that the synthesized polymer has better linear structure.
In the invention, the solid content of the mixed solution is preferably 15 to 25% by mass, more preferably 18 to 22% by mass, and even more preferably 19 to 21% by mass. The amount of the organic solvent used in the present invention preferably satisfies the above solid content.
In the invention, the temperature of the polymerization reaction is 80-110 ℃, more preferably 85-105 ℃, further preferably 90-100 ℃, and the time of the polymerization reaction is preferably 20-35 h, more preferably 25-30 h; the polymerization reaction is preferably carried out under stirring conditions, and the stirring rate is not particularly limited in the present invention and may be carried out according to a procedure well known in the art. In the polymerization reaction process, the phenolic hydroxyl groups on the hexafluorobisphenol A and the bisphenol fluorene are firstly salified with a catalyst, then attack the para-fluorine of the decafluorobiphenyl, and carry out nucleophilic substitution reaction to form the polyarylether.
After the polymerization reaction is finished, the invention also preferably comprises the steps of separating out the obtained product solution in deionized water, and then sequentially crushing, washing and drying to obtain the fluorine-containing polyarylether containing fluorene. The process of pulverizing, washing and drying is not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art. In the examples of the present invention, the washing and drying processes are specifically washing 3 times with water and methanol, respectively, and drying at 120 ℃ for 24h in a vacuum oven.
The invention provides application of fluorine-containing polyarylether containing fluorene or prepared by the preparation method in the technical scheme in the field of triboelectric nano-generators.
In the present invention, the method of application preferably comprises the steps of: mixing fluorine-containing polyarylether containing fluorene with an organic solvent, and sequentially casting and curing to obtain a polyarylether film;
assembling the polyarylether film and the polyetheretherketone film into a triboelectric nano generator;
the fluorine-containing polyarylether containing fluorene is the fluorine-containing polyarylether containing fluorene in the technical scheme or the fluorine-containing polyarylether containing fluorene prepared by the preparation method in the technical scheme.
In the present invention, the organic solvent is preferably chloroform. In the invention, the use amount ratio of the fluorine-containing polyarylether containing fluorene to the organic solvent is preferably (0.8-1.5) g: (8-15) mL, more preferably (0.9-1.2) g: (10-13) mL. The process for mixing the fluorine-containing poly aryl ether containing fluorine and the organic solvent is not limited in any way, and can be carried out by adopting the process well known by the technical personnel in the field.
In the present invention, the pouring is preferably performed by pouring the mixed solution obtained by mixing onto a glass plate. The glass sheet is not particularly limited in the present invention, and any glass sheet known in the art may be used.
In the invention, the curing temperature is preferably 30-120 ℃, and more preferably 50-100 ℃; in the invention, the curing mode is preferably gradient drying, and the temperature and the time of the gradient drying are preferably 30 ℃ drying for 4h, 50 ℃ drying for 4h, 70 ℃ drying for 4h, 100 ℃ drying for 4h and 120 ℃ drying for 4h in sequence. In the invention, the gradient drying can ensure that the organic solvent is removed more thoroughly, and a large amount of bubbles on the surface of the film are avoided.
After the polyarylether film is obtained, the polyarylether film and the polyetheretherketone film are preferably assembled into the triboelectric nano generator. The polyetheretherketone film and the assembly process are not particularly limited in the present invention, and commercially available polyetheretherketone films well known in the art may be selected and assembled according to the process well known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Under the condition of argon atmosphere, hexafluorobisphenol A (58.84g, 0.175mol), bisphenol fluorene (26.28g,0.075mol), and K2CO3(41.46g, 0.3000mol), dimethylacetamide (1030mL) and toluene (343.0mL) for 0.5h, heating the obtained mixture to 120 ℃ for 3h under azeotropic reflux, continuing to heat the reaction system to 140 ℃ for 1h, and then cooling to room temperature to obtain a mixed solution (the solid content is 15%); adding decafluorobiphenyl (85.20g, 0.2550mol) into the mixed solution, stirring for 0.5h, heating to 100 ℃ under vigorous stirring for continuous polymerization reaction for 24h, adding the obtained material into deionized water for precipitation, crushing the obtained precipitate, washing with water and methanol for 3 times respectively, and drying in a vacuum oven at 120 ℃ for 24h to obtain the fluorine-containing polyarylether containing fluorene, wherein the fluorine-containing polyarylether is named as FPAE-W30, and n in the formula I is 0.3.
Example 2
Under the condition of argon atmosphere, hexafluorobisphenol A (42.03g, 0.125mol), bisphenol fluorene (43.8g,0.125mol), and K2CO3(41.46g, 0.3000mol), dimethylacetamide (1034mL) and toluene (344.0mL) for 0.5h, heating the mixture to 120 ℃ for 3h under azeotropic reflux, continuing to heat the reaction system to 140 ℃ for 1h, and then cooling to room temperature to obtain a mixed solution (solid content is 2)0%); adding decafluorobiphenyl (85.20g, 0.2550mol) into the mixed solution, stirring for 0.5h, heating to 100 ℃ under vigorous stirring for continuous polymerization reaction for 24h, adding the obtained material into deionized water for precipitation, crushing the obtained precipitate, washing with water and methanol for 3 times respectively, and drying in a vacuum oven at 120 ℃ for 24h to obtain the fluorine-containing polyarylether containing fluorene, wherein the name of the fluorine-containing polyarylether containing fluorene is FPAE-W50, and n in the formula I is 0.5.
Example 3
Under the condition of argon atmosphere, hexafluorobisphenol A (25.22g, 0.075mol), bisphenol fluorene (61.32g,0.175mol), and K2CO3(41.46g, 0.3000mol), dimethylacetamide (1039mL) and toluene (346.0mL) for 0.5h, heating the mixture to 120 ℃ for 3h under azeotropic reflux, continuing to heat the reaction system to 140 ℃ for 1h, and then cooling to room temperature to obtain a mixed solution (with a solid content of 20%); adding decafluorobiphenyl (85.20g, 0.2550mol) into the mixed solution, stirring for 0.5h, heating to 110 ℃ under vigorous stirring for continuous polymerization reaction for 24h, adding the obtained material into deionized water for precipitation, crushing the obtained precipitate, washing with water and methanol for 3 times respectively, and drying in a vacuum oven at 120 ℃ for 24h to obtain the fluorine-containing polyarylether containing fluorene, wherein the name of the fluorine-containing polyarylether containing fluorene is FPAE-W70, and n in the formula I is 0.7.
Example 4
Bisphenol fluorene (87.6g, 0.25mol), K, was reacted under an argon atmosphere2CO3(41.46g, 0.3000mol), dimethylacetamide (1046mL) and toluene (348.0mL) for 0.5h, heating the obtained mixture to 120 ℃ for 3h under azeotropic reflux, continuously heating the reaction system to 140 ℃ for 1h, and then cooling to room temperature to obtain a mixed solution (the solid content is 20%); adding decafluorobiphenyl (85.20g, 0.2550mol) into the mixed solution, stirring for 0.5h, heating to 110 ℃ under vigorous stirring for continuously carrying out polymerization reaction for 24h, adding the obtained material into deionized water for precipitation, crushing the obtained precipitate, washing with water and methanol for 3 times respectively, and drying in a vacuum oven at 120 ℃ for 24h to obtain the fluorine-containing polyarylether containing fluorene, wherein the fluorine-containing polyarylether is named as FPAE-W100, and n is 1 in the formula I.
Characterization and Performance testing
1) For example 14, performing nuclear magnetic characterization on the prepared fluorine-containing polyarylether, wherein the result is shown in figure 1, and (a) is a nuclear magnetic hydrogen spectrum test result; (b) the result is a nuclear magnetic fluorine spectrum test result; as is clear from FIG. 1 (a), the characteristic peaks at chemical shifts of 7.41ppm and 7.05ppm were ascribed to the magnetic resonance of the hydrogen nucleus in the benzene ring bonded to the hexafluoroisopropyl group of the polymer, and the characteristic peaks at 6.88ppm, 7.18ppm, 7.30ppm, 7.35 to 7.38ppm and 7.77ppm were ascribed to the magnetic resonance of the hydrogen nucleus in the fluorene group. As can be seen from (b) in FIG. 1, the characteristic peak at chemical shift-64.09 ppm is attributed to the magnetic resonance of the fluorine nucleus in hexafluoroisopropyl group, and the characteristic peaks at chemical shifts-137.50 ppm and-152.38 ppm are attributed to the magnetic resonance of the fluorine nucleus in octafluorobiphenyl group. Introduction of the fluorene group changes the chemical environment of fluorine atoms on the octafluorobiphenyl group in the polymer molecular chain, and thus, in FPAE-W30-W7019Not only the three characteristic peaks appear in F NMR, but also two groups of characteristic peaks appear at-138.06 ppm and-152.77 ppm, which shows that all the characteristic peaks have definite attribution and prove that the synthesized fluorine-containing polyarylether containing fluorine accords with the expected structure.
2) The fluorine-containing polyarylether containing fluorene prepared in the examples 1 to 4 is subjected to molecular weight, DSC and TGA tests, and the test methods respectively comprise the following steps: the molecular weight was characterized using high temperature Gel Permeation Chromatography (GPC) under the conditions: mobile phase DMF, testing at 80 ℃; DSC is carried out at the speed of 10 ℃/min under the nitrogen atmosphere at the temperature of 80-400 ℃; the TGA test range is 100-800 ℃, the speed is 10 ℃/min under the air atmosphere, and the test results are shown in Table 1.
TABLE 1 Performance parameters of fluorine-containing polyarylether prepared in examples 1 to 4
As shown in Table 1, the fluorine-containing polyarylether containing fluorene synthesized by the invention has higher molecular weight and lower molecular weight distribution index; meanwhile, the fluorine-containing polyarylether containing fluorene has higher glass transition temperature which is above 180 ℃. Under the air atmosphere, the 5 percent thermal weight loss temperature of the fluorine-containing polyarylether containing fluorene is above 490 ℃, which shows that the fluorine-containing polyarylether containing fluorene has excellent thermal stability.
Application example
Respectively mixing 1.0g of fluorine-containing polyarylether powder (FPAE-W30-W100) containing fluorine prepared in examples 1-4 with 10mL of chloroform, casting the obtained mixed solution onto a glass plate, and drying the glass plate for 4 hours at 30 ℃, 50 ℃, 70 ℃, 100 ℃ and 120 ℃ in sequence after the mixed solution is uniformly dispersed on the surface of the glass plate and forms a horizontal surface to obtain a fluorine-containing polyarylether film containing fluorine with the thickness of 60 +/-5 mu m;
assembling the fluorine-containing polyarylether film containing fluorine and a PEEK film into a friction electric nano generator, assembling according to the structure shown in figure 2, and arranging an upper layer: the acrylic plate is a supporting layer, the copper sheet is an electrode, the fluorine-containing polyarylether film containing fluorine is a friction layer, and the fluorine-containing polyarylether film containing fluorine is arranged on the copper sheet; the lower layer: the acrylic plate is used as a supporting layer, the copper sheet is used as an electrode, and the polyetheretherketone film (Weigsi APTIV)TMFilm) is a friction layer.
1) And (3) carrying out performance test on the output performance of the assembled triboelectric nano generator under the room temperature atmospheric environment: the test mode is a vertical contact separation type; the test frequency is 1.5 Hz; data were collected using a KEITHLEY6514 electrometer and the test results are shown in figure 3 and summarized in table 2.
TABLE 2 triboelectric output Performance data for FPAE-W30-W100 prepared in examples 1-4
As can be seen from Table 2 and FIG. 3, the fluorine-containing polyarylether containing fluorene prepared by the present invention has high output performance, wherein FPAE-W50 has the highest output performance, the output voltage reaches 70V, and the output current reaches 5.8 muA.
2) The stability of the output performance of the triboelectric nanogenerator assembled from the FPAE-W50 was continuously tested for 24 hours, and data was collected every two hours (in each row of fig. 4, 4 time periods are represented from left to right, and each time period represents 2 hours), with the test results shown in fig. 4. As can be seen from FIG. 4, there was no significant attenuation in the output current after 24 hours of continuous testing, demonstrating that DFAF-W5 has excellent stability of output performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A fluorine-containing polyarylether containing fluorene is characterized by having a structure shown in a formula I:
wherein n is 0 to 1 and n is not 0, and the symbol represents a connecting site.
2. The fluorine-containing polyarylether containing fluorene of claim 1, wherein n is 0.3, 0.5, 0.7 or 1.
3. The method for preparing fluorine-containing polyarylether containing fluorene of claim 1 or 2, comprising the following steps:
mixing hexafluorobisphenol A, bisphenol fluorene, decafluorobiphenyl, a dehydrating agent, a catalyst and an organic solvent, and carrying out polymerization reaction to obtain fluorine-containing polyarylether containing fluorene;
the molar ratio of the hexafluorobisphenol A to the bisphenol fluorene to the decafluorobiphenyl is (0.04-0.2): (0.04-0.2): (0.06-0.3).
4. The preparation method according to claim 3, wherein the dehydrating agent is one or more of benzene, toluene, xylene and cyclohexane; the volume ratio of the dehydrating agent to the organic solvent is (30-50): 100.
5. the preparation method according to claim 3, wherein the catalyst is one or more of sodium carbonate, potassium carbonate, cesium carbonate, calcium hydride and potassium fluoride; the molar ratio of the catalyst to the decafluorobiphenyl is (0.9-1.2): (0.9-1.2).
6. The method according to claim 3, wherein the organic solvent is one or more selected from the group consisting of dioxane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and N-methylpyrrolidone.
7. The method according to any one of claims 3 to 6, wherein a solid content of a mixed solution obtained by mixing hexafluorobisphenol A, bisphenol fluorene, decafluorobiphenyl, a dehydrating agent, a catalyst and an organic solvent is 15 to 25% by mass.
8. The method according to claim 3, wherein the polymerization temperature is 80 to 110 ℃ and the polymerization time is 20 to 35 hours.
9. The fluorine-containing poly (aryl ether) containing fluorene as claimed in claim 1 or 2 or the fluorine-containing poly (aryl ether) containing fluorene prepared by the preparation method as claimed in any one of claims 3 to 8 is applied to the field of triboelectric nano-generators.
10. The application according to claim 9, characterized in that the method of application comprises the steps of: mixing fluorine-containing polyarylether containing fluorene with an organic solvent, and sequentially casting and curing to obtain a polyarylether film;
assembling the polyarylether film and the polyetheretherketone film into a triboelectric nano generator;
the fluorine-containing polyarylether containing fluorene is the fluorine-containing polyarylether containing fluorene of claim 1 or 2 or the fluorine-containing polyarylether containing fluorene prepared by the preparation method of any one of claims 3 to 8.
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