Copolymerized polyurethane material with opto-electro-mechanical effect as well as preparation method and application of copolymerized polyurethane material

Abstract

The invention relates to a copolymerized polyurethane material with a photo-electro-mechanical effect as well as a preparation method and application thereof, and belongs to the technical field of self-powered energy conversion. The preparation method comprises the following steps: S1, synthesizing bis (p-hydroxyethyl) azobenzene; s2, synthesis of azobenzene polyurethane is carried out; s3, synthesis of diethanol amine bromine salt; s4, synthesizing quaternary ammonium salt ionic liquid based polyurethane; s5, synthesizing azobenzene-quaternary ammonium salt ionic liquid copolymerized polyurethane; and S6, preparing the copolymerized polyurethane material. In the application which is prepared from the copolymerized polyurethane material and has the photoelectric effect, the quaternary ammonium salt ionic liquid is used for replacing imidazole ionic liquid, so that the influence of cytotoxicity of the quaternary ammonium salt ionic liquid can be effectively weakened or avoided, and the quaternary ammonium salt ionic liquid can be directly used as a nano-generator without polarization treatment and has better flexibility and ductility.

Description

Technical Field

[0001] The present invention belongs to the technical field of self-powered energy conversion, and in particular relates to a copolymer polyurethane material with photomechanical effect, a preparation method and application thereof. Background Art

[0002] In recent years, some studies have reported nanogenerators that can harvest green energy through several conduction methods such as piezoelectric, triboelectric, electromagnetic and thermoelectric effects. They can harvest green energy from natural resources such as wind, water, heat, and the sun, as well as mechanical vibration and human movement. Compared with traditional batteries, nanogenerators have unique advantages such as light weight, low manufacturing cost, small size, simple signal processing functions, high power density, and long service life. Piezoelectric nanogenerators and triboelectric nanogenerators were first invented by the team of Academician Wang Zhonglin of the Chinese Academy of Sciences. They are a clean and efficient mechanical energy harvester. Piezoelectric nanogenerators (PENGs) harvest low-frequency vibration / friction energy into electrical energy by utilizing the piezoelectric and semiconductor capabilities of nanowires / nanobelts and the influence of Schottky barriers at metal semiconductors. The simplest piezoelectric nanogenerator can be composed of a piezoelectric layer, a substrate, and two electrodes.

[0003] At present, a series of polyurethanes capable of converting light energy into electrical energy via mechanical energy have been successfully developed using imidazolium ionic liquids and azobenzene as raw materials. However, the present invention chooses to use quaternary ammonium salt ionic liquids with small steric hindrance and simple structure as monomers of dipole units, in order to obtain optical-mechanical-electrical polyurethanes with better flexibility and ductility; at the same time, the cytotoxicity of the quaternary ammonium salt cationic core is weaker than that of the imidazolium ionic liquid, so using quaternary ammonium salt ionic liquids instead of imidazolium ionic liquids can effectively weaken or avoid the influence of their cytotoxicity.

[0004] The steric hindrance of the imidazole group is large, which makes the synthesized polyurethane brittle and not resistant to bending. The product has a large refractive index, dark color and poor transparency, and its scope of application is limited. Imidazole ionic liquids are toxic to the natural environment, enzyme activity, cell or bacterial activity, and even animals and plants. Summary of the invention

[0005] The invention provides a copolymer polyurethane material with photomechanical effect, a preparation method and application thereof, which are used to solve the technical problems in the prior art that the steric hindrance of the imidazole group is large, resulting in obvious brittleness of the synthesized polyurethane, poor bending resistance, large refractive index, dark color and poor transparency, limited application scope and toxicity of imidazole ionic liquid to the natural environment, enzyme activity, cell or bacterial activity and even animals and plants.

[0006] In order to achieve the above object, the present invention is implemented by the following technical solutions:

[0007] A method for preparing a copolymer polyurethane material with a photomechanical effect, comprising: S1, uniformly stirring a strong base, p-nitrophenylethanol, an alcohol and a catalyst, and reacting them at 70° C. to obtain bis-p-hydroxyethylazobenzene;

[0008] S2: dissolving bis-p-hydroxyethylazobenzene with N,N-dimethylacetamide, adding a polymerization promoter and hexamethylene diisocyanate, reacting at room temperature for 5 hours, adding deionized water and precipitating, filtering after precipitation to obtain a filter cake, drying the filter cake to constant weight, adding the dried filtrate to N,N-dimethylacetamide, and stirring at 80° C. to completely dissolve the filtrate to obtain a first mixed solution, and then distilling the first mixed solution under reduced pressure at 120° C. to prepare an azophenyl polyurethane oligomer;

[0009] S3, diethanolamine and acetonitrile were stirred at 75°C until no layers were separated, ethyl bromide was added, refluxed and stirred for 48 hours, acetonitrile was separated by reduced pressure distillation at 40°C, and diethanolamine bromide was obtained after cooling;

[0010] S4, stirring diethanolamine bromide, N,N-dimethylacetamide and hexamethylene diisocyanate at room temperature for a certain period of time to obtain a second mixed solution, and rotary evaporating the second mixed solution under vacuum at 105° C. to prepare a quaternary ammonium salt ionic liquid-based polyurethane;

[0011] S5, dissolving diethanolamine bromide and azophenyl polyurethane oligomer in N,N-dimethylacetamide at 80° C., adding hexamethylene diisocyanate to react for 0.5 to 1 hour, and then adding 1,4-butanediol and stirring to react for 1 hour to obtain a third mixed solution, and vacuum drying the third mixed solution after reduced pressure distillation to prepare azobenzene-quaternary ammonium salt ionic liquid copolymer polyurethane;

[0012] S6. Dissolve azobenzene-quaternary ammonium salt ionic liquid copolymerized polyurethane and polyethylene oxide in N,N-dimethylacetamide, and control the concentration of azobenzene-quaternary ammonium salt ionic liquid copolymerized polyurethane to be 0.05 g / mL.

[0013] Furthermore, the strong base is one of sodium hydroxide and potassium hydroxide, the amount of sodium hydroxide is 8.8g~17.6g, the amount of potassium hydroxide is 18.48g, the amount of nitrobenzeneethanol is 20~40mmol, the alcohol is one of methanol, ethanol, and propanol, the amount of methanol is 60mL~120mL, the catalyst is one of zinc powder, magnesium powder, and lithium aluminum hydride, the amount of zinc powder is 1.8g~7g, and the amount of lithium aluminum hydride is 1.8~2.8g.

[0014] Furthermore, the polymerization promoter is one of dibutyltin dilaurate, zinc octoate, and zinc cyclohexaneate, the mass fraction of dibutyltin dilaurate ranges from 0.05% to 0.1%, and the mass fraction of zinc octoate is 0.075%.

[0015] Furthermore, the amount of diethanolamine used is 10-20 mmol, the amount of acetonitrile used is 25-50 mL, and the amount of ethyl bromide used is 15-30 mmol.

[0016] Furthermore, the amount of hexamethylene diisocyanate used is 2-4 mmol, and the amount of 1,4-butanediol used is 0.135-0.27 g.

[0017] Furthermore, the amount of N,N-dimethylacetamide used is 15-30 mL.

[0018] Furthermore, the mass ratio of the azobenzene-quaternary ammonium salt ionic liquid copolymer polyurethane to polyethylene oxide is 100:15.

[0019] Another aspect of the present invention provides a copolymer polyurethane material having a photomechanical effect, which is prepared according to the method for preparing the copolymer polyurethane material as described above.

[0020] On the other hand, the present invention also provides an application of a copolymer polyurethane material with a photomechanical effect. The copolymer polyurethane material with a photomechanical effect as described above is applied to prepare a flexible nanogenerator. The flexible nanogenerator includes a first conductive film and a second conductive film, and a photoelectric effect layer is arranged between the first conductive film and the second conductive film. The photoelectric effect layer is the copolymer polyurethane material as described above. The first conductive film and the second conductive film are both polymer conductive films, and the polymer conductive film is any one of polyethylene terephthalate, polydimethylsiloxane, polybutylene terephthalate, and polyethylene succinate.

[0021] The present invention provides a copolymer polyurethane material with photomechanical effect, a preparation method and its application. Using quaternary ammonium salt ionic liquid instead of imidazole ionic liquid can effectively weaken or avoid its cytotoxicity, and can be directly used as a nanogenerator without polarization treatment, and has better flexibility and ductility. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0023] Figure 1Schematic diagram of the flexible nanogenerator structure;

[0024] Figure 2 This is an open circuit voltage diagram of PME-Br provided in the experimental example of the present invention under different irradiation intensities;

[0025] Figure 3 The open circuit voltage diagram of PME-Br under 3100μW / cm2 irradiation provided for the experimental example of the present invention;

[0026] Figure 4 The short-circuit current diagram of PME-Br at different irradiation intensities provided in the experimental example of the present invention;

[0027] Figure 5 The short-circuit current diagram of PME-Br at 3100μW / cm2 provided for the experimental example of the present invention.

[0028] In the figure: 1-first conductive film; 2-second conductive film; 3-photoelectric effect layer. DETAILED DESCRIPTION

[0029] The embodiments of the present application are described in detail below with reference to the accompanying drawings.

[0030] In the description of the present application, it should be understood that the terms "center", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0031] The terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of this application, unless otherwise specified, "plurality" means two or more.

[0032] In the description of this application, it should be noted that, unless otherwise clearly specified and limited, the terms "installation", "connection" and "connection" should be understood in a broad sense, for example, it can be welding, bolt connection, or riveting; it can be fixed connection, detachable connection, or integral connection; it can be mechanical connection or electrical connection; it can be directly connected or indirectly connected through an intermediate medium, or it can be internal communication between two components. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0033] Embodiment 1:

[0034] (1) Synthesis of azophenyl polyurethane

[0035] 17.6 g of sodium hydroxide, 40 mmol of p-nitrophenylethanol, 120 mL of methanol and 7 g of zinc powder were reacted at 70° C. with stirring to obtain bis-p-hydroxyethylazobenzene (Az2).

[0036] 1.36 g Az2 was dissolved in 30 mL N, N-dimethylacetamide (DMAc), and a drop of 0.1% dibutyltin dilaurate and 4 mmol hexamethylene diisocyanate (HDI) was added. After reacting at room temperature for 5 h, 100 mL deionized water was added, and the precipitate was dried to constant weight. The obtained orange-red solid was dissolved in DMAc under stirring at 80 °C and then distilled under reduced pressure at 120 °C to obtain an azophenyl polyurethane oligomer (Azo-9).

[0037] (2) Synthesis of quaternary ammonium salt ionic liquid-based polyurethane

[0038] Stir 20mmol of diethanolamine and 50mL of acetonitrile at 75℃ until there is no stratification. Add 30mmol of ethyl bromide and reflux and stir for 48h. Remove the solvent acetonitrile by vacuum distillation at 40℃, and obtain milky white crystals after cooling, named DEA-Br. Stir DEA-Br, DMAc and HDI at room temperature for 6h, and obtain a light yellow transparent colloidal fluid after vacuum rotary evaporation at 105℃, named ILO-Br.

[0039] (3) Synthesis of azobenzene-quaternary ammonium salt ionic liquid copolymer polyurethane

[0040] 1.88 g of ILO-Br and 2.02 g of Azo-9 were dissolved in DMAc at 80 °C, 0.16 g of HDI was added and reacted for 30 min-60 min, then 0.27 g of 1,4-butanediol (BDO) was added, and the mixture was stirred for 1 h and then distilled under reduced pressure and dried in vacuum to obtain a solid product named PME-Br.

[0041] (4) Assembly of nanogenerator

[0042] PME-Br was mixed with polyethylene oxide (PEO) and dissolved with DMAc, the concentration of PME material was controlled to be 0.05 g / mL, and the mass ratio of PME material to PEO was 100:15. A 2cm×2.5cm transparent PET conductive film was cut, and the sample solution was evenly coated on the conductive side with an area of ​​2cm×2cm. After drying, another 2cm×2.5cm PET conductive film was used to cover and encapsulate the film, and the electrodes on both sides were led out with copper wires.

[0043] Embodiment 2:

[0044] (1) Synthesis of azophenyl polyurethane

[0045] 8.8g of sodium hydroxide, 20mmol of p-nitrophenylethanol, 60mL of methanol and 3.5g of zinc powder were reacted under stirring conditions at 70°C to obtain bis-p-hydroxyethylazobenzene (Az2). 0.68g of Az2 was dissolved in 15mL of N,N-dimethylacetamide (DMAc), and a drop of 0.05% dibutyltin dilaurate and 2mmol of hexamethylene diisocyanate (HDI) was added. After reacting at room temperature for 5h, 100mL of deionized water was added, and the precipitate was dried to constant weight. The orange-red solid was dissolved in DMAc under stirring conditions at 80°C and then distilled under reduced pressure at 120°C to obtain an azophenyl polyurethane oligomer named Azo-9.

[0046] (2) Synthesis of quaternary ammonium salt ionic liquid-based polyurethane

[0047] Stir 10 mmol of diethanolamine and 25 mL of acetonitrile at 75°C until there is no stratification. Add 15 mmol of ethyl bromide and reflux and stir for 24 hours. Remove the solvent acetonitrile by vacuum distillation at 40°C, and obtain milky white crystals after cooling, named DEA-Br. Stir DEA-Br, DMAc and HDI at room temperature for 3 hours, and obtain a light yellow transparent colloidal fluid after vacuum rotary evaporation at 105°C, named ILO-Br.

[0048] (3) Synthesis of azobenzene-quaternary ammonium salt ionic liquid copolymer polyurethane

[0049] 0.94 g of ILO-Br and 1.01 g of Azo-9 were dissolved in DMAc at 80 °C, 0.08 g of HDI was added, and the reaction was continued for 30 min-60 min, followed by 0.135 g of 1,4-butanediol (BDO). After stirring for 1 h, the mixture was distilled under reduced pressure and dried in vacuum to obtain a solid product named PME-Br.

[0050] (4) Assembly of nanogenerator

[0051] PME-Br was mixed with polyethylene oxide (PEO) and dissolved with DMAc, the concentration of PME material was controlled to be 0.05 g / mL, and the mass ratio of PME material to PEO was 100:15. A 2cm×2.5cm transparent PET conductive film was cut, and the sample solution was evenly coated on the conductive side with an area of ​​2cm×2cm. After drying, another 2cm×2.5cm PET conductive film was used to cover and encapsulate the film, and the electrodes on both sides were led out with copper wires.

[0052] Embodiment 3:

[0053] (1) Synthesis of azophenyl polyurethane

[0054] 18.48g potassium hydroxide, 30mmol p-nitrophenylethanol, 90mL methanol and 2.8g lithium aluminum hydride were reacted under stirring conditions at 70°C to obtain bis-p-hydroxyethylazobenzene (Az2). 1.02g Az2 was dissolved in 22.5mL N,N-dimethylacetamide (DMAc), and a drop of 0.075% zinc octanoate and 3mmol hexamethylene diisocyanate (HDI) was added. After reacting at room temperature for 5h, 100mL deionized water was added, and the precipitate was dried to constant weight. The orange-red solid was dissolved in DMAc under stirring conditions at 80°C and then distilled under reduced pressure at 120°C to obtain an azophenyl polyurethane oligomer, named Azo-9.

[0055] (2) Synthesis of quaternary ammonium salt ionic liquid-based polyurethane

[0056] 15mmol of diethanolamine and 37.5mL of acetonitrile were stirred at 75℃ until no stratification. 22.5mmol of ethyl bromide was added and refluxed and stirred for 36h. The solvent acetonitrile was removed by vacuum distillation at 40℃, and milky white crystals were obtained after cooling, which were named DEA-Br. DEA-Br, DMAc and HDI were stirred and reacted at room temperature for 4.5h, and a light yellow transparent colloidal fluid was obtained after vacuum rotary evaporation at 105℃, which was named ILO-Br.

[0057] (3) Synthesis of azobenzene-quaternary ammonium salt ionic liquid copolymer polyurethane

[0058] 1.41 g of ILO-Br and 1.52 g of Azo-9 were dissolved in DMAc at 80 °C, 0.12 g of HDI was added and reacted for 30 min-60 min, then 0.2 g of 1,4-butanediol (BDO) was added, and the mixture was stirred for 1 h and then distilled under reduced pressure and dried in vacuum to obtain a solid product named PME-Br.

[0059] (4) Assembly of nanogenerator

[0060] PME-Br was mixed with polyethylene oxide (PEO) and dissolved with DMAc, the concentration of PME material was controlled to be 0.05 g / mL, and the mass ratio of PME material to PEO was 100:15. A 2cm×2.5cm transparent PDMS conductive film was cut, and a 2cm×2cm area of ​​sample solution was evenly coated on the conductive side. After drying, another 2cm×2.5cm PDMS conductive film was used to cover and encapsulate, and the electrodes on both sides were led out with copper wires.

[0061] Embodiment 4:

[0062] (1) Synthesis of azophenyl polyurethane

[0063] 12.32g of sodium hydroxide, 20mmol of p-nitrophenylethanol, 60mL of methanol and 1.8g of lithium aluminum hydride were reacted under stirring conditions at 70°C to obtain bis-p-hydroxyethylazobenzene (Az2). 0.68g of Az2 was dissolved in 15mL of N,N-dimethylacetamide (DMAc), and a drop of 0.05% zinc octanoate and 2mmol of hexamethylene diisocyanate (HDI) was added. After reacting at room temperature for 5h, 100mL of deionized water was added, and the precipitate was dried to constant weight. The obtained orange-red solid was dissolved in DMAc under stirring conditions at 80°C and then distilled under reduced pressure at 120°C to obtain an azophenyl polyurethane oligomer, named Azo-9.

[0064] (2) Synthesis of quaternary ammonium salt ionic liquid-based polyurethane

[0065] Stir 10 mmol of diethanolamine and 25 mL of acetonitrile at 75°C until there is no stratification. Add 15 mmol of ethyl bromide and reflux and stir for 24 hours. Remove the solvent acetonitrile by vacuum distillation at 40°C, and obtain milky white crystals after cooling, named DEA-Br. Stir DEA-Br, DMAc and HDI at room temperature for 3 hours, and obtain a light yellow transparent colloidal fluid after vacuum rotary evaporation at 105°C, named ILO-Br.

[0066] (3) Synthesis of azobenzene-quaternary ammonium salt ionic liquid copolymer polyurethane

[0067] 0.94 g of ILO-Br and 1.01 g of Azo-9 were dissolved in DMAc at 80 °C, 0.08 g of HDI was added, and the reaction was continued for 30 min-60 min, followed by 0.135 g of 1,4-butanediol (BDO). After stirring for 1 h, the mixture was distilled under reduced pressure and dried in vacuum to obtain a solid product named PME-Br.

[0068] (4) Assembly of nanogenerator

[0069] PME-Br was mixed with polyethylene oxide (PEO) and dissolved with DMAc, the concentration of PME material was controlled to be 0.05 g / mL, and the mass ratio of PME material to PEO was 100:15. A 2cm×2.5cm transparent PDMS conductive film was cut, and a 2cm×2cm area of ​​sample solution was evenly coated on the conductive side. After drying, another 2cm×2.5cm PDMS conductive film was used to cover and encapsulate, and the electrodes on both sides were led out with copper wires.

[0070] Experimental example:

[0071] The nanogenerator prepared by the method described in Example 1 has a structure as shown in Figure 1As shown in the figure, the first conductive film 1, the second conductive film 2 and the photoelectric effect layer 3 are included. The open circuit voltage test of the PME nanogenerator is completed in a dark light environment. The test method is as follows:

[0072] ① Fix the PME nanogenerator on the breadboard, connect it in series with a 10GΩ resistor, and connect the input and output interfaces of the oscilloscope to both ends of the resistor; ② Fix the probe of the UV irradiator next to the sample, and ensure that the upper surface of the probe is at the same horizontal height as the sample; ③ First record the oscilloscope reading when the sample is not irradiated with UV light to confirm that there is no background radiation interference, and use it as a blank control; ④ Use UV lamp to irradiate vertically from directly above the sample, and control the irradiation intensity of the sample by adjusting the distance between the UV lamp and the sample. Five different irradiation intensities are shown in Table 1.

[0073] Table 1 UV radiation intensity in photo-mechanical-electrical effect test

[0074]

[0075] The open circuit voltage test results are as follows: Figure 2 As shown. Figure 2 The data shows that the maximum output voltage of the PME nanogenerator can reach 17.4V.

[0076] Then, the short-circuit current test device of the PME nanogenerator was changed to fix the nanogenerator on the breadboard and connect it in series with the input of the SR570 low-noise current preamplifier, then connect its output to the input of the oscilloscope, set the amplification level to 50A / V, and keep other test conditions unchanged. The short-circuit current of the sample device was tested under the same irradiation intensity. The short-circuit current test results are shown in Figure 2. Figure 3 As shown. Figure 3 The data show that the maximum short-circuit current of the PME-Br sample can reach 696μA under an irradiation intensity of 3100μW / cm2, indicating that the prepared PME nanogenerator has good opto-mechanical-electrical properties.

[0077] In summary, a flexible nanogenerator with photomechanical effect chooses to use a quaternary ammonium salt ionic liquid with small steric hindrance and simple structure as the monomer of the dipole unit, in order to obtain a photomechanical-electrical polyurethane with better flexibility and ductility; and the cytotoxicity of the quaternary ammonium salt cationic core is weaker than that of the imidazolium ionic liquid, so using a quaternary ammonium salt ionic liquid instead of the imidazolium ionic liquid can effectively weaken or avoid the influence of its cytotoxicity, and it can be directly used as a nanogenerator without polarization treatment. It has a small size, light weight, and good flexibility and ductility.

[0078] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope of the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing a copolymer polyurethane material having a photomechanical effect, characterized in that: The preparation method comprises the following steps: S1. Stir the strong base, p-nitrophenylethanol, alcohol and catalyst evenly, and react at 70°C to obtain bis-p-hydroxyethylazobenzene; S2: dissolving bis-p-hydroxyethylazobenzene with N,N-dimethylacetamide, adding a polymerization promoter and hexamethylene diisocyanate, reacting at room temperature for 5 hours, adding deionized water and precipitating, filtering after precipitation to obtain a filter cake, drying the filter cake to constant weight, adding the dried filtrate to N,N-dimethylacetamide, and stirring at 80° C. to completely dissolve the filtrate to obtain a first mixed solution, and then distilling the first mixed solution under reduced pressure at 120° C. to prepare an azophenyl polyurethane oligomer; S3, diethanolamine and acetonitrile were stirred at 75°C until no layers were separated, ethyl bromide was added, refluxed and stirred for 48 hours, acetonitrile was separated by reduced pressure distillation at 40°C, and diethanolamine bromide was obtained after cooling; S4, stirring diethanolamine bromide, N,N-dimethylacetamide and hexamethylene diisocyanate at room temperature for a certain period of time to obtain a second mixed solution, and rotary evaporating the second mixed solution under vacuum at 105° C. to prepare a quaternary ammonium salt ionic liquid-based polyurethane; S5, dissolving diethanolamine bromide and azophenyl polyurethane oligomer in N,N-dimethylacetamide at 80° C., adding hexamethylene diisocyanate to react for 0.5 to 1 hour, and then adding 1,4-butanediol and stirring to react for 1 hour to obtain a third mixed solution, and vacuum drying the third mixed solution after reduced pressure distillation to prepare azobenzene-quaternary ammonium salt ionic liquid copolymer polyurethane; S6. Dissolve azobenzene-quaternary ammonium salt ionic liquid copolymerized polyurethane and polyethylene oxide in N,N-dimethylacetamide, and control the concentration of azobenzene-quaternary ammonium salt ionic liquid copolymerized polyurethane to be 0.05 g / mL.

2. The method for preparing a copolymer polyurethane material having a photomechanical effect according to claim 1, characterized in that: The strong base is one of sodium hydroxide and potassium hydroxide, the amount of the sodium hydroxide is 8.8g~17.6g, and the amount of the potassium hydroxide is 18.48g; The amount of nitrobenzeneethanol is 20-40 mmol; The alcohol is one of methanol, ethanol and propanol, and the amount of methanol is 60mL~120mL; The catalyst is one of zinc powder, magnesium powder and lithium aluminum hydride. The amount of zinc powder is 1.8g-7g, and the amount of lithium aluminum hydride is 1.8-2.8g.

3. According to the preparation method of a copolymer polyurethane material with photomechanical effect described in claim 1, the polymerization promoter is one of dibutyltin dilaurate, zinc octoate, and zinc naphthenate, the mass fraction of dibutyltin dilaurate ranges from 0.05% to 0.1%, and the mass fraction of zinc octoate is 0.075%.

4. The method for preparing a copolymer polyurethane material having a photomechanical effect according to claim 1, characterized in that: The diethanolamine is used in an amount of 10 to 20 mmol; The acetonitrile dosage is 25-50 mL; The amount of ethyl bromide used is 15-30 mmol.

5. The method for preparing a copolymer polyurethane material having a photomechanical effect according to claim 1, characterized in that: The amount of hexamethylene diisocyanate is 2-4 mmol; The amount of 1,4-butanediol used is 0.135~0.27g.

6. The method for preparing a copolymer polyurethane material having a photomechanical effect according to claim 1, characterized in that: The amount of N,N-dimethylacetamide used is 15~30mL.

7. A copolymer polyurethane material having a photomechanical effect, characterized in that: The mass ratio of the azobenzene-quaternary ammonium salt ionic liquid copolymer polyurethane to polyethylene oxide is 100:

15.

8. The method for preparing a copolymer polyurethane material having a photomechanical effect according to claim 1, characterized in that: The copolymer polyurethane material is prepared according to the preparation method according to any one of claims 1 to 7.

9. An application of a copolymer polyurethane material having a photomechanical effect, characterized in that: The copolymerized polyurethane material is used for preparing a material having a photoelectric effect.

10. The use of the copolymerized polyurethane material according to claim 9, characterized in that: The material with photoelectric effect is used to prepare a flexible nanogenerator, which includes a first conductive film and a second conductive film, a photoelectric effect layer is arranged between the first conductive film and the second conductive film, and the photoelectric effect layer is the copolymer polyurethane material described in claim 14, the first conductive film and the second conductive film are both polymer conductive films, and the polymer conductive film is any one of polyethylene terephthalate, polydimethylsiloxane, polybutylene terephthalate, and polyethylene succinate.

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