Spirooxazine-based polyionic liquid ultraviolet photoelectric conversion material, preparation method and application thereof

Abstract

The present application relates to a polyionic liquid ultraviolet photoelectric conversion material based on spirooxazine and a preparation method and application thereof, relates to the technical field of preparation of a polyionic liquid ultraviolet photoelectric conversion material, and mainly solves the problems of low output voltage, single application type and toxic risk of existing materials; the method comprises the following steps: preparing a spirooxazine compound; preparing an ionic liquid; performing a polymerization reaction on the spirooxazine compound and the ionic liquid to obtain a polyionic liquid ultraviolet photoelectric conversion material; the material has a high output voltage; the use of toxic azobenzene substances is avoided; meanwhile, the present application enriches the types of existing ultraviolet photoelectric conversion polyionic liquid materials and has great application value.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of solar cells, and relates to a preparation technology of a polyionic liquid ultraviolet photoelectric conversion material, in particular to a polyionic liquid ultraviolet photoelectric conversion material based on a spirooxazine and a preparation method and application thereof. BACKGROUND

[0002] At present, commercial solar cells mainly utilize visible light and near-infrared light in the solar spectrum, and less utilize ultraviolet light. At present, there are few reports on "photosensitive polyionic liquid ultraviolet photoelectric conversion" at home and abroad, and all of them are based on azobenzene photosensitive units. The specific idea is that azobenzene is used as a photosensitive unit, an ionic liquid is used as a piezoelectric unit, and the two are introduced into the same polymer main chain through a polymerization reaction to prepare a polyionic liquid with ultraviolet photoelectric conversion performance. Under ultraviolet light irradiation, the azobenzene unit undergoes ring-opening reaction, inducing endogenous force, and the rigid segment in the polymer acts as a "lever" to amplify and transmit the force, prying the cation movement of the ionic liquid on the same main chain, while the larger anion lags behind the cation movement, and the anion and the cation undergo relative displacement, thereby generating a potential difference and converting light energy into electrical energy.

[0003] In the prior art, the synthesized azobenzene monomer and imidazole ionic liquid monomer are first reacted with HDI to prepare prepolymers (AZO-X and ILO-Y) with different polymerization degrees. Then, the prepolymers AZO-X, ILO-Y, HDI and MDI are polymerized to prepare an azobenzene-based polyionic liquid PME-XY with ultraviolet photoelectric conversion performance.

[0004] The above-mentioned technology has the following problems: (1) the output voltage is low (the highest is currently 17.4V), which is far from practical application; (2) azobenzene is toxic; as a photosensitive unit, azobenzene is highly toxic and has a potential carcinogenic risk, which is not suitable for application in the field of human wear; (3) the types are relatively single, which is not conducive to in-depth theoretical research on energy conversion mechanism. SUMMARY

[0005] The application provides a polyionic liquid ultraviolet photoelectric conversion material based on a spirooxazine and a preparation method and application thereof, which are used to solve the problems of low output voltage, single application type and toxic risk of the existing materials.

[0006] According to a first aspect of the application disclosed in the application, a preparation method of a polyionic liquid ultraviolet photoelectric conversion material based on a spirooxazine is provided, which comprises the following steps:

[0007] Preparation of a spirooxazine compound;

[0008] Preparation of an ionic liquid; the ionic liquid is an imidazole ionic liquid or a quaternary ammonium salt ionic liquid;

[0009] The spirooxazine compound is subjected to a polymerization reaction with an ionic liquid to obtain a polyionic liquid ultraviolet photoelectric conversion material.

[0010] The beneficial effects of the above technical solution are: the polyionic liquid ultraviolet photoelectric conversion material based on spirooxazine combines the spirooxazine unit with ultraviolet light-induced ring-opening effect and the ionic liquid unit with piezoelectric effect (generating electric energy in the molecule when subjected to pressure) into the same main chain; under the stimulation of ultraviolet light, the spirooxazine unit undergoes ring-opening isomerization, bringing about the change of the micro shape and size of the molecule, generating endogenous force, driving the cation movement of the ionic liquid unit on the same main chain, and relatively lagging behind the anion movement, thus generating endogenous electromotive force; the polyionic liquid ultraviolet photoelectric conversion material greatly improves the output voltage, which is up to 28.99 V; meanwhile, the use of toxic substances such as azobenzene is avoided; in addition, the spirooxazine is further modified with a functional group, which can simply and conveniently adjust the electronic effect, steric effect, etc. of the spirooxazine by introducing a substituent, so as to change the light response performance, such as absorbance, maximum absorption wavelength and ring-opening isomerization deformation, thus being more conducive to the subsequent energy conversion structure-activity relationship, micro mechanism and other theoretical researches; meanwhile, the polyionic liquid ultraviolet photoelectric conversion material can also enrich the types of existing ultraviolet photoelectric conversion materials, and has great application value.

[0011] In a feasible implementation manner, the preparation method of the spirooxazine compound comprises the following steps:

[0012] 3-methoxyphenylhydrazine hydrochloride and methyl isopropyl ketone are dissolved in anhydrous ethanol, heated to reflux at 100-110 DEG C for 6-8 h to obtain a black solution; the black solution is filtered, the filtrate is subjected to rotary evaporation, washed with water to obtain an oil phase, and the liquid separation is performed for 2-3 times until the waste liquid color becomes light yellow or close to colorless and there is no obvious solid particles in the product, to obtain a black viscous product 2,3,3-trimethyl-5-methoxy-3H-indole, and the product is dried;

[0013] hydrogen bromide is added to 2,3,3-trimethyl-5-methoxy-3H-indole, heated to reflux at 100-130 DEG C for 8-10 h; the solution is diluted with ice water, and sodium bicarbonate is added for neutralization to weak alkalinity (pH 7-8) or neutrality, then filtered and washed with deionized water until neutral, to obtain a brown solid 2,3,3-trimethyl-5-hydroxy-3H-indole;

[0014] alkyl iodine is added to 2,3,3-trimethyl-5-hydroxy-3H-indole, and acetonitrile solution is added for dissolution, heated to reflux at 60-80 DEG C for 10-12 h, and the acetonitrile is removed by rotary evaporation to obtain 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary ammonium salt;

[0015] Preparation of 1-nitroso-2,7-naphthalenediol;

[0016] The 1-nitroso-2,7-naphthalenediol is added to the 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt, and then ethanol and piperidine are added. The mixture is heated to reflux at 80-85°C under nitrogen for 3-5h, and then rotary evaporation is performed to obtain 1-alkyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine, i.e. spirooxazine compound.

[0017] In a feasible embodiment, the alkyl iodide is methyl iodide or butyl iodide or hexyl iodide; the 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt is 1-methyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt or 1-n-butyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt or 1-hexyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt; and the 1-alkyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine is 1-methyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine or 1-n-butyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine or 1-hexyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine.

[0018] In a feasible embodiment, the molar volume ratio of 3-methoxyphenylhydrazine hydrochloride, methyl isopropyl ketone and ethanol is 0.1 mol:0.15 mol:150 ml; the molar volume ratio of 2,3,3-trimethyl-5-methoxy-3H-indole and hydrogen bromide is 1:5-5.2; the molar volume ratio of 2,3,3-trimethyl-5-hydroxy-3H-indole, alkyl iodide and acetonitrile is 0.1 mol:0.15 mol:200-250 ml; the molar ratio of 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt, 1-nitroso-2,7-naphthalenediol and piperidine is 1:1:1; and the amount of ethanol used is 150 mL per 0.016-0.025 mol of 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt.

[0019] In a feasible embodiment, the step of drying the black viscous product 2,3,3-trimethyl-5-methoxy-3H-indole includes:

[0020] First, the product is placed in a 80°C air oven for 0.5-1h, and then placed in a 85°C vacuum oven for 10h, and then heated to 103°C and placed for another 10h.

[0021] In a feasible implementation, the ice water has a temperature of 0-4°C, and the ice water is used in an amount of 30-50 mL per 1 g of 2,3,3-trimethyl-5-methoxy-3H-indole.

[0022] In a feasible implementation, the preparation method of the 1-nitroso-2,7-naphthalene-diol comprises the following steps:

[0023] The 2,7-dihydroxynaphthalene is dissolved in 1-2 mol / L sodium hydroxide aqueous solution under the condition of an ice water bath, and stirred for 0.5-1 h until no obvious particles are felt; then sodium nitrite is added and stirred uniformly; then 40-50% sulfuric acid is added dropwise, and the dropwise addition is completed in 0.3-0.5 h, and then the reaction is performed for 3-5 h to obtain a wine red solution; the wine red solution is filtered, and washed with deionized water until the filtrate is neutral to obtain red solid 1-nitroso-2,7-naphthalene-diol; the molar ratio of the 2,7-dihydroxynaphthalene, sodium hydroxide, and sodium nitrite is 1:2:1; and the volume ratio of the sodium hydroxide aqueous solution and sulfuric acid is 4.3-4.6:1.

[0024] Further, the ice water bath has a temperature of 0-4°C.

[0025] In a feasible implementation, the preparation method of the quaternary ammonium salt ionic liquid comprises the following steps:

[0026] The diethanolamine is added with acetonitrile, and stirred at 70-75°C until no delamination is felt; then 2-5 times of n-bromobutane is added at intervals, and the reaction is performed under the condition of airtight sealing and reflux stirring for 40-50 h to obtain a transparent solution, which is spin-dried to obtain the quaternary ammonium salt-Br ionic liquid.

[0027] Further, the interval time for adding the n-bromobutane in batches is about 10-20 min.

[0028] In a feasible implementation, the molar volume of the diethanolamine, acetonitrile, and n-bromobutane is 0.1 mol: 200-250 ml: 0.21 mol.

[0029] In a feasible implementation, the polymerization reaction of the spirooxazine compound and the ionic liquid to obtain the polyionic liquid ultraviolet photoelectric conversion material comprises the following steps:

[0030] After the soft segment compound is vacuumed to remove water, then the isocyanate and the catalyst are sequentially added, and the reaction is performed at 40-60°C for 0.5-2 h, and then the temperature is increased to 80-100°C for 0.2-2 h; then the spirooxazine compound is added, and the reaction is performed at 100-140°C for 2-4 h; then the ionic liquid is added, and the reaction is performed at 100-140°C for 1-3 h to complete the polymerization reaction.

[0031] In an available embodiment, the molar ratio of the isocyanate, the soft segment compound, the spirooxazine compound and the ionic liquid is 10:6-8:1-2:1-2; the soft segment compound is polytetramethylene glycol (PTMG) or polypropylene glycol (PPG); the isocyanate is hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI); and the catalyst is dibutyltin dilaurate (DBTDL). The amount of the catalyst can be added according to the amount of the raw materials, as long as the reaction can be carried out. In a preferred embodiment, the amount of the catalyst is 0.01-0.03% of the total mass of the soft segment compound, the isocyanate, the spirooxazine compound and the ionic liquid.

[0032] According to the second aspect of the present application, the present application provides a spirooxazine-based polyionic liquid ultraviolet photoelectric conversion material prepared by the preparation method of the spirooxazine-based polyionic liquid ultraviolet photoelectric conversion material.

[0033] According to the third aspect of the present application, the present application provides an application of the spirooxazine-based polyionic liquid ultraviolet photoelectric conversion material in the preparation of a photoelectric device.

[0034] In an available embodiment, the preparation of the photoelectric device comprises:

[0035] The spirooxazine-based polyionic liquid ultraviolet photoelectric conversion material is dissolved in N,N-dimethylacetamide to prepare a solution with a concentration of 0.03-0.05 g / mL; a wire bar is used to coat the solution in a pre-made mold in one direction, and a film is prepared after drying to a constant weight;

[0036] The conductive adhesive is uniformly applied to the surface of the film sample and is pasted to a PET transparent electrode; the same method is used to paste a PET transparent electrode on the other side of the sample; and then the sample is packaged to obtain a photoelectric device.

[0037] Further, the film can be cut into various shaped samples, such as square, rectangular, circular and the like.

[0038] Further, the PET transparent electrode is a PET transparent electrode with a grid-shaped Ni-Cu alloy deposited on the surface (commercially available, 190116-1.46).

[0039] Further, the sample pasted with the PET transparent electrode can be packaged using polydimethylsiloxane (PDMS).

[0040] Compared with the prior art, the present application has the following beneficial effects:

[0041] The present application uses spirooxazine as a photosensitive unit to replace azobenzene, under the stimulation of ultraviolet light, spirooxazine undergoes ring-opening isomerization, which brings changes in the micro shape and size of the molecule, generates endogenous forces, drives the movement of the cation of the ionic liquid unit on the same main chain, and the movement of the anion is relatively lagging, which produces endogenous electromotive force; has the following advantages:

[0042] (1) The output voltage of the existing polyionic liquid ultraviolet photoelectric conversion material is significantly improved, and the highest is 28.99V;

[0043] (2) The use of toxic substances such as azobenzene is avoided, and the safety is greatly improved;

[0044] (3) The spirooxazine is more modified with functional groups, which can simply and conveniently adjust its electronic effect, steric effect, etc. by introducing substituents, so as to change its light response performance, such as absorbance, maximum absorption wavelength, ring-opening isomerization deformation, etc. Therefore, it is more conducive to the subsequent energy conversion structure-activity relationship, micro mechanism and other theoretical researches, and at the same time, it can also enrich the types of existing ultraviolet photoelectric conversion polyionic liquid materials. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 The structure of the photoelectric device assembled by the ultraviolet photoelectric conversion material prepared in Example 1 of the present application is a schematic view;

[0046] Figure 2 It is a test device diagram of the open-circuit voltage of the photoelectric device assembled by the ultraviolet photoelectric conversion material prepared in Example 1.

[0047] Figure 3 It is a test result diagram of the open-circuit voltage test of the photoelectric device. DETAILED DESCRIPTION

[0048] The principles and characteristics of the present application are described below, and the examples are only used to explain the present application, and are not used to limit the scope of the present application.

[0049] Example 1

[0050] A preparation method of a polyionic liquid ultraviolet photoelectric conversion material based on spirooxazine, the method uses spirooxazine as a photosensitive unit, and uses the easy modification of the spirooxazine structure to synthesize a photoelectric conversion material with higher output voltage, while avoiding the toxicity risk of azobenzene in the literature, enriching the types and preparation methods of ultraviolet photoelectric conversion materials; the specific preparation method comprises:

[0051] (1) Preparation of spirooxazine photosensitive monomer (SO1)

[0052] Dissolve 3-methoxyphenylhydrazine hydrochloride (17.5 g, 0.1 mol), methyl isopropyl ketone (12.9 g, 0.15 mol) in 150 ml of absolute ethanol and heat to reflux at 110°C for 8 h to obtain a black solution;

[0053]

[0054] Filter the black solution through a sand core funnel and distill off the ethanol from the filtrate. Wash with water and separate the aqueous phase from the oily phase (black in color). Keep the oily phase and separate it three times until the waste solution is light yellow or nearly colorless and there are no solid particles in the product. Obtain the product (2,3,3-trimethyl-5-methoxy-3H-indole) as a black viscous mass. Dry in an 80°C forced air oven for 1 h and then in a vacuum oven at 85°C for 10 h and then at 103°C for 10 h.

[0055] Dissolve the black viscous mass of 2,3,3-trimethyl-5-methoxy-3H-indole (10 g, 0.053 mol) in HBr (30 ml, 0.27 mol) and heat to 130°C for 8 h. Dilute the solution with 400 ml of ice water and neutralize with sodium bicarbonate until pH = 7. Filter through a Buchner funnel and wash with deionized water until neutral to obtain a brown solid (2,3,3-trimethyl-5-hydroxy-3H-indole). Dry in a vacuum oven at 105°C to remove water.

[0056]

[0057] Dissolve 2,3,3-trimethyl-5-hydroxy-3H-indole (17.5 g, 0.1 mol) in 500 ml of a single-necked flask. Add iodomethane (21.5 g, 0.15 mol) dropwise and then dissolve in 250 ml of acetonitrile. React at 80°C for 12 h and then distill off the acetonitrile at 80°C to obtain a brown-yellow solid (1-methyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt). Dry in a vacuum oven at 80°C to constant weight.

[0058]

[0059] Preparation of 1-nitroso-2,7-naphthalenediol: 2,7-dihydroxynaphthalene (11.20 g, 0.07 mol) was taken in a 500 mL single neck flask and dissolved in 120 mL of 1.16 mol / L aqueous sodium hydroxide solution and stirred at 0 °C (ice water bath) until no obvious particles were observed, about 0.5 h; sodium nitrite (5.00 g, 0.07 mol) was added and stirred until homogeneous; 36 g of 48% sulfuric acid (about 26.27 mL) was added slowly through a constant pressure dropping funnel, the dropping was completed in 0.5 h and the reaction was continued for 2 h after the dropping was completed to obtain a wine red solution; the wine red solution was filtered through a Buchner funnel and washed with deionized water until the filtrate was neutral to obtain a red solid (1-nitroso-2,7-naphthalenediol); the product was dried in a vacuum oven at 75 °C for about 3 days.

[0060]

[0061] 1-methyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt (7.925 g, 0.025 mol) was taken in a 250 mL two-neck flask, then 1-nitroso-2,7-naphthalenediol (4.725 g, 0.025 mol) was added in about 150 mL of ethanol as a solvent, and piperidine (2.125 g, 0.025 mol) was added, and the reaction was carried out at 85 °C under reflux for 5 h to obtain a black solution, and a small part of the solution was diluted to obtain a purple solution; the black solution was rotary evaporated at 85 °C to obtain a black viscous product (1-methyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine) SO1, which was scraped after being frozen in a freezer for 24 h to obtain the spirooxazine compound SO1.

[0062]

[0063] (2) Preparation of ionic liquid (IL)

[0064] Diethanolamine (colorless transparent viscous) (10.5 g, 0.1 mol) was taken in a 500 mL single neck flask, 250 mL of acetonitrile was added, and stirred at 75 °C until no layering was observed; n-butyl bromide (28.56 g, 0.21 mol) was added in three portions with a certain time interval (about 15 min), a balloon was sleeved on the upper end of the condenser tube to maintain airtightness, and the reaction was carried out under reflux for 48 h to obtain a transparent solution, which was rotary evaporated at 80 °C to obtain a quaternary ammonium salt-Br ionic liquid (slightly yellow transparent viscous fluid).

[0065]

[0066] (3) Preparation of polyionic liquid ultraviolet photoelectric conversion material (SO-LI)

[0067] PTMG (molecular weight 1000) was vacuumed at 103°C for 1 h, then HDI and catalyst DBTDL were added in sequence, and reacted at 60°C for 1 h, and then the temperature was increased to 80°C for 1 h; then the spirooxazine compound was added for chain extension, and reacted at 120°C for 3 h; then the ionic liquid was added, and reacted at 120°C for 2 h, and the product was discharged to obtain the poly-ionic liquid ultraviolet photoelectric conversion material; the amount of catalyst DBTDL was 0.02% of the total mass of PTMG, HDI, spirooxazine compound and ionic liquid.

[0068] Example 2

[0069] A preparation method of a spirooxazine-based poly-ionic liquid ultraviolet photoelectric conversion material, the main contents of the method and example 1 are the same, the difference is that when preparing the spirooxazine compound: 2,3,3-trimethyl-5-hydroxy-3H-indole reacts with iodobutane, specifically:

[0070] 2,3,3-trimethyl-5-hydroxy-3H-indole (17.5 g, 0.1 mol) was added dropwise into a 500 ml single-necked flask, iodobutane (27.6 g, 0.15 mol) was added, and 200 ml of acetonitrile solution was added for dissolution, and reacted at 80°C and refluxed for 24 h, after which the acetonitrile was removed by rotary evaporation at 80°C to obtain a black viscous product (1-n-butyl-3,3-dimethyl-5-hydroxy-2-methylene indoline quaternary ammonium salt); dried in a vacuum oven at 80°C to constant weight.

[0071]

[0072] Meanwhile, 1-n-butyl-3,3-dimethyl-5-hydroxy-2-methylene indoline quaternary ammonium salt (5.744 g, 0.016 mol) was taken in a 250 ml two-necked flask, then 1-nitroso-2,7-naphthalenediol (3.024 g, 0.016 mol) was weighed, 150 ml of ethanol was added as a solvent, and piperidine (1.36 g, 0.016 mol) was added, and heated and refluxed at 85°C for 5 h to obtain a black solution, a small part of the black solution was diluted to obtain a dark green solution, and the black solution was rotary evaporated at 85°C to obtain a black viscous product (1-n-butyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolino spiro naphthoxazine) SO4;

[0073]

[0074] Example 3

[0075] Preparation of a photoelectric device: the spirooxazine-based poly-ionic liquid ultraviolet photoelectric conversion material prepared in example 1 was used for preparation, specifically including:

[0076] The synthesized polyion liquid based on spirooxazine UV photoelectric conversion material is dissolved in N,N-dimethylacetamide (DMAc) to prepare a polymer solution with a concentration of 0.05 g / mL; a wire bar is used to coat the solution in a pre-made mold along one direction, and a film sample is prepared after drying to a constant weight.

[0077] The film prepared above is cut into a rectangular sample with an area of 1.5 cm x 2.0 cm; conductive glue is evenly applied to the surface of the sample and pasted onto a PET transparent electrode (commercially available, model 190116-1.46) with a grid-shaped Ni-Cu alloy deposited on the surface; a layer of PET transparent electrode of the same material is pasted on the other side of the sample by the same method; after the lead wire is drawn, it is packaged with polydimethylsiloxane (PDMS) to obtain a photoelectric device.

[0078] Experimental Example

[0079] The spirooxazine units SO1 and SO4 with different N-position substituents are prepared, and are introduced into the polyion liquid molecular main chain in three different molar ratios (SO:IL:PTMG:HDI = 1:1:8:10, 1.5:1.5:7:10, 2:2:6:10) with IL, HDI, respectively; the specific formula and material ratio are as follows:

[0080] Dosage of each raw material of SO1 and SO4:

[0081]

[0082] Dosage of each raw material of IL:

[0083]

[0084] Molar ratio of each raw material of SO-LI:

[0085]

[0086] After the photoelectric device prepared in Example 3 is assembled, the ultraviolet light source, the photoelectric device and the oscilloscope are connected according to Figure 2 The power of the ultraviolet lamp is 4 W, the light intensity is 3100 μW / cm2, and the material prepared according to the method of the application under the conditions designed according to the above test is tested and the real-time open circuit voltage data of the device under ultraviolet irradiation are recorded; as shown in Figures 1-3 As can be seen from the figure, from SO-IL-1 to SO-IL-3, the higher the molar ratio of SO1 and IL, the higher the output open circuit voltage of the device prepared from the sample, and the same law is also reflected in the voltage test of SO-IL-4 to SO-IL-6;

[0087] When the molar ratio of SO, IL and HDI is the same (for example, SO-IL-1 and SO-IL-4, SO-IL-2 and SO-IL-5, SO-IL-3 and SO-IL-6), the spirooxazine unit (SO4) with N substituent of -CH2CH2CH2CH3 is selected instead of the spirooxazine unit (SO1) with N substituent of -CH3, which can produce higher open circuit voltage and achieve better photoelectric conversion effect; and the open circuit voltage can reach about 30v, so it can be known that the output voltage of the prepared spirooxazine-based polyionic liquid ultraviolet photoelectric conversion material has obvious improvement compared with the prior art, and the method and material have great application value.

[0088] Although the embodiments of the present application have been shown and described above, it should be understood that the above-described embodiments are exemplary, and should not be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above-described embodiments within the scope of the present application.

Claims

1. A method for preparing a spirooxazine-based polyionic liquid UV photoelectric conversion material, characterized in that, Comprise; The spirooxazine compound is prepared according to the following steps: 3-methoxyphenylhydrazine hydrochloride and methyl isopropyl ketone are dissolved in anhydrous ethanol, heated to reflux at 100-110 DEG C for 6-8 h to obtain a black solution; the black solution is filtered, the filtrate is rotary evaporated, washed with water to obtain an oil phase, and separated for 2-3 times to obtain a black viscous product 2,3,3-trimethyl-5-methoxy-3H-indole, and dried; Then, hydrogen bromide is added to the 2,3,3-trimethyl-5-methoxy-3H-indole, heated to reflux at 100-130 DEG C for 8-10 h; the solution is diluted with ice water, and then neutralized to weak alkaline or neutral by adding sodium bicarbonate, filtered, and washed with deionized water until neutral to obtain a brown solid 2,3,3-trimethyl-5-hydroxy-3H-indole; Alkyl iodide is added to the 2,3,3-trimethyl-5-hydroxy-3H-indole, and then dissolved in acetonitrile solution, heated to reflux at 60-80 DEG C for 10-12 h, and then rotary evaporated to remove acetonitrile to obtain 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt; 1-nitroso-2,7-naphthalenediol is prepared; The 1-nitroso-2,7-naphthalenediol is added to the 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt, and then ethanol and piperidine are added, heated to reflux at 80-85 DEG C under nitrogen for 3-5 h, and then rotary evaporated to obtain 1-alkyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinespiro naphthoxazine, i.e. the spirooxazine compound; An ionic liquid is prepared; the ionic liquid is imidazole ionic liquid or quaternary ammonium salt ionic liquid; The spirooxazine compound and the ionic liquid are subjected to a polymerization reaction to obtain a polyionic liquid ultraviolet photoelectric conversion material, comprising: vacuuming water from a soft segment compound, then adding isocyanate and a catalyst in sequence, reacting at 40-60 DEG C for 0.5-2 h, and then increasing the temperature to 80-100 DEG C for 0.2-2 h; then adding the spirooxazine compound, reacting at 100-140 DEG C for 2-4 h; and then adding the ionic liquid, reacting at 100-140 DEG C for 1-3 h to complete the polymerization reaction; the molar ratio of the isocyanate, the soft segment compound, the spirooxazine compound and the ionic liquid is 10:6-7:1.5-2:1.5-2; and the soft segment compound is polybutylene glycol or polypropylene glycol.

2. The preparation method of the polyionic liquid ultraviolet photoelectric conversion material based on spiroxazine according to claim 1, characterized in that: The alkyl iodide is methyl iodide or butyl iodide or hexyl iodide; the 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt is 1-methyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt or 1-n-butyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt or 1-hexyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt; and the 1-alkyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine is 1-methyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine or 1-n-butyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine or 1-hexyl-3,3-dimethyl-5,9'-dihydroxy-3H-indolinospiro naphthoxazine.

3. The preparation method of the polyionic liquid ultraviolet photoelectric conversion material based on spiroxazine according to claim 1, characterized in that: The molar volume ratio of the 3-methoxyphenylhydrazine hydrochloride, methyl isopropyl ketone and ethanol is 0.1 mol:0.15 mol:150 ml; the molar ratio of the 2,3,3-trimethyl-5-methoxy-3H-indole and hydrogen bromide is 1:5-5.2; the molar volume ratio of the 2,3,3-trimethyl-5-hydroxy-3H-indole, alkyl iodide and acetonitrile is 0.1 mol:0.15 mol:200-250 ml; the molar ratio of the 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt, 1-nitroso-2,7-naphthalenediol and piperidine is 1:1:1; and the amount of the ethanol used is 150 mL per 0.016-0.025 mol of 1-alkyl-3,3-dimethyl-5-hydroxy-2-methyleneindolinium quaternary salt.

4. The preparation method of the polyionic liquid ultraviolet photoelectric conversion material based on spiroxazine according to claim 1, characterized in that: The preparation method of the 1-nitroso-2,7-naphthalenediol comprises: 2,7-dihydroxynaphthalene is dissolved in 1-2 mol / L sodium hydroxide aqueous solution, stirred for 0.5-1 h under ice water bath condition, then sodium nitrite is added and stirred uniformly, then 40-50% sulfuric acid is added dropwise, the dropwise addition is completed in 0.3-0.5 h, and then the reaction is carried out for 3-5 h to obtain a wine red solution, the wine red solution is filtered, washed with deionized water until the filtrate is neutral, and then a red solid 1-nitroso-2,7-naphthalenediol is obtained; the molar ratio of the 2,7-dihydroxynaphthalene, sodium hydroxide and sodium nitrite is 1:2:1; and the volume ratio of the sodium hydroxide aqueous solution and sulfuric acid is 4.3-4.6:

1.

5. The preparation method of the polyionic liquid ultraviolet photoelectric conversion material based on spiroxazine according to claim 1, characterized in that: The preparation method of the quaternary ammonium salt ionic liquid comprises: diethanolamine is added with acetonitrile, and then stirred and reacted at 70-75℃ until there is no delamination; then 1-n-bromobutane is added in 2-5 times at intervals, and then refluxed and stirred for 40-50 h under airtight condition to obtain a transparent solution, which is spin-dried to obtain a quaternary ammonium salt-Br ionic liquid.

6. The method for preparing the polyionic liquid ultraviolet photoelectric conversion material based on spiroxazine according to claim 5, characterized in that: The molar volume of the diethanolamine, acetonitrile and 1-n-bromobutane is 0.1 mol:200-250 ml:0.21 mol.

7. The method for preparing the polyionic liquid ultraviolet photoelectric conversion material based on spiroxazine according to claim 1, characterized in that: The isocyanate is hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, diphenylmethane diisocyanate or toluene diisocyanate; and the catalyst is dibutyl tin dilaurate.

8. The spirooxazine-based polyionic liquid UV photoelectric conversion material prepared by the method according to any one of claims 1-7.

9. The use of the spirooxazine-based polyionic liquid UV photoelectric conversion material according to claim 8 in the preparation of photoelectric devices.

10. Use of the spirooxazine-based polyionic liquid UV-photovoltaic conversion material according to claim 9, characterized in that, The preparation of the photoelectric device comprises: The spirooxazine-based polyionic liquid UV photoelectric conversion material is dissolved in N,N-dimethylacetamide to prepare a solution with a concentration of 0.03-0.05 g / mL; a wire bar is used to coat the solution in a pre-made mold in one direction, and a film is prepared after drying to a constant weight; The conductive adhesive is uniformly applied to the surface of the film sample and pasted to a PET transparent electrode; the same method is used to paste a PET transparent electrode on the other side of the sample; and packaging treatment is performed to obtain a photoelectric device.

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