Anthracene-based compound, preparation method therefor and use thereof as solar thermal fuel

Abstract

The present invention relates to the field of energy and chemical engineering, and provides an anthracene-based compound, a preparation method therefor, and a use thereof as a solar thermal fuel. The anthracene-based compound of the present invention can be converted into a dimer and store light energy as chemical energy under irradiation with 365 nm ultraviolet light, and under irradiation with 254 nm ultraviolet light, undergoes a photodepolymerization reaction and releases heat, that is, an anthracene-based solar thermal fuel can store or release photothermal energy by means of a reversible photodimerization / depolymerization reaction. In addition, the anthracene-based compound also has the unique advantage of light-controlled reversible solid-liquid phase change and can realize the simultaneous storage of photon energy and phase change energy. The anthracene-based compound has a storage energy density of about 65 kJ / mol and a storage half-life of up to 60 days. The anthracene-based compound and the preparation method therefor provided by the present invention provide a new strategy for light energy storage and utilization.

Description

Anthryl compound, preparation method thereof and application as solar thermal fuel TECHNICAL FIELD

[0001] The present application relates to the field of energy chemical industry, in particular to an anthryl compound, a preparation method thereof and an application as solar thermal fuel. BACKGROUND

[0002] Anthracene, as a condensed ring aromatic hydrocarbon containing three rings, is widely used in chemical production. Industrially, anthracene is generally oxidized first, and then subjected to nitration, sulfonation and other processes to provide intermediates for the fields of dyes, pharmaceuticals and optoelectronic materials. Anthracene has a high content in coal tar, and a method for separating anthracene from coal tar with simple operation, mild conditions and low cost is provided in patent CN115141077B. In addition, anthracene has the advantages of controllable luminescence, easy transfer of energy and charge, and unique photo-thermal reversible dimerization. However, the current preparation method of anthryl compounds is relatively complex, and there are few reports on the development of anthryl solar thermal fuel based on photo-dimerization / de-dimerization reaction. Solar thermal fuel is a kind of molecular photo-switch based on reversible transformation of molecular spatial configuration to realize light energy storage and heat release, and its utilization process is stable and does not emit any gas and pollutants. Anthryl compounds have relatively low electronic energy gap due to their extended aromatic π system, and are easy to form dimers, and the dimers can quickly de-dimerize under light conditions. Therefore, the preparation of new anthryl compounds and their exploration as solar thermal fuel have important application value for expanding the application of condensed ring aromatic hydrocarbon anthracene.

[0003] SUMMARY

[0004] The present application relates to the field of energy chemical industry, in particular to an anthryl compound, a preparation method thereof and an application as solar thermal fuel.

[0005] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0006] The present application provides an anthryl compound having the structure shown in formula 1:

[0007] In formula 1, n=10-16.

[0008] Preferably, n=10, 13 or 16.

[0009] The present application provides a preparation method of the anthryl compound according to the above technical solution, comprising the following steps:

[0010] Mixing anthracene, N-methylformanilide, phosphorus oxychloride and a first solvent to perform formylation-condensation reaction to obtain 9-anthraldehyde;

[0011] Mixing the 9-anthracene formaldehyde, sodium borohydride and the second solvent, a reduction reaction is carried out to obtain 9-anthracene methanol;

[0012] Mixing the 9-anthracene methanol, succinic anhydride, 4-dimethylaminopyridine and the third solvent, a substitution reaction is carried out to obtain 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid;

[0013] Mixing the 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, long-chain fatty alcohol and the fourth solvent, an esterification reaction is carried out to obtain an anthryl compound;

[0014] The number of carbon atoms of the long-chain fatty alcohol is 12-18.

[0015] Preferably, the anthracene is prepared from coal tar.

[0016] Preferably, the molar ratio of the anthracene, N-methylformanilide and phosphorus oxychloride is 1:2:2-1:4:4; the volume ratio of the N-methylformanilide and the first solvent is 10:1-5:1.

[0017] The temperature of the formylation-condensation reaction is 90-100℃, and the time is 2-8h.

[0018] Preferably, the molar ratio of the 9-anthracene formaldehyde and sodium borohydride is 1:2-1:3; the temperature of the reduction reaction is 25℃, and the time is 4-8h.

[0019] Preferably, the third solvent comprises dichloromethane and pyridine; the volume ratio of the dichloromethane and pyridine is 1:1-3:1.

[0020] Preferably, the molar ratio of the 9-anthracene formaldehyde, 4-dimethylaminopyridine and succinic anhydride is 1:1:4-1:2:6.

[0021] The temperature of the substitution reaction is 25℃, and the time is 24-48h.

[0022] Preferably, the molar ratio of the 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine and long-chain fatty alcohol is 1:4:2:1-1:6:5:3.

[0023] The temperature of the esterification reaction is 25℃, and the time is 24-48h.

[0024] The anthryl compound prepared by the preparation method is used as a solar thermal fuel.

[0025] The anthracene-based compound can occur photodimerization under irradiation of ultraviolet light at a specific wavelength to store photo-thermal energy, and occur photodepolymerization under irradiation of ultraviolet light at another wavelength to release heat, i.e. the anthracene-based compound can effectively occur reversible photodimerization / depolymerization to store or release photo-thermal energy, and has the unique advantage of photo-controlled reversible solid-liquid phase change. In addition, the anthracene-based compound has high storage energy density (65 kJ / mol) and long storage half-life (3 days), can realize simultaneous utilization of stored photon energy and phase change energy, effectively improve the storage performance of solar thermal fuel, and the utilization process is stable and does not release any greenhouse gas.

[0026] The anthracene-based compound is prepared by formylation-condensation reaction, substitution reaction and esterification reaction through the reversible photodimerization / depolymerization reaction of anthracene, and the prepared anthracene-based compound can occur photodimerization under irradiation of 365 nm light and accompany solid-liquid phase change to simultaneously store photon energy and phase change energy, and occur depolymerization under irradiation of 254 nm light and accompany liquid-solid phase change, and simultaneously release stored light energy and phase change energy in the form of heat energy.

[0027] The raw material anthracene used in the application is obtained from commercial or coal tar separation products, and the application of the anthracene-based compound as solar thermal fuel can not only broaden the diversified utilization road, but also further enrich the molecular system of solar thermal fuel.

[0028] The synthesis process of the anthracene-based compound is simple, has high yield, is easy to mass-produce, is stable in circulation, and is environmentally friendly in utilization process, and can improve the clean utilization level of coal tar. BRIEF DESCRIPTION OF DRAWINGS

[0029] Fig. 1 is a synthesis route diagram of the anthracene-based compound in the application;

[0030] Fig. 2 is a nuclear magnetic hydrogen spectrum diagram (deuterated chloroform) of 9-anthracene methanol (a), intermediate product 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid (b), anthracene-based compound (c) and mass spectrum diagram (d) of the anthracene-based compound prepared in Example 1;

[0031] Fig. 3 is an ultraviolet-visible absorption spectrum diagram of the anthracene-based compound in Example 1 after irradiation (light irradiation power 10 mW / cm 2 ) of 365 nm ultraviolet light (a) and 254 nm ultraviolet light (b) for different time, and a photodimerization / depolymerization schematic diagram (c) of the anthracene-based compound under alternate irradiation of 365 nm and 254 nm ultraviolet light;

[0032] Fig. 4 is an optical photo of the reversible solid-liquid phase change of the anthracene-based compound prepared in Example 2 under alternate excitation of ultraviolet light (light irradiation power 50 mW / cm 2 );

[0033] Figure 5 is a (a) storage energy density test curve and (b) recovery half-life curve of the anthryl compound in Example 3. DETAILED DESCRIPTION

[0034] The present application provides an anthryl compound having the structure shown in Formula 1:

[0035] In Formula 1, n = 10-16.

[0036] In the present application, n = 10, 13 or 16.

[0037] As shown in Figure 1, the present application provides a preparation method of the anthryl compound described in the above technical solution, comprising the following steps:

[0038] Mixing anthracene, N-methylformanilide, phosphorus oxychloride and a first solvent to perform formylation-condensation reaction to obtain 9-anthracene formaldehyde;

[0039] Mixing the 9-anthracene formaldehyde, sodium borohydride and a second solvent to perform reduction reaction to obtain 9-anthracene methanol;

[0040] Mixing the 9-anthracene methanol, succinic anhydride, 4-dimethylaminopyridine and a third solvent to perform substitution reaction to obtain 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid;

[0041] Mixing the 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, long-chain fatty alcohol and a fourth solvent to perform esterification reaction to obtain the anthryl compound;

[0042] The long-chain fatty alcohol has 12-18 carbon atoms.

[0043] In the present application, if not otherwise specified, the required preparation raw materials or reagents are all commercially available goods well known to those skilled in the art.

[0044] The present application mixes anthracene, N-methylformanilide, phosphorus oxychloride and a first solvent to perform formylation-condensation reaction to obtain 9-anthracene formaldehyde.

[0045] In the present application, the anthracene is preferably a commercially available product or obtained by separation from coal tar; the anthracene is preferably extracted by the method for separating anthracene from coal tar disclosed in patent CN115141077B.

[0046] In the present application, the molar ratio of the anthracene, N-methylformanilide and phosphorus oxychloride is preferably 1:2:2-1:4:4, more preferably 1:3:3.

[0047] In the present application, the first solvent is preferably o-dichlorobenzene; the volume ratio of N-methylformanilide to the first solvent is preferably 10:1-5:1, more preferably 7-9:1.

[0048] In the present application, the anthracene, N-methylformanilide and phosphorus oxychloride are mixed, the first solvent is added, the mixture is heated and stirred in an oil bath to the reaction temperature, and maintained for 30-60 min, more preferably 50 min, the anthracene is dissolved to form a deep red solution, hydrochloric acid is precipitated, and the formylation-condensation reaction is carried out.

[0049] In the present application, the temperature of the formylation-condensation reaction is preferably 90-100℃, more preferably 95-98℃, and the time is preferably 2-8 h, more preferably 3-6 h.

[0050] After the formylation-condensation reaction is completed, dichloromethane is added to the obtained product, which is washed with saturated sodium chloride solution for several times; the organic phase is dried over magnesium sulfate, filtered, and the solvent is evaporated to obtain 9-anthracene formaldehyde. The washing, drying, filtering and solvent evaporation in the present application are not particularly limited, and can be carried out according to the processes well known in the art.

[0051] In the present application, the 9-anthracene formaldehyde, sodium borohydride and the second solvent are mixed to carry out a reduction reaction to obtain 9-anthracene methanol.

[0052] In the present application, the molar ratio of 9-anthracene formaldehyde to sodium borohydride is preferably 1:2-1:3; the second solvent is preferably ethanol; and the amount of the second solvent is not particularly limited, as long as the reaction can be carried out smoothly.

[0053] In the present application, sodium borohydride is added to the solvent containing 9-anthracene formaldehyde at 0℃, and the mixture is subjected to a reduction reaction under stirring; the temperature of the reduction reaction is preferably 25℃, and the time is preferably 4-8 h.

[0054] After the reduction reaction is completed, concentrated hydrochloric acid is preferably added dropwise to the obtained product to decompose the unreacted sodium borohydride, and then water is added to neutralize; dichloromethane is further added to separate the organic layer, which is washed with saturated sodium chloride solution for several times, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure; the obtained crude product is recrystallized with ethanol to obtain 9-anthracene methanol.

[0055] In the present application, the mass concentration of the concentrated hydrochloric acid is preferably 12M; the volume ratio of the concentrated hydrochloric acid to the second solvent is preferably 1:15-1:10, more preferably 1:12.5; the volume ratio of dichloromethane to saturated sodium chloride solution is preferably 1:2-1:6, more preferably 1:3-4.8; the number of times of washing with the saturated sodium chloride solution is preferably 2-6 times, more preferably 3-4 times; and the number of times of recrystallization is preferably 2-5 times, more preferably 3 times.

[0056] The 9-anthracene methanol, succinic anhydride and 4-dimethylaminopyridine are mixed to carry out substitution reaction to obtain 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid.

[0057] In the present application, the molar ratio of the 9-anthracene methanol, 4-dimethylaminopyridine and succinic anhydride is preferably 1:1:4-1:2:6, and more preferably 1:1:5-1:2:6.

[0058] In the present application, the third solvent preferably includes dichloromethane and pyridine; the volume ratio of the dichloromethane and pyridine is preferably 1:1-3:1, and more preferably 2:1; the present application does not have special limitation on the amount of the third solvent, which can ensure the smooth progress of the reaction.

[0059] The 9-anthracene methanol, 4-dimethylaminopyridine and succinic anhydride are mixed to carry out substitution reaction.

[0060] In the present application, the temperature of the substitution reaction is preferably 25°C, and the time is preferably 24-48h, and more preferably 36h.

[0061] After the substitution reaction is completed, the obtained mixture is poured into an ice / water mixture and heated to room temperature; dichloromethane is added to separate the organic layer, and then the organic layer is extracted with saturated sodium chloride solution for several times; the collected organic layer is dried over anhydrous magnesium sulfate, filtered, and vacuum concentrated to obtain 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid. In the present application, the volume ratio of the dichloromethane and saturated sodium chloride solution is preferably 1:2-1:6, and more preferably 1:2.5; the extraction times of the saturated sodium chloride solution is preferably 2-5 times, and more preferably 4 times.

[0062] The 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, long-chain fatty alcohol and fourth solvent are mixed to carry out esterification reaction to obtain an anthracene compound.

[0063] In the present application, the molar ratio of the 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine and long-chain fatty alcohol is preferably 1:4:2:1-1:6:5:3, and more preferably 1:5:3:3; the long-chain fatty alcohol has 12-18 carbon atoms, and preferably 12, 15 or 18.

[0064] In the present application, the fourth solvent is preferably chloroform; the present application does not have special limitation on the amount of the fourth solvent, which can ensure the smooth progress of the reaction.

[0065] The present application preferably mixes 4-(anthracen-9-ylmethoxy)-4-oxobutanoic acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride (EDAC) and 4-dimethylaminopyridine (DMAP) after adding a fourth solvent, magnetically stirring to dissolve the solid, then adding a long-chain fatty alcohol, and performing an esterification reaction on the resulting mixture under continuous stirring.

[0066] In the present application, the temperature of the esterification reaction is preferably 25℃, and the time is preferably 24-48h, more preferably 36h.

[0067] After the esterification reaction is completed, the present application preferably adds 5wt% dilute hydrochloric acid aqueous solution to the resulting product system and extracts the combined organic layer with saturated sodium bicarbonate aqueous solution, dries the resulting organic layer with magnesium sulfate, filters under reduced pressure, concentrates by rotary evaporation, purifies by column chromatography, and then obtains an anthryl compound.

[0068] In the present application, the volume ratio of the dilute hydrochloric acid aqueous solution to the fourth solvent is preferably 1:3-1:6, more preferably 1:3.75-5; the number of times of extraction with saturated sodium bicarbonate aqueous solution is preferably 3-5 times; the developing agent used for column chromatography purification is preferably ethyl acetate and n-hexane, and the volume ratio of the ethyl acetate and n-hexane is preferably 1:1-1:3, more preferably 1:2.

[0069] The present application provides the use of the anthryl compound described in the above technical solution or the anthryl compound prepared by the preparation method described in the above technical solution as a solar thermal fuel.

[0070] The present application does not have special limitations on the application method, and the anthryl compound can be directly used as a solar thermal fuel.

[0071] The technical solutions provided by the present application will be described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0072] Example 1

[0073] 1) Anthracene (5.00 g, 28.00 mmol), N-methylformanilide (6.3 mL, 7.58 g, 56.00 mmol) and phosphorus oxychloride (8.56 g, 56.00 mmol) were placed in a 100 mL round bottom flask containing 0.7 mL of o-dichlorobenzene and then heated in an oil bath with stirring at 1500 r / min to 95 °C for 30 min; during this time, the anthracene dissolved to form a dark red solution and hydrochloric acid precipitated, and heating was continued for 3 h; after the reaction was completed, 25 mL of dichloromethane was added and then washed with 50 mL of saturated sodium chloride solution 3 times; the organic phase was dried over magnesium sulfate at room temperature for 12 h, filtered, and the solvent was evaporated at 30 °C for 1 h to obtain 9-anthracene formaldehyde; sodium borohydride (0.34 g, 9.60 mmol) was added to a solution of 9-anthracene formaldehyde (1.00 g, 4.80 mmol) in ethanol (50 mL) at 0 °C, and the reaction mixture was stirred at 25 °C at 1500 r / min for 4 h; 5 mL of concentrated hydrochloric acid (concentration of 12 M) was added dropwise, and then water was added to neutralize; 25 mL of dichloromethane was added to separate the organic layer, which was washed with 50 mL of saturated sodium chloride solution 3 times, and 150 g of anhydrous magnesium sulfate was dried at 45 °C for 12 h, filtered, and distilled under reduced pressure (0.02 MPa, 30 °C, 1 h); the resulting crude product was recrystallized from 50 mL of ethanol at 4 °C for 12 h, and after recrystallization twice, a light yellow 9-anthracene methanol was obtained;

[0074] 2) A mixture of 9-anthracene methanol (2.08 g, 10.00 mmol), 4-dimethylaminopyridine (1.23 g, 10.01 mmol) and succinic anhydride (4.00 g, 40.02 mmol) was placed in a 250 mL round bottom flask, followed by the addition of a mixed solution of 50 mL of anhydrous dichloromethane and 50 mL of anhydrous pyridine, and the resulting mixed solution was stirred at 25 °C at 1500 r / min for 24 h; after the reaction was completed, the mixed solution was poured into a 200 mL ice / water mixture and heated to room temperature, 50 mL of dichloromethane was added to separate the organic layer, and then the organic layer was washed with 100 mL of saturated sodium chloride solution 3 times; the collected organic layer was dried over 150 g of anhydrous magnesium sulfate at room temperature for 12 h, filtered, and concentrated under vacuum at 0.02 MPa and 30 °C for 1 h to obtain the intermediate product 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid.

[0075] 3) 4-(anthracen-9-ylmethoxy)-4-oxobutanoic acid (1.48 g, 4.80 mmol), 1- ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride (3.67 g, 19.20 mmol) and p-dimethylaminopyridine (1.17 g, 9.60 mmol) were sequentially placed in a 250 mL single-necked round-bottom flask and 150 mL of chloroform was added, and the solution was dissolved by magnetic stirring at 1500 r / min, then n-dodecanol (0.89 g, 4.80 mmol) was added to the round-bottom flask, and the mixture was continuously stirred at 25 °C for 24 h; after the reaction was completed, 50 mL of 5 wt% dilute hydrochloric acid aqueous solution was added, washed with 50 mL of saturated sodium bicarbonate aqueous solution 3 times, and the obtained organic layer was dried over 150 g of magnesium sulfate, filtered under reduced pressure (0.02 MPa), concentrated by rotary evaporation at 45 °C for 1 h, and purified by column chromatography (ethyl acetate and n-hexane, volume ratio = 1:2) to obtain the anthryl compound.

[0076] Example 2

[0077] 1) Anthracene (5.00 g, 28.00 mmol), N-methylformanilide (9.45 mL, 11.34 g, 84.00 mmol) and phosphorus oxychloride (12.85 g, 84.00 mmol) were placed in a 100 mL round-bottom flask containing 1.35 mL of o-dichlorobenzene, and then heated and stirred in an oil bath at 1500 r / min to 98 °C for 50 min; during this period, anthracene was dissolved to form a deep red solution, and hydrochloric acid was precipitated, and heating was continued for 6 h; after the reaction was completed, 25 mL of dichloromethane was first added, and then washed with 75 mL of saturated sodium chloride solution 4 times; the organic phase was dried over magnesium sulfate at room temperature for 12 h, filtered, and the solvent was evaporated at 30 °C for 1 h to obtain 9-anthracene formaldehyde; sodium borohydride (0.34 g, 9.60 mmol) was added to an ethanol solution (50 mL) containing 9-anthracene formaldehyde (1.00 g, 4.80 mmol) at 0 °C, and the reaction mixture was stirred at 1500 r / min at 25 °C for 4 h; 4 mL of concentrated hydrochloric acid (concentration of 12 M) was added dropwise, and then water was added to neutralize; after the reaction was completed, 25 mL of dichloromethane was added to separate the organic layer, which was washed with 75 mL of saturated sodium chloride solution 4 times, and 150 g of anhydrous magnesium sulfate was dried at 45 °C for 12 h, filtered and distilled under reduced pressure (0.02 MPa, 30 °C, 1 h), and then the obtained crude product was recrystallized from 50 mL of ethanol at 4 °C for 12 h, and after recrystallization for 3 times, a light yellow 9-anthracene methanol was obtained;

[0078] 2) A mixture of 9-anthracenemethanol (2.08 g, 10.00 mmol), 4-dimethylaminopyridine (2.44 g, 20.01 mmol) and succinic anhydride (5.00 g, 50.02 mmol) was placed in a 250 mL round bottom flask, followed by adding a mixed solution of 100 mL of anhydrous dichloromethane and 50 mL of anhydrous pyridine, and the resulting mixed solution was stirred at 1500 r / min at 25°C for 36 h. After the reaction was completed, the mixed solution was poured into 200 mL of an ice / water mixture and heated to room temperature, 100 mL of dichloromethane was added to separate the organic layer, and then the organic layer was washed with 250 mL of a saturated sodium chloride solution 4 times. The collected organic layer was dried over 150 g of anhydrous magnesium sulfate at room temperature for 12 h, filtered, and concentrated under vacuum at 0.02 MPa and 30°C for 1 h to obtain an intermediate product 4-(anthracen-9-ylmethoxy)-4-oxobutanoic acid;

[0079] 3) 4-(anthracen-9-ylmethoxy)-4-oxobutanoic acid (1.48 g, 4.80 mmol), 1-ethyl(3- dimethylaminopropyl)-3-carbodiimide hydrochloride (3.67 g, 19.20 mmol), and p- dimethylaminopyridine (1.17 g, 9.60 mmol) were sequentially placed in a 250 mL single-necked round bottom flask and 150 mL of chloroform was added to dissolve the mixture by magnetic stirring at 1500 r / min. Then, n-dodecanol (1.78 g, 9.60 mmol) was added to the round bottom flask, and the mixture was continuously stirred at 25°C for 36 h. After the reaction was completed, 30 mL of a 5 wt% dilute hydrochloric acid aqueous solution was added, and the resulting organic layer was washed with 50 mL of a saturated sodium bicarbonate aqueous solution 4 times, dried over 150 g of magnesium sulfate, filtered under reduced pressure at 0.02 MPa, and concentrated by rotary evaporation at 45°C for 1 h. After column chromatography purification (ethyl acetate and n-hexane, volume ratio = 1:3), an anthracene compound was obtained.

[0080] Example 3

[0081] 1) Anthracene (2.50 g, 14.00 mmol), N-methylformanilide (6.3 mL, 7.56 g, 56.00 mmol) and phosphorus oxychloride (8.57 g, 56.00 mmol) were placed in a 100 mL round bottom flask containing 1.20 mL of o-dichlorobenzene and then heated in an oil bath at 1500 r / min to 100°C for 60 min; during this time, the anthracene dissolved to form a dark red solution and hydrochloric acid precipitated, continuing the heating for 8 h; after the reaction was completed, 25 mL of dichloromethane was added and then washed with 150 mL of saturated sodium chloride solution 5 times; the organic phase was dried over magnesium sulfate at room temperature for 12 h, filtered, and the solvent was evaporated at 30°C for 1 h to obtain 9-anthracene formaldehyde; sodium borohydride (0.51 g, 14.40 mmol) was added to a solution of 9-anthracene formaldehyde (1.00 g, 4.80 mmol) in ethanol (50 mL) at 0°C, and the reaction mixture was stirred at 1500 r / min at 25°C for 8 h; 5 mL of concentrated hydrochloric acid (concentration of 12 M) was added dropwise, and then water was added to neutralize; after the reaction was completed, 25 mL of dichloromethane was added to separate the organic layer, which was washed with saturated sodium chloride solution (120 mL) 5 times, dried over 150 g of anhydrous magnesium sulfate at 45°C for 12 h, filtered, and distilled under reduced pressure (0.02 MPa, 30°C, 1 h); the resulting crude product was recrystallized from 50 mL of ethanol at 4°C for 12 h, and after recrystallization 3 times, a light yellow 9-anthracene methanol was obtained;

[0082] 2) A mixture of 9-anthracene methanol (2.08 g, 10.00 mmol), 4-dimethylaminopyridine (2.44 g, 20.01 mmol) and succinic anhydride (6.00 g, 60.02 mmol) was placed in a 250 mL round bottom flask, followed by the addition of a mixed solution of 150 mL of anhydrous dichloromethane and 50 mL of anhydrous pyridine, and the resulting mixed solution was stirred at 1500 r / min at 25°C for 48 h; after the reaction was completed, the mixed solution was poured into 200 mL of an ice / water mixture and heated to room temperature, 150 mL of dichloromethane was added to separate the organic layer, which was then washed with 300 mL of saturated sodium chloride solution 5 times, and the collected organic layer was dried over 150 g of anhydrous magnesium sulfate at room temperature for 12 h, filtered, and concentrated under vacuum at 0.02 MPa and 30°C for 1 h to obtain the intermediate product 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid;

[0083] 3) 4-(anthracen-9-ylmethoxy)-4-oxobutanoic acid (1.48 g, 4.80 mmol), 1- ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride (4.58 g, 24.00 mmol) and 4-dimethylaminopyridine (1.75 g, 14.40 mmol) were sequentially placed in a 250 mL single-mouth round-bottom flask and 150 mL of chloroform was added, and the solution was dissolved by magnetic stirring at 1500 r / min, then n-dodecanol (2.68 g, 14.40 mmol) was added to the round-bottom flask, and the mixture was continuously stirred at 25°C for 48 h; after the reaction was completed, 40 mL of 5 wt% dilute hydrochloric acid aqueous solution was added, and the organic layer was washed with 50 mL of saturated sodium bicarbonate aqueous solution for 5 times, and then the obtained organic layer was dried over 150 g of magnesium sulfate, filtered under reduced pressure of 0.02 MPa, and concentrated by rotary evaporation at 45°C for 1 h, and then column chromatography (ethyl acetate and n-hexane = 1:2) was used for purification, to obtain the anthryl compound.

[0084] Characterization and performance test

[0085] Figure 2 is the nuclear magnetic resonance spectrum (deuterated chloroform) of 9-anthracenemethanol (a), the intermediate product 4-(anthracen-9-ylmethoxy)-4-oxobutanoic acid (b), and the anthryl compound (c) prepared in Example 1, and the mass spectrum of the anthryl compound (d). As can be seen from Figure 2, the products 9-anthracenemethanol, the intermediate product 4-(anthracen-9-ylmethoxy)-4-oxobutanoic acid, and the target anthryl compound have all been successfully synthesized.

[0086] Figure 3 is the ultraviolet-visible absorption spectrum of the anthryl compound prepared in Example 1 under irradiation of 365 nm ultraviolet light (a) and 254 nm ultraviolet light (b) for different times (methanol solution, 1M, light power 10 mW / cm 2 ), and a schematic diagram of the photo-dimerization / de-polymerization of the anthryl compound under alternating irradiation of 365 nm and 254 nm ultraviolet light (c). As can be seen from Figure 3, the anthryl compound can effectively complete the reversible photo-dimerization / de-polymerization reaction under ultraviolet light irradiation.

[0087] Figure 4 is the optical photograph of the anthryl compound prepared in Example 2 under alternating excitation of ultraviolet light (light power 50 mW / cm 2 ). As can be seen from Figure 4, the prepared anthryl compound can realize reversible solid-liquid phase transition under ultraviolet light irradiation.

[0088] Figure 5 is the (a) energy storage density test curve and (b) recovery half-life curve of the anthryl compound in Example 3. As can be calculated from Figure 5, the energy density of the anthryl compound is 65 kJ / mol, and the energy storage time is up to 60 days.

[0089] The above merely describes the preferred embodiments of the present application, and it should be pointed out that, for those skilled in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as falling within the protection scope of the present application.

Claims

1. An anthryl compound, characterized by, having the structure of Formula 1: In formula 1, n = 10-16.

2. The anthryl compound according to claim 1, characterized by The n = 10, 13 or 16.

3. The method of producing the anthryl compound according to claim 1 or 2, characterized by, The method comprises the following steps: Mixing anthracene, N-methylformanilide, phosphorus oxychloride and a first solvent to perform a formylation-condensation reaction to obtain 9-anthracene formaldehyde; Mixing the 9-anthracene formaldehyde, sodium borohydride and a second solvent to perform a reduction reaction to obtain 9-anthracene methanol; Mixing the 9-anthracene methanol, succinic anhydride, 4-dimethylaminopyridine and a third solvent to perform a substitution reaction to obtain 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid; Mixing the 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, a long-chain fatty alcohol and a fourth solvent to perform an esterification reaction to obtain an anthracene-based compound; The long-chain fatty alcohol has 12-18 carbon atoms.

4. The production method according to claim 3, characterized by, The anthracene is obtained by separation from coal tar.

5. The preparation method according to claim 3, characterized in that, The molar ratio of the anthracene, N-methylformanilide and phosphorus oxychloride is 1:2:2-1:4:4; the volume ratio of the N-methylformanilide to the first solvent is 10:1-5:

1. The formylation-condensation reaction is performed at a temperature of 90-100℃ for 2-8h.

6. The preparation method according to claim 3, characterized in that, The molar ratio of the 9-anthracene formaldehyde to sodium borohydride is 1:2-1:3; the reduction reaction is performed at a temperature of 25℃ for 4-8h.

7. The preparation method according to claim 3, characterized in that, The third solvent comprises dichloromethane and pyridine; the volume ratio of the dichloromethane to the pyridine is 1:1-3:

1.

8. The production method according to claim 3 or 7, characterized by, The molar ratio of the 9-anthracene methanol, 4-dimethylaminopyridine and succinic anhydride is 1:1:4-1:2:6; The substitution reaction is performed at a temperature of 25℃ for 24-48h.

9. The preparation method according to claim 3, characterized in that, The molar ratio of the 4-(anthracene-9-ylmethoxy)-4-oxobutanoic acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine and long-chain fatty alcohol is 1:4:2:1-1:6:5:3; The esterification reaction is performed at a temperature of 25℃ for 24-48h.

10. Application of the anthracene-based compound of any one of claims 1-2 or prepared by the preparation method of any one of claims 3-9 as a solar thermal fuel.

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