Preparation method and application of metal phthalocyanine compound with efficient photothermal conversion capability

Abstract

The invention relates to a preparation method and application of a metal phthalocyanine compound with efficient photothermal conversion capacity. The preparation method comprises the following steps: (1) taking benzophenone, 4-hydroxybenzophenone and the like as initial raw materials, and reacting with 4-nitrophthalonitrile in one step or multiple steps to prepare a phthalocyanine precursor; (2) preparing a green metal copper phthalocyanine compound under solvothermal or solvent reflux with a copper salt (such as copper chloride, copper acetate and the like), and after the preparation is finished, washing the green metal copper phthalocyanine compound for multiple times by using ethanol, deionized water and ethanol; and (3) the green metal copper phthalocyanine compound has good high-heat photo-thermal conversion capacity under xenon lamps, sunlight and simulated sunlight, the preparation method is simple in process and easy for industrial production, and the obtained green metal copper phthalocyanine compound can be applied to photo-thermal materials, light therapy, solar seawater evaporators and the like.

Description

Technical Field

[0001] The invention relates to the preparation and application of metal phthalocyanine compounds, and in particular to a preparation method and application of metal phthalocyanine with high-efficiency light-heat conversion capability. Background Art

[0002] Phthalocyanine was first discovered by Braun and Tcherniac in the process of preparing o-cyanobenzamide from phthalamide and acetic anhydride. It is a blue substance. Studies have shown that the specific structure of phthalocyanine is a conjugated macrocyclic system with 18π electrons composed of four symmetrical isoindole units connected by imine bridge bonds. There is a hole in the phthalocyanine ring, which is coupled to more than 70 metal elements such as iron, cobalt, copper, aluminum, nickel, sodium, calcium, zinc, and magnesium through coordination. However, only Fe, Co, Cu, Ru, Mn, Cr, Al, and Zn have really attracted the interest of scientists. At the same time, a variety of substituents can be introduced on the benzene ring outside the phthalocyanine molecule, such as carboxyl, nitro, amino, etc. In addition, metal phthalocyanines can also be polymerized by sharing one or more benzene rings to form single metal or multi-metal polyphthalocyanines. Metal phthalocyanine molecules have the following characteristics: (1) Aromatic π electrons form conjugation on the entire phthalocyanine ring, and the conjugated macromolecule is highly planar. Catalytic reactions mainly occur through the axial position of the plane; (2) Due to the large π conjugation system, the aromatic ring on phthalocyanine has both the characteristics of an electron donor and an electron acceptor; (3) The phthalocyanine ring structure is stable, so its chemical properties are also very stable, and it is resistant to acid, alkali, water immersion, heat, light, and various organic solvents. Due to its unique structure and nearly perfect performance, it has now been made into homogeneous, heterogeneous, and enzyme-mimicking catalysts to catalyze and oxidize many types of organic reactions.

[0003] All forms of energy obey the law of conservation of energy, according to which they can neither be created nor destroyed. Photothermal conversion, as a traditional but evolving method of converting light into thermal energy, has always had a lasting appeal to researchers and the public. In the currently published literature (such as CN113233532A, CN113401959A, CN113633770A, CN116607318A, CN116618640A, etc.), melamine foam / TiO2, MXene Ti3C2 nanosheets, polydopamine / copper selenide, two-dimensional antimonene / nanosilver, polypyrrole / nanosilver, Cu@ZIF-C photothermal materials, etc. The materials mentioned in the above documents have complex synthesis routes, low yields, and the use of precious metals, which limits their large-scale use; in addition, in existing public documents (such as CN108752357A, CN107915739A, CN107915740A, CN110808329A, etc.), phthalocyanine is used for photothermal applications, such as photothermal therapy and photothermal conversion. The above documents involve different tetraaminophthalocyanine compounds, aminophenoxy tetrasubstituted metal phthalocyanine, tetrasulfonic acid-substituted copper phthalocyanine, copper phthalocyanine sulfonic acid-doped polymers and other copper phthalocyanine or phthalocyanine compounds. Abdelmohsen et al. from Eindhoven University of Technology in the Netherlands (J.Am.Chem.Soc.2023,145,36,20073–20080) found that the introduction of tetraphenylethylene (TPE) blocked the radiation release channel, and the highly twisted molecular skeleton of TPE not only restricted intermolecular interactions, but also stimulated intramolecular motion, promoting photothermal conversion.

[0004] Phthalocyanine has unique advantages (clear structure, high safety, high molar absorption coefficient, strong photosensitization ability, etc.), but there are no reports on the introduction of highly twisted molecular skeletons to limit the interaction between molecules and improve its photothermal conversion ability. Therefore, through the study and regulation of structure-activity relationship, finding and designing the synthesis of phthalocyanine compounds with better photothermal effect is of great significance for the development of photothermal materials, phototherapy, solar seawater evaporators, etc. Summary of the invention

[0005] In view of the deficiencies of the prior art, the present invention proposes a preparation method and application of a metal phthalocyanine compound with high-efficiency light-to-heat conversion capability.

[0006] The preparation and application of a metal phthalocyanine compound with high-efficiency light-to-heat conversion capability of the present invention, preferably a metal copper phthalocyanine compound, specifically comprises the following steps:

[0007] (1) Benzophenone, 4-hydroxybenzophenone, etc. are used as starting materials and mixed with zinc powder. A certain amount of tetrahydrofuran is added under nitrogen protection, and the mixture is cooled and stirred at -78°C for 1 hour. Titanium tetrachloride is added and stirred for 1.5 hours. The reaction mixture is warmed to room temperature and then refluxed overnight. Deionized water is added and extracted with ethyl acetate. After the organic phase is concentrated and dried, the product is purified by a silica gel column using petroleum ether / ethyl acetate (15:1 v / v) as an eluent to obtain 4-(1,2,2-triphenylvinyl)phenol (TPE-1); as shown in Formula 1;

[0008]

[0009] (2) 4-(1,2,2-triphenylvinyl)phenol (TPE-1) was mixed with 3-nitrophthalonitrile or 4-nitrophthalonitrile and a certain amount of anhydrous potassium carbonate, and a certain amount of DMSO was added as a solvent under a nitrogen environment. After stirring at 25° C. for 4 hours, a certain amount of anhydrous potassium carbonate was added under a nitrogen environment, and the stirring was continued for 12 hours. Then, a certain amount of anhydrous potassium carbonate was added and the stirring was continued for 12 hours. Deionized water was added, and the precipitation was filtered to prepare phthalocyanine precursors TPE-13 and TPE-14, wherein 3 represents 3-nitrophthalonitrile and 4 represents 4-nitrophthalonitrile; as shown in Formula 2 and Formula 3;

[0010]

[0011] (3) dissolving the phthalocyanine precursor (TPE-13, TPE-14) in n-hexanol, adding a certain amount of copper salt, and preparing a metallic copper phthalocyanine compound by a solvothermal method at 160° C. or by reflux of n-hexanol under the condition of DBU as a catalyst, and washing the mixture with ethanol, deionized water, and ethanol for multiple times after centrifugation and separation, and then drying the mixture to obtain a pure metallic copper phthalocyanine compound (TPE-13-Cu, TPE-14-Cu);

[0012] See formula 4

[0013]

[0014] Formula 4 (4) About 20 mg of the metallic copper phthalocyanine compound was placed in a xenon lamp, sunlight, or simulated sunlight for photothermal conversion measurement, and measured using an infrared thermal imager;

[0015] The green metal copper phthalocyanine compound is applied to photothermal materials, phototherapy and solar seawater evaporator.

[0016] The molar ratio of nitro to hydroxyl in TPE-1 and 3-nitrophthalonitrile or 4-nitrophthalonitrile is 1:1, and the TPE involved is selected from one of the following: R1, R2, R3 are one or more of H, F, Cl, Br, I, NO2, OH, CN, OCH3, CH3, CH3CH2; preferably R1, R2, R3 are H.

[0017] The reaction solvent is a high boiling point solvent (greater than 120° C.) such as n-hexanol, and the aprotic solvent involved is one or a mixed solvent of the following: ethylene glycol monomethyl ether, octane, butyl acetate morpholine, chlorobenzene, ethylene glycol monoethyl ether, p-xylene, xylene, m-xylene, o-xylene, N,N-dimethylformamide, cyclohexanone, n-hexanol, cyclohexanol, N,N-dimethylacetamide, N-methylformamide, phenol, 1,2-propylene glycol, dimethyl sulfoxide, o-cresol, ethylene glycol, p-cresol, N-methylpyrrolidone, m-cresol, benzyl alcohol, cresol, formamide, nitrobenzene, acetamide, hexamethylphosphoric acid triamide, quinoline, ethylene glycol carbonate, succinonitrile, cyclopentane, glycerol, the reaction temperature is 120° C. or above or solvent heat is 120° C. or above in a reactor, preferably n-hexanol, and the reaction temperature is reflux.

[0018] The metal copper salts include one or a mixture of the following salts: cuprous chloride, cupric chloride dihydrate, anhydrous cupric chloride, anhydrous cupric sulfate, cupric sulfate pentahydrate, copper (I) acetate (II) (copper acetate monohydrate), copper citrate, copper pyrophosphate, copper pyrophosphate hydrate, copper isooctanoate, copper gluconate, copper fluoroborate, copper glycinate, copper oxalate, copper naphthenate, copper (II) / chitosan, copper acetylacetonate, basic copper carbonate, copper thiophenate, copper (II) formate tetrahydrate, copper chromite,

[0019] 8-Hydroxyquinoline Copper (II), Copper (II) Phosphate, Isopropyl Copper (II), Copper Formate Hydrate, Methyl Isobutyl Copper, Methanol Copper (II), Butyrate Copper (II), Ethylenediamine Copper (II) Hydroxide Solution, Anhydrous Copper Iodate, Copper (II) Trifluoromethanesulfonate, Copper (II) Methacrylate, Copper (II) Acrylate, Copper Trifluoroacetate Hydrate, Copper Perchlorate Hexahydrate, Bis(8-Hydroxyquinoline) Copper (II), Copper (II) Acetoacetate, Phenylacetylene Copper(I), Copper(II) Neodecanoate, Copper(II) Isobutyrate, Copper(II) Ethylenediaminetetraacetate Disodium Salt, Copper(I) Tetrafluoroborate Tetra(acetonitrile), Copper(I) Hexafluorophosphate Tetra(acetonitrile), Copper(I) Bromide, Copper(II) Oxalate Hemihydrate, Copper(II) Tetrafluoroborate Hydrate, Copper(I) Bis(3,5-Diisopropyl) Salicylate, Copper(I) 3-Methyl Salicylate, Tetrabutylammonium Tetra(trifluoromethyl) Copper(III) Salt, Copper(I) Dibutyldithiocarbamate I), dichloro(1,10-phenanthroline)copper(II), bis(hexafluoroacetylacetonate)copper(II) hydrate, trifluoromethanethiol copper(I), (trifluoromethyl)tris(triphenylphosphine)copper(I), bis(trifluoromethanesulfonyl)imide copper(II), tetrafluoroborate copper(II) hexahydrate, copper selenite dihydrate, bis(tert-butylacetoacetate)copper(II), bis(triphenylphosphine)copper(I) nitrate, tetraacetonitrile trifluoromethanesulfonate copper(I), tetraamminecopper sulfate (II) hydrate, trifluoromethyl (1,10-phenanthroline) copper (I), tetrakis (acetonitrile) trifluoromethanesulfonate copper (I), bis [(tetrabutylammonium iodide) copper (I) iodide], bis (trifluoro-2,4-pentanedione) copper (II), monobutyl phthalate copper (II) salt, trifluoromethanesulfonyl imide copper (II) hydrate, bis (hexafluoroacetylacetonate) copper (II) hydrate, cyclopentadienyl (triethylphosphine) copper (I), preferably cupric chloride dihydrate).

[0020] Preferably, the reaction time is 2 h to 72 h or longer, preferably 24 h.

[0021] Preferably, the catalyst in step three is one or a mixture of the following: DBU, DCC (N,N'-dicyclohexylcarbodiimide), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI), ammonium molybdate, preferably DBU, which is 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0022] 7. The method for preparing the metallic copper phthalocyanine compound according to claim 1 is prepared by the following method:

[0023] (1) Benzophenone (8.00 g) was mixed with 4-hydroxybenzophenone (8.71 g) and zinc powder (12.28 g). 365 mL of tetrahydrofuran was added under nitrogen protection. The mixture was cooled and stirred at -78 °C for 1 hour. Titanium tetrachloride (15 mL) was added and stirred for 1.5 hours. The reaction mixture was warmed to room temperature and then refluxed overnight. Deionized water was added and extracted with ethyl acetate. After the organic phase was concentrated and dried, the product was purified by silica gel column using petroleum ether / ethyl acetate (15:1 v / v) as eluent to obtain 4-(1,2,2-triphenylvinyl)phenol (TPE-1) (6.3 g).

[0024] (2) 4-(1,2,2-Triphenylvinyl)phenol (TPE-1) (5.22 g) was uniformly mixed with 4-nitrophthalonitrile (2.95 g) and anhydrous potassium carbonate (4.15 g). 100 mL of DMSO was injected under nitrogen atmosphere. After stirring at 25°C for 4 hours, 3.5 g of anhydrous potassium carbonate was added under nitrogen atmosphere. After stirring for 12 hours, 3.5 g of anhydrous potassium carbonate was added again. After stirring for 12 hours, deionized water was added to precipitate. The mixture was filtered to obtain 6.9 g of phthalocyanine precursor (TPE-14).

[0025] (3) 0.474 g of the phthalocyanine precursor and 0.043 g of cupric chloride dihydrate were added to a single-necked flask, and then 0.6 mL of DBU and 40 mL of n-hexanol were added to the mixture. The mixture was heated under reflux for 24 hours. The solid was washed by centrifugation with ethanol and deionized water for 5 times, respectively, and dried to obtain tetraphenylethylene-based metal cobalt phthalocyanine (TPE-14-Cu) (0.23 g).

[0026] Preferably, the molar ratio of the phthalocyanine precursor to the copper salt is 1:2.0 or above.

[0027] Metallic copper phthalocyanine compounds are used in photothermal materials, phototherapy, and solar seawater evaporators.

[0028] The metal phthalocyanine compound has good high-heat photothermal conversion ability under xenon lamp, simulated sunlight and sunlight, and metal phthalocyanine copper is preferred.

[0029] (1) Xenon lamp test: The light source system is the CEL-HXF300-T3 xenon lamp of Beijing Zhongjiao Jinyuan Technology Co., Ltd. The test sample mass is 20 mg, the distance from the light source is 11 cm, and the room temperature is 30°C. Place the powder sample in the center of the glass dish, and then place it in the center of the light spot for irradiation. The temperature measurement equipment is a HIKMICRO handheld temperature measurement thermal imager, product model HM-TPH21-3AXF. The recorded temperature is the highest temperature point temperature indicated by the red cross cursor in the infrared thermal imaging image. Read the temperature once at 5 minutes and 10 minutes of irradiation. After at least 3 repeated tests, take 3 groups with similar values ​​to calculate the average temperature.

[0030] (2) Simulated sunlight test: The light source system is a CEL-S500 simulated sunlight xenon lamp from Beijing Zhongjiao Jinyuan Technology Co., Ltd. The test sample mass is 20 mg, the distance from the light source is 27 cm, and the room temperature is 20°C. The powder sample is placed in the center of the glass dish, and then placed in the center of the light spot for irradiation. The CEL-FZ-A irradiator (optical power meter) from Beijing Zhongjiao Jinyuan Technology Co., Ltd. is used to adjust the optical power so that the optical power irradiated on the sample is 100 mW / cm 2 The temperature measurement device is a HIKMICRO handheld thermal imager, product model HM-TPH21-3AXF. The recorded temperature is the highest temperature point temperature indicated by the red cross cursor in the infrared thermal image. The temperature is read once at 5 minutes and 10 minutes of irradiation. After at least 3 repeated tests, the average temperature is calculated for 3 groups with similar values.

[0031] (3) Sunlight test: The test sample mass is 20 mg, the outdoor temperature is 28°C, and it is sunny. The powder sample is placed in the center of a glass dish and then exposed to sunlight. The temperature measurement device is a HIKMICRO handheld temperature measuring thermal imager, product model HM-TPH21-3AXF. The recorded temperature is the highest temperature point indicated by the red cross cursor in the infrared thermal imaging image. The temperature is read once at 20 minutes and 40 minutes of exposure.

[0032] After the metal copper phthalocyanine compound is fully shaken in the solvent so that it can be dissolved or evenly dispersed, it has good high-heat photothermal conversion ability under xenon lamp, sunlight and simulated sunlight. Preferably, under a xenon lamp, the sample is fully shaken so that it can be dissolved or evenly dispersed in the solvent, and then the top of the mercury thermometer is immersed under the liquid surface. The light source system used is the CEL-HXF300-T3 model xenon lamp of Beijing Zhongjiao Jinyuan Technology Co., Ltd., and the center of the light column irradiates the liquid horizontally, 8.0 cm away from the light source. The invention is characterized in that the reaction solvent (if necessary) is a common chemical solvent (boiling point higher than 60°C, under standard atmospheric pressure), and the solvent involved is one or a mixed solvent of the following: 1,1-dichloroethane, chloroform, methanol, tetrahydrofuran, hexane, trifluoroacetic acid, 1,1,1-trichloroethane, carbon tetrachloride, ethyl acetate, ethanol, butanone, benzene, cyclohexane, acetonitrile, isopropanol, 1,2-dichloroethane, ethylene glycol dimethyl ether, trichloroethylene, triethylamine, propionitrile, heptane, water, nitromethane, 1,4-dioxane, toluene, nitro Ethane, pyridine, 4-methyl-2-pentanone, ethylenediamine, butanol, butyric acid, ethylene glycol monomethyl ether, octane, butyl acetate, morpholine, chlorobenzene, ethylene glycol monoethyl ether, p-xylene, xylene, m-xylene, acetic anhydride, o-xylene, N,N-dimethylformamide, cyclohexanone, cyclohexanol, N,N-dimethylacetamide, furfural, N-methylformamide, 1,2-propylene glycol, dimethyl sulfoxide, ethylene glycol, N-methylpyrrolidone, nitrobenzene, formamide, acetamide, quinoline, ethylene glycol carbonate, diethylene glycol, succinonitrile, cyclopentane sulfone, glycerol. N,N-dimethylformamide, xenon lamp, and metal copper phthalocyanine TPE-14-Cu are preferred.

[0033] The beneficial effects of the present invention are as follows: 1. The synthetic steps designed by the present invention are simple, the separation and purification are simple, and the yield of the product is simple. 2. The metal phthalocyanine polymer designed by the present invention introduces a highly twisted tetraphenylethylene (TPE) molecular skeleton, which not only limits the interaction between molecules by blocking the radiation release channel, but also stimulates the intramolecular motion and promotes photothermal conversion. 3. The metal phthalocyanine compound prepared by the present invention has a higher photothermal conversion efficiency than that reported in the existing literature, and the operation is simple and easy to obtain. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1-1 is the hydrogen spectrum of TPE-1 in the example;

[0035] Figure 1-2 is the hydrogen spectrum of TPE-13 in the example;

[0036] Figure 1-3 It is the hydrogen spectrum of TPE-14 in the example; Figure 2XRD patterns of Example 3 TPE-13-Cu, TPE-14-Cu, TPE-13-Co, TPE-14-Co TPE-13-Zn, TPE-14-Zn;

[0037] Figure 3 The UV absorption graphs of Example 3 TPE-13-Cu, TPE-14-Cu, TPE-13-Co, TPE-14-Co TPE-13-Zn, and TPE-14-Zn;

[0038] Figure 4 NIR images of Example 3 TPE-13-Cu, TPE-14-Cu, TPE-13-Co, TPE-14-Co TPE-13-Zn, TPE-14-Zn;

[0039] Figure 5 TGA and DSC graphs of Example 3 TPE-13-Cu, TPE-14-Cu, TPE-13-Co, TPE-14-Co TPE-13-Zn, TPE-14-Zn;

[0040] Figure 6 These are the fluorescence images of Example 3 TPE-13-Cu, TPE-14-Cu, TPE-13-Co, TPE-14-Co TPE-13-Zn, and TPE-14-Zn. DETAILED DESCRIPTION

[0041] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with embodiments, but the present invention is not limited to the following examples.

[0042] Unless otherwise specified in the following examples, the reagents used are all commercially available chemical reagents or industrial products.

[0043] 1. Mix benzophenone (8.00 g) with 4-hydroxybenzophenone (8.71 g) and zinc powder (12.28 g), add 365 mL of tetrahydrofuran under nitrogen protection, cool and stir at -78 ° C for 1 hour, add titanium tetrachloride (15 mL) and continue stirring for 1.5 hours, warm the reaction mixture to room temperature, and then reflux overnight. Add deionized water and extract with ethyl acetate. After the organic phase is concentrated and dried, the product is purified by silica gel column, using petroleum ether / ethyl acetate (15:1 v / v) as eluent to obtain 4-(1,2,2-triphenylvinyl)phenol (TPE-1) (6.3 g).

[0044] 2. Evenly mix 4-(1,2,2-triphenylvinyl)phenol (TPE-1) (5.22g) with 4-nitrophthalonitrile (2.95g) and anhydrous potassium carbonate (4.15g), inject 100mL DMSO under nitrogen atmosphere, stir at 25℃ for 4 hours, add 3.5g anhydrous potassium carbonate under nitrogen atmosphere, continue stirring for 12 hours, and then add 3.5g anhydrous potassium carbonate again. Continue stirring for 12 hours, add deionized water, precipitate appears, filter, and obtain phthalocyanine precursor (TPE-14) (6.9g). TPE-13 (6.7g) with 3-nitrophthalonitrile (2.95g); Figure 1-1 , Figure 1-2 , Figure 1-3 Shown are the hydrogen spectra of TPE-1, TPE-13, and TPE-14;

[0045] 3. Preparation of TPE-13-Cu, TPE-14-Cu, TPE-13-Co, TPE-14-Co, TPE-13-Zn and TPE-14-Zn. Using TPE-14 as a phthalocyanine precursor, metal phthalocyanine compounds with different metal centers were prepared.

[0046] Example 1 Preparation of TPE-14-Cu

[0047] 0.474 g of phthalocyanine precursor (TPE-14) and 0.043 g of cupric chloride dihydrate were added to a single-necked flask, and then 0.6 mL of DBU and 40.0 mL of n-hexanol were added to the mixture. The mixture was heated to reflux for 24 hours, and the solid was centrifuged and washed 5 times with ethanol and deionized water respectively. After drying, tetraphenylethylene-based metallic copper phthalocyanine (TPE-14-Cu) (0.23 g) was obtained; TPE-13-Cu was prepared as above.

[0048] Example 2 Preparation of TPE-14-Co

[0049] 0.474 g of phthalocyanine precursor (TPE-14) and 0.060 g of cupric chloride hexahydrate were added to a single-necked flask, and then 0.6 mL of DBU and 40.0 mL of n-hexanol were added to the mixture. The mixture was heated to reflux for 24 hours, and the solid was centrifuged and washed 5 times with ethanol and deionized water respectively. After drying, tetraphenylethylene-based metal cobalt phthalocyanine (TPE-14-Co) (0.21 g) was obtained; TPE-13-Co was prepared as above.

[0050] Example 3 Preparation of TPE-14-Zn

[0051] 0.474 g of phthalocyanine precursor (TPE-14) and 0.055 g of zinc acetate dihydrate were added to a single-necked flask, and then 0.6 mL of DBU and 40.0 mL of n-hexanol were added to the mixture, and the mixture was heated under reflux for 24 hours. The solid was centrifugally washed with ethanol and deionized water for 5 times, and dried to obtain metal zinc phthalocyanine (TPE-14-Zn) (0.30 g) based on tetraphenylethylene; TPE-13-Zn was prepared in the same manner as above. Figure 2 , Figure 3 , Figure 4 , Figure 5 , Figure 6 Shown are XRD patterns, UV absorption patterns, NIR patterns, TGA patterns, DSC patterns and fluorescence patterns of Example 3 TPE-13-Cu, TPE-14-Cu, TPE-13-Co, TPE-14-Co TPE-13-Zn and TPE-14-Zn;

[0052] 4. Metal phthalocyanine compounds have good high-heat photothermal conversion capabilities under xenon lamps, simulated sunlight and sunlight, and metal phthalocyanine copper is preferred.

[0053] (1) Xenon lamp test: The light source system is the CEL-HXF300-T3 xenon lamp of Beijing Zhongjiao Jinyuan Technology Co., Ltd. The test sample mass is 20 mg, the distance from the light source is 11 cm, and the room temperature is 30°C. Place the powder sample in the center of the glass dish, and then place it in the center of the light spot for irradiation. The temperature measurement equipment is a HIKMICRO handheld temperature measurement thermal imager, product model HM-TPH21-3AXF. The recorded temperature is the highest temperature point temperature indicated by the red cross cursor in the infrared thermal imaging image. Read the temperature once at 5 minutes and 10 minutes of irradiation. After at least 3 repeated tests, take 3 groups with similar values ​​to calculate the average temperature.

[0054] Table 1 Test results of various materials under xenon lamp

[0055]

[0056] (2) Simulated sunlight test: The light source system is the CEL-S500 model simulated sunlight xenon lamp of Beijing Zhongjiao Jinyuan Technology Co., Ltd. The test sample mass is 20 mg, the distance from the light source is 27 cm, and the room temperature is 20°C. The powder sample is placed in the center of the glass dish, and then placed in the center of the light spot for irradiation. The CEL-FZ-A irradiator (optical power meter) of Beijing Zhongjiao Jinyuan Technology Co., Ltd. is used to adjust the optical power so that the optical power irradiated on the sample is 100mW / cm2. The temperature measurement equipment is a HIKMICRO handheld temperature measurement thermal imager, product model HM-TPH21-3AXF. The recorded temperature is the temperature of the highest temperature point indicated by the red cross cursor in the infrared thermal imaging image. The temperature is read once at 5min and 10min of irradiation. After at least 3 repeated tests, the average temperature is calculated for 3 groups with similar values.

[0057] Table 2 Test results of various materials under simulated sunlight

[0058]

[0059] (3) Sunlight test: The test sample mass is 20 mg, the outdoor temperature is 28°C, and it is sunny. The powder sample is placed in the center of a glass dish and then exposed to sunlight. The temperature measurement device is a HIKMICRO handheld temperature measuring thermal imager, product model HM-TPH21-3AXF. The recorded temperature is the highest temperature point indicated by the red cross cursor in the infrared thermal imaging image. The temperature is read once at 20 minutes and 40 minutes of exposure.

[0060] Table 3 Test results of various materials under sunlight

[0061]

[0062]

[0063] 5. The metal copper phthalocyanine compound according to claim 1 has good high-heat photothermal conversion ability under xenon lamp, sunlight and simulated sunlight after being fully shaken in a solvent so that it can be dissolved or evenly dispersed.

[0064] (1) Under a xenon lamp, shake the sample thoroughly to make it dissolve or disperse evenly in the solvent, and then immerse the top of the mercury thermometer under the liquid surface. The light source system used is the CEL-HXF300-T3 xenon lamp of Beijing Zhongjiao Jinyuan Technology Co., Ltd. The center of the light column irradiates the liquid horizontally, 8.0 cm away from the light source, and the room temperature is 28°C. Metal phthalocyanine copper TPE-14-Cu is preferred, 5 μmol sample + 2.0 mL DMF, concentration: 2.5 mmol / L.

[0065] Table 3 Results of the tests on the dispersion or dissolution of various materials in DMF under a xenon lamp

[0066]

[0067] The difference between the present invention and the traditional literature or patents on phthalocyanine compounds is that the obtained metal phthalocyanine compound with tetraphenylethylene group. Different from other metal phthalocyanine compounds, the introduction of tetraphenylethylene (TPE) blocks the electron radiation release channel, and the highly twisted molecular skeleton of TPE not only limits the interaction between molecules, but also stimulates the intramolecular motion, promotes photothermal conversion, etc.; the present invention only needs the phthalocyanine precursor and the corresponding copper salt in a solvent heating system or a solvent thermal reaction system, and the corresponding metal phthalocyanine compound with tetraphenylethylene group is obtained in high yield by simple centrifugation and washing. The tetraphenylethylene metal phthalocyanine compound polymer of the present invention can be used for photothermal materials, phototherapy, solar seawater evaporator, etc., and can also be used in other catalytic reactions, and the preparation method is simple and environmentally friendly.

[0068] As described above, without departing from the spirit and technical solution of the present invention, the above methods and technical contents can be used to make many possible changes to the technology of the present invention, or modified into equivalent embodiments with equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still falls within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing a metal phthalocyanine compound with high photothermal conversion capability, characterized in that: The method comprises the following steps: Step 1: Mix benzophenone and 4-hydroxybenzophenone as starting materials with zinc powder, add a certain amount of tetrahydrofuran under nitrogen protection, cool and stir at -78°C for 1 hour, add titanium tetrachloride and continue stirring for 1.5 hours, warm the reaction mixture to room temperature, and then reflux overnight; add deionized water and extract with ethyl acetate, concentrate and dry the organic phase, purify the product through a silica gel column, use petroleum ether / ethyl acetate as an eluent, and obtain 4-(1,2,2-triphenylvinyl)phenol, namely TPE-1, wherein the volume ratio of the product to the eluent is 15:1, as shown in Formula 1; Step 2: 4-(1,2,2-triphenylvinyl)phenol is mixed with 4-nitrophthalonitrile or 3-nitrophthalonitrile and a certain amount of anhydrous potassium carbonate, a certain amount of DMSO is added as a solvent under a nitrogen environment, and stirred at 25°C for 4 hours. A certain amount of anhydrous potassium carbonate is added under a nitrogen environment, and the mixture is stirred for 12 hours. Then, a certain amount of anhydrous potassium carbonate is added and stirred for 12 hours. Deionized water is added, and the mixture is precipitated and filtered to prepare phthalocyanine precursors TPE-14 and TPE-13, wherein 3 represents 3-nitrophthalonitrile and 4 represents 4-nitrophthalonitrile; as shown in Formula 2 and Formula 3; Step 3: dissolving the phthalocyanine precursors TPE-13 and TPE-14 in n-hexanol, adding a certain amount of copper salt and a catalyst, and reacting at 160°C by solvent thermal method or under n-hexanol reflux for 2h to 72h to prepare a metal copper phthalocyanine compound. After centrifugation and separation, washing with ethanol, deionized water, and ethanol for multiple times and drying, pure metal copper phthalocyanine compounds TPE-13-Cu and TPE-14-Cu are obtained; see Formula 4 2. The method for preparing a metal phthalocyanine compound with high photothermal conversion capability according to claim 1, characterized in that: TPE-1 is mixed with a certain amount of 3-nitrophthalonitrile or 4-nitrophthalonitrile, wherein the molar ratio of nitro to hydroxyl in TPE-1 and 3-nitrophthalonitrile or 4-nitrophthalonitrile is 1:1, and the TPE involved is selected from one of the following: R1, R2, and R3 are one or more of H, F, Cl, Br, I, NO2, OH, CN, OCH3, CH3, and CH3CH2, and preferably R1, R2, and R3 are H.

3. The method for preparing a metal phthalocyanine compound with high photothermal conversion capability according to claim 1, characterized in that: The solvent in step three is one or more of the following mixed solvents: ethylene glycol monomethyl ether, octane, butyl acetate morpholine, chlorobenzene, ethylene glycol monoethyl ether, p-xylene, xylene, m-xylene, o-xylene, N,N-dimethylformamide, cyclohexanone, n-hexanol, cyclohexanol, N,N-dimethylacetamide, N-methylformamide, phenol, 1,2-propylene glycol, dimethyl sulfoxide, o-cresol, ethylene glycol, p-cresol, N-methylpyrrolidone, m-cresol, benzyl alcohol, cresol, formamide, nitrobenzene, acetamide, hexamethylphosphoric acid triamide, quinoline, ethylene glycol carbonate, succinonitrile, cyclopentane sulfone, glycerol, the reaction temperature is 120°C or above or solvent heat in a reactor at 120°C or above, preferably n-hexanol, and the reaction temperature is reflux.

4. The method for preparing a metal phthalocyanine compound with high photothermal conversion capability according to claim 1, characterized in that: The copper salt in step 3 is one of the following or a mixed salt: cuprous chloride, cupric chloride dihydrate, anhydrous copper chloride, anhydrous copper sulfate, copper sulfate pentahydrate, copper (I) (II) acetate, copper citrate, copper pyrophosphate, copper pyrophosphate hydrate, copper isooctanoate, copper gluconate, copper fluoroborate, copper glycinate, copper oxalate, copper naphthenate, copper (II) / chitosan, copper acetylacetonate, basic copper carbonate, copper thiophenol, copper (II) formate tetrahydrate, copper chromite, 8-hydroxyquinoline copper, copper (II) phosphate, copper (II) isopropoxide, copper formate hydrate, methyl isobutylene copper, methyl Copper(II) alkoxide, copper(II) butyrate, ethylenediamine copper(II) double hydroxide solution, anhydrous copper iodate, copper(II) trifluoromethanesulfonate, copper(II) methacrylate, copper(II) acrylate, copper(II) trifluoroacetate hydrate, copper perchlorate hexahydrate, bis(8-hydroxyquinoline)copper(II), copper(II) acetoacetate, copper(I) phenylacetylene, copper(II) neodecanoate, copper(II) isobutyrate, copper(II) ethylenediaminetetraacetate disodium salt, copper(I) tetra(acetonitrile)tetrafluoroborate, copper(I) tetra(acetonitrile)hexafluorophosphate, copper(I) bromide, oxalic acid Copper(II) hemihydrate, copper tetrafluoroborate hydrate, copper(II) bis(3,5-diisopropylsalicylate), copper(I) 3-methylsalicylate, tetrabutylammonium tetra(trifluoromethyl)copper(III) salt, copper(II) dibutyldithiocarbamate, copper(II) dichloro(1,10-phenanthroline), copper(II) bis(hexafluoroacetylacetonate), copper(I) trifluoromethanethiol, copper(I) tri(trifluoromethyl)tris(triphenylphosphine), copper(II) bis(trifluoromethanesulfonyl)imide, copper(II) tetrafluoroborate hexahydrate, copper(II) selenite dihydrate, bis(tert-butylacetoacetate ) copper (II), bis(triphenylphosphine) copper (I) nitrate, tetraacetonitrile trifluoromethanesulfonate copper (I), tetraammine copper (II) sulfate hydrate, trifluoromethyl (1,10-phenanthroline) copper (I), tetra(acetonitrile) trifluoromethanesulfonate copper (I), bis[(tetrabutylammonium iodide) copper (I) iodide], bis(trifluoro-2,4-pentanedione) copper (II), monobutyl phthalate copper (II) salt, trifluoromethanesulfonylimide copper (II) hydrate, bis(hexafluoroacetylacetonate) copper (II) hydrate, cyclopentadienyl (triethylphosphine) copper (I), preferably cupric chloride dihydrate.

5. The method for preparing a metal phthalocyanine compound with high photothermal conversion capability according to claim 1, characterized in that: The reaction time in step 3 is 24 h.

6. The method for preparing a metal phthalocyanine compound with high photothermal conversion capability according to claim 1, characterized in that: The catalyst in step 3 is one or a mixture of the following: DBU, DCC (N,N'-dicyclohexylcarbodiimide), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI), ammonium molybdate, preferably DBU, DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene.

7. The method for preparing a metal phthalocyanine compound with high-efficiency light-to-heat conversion capability according to claim 1, characterized in that: The molar ratio of the phthalocyanine precursor to the copper salt is 1:2.0 or above.

8. Metallic copper phthalocyanine compounds are used in photothermal materials, phototherapy, and solar seawater evaporators.

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