A zinc complex nanomaterial of substituted o-hydroxybenzoic acid, a preparation method thereof, and applications thereof

Abstract

The present invention discloses a preparation method of a zinc complex nanomaterial of a substituted o-hydroxybenzoic acid, comprising the following steps: dissolving a substituted hydroxybenzoic acid derivative coordination monomer in a solution of an organic solvent; dispersing an oxide, carbonate, basic carbonate or hydroxide of a coordination metal zinc in an organic solvent system containing water to prepare a dispersion; adding the solution in batches to the dispersion and continuously stirring to obtain a mixed solution; adding an inorganic salt of an alkali metal to the mixed solution, stirring and reacting the mixed solution, and filtering to obtain crystals; placing the crystals in water and continuing to stir until a gel is obtained; filtering the gel to squeeze out water, and then performing air drying to obtain the nanomaterial. The present invention uses the spontaneous intermolecular force during the reaction to replace the high-temperature and high-pressure explosion force for artificially synthesizing nanomaterials or the mechanical force required for crushing large crystals into nanocrystals to obtain a nanomorphological product. The process is simple, safe, low-cost, green and environmentally friendly.

Description

Technical Field

[0001] The present invention belongs to the technical field of nanomaterial preparation, and particularly relates to a zinc complex nanomaterial of o-hydroxybenzoic acid with substituents, a preparation method thereof and an application thereof. Background Art

[0002] Metal complexes of hydroxybenzoic acid derivatives with substituents have diverse structures and excellent electrical, luminescent, catalytic and other properties, attracting the attention of many coordination chemists. The applications that have been discovered include magnetic materials, anti-cancer drugs, charge control, dielectric material functional additives, and the preparation of porous carbon for supercapacitors. In order to fully utilize the atom economy of such complexes and obtain the functional characteristics of such substances with less usage, such complexes are usually prepared into various nanomaterials.

[0003] However, compared with micron-sized or larger-sized materials, the preparation of nanomaterials usually requires more complex processes and higher costs. Because nanoparticles are prone to agglomeration and growth, once they agglomerate and grow, they lose their nanoscale properties. Therefore, nanometer powders need to be surface-treated, or nanomaterials are stored in the form of suspensions, and the latter uses a dispersion inhibitor to prevent particle agglomeration in the liquid phase. The preparation of these nanomaterials is usually targeted at specific application fields, and the dispersion aids used cannot interfere with the performance of the substances. Therefore, the preparation method will limit the application fields of the materials.

[0004] For example, Chinese Patent Document (Publication No.: CN113476475A) discloses a zinc salicylate nanoparticle, a preparation method thereof and an application thereof. Vitamin E polyethylene glycol succinate and lecithin are mixed and then dissolved in a first solvent to obtain a first clear solution; zinc 3,5-di-tert-butylsalicylate is dissolved in a second solvent to obtain a second clear solution; the above-mentioned first clear solution and the second clear solution are mixed to obtain a third clear solution; then the third clear solution is dispersed in water, and then the system is stabilized to obtain a fourth clear solution; the fourth clear solution is centrifuged to obtain the supernatant; the solvent is removed from the supernatant to obtain nanometer zinc salicylate. This patent uses a relatively large amount of lecithin and TPGS as emulsifiers to prepare a nanoparticle dispersion to enhance its anti-cancer activity. Although it does not interfere with its use in medicine, this method cannot be generally promoted. On the other hand, although the nanoparticle preparation method provided by this invention can significantly improve the water solubility of zinc 3,5-di-tert-butylsalicylate, it is still very low (the concentration of stably existing nanoparticles is about 38mg / 27000ml of water). It is calculated that each maximum synthesis of nanoparticles in a 2.5 cubic meter mixing kettle is less than 4kg, so the preparation efficiency is low; another point is that this process requires zinc salicylate with a smaller particle size and higher purity as raw materials for preparation. Generally speaking, the preparation cost is large.

[0005] For example, a Chinese patent document (publication number: CN107602377A) discloses a method for preparing lanthanum p-hydroxybenzoate rare earth complex nanospheres, which are prepared using polyvinyl pyrrolidone and fatty alcohol polyoxyethylene ether as surfactants. This method also uses a dispersing aid or a dispersion liquid to obtain nanomaterials, and there are also problems such as high additive cost and low preparation efficiency.

[0006] For example, the Chinese patent document (Announcement No.: CN104030918B) discloses a method for preparing metal complex-(3,5-di-tert-butyl salicylic acid). 3,5-di-tert-butyl salicylic acid is dissolved in an alkali metal hydroxide solution, and the metal complex-(3,5-di-tert-butyl salicylic acid) is synthesized by mixing it with a zinc salt solution at 60-70°C in different ways, and it can be used as an antistatic agent and a charge control agent for toner. The process is as follows: (1) dissolving salicylic acid and sodium hydroxide in a molar ratio of 1:2 in water at 60-70°C to prepare a sodium salicylate solution as a reaction liquid; (2) dissolving zinc sulfate heptahydrate and water at 60-70°C to prepare a zinc sulfate solution as a reaction liquid; (3) adding zinc sulfate and sodium salicylate in a molar ratio of 1:1; at 60-70°C, adding the sodium salicylate solution dropwise into the zinc sulfate solution, or adding the materials in the opposite direction or dropping them simultaneously to mix; (4) keeping the temperature for 1-5 hours after the addition is completed, washing with water, filtering, and drying to obtain a zinc salicylate product. In actual production, in order to reduce the influence of inorganic salts contained in the product on the charging performance and weather resistance of the toner, a large amount of special water is needed to wash the sodium ions and sulfate ions in the product until the conductivity of the filtrate is less than 50μs / cm. After the product is dried, it needs to be crushed to ultrafine powder (3-5 microns). The crushing process will produce a lot of dust, which requires a special exhaust gas collection system. Since the friction of the product carries static electricity, the crushing equipment needs to have a special explosion-proof function, which has the problems of high equipment investment and low crushing efficiency. Summary of the invention

[0007] As can be seen from the above background technology, the preparation of zinc salicylate is time-consuming, generates a large amount of wastewater, requires special crushing equipment and is inefficient. In order to solve this situation, the present invention analyzes that the fundamental reason is the large amount of alkali metal ions and sulfate ions introduced. For this reason, the inventors conducted experiments on the reduction of alkali metal ions and sulfate ions in the laboratory, and finally obtained a new process. The process is to react salicylic acid with a special zinc compound such as zinc oxide, zinc hydroxide, zinc carbonate, and basic zinc carbonate in an organic solvent-water system, and add a trace amount of inorganic alkali metal salt at the same time. The crystals obtained by filtration are added to water to form a colloidal material, and then the material is filtered and dried, and the product can be obtained by simple crushing. The process of the present invention uses less than 1% of the ion dosage of the existing process, does not require washing, and obtains a zinc salicylate product with a nanowire structure, saves the crushing process and equipment investment, and improves production efficiency.

[0008] To achieve the above technical objectives, the present invention adopts the following technical solutions:

[0009] A preparation method of a zinc complex nanomaterial of o-hydroxybenzoic acid with substituents, comprising the following steps:

[0010] (1) Dissolve the coordination monomer of the hydroxybenzoic acid derivative with substituents in an organic solvent to form solution 1;

[0011] (2) Disperse the oxide, carbonate, basic carbonate or hydroxide of the coordination metal zinc in an organic solvent system capable of mixing and dissolving with water to form dispersion 2;

[0012] (3) Add the solution 1 prepared in step (1) to the dispersion 2 prepared in step (2) in batches, and continuously stir at an appropriate temperature to obtain a mixed solution;

[0013] (4) Add the inorganic salt of an alkali metal to the mixed solution obtained in step (3), continue to stir and react the mixed solution for a certain time, and filter to obtain crystals;

[0014] (5) Place the crystals obtained in step (4) in deionized water, and continue to stir until the system becomes gel-like to obtain a gel;

[0015] (6) Press-filter the gel prepared in step (5) to squeeze out the moisture, and perform blast drying on the obtained solid to obtain the zinc complex nanomaterial of o-hydroxybenzoic acid with substituents.

[0016] Preferably, the chemical formula of the o-hydroxybenzoic acid with substituents in step (1) or step (2) is as follows:

[0017]

[0018] In the formula, n represents 0, 1 or 2, and the R groups are the same or different groups, and the groups are: hydrogen atom, halogen atom, nitro group or alkyl group, alkoxy group containing 1-5 carbon atoms or hydroxyalkyl group containing 1-3 carbon atoms.

[0019] Preferably, the organic solvent in step (1) or step (2) includes one or more mixtures of methanol, ethanol, N,N-dimethylformamide, N,N-dimethylpropionamide, dimethyl sulfoxide, and tetrahydrofuran.

[0020] Preferably, the water-mixed organic solvent system in step (2) is a mixture of water and a polar organic solvent, and the weight percentage of water in the mixed solvent is 0%-10%, and the rest is a polar organic solvent.

[0021] Preferably, in step (2), the oxide, carbonate, basic carbonate or hydroxide of the coordinated metal zinc is dispersed in an organic solvent system that can be mixed and dissolved with water, and processed in an ultrasonic device to obtain dispersion liquid 2.

[0022] Preferably, in step (3), the appropriate temperature is equal to or lower than 30 °C.

[0023] Preferably, in step (4), the inorganic salts include one or more of hydrochlorides, sulfates, phosphates, and acetates.

[0024] Preferably, in step (5), the conductivity of the deionized water is equal to or less than 50 μs / cm.

[0025] Technical principle of the present invention:

[0026] The technology of the present invention is to dissolve the substituted hydroxybenzoic acid derivative coordination monomer in an organic solvent to form solution 1, disperse the oxide, carbonate, basic carbonate or hydroxide of the coordinated metal zinc in a preferred organic solvent system that can be mixed and dissolved with water to form dispersion liquid 2, add solution 1 to dispersion liquid 2 in batches, and continuously stir at an appropriate temperature. Finally, inorganic salts of alkali metals, such as hydrochlorides, sulfates, phosphates, acetates, etc., are added to the above-mentioned mixed solution, and the mixed solution is continuously stirred and reacted for a certain period of time, and then filtered to obtain transparent crystals. The above crystals are placed in an appropriate amount of deionized water with a conductivity less than 50 μs / cm, and continuously stirred until the system becomes gel-like. The gel is press-filtered to squeeze out the water, and the obtained solid is dried by blowing air at a low temperature to obtain the target product, the nano aggregate.

[0027] In the preparation process of the metal complex of the substituted hydroxybenzoic acid derivative of the present invention, a polar organic solvent miscible with water is preferably used to participate in the formation of the complex crystal, and then the small and strongly polar water molecules are used for intercalation to replace the guest organic solvent molecules, thereby destroying the hydrogen bonds in the neutral layer of the large complex crystal, resulting in the collapse of its close-packed structure and obtaining a micron product with disordered nano-scale packing.

[0028] The preparation method of the metal complex nano material of the substituted hydroxybenzoic acid derivative obtained by the present invention utilizes the spontaneous intermolecular force to replace the high-temperature and high-pressure explosion force of artificial synthetic nano materials and the mechanical force required for crushing large crystals to obtain nano-shaped substances. The process is simple and safe, with low cost, green and environmentally friendly, and does not require auxiliary dispersion aids. The nano material has high purity and can exert the functional properties of the material in the form of solid powder.

[0029] The nanomaterials prepared by the present invention can be used as functional additives for charge control and dielectric materials. When kneaded with molten polymer materials, they can be easily broken and collapsed into nanocrystals to exert their functional properties. It can also be used as a precursor for porous carbon in supercapacitors. After calcination in an inert atmosphere, a porous carbon material with a high specific surface area can be obtained.

[0030] Compared with the prior art, the technology of the present invention has the following advantages:

[0031] 1. The preparation method of the nanomaterials provided by the present invention uses the spontaneous intermolecular force during the reaction to replace the high-temperature and high-pressure explosion force for artificial synthesis of nanomaterials or the mechanical force required to crush large crystals into nanocrystals to obtain nanomorphological products. The process is simple, safe, low-cost, green and environmentally friendly.

[0032] 2. The preparation method of the nanomaterials provided by the present invention does not require additional addition of dispersion aids. The nanomaterials have high purity and can exert their functional properties in the form of solid powders.

[0033] 3. The technical method of the present invention can obtain the large-scale preparation of nanoaggregated materials at a relatively low cost, and has significant industrial application prospects.

[0034] 4. During the use of the nanomaterials of the present invention, especially when applied as functional additives for charge control and dielectric materials, the nanoaggregates can collapse into nanocrystals through the shear force during melt kneading and be uniformly dispersed in the polymer matrix, achieving high functionality with a low addition amount. Description of the Drawings

[0035] Figure 1 SEM image of the zinc 3,5-di-tert-butylhydroxybenzoate product in the form of nano-linear aggregates obtained under a lower magnification electron microscope in Example 1.

[0036] Figure 2 SEM image of the zinc 3,5-di-tert-butylhydroxybenzoate product in the form of nano-linear aggregates obtained under a higher magnification electron microscope in Example 1.

[0037] Figure 3 SEM image of the zinc 3,5-di-tert-butylhydroxybenzoate product with a mixture of nanowires and bulk crystals obtained in Comparative Example 1.

[0038] Figure 4 SEM image of the bulk crystal of the zinc 3,5-di-tert-butylhydroxybenzoate product obtained in Comparative Example 4. Detailed Embodiments

[0039] To better understand the present invention, it is illustrated by the following examples. These examples belong to the protection scope of the present invention, but do not limit the protection scope of the present invention.

[0040] 1. The chemical formula of the substituted o-hydroxybenzoic acid described in the present invention is as follows:

[0041]

[0042] In the formula, n represents 0, 1 or 2, and the R groups can be the same or different groups, and the groups are: hydrogen atom, halogen atom, nitro group, or alkyl group, alkoxy group containing 1-5 carbon atoms, or hydroxyalkyl group with 1-3 carbons.

[0043] 2. The coordinated metal zinc in the present invention participates in the reaction in the form of zinc carbonate, zinc oxide, zinc hydroxide or basic zinc carbonate;

[0044] 3. The water-mixed organic solvent system described in the present invention is a mixture of water and a polar organic solvent, and the weight percentage of water in the mixed solvent is 0%-10%, and the rest is a polar organic solvent.

[0045] 4. The polar organic solvents miscible with water include one or more mixtures of methanol, ethanol, N,N-dimethylformamide (DMF), N,N-dimethylpropionamide (DMA), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF).

[0046] 5. The alkali metal inorganic salts described in the present invention include inorganic salts of sodium and inorganic salts of potassium, such as a mixture of one or several of hydrochloride, sulfate, phosphate, acetate, etc.

[0047] 6. The deionized water described in the present invention refers to deionized water with a conductivity equal to or less than 50 μs / cm.

[0048] 7. The reaction temperature described in the present invention refers to a reaction temperature equal to or lower than 30°C.

[0049] The following is further illustrated by more specific examples.

[0050] Example 1

[0051] Dissolve 0.1 mol of 3,5 - di - tert - butylhydroxybenzoic acid in 60 ml of absolute ethanol until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 0 °C. Add 0.05 mol of Zn(OH)₂ to 20 ml of absolute ethanol, and add 1 ml of a saturated solution of the alkali metal salt sodium sulfate. Place it in an ultrasonic device and process for 1 hour to obtain a zinc - containing agent dispersion, and maintain the temperature at 0 °C. Slowly add the 3,5 - di - tert - butylhydroxybenzoic acid solution to the zinc - containing agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain 3,5 - di - tert - butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 5 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 0 °C, add 3,5 - di - tert - butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes to a translucent gel state. After the reaction, centrifuge, filter, wash, and dry to obtain a 3,5 - di - tert - butylhydroxybenzoic acid zinc product in a nano - wire - like aggregated state.

[0052] The nano - products prepared by the process of the embodiment of the present invention appear as microns or even larger under a lower - magnification electron microscope, presenting a disordered accumulation state of nano - particles, nano - wires, or nano - sheets (see the SEM image of the product in Figure 1 ). However, under a higher - magnification electron microscope, it can be seen that they are arranged disorderly like fibers, and the fiber diameter is not more than 50 nanometers (see the SEM image of the product in Figure 2 ). Such micron - sized products can be easily broken into nano - powders and nano - wires during application.

[0053] Example 2

[0054] Dissolve 0.1 mol of 3 - nitro - o - hydroxybenzoic acid in 60 ml of 90% ethanol until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 30 °C. Add 0.05 mol of ZnCO₃ to 20 ml of 90% ethanol, add 3 ml of a saturated solution of the alkali metal salt sodium chloride. Place it in an ultrasonic device and process for 1 hour to obtain a zinc - containing agent dispersion, and maintain the temperature at 30 °C. Slowly add the 3,5 - di - tert - butylhydroxybenzoic acid solution to the zinc - containing agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain 3,5 - di - tert - butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 10 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 30 °C, add 3,5 - di - tert - butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes to a translucent gel state. After the reaction, centrifuge, filter, wash, and dry to obtain a 3,5 - di - tert - butylhydroxybenzoic acid zinc product in a nano - wire - aggregated state.

[0055] Example 3

[0056] Dissolve 0.1 mol of 5-methyl-o-hydroxybenzoic acid in 60 ml of 95% methanol until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 10°C. Add 0.05 mol of ZnO to 20 ml of 95% ethanol, add 1 ml of a saturated solution of the alkali metal salt sodium acetate, and place it in an ultrasonic device for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 10°C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 30 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control it at 10°C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes and presents a translucent gel state. After the reaction is completed, centrifuge, filter, wash, and dry to obtain a 3,5-di-tert-butylhydroxybenzoic acid zinc product in the form of aggregated nanowires.

[0057] Example 4

[0058] Dissolve 0.1 mol of 3-ethyl-5-methoxy-o-hydroxybenzoic acid in 60 ml of N,N-dimethylformamide (DMF) until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 20°C. Add 0.025 mol of Zn2(OH)2CO3 to 20 ml of N,N-dimethylformamide (DMF), and add 3 ml of a saturated solution of the alkali metal salt sodium phosphate, and place it in an ultrasonic device for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 20°C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 50 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control it at 20°C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes and presents a translucent gel state. After the reaction is completed, centrifuge, filter, wash, and dry to obtain a product of 3,5-di-tert-butylhydroxybenzoic acid zinc in the form of aggregated nanowires.

[0059] Example 5

[0060] Dissolve 0.1 mol of 3,5-dichloro-o-hydroxybenzoic acid in 60 ml of dimethyl sulfoxide (DMSO) until it becomes a transparent solution, turn on the cooling circulation pump, and keep the solution temperature at 30°C. Add 0.05 mol of ZnCO3 to 20 ml of dimethyl sulfoxide (DMSO), add 1 ml of saturated solution of alkali metal salt sodium chloride, place it in an ultrasonic device for treatment for 1 hour, obtain a zinc-containing agent dispersion, and maintain the temperature at 30°C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-containing agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 5 μs / cm to the beaker, start stirring, turn on the cooling circulation pump water, control it at 30°C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continue to stir until the system gelatinizes and presents a translucent gel. After the reaction is completed, the product is centrifuged, filtered, washed, and dried to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc in the aggregated state of nanowires.

[0061] Example 6

[0062] Dissolve 0.1 mol of 3-bromo-5-ethoxy-o-hydroxybenzoic acid in 60 ml of tetrahydrofuran (THF) until it becomes a transparent solution, turn on the cooling circulation pump, and make the solution temperature 0°C. Add 0.05 mol of Zn(OH)2 to 20 ml of tetrahydrofuran (THF), add 3 ml of saturated solution of alkali metal salt sodium sulfate, place it in an ultrasonic device for treatment for 1 hour, obtain a zinc-containing agent dispersion, and maintain the temperature at 0°C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-containing agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 10 μs / cm to the beaker, start stirring, turn on the cooling circulation pump water, control it at 0°C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and stir continuously until the system gelatinizes and presents a translucent gel. After the reaction is completed, the product is centrifuged, filtered, washed, and dried to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc in the aggregated state of nanowires.

[0063] Example 7

[0064] Dissolve 0.1 mol of 3,5-dipropoxy o-hydroxybenzoic acid in 60 ml of N,N-dimethylpropionamide (DMA) until it forms a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 10 °C. Add 0.05 mol of ZnO to 20 ml of N,N-dimethylpropionamide (DMA), add 1 ml of a saturated solution of alkali metal salt potassium sodium sulfate, place it in an ultrasonic device and process for 1 hour to obtain a zinc-enriched agent dispersion, and maintain the temperature at 10 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-enriched agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain zinc 3,5-di-tert-butylhydroxybenzoate complex crystals. Add 100 ml of deionized water with a conductivity of 30 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 10 °C, add zinc 3,5-di-tert-butylhydroxybenzoate crystals, and continuously stir until the system gelatinizes to a translucent gel state. After the reaction is completed, centrifuge, filter, wash, and dry to obtain the product zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0065] Example 8

[0066] Dissolve 0.1 mol of 3-isopropoxy-5-hydroxymethyl o-hydroxybenzoic acid in a mixed solution of 60 ml of anhydrous ethanol and methanol (the mixing ratio of methanol to ethanol is arbitrary) until it forms a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 20 °C. Add 0.025 mol of Zn2(OH)2CO3 to 20 ml of a mixed solution of anhydrous ethanol and methanol (the mixing ratio of methanol to ethanol is arbitrary), and add 1 ml of a saturated solution of alkali metal salt potassium chloride, place it in an ultrasonic device and process for 1 hour to obtain a zinc-enriched agent dispersion, and maintain the temperature at 20 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-enriched agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain zinc 3,5-di-tert-butylhydroxybenzoate complex crystals. Add 100 ml of deionized water with a conductivity of 50 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 20 °C, add zinc 3,5-di-tert-butylhydroxybenzoate crystals, and continuously stir until the system gelatinizes to a translucent gel state. After the reaction is completed, centrifuge, filter, wash, and dry to obtain the product zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0067] Example 9

[0068] Dissolve 0.1 mol of 3,5-dibromo-o-hydroxybenzoic acid in 60 ml of dimethyl sulfoxide (DMSO) until it becomes a transparent solution. Turn on the cooling circulation pump to keep the solution temperature at 30 °C. Add 0.05 mol of ZnCO3 to 20 ml of dimethyl sulfoxide (DMSO), add 1 ml of a saturated solution of alkali metal salt sodium chloride, and place it in an ultrasonic device for 1 hour to obtain a zinc-impregnating agent dispersion, while maintaining the temperature at 30 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 5 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control the temperature at 30 °C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system pastes and presents a translucent gel state. After the reaction, centrifuge, filter, wash, and dry to obtain the product, zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0069] Example 10

[0070] Dissolve 0.1 mol of 3-tert-butyl-5-butoxy-o-hydroxybenzoic acid in 60 ml of tetrahydrofuran (THF) until it becomes a transparent solution. Turn on the cooling circulation pump to keep the solution temperature at 0 °C. Add 0.05 mol of Zn(OH)2 to 20 ml of tetrahydrofuran (THF), add 3 ml of a saturated solution of alkali metal salt potassium acetate, and place it in an ultrasonic device for 1 hour to obtain a zinc-impregnating agent dispersion, while maintaining the temperature at 0 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 10 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control the temperature at 0 °C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system pastes and presents a translucent gel state. After the reaction, centrifuge, filter, wash, and dry to obtain the product, zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0071] Example 11

[0072] Dissolve 0.1 mol of 3-ethyl-5-isobutyl o-hydroxybenzoic acid in 60 ml of N,N-dimethylpropionamide (DMA) until it becomes a transparent solution. Turn on the cooling circulation pump to keep the solution temperature at 20°C. Add 0.05 mol of ZnO to 20 ml of N,N-dimethylpropionamide (DMA), add 1 ml of a saturated solution of alkali metal salt sodium phosphate, place it in an ultrasonic device and process for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 20°C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 30 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 20°C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes to a translucent gel state. After the reaction, centrifuge, filter, wash, and dry to obtain the product, zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0073] Example 12

[0074] Dissolve 0.1 mol of 3,5-dibutoxy o-hydroxybenzoic acid in a mixed solution of 60 ml of anhydrous ethanol and methanol (the mixing ratio of methanol to ethanol is arbitrary) until it becomes a transparent solution. Turn on the cooling circulation pump to keep the solution temperature at 10°C. Add 0.025 mol of Zn2(OH)2CO3 to 20 ml of the mixed solution of anhydrous ethanol and methanol (the mixing ratio of methanol to ethanol is arbitrary), and add 1 ml of a saturated solution of alkali metal salt sodium sulfate, place it in an ultrasonic device and process for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 10°C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 50 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 10°C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes to a translucent gel state. After the reaction, centrifuge, filter, wash, and dry to obtain the product, zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0075] Example 13

[0076] Dissolve 0.1 mol of 3-ethyl-5-pentyloxy o-hydroxybenzoic acid in 60 ml of dimethyl sulfoxide (DMSO) until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 30 °C. Add 0.05 mol of ZnCO3 to 20 ml of dimethyl sulfoxide (DMSO), add 1 ml of a saturated solution of alkali metal salt sodium chloride, and place it in an ultrasonic device for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 30 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain zinc 3,5-di-tert-butylhydroxybenzoate complex crystals. Add 100 ml of deionized water with a conductivity of 5 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 30 °C, add zinc 3,5-di-tert-butylhydroxybenzoate crystals, and continuously stir until the system gelatinizes to a translucent gel state. After the reaction, centrifuge, filter, wash, and dry to obtain the product, zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0077] Example 14

[0078] Dissolve 0.1 mol of 3-nitro-5-butoxy o-hydroxybenzoic acid in 60 ml of tetrahydrofuran (THF) until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 0 °C. Add 0.05 mol of Zn(OH)2 to 20 ml of tetrahydrofuran (THF), add 3 ml of a saturated solution of alkali metal salt sodium chloride, and place it in an ultrasonic device for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 0 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain zinc 3,5-di-tert-butylhydroxybenzoate complex crystals. Add 100 ml of deionized water with a conductivity of 10 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 0 °C, add zinc 3,5-di-tert-butylhydroxybenzoate crystals, and continuously stir until the system gelatinizes to a translucent gel state. After the reaction, centrifuge, filter, wash, and dry to obtain the product, zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0079] Example 15

[0080] Dissolve 0.1 mol of 3-chloro-5-hydroxymethyl-o-hydroxybenzoic acid in 60 ml of N,N-dimethylpropionamide (DMA) until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 20 °C. Add 0.05 mol of ZnCO3 to 20 ml of N,N-dimethylpropionamide (DMA), add 1 ml of a saturated solution of alkali metal salt sodium chloride, place it in an ultrasonic device and process for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 20 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 30 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control the temperature at 20 °C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes and presents a translucent gel state. After the reaction is completed, centrifuge, filter, wash, and dry to obtain the product, zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0081] Example 16

[0082] Dissolve 0.1 mol of 3-iodo-5-nitro-o-hydroxybenzoic acid in a mixed solution of 60 ml of anhydrous ethanol and methanol (the mixing ratio of methanol to ethanol is arbitrary) until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 10 °C. Add 0.025 mol of Zn2(OH)2CO3 to 20 ml of the mixed solution of anhydrous ethanol and methanol (the mixing ratio of methanol to ethanol is arbitrary), and add 1 ml of a saturated solution of alkali metal salt sodium sulfate, place it in an ultrasonic device and process for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 10 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 50 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control the temperature at 10 °C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes and presents a translucent gel state. After the reaction is completed, centrifuge, filter, wash, and dry to obtain the product, zinc 3,5-di-tert-butylhydroxybenzoate in the form of nanowire aggregates.

[0083] It can be easily seen from the above several examples that polar organic solvents are selected to participate in coordination during the synthesis process of the complex, and then small and strongly polar water molecules are used to replace the guest organic solvent molecules, which can break the close-packed structure of the large crystals of the complex. By adopting the process conditions within the scope of the claims of the present invention, it is possible to successfully obtain perfect micron products with disordered packing of nanosized particles.

[0084] Comparative Example 1

[0085] Dissolve 0.1 mol of 3,5 - di - tert - butylhydroxybenzoic acid in 60 ml of 85% ethanol until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 0 °C. Add 0.05 mol of Zn(OH)₂ to 20 ml of 85% ethanol, add 1 ml of a saturated solution of alkali metal salt sodium chloride, place it in an ultrasonic device for 1 hour to obtain a zinc - containing agent dispersion, and maintain the temperature at 0 °C. Slowly add the 3,5 - di - tert - butylhydroxybenzoic acid solution to the zinc - containing agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain 3,5 - di - tert - butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 5 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 0 °C, add 3,5 - di - tert - butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes. After the reaction, centrifuge, filter, wash, and dry to obtain a product of 3,5 - di - tert - butylhydroxybenzoic acid zinc with a mixture of nanowires and bulk crystals. The SEM image of the product is shown in Figure 3 。

[0086] Comparative Example 2

[0087] Dissolve 0.1 mol of 3,5 - di - tert - butylhydroxybenzoic acid in 60 ml of absolute ethanol until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 50 °C. Add 0.05 mol of ZnCO₃ to 20 ml of absolute ethanol, add 1 ml of a saturated solution of alkali metal salt sodium sulfate, place it in an ultrasonic device for 1 hour to obtain a zinc - containing agent dispersion, and maintain the temperature at 50 °C. Slowly add the 3,5 - di - tert - butylhydroxybenzoic acid solution to the zinc - containing agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain 3,5 - di - tert - butylhydroxybenzoic acid zinc complex crystals. Add 100 ml of deionized water with a conductivity of 5 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 50 °C, add 3,5 - di - tert - butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes. After the reaction, centrifuge, filter, wash, and dry to obtain a product of 3,5 - di - tert - butylhydroxybenzoic acid zinc with a mixture of nanowires and bulk crystals.

[0088] Comparative Example 3

[0089] Dissolve 0.1 mol of 3,5-di-tert-butylhydroxybenzoic acid in 60 ml of absolute ethanol until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 0 °C. Add 0.05 mol of ZnO to 20 ml of absolute ethanol, add 1 ml of saturated solution of alkali metal salt sodium chloride, place it in an ultrasonic device and process for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 0 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain zinc 3,5-di-tert-butylhydroxybenzoate complex crystals. Add 100 ml of deionized water with a conductivity of 100 μs / cm to the beaker, start stirring, turn on the cooling circulation pump water, control at 0 °C, add zinc 3,5-di-tert-butylhydroxybenzoate crystals, and keep stirring until the system gelatinizes. After the reaction, centrifuge, filter, wash, and dry to obtain a product of zinc 3,5-di-tert-butylhydroxybenzoate mixed with nanowires and bulk crystals.

[0090] Comparative Example 4

[0091] Dissolve 0.1 mol of 3,5-di-tert-butylhydroxybenzoic acid in 60 ml of 85% ethanol until it becomes a clear solution. Turn on the cooling circulation pump to keep the solution temperature at 50 °C. Add 0.05 mol of Zn(OH)₂ to 20 ml of 85% ethanol, add 10 ml of saturated solution of alkali metal salt sodium chloride, place it in an ultrasonic device and process for 1 hour to obtain a zinc-impregnating agent dispersion, and maintain the temperature at 50 °C. Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-impregnating agent dispersion, and then continue to stir and react for 3 hours. After the reaction, vacuum filter to obtain zinc 3,5-di-tert-butylhydroxybenzoate complex crystals. Add 100 ml of deionized water with a conductivity of 100 μs / cm to the beaker, start stirring, turn on the cooling circulation pump water, control at 50 °C, add zinc 3,5-di-tert-butylhydroxybenzoate crystals, and keep stirring. The system cannot gelatinize. After the reaction, centrifuge, filter, wash, and dry to obtain a product of zinc 3,5-di-tert-butylhydroxybenzoate in bulk crystals. The SEM micro-morphology of the product is shown in Figure 4

[0092] Comparative Examples 1-4 illustrate that process conditions outside the scope of the claimed rights of the present invention are not conducive to obtaining perfect micron-sized products with disordered nano-sized packing, and only flaky products or mixtures of nanowires and flaky crystals can be obtained. Therefore, in order to obtain perfect micron-sized products with disordered nano-sized packing, the process conditions must be strictly controlled.

[0093] The protection scope of the present invention is not limited to the above embodiments. All technical solutions falling within the concept of the present invention belong to the protection scope of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements should also be regarded as within the protection scope of the present invention.

Claims

1. A preparation method of a zinc complex nanomaterial of substituted o-hydroxybenzoic acid, characterized in that, It includes the following steps: (1) Dissolve 0.1 mol of 3,5-di-tert-butylhydroxybenzoic acid in 60 ml of absolute ethanol until it becomes a transparent solution. Turn on the cooling circulation pump to keep the solution temperature at 0 °C; (2) Add 0.05 mol of Zn(OH)2 to 20 ml of absolute ethanol, and add 1 ml of a saturated solution of alkali metal salt sodium sulfate. Place it in an ultrasonic device and process for 1 hour to obtain a zinc-enriched agent dispersion, and maintain the temperature at 0 °C; (3) Slowly add the 3,5-di-tert-butylhydroxybenzoic acid solution to the zinc-enriched agent dispersion, and then continue to stir and react for 3 hours. After the reaction is completed, vacuum filter to obtain 3,5-di-tert-butylhydroxybenzoic acid zinc complex crystals; (4) Add 100 ml of deionized water with a conductivity of 5 μs / cm to a beaker, start stirring, turn on the cooling circulation pump water, control at 0 °C, add 3,5-di-tert-butylhydroxybenzoic acid zinc crystals, and continuously stir until the system gelatinizes and presents a translucent gel state. After the reaction is completed, centrifuge, filter, wash, and dry to obtain a 3,5-di-tert-butylhydroxybenzoic acid zinc product in a nano-linear aggregated state.

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