Hydrogen peroxide gel capable of emitting light for long time as well as preparation method and application of hydrogen peroxide gel

Abstract

The invention provides hydrogen peroxide gel capable of emitting light for a long time as well as a preparation method and application of the hydrogen peroxide gel. The hydrogen peroxide gel provided by the invention is prepared from the following raw materials in parts by weight: 70 to 90 parts of hydrogen peroxide solution, 1 to 5 parts of glycyrrhizic acid compounds, 0.03 to 5 parts of polyvinyl alcohol, 10 to 20 parts of oxalate compounds, 10 to 20 parts of phthalate compounds, 0.05 to 0.4 part of sodium salicylate and 0.05 to 5 parts of fluorescent dye, the mass fraction of the hydrogen peroxide solution is 10%-50%; the preparation method comprises the following steps: preparing a hydrogen peroxide gel, adding a fluorescent dye suspension, uniformly stirring, recovering the gel state by using the thixotropy of the gel, slowly releasing hydrogen peroxide, and realizing long-time luminescence, the process is simple, and the cost is low. The hydrogen peroxide gel provided by the invention is good in stability, long in storage time, good in thixotropy, capable of emitting light for a long time and good in application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of supramolecular gel, in particular to a hydrogen peroxide gel capable of long-term luminescence and a preparation method and application thereof. Background Art

[0002] Hydrogen peroxide is a high-density, strongly oxidizing liquid composed of hydrogen and oxygen elements. Its decomposition products are water and oxygen. Due to its high energy and environmentally friendly decomposition products, it has become a research hotspot in various countries in the fields of propellants. However, the strong oxidizing, flammable and explosive, and easy flow characteristics of hydrogen peroxide liquid bring great risks for possible and existing leakage during the application process. The gelation of hydrogen peroxide is conducive to reducing the leakage risk of its liquid flow state and increasing the safety factor during storage, transportation, and application.

[0003] Hydrogen peroxide gel is formed by adding a gelling agent to its solution and forming a semi-solid with a three-dimensional network structure through physical or chemical cross-linking. The hydrogen peroxide solution will be confined in the three-dimensional network gaps formed by the cross-linking agent as a dispersion medium, so it can effectively reduce the fluidity of the hydrogen peroxide solution and reduce the risk of leakage.

[0004] In the oxalate chemiluminescent reaction, the reaction of oxalate with hydrogen peroxide to generate high-energy intermediate dioxyethylenedione is the rate-determining step of the chemiluminescent reaction. Dioxyethylenedione transfers energy to different fluorescent dyes, which can continuously emit light of different colors. This reaction does not require alkaline conditions and has strong environmental tolerance.

[0005] However, the current luminous time is relatively short and cannot meet the demand for outdoor cold light sources. Summary of the invention

[0006] In order to solve the problem of short luminescence time in the prior art, the present invention provides a hydrogen peroxide gel that can emit light for a long time to meet the demand for outdoor cold light sources.

[0007] Based on this, the first aspect of the present invention provides a hydrogen peroxide gel that can emit light for a long time. The raw materials thereof include, by weight: 70-90 parts of hydrogen peroxide solution, 1-5 parts of glycyrrhizic acid compounds, 0.03-5 parts of polyvinyl alcohol, 10-20 parts of oxalate compounds, 10-20 parts of phthalate compounds, 0.05-0.4 parts of sodium salicylate, and 0.05-5 parts of fluorescent dye; wherein the mass fraction of the hydrogen peroxide solution is 10%-50%.

[0008] In the hydrogen peroxide gel provided by the present invention, glycyrrhizic acid compounds and polyvinyl alcohol can interact through non-covalent bonds to form a three-dimensional network structure in the hydrogen peroxide solution to obtain hydrogen peroxide gel, which reduces the potential leakage risk of the hydrogen peroxide solution during storage, transportation and application, and has good stability. The introduction of polyvinyl alcohol makes the hydrogen peroxide gel have better thixotropy, and after shearing and stirring, it can restore the gel state by itself. By introducing oxalate compounds and fluorescent dyes, the luminescent performance of the hydrogen peroxide gel is achieved under the action of the catalyst sodium salicylate; the thixotropy of the hydrogen peroxide gel provided by the present invention enables the gel to remain in the gel state after physical stirring and shearing; at the same time, the three-dimensional spatial network structure of the hydrogen peroxide gel provided by the present invention provides a basis for the slow release of hydrogen peroxide to achieve long-term luminescence, meets people's needs for long-term luminous cold light sources, and provides a basis for developing new uses of hydrogen peroxide gel. By optimizing the concentration of the hydrogen peroxide solution, a longer storage time of the hydrogen peroxide gel is achieved. At the same time, the preparation process of various raw materials used is mature, cheap and easy to obtain, which helps to control costs.

[0009] In some embodiments, the mass fraction of the hydrogen peroxide solution is 10%-30%. It has been verified that the use of a hydrogen peroxide solution with a mass fraction of 10%-30% has better stability and can obtain a longer storage time.

[0010] In some embodiments, the glycyrrhizic acid compound is selected from at least one of glycyrrhizic acid, dipotassium glycyrrhizinate, ammonium glycyrrhizinate, diammonium glycyrrhizinate, trisodium glycyrrhizinate, and glycyrrhetinic acid. The above glycyrrhizic acid compounds have a better effect of gelling mechanical properties.

[0011] In some embodiments, the average molecular weight of the polyvinyl alcohol is 80,000 to 200,000, and / or the alcoholysis degree is 80 to 99%. Using polyvinyl alcohol with the above molecular weight and alcoholysis degree is helpful to obtain better thixotropy.

[0012] In some embodiments, the oxalate compound is selected from at least one of bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl]oxalate, bis(2,4-dinitrophenyl)oxalate, and bis(2,4,6-trichlorophenyl)oxalate.

[0013] In some embodiments, the fluorescent dye is selected from at least one of rhodamine B, eosin Y, 5,6,11,12-tetraphenyl tetracene, 9,10-bis(phenylethynyl)anthracene, 1,8-dichloro-9,10-bis(phenylethynyl)anthracene, 1-chloro-9,10-bis(phenylethynyl)anthracene, 9,10-diphenylanthracene, and 2-chloro-9,10-diphenylanthracene. By selecting different fluorescent dyes, the luminescent color can be freely changed.

[0014] In some embodiments, the phthalate compound is selected from at least one of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, and dibutyl phthalate.

[0015] In a second aspect, a method for preparing the hydrogen peroxide gel is provided, comprising the following steps: (a) adding a glycyrrhizic acid compound to a hydrogen peroxide solution at a temperature of 40 to 60° C. and normal pressure, and stirring until the glycyrrhizic acid compound is completely dispersed or dissolved to obtain a hydrogen peroxide solution A containing a glycyrrhizic acid compound; (b) adding polyvinyl alcohol to the hydrogen peroxide solution at a temperature of 40-60° C. and normal pressure, stirring until the polyvinyl alcohol is completely dispersed or dissolved, adding sodium salicylate at normal temperature and normal pressure, stirring until the polyvinyl alcohol is completely dispersed or dissolved, to obtain a hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate; adding the hydrogen peroxide solution B to the hydrogen peroxide solution A obtained in step (a), shaking and mixing, and standing at normal temperature and normal pressure for 3-5 hours to obtain a hydrogen peroxide gel; (c) adding an oxalate compound to the phthalate compound at a temperature of 70 to 90° C. and normal pressure, and stirring until the phthalate compound is completely dispersed or dissolved to obtain an oxalate saturated solution; (d) adding a fluorescent dye to the saturated oxalate solution obtained in step (c) at room temperature and pressure, and stirring until the fluorescent dye is completely dispersed to obtain a fluorescent dye suspension; (e) adding the fluorescent dye suspension obtained in step (d) to the hydrogen peroxide gel obtained in step (b), stirring evenly and fully mixing, and standing at room temperature and pressure for 3-5 hours to obtain a long-lasting luminescent hydrogen peroxide gel.

[0016] The preparation method provided by the invention comprises the following steps: a glycyrrhizic acid compound and polyvinyl alcohol interact with each other through non-covalent bonds, are cross-linked in a hydrogen peroxide solution, and a hydrogen peroxide gel with a three-dimensional network structure is formed; a saturated solution of phthalate of an oxalate compound is simply mixed, a fluorescent dye is added to obtain a fluorescent dye suspension, the fluorescent dye suspension is added to the hydrogen peroxide gel, and the mixture is stirred evenly; the thixotropy of the gel is utilized to restore the gel state, and hydrogen peroxide is slowly released, thereby realizing long-term luminescence; the preparation method has a simple process, and the raw materials are cheap and easily available, and the cost is low, so that the requirements of industrial production are met.

[0017] In some embodiments, the stirring in step (a) is carried out at a rate of 300 to 3000 r / min for a time of 0.1 to 5 h.

[0018] In some embodiments, the stirring in step (b) is carried out at a rate of 300 to 3000 r / min for a time of 0.5 to 5 h.

[0019] The hydrogen peroxide gel obtained in step (b) can be stored at low temperature, wherein the storage temperature is -5 to 10°C.

[0020] In some embodiments, the stirring in step (c) is carried out at a rate of 300 to 3000 r / min for a time of 0.5 to 5 h.

[0021] In some embodiments, the stirring in step (d) is carried out at a rate of 300 to 3000 r / min for a time of 0.1 to 1 h.

[0022] In some embodiments, the stirring in step (e) is carried out at a rate of 300 to 3000 r / min for a time of 0.1 to 1 h.

[0023] The use of the above stirring rate, stirring time and storage temperature is conducive to more efficient dissolution of glycyrrhizic acid compounds and polyvinyl alcohol, helps to better form a three-dimensional spatial network structure, and helps to extend the storage time of the gel.

[0024] In a third aspect, there is provided application of the hydrogen peroxide gel and / or the hydrogen peroxide gel prepared by the preparation method in fluorescent sticks and outdoor cold light sources.

[0025] The hydrogen peroxide gel provided by the present invention has a long storage time, good thixotropy, can realize self-recovery after shearing and stirring, has a luminescence time of up to 216 hours, and can realize luminescence of different colors by selecting different fluorescent dyes. The preparation method of the hydrogen peroxide gel provided by the present invention has a simple process, does not require expensive instruments, and is easy to operate. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0027] Figure 1 This is one of the atomic force microscope images of the hydrogen peroxide gel capable of long-term luminescence provided by the present invention.

[0028] Figure 2 This is one of the atomic force microscope images of the comparative example of the hydrogen peroxide gel capable of long-term luminescence provided by the present invention.

[0029] Figure 3 One of the thixotropy test results of the hydrogen peroxide gel containing glycyrrhizic acid compounds provided by the present invention.

[0030] Figure 4The second thixotropy test result of the hydrogen peroxide gel containing glycyrrhizic acid compounds provided by the present invention.

[0031] Figure 5 The third thixotropy test result of the hydrogen peroxide gel containing glycyrrhizic acid compounds provided by the present invention.

[0032] Figure 6 The fourth thixotropy test result of the hydrogen peroxide gel containing glycyrrhizic acid compounds provided by the present invention.

[0033] Figure 7 This is one of the luminescence time test result diagrams of the hydrogen peroxide gel capable of long-term luminescence provided by the present invention.

[0034] Figure 8 This is the second figure showing the luminescence time test result of the hydrogen peroxide gel capable of long-term luminescence provided by the present invention.

[0035] Fig. 9 This is one of the luminescent color diagrams of the hydrogen peroxide gel capable of long-term luminescence provided by the present invention. DETAILED DESCRIPTION

[0036] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making any creative work shall fall within the scope of protection of the present invention.

[0037] In the first aspect of the present invention, the present invention provides a hydrogen peroxide gel capable of long-term luminescence, wherein the raw materials include, by weight: 70-90 parts of hydrogen peroxide solution, 1-5 parts of glycyrrhizic acid compounds, 0.03-5 parts of polyvinyl alcohol, 10-20 parts of oxalate compounds, 10-20 parts of phthalate compounds, 0.05-0.4 parts of sodium salicylate, and 0.05-5 parts of fluorescent dye; wherein the mass fraction of the hydrogen peroxide solution is 10%-50%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or the range of these specific concentrations, such as 10-30%, 10-40%, 20-50%, 10-25%, 10-35%, 25-35%, 20-40%, etc., which are not listed one by one here. Preferably, the total amount of the raw materials is 100 parts.

[0038] In some embodiments, the mass fraction of the hydrogen peroxide solution is 10%-30%, for example, 10%, 15%, 20%, 25%, 30% or other mass fractions, or a range formed by a combination of these point values, such as 10%-20%, 10-25%, 15-25%, 15-20%, etc.

[0039] In some embodiments, the glycyrrhizic acid compound is selected from at least one of glycyrrhizic acid, dipotassium glycyrrhizinate, ammonium glycyrrhizinate, diammonium glycyrrhizinate, trisodium glycyrrhizinate, and glycyrrhetinic acid.

[0040] In some embodiments, the average molecular weight of the polyvinyl alcohol is 80,000 to 200,000. Preferably, the average molecular weight of the polyvinyl alcohol is 80,000 to 120,000, such as 80,000, 90,000, 100,000, 110,000, 120,000 or other molecular weights, or a range consisting of these point values; the alcoholysis degree of the polyvinyl alcohol is 80 to 99%. Preferably, the alcoholysis degree is 87-99%, such as 87%, 88%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or a range consisting of these point values, such as 90%-99%, 95%-99%, etc.

[0041] In some embodiments, the oxalate compound is selected from at least one of bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl] oxalate, bis(2,4-dinitrophenyl) oxalate, and bis(2,4,6-trichlorophenyl) oxalate. Preferably, the oxalate compound is selected from at least one of bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl] oxalate and bis(2,4-dinitrophenyl) oxalate.

[0042] In some embodiments, the fluorescent dye is at least one of rhodamine B, eosin Y, 5,6,11,12-tetraphenyl tetracene, 9,10-bis(phenylethynyl)anthracene, 1,8-dichloro-9,10-bis(phenylethynyl)anthracene, 1-chloro-9,10-bis(phenylethynyl)anthracene, 9,10-diphenylanthracene, and 2-chloro-9,10-diphenylanthracene. Among them, eosin includes eosin Y (alcohol soluble) and / or eosin Y (water soluble). Preferably, the fluorescent dye is at least one of rhodamine B, 5,6,11,12-tetraphenyl tetracene, 9,10-bis(phenylethynyl)anthracene, 1,8-dichloro-9,10-bis(phenylethynyl)anthracene, 1-chloro-9,10-bis(phenylethynyl)anthracene, 9,10-diphenylanthracene, and 2-chloro-9,10-diphenylanthracene.

[0043] In some embodiments, the phthalate compound is selected from at least one of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, and dibutyl phthalate. Preferably, the solvent is at least one of dimethyl phthalate and dibutyl phthalate.

[0044] On the other hand, the present invention provides a method for preparing the above-mentioned hydrogen peroxide gel capable of long-term luminescence, comprising the following steps: (a) adding a glycyrrhizic acid compound to a hydrogen peroxide solution at a temperature of 40 to 60° C. and normal pressure, and stirring until the glycyrrhizic acid compound is completely dispersed or dissolved to obtain a hydrogen peroxide solution A containing a glycyrrhizic acid compound; (b) adding polyvinyl alcohol to the hydrogen peroxide solution at a temperature of 40-60° C. and normal pressure, stirring until the polyvinyl alcohol is completely dispersed or dissolved, adding sodium salicylate at normal temperature and normal pressure, stirring until the polyvinyl alcohol is completely dispersed or dissolved, to obtain a hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate; adding the hydrogen peroxide solution B to the hydrogen peroxide solution A obtained in step (a), shaking and mixing, and standing at normal temperature and normal pressure for 3-5 hours to obtain a hydrogen peroxide gel, which is stored at low temperature; (c) adding an oxalate compound to the phthalate compound at a temperature of 70 to 90° C. and normal pressure, and stirring until the phthalate compound is completely dispersed or dissolved to obtain an oxalate saturated solution; (d) adding a fluorescent dye to the saturated oxalate solution obtained in step (c) at room temperature and pressure, and stirring until the fluorescent dye is completely dispersed to obtain a fluorescent dye suspension; (e) adding the fluorescent dye suspension obtained in step (d) to the hydrogen peroxide gel obtained in step (b), stirring evenly and fully mixing, and standing at room temperature and pressure for 3-5 hours to obtain a long-lasting luminescent hydrogen peroxide gel.

[0045] In steps (b) and (e), the standing time can be 3 h, 3.5 h, 4 h, 4.5 h, 5 h, etc., or can be a range of these specific time periods, such as 3-4 h, 3.5-4.5 h, etc.

[0046] In some embodiments, the stirring speed in step (a) is 300-3000 r / min, preferably 600-2000 r / min, such as 600 r / min, 800 r / min, 1000 r / min, 1200 r / min, 1500 r / min, 1800 r / min, 2000 r / min or other speeds, and can also be a range composed of these point values, such as 600-800 r / min, 800-1500 r / min, 800-1000 r / min, etc.; the time is 0.1-5 h; preferably 0.3-2.5 h, for example 0.3 h, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h or other times, and can also be a range composed of these point values, such as 0.3-0.5 h, 0.3-1.5 h, 0.3-1 h, 0.5-2 h, etc.

[0047] In some embodiments, the stirring speed in step (b) is 300-3000 r / min, preferably 600-2000 r / min, such as 600 r / min, 800 r / min, 1000 r / min, 1200 r / min, 1500 r / min, 1800 r / min, 2000 r / min or other speeds, and can also be a range of these point values, such as 600-800 r / min, 800-1500 r / min, 80 0-1000r / min, etc.; the time is 0.5-5h, preferably 2-5h, for example 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or other times, and can also be a range composed of these point values, such as 2-4h, 3-5h, 2.5-3.5h, etc.; the temperature of the low-temperature storage is -5-10℃; preferably -5-5℃, for example -5℃, 0℃, 5℃ or other temperatures, and can also be a range composed of these point values, such as -5~0℃, 0~-5℃, etc.

[0048] In some embodiments, the stirring rate in step (c) is 300-3000 r / min, preferably 600-1000 r / min, such as 600 r / min, 700 r / min, 800 r / min, 900 r / min, 1000 r / min or other speeds, and can also be a range composed of these point values, such as 600-800 r / min, 800-1000 r / min, etc.; the time is 0.5-5 h; preferably 2-5 h, for example 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h or other times, and can also be a range composed of these point values, such as 2-4 h, 3-5 h, 2.5-3.5 h, etc.

[0049] In some embodiments, the stirring rate in step (d) is 300-3000 r / min, preferably 600-1000 r / min, such as 600 r / min, 700 r / min, 800 r / min, 900 r / min, 1000 r / min or other speeds, and can also be a range composed of these point values, such as 600-800 r / min, 800-1000 r / min, etc.; the time is 0.1-1 h; preferably 0.5-1 h, for example 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1 h or other times, and can also be a range composed of these point values, such as 0.5-0.8 h, 0.6-1 h, etc.

[0050] In some embodiments, the stirring speed in step (e) is 300-3000 r / min, preferably 600-1000 r / min, such as 600 r / min, 700 r / min, 800 r / min, 900 r / min, 1000 r / min or other speeds, and can also be a range composed of these point values, such as 600-800 r / min, 800-1000 r / min, etc.; the time is 0.1-1h, preferably 0.1-0.5h, for example 0.1h, 0.2h, 0.3h, 0.4h, 0.5h, or other times, and can also be a range composed of these point values, such as 0.1-0.3h, 0.2-0.5h, etc.

[0051] The hydrogen peroxide gel provided in the examples of the present invention and / or the hydrogen peroxide gel prepared by the preparation method can emit light for up to 216 hours and can be applied to fluorescent sticks and outdoor cold light sources to meet the needs of long-term cold light sources.

[0052] In the examples, the information of each raw material is shown in the following table.

[0053]

[0054] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0055] In actual examples, concentration refers to the mass fraction and mass percentage mentioned in the previous text.

[0056] The present invention is described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0057] Example 1 This embodiment provides a hydrogen peroxide gel capable of long-term luminescence, and its raw material composition is shown in Table 1.

[0058] Table 1 Raw material formula composition

[0059] This embodiment also provides a method for preparing the above-mentioned hydrogen peroxide gel capable of long-term luminescence, comprising the following steps: (a) Weigh 200 mg of glycyrrhizic acid and add it to 4.36 ml of 30% hydrogen peroxide solution. Stir at 40°C, atmospheric pressure and 1000 r / min for 0.5 h until the solution is completely dissolved to obtain hydrogen peroxide solution A containing glycyrrhizic acid compounds.

[0060] (b) Weigh 60 mg of polyvinyl alcohol and add it to 2 ml of hydrogen peroxide solution, stir at 40°C, normal pressure and 1500 r / min for 3 h until completely dissolved, weigh 50 mg of sodium salicylate and add it to the solution, stir at 40-60°C, normal pressure and 800 r / min for 0.5 h until completely dissolved, to obtain hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate. Then, add 2 ml of hydrogen peroxide solution B to hydrogen peroxide solution A obtained in step (a), shake and mix, and let the resulting mixture stand at room temperature and pressure for 3 h to obtain hydrogen peroxide gel, which is stored at 5°C.

[0061] (c) Weigh 1490 mg of bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl] oxalate and add it to 0.96 ml of dibutyl phthalate. Stir at 80°C, atmospheric pressure and 1500 r / min for 3 h until the oxalate is completely dissolved to obtain an oxalate solution.

[0062] (d) Weigh 200 mg of 5,6,11,12-tetraphenyltetracene and add it to the oxalate solution obtained in step (c). Stir at a speed of 800 r / min at room temperature and pressure for 0.5 h until it is completely dispersed to obtain a fluorescent dye suspension.

[0063] (e) 1 ml of the fluorescent dye suspension obtained in step (d) was added to the hydrogen peroxide gel obtained in step (b), and the mixture was stirred at a speed of 1000 r / min for 0.1 h at room temperature and pressure until the mixture was completely dispersed, and then allowed to stand at room temperature and pressure for 3 h to obtain 10 ml of long-lasting luminescent hydrogen peroxide gel.

[0064] Example 2 This embodiment provides a hydrogen peroxide gel capable of long-term luminescence, the components and mass ratios of which are shown in Table 2.

[0065] Table 2 Components and mass ratios

[0066] This embodiment also provides a method for preparing the above-mentioned hydrogen peroxide gel capable of long-term luminescence, comprising the following steps: (a) Weigh 300 mg of glycyrrhizic acid and add it to 6.26 ml of 10% hydrogen peroxide solution. Stir at 60°C, atmospheric pressure and 800 r / min for 0.3 h until the solution is completely dissolved to obtain hydrogen peroxide solution A containing glycyrrhizic acid compounds.

[0067] (b) Weigh 100 mg of polyvinyl alcohol and add it to 1.5 ml of 10% hydrogen peroxide solution, stir at 40°C, normal pressure and 1000 r / min for 3 h until completely dissolved, and after cooling to room temperature, weigh 50 mg of sodium salicylate and add it to the solution, stir at 40-60°C, normal pressure and 800 r / min for 1 h until completely dissolved, to obtain hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate. Then, 1.5 ml of hydrogen peroxide solution B is added to the hydrogen peroxide solution obtained in step (a), and the mixture is shaken and mixed. The obtained mixture is allowed to stand at room temperature and pressure for 3 h to obtain hydrogen peroxide gel, which is stored at 5°C.

[0068] (c) Weigh 750 mg of bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl] oxalate and add it to 0.48 ml of dimethyl phthalate. Stir at 90°C, atmospheric pressure and 1500 r / min for 3 h until the oxalate is completely dissolved to obtain an oxalate solution.

[0069] (d) Weigh 300 mg of 1,8-dichloro-9,10-bis(phenylethynyl)anthracene and add it to the oxalate solution obtained in step (c). Stir at room temperature and pressure at a speed of 800 r / min for 0.5 h until it is completely dispersed to obtain a fluorescent dye suspension.

[0070] (e) 0.5 ml of the fluorescent dye suspension obtained in step (d) was added to the hydrogen peroxide gel obtained in step (b), and the mixture was stirred at a speed of 1000 r / min for 0.3 h at room temperature and pressure until the mixture was completely dispersed, and then allowed to stand at room temperature and pressure for 3 h to obtain 10 ml of long-lasting luminescent hydrogen peroxide gel.

[0071] Example 3 This embodiment provides a hydrogen peroxide gel capable of long-term luminescence, the components and mass ratios of which are shown in Table 3.

[0072] Table 3 Components and mass ratios

[0073] This embodiment also provides a method for preparing the above-mentioned hydrogen peroxide gel capable of long-term luminescence, comprising the following steps: (a) 300 mg of glycyrrhizic acid was weighed and added to 2.94 ml of 50% hydrogen peroxide solution. The mixture was stirred at 800 r / min for 0.3 h at 40°C and atmospheric pressure until the solution was completely dissolved, thereby obtaining hydrogen peroxide solution A containing glycyrrhizic acid compounds.

[0074] (b) 160 mg of polyvinyl alcohol was weighed and added to 2 ml of hydrogen peroxide solution, and stirred at 40°C, normal pressure and rotation speed of 1000 r / min for 3 h until completely dissolved. After cooling to room temperature, 30 mg of sodium salicylate was weighed and added to the solution, and stirred at 40-60°C, normal pressure and rotation speed of 800 r / min for 1 h until completely dissolved, to obtain hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate. Subsequently, 2 ml of the solution obtained by hydrogen peroxide solution B was added to the hydrogen peroxide solution obtained in step (a), and the mixture was shaken and mixed. The obtained mixed solution was allowed to stand at room temperature and pressure for 2 h to obtain hydrogen peroxide gel, which was stored at 5°C.

[0075] (c) Weigh 1210 mg of bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl] oxalate and add it to 0.96 ml of dimethyl phthalate. Stir at 80°C, atmospheric pressure and 1000 r / min for 3 h until the oxalate is completely dissolved to obtain an oxalate solution.

[0076] (d) Weigh 300 mg of 9,10-diphenylanthracene and add it to the oxalate solution obtained in step (c), and stir at a speed of 800 r / min at room temperature and pressure for 0.5 h until it is completely dispersed to obtain a fluorescent dye suspension.

[0077] (e) 1 ml of the fluorescent dye suspension obtained in step (d) was added to the hydrogen peroxide gel obtained in step (b), and the mixture was stirred at a speed of 1000 r / min for 0.2 h at room temperature and pressure until the mixture was completely dispersed, and then allowed to stand at room temperature and pressure for 3 h to obtain 10 ml of long-lasting luminescent hydrogen peroxide gel.

[0078] Example 4 This embodiment provides a hydrogen peroxide gel capable of long-term luminescence, which is basically the same as Embodiment 1, except that the concentration of the hydrogen peroxide solution is 25%.

[0079] Comparative Example 1 This comparative example provides a hydrogen peroxide gel, which is basically the same as Example 1, except that no polyvinyl alcohol is added. The composition of the raw materials in this comparative example is shown in Table 4.

[0080] Table 4 Raw material composition ratio

[0081] Test Example 1 Test object: hydrogen peroxide gel obtained in Example 1 and Comparative Example 1.

[0082] Experimental method: The internal structure of hydrogen peroxide gel was observed by atomic force microscopy (AFM), and the information of atomic force microscopy is as follows: The internal structure of hydrogen peroxide gel was observed by atomic force microscopy (AFM), and the information of atomic force microscopy is as follows: Bruker Nanoscope, in Fast-scan mode, measured using Fast-scanB trip.

[0083] Test results: The AFM images of the hydrogen peroxide gel obtained in Example 1 and Comparative Example 1 are as follows: Figure 1 and Figure 2 shown.

[0084] from Figure 1 and Figure 2 It can be seen that polyvinyl alcohol is added in Example 1, and the glycyrrhizic acid fibers are coated with polyvinyl alcohol. In Comparative Example 1, no polyvinyl alcohol is added and the fibers exist in the form of nanofibers, indicating that polyvinyl alcohol and glycyrrhizic acid fibers are cross-linked and tightly combined together, thereby improving the mechanical properties of the gel and making the gel thixotropic.

[0085] Test Example 2 Thixotropy Test Test object: hydrogen peroxide gel obtained in Example 1 and Comparative Example 1.

[0086] Test method: The gel storage modulus is measured at low and high deformations by a rheometer to verify the gel thixotropy. The information of the rheometer is as follows: HAKKE MARS40, ThermoFisher.

[0087] Test results: The thixotropy test of the hydrogen peroxide gel obtained in Example 1 and Comparative Example 1 is as follows: Figure 3 , Figure 4 , Figure 5 , Figure 6 shown.

[0088] from Figure 3 and Figure 4 It can be seen from the figure that the hydrogen peroxide gel obtained in Example 1 can recover to a gel state after a short period of standing after undergoing high deformation damage. Figure 5 and Figure 6 It can be seen that the comparative example 1 cannot be recovered. These results show that the hydrogen peroxide gel obtained in Example 1 has thixotropy and self-recovery in the gel state.

[0089] Test Example 3 Luminous Time Test object: hydrogen peroxide gel obtained in Example 1 and Comparative Example 1.

[0090] Test method: The luminescence intensity of the sample was tested by steady-state / transient fluorescence spectrometer NanoLOG-TCSPC, and the luminescence intensity and luminescence time were recorded.

[0091] Test results: The luminescence test results of the hydrogen peroxide gel obtained in Example 1 and Comparative Example 1 are as follows: Figure 7 , Figure 8 shown.

[0092] from Figure 7 , Figure 8 It can be seen that the luminescence time of the hydrogen peroxide gel obtained in Example 1 can be as long as 216 hours, and the luminescence time of the hydrogen peroxide gel in Comparative Example 1 is 72 hours, which indicates that the use of the hydrogen peroxide gel provided by the present invention (especially Example 1) can significantly increase the luminescence time.

[0093] Test Example 4 Luminous Color Test object: hydrogen peroxide gel obtained in Examples 1, 2 and 3.

[0094] Test method: Place the hydrogen peroxide gel obtained in Examples 1, 2, and 3 in a dark place, observe the luminescent color and take a photo.

[0095] Test results: Fig. 9 As shown, from left to right are the luminescent color results of the hydrogen peroxide gel obtained in Examples 1, 2 and 3. The luminescent color results indicate that different luminescent colors can be obtained by adding different fluorescent dyes.

[0096] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A hydrogen peroxide gel capable of long-term luminescence, characterized in that: The raw materials include, by weight: 70-90 parts of hydrogen peroxide solution, 1-5 parts of glycyrrhizic acid compounds, 0.03-5 parts of polyvinyl alcohol, 10-20 parts of oxalate compounds, 10-20 parts of phthalate compounds, 0.05-0.4 parts of sodium salicylate, and 0.05-5 parts of fluorescent dye; wherein the mass fraction of the hydrogen peroxide solution is 10%-50%.

2. The hydrogen peroxide gel according to claim 1, characterized in that The mass fraction of the hydrogen peroxide solution is 10%-30%.

3. The hydrogen peroxide gel according to claim 1 or 2, characterized in that: The glycyrrhizic acid compound is selected from at least one of glycyrrhizic acid, dipotassium glycyrrhizinate, ammonium glycyrrhizinate, diammonium glycyrrhizinate, trisodium glycyrrhizinate and glycyrrhetinic acid.

4. The hydrogen peroxide gel according to claim 3, characterized in that: The average molecular weight of the polyvinyl alcohol is 80,000 to 200,000, and / or the alcoholysis degree is 80 to 99%.

5. The hydrogen peroxide gel according to claim 1, 2 or 4, characterized in that: The oxalate compound is at least one selected from bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl]oxalate, bis(2,4-dinitrophenyl)oxalate and bis(2,4,6-trichlorophenyl)oxalate.

6. The hydrogen peroxide gel according to claim 5, characterized in that: The fluorescent dye is selected from at least one of rhodamine B, eosin Y, 5,6,11,12-tetraphenyl tetracene, 9,10-bis(phenylethynyl)anthracene, 1,8-dichloro-9,10-bis(phenylethynyl)anthracene, 1-chloro-9,10-bis(phenylethynyl)anthracene, 9,10-diphenylanthracene and 2-chloro-9,10-diphenylanthracene.

7. The hydrogen peroxide gel according to claim 1, 2, 4 or 6, characterized in that: The phthalate compound is selected from at least one of dimethyl phthalate, diethyl phthalate, dipropyl phthalate and dibutyl phthalate.

8. The method for preparing the hydrogen peroxide gel according to any one of claims 1 to 7, characterized in that: The following steps are involved: (a) adding a glycyrrhizic acid compound to a hydrogen peroxide solution at a temperature of 40 to 60° C. and normal pressure, and stirring until the glycyrrhizic acid compound is completely dispersed or dissolved to obtain a hydrogen peroxide solution A containing a glycyrrhizic acid compound; (b) adding polyvinyl alcohol to the hydrogen peroxide solution at a temperature of 40-60° C. and normal pressure, stirring until the polyvinyl alcohol is completely dispersed or dissolved, adding sodium salicylate, stirring until the polyvinyl alcohol is completely dispersed or dissolved, to obtain a hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate; adding the hydrogen peroxide solution B to the hydrogen peroxide solution A obtained in step (a), shaking and mixing, and standing at room temperature and pressure for 3-5 hours to obtain a hydrogen peroxide gel; (c) adding an oxalate compound to the phthalate compound at a temperature of 70 to 90° C. and normal pressure, and stirring until the phthalate compound is completely dispersed or dissolved to obtain an oxalate saturated solution; (d) adding a fluorescent dye to the saturated oxalate solution obtained in step (c) at room temperature and pressure, and stirring until the fluorescent dye is completely dispersed to obtain a fluorescent dye suspension; (e) adding the fluorescent dye suspension obtained in step (d) to the hydrogen peroxide gel obtained in step (b), stirring evenly and fully mixing, and standing at room temperature and pressure for 3-5 hours to obtain a long-lasting luminescent hydrogen peroxide gel.

9. The preparation method according to claim 8, characterized in that: The stirring in step (a) is carried out at a rate of 300 to 3000 r / min for a time of 0.1 to 5 h; And / or, the stirring in step (b) is carried out at a rate of 300 to 3000 r / min for a time of 0.5 to 5 h; and / or, the stirring in step (c) is carried out at a rate of 300 to 3000 r / min for a time of 0.5 to 5 h; and / or, the stirring in step (d) is carried out at a rate of 300 to 3000 r / min for a time of 0.1 to 1 h; And / or, the stirring in step (e) is carried out at a rate of 300 to 3000 r / min for a time of 0.1 to 1 h.

10. Use of the hydrogen peroxide gel according to any one of claims 1 to 7 and / or the hydrogen peroxide gel prepared by the preparation method according to claim 8 or 9 in fluorescent sticks and outdoor cold light sources.

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