A hydrogen peroxide gel capable of long-term luminescence, its preparation method and application

Abstract

The present invention provides a hydrogen peroxide gel capable of long-term luminescence, its preparation method and application. The hydrogen peroxide gel provided by the present invention, by weight, its raw materials include: 70-90 parts of hydrogen peroxide solution, 1-5 parts of glycyrrhizin 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, 0.05-5 parts of fluorescent dye; the mass fraction of the hydrogen peroxide solution is 10%-50%; its preparation method includes: preparing a hydrogen peroxide gel, adding a fluorescent dye suspension, stirring evenly, utilizing the thixotropy of the gel, restoring the gel state, slowly releasing hydrogen peroxide, achieving long-term luminescence, with a simple process and low cost. The hydrogen peroxide gel provided by the present invention has good stability, a long storage time, good thixotropy, can emit light for a long time, and has good application prospects.

Description

Technical Field

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

[0002] Hydrogen peroxide is a high-density strong 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 the fields of propellants and others in various countries. However, the strong oxidizing, flammable, explosive, and easy-flowing characteristics of liquid hydrogen peroxide bring great risks to the possible leakage during the application process. The gelation of hydrogen peroxide is beneficial to reducing the leakage risk of its liquid flowing state and increasing the safety factor during storage, transportation, and application.

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

[0004] In the oxalate chemiluminescence reaction, the reaction of oxalate with hydrogen peroxide to form the high-energy intermediate dioxetanedione is the rate-determining step of the chemiluminescence reaction. The energy is transferred from dioxetanedione to different fluorescent dyes, and different colors of light can be continuously emitted. This reaction does not require an alkaline condition and has strong environmental tolerance.

[0005] However, the current luminescence time is short and cannot meet the requirements of 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 capable of long-term luminescence to meet the requirements of outdoor cold light sources.

[0007] Based on this, in the first aspect of the present invention, a hydrogen peroxide gel capable of long-term luminescence is proposed. By weight, its raw materials include: 70-90 parts of hydrogen peroxide solution, 1-5 parts of glycyrrhizin 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 dyes; wherein, the mass fraction of the hydrogen peroxide solution is 10%-50%.

[0008] The hydrogen peroxide gel provided by the present invention enables glycyrrhinic acid compounds and polyvinyl alcohol to interact through non-covalent bonds, forming a three-dimensional network structure in the hydrogen peroxide solution to obtain the hydrogen peroxide gel, reducing the potential leakage risk during storage, transportation, and application of the hydrogen peroxide solution, and having good stability at the same time. The introduction of polyvinyl alcohol endows the hydrogen peroxide gel with better thixotropy, and it can self-recover to the gel state after shear stirring. By introducing oxalate compounds and fluorescent dyes, the luminescence performance of the hydrogen peroxide gel is realized 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, meeting people's needs for long-term luminescence cold light sources, and providing a basis for developing new uses of hydrogen peroxide gels. 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 processes of the various raw materials used are mature and inexpensive and easily available, 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 using 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 glycyrrhinic acid compounds are selected from at least one of glycyrrhizic acid, dipotassium glycyrrhizinate, ammonium glycyrrhizinate, diammonium glycyrrhizinate, trisodium glycyrrhizinate, and glycyrrhetinic acid. Using the above glycyrrhinic acid compounds has the effect of better gel-forming mechanical properties.

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

[0012] In some embodiments, the oxalate compounds are 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 dyes are selected from at least one of rhodamine B, eosin Y, 5,6,11,12-tetraphenyltetracene, 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 luminescence 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:

[0016] (a) At a temperature of 40-60°C and normal pressure, add a glycyrrhizic acid compound to a hydrogen peroxide solution, and stir until it is completely dispersed or dissolved to obtain a hydrogen peroxide solution A containing the glycyrrhizic acid compound;

[0017] (b) At a temperature of 40-60°C and normal pressure, add polyvinyl alcohol to a hydrogen peroxide solution, stir until it is completely dispersed or dissolved, add sodium salicylate at normal temperature and pressure, and stir until it is completely dispersed or dissolved to obtain a hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate; Take the hydrogen peroxide solution B and add it to the hydrogen peroxide solution A obtained in step (a), shake and mix well, and then let it stand at normal temperature and pressure for 3-5 h to obtain a hydrogen peroxide gel;

[0018] (c) At a temperature of 70-90°C and normal pressure, add an oxalate compound to a phthalate compound, and stir until it is completely dispersed or dissolved to obtain a saturated oxalate solution;

[0019] (d) At normal temperature and pressure, add a fluorescent dye to the saturated oxalate solution obtained in step (c), and stir until it is completely dispersed to obtain a fluorescent dye suspension;

[0020] (e) Add the fluorescent dye suspension obtained in step (d) to the hydrogen peroxide gel obtained in step (b), stir evenly and mix well, and let it stand at normal temperature and pressure for 3-5 h to obtain a long-luminescence hydrogen peroxide gel.

[0021] In the preparation method provided by the present invention, a glycyrrhizic acid compound and polyvinyl alcohol interact through non-covalent bonds and crosslink with each other in a hydrogen peroxide solution to form a hydrogen peroxide gel with a three-dimensional network structure. By simply mixing and homogenizing a saturated solution of an oxalate compound and a phthalate, adding a fluorescent dye to obtain a fluorescent dye suspension, adding the fluorescent dye suspension to the hydrogen peroxide gel, stirring evenly, and utilizing the thixotropy of the gel to restore the gel state and slowly release hydrogen peroxide, long-term luminescence is achieved; the preparation method has a simple process, cheap and easily available raw materials, low cost, and meets the requirements of industrial production.

[0022] In some embodiments, in step (a), the stirring rate is 300-3000 r / min, and the time is 0.1-5 h.

[0023] In some embodiments, the stirring in step (b) is carried out at a rate of 300 - 3000 r / min for 0.5 - 5 h.

[0024] The hydrogen peroxide gel obtained in step (b) can be stored at low temperature, and the low temperature storage temperature is -5 - 10°C.

[0025] In some embodiments, the stirring in step (c) is carried out at a rate of 300 - 3000 r / min for 0.5 - 5 h.

[0026] In some embodiments, the stirring in step (d) is carried out at a rate of 300 - 3000 r / min for 0.1 - 1 h.

[0027] In some embodiments, the stirring in step (e) is carried out at a rate of 300 - 3000 r / min for 0.1 - 1 h.

[0028] Adopting the above stirring rate, stirring time, and storage temperature helps to dissolve glycyrrhizin compounds and polyvinyl alcohol more efficiently, helps to better form a three-dimensional spatial network structure, and helps to extend the gel storage time.

[0029] In a third aspect, there is provided the application of the hydrogen peroxide gel and / or the hydrogen peroxide gel prepared by the preparation method in glow sticks and outdoor cold light sources.

[0030] The hydrogen peroxide gel provided by the present invention has a long storage time, good thixotropy, can achieve self-recovery after shear stirring, has a luminescence time up to 216 h, and can emit light 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

[0031] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0032] Figure 1 is one of the atomic force microscope images of the hydrogen peroxide gel that can emit light for a long time provided by the present invention.

[0033] Figure 2 is one of the atomic force microscope images of the comparative example of the hydrogen peroxide gel that can emit light for a long time provided by the present invention.

[0034] Figure 3One of the thixotropy test results of the hydrogen peroxide gel containing glycyrrhizin compounds provided by the present invention.

[0035] Figure 4 Another thixotropy test result of the hydrogen peroxide gel containing glycyrrhizin compounds provided by the present invention.

[0036] Figure 5 Another thixotropy test result of the hydrogen peroxide gel containing glycyrrhizin compounds provided by the present invention.

[0037] Figure 6 Another thixotropy test result of the hydrogen peroxide gel containing glycyrrhizin compounds provided by the present invention.

[0038] Figure 7 One of the graphs of the luminescence time test results of the hydrogen peroxide gel capable of long-term luminescence provided by the present invention.

[0039] Figure 8 Another graph of the luminescence time test results of the hydrogen peroxide gel capable of long-term luminescence provided by the present invention.

[0040] Figure 9 One of the graphs of the luminescence color of the hydrogen peroxide gel capable of long-term luminescence provided by the present invention. Detailed implementation manners

[0041] Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0042] In the first aspect of the present invention, the present invention provides a hydrogen peroxide gel capable of long-term luminescence. By weight, its raw materials include: 70-90 parts of hydrogen peroxide solution, 1-5 parts of glycyrrhizin 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 dyes; 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 ranges composed 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.

[0043] 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 it can also be a range formed by combining these point values, such as 10% - 20%, 10 - 25%, 15 - 25%, 15 - 20%, etc.

[0044] In some embodiments, the glycyrrhizin compounds are selected from at least one of glycyrrhizin, dipotassium glycyrrhizinate, ammonium glycyrrhizinate, diammonium glycyrrhizinate, trisodium glycyrrhizinate, and glycyrrhetinic acid.

[0045] In some embodiments, the average molecular weight of the polyvinyl alcohol is 80,000 - 200,000. Preferably, the average molecular weight of the polyvinyl alcohol is 80,000 - 120,000, such as 80,000, 90,000, 100,000, 110,000, 120,000 or other molecular weights, or it can also be a range formed by these point values; the degree of alcoholysis of the polyvinyl alcohol is 80 - 99%. Preferably, the degree of alcoholysis is 87 - 99%, such as 87%, 88%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or it can also be a range formed by these point values, such as 90% - 99%, 95% - 99%, etc.

[0046] In some embodiments, the oxalate compounds are 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 compounds are selected from at least one of bis[2,4,5 - trichloro - 6 - (pentyloxycarbonyl)phenyl] oxalate and bis(2,4 - dinitrophenyl) oxalate.

[0047] In some embodiments, the fluorescent dyes are at least one of rhodamine B, eosin Y, 5,6,11,12 - tetraphenyltetracene, 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 dyes are at least one of rhodamine B, 5,6,11,12 - tetraphenyltetracene, 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.

[0048] 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.

[0049] On the other hand, the embodiments of the present invention provide a method for preparing the above-mentioned hydrogen peroxide gel that can emit light for a long time, including the following steps:

[0050] (a) At a temperature of 40-60°C and normal pressure, add a glycyrrhizic acid compound to a hydrogen peroxide solution, and stir until it is completely dispersed or dissolved to obtain a hydrogen peroxide solution A containing the glycyrrhizic acid compound;

[0051] (b) At a temperature of 40-60°C and normal pressure, add polyvinyl alcohol to a hydrogen peroxide solution, stir until it is completely dispersed or dissolved, add sodium salicylate at normal temperature and normal pressure, and stir until it is completely dispersed or dissolved to obtain a hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate; Take the hydrogen peroxide solution B and add it to the hydrogen peroxide solution A obtained in step (a), shake and mix well, and then stand at normal temperature and normal pressure for 3-5 h to obtain a hydrogen peroxide gel, which is stored at a low temperature;

[0052] (c) At a temperature of 70-90°C and normal pressure, add an oxalate compound to a phthalate compound, and stir until it is completely dispersed or dissolved to obtain a saturated oxalate solution;

[0053] (d) At normal temperature and normal pressure, add a fluorescent dye to the saturated oxalate solution obtained in step (c), and stir until it is completely dispersed to obtain a fluorescent dye suspension;

[0054] (e) Add the fluorescent dye suspension obtained in step (d) to the hydrogen peroxide gel obtained in step (b), stir evenly and mix well, and stand at normal temperature and normal pressure for 3-5 h to obtain a long-lasting luminous hydrogen peroxide gel.

[0055] Among them, in steps (b) and (e), the standing time can be 3 h, 3.5 h, 4 h, 4.5 h, 5 h, etc., or it can be a range composed of these specific times, such as 3-4 h, 3.5-4.5 h, etc.

[0056] In some embodiments, for the stirring in step (a), the rate is 300 to 3000 r / min, preferably 600 to 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 rotational speeds, or 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 to 5 h; preferably 0.3 to 2.5 h, for example 0.3 h, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h or other times, or 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.

[0057] In some embodiments, for the stirring in step (b), the rate is 300 to 3000 r / min, preferably 600 to 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 rotational speeds, or 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 0.5 to 5 h, preferably 2 to 5 h, for example 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h or other times, or can also be a range composed of these point values, such as 2 - 4 h, 3 - 5 h, 2.5 - 3.5 h, etc.; the temperature for low-temperature storage is -5 to 10 °C; preferably -5 to 5 °C, for example -5 °C, 0 °C, 5 °C or other temperatures, or can also be a range composed of these point values, such as -5~0 °C, 0~-5 °C, etc.

[0058] In some embodiments, for the stirring in step (c), the rate is 300 to 3000 r / min, preferably 600 to 1000 r / min, such as 600 r / min, 700 r / min, 800 r / min, 900 r / min, 1000 r / min or other rotational speeds, or 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 to 5 h; preferably 2 to 5 h, for example 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h or other times, or can also be a range composed of these point values, such as 2 - 4 h, 3 - 5 h, 2.5 - 3.5 h, etc.

[0059] In some embodiments, for the stirring in step (d), the rate 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 rotational 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.

[0060] In some embodiments, for the stirring in step (e), the rate 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 rotational 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 0.1 - 0.5 h, for example 0.1 h, 0.2 h, 0.3 h, 0.4 h, 0.5 h, or other times, and can also be a range composed of these point values, such as 0.1 - 0.3 h, 0.2 - 0.5 h, etc.

[0061] The hydrogen peroxide gel provided in the embodiment part of the present invention and / or the hydrogen peroxide gel prepared by the preparation method can have a luminescence duration of up to 216 hours, and can be applied to fluorescent rods and outdoor cold light sources to meet the need for long - time luminescent cold light sources.

[0062] In the examples, the information of each raw material is shown in the following table.

[0063]

[0064] In the examples, for those without specifying specific techniques or conditions, they are carried out according to the techniques or conditions described in the literature in this field or according to the product instructions. For reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0065] In actual examples, when referring to concentration, it refers to the mass fraction and mass percentage described above.

[0066] Next, with reference to specific examples, the present invention will be described. It should be noted that these examples are only descriptive and do not limit the present invention in any way.

[0067] Example 1

[0068] This embodiment provides a hydrogen peroxide gel that can emit light for a long time, and its raw material composition is shown in Table 1.

[0069] Table 1 Raw material formula composition

[0070]

[0071] This embodiment also provides a preparation method of the above hydrogen peroxide gel that can emit light for a long time, including the following steps:

[0072] (a) Weigh 200 mg of glycyrrhizic acid and add it to 4.36 ml of a 30% hydrogen peroxide solution. Stir at a temperature of 40 °C and normal pressure at a rotation speed of 1000 r / min for 0.5 h until completely dissolved to obtain hydrogen peroxide solution A containing glycyrrhizic acid compounds.

[0073] (b) Weigh 60 mg of polyvinyl alcohol and add it to 2 ml of hydrogen peroxide solution. Stir at a temperature of 40 °C and normal pressure at a rotation speed of 1500 r / min for 3 h until completely dissolved. Weigh 50 mg of sodium salicylate and add it to this solution. Stir at a temperature of 40 - 60 °C and normal pressure at a rotation speed of 800 r / min for 0.5 h until completely dissolved to obtain hydrogen peroxide solution B containing polyvinyl alcohol and sodium salicylate. Subsequently, add 2 ml of the hydrogen peroxide solution B to the hydrogen peroxide solution A obtained in step (a), shake and mix well. Let the resulting mixture stand at normal temperature and pressure for 3 h to obtain the hydrogen peroxide gel, and store it at 5 °C.

[0074] (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 a temperature of 80 °C and normal pressure at a rotation speed of 1500 r / min for 3 h until completely dissolved to obtain an oxalate solution.

[0075] (d) Weigh 200 mg of 5,6,11,12-tetraphenyltetracene and add it to the oxalate solution obtained in step (c). Stir at normal temperature and pressure at a rotation speed of 800 r / min for 0.5 h until completely dispersed to obtain a fluorescent dye suspension.

[0076] (e) Measure 1 ml of the fluorescent dye suspension obtained in step (d) and add it to the hydrogen peroxide gel obtained in step (b). Stir at normal temperature and pressure at a rotation speed of 1000 r / min for 0.1 h until completely dispersed, and let it stand at normal temperature and pressure for 3 h to obtain 10 ml of a hydrogen peroxide gel that can emit light for a long time.

[0077] Example 2

[0078] This embodiment provides a hydrogen peroxide gel that can emit light for a long time, and its components and mass ratios are shown in Table 2.

[0079] Components and mass ratios contained in Table 2

[0080]

[0081] This example also provides a method for preparing the above-mentioned hydrogen peroxide gel that can emit light for a long time, including the following steps:

[0082] (a) Weigh 300 mg of glycyrrhizic acid and add it to 6.26 ml of a 10% hydrogen peroxide solution. Stir at a temperature of 60 °C and normal pressure at a rotation speed of 800 r / min for 0.3 h until completely dissolved to obtain hydrogen peroxide solution A containing glycyrrhizic acid compounds.

[0083] (b) Weigh 100 mg of polyvinyl alcohol and add it to 1.5 ml of a 10% hydrogen peroxide solution. Stir at a temperature of 40 °C and normal pressure at a rotation speed of 1000 r / min for 3 h until completely dissolved. After cooling to room temperature, weigh 50 mg of sodium salicylate and add it to the solution. Stir at a temperature of 40 - 60 °C and normal pressure at a 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, add 1.5 ml of the hydrogen peroxide solution B to the hydrogen peroxide solution obtained in step (a), shake and mix well, and let the resulting mixture stand at room temperature and normal pressure for 3 h to obtain a hydrogen peroxide gel, which is stored at 5 °C.

[0084] (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 a temperature of 90 °C and normal pressure at a rotation speed of 1500 r / min for 3 h until completely dissolved to obtain an oxalate solution.

[0085] (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 normal pressure at a rotation speed of 800 r / min for 0.5 h until completely dispersed to obtain a fluorescent dye suspension.

[0086] (e) Measure 0.5 ml of the fluorescent dye suspension obtained in step (d) and add it to the hydrogen peroxide gel obtained in step (b). Stir at room temperature and normal pressure at a rotation speed of 1000 r / min for 0.3 h until completely dispersed, and let it stand at room temperature and normal pressure for 3 h to obtain 10 ml of a hydrogen peroxide gel that can emit light for a long time.

[0087] Example 3

[0088] This example provides a hydrogen peroxide gel that can emit light for a long time, and the components and mass ratios it contains are shown in Table 3.

[0089] Table 3 Components and mass ratios contained

[0090]

[0091] This example also provides a preparation method of the above-mentioned hydrogen peroxide gel that can emit long-lasting light, including the following steps:

[0092] (a) Weigh 300 mg of glycyrrhizic acid and add it to 2.94 ml of a 50% hydrogen peroxide solution. Stir at a temperature of 40 °C and normal pressure at a rotation speed of 800 r / min for 0.3 h until completely dissolved to obtain hydrogen peroxide solution A containing glycyrrhizic acid compounds.

[0093] (b) Weigh 160 mg of polyvinyl alcohol and add it to 2 ml of hydrogen peroxide solution. Stir at a temperature of 40 °C and normal pressure at a rotation speed of 1000 r / min for 3 h until completely dissolved. After cooling to room temperature, weigh 30 mg of sodium salicylate and add it to the solution. Stir at a temperature of 40 - 60 °C and normal pressure at a 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, add 2 ml of the solution obtained from hydrogen peroxide solution B to the hydrogen peroxide solution obtained in step (a), shake and mix well, and let the resulting mixture stand at room temperature and normal pressure for 2 h to obtain hydrogen peroxide gel, which is stored at 5 °C.

[0094] (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 a temperature of 80 °C and normal pressure at a rotation speed of 1000 r / min for 3 h until completely dissolved to obtain an oxalate solution.

[0095] (d) Weigh 300 mg of 9,10-diphenylanthracene and add it to the oxalate solution obtained in step (c). Stir at room temperature and normal pressure at a rotation speed of 800 r / min for 0.5 h until completely dispersed to obtain a fluorescent dye suspension.

[0096] (e) Measure 1 ml of the fluorescent dye suspension obtained in step (d) and add it to the hydrogen peroxide gel obtained in step (b). Stir at room temperature and normal pressure at a rotation speed of 1000 r / min for 0.2 h until completely dispersed, and let it stand at room temperature and normal pressure for 3 h to obtain 10 ml of long-lasting light-emitting hydrogen peroxide gel.

[0097] Example 4

[0098] This example provides a hydrogen peroxide gel that can emit long-lasting light, which is basically the same as Example 1, except that the concentration of the hydrogen peroxide solution is 25%.

[0099] Comparative Example 1

[0100] This comparative example provides a hydrogen peroxide gel, which is basically the same as Example 1, except that polyvinyl alcohol is not added.

[0101] Test Example 1

[0102] Test objects: The hydrogen peroxide gels obtained in Example 1 and Comparative Example 1.

[0103] Test method: Observe the internal structure of the hydrogen peroxide gel by atomic force microscopy (AFM). The information of the atomic force microscopy is as follows: Observe the internal structure of the hydrogen peroxide gel by atomic force microscopy (AFM). The information of the atomic force microscopy is as follows: Bruker Nanoscope, measured in Fast-scan mode using Fast-scanB trip.

[0104] Test results: The AFM images of the hydrogen peroxide gels obtained in Example 1 and Comparative Example 1 are respectively as Figure 1 and Figure 2 shown.

[0105] From Figure 1 and Figure 2 it can be seen that polyvinyl alcohol was added in Example 1, and the glycyrrhizic acid fibers were coated with polyvinyl alcohol. In Comparative Example 1, polyvinyl alcohol was not added and existed in the form of nanofibers, indicating that polyvinyl alcohol and glycyrrhizic acid fibers were crosslinked and tightly bound together, improving the mechanical properties of the gel and endowing the gel with thixotropy.

[0106] Test Example 2 Thixotropy detection

[0107] Test objects: The hydrogen peroxide gels obtained in Example 1 and Comparative Example 1.

[0108] Test method: Measure the storage modulus of the gel under low deformation and high deformation by a rheometer to verify the thixotropy of the gel. The information of the rheometer is as follows: HAKKE MARS40, ThermoFisher.

[0109] Test results: The thixotropy tests of the hydrogen peroxide gels obtained in Example 1 and Comparative Example 1 are respectively as Figure 3 , Figure 4 , Figure 5 , Figure 6 shown.

[0110] From Figure 3 and Figure 4 it can be seen that the hydrogen peroxide gel obtained in Example 1 can resume the gel state after a short static rest after being damaged by high deformation. From Figure 5 and Figure 6It can be seen from the comparative example 1 that it cannot be restored. These results show that the hydrogen peroxide gel obtained in Example 1 has thixotropy and self-recovery of the gel state.

[0111] Test Example 3 Luminescence Time

[0112] Test objects: Hydrogen peroxide gels obtained in Example 1 and Comparative Example 1.

[0113] Test method: The luminescence intensity of the samples was measured by a steady-state / transient fluorescence spectrometer NanoLOG-TCSPC, and the luminescence intensity and luminescence time were recorded.

[0114] Test results: The luminescence test results of the hydrogen peroxide gels obtained in Example 1 and Comparative Example 1 are as Figure 7 、 Figure 8 shown.

[0115] 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 h, and the luminescence time of the hydrogen peroxide gel in Comparative Example 1 is 72 h; it shows that using the hydrogen peroxide gel provided by the present invention (especially Example 1) can significantly increase the luminescence time.

[0116] Test Example 4 Luminescence Color

[0117] Test objects: Hydrogen peroxide gels obtained in Examples 1, 2, and 3.

[0118] Test method: The hydrogen peroxide gels obtained in Examples 1, 2, and 3 were placed in the dark, and the luminescence color was observed and photographed.

[0119] Test results: As Figure 9 shown, from left to right are the luminescence color results of the hydrogen peroxide gels obtained in Examples 1, 2, and 3. The luminescence color results show that different luminescence colors can be obtained by adding different fluorescent dyes.

[0120] 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 them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate 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%; The glycyrrhizic acid compound is selected from at least one of glycyrrhizic acid, dipotassium glycyrrhizinate, ammonium glycyrrhizinate, diammonium glycyrrhizinate, trisodium glycyrrhizinate and glycyrrhetinic acid.

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, 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%.

4. The hydrogen peroxide gel according to any one of claims 1 to 3, 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.

5. The hydrogen peroxide gel according to any one of claims 1 to 3, 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.

6. The hydrogen peroxide gel according to any one of claims 1 to 3, characterized in that: The phthalate compound is selected from at least one of dimethyl phthalate, diethyl phthalate, dipropyl phthalate and dibutyl phthalate.

7. The method for preparing the hydrogen peroxide gel according to any one of claims 1 to 6, 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.

8. The preparation method according to claim 7, 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.

9. Use of the hydrogen peroxide gel according to any one of claims 1 to 6 and / or the hydrogen peroxide gel prepared by the preparation method according to claim 7 or 8 in fluorescent sticks and outdoor cold light sources.

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