Hydrogen peroxide gel containing amphiphilic Bola molecules and its preparation method

Abstract

This invention relates to the field of hydrogen peroxide gel technology, specifically to a hydrogen peroxide gel containing amphiphilic Bola molecules and its preparation method. The gel comprises, by mass percentage: 93-99.4 wt% of a hydrogen peroxide aqueous solution (30-98%); 0.5-5 wt% of a gelling agent; and 0.1-2 wt% of a stabilizer. The gelling agent is an amphiphilic Bola molecule, HDGA, synthesized with glutamic acid as the hydrophilic head group and a long alkyl chain as the hydrophobic chain. The preparation method involves heating and cooling HDGA in a hydrogen peroxide solution system to obtain a hydrogen peroxide hydrogel with a three-dimensional network structure. The preparation method provided by this invention is simple, and the prepared hydrogen peroxide hydrogel exhibits stable low-temperature performance, is easy to store and transport, and shows enhanced flowability after shearing, making it convenient for use.

Description

Technical Field

[0001] This invention relates to the field of hydrogen peroxide gel technology, and more particularly to a hydrogen peroxide gel containing amphiphilic Bola molecules and its preparation method. Background Technology

[0002] Amphiphiles are the earliest studied and most common building blocks of supramolecular gels. They typically consist of a hydrophilic head group (usually composed of amino acids, carboxylic acids, phosphates, etc.) and a hydrophobic tail chain (usually composed of long fatty acid chains), linked by covalent bonds to form compounds that are both hydrophilic and hydrophobic. The hydrogen bonds and electrostatic interactions between the hydrophilic head groups and the hydrophobic interactions between the alkyl tail chains give amphiphiles strong intermolecular interactions, allowing them to assemble into monolayer or bilayer structures in solvents, and further form one-dimensional nanostructures such as nanofibers, nanotubes, and nanobelts, while simultaneously gelling the solvent. The structure of the amphiphilic molecule directly affects the nanostructure of the resulting supramolecular gel, and the shape of the nanostructure is closely related to its function.

[0003] Hydrogen peroxide is a high-density, strong oxidizing liquid composed of hydrogen and oxygen. Its decomposition products are water and oxygen. Due to its high energy and environmentally friendly decomposition products, it has become a research hotspot in propellants and other fields in various countries. However, the strong oxidizing, flammable, explosive, and easily flowing characteristics of hydrogen peroxide liquid pose a great risk of leakage during application. The gelation of hydrogen peroxide can help reduce the risk of leakage due to its liquid flow dynamics and increase the safety factor during storage, transportation, and application.

[0004] In view of this, it is necessary to provide an improved hydrogen peroxide gel containing amphiphilic Bola molecules and a method for preparing the same, in order to solve the above problems. Summary of the Invention

[0005] The purpose of this invention is to provide a hydrogen peroxide gel containing amphiphilic Bola molecules and its preparation method, in order to overcome the defects of hydrogen peroxide in the prior art, such as high fluidity and difficulty in storage.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a hydrogen peroxide gel, comprising, by weight percentage:

[0007] Hydrogen peroxide aqueous solution with a mass fraction of 30-98%: 93-99.4 wt%;

[0008] Gelling agent: 0.5%–5 wt%;

[0009] Stabilizer: 0.1–2 wt%;

[0010] The structural formula of the gelling agent is as follows:

[0011]

[0012] The value of n ranges from 10 to 16.

[0013] This invention adds a gelling agent to an aqueous hydrogen peroxide solution, forming a semi-solid with a three-dimensional network structure through physical or chemical cross-linking. This confines the hydrogen peroxide solution as a dispersion medium within the voids of the three-dimensional network formed by the cross-linking agent, effectively reducing the fluidity of the hydrogen peroxide solution and minimizing the risk of leakage. If the hydrogen peroxide content in the aqueous solution is too low, the relative hydrogen peroxide content in the gel will decrease, indirectly increasing its usage cost. If the gelling agent content is too low, it is difficult to form a gel with a three-dimensional network structure; if the content is too high, it is prone to agglomeration and precipitation, affecting the uniformity and stability of the gel.

[0014] Furthermore, the stabilizer includes one or more of phosphoric acid, sodium silicate, ATMP (aminotrimethylphosphonic acid), EDTMP (ethylenediaminetetramethylphosphonic acid), DETPMP (diethylenetriaminepentamethylenephosphonic acid), HEDP (hydroxyethylidene diphosphonic acid), Span 80, and Tween 60. The stabilizer is preferably at least one of phosphoric acid, ATMP, EDTMP, DETPMP, and HEDP.

[0015] Secondly, the present invention provides a method for preparing the above-mentioned hydrogen peroxide gel, comprising: adding a gelling agent to an aqueous hydrogen peroxide solution, heating to dissolve, and obtaining a transparent hydrogen peroxide solution; then adding a stabilizer, mixing evenly, cooling and allowing to stand, and obtaining a hydrogen peroxide hydrogel, which is then stored at low temperature.

[0016] Furthermore, the heating and melting temperature is 30-60℃, preferably 35-50℃;

[0017] And / or, the stirring rate for heating and dissolving is 200-2000 r / min, preferably 500-1000 r / min; the time is 0.1-0.5 h, preferably 0.1-0.3 h.

[0018] Furthermore, the temperature for cooling and settling is 10-25℃;

[0019] And / or, the temperature for cryopreservation is -10 to 5°C, preferably -5 to 5°C.

[0020] The stirring rate after adding the stabilizer is 200-2000 r / min, preferably 600-1200 r / min; the stirring time is 0.1-0.5 h, preferably 0.1-0.3 h.

[0021] Furthermore, the gelling agent is an amphiphilic Bola molecule HDGA gelling agent, which is synthesized by using glutamic acid as the hydrophilic head group and a long alkyl chain as the hydrophobic chain. The preparation method includes the following steps:

[0022] S1. An amidation reaction is carried out between an alkyl diacid and diethyl glutamic acid hydrochloride to obtain compound B;

[0023] S2. Hydrolyze the compound B, then add acid to adjust the pH to obtain the gelling agent.

[0024] This invention utilizes the amphiphilic Bola molecule HDGA as a gelling agent, enabling the gelation of high-concentration hydrogen peroxide to obtain a hydrogen peroxide hydrogel with a three-dimensional network structure. Furthermore, the formulation is simple, reproducible, and low-cost, and gels readily form at room temperature and pressure. The resulting hydrogen peroxide gel exhibits strong fluidity under shear force, allowing it to flow like a liquid when squeezed or pumped, facilitating storage, transportation, and utilization.

[0025] Further, step S1 includes: adding the alkyl diacid, carbodiimide hydrochloride and 1-hydroxybenzotriazole to an organic solvent, mixing them evenly, then adding the diethyl glutamate hydrochloride, stirring the reaction to obtain compound B.

[0026] The stirring rate in step S1 is 200–2500 r / min, preferably 500–1200 r / min; the time is 1–3 days, preferably 1–2 days.

[0027] Furthermore, the organic solvent includes one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, ethyl acetate, acetonitrile, or acetone, preferably at least one of tetrahydrofuran, dichloromethane, and chloroform.

[0028] Further, step S2 includes: adding an aqueous NaOH solution to the compound B and stirring until clear; then adding at least one of hydrochloric acid, sulfuric acid, and acetic acid to adjust the pH to 0-3, obtaining a white precipitate, filtering and drying to obtain the gelling agent. The acid is preferably at least one of hydrochloric acid and sulfuric acid.

[0029] The stirring rate in step S2 is 200–2500 r / min, preferably 600–1200 r / min; the time is 2–10 h, preferably 3–6 h.

[0030] Furthermore, the structural formula of the alkyl diacid is as follows:

[0031]

[0032] And / or, the structural formula of compound B is as follows:

[0033]

[0034] And / or, the structural formula of the gelling agent is as follows:

[0035]

[0036] The value of n ranges from 10 to 16.

[0037] Specifically, the preparation flow chart of the amphiphilic Bola molecule HDGA gelling agent is as follows:

[0038]

[0039] The beneficial effects of this invention are as follows:

[0040] The hydrogen peroxide gel provided by this invention uses the amphiphilic Bola molecule HDGA as a gelling agent, which enables the gelation of high-concentration hydrogen peroxide. Furthermore, the formulation is simple, reproducible, and low-cost, and gels at room temperature and pressure. The resulting hydrogen peroxide gel exhibits strong fluidity under shear force, allowing it to flow like a liquid when squeezed or pumped, facilitating storage, transportation, and utilization. Attached Figure Description

[0041] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0042] Figure 1 The image shows a scanning electron microscope (SEM) image of the hydrogen peroxide gel containing the amphiphilic Bola molecule HDGA prepared in Example 3.

[0043] Figure 2 This is a scanning electron microscope (SEM) image of the HDGA hydrogen peroxide gel containing amphiphilic Bola molecules prepared in Example 3, under another scale.

[0044] Figure 3 The image shows the hydrogen peroxide gel containing amphiphilic Bola molecules (HDGA) prepared in Example 3, placed upside down in a bottle.

[0045] Figure 4 This is a photograph of the extrusion process of the HDGA hydrogen peroxide gel containing amphiphilic Bola molecules prepared in Example 3. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention are described clearly and completely below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0047] Example 1

[0048] A hydrogen peroxide gel, comprising, by weight percentage:

[0049] A 30% hydrogen peroxide aqueous solution: 94.5 wt%;

[0050] Gelling agent 10-HDGA: 5wt%;

[0051] Stabilizer ATMP: 0.5 wt%. Preparation method is as follows:

[0052] a. In a single-necked flask, add decadecanoic acid, EDCI (carbodiimide hydrochloride), HOBT (1-hydroxybenzotriazole), and dichloromethane. Mix and stir at room temperature for half an hour, then add L-glutamic acid diethyl ester hydrochloride. Continue stirring at room temperature for 24 hours. Monitor the reaction for completion by TLC (methanol:dichloromethane = 1:50). Adjust the pH to 5-6 with HCl, wash the organic phase three times with distilled water, combine the organic phases, dry them with anhydrous MgSO4, and rotary evaporate to give a pale yellow solid. Column chromatography (ethyl acetate / petroleum ether = 1:1) gives a white solid.

[0053] b. Add NaOH aqueous solution to the obtained white solid, stir at 40℃ for 3h until clear, filter, take the clear mother liquor, adjust pH=1 with HCl aqueous solution, a white precipitate appears, filter, take the filter cake and freeze dry to obtain the target product 10-HDGA.

[0054] c. At room temperature and pressure, add 5% 10-HDGA gelling agent to a 30% hydrogen peroxide aqueous solution, stir until the gelling agent is completely dispersed or dissolved, and heat in a water bath to 40°C to obtain a transparent hydrogen peroxide solution.

[0055] d. Add 0.5% ATMP stabilizer to the hydrogen peroxide solution obtained in step c, stir until uniformly mixed, let stand at room temperature to obtain hydrogen peroxide hydrogel, and store at -5℃.

[0056] Example 2

[0057] A hydrogen peroxide gel, comprising, by weight percentage:

[0058] A 50% hydrogen peroxide aqueous solution: 96.5 wt%;

[0059] Gelling agent 12-HDGA: 3wt%;

[0060] Stabilizer ATMP: 0.5 wt%. Preparation method is as follows:

[0061] a. In a single-necked flask, add dodecanoic acid, EDCI, HOBT, and dichloromethane. Mix and stir at room temperature for half an hour, then add L-glutamic acid diethyl ester hydrochloride. Continue stirring at room temperature for 26 hours. Monitor the reaction for completion by TLC (methanol:dichloromethane = 1:50). Adjust the pH to 5-6 with HCl, wash the organic phase three times with distilled water, combine the organic phases, dry them with anhydrous MgSO4, and rotary evaporate to give a pale yellow solid. Column chromatography (ethyl acetate / petroleum ether = 1:1) gives a white solid.

[0062] b. Add NaOH aqueous solution to the obtained white solid, stir at 40℃ for 3h until clear, filter, take the clear mother liquor, adjust pH=1 with HCl aqueous solution, a white precipitate appears, filter, take the filter cake and freeze dry to obtain the target product 12-HDGA.

[0063] c. At room temperature and pressure, add 3% 12-HDGA gelling agent to a 50% hydrogen peroxide aqueous solution, stir until the gelling agent is completely dispersed or dissolved, and heat in a water bath to 45°C to obtain a transparent hydrogen peroxide solution.

[0064] d. Add 0.5% ATMP stabilizer to the hydrogen peroxide solution obtained in step c, stir until homogeneous, let stand at room temperature to obtain hydrogen peroxide hydrogel, and store at 0℃.

[0065] Example 3

[0066] A hydrogen peroxide gel, comprising, by weight percentage:

[0067] A 98% hydrogen peroxide aqueous solution: 97.8 wt%;

[0068] Gelling agent 15-HDGA: 2wt%;

[0069] Stabilizer ATMP: 0.2 wt%. Preparation method is as follows:

[0070] a. In a single-necked flask, add pentadecanoic acid, EDCI, HOBT, and dichloromethane. Mix and stir at room temperature for half an hour, then add L-glutamic acid diethyl ester hydrochloride. Continue stirring at room temperature for 30 hours. Monitor the reaction for completion by TLC (methanol:dichloromethane = 1:50). Adjust the pH to 5-6 with HCl, wash the organic phase three times with distilled water, combine the organic phases, dry them with anhydrous MgSO4, and rotary evaporate to give a pale yellow solid. Column chromatography (ethyl acetate / petroleum ether = 1:1) gives a white solid.

[0071] b. Add NaOH aqueous solution to the obtained white solid, stir at 40℃ for 3.5h until clear, filter, take the clear mother liquor, adjust the pH to 1 with HCl aqueous solution, a white precipitate appears, filter, take the filter cake and freeze dry to obtain the target product 15-HDGA.

[0072] c. At room temperature and pressure, add 2% 15-HDGA gelling agent to a 98% hydrogen peroxide aqueous solution, stir until the gelling agent is completely dispersed or dissolved, and heat in a water bath to 45°C to obtain a transparent hydrogen peroxide solution.

[0073] d. Add 0.2% ATMP stabilizer to the hydrogen peroxide solution obtained in step c, stir until homogeneous, let stand at room temperature to obtain hydrogen peroxide hydrogel, and store at 5°C.

[0074] like Figure 1 and 2 As shown, hydrogen peroxide hydrogel forms a three-dimensional network structure under the action of gelling agent 10-HDGA.

[0075] like Figure 3 As shown (the left side is the initial state, and the right side is the state after one week), it can be seen that when the hydrogen peroxide hydrogel is placed in the bottle upside down, the gel basically does not flow under the influence of gravity, indicating that its fluidity is significantly reduced compared to hydrogen peroxide solution, making it easier to store stably.

[0076] Figure 4 The top part is a pressurization device that applies atmospheric pressure to the system. After pressurization, the gel is extruded like a fluid. The hydrogen peroxide gel in the storage tank can still be transported to the application end through the connected pipeline by simply pressurizing it, just like hydrogen peroxide solution, which improves storage safety while still being easy to use.

[0077] Example 4

[0078] A hydrogen peroxide gel, comprising, by weight percentage:

[0079] A 90% hydrogen peroxide aqueous solution: 97.8 wt%;

[0080] Gelling agent 16-HDGA: 2wt%;

[0081] Stabilizer ATMP: 0.2 wt%. Preparation method is as follows:

[0082] a. In a single-necked flask, hexadecanoic acid, EDCI, HOBT, and dichloromethane were added and stirred at room temperature for half an hour. Then, L-glutamic acid diethyl ester hydrochloride was added. The mixture was stirred at room temperature for another 36 hours. The reaction was monitored by TLC (methanol:dichloromethane = 1:50) to indicate completion. The pH was adjusted to 5-6 with HCl, and the organic phase was washed three times with distilled water. The combined organic phases were dried over anhydrous MgSO4 and rotary evaporated to give a pale yellow solid. Column chromatography (ethyl acetate / petroleum ether = 1:1) yielded a white solid.

[0083] b. Add NaOH aqueous solution to the obtained white solid, stir at 50℃ for 4h until clear, filter, take the clear mother liquor, adjust pH=1 with HCl aqueous solution, a white precipitate appears, filter, take the filter cake and freeze dry to obtain the target product 16-HDGA.

[0084] c. At room temperature and pressure, add 2% 16-HDGA gelling agent to a 90% hydrogen peroxide aqueous solution, stir until the gelling agent is completely dispersed or dissolved, and heat in a water bath to 50°C to obtain a transparent hydrogen peroxide solution.

[0085] d. Add 0.2% ATMP stabilizer to the hydrogen peroxide solution obtained in step c, stir until homogeneous, let stand at room temperature to obtain hydrogen peroxide hydrogel, and store at 5°C.

[0086] Hydrogen peroxide gels were obtained in Examples 1-4, with slight differences in fluidity.

[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A hydrogen peroxide gel, characterized in that, Included by mass percentage: Hydrogen peroxide aqueous solution with a mass fraction of 30-98%: 93-99.4%; Gelling agent: 0.5-5%; Stabilizer: 0.1–2%; The structural formula of the gelling agent is as follows: The value of n is in the range of 10-16.

2. The hydrogen peroxide gel according to claim 1, characterized in that, The stabilizer includes one or more of phosphoric acid, sodium silicate, ATMP, EDTMP, DETPMP, HEDP, Span 80, and Tween 60.

3. A method for preparing the hydrogen peroxide gel according to claim 1 or 2, characterized in that, include: Add a gelling agent to an aqueous solution of hydrogen peroxide and heat to dissolve it; then add a stabilizer, mix well, cool and let stand to obtain hydrogen peroxide hydrogel.

4. The method for preparing hydrogen peroxide gel according to claim 3, characterized in that, The heating and melting temperature is 30-60℃; And / or, the stirring rate for heating and dissolving is 200-2000 r / min, and the time is 0.1-0.5 h.

5. The method for preparing hydrogen peroxide gel according to claim 4, characterized in that, The heating and melting temperature is 35–50°C.

6. The method for preparing hydrogen peroxide gel according to claim 3, characterized in that, The temperature for cooling and settling is 10-25℃; And / or, the hydrogen peroxide hydrogel is stored at a low temperature of -10 to 5°C.

7. The method for preparing hydrogen peroxide gel according to any one of claims 3-6, characterized in that, The preparation method of the gelling agent includes the following steps: S1. An amidation reaction is carried out between an alkyl diacid and diethyl glutamate hydrochloride to obtain compound B; S2. Hydrolyze the compound B, then add acid to adjust the pH to obtain the gelling agent.

8. The method for preparing hydrogen peroxide gel according to claim 7, characterized in that, Step S1 includes: adding the alkyl diacid, carbodiimide hydrochloride and 1-hydroxybenzotriazole to an organic solvent, mixing them evenly, then adding the diethyl glutamic acid hydrochloride, stirring the reaction to obtain compound B.

9. The method for preparing hydrogen peroxide gel according to claim 8, characterized in that, The organic solvent includes one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, ethyl acetate, acetonitrile, or acetone.

10. The method for preparing hydrogen peroxide gel according to claim 9, characterized in that, The organic solvent is at least one of tetrahydrofuran, dichloromethane, and chloroform.

11. The method for preparing hydrogen peroxide gel according to claim 7, characterized in that, Step S2 includes: adding NaOH aqueous solution to compound B and stirring until clear; then adding at least one of hydrochloric acid, sulfuric acid and acetic acid to adjust the pH to 0-3, obtaining a white precipitate, filtering and drying to obtain the gelling agent.

12. The method for preparing hydrogen peroxide gel according to any one of claims 8-11, characterized in that, The structural formula of the alkyl diacid is as follows: And / or, the structural formula of compound B is as follows: And / or, the structural formula of the gelling agent is as follows: The value of n ranges from 10 to 16.

Images