CN114672065A - Preparation method of porous crystal glue by using eutectic solvent as crystallization pore-foaming agent - Google Patents

Abstract

The invention relates to a preparation method of porous crystal glue by taking a eutectic solvent as a crystallization pore-forming agent. The preparation method of the porous crystal glue by taking the eutectic solvent as the crystallization pore-foaming agent comprises the following steps: (1) dissolving a reaction monomer in a eutectic solvent to obtain a mixed solution 1; (2) sequentially dissolving a cross-linking agent, an oxidant and a reducing agent in the mixed solution 1 to obtain a mixed solution 2; (3) after bubbles are discharged from the mixed solution 2, freezing the mixed solution at the temperature of-10 to-30 ℃ for 24 to 48 hours, and unfreezing the mixed solution in deionized water for 5 to 30min to obtain wet crystal glue; (4) and repeatedly soaking the wet crystal glue by using deionized water or ethanol, removing unreacted substances and eutectic solvents, and then carrying out vacuum drying treatment to obtain the porous crystal glue. The preparation method of the porous crystal glue with the eutectic solvent as the crystallization pore-forming agent adopts the eutectic solvent as the crystallization pore-forming solvent, and prepares the hydrophobic crystal glue material by a crystallization/freezing pore-forming method.

Description

Preparation method of porous crystal glue using deep eutectic solvent as crystal porogen

technical field

The invention belongs to the technical field of porous materials, and in particular relates to a preparation method of a porous crystal glue using a deep eutectic solvent as a crystal porogen.

Background technique

As an inexpensive and nontoxic crystalline porogen, water has been widely used in the preparation of different matrix crystalline colloid materials. The prepared crystal colloid material has an interconnected super-large pore structure, high specific surface area and good mechanical properties at the same time. Therefore, crystal colloid materials have been widely used in the fields of adsorption separation, catalyst support and tissue engineering. However, as a crystalline porogen, water cannot meet the requirements for the preparation of hydrophobic crystalline colloidal materials, and the crystalline form of water limits the diversification of crystalline colloidal pore structures.

In view of this, the present invention proposes a new preparation method of porous crystal glue, which can prepare hydrophobic crystal glue and has abundant porous structure.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a preparation method of porous crystal glue using a deep eutectic solvent as a crystalline pore-forming agent. Hydrophobic crystal gel materials were prepared by water and organic solvents such as benzene, cyclohexane, dioxane, formamide and camphene.

In order to achieve the above purpose, the adopted technical scheme is:

The preparation method of the porous crystalline glue using a deep eutectic solvent as a crystalline porogen comprises the following steps:

(1) the reaction monomer is dissolved in the deep eutectic solvent to obtain the mixed solution 1;

(2) the crosslinking agent, the oxidizing agent and the reducing agent are successively dissolved in the described mixed solution 1 to obtain the mixed solution 2;

(3) After discharging the bubbles of the mixed solution 2, place it at -10～-30°C and freeze for 24～48h, and then thaw it in deionized water or ethanol for 5～30min to obtain wet crystal glue;

(4) repeatedly using deionized water or ethanol to soak the wet crystal glue, removing unreacted substances and eutectic solvent, and then vacuum drying to obtain the porous crystal glue.

Further, in the step (1), the mass ratio of the reaction monomer and the deep eutectic solvent in the mixed solution 1 is 2-10:100;

The deep eutectic solvent contains a hydrogen bond donor and a hydrogen bond acceptor, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1.5-1:1-2.125.

Still further, the hydrogen bond donor is at least one of 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol;

Described hydrogen bond acceptor is at least one in tetrabutylammonium chloride, tetrabutylammonium bromide;

The reaction monomer is at least one of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and 4-vinylpyridine.

Still further, the preparation process of the deep eutectic solvent is as follows: mixing the hydrogen bond donor and the hydrogen bond acceptor at 30-100° C. to form a clear liquid to obtain the deep eutectic solvent.

Further, in the step (2), the molar ratio of the crosslinking agent, the oxidizing agent, the reducing agent and the reaction monomer is (5-100):(1-10):(1-10):100.

Further, in the step (2), the crosslinking agent is at least one of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.

Further, in the step (3), ultrasonic treatment is used to remove air bubbles.

Further, in the step (4), soak the wet crystal glue with deionized water or ethanol, replace the deionized water or ethanol after 1 to 2 hours, and repeat this step 5 to 10 times to remove unreacted Substances and deep eutectic solvents.

Further, in the step (4), the temperature of vacuum drying is 40-60° C., and the time is 6-24 h.

Further, the pore diameter of the pores of the porous crystal gel is 0.1-100 μm, and the porosity is 80-95%.

Compared with the prior art, the beneficial effects of the present invention are:

1. The technical scheme of the present invention adopts a low-toxic and non-toxic low eutectic solvent as a crystalline pore-forming solvent, which can not only be used to prepare hydrophilic crystal glue, but also can replace toxic and harmful traditional solvents to prepare hydrophobic crystal glue. Therefore, it can be used as a general-purpose crystalline porogen and used in the preparation of various matrix crystal colloid materials.

2. The technical solution of the present invention can be used to prepare the hydrophobic porous crystal glue material by one-step method without going through an additional hydrophobic modification process. The prepared hydrophobic porous crystal glue material has abundant porous structure, good hydrophobicity and good mechanical properties.

3. In the technical scheme of the present invention, a deep eutectic solvent is used as a crystalline pore-forming solvent, and its properties can be adjusted according to the constituent substances and composition ratios, so that the composition of the deep eutectic solvent can be adjusted according to the hydrophilicity and hydrophobicity of the reaction system to dissolve different reactions. And the composition molar ratio can be changed to adjust the freezing point of the deep eutectic solvent to adapt to the freezing conditions, so as to meet the needs of different crystal glue materials.

4. According to the technical solution of the present invention, different kinds of deep eutectic solvents have different crystal morphologies, and can be used to prepare crystal glue materials with specific pore structures.

Description of drawings

Figure 1 shows the different molar ratios of deep eutectic solvents (TBAC: 1,6-hexanediol, TBAC: 1,8-octanediol, 1,9-nonanediol) prepared in Example 6 at room temperature (25°C) Optical photos below;

Figure 2 is the infrared spectrum of the deep eutectic solvent (TBAC: 1,6-hexanediol, TBAC: 1,8-octanediol, 1,9-nonanediol) prepared in Examples 1-3; wherein, A For embodiment 1, B is embodiment 2, C is embodiment 3;

Figure 3 is the X-ray diffraction pattern of the deep eutectic solvent (TBAC: 1,6-hexanediol, TBAC: 1,8-octanediol, 1,9-nonanediol) prepared in Examples 1-3; wherein , A is embodiment 1, B is embodiment 2, C is embodiment 3;

Figure 4 is the differential scanning calorimetry curve of the deep eutectic solvent (TBAC: 1,6-hexanediol, TBAC: 1,8-octanediol, 1,9-nonanediol) prepared in Examples 1-3; Wherein, A is embodiment 1, B is embodiment 2, and C is embodiment 3;

Fig. 5 is the scanning electron microscope picture of the polymethyl methacrylate crystal glue prepared by embodiment 1-3; wherein, A is embodiment 1, B is embodiment 2, C is embodiment 3;

6 is a picture of the contact angle of the polymethyl methacrylate crystal glue prepared in Examples 1-3; wherein, A is Example 1, B is Example 2, and C is Example 3.

Detailed ways

In order to further describe the preparation method of the porous crystalline glue using a deep eutectic solvent as a crystalline porogen according to the present invention and achieve the intended purpose of the invention, the following is a combination of preferred embodiments and the present invention. The preparation method of the porous crystal glue of the agent, its specific embodiment, structure, characteristics and efficacy, are described in detail as follows. In the following description, different "an embodiment" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures or characteristics in one or more embodiments may be combined in any suitable form.

Below in conjunction with specific embodiment, the preparation method of the porous crystalline glue of the present invention taking deep eutectic solvent as crystalline porogen will be further introduced in detail:

A deep eutectic solvent (DES) is a mixture of hydrogen bond donors (HBD) and hydrogen bond acceptors (HBA). Since the formation of hydrogen bonds by its constituent substances will reduce the lattice energy of the mixed system and lead to a significant reduction in the freezing point, a liquid solvent can be formed at room temperature by adjusting the ratio of hydrogen bond donors and hydrogen bond acceptors. This kind of solvent has the advantages of good thermal stability, strong dissolving ability, high electrical conductivity, green environmental protection and the like, and at the same time, the preparation cost is low and the preparation process is extremely simple. By studying the properties of the solvent, such as solubility, viscosity, electrical conductivity and thermal conductivity, it is widely used in metal electrodeposition, metal electropolishing, biotransformation, organic synthesis, gas adsorption, biodiesel purification and other fields. The freezing point depression of deep eutectic solvents provides a possibility for the preparation of porous crystalline gels by freeze crystallization.

The present invention adopts low-toxicity, non-toxic, simple preparation and designable low eutectic solvent as crystallization pore-forming solvent, instead of water and organic solvents such as benzene, cyclohexane, dioxane, formamide and camphene, through crystallization Preparation of hydrophobic crystal gel materials by cryoporation method. The technical scheme of the present invention is:

The preparation method of the porous crystalline glue using a deep eutectic solvent as a crystalline porogen comprises the following steps:

(1) the reaction monomer is dissolved in the deep eutectic solvent to obtain the mixed solution 1;

(2) the crosslinking agent, the oxidizing agent and the reducing agent are successively dissolved in the described mixed solution 1 to obtain the mixed solution 2;

(3) After the mixed solution 2 is discharged from the bubbles, it is placed in a mold and frozen at -10 to -30° C. for 24 to 48 hours, and then thawed in deionized water for 5 to 30 minutes to obtain wet crystal glue;

(4) repeatedly using deionized water to soak the wet crystal glue, removing unreacted substances and deep eutectic solvent, and then vacuum drying to obtain the porous crystal glue.

Preferably, in the step (1), the mass ratio of the reaction monomer and the deep eutectic solvent in the mixed solution 1 is 2-10:100;

The deep eutectic solvent contains a hydrogen bond donor and a hydrogen bond acceptor, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1.5-1:1-2.125.

Further preferably, the hydrogen bond donor is at least one of 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol;

Described hydrogen bond acceptor is at least one in tetrabutylammonium chloride, tetrabutylammonium bromide;

The reaction monomer is at least one of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and 4-vinylpyridine.

Further preferably, the preparation process of the deep eutectic solvent is as follows: mixing the hydrogen bond donor and the hydrogen bond acceptor at 30-100° C. to form a clear liquid to obtain the deep eutectic solvent.

Preferably, in the step (2), the molar ratio of the crosslinking agent, the oxidizing agent, the reducing agent and the reaction monomer is (5-100):(1-10):(1-10):100.

Preferably, in the step (2), the crosslinking agent is at least one of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.

Preferably, in the step (3), ultrasonic treatment is used to remove air bubbles;

The mold is a cylindrical quartz tube with a diameter of 0.5 to 3 cm and a height of 5 to 20 cm.

Preferably, in the step (4), soak the wet gelatin with deionized water or ethanol, replace the deionized water or ethanol after 1 to 2 hours, and repeat this step 5 to 10 times to remove unreacted Substances and deep eutectic solvents.

Preferably, in the step (4), the temperature of vacuum drying is 40-60° C., and the time is 6-24 h.

Preferably, the pore size of the pores of the porous crystal gel is 0.1-100 μm, and the porosity is 80-95%.

Example 1.

The specific operation steps are as follows:

(1) 35.09 g of tetrabutylammonium chloride and 14.91 g of 1,6-hexanediol were heated and stirred at 50° C. for 2 h until melted into a clear liquid, and then cooled to room temperature to obtain a liquid deep eutectic solvent (TBAC:molar ratio of 1,6-hexanediol=1:1).

(2) Subsequently, 2.5g of methyl methacrylate was dissolved in 50g of deep eutectic solvent to configure mixed solution 1, and then 0.495g of cross-linking agent (ethylene glycol dimethacrylate) and 0.083g of oxidizing agent were sequentially added. After the (benzoyl peroxide) was dissolved in the mixed solution 1, 0.083 g of a reducing agent (N'N-dimethylaniline) was then added dropwise to the mixed solution, and stirred for 5 min to form a uniform mixed solution 2.

(3) After placing the mixed solution 2 on an ultrasonic oscillator for 5-10 minutes to remove air bubbles, it was dispensed into a cylindrical quartz tube mold with a diameter of 10 mm and a height of 100 mm, and then placed in a -20°C ethanol bath for freezing for 24 hours.

(4) After the freezing is completed, the frozen mold is thawed in a room temperature water bath for 5-30 minutes to obtain a polymethyl methacrylate crystal glue.

(5) Take the polymethyl methacrylate crystal glue out of the mold, soak in deionized water or ethanol to remove the solvent and unreacted substances, replace the deionized water or ethanol every 1 to 2 hours, and repeat 5 to 10 times. Finally, vacuum drying at 50 °C for 12 h to obtain dry polymethyl methacrylate crystal glue.

The deep eutectic solvent (molar ratio of TBAC:1,6-hexanediol=1:1) can be soaked in either ethanol or deionized water, indicating that the deep eutectic solvent has both hydrophilicity and Hydrophobic.

2A, 3A and 4A are the infrared spectrum, X-ray spectrum and differential scanning calorimetry curve of the deep eutectic solvent prepared in Example 1 of the present invention. It can be seen from Figures 2A, 3A and 4A that a hydrogen bond is formed between the two components of the synthesized deep eutectic solvent, a eutectic is formed during the crystallization of the deep eutectic solvent, and the melting point is -14.77°C.

Figures 5A and 6A are SEM pictures and contact angle pictures of the polymethyl methacrylate crystal glue prepared in Example 1 of the present invention. It can be seen from Figures 5A and 6A that the product has a rich pore structure, and its pore size is 20-75 μm , the porosity is 85.2-91.3% as determined by the weighing method, the contact angle can reach 126.7°, and the hydrophobicity is good.

Example 2.

The specific operation steps are as follows:

(1) 23.61g of tetrabutylammonium chloride and 26.39g of 1,8-octanediol were heated and stirred at 60°C for 2h to melt into a liquid, and cooled to room temperature to obtain a liquid deep eutectic solvent (TBAC: 1, 8-octanediol = 1:2.125).

(2) Subsequently, 2.5g of methyl methacrylate was dissolved in 50g of deep eutectic solvent to configure mixed solution 1, and then 0.495g of crosslinking agent (ethylene glycol dimethacrylate) and 0.083g of oxidant ( After benzoyl peroxide) was dissolved in the mixed solution, 0.083 g of a reducing agent (N'N-dimethylaniline) was added dropwise to the mixed solution, and stirred for 5 min to form a uniform mixed solution 2.

(3) After placing the mixed solution 2 on an ultrasonic oscillator for 5-10 minutes to remove air bubbles, it was dispensed into a cylindrical quartz tube mold with a diameter of 10 mm and a height of 100 mm, and then placed in a -10°C ethanol bath for freezing for 24 hours.

(4) After the freezing is completed, the frozen mold is thawed in a room temperature water bath for 5-30 minutes to obtain a polymethyl methacrylate crystal glue.

(5) Take the polymethyl methacrylate crystal glue out of the mold, soak it in ethanol to remove the solvent and unreacted substances, replace the ethanol every 1-2 hours, and repeat 5-10 times. Finally, vacuum drying at 50 °C for 12 h to obtain dry polymethyl methacrylate crystal glue.

2B, 3B and 4B are the infrared spectrum, X-ray spectrum and differential scanning calorimetry curve of the deep eutectic solvent prepared in Example 2 of the present invention. It can be seen from Figures 2B, 3B and 4B that a hydrogen bond is formed between the two components of the synthesized deep eutectic solvent, a eutectic is formed during the crystallization of the deep eutectic solvent, and the melting point is 22.65°C.

Figures 5B and 6B are SEM pictures and contact angle pictures of the polymethyl methacrylate crystal glue prepared in Example 2 of the present invention. It can be seen from Figures 5B and 6B that the product has a rich pore structure, and its pore size is 15-60 μm , the porosity is 83.2-90.5% as determined by the weighing method, the contact angle can reach 121.9°, and the hydrophobicity is good.

Example 3.

The specific operation steps are as follows:

(1) 36.11g of tetrabutylammonium chloride and 13.88g of 1,9-nonanediol were heated and stirred at 50°C for 2h until melted into a clear liquid, and then cooled to room temperature to obtain a liquid deep eutectic solvent (TBAC: 1,6-hexanediol = 1.5:1).

(2) Subsequently, 2.5g of methyl methacrylate was dissolved in 50g of deep eutectic solvent to configure mixed solution 1, and then 0.495g of cross-linking agent (ethylene glycol dimethacrylate) and 0.083g of oxidizing agent were sequentially added. After the (benzoyl peroxide) was dissolved in the mixed solution 1, 0.083 g of a reducing agent (N'N-dimethylaniline) was then added dropwise to the mixed solution, and stirred for 5 min to form a uniform mixed solution 2.

(3) After placing the mixed solution 2 on an ultrasonic oscillator for 5-10 minutes to remove air bubbles, it was dispensed into a cylindrical quartz tube mold with a diameter of 10 mm and a height of 100 mm, and then placed in a -10°C ethanol bath for freezing for 24 hours.

(4) After the freezing is completed, the frozen mold is thawed in a room temperature water bath for 5-30 minutes to obtain a polymethyl methacrylate crystal glue.

(5) Take the polymethyl methacrylate crystal glue out of the mold, soak it in ethanol to remove the solvent and unreacted substances, replace the ethanol every 1-2 hours, and repeat 5-10 times. Finally, vacuum drying at 50 °C for 12 h to obtain dry polymethyl methacrylate crystal glue.

2C, 3C and 4C are the infrared spectrum, X-ray spectrum and differential scanning calorimetry curve of the deep eutectic solvent prepared in Example 1 of the present invention. It can be seen from Figures 2C, 3C and 4C that a hydrogen bond is formed between the two components of the synthesized deep eutectic solvent, a eutectic is formed during the crystallization of the deep eutectic solvent, and the melting point is -8.34°C.

Figures 5C and 6C are SEM pictures and contact angle pictures of the polymethyl methacrylate crystal glue prepared in Example 1 of the present invention. It can be seen from Figures 5C and 6C that the product has a rich pore structure, and its pore size is 5-30 μm , the porosity is 87.2-95.5% as determined by the weighing method, the contact angle can reach 124.5°, and the hydrophobicity is good.

The infrared spectrograms of the deep eutectic solvent and the components constituting the deep eutectic solvent in Examples 1-3 of the present invention prove the successful preparation of the deep eutectic solvent; the X-ray diffraction pattern proves that the deep eutectic solvent is formed during the crystallization process Eutectic; Differential Scanning Calorimetry Determination of Melting Points of Deep Eutectic Solvents.

Example 4.

The specific operation steps are as follows:

(1) 25.92g of tetrabutylammonium bromide and 24.07g of 1,10-decanediol are heated and stirred at 50 ° C to melt into a clear liquid, then cooled to room temperature to obtain a liquid deep eutectic solvent ( Tetrabutylammonium bromide: 1,10-decanediol = 1:1.25).

(2) Subsequently, 1.0 g of butyl methacrylate was dissolved in 50 g of a deep eutectic solvent to prepare a mixed solution 1, and then 0.943 g of a crosslinking agent (polyethylene glycol diacrylate), 0.170 g of an oxidizing agent ( After benzoyl peroxide) was dissolved in mixed solution 1, then 0.085 g of reducing agent (N'N-dimethylaniline) was added dropwise to the mixed solution, and stirred for 5 min to form a uniform mixed solution 2.

(3) After placing the mixed solution 2 in an ultrasonic oscillator for 5-10 minutes to remove air bubbles, it was dispensed into a cylindrical quartz tube mold with a diameter of 5 mm and a height of 200 mm, and then placed in an ethanol bath at -20°C for 48 hours of freezing.

(4) After the freezing is completed, the frozen mold is thawed in a room temperature water bath for 5-30 minutes to obtain a wet crystal glue.

(5) Take the wet crystal glue out of the mold, soak it in ethanol to remove the solvent and unreacted substances, replace the deionized water or ethanol every 1-2 hours, and repeat 5-10 times. Finally, vacuum drying at 40 °C for 24 h to obtain dry crystal glue.

Example 5.

The specific operation steps are as follows:

(1) 35.09g of tetrabutylammonium chloride and 14.91g of 1,6-hexanediol were heated and stirred at 50°C to melt into a clear liquid, then cooled to room temperature to obtain a liquid deep eutectic solvent ( Molar ratio of TBAC:1,6-hexanediol=1:1).

(2) Then 5g of 4-vinylpyridine was dissolved in 50g of deep eutectic solvent to configure mixed solution 1, and then 0.471g of crosslinking agent (ethylene glycol dimethacrylate) and 0.115g of oxidizing agent were sequentially added. After the (benzoyl peroxide) was dissolved in the mixed solution 1, 0.058 g of a reducing agent (N'N-dimethylaniline) was added dropwise to the mixed solution and stirred to form a uniform mixed solution 2.

(3) After placing the mixed solution 2 on an ultrasonic oscillator for 5-10 minutes to remove air bubbles, it was dispensed into a cylindrical quartz tube mold with a diameter of 30 mm and a height of 50 mm, and then placed in a -30°C ethanol bath for freezing for 24 hours.

(4) After the freezing is completed, the frozen mold is thawed in a room temperature water bath for 5-30 minutes to obtain a wet crystal glue.

(5) Take out the wet state from the mold, soak in deionized water to remove the solvent and unreacted substances, replace the deionized water every 1-2 hours, repeat 5-10 times, and vacuum dry at 60 ° C for 6 hours to obtain dry crystal glue.

Example 6.

Using the raw materials of the deep eutectic solvent of Examples 1-3, respectively prepare a deep eutectic solvent with the molar ratios of the hydrogen bond donor and the hydrogen bond acceptor of 10:1, 1:1 and 1:10, and then at 50 ° C. Continue heating with stirring and cooling to room temperature. The results are shown in Figure 1.

It can be seen from Figure 1 that when the molar ratio of the hydrogen bond donor and the hydrogen bond acceptor is 10:1 and 1:10, the deep eutectic solvent cannot form a clear solution, so it cannot be used to prepare the porous gel.

The above descriptions are only preferred embodiments of the embodiments of the present invention, and are not intended to limit the embodiments of the present invention in any form. Any simple modifications, equivalent changes and Modifications still fall within the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The preparation method of the porous crystal glue by taking the eutectic solvent as the crystallization pore-foaming agent is characterized by comprising the following steps:

(1) dissolving a reaction monomer in a eutectic solvent to obtain a mixed solution 1;

(2) sequentially dissolving a cross-linking agent, an oxidant and a reducing agent in the mixed solution 1 to obtain a mixed solution 2;

(3) after bubbles are discharged from the mixed solution 2, freezing the mixed solution at the temperature of-10 to-30 ℃ for 24 to 48 hours, and unfreezing the mixed solution in deionized water for 5 to 30min to obtain wet crystal glue;

(4) and repeatedly soaking the wet crystal glue by using deionized water or ethanol, removing unreacted substances and eutectic solvents, and then carrying out vacuum drying treatment to obtain the porous crystal glue.

2. The production method according to claim 1,

in the step (1), the mass ratio of the reaction monomer to the eutectic solvent in the mixed solution 1 is 2-10: 100;

the eutectic solvent contains a hydrogen bond donor and a hydrogen bond acceptor, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1.5-1: 1-2.125.

3. The production method according to claim 2,

the hydrogen bond donor is at least one of 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol;

the hydrogen bond acceptor is at least one of tetrabutylammonium chloride and tetrabutylammonium bromide;

the reaction monomer is at least one of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and 4-vinylpyridine.

4. The production method according to claim 2,

the preparation process of the eutectic solvent comprises the following steps: and mixing the hydrogen bond donor and the hydrogen bond acceptor at 30-100 ℃ until clear liquid is formed, thus obtaining the eutectic solvent.

5. The production method according to claim 1,

in the step (2), the molar ratio of the cross-linking agent, the oxidant, the reducing agent and the reaction monomer is (5-100): (1-10): (1-10): 100.

6. the production method according to claim 1,

in the step (2), the cross-linking agent is at least one of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.

7. The production method according to claim 1,

in the step (3), bubbles are removed by adopting an ultrasonic treatment mode.

8. The method according to claim 1,

and (4) soaking the wet crystal glue in deionized water or ethanol, replacing the deionized water or ethanol after 1-2 hours, repeating the step for 5-10 times, and removing unreacted substances and the eutectic solvent.

9. The production method according to claim 1,

in the step (4), the temperature of vacuum drying is 40-60 ℃, and the time is 6-24 hours.

10. The method according to claim 1,

the pore diameter of the porous crystal glue pores is 0.1-100 mu m, and the porosity is 80-95%.

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