CN114405486B - Preparation method of porous cryogel with antifouling, antibacterial and anti-dye adsorption functions - Google Patents

Abstract

The invention relates to the technical field of oil-water separation of underwater super oleophobic membrane materials, in particular to a preparation method of an underwater super oleophobic porous gel with functions of antifouling, antibacterial and dye adsorption prevention; dispersing lithium magnesium silicate and Lap modified by antibacterial silver ions in a polyethylene glycol diacrylate prepolymer solution to obtain a first solvent, adding a reactant into the first solvent, uniformly mixing to obtain a mixture, timely sucking the mixture into a mold, placing the mold in an environment with the temperature of-80 ℃ for freezing, transferring the mold to the environment with the temperature of-20 ℃ for placing after the mixture is crystallized, and thawing the mixture to obtain the porous cryogel with the functions of antifouling, antibacterial and dye adsorption prevention.

Description

Preparation method of porous cryogel with antifouling, antibacterial and anti-dye adsorption functions

technical field

The invention relates to the technical field of oil-water separation of underwater super-oleophobic membrane materials, in particular to a preparation method of an underwater super-oleophobic porous cryogel with antifouling, antibacterial and anti-dye adsorption functions.

Background technique

The development of industrialization and the rapid growth of population have led to the discharge of a large amount of oily sewage, resulting in serious waste of resources and environmental ecological damage, posing a serious threat to human life and health. The dye pollutants in sewage are stable in nature, complex in chemical composition and highly toxic, and most of them are difficult to be biodegraded, causing serious pollution to the ecological environment. In addition, bacteria are very easy to attach to the surface of the material, causing fouling to the material, affecting its permeability and separation effect, and adding great difficulties to the separation and purification technology. Traditional oil-water separation technology is subject to many limitations. The complex pollution components of bacteria, dyes, and oil contained in industrial wastewater and domestic sewage are difficult to completely treat with one-step membrane separation.

At present, membrane separation water treatment technology is used to solve the traditional oil-water separation, but the underwater super-oleophobic membrane materials currently prepared cannot realize the integration of oil-water separation, and cannot realize the one-step separation of bacteria, dyes, and oily complex sewage.

Contents of the invention

The purpose of the present invention is to provide a preparation method of porous cryogel with anti-fouling, anti-bacterial and anti-dye adsorption functions, aiming to solve the problem in the prior art that the integration of oil-water separation and the one-step separation of bacteria, dyes, and oil complex sewage cannot be realized technical problems.

In order to achieve the above object, a method for preparing a porous cryogel with antifouling, antibacterial and anti-dye adsorption functions, the present invention comprises the following steps:

Dispersing Lap modified with antibacterial silver ions in polyethylene glycol diacrylate prepolymer solution to obtain the first solvent;

adding a reactant to the first solvent, and mixing uniformly to obtain a mixture;

The mixture is sucked into the mold in time, and placed in an environment with a temperature of -80°C for freezing;

After the mixture is crystallized, it is transferred to an environment with a temperature of -20°C for storage;

After the mixture is thawed, a porous cryogel with anti-fouling, anti-bacterial and anti-dye adsorption functions is prepared.

Wherein, in the step of obtaining the first solvent by dispersing Lap and the Lap after the antibacterial silver ion modification together in the polyethylene glycol diacrylate prepolymer solution:

The mass volume ratio of Lap and polyethylene glycol diacrylate prepolymer solution modified with antibacterial silver ions is 48mg:2mg:1ml.

Wherein, in the step of adding the reactant to the first solvent and mixing uniformly to obtain the mixture:

The reactant is tetramethylethylenediamine and ammonium persulfate, and the volume ratio to the polyethylene glycol diacrylate prepolymer solution is 3.5:75:1000.

Wherein, in the step of adding the reactant to the first solvent and mixing uniformly to obtain the mixture:

The ammonium persulfate in the reactant is an ammonium persulfate solution with a mass concentration of 10% using PBS buffer as a solvent.

Wherein, in the step of obtaining the first solvent by dispersing Lap and Lap modified by antibacterial silver ions in polyethylene glycol diacrylate prepolymer solution, the preparation method of Lap modified by said antibacterial silver ions for:

Take by weighing 0.68g silver nitrate and add 40ml deionized water to obtain silver nitrate solution,

Weigh 0.2g Lap into the silver nitrate solution, stir it, and put it into a -80°C refrigerator;

After freeze-drying, Lap modified with antibacterial silver ions was obtained.

Wherein, according to the preparation method of the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions, the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions can simultaneously realize the one-step process of bacteria, dyes, and anti-adhesive pollution. separate.

The beneficial effect of the present invention is reflected in: first Lap after Lap and antibacterial silver ion modification are dispersed in polyethylene glycol diacrylate prepolymer solution, obtain described first solvent, then pour into described first solvent Add the reactant and mix evenly to obtain the mixture, then suck the mixture into the mold in time, and place it in an environment with a temperature of -80°C for freezing, and then transfer the mixture to a temperature of -20°C after the mixture crystallizes. ℃ environment, and finally thaw the mixture to prepare the porous cryogel with anti-fouling, anti-bacterial and anti-dye adsorption functions, combining special wetting properties with functional green materials, polyethylene glycol as Raw materials, combined with the excellent ion exchange capacity of Lap, adopt low-temperature controlled freeze polymerization, the preparation method is simple and easy to operate, the reaction conditions are mild, the cost is low and no large-scale instruments and equipment are required, and the product can be biodegradable. The application of wastewater treatment has laid a foundation, and the cryogel material obtained through the preparation method of the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions can realize antifouling, antibacterial, dye adsorption, and oil-water separation.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.

Fig. 1 is a flowchart of the steps of Embodiment 1 of the present invention.

Fig. 2 is a flowchart of the steps of Embodiment 2 of the present invention.

Fig. 3 is a flowchart of the steps of Embodiment 3 of the present invention.

Fig. 4 is that polyethylene glycol diacrylate solution is 200mg/ml preparation antifouling antibacterial and the porous cryogel separation soybean oil, motor oil, diesel oil, kerosene, n-hexane five kinds of oils and their separation diagrams separation efficiency.

Fig. 5 is an antifouling self-cleaning picture of a porous cryogel with antifouling, antibacterial and anti-dye adsorption functions prepared with a polyethylene glycol diacrylate solution of 200 mg/ml.

Fig. 6 is a graph showing the experimental results of the adsorption of methine blue and rhodamine B by the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions prepared with a polyethylene glycol diacrylate solution of 200 mg/ml.

Figure 7 shows the porous cryogel prepared by polyethylene glycol diacrylate solution of 200mg/ml antifouling, antibacterial and anti-dye adsorption functions and the porous cryogel prepared by Lap without antibacterial silver ion modification and without any Lap Comparison test results of the prepared porous cryogel against Escherichia coli and Staphylococcus aureus.

Detailed ways

Embodiment 1, please refer to Fig. 1, the present invention provides a kind of preparation method of the porous cryogel of antifouling antibacterial and anti-dye adsorption function, comprises the following steps:

S1: Weigh 0.68g of silver nitrate and add 40ml of deionized water to obtain a silver nitrate solution, then weigh 0.2g of Lap into the silver nitrate solution, stir magnetically for 24 hours, take it out and centrifuge at 5000rpm/min for 15 minutes, repeat 3-4 times, Then put it into a -80°C refrigerator, freeze-dry, and pass through a 120-mesh filter to obtain Lap modified with antibacterial silver ions;

S2: Weigh 200mg of polyethylene glycol diacrylate and dissolve it in 2ml PBS, then weigh 96mg of Lap and 4mg of Lap modified by the antibacterial silver ion, mix them in the polyethylene glycol diacrylate solution, and put them in 60 ℃ water bath to heat to obtain the mixture;

S3: Weigh 0.1g of ammonium persulfate and dissolve in 1ml of deionized water, and store at low temperature;

S4: Put the mixture into the ice-water mixture for 2 minutes, and put a cylindrical silicone mold with a diameter of 8mm and a height of 5mm into an environment with a temperature of -80°C for freezing;

S5: Take 0.15ml of the mixture and 0.007ml of tetramethylethylenediamine in the mixture and ice-water mixture, inhale it into a silicone mold in time, and place it in an environment with a temperature of -80°C for freezing, waiting for crystallization;

S6: transfer the obtained material to an environment with a temperature of -20°C after solidification, take it out after 24 hours of reaction, and thaw it with deionized water to obtain the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions .

In this embodiment, first weigh 0.68g of silver nitrate and add 40ml of deionized water to obtain a silver nitrate solution, then weigh 0.2g of Lap in the silver nitrate solution, stir magnetically for 24 hours and then take it out and centrifuge at 5000rpm/min for 15 minutes. Repeat 3-4 times, then put it into -80℃ refrigerator, freeze-dry it, and pass it through a 120-mesh filter to obtain Lap modified with antibacterial silver ions, then weigh 200mg of polyethylene glycol diacrylate and dissolve it in 2ml of PBS, and weigh again Take 96mg of Lap and 4mg of the antibacterial silver ion-modified Lap in polyethylene glycol diacrylate solution, mix them evenly, put them in a 60°C water bath and heat to obtain the mixture, then weigh 0.1g of ammonium persulfate and dissolve it in 1ml Deionized water, stored at low temperature, then put the mixture into the ice-water mixture for 2 minutes, put a cylindrical silicone mold with a diameter of 8mm and a height of 5mm into an environment with a temperature of -80°C for freezing, and then take 0.15ml of the Put the mixture and 0.007ml of tetramethylethylenediamine in the mixture and ice-water mixture, suck it into the silicone mold in time, and place it in an environment with a temperature of -80°C for freezing, wait for crystallization, and finally crystallize and solidify the obtained material Transfer to an environment with a temperature of -20°C for storage, take it out after 24 hours of reaction, and thaw it with deionized water to obtain the porous cryogel with anti-fouling, anti-bacterial and anti-dye adsorption functions. The special wetting properties and functional green The combination of environmentally friendly materials, polyethylene glycol as raw material, combined with the excellent ion exchange capacity of Lap, adopts the method of low-temperature controlled freeze polymerization, the preparation method is simple and easy to operate, the reaction conditions are mild, the cost is low, and large-scale instruments and equipment are not required. The product can be biodegradable, which lays the foundation for the application of multifunctional complex wastewater treatment, and the cryogel material prepared by the method for preparing the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions can realize anti-fouling Pollution, antibacterial, dye adsorption, oil-water separation.

Embodiment 2, please refer to Fig. 2, the present invention provides a kind of preparation method of the porous cryogel of antifouling antibacterial and anti-dye adsorption function, comprises the following steps:

S1: Weigh 0.68g of silver nitrate and add 40ml of deionized water to obtain a silver nitrate solution, then weigh 0.2g of Lap into the silver nitrate solution, stir magnetically for 24 hours, take it out and centrifuge at 5000rpm/min for 15 minutes, repeat 3-4 times, Then put it into a -80°C refrigerator, freeze-dry, and pass through a 120-mesh filter to obtain Lap modified with antibacterial silver ions;

S2: Weigh 600mg of polyethylene glycol diacrylate and dissolve it in 2ml PBS, then weigh 96mg of Lap and 4mg of Lap modified by the antibacterial silver ion, mix them in the polyethylene glycol diacrylate solution, put them into 60 ℃ water bath to heat to obtain the mixture;

S3: Weigh 0.1g of ammonium persulfate and dissolve in 1ml of deionized water, and store at low temperature;

S4: Put the mixture into the ice-water mixture for 2 minutes, and put a cylindrical silicone mold with a diameter of 8mm and a height of 5mm into an environment with a temperature of -80°C for freezing;

S5: Take 0.15ml of the mixture and 0.007ml of tetramethylethylenediamine in the mixture and ice-water mixture, inhale it into a silicone mold in time, and place it in an environment with a temperature of -80°C for freezing, waiting for crystallization;

S6: transfer the obtained material to an environment with a temperature of -20°C after solidification, take it out after 24 hours of reaction, and thaw it with deionized water to obtain the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions .

In this embodiment, first weigh 0.68g of silver nitrate and add 40ml of deionized water to obtain a silver nitrate solution, then weigh 0.2g of Lap in the silver nitrate solution, stir magnetically for 24 hours and then take it out and centrifuge at 5000rpm/min for 15 minutes. Repeat 3-4 times, then put it in -80℃ refrigerator, freeze-dry it, and pass through a 120-mesh filter to obtain Lap modified with antibacterial silver ions, then weigh 600mg polyethylene glycol diacrylate and dissolve it in 2ml PBS, and then weigh Take 96mg of Lap and 4mg of the antibacterial silver ion-modified Lap in polyethylene glycol diacrylate solution, mix them evenly, put them in a 60°C water bath and heat to obtain the mixture, then weigh 0.1g of ammonium persulfate and dissolve it in 1ml Deionized water, stored at low temperature, then put the mixture into the ice-water mixture for 2 minutes, put a cylindrical silicone mold with a diameter of 8mm and a height of 5mm into an environment with a temperature of -80°C for freezing, and then take 0.15ml of the Put the mixture and 0.007ml of tetramethylethylenediamine in the mixture and ice-water mixture, suck it into the silicone mold in time, and place it in an environment with a temperature of -80°C for freezing, wait for crystallization, and finally crystallize and solidify the obtained material Transfer to an environment with a temperature of -20°C for storage, take it out after 24 hours of reaction, and thaw it with deionized water to obtain the porous cryogel with anti-fouling, anti-bacterial and anti-dye adsorption functions. The special wetting properties and functional green The combination of environmentally friendly materials, polyethylene glycol as raw material, combined with the excellent ion exchange capacity of Lap, adopts the method of low-temperature controlled freeze polymerization, the preparation method is simple and easy to operate, the reaction conditions are mild, the cost is low, and large-scale instruments and equipment are not required. The product can be biodegradable, which lays the foundation for the application of multifunctional complex wastewater treatment, and the cryogel material prepared by the method for preparing the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions can realize anti-fouling Pollution, antibacterial, dye adsorption, oil-water separation.

Example 3, please refer to Fig. 3 to Fig. 7, the present invention provides a preparation method of a porous cryogel with anti-fouling, anti-bacterial and anti-dye adsorption functions, comprising the following steps:

S1: Weigh 0.68g of silver nitrate and add 40ml of deionized water to obtain a silver nitrate solution, then weigh 0.2g of Lap into the silver nitrate solution, stir magnetically for 24 hours, take it out and centrifuge at 5000rpm/min for 15 minutes, repeat 3-4 times , and then placed in a -80°C refrigerator, freeze-dried and sieved through a 120-mesh filter to obtain Lap modified with antibacterial silver ions;

S2: Weigh 400mg of polyethylene glycol diacrylate and dissolve it in 2ml PBS, then weigh 96mg of Lap and 4mg of Lap modified by the antibacterial silver ion, mix them in the polyethylene glycol diacrylate solution, and put them in 60 ℃ water bath to heat to obtain the mixture;

S3: Weigh 0.1g of ammonium persulfate and dissolve in 1ml of deionized water, and store at low temperature;

S4: Put the mixture into the ice-water mixture for 2 minutes, and put a cylindrical silicone mold with a diameter of 8mm and a height of 5mm into an environment with a temperature of -80°C for freezing;

S5: Take 0.15ml of the mixture and 0.007ml of tetramethylethylenediamine in the mixture and ice-water mixture, inhale it into a silicone mold in time, and place it in an environment with a temperature of -80°C for freezing, waiting for crystallization;

S6: transfer the obtained material to an environment with a temperature of -20°C after solidification, take it out after 24 hours of reaction, and thaw it with deionized water to obtain the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions .

In this embodiment, first weigh 0.68g of silver nitrate and add 40ml of deionized water to obtain a silver nitrate solution, then weigh 0.2g of Lap in the silver nitrate solution, stir magnetically for 24 hours and then take it out and centrifuge at 5000rpm/min for 15 minutes. Repeat 3-4 times, then put it into -80℃ refrigerator, freeze-dry it, and pass it through a 120-mesh filter to obtain the antibacterial silver ion-modified Lap, then weigh 400mg polyethylene glycol diacrylate and dissolve it in 2ml PBS, and then weigh Take 96mg of Lap and 4mg of the antibacterial silver ion-modified Lap in polyethylene glycol diacrylate solution, mix them evenly, put them in a 60°C water bath and heat to obtain the mixture, then weigh 0.1g of ammonium persulfate and dissolve it in 1ml Deionized water, stored at low temperature, then put the mixture into the ice-water mixture for 2 minutes, put a cylindrical silicone mold with a diameter of 8mm and a height of 5mm into an environment with a temperature of -80°C for freezing, and then take 0.15ml of the Put the mixture and 0.007ml of tetramethylethylenediamine in the mixture and ice-water mixture, suck it into the silicone mold in time, and place it in an environment with a temperature of -80°C for freezing, wait for crystallization, and finally crystallize and solidify the obtained material Transfer to an environment with a temperature of -20°C for storage, take it out after 24 hours of reaction, and thaw it with deionized water to obtain the porous cryogel with anti-fouling, anti-bacterial and anti-dye adsorption functions. The special wetting properties and functional green The combination of environmentally friendly materials, polyethylene glycol as raw material, combined with the excellent ion exchange capacity of Lap, adopts the method of low-temperature controlled freeze polymerization, the preparation method is simple and easy to operate, the reaction conditions are mild, the cost is low, and large-scale instruments and equipment are not required. The product can be biodegradable, which lays the foundation for the application of multifunctional complex wastewater treatment, and the cryogel material prepared by the method for preparing the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions can realize anti-fouling pollution, antibacterial, dye adsorption, and oil-water separation, the porous cryogels with antifouling, antibacterial and anti-dye adsorption functions were respectively tested for the separation of soybean oil, engine oil, diesel oil, kerosene, and n-hexane, and the separation was calculated. Efficiency, obtain separation figure and separation efficiency thereof, show that the porous cryogel of described antifouling antibacterial and anti-dye adsorption function has efficient separation efficiency to these five kinds of oils, all exceeds 98%; Further described antifouling antibacterial and antifouling antibacterial and The porous cryogel with anti-dye adsorption function was tested for anti-pollution adhesion, and the anti-fouling and self-cleaning pictures were obtained, showing that the porous cryogel with anti-fouling, antibacterial and anti-dye adsorption functions has anti-fouling functions, and oil droplets are not easy to adhere to the material; Further carry out the adsorption test of methylene blue and rhodamine B dyes on the porous cryogel with antifouling, antibacterial and anti-dye adsorption functions, and obtain the experimental result diagram of adsorption of methylene blue and rhodamine B, showing that the antifouling Porous cryogels with antibacterial and anti-dye adsorption functions have obvious adsorption effects on methylene blue and rhodamine B dyes; further, the materials prepared in this example and Example 4 are tested against Escherichia coli and anti-staphylococcus aureus , to obtain the picture as shown in Figure 4, which shows that the cryogel material prepared in this embodiment exhibits antibacterial and antibacterial effects on Escherichia coli and Staphylococcus aureus.

What is disclosed above is only a preferred embodiment of the present invention, and of course it cannot limit the scope of rights of the present invention. Those of ordinary skill in the art can understand all or part of the process for realizing the above embodiments, and according to the rights of the present invention The equivalent changes required still belong to the scope covered by the invention.

Claims (2)

1. The preparation method of the porous cryogel with the functions of antifouling, antibacterial and dye adsorption prevention is characterized by comprising the following steps:

dispersing Lap modified by Lap and antibacterial silver ions in a polyethylene glycol diacrylate prepolymer solution to obtain a first solvent, wherein the volume ratio of the Lap modified by Lap and antibacterial silver ions to the polyethylene glycol diacrylate prepolymer solution is 48mg:2mg:1ml;

adding a reactant into the first solvent, and uniformly mixing to obtain a mixture, wherein the reactant is tetramethyl ethylenediamine and ammonium persulfate, and the volume ratio of the reactant to the polyethylene glycol diacrylate prepolymer solution is 3.5:75:1000, wherein the ammonium persulfate is ammonium persulfate solution with a mass concentration of 10% by taking PBS buffer solution as a solvent;

sucking the mixture into a die in time, and placing the die in an environment with the temperature of-80 ℃ for freezing;

after the mixture is crystallized, transferring to an environment with the temperature of minus 20 ℃ for standing;

thawing the mixture to obtain the porous cryogel with antifouling, antibacterial and dye adsorption preventing functions;

the preparation method of the antibacterial silver ion modified Lap comprises the following steps: weighing 0.68g of silver nitrate, adding 40ml of deionized water to obtain a silver nitrate solution, weighing 0.2g of Lap into the silver nitrate solution, stirring, and then placing into a refrigerator at the temperature of minus 80 ℃; and (5) freeze-drying to obtain the antibacterial silver ion modified Lap.

2. The method for preparing the porous cryogel with the functions of antifouling, antibacterial and dye adsorption prevention according to claim 1, wherein,

the porous cryogel with the functions of antifouling, antibacterial and dye adsorption prevention is prepared according to the preparation method of the porous cryogel with the functions of antifouling, antibacterial and dye adsorption prevention, and simultaneously realizes one-step separation of bacteria, dyes and adhesion pollution resistance.

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