CN114381024A - A kind of preparation method of interface super-assembled polyurea/porous material/alumina functional film - Google Patents

Abstract

The invention discloses a preparation method of an interface super-assembly polyurea/porous material/alumina functional membrane. The mesoporous silica layer has extraordinary hydrophilicity, and the fragile property of the ceramic membrane limits the practical application value of the ceramic membrane. Polyurea is used as a waterproof super-strong coating and can be used for improving the surface property of the membrane. The polyurea coating is grown on the MS/AAO substrate by a secondary interface super-assembly method, so that the surface property of the MS/AAO composite membrane can be well improved. The PMSA composite membrane is prepared by adopting a twice interface super-assembly method, and has potential practical application value.

Description

A kind of preparation method of interface super-assembled polyurea/porous material/alumina functional film

technical field

The invention belongs to the technical field of membrane science, and in particular relates to a preparation method of an interface super-assembled polyurea/porous material/alumina functional membrane.

Background technique

In recent years, membrane materials containing nanoscale channels are ideal materials for the construction of nanofluidic ion transport devices. At present, many membrane materials are mainly polymer membranes prepared based on phase separation methods, which generally have relatively loose and irregular pores, which are limited in the field of controllable ion transport. In contrast, ordered mesoporous films have attracted extensive attention due to their regular pore size, tunable pore size, and controllable film thickness. Compared with other nanochannel membrane materials, mesopores have high porosity and regular pore structure, but this also leads to poor mechanical properties of mesoporous films. There is still no good solution for this problem.

Patent CN111766285A discloses a PDDA-modified mesoporous silicon oxide/anodic aluminum oxide film, super-assembly preparation method and application. F127 and TEOS are used as raw materials to prepare mesoporous silicon oxide precursor solution. A layer of ultra-thin mesoporous silica coating was prepared on the porous AAO substrate; after the evaporation-induced self-assembly process, a well-ordered mesoporous silica framework was obtained; after calcination to remove the template agent F127 and PMMA, MS/AAO was obtained membrane, and then immersed the MS/AAO membrane in a 0.02wt%–1.0wt% PDDA aqueous solution, and modified PDDA with a permanent positive charge on the MS side to obtain a PDDA@MS/AAO composite membrane. However, PDDA as a kind of Polycations are only electrostatically adsorbed in mesoporous silica channels. Although they can detect the types of amino acids, they cannot fundamentally solve the mechanical stability of inorganic mesoporous silica materials, and the detection performance is also limited by mechanical properties. There are still challenges in practical applications.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation method of interface super-assembled polyurea/porous material/alumina functional film in order to solve the above problems. Stability and water repellency of porous silica films.

The object of the present invention is achieved through the following technical solutions:

A preparation method of interface super-assembled polyurea/porous material/alumina functional film, comprising the following steps:

(1) An ordered mesoporous silica film was grown on an AAO substrate by an interfacial superassembly method to obtain a mesoporous silica/alumina (MS/AAO) composite film;

(2) configure the water-oil phase solution for synthesizing the polyurea monomer;

(3) drop the PEI onto the surface of the MS/AAO film, and volatilize the water to dryness;

(4) The TDI solution was added dropwise to the surface of MS/AAO containing PEI polymer chains, and the interfacial polymerization of amino groups between the two phases and isocyanate occurred to form a dense polyurea film, and a PMSA composite film with high mechanical properties was obtained.

In the present invention, an MS/AAO composite film with ordered pores is prepared by an interfacial super-assembly method with the assistance of PMMA, and then a polyurea coating with ultra-high mechanical properties and waterproof capability is grown on the surface of MS by an interfacial polymerization method. , the final PMSA film exhibits a certain waterproof performance, has very good thermal stability, and has potential value in practical applications.

Further, step (1) specifically includes the following steps:

(1-1) adopt polymethyl methacrylate to carry out pore blocking treatment to AAO;

(1-2) spin-coating the polymethyl methacrylate solution onto the AAO substrate;

(1-3) The spin-coated PMMA/AAO film is dried to ensure that the PMMA penetrates into the AAO pores;

(1-4) Prepare a precursor solution of mesoporous silica and prepolymerize at 60°C;

(1-5) Preparation of F127 template agent solution;

(1-6) dropping the prepolymerized mesoporous silica into the F127 template solution, stirring at room temperature, to obtain the final mesoporous silica precursor solution;

(1-7) spin-coating the mesoporous silicon oxide precursor solution onto the plugged AAO substrate;

(1-8) Evaporation-induced self-assembly at 40 °C for 24 h and thermal polymerization at 100 °C for 24 h to obtain the final mesoporous silica/alumina (MS/AAO) composite film.

Further, the specific method of step (1-1) is as follows: dissolve 2.3-2.7 g of polymethyl methacrylate (PMMA) into 23-27 ml of acetone solution, and heat and stir at 40-45° C. until dissolved.

The present invention uses AAO as a substrate, AAO contains abundant nano-sized ion transport channels, and in addition, it acts as a substrate of mesoporous silicon oxide and functions as a support layer. Using PMMA as the pore blocking agent, mesoporous silicon can be grown regularly on AAO substrates. A layer of mesoporous silica film is grown on the surface of alumina. On the one hand, the surface of mesoporous silica is rich in hydroxyl groups, which can super-assemble and interact with the hydroxyl groups between AAO and provide abundant nanochannels; The hydroxyl groups on the silicon surface can generate non-covalent van der Waals forces with the amino groups on the PEI chain, and the PEI polymer chains are grafted on the surface of the MS membrane.

Further, in step (1-2), the rotational speed of the spin coating is 3000-3500 revolutions, and the spin coating time is 30-40 seconds. The invention adopts the spin coating method to prepare the mesoporous silicon oxide layer, and the uniform mesoporous film can be obtained by this method.

Further, the spin-coated PMMA/AAO film in step (1-3) was dried in a fume hood for two hours, and then placed in an oven at 200° C. for 5-6 hours.

Further, the specific method of step (1-4) is: preparing prepolymerized mesoporous silica oligomer, adding 2-2.2g tetraethyl silicate to 10-12g absolute ethanol and 1.0-1.5g In the mixed solution of deionized water and 0.5-0.6g of 0.2M hydrochloric acid, prepolymerized at 60°C for 1h.

The invention adopts the interfacial polymerization method to prepare the polyurea coating, the method is simple and low in by-products, and the coating can be well grown on the surface of the mesoporous silicon oxide to protect the silicon oxide film.

Further, the specific method for preparing the F127 template agent solution in step (1-5) is: dissolving 0.8-1 g of F127 into 9-12 g of absolute ethanol, and ultrasonically dispersing and dissolving until clear.

Further, in step (1-7), 200-250 μl of the mesoporous silicon oxide precursor solution is spin-coated on the plugged AAO substrate, the spin-coating speed is 3000-3500 rpm, and the spin-coating time is 40-60 seconds.

Further, the specific method for configuring the water-oil phase solution of the synthetic polyurea monomer in step (2) is: configuring 1.0-1.8w/v% polyethyleneimine (PEI) aqueous solution, mixing 110-260mg of 50wt% PEI solution Dissolve in 55-65ml of deionized water; then prepare 0.3-0.8w/v% of 2,4-diisocyanate (TDI), weigh about 0.01-0.05g of TDI and dissolve it in 55-65ml of n-hexane In alkane, the two prepared solutions were placed in an oven at 60 °C. Preferably, 1.5w/v% PEI and 0.5w/v% TDI monomer are used to prepare polyurea. The PEI polymer chain is rich in amino groups, which can ensure better formation of polyurea film, and at this concentration condition In this way, a polyurea film with a high degree of adhesion and a denser polyurea film can be obtained.

The present invention adopts polyurea as the modified coating of mesoporous silica, and the polyurea has very good mechanical stability, waterproof performance, anti-corrosion performance and very good thermal stability, which can improve the mechanical properties of the MS/AAO composite film, and improve the its practical application value.

Further, in step (3), 200-250 μL of PEI was added dropwise to the surface of the MS/AAO membrane, and the water was evaporated to dryness at 60° C.;

In step (4), 160-200 μL of TDI solution was added dropwise to the surface of MS/AAO containing PEI polymer chains, and the interfacial polymerization reaction between the amino group and isocyanate between the two phases occurred in an oven at 60° C. The reaction time was 1 min. The whole reaction was carried out at 60 °C to ensure a relatively fast reaction rate between PEI and TDI; the interfacial polymerization reaction time was 1 min to maintain the membrane with a certain permeability while keeping the membrane dense, ensuring its potential. Value.

The invention firstly prepares a mesoporous silica/alumina composite film by an interface super-assembly method, and then grows a waterproof, anti-corrosion and impact-resistant polyurea coating on the surface of the mesoporous silica by an interfacial polymerization method, It can improve the waterproof performance and mechanical stability of MS/AAO, and has potential practical application value. Among them, polyurea, as a coating with good mechanical properties, has the characteristics of anti-corrosion, waterproof and wear-resistant, which can improve the mechanical properties of the material well, and it also has excellent thermal stability, which can be used at 100-120 ° C. Under long-term use, in addition, it can withstand thermal shock of about 300 ℃ in a short time, so it can be considered to use polyurea layer to increase the mechanical stability of the material. Compared with MS/AAO, the polyurea-modified mesoporous silica/alumina composite membrane (PMSA) has a hydrophobic outer surface and plays a waterproof role, so it has very good stability in water and has potential. practical application value.

Description of drawings

Fig. 1 is the preparation flow chart that the present invention prepares PMSA composite membrane;

Fig. 2 is the optical picture of the PMSA composite film that the present invention prepares;

Fig. 3 is the surface morphology comparison diagram of MS/AAO composite film and PMSA composite film prepared by the present invention;

4 is a cross-sectional comparison diagram of the MS/AAO composite membrane and the PMSA composite membrane prepared by the present invention;

Fig. 5 is the point element analysis diagram of the PMSA composite film surface prepared by the present invention;

Fig. 6 is the surface element distribution figure of the PMSA composite film prepared by the present invention;

FIG. 7 is a graph showing the surface hydrophilicity and hydrophobicity of the MS/AAO composite membrane prepared by the present invention and the PMSA composite membrane.

Detailed ways

The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

Example 1

The preparation method of PMSA composite membrane specifically comprises the following steps:

Step 1: First, an ordered mesoporous silicon oxide film is grown on the AAO substrate by the interfacial super-assembly method;

(1-1) Before preparing MS, firstly, polymethyl methacrylate was used to block the pores of AAO. The specific method was to dissolve 2.3 g of polymethyl methacrylate (PMMA) into 23 ml of acetone solution, and 40 ℃ heated and stirred until dissolved;

(1-2) spin-coating the polymethyl methacrylate solution on the AAO substrate afterwards, the spin-coating speed is 3000 rpm, and the spin-coating time is 30 seconds;

(1-3) Dry the spin-coated PMMA/AAO film for two hours in a fume hood, and then place it in an oven at 200°C for 5-6 hours to ensure that PMMA can penetrate into the AAO pores, thereby blocking the pores;

(1-4) Then prepare the precursor solution of mesoporous silica, firstly prepare the prepolymerized mesoporous silica oligomer, add 2g of tetraethyl silicate to 10g of absolute ethanol and 1.0g of deionized In a mixed solution of water and 0.5g of 0.2M hydrochloric acid, prepolymerized at 60°C for 1h;

(1-5) Preparation of F127 template agent solution: dissolve 0.8g of F127 into 9g of absolute ethanol, and ultrasonically disperse and dissolve until clear;

(1-6) 8 g of prepolymerized tetraethyl silicate was slowly added dropwise to the F127 template solution, and stirred at room temperature for 1 h to obtain the final mesoporous silica precursor solution;

(1-7) After that, spin-coat 200 μl of the mesoporous silicon oxide precursor solution onto the plugged AAO substrate at a spin-coating speed of 3000 rpm and a spin-coating time of 40 seconds;

(1-8) After that, the final mesoporous silica/alumina (MS/AAO) composite film can be obtained by evaporation-induced self-assembly at 40°C for 24h and thermal polymerization at 100°C for 24h.

Step 2: Then configure the water-oil phase solution for synthesizing the polyurea monomer: first, configure a 1.0w/v% polyethyleneimine (PEI) aqueous solution, and dissolve 110mg of 50wt% PEI solution in 55ml of deionized water; Then, 0.3w/v% of 2,4-diisocyanate (TDI) was prepared. About 0.0165g of TDI was weighed and dissolved in 55ml of n-hexane. The two prepared solutions were placed in an oven at 60°C. middle;

Step 3: After that, first drop 200 μL of PEI onto the surface of the MS/AAO membrane, and wait for it to volatilize the water to dryness at 60°C;

Step 4: After that, 160 μL of TDI solution was added dropwise to the surface of MS/AAO containing PEI polymer chains, and the interfacial polymerization reaction between the amino group and isocyanate between the two phases occurred in an oven at 60 °C, and the reaction time was 1 min. Polyurea film, then the final PMSA composite film with high mechanical properties is obtained.

Figure 1 shows Example 1. First, a layer of mesoporous silica composite film was grown on the AAO substrate by the interfacial super-assembly method, and then a layer of waterproof polyurea coating was grown on the surface of the mesoporous silica by the interfacial polymerization method to obtain The final polyurea/mesoporous silica/alumina composite membrane (PMSA) with water repellency properties.

Figure 2 is an optical picture of the PMSA composite film prepared in Example 1, and Figure 2a is a model diagram of the PMSA composite film. Figure 2(b-f) shows the growth of one to five layers of polyurea coatings on the MS/AAO surface, respectively.

Example 2

The preparation method of PMSA composite membrane specifically comprises the following steps:

Step 1: First, an ordered mesoporous silicon oxide film is grown on the AAO substrate by the interfacial super-assembly method;

(1-1) Before the preparation of MS, firstly use polymethyl methacrylate to block the pores of AAO. The specific method is to dissolve 2.5g of polymethyl methacrylate (PMMA) into 25ml of acetone solution, 42 ℃ heated and stirred until dissolved;

(1-2) spin-coating the polymethyl methacrylate solution on the AAO substrate afterwards, the spin-coating speed is 3200 rpm, and the spin-coating time is 35 seconds;

(1-3) Dry the spin-coated PMMA/AAO film in a fume hood for two hours, and then place it in an oven at 200°C for 5.5 hours to ensure that PMMA can penetrate into the AAO pores, thereby blocking the pores;

(1-4) After preparing the precursor solution of mesoporous silica, firstly prepare the prepolymerized mesoporous silica oligomer, add 2.1g of tetraethyl silicate to 11g of absolute ethanol and 1.25g of dehydrated In a mixed solution of ionized water and 0.55g of 0.2M hydrochloric acid, prepolymerized at 60°C for 1h;

(1-5) Preparation of F127 template agent solution: dissolve 0.9g of F127 into 10g of absolute ethanol, disperse and dissolve by ultrasonic until it becomes clear;

(1-6) 8 g of prepolymerized tetraethyl silicate was slowly added dropwise to the F127 template solution, and stirred at room temperature for 1 h to obtain the final mesoporous silica precursor solution;

(1-7) After that, spin-coat 220 μl of the mesoporous silicon oxide precursor solution on the AAO substrate with the pores blocked, the spin-coating speed is 3200 rpm, and the spin-coating time is 50 seconds;

(1-8) After that, the final mesoporous silica/alumina (MS/AAO) composite film can be obtained by evaporation-induced self-assembly at 40°C for 24h and thermal polymerization at 100°C for 24h.

Step 2: Then configure the water-oil phase solution for synthesizing the polyurea monomer: firstly, configure 1.5w/v% polyethyleneimine (PEI) aqueous solution, and dissolve 180mg of 50wt% PEI solution into 60ml of deionized water; Then, 0.5w/v% of 2,4-diisocyanate (TDI) was prepared. About 0.03g of TDI was weighed and dissolved in 60ml of n-hexane. The two prepared solutions were placed in an oven at 60°C. middle;

Step 3: After that, 220 μL of PEI was firstly added dropwise to the surface of the MS/AAO membrane, and the water was evaporated to dryness at 60°C;

Step 4: After that, 220 μL of TDI solution was added dropwise to the surface of MS/AAO containing PEI polymer chains, and the interfacial polymerization reaction between the amino group and isocyanate between the two phases occurred in an oven at 60 °C, and the reaction time was 1 min. Polyurea film, then the final PMSA composite film with high mechanical properties is obtained.

Example 3

The preparation method of PMSA composite membrane specifically comprises the following steps:

Step 1: First, an ordered mesoporous silicon oxide film is grown on the AAO substrate by the interfacial super-assembly method;

(1-1) Before the preparation of MS, firstly, polymethyl methacrylate was used to block the pores of AAO. The specific method was to dissolve 2.7 g of polymethyl methacrylate (PMMA) into 27 ml of acetone solution, and 45 ℃ heated and stirred until dissolved;

(1-2) spin-coating the polymethyl methacrylate solution on the AAO substrate afterwards, the spin-coating speed is 3500 revs, and the spin-coating time is 40 seconds;

(1-3) Dry the spin-coated PMMA/AAO film for two hours in a fume hood, and then place it in an oven at 200°C for 5-6 hours to ensure that PMMA can penetrate into the AAO pores, thereby blocking the pores;

(1-4) Then prepare the precursor solution of mesoporous silica, firstly prepare the prepolymerized mesoporous silica oligomer, add 2.2g of tetraethyl silicate to 12g of absolute ethanol and 1.5g of desulfurization In a mixed solution of ionized water and 0.6g of 0.2M hydrochloric acid, prepolymerized at 60°C for 1h;

(1-5) Preparation of F127 template agent solution: dissolve 1 g of F127 into 12 g of absolute ethanol, disperse and dissolve by ultrasonic until it becomes clear;

(1-6) 8 g of prepolymerized tetraethyl silicate was slowly added dropwise to the F127 template solution, and stirred at room temperature for 1 h to obtain the final mesoporous silica precursor solution;

(1-7) After that, spin-coat 250 μl of the mesoporous silicon oxide precursor solution on the AAO substrate with the pores blocked, the spin-coating speed is 3500 rpm, and the spin-coating time is 60 seconds;

(1-8) After that, the final mesoporous silica/alumina (MS/AAO) composite film can be obtained by evaporation-induced self-assembly at 40°C for 24h and thermal polymerization at 100°C for 24h.

Step 2: Then configure the water-oil phase solution for synthesizing the polyurea monomer: first, configure a 1.8w/v% polyethyleneimine (PEI) aqueous solution, and dissolve 260mg of 50wt% PEI solution into 65ml of deionized water; Then, 0.8w/v% of 2,4-diisocyanate (TDI) was prepared. About 0.05g of TDI was weighed and dissolved in 65ml of n-hexane. The two prepared solutions were placed in an oven at 60°C. middle;

Step 3: After that, first drop 250 μL of PEI onto the surface of the MS/AAO membrane, and wait for it to volatilize the water to dryness at 60°C;

Step 4: After that, 200 μL of TDI solution was added dropwise to the surface of MS/AAO containing PEI polymer chains, and the interfacial polymerization reaction between the amino group and isocyanate between the two phases occurred in an oven at 60 °C, and the reaction time was 1 min. Polyurea film, then the final PMSA composite film with high mechanical properties is obtained.

Taking Example 1 as an example, the obtained PMSA composite membrane was tested

1. Morphology characterization of PMSA composite film

The MS/AAO and PMSA were carefully cut into small pieces, and then pasted on the scanning stage with conductive adhesive. The surface and cross-sectional morphology of the MS/AAO and PMSA composite films were observed. Figure 3 compares the surface topography of the MS/AAO composite film on the MS side and the PU-MS surface topography of the PMSA composite film. Figure 3a,b is the surface appearance of the MS/AAO composite film on the MS side, it can be seen that mesoporous silicon oxide grows on the AAO substrate; Figure 3c,d is the MS/AAO film with a PU layer grown on the surface, it can be seen Compared with the MS/AAO surface, a polyurea coating grows on the MS/AAO surface.

Figure 4 is a cross-sectional view of the MS/AAO composite membrane and the PMSA composite membrane, and a polyurea coating is grown on the surface of the MS/AAO composite membrane. Figure 5 is a point scan on the surface of the PMSA composite membrane. Two points were selected on the PMSA surface, and it was found that both were rich in nitrogen elements, which also indicated that the polyurea coating was successfully grown on the surface of the MS/AAO composite membrane. Figure 6 is a surface scan of the elements on the PMSA surface. It can be seen that nitrogen elements are uniformly distributed on the selected MS surface, which indicates that the polyurea coating is uniformly grown on the surface of the GO layer.

2. Hydrophilic and hydrophobic test of PMSA composite membrane

Figure 7 is a test of the hydrophilicity and hydrophobicity of the MS/AAO composite membrane and the PMSA composite membrane. 0.2 μL of water droplets were added to the surface of the film, and the contact angle after stabilization was measured and photographed. Figure 7a is the contact angle of the MS/AAO composite film. When the water droplets are added to the surface of the mesoporous silica, the water droplets spread out very quickly, and there is basically no obvious contact angle. This is due to the smooth channel wall of MS and the very good caused by the hydrophilicity. Figure 7b-f shows the hydrophilicity and hydrophobicity of PMSA composite membranes modified with polyurea with different layers (1-5 times). It can be seen that the surface of PMSA composite membrane modified with polyurea has very good water resistance, indicating that polyurea plays a role in The role of the protective layer endows it with potential practical application value.

The foregoing description of the embodiments is provided to facilitate understanding and use of the invention by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the generic principles described herein can be applied to other embodiments without inventive step. Therefore, the present invention is not limited to the above-mentioned embodiments, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should all fall within the protection scope of the present invention.

Claims (10)

1. a preparation method of interface super-assembly polyurea/porous material/alumina functional membrane, is characterized in that, comprises the following steps: (1) An ordered mesoporous silica film was grown on an AAO substrate by an interfacial superassembly method to obtain a mesoporous silica/alumina (MS/AAO) composite film; (2) configure the water-oil phase solution for synthesizing the polyurea monomer; (3) drop the PEI onto the surface of the MS/AAO film, and volatilize the water to dryness; (4) The TDI solution was added dropwise to the surface of MS/AAO containing PEI polymer chains, and the interfacial polymerization of amino groups between the two phases and isocyanate occurred to form a dense polyurea film, and a PMSA composite film with high mechanical properties was obtained. 2. the preparation method of a kind of interface super-assembly polyurea/porous material/alumina functional membrane according to claim 1, is characterized in that, step (1) specifically comprises the following steps: (1-1) adopt polymethyl methacrylate to carry out pore blocking treatment to AAO; (1-2) spin-coating the polymethyl methacrylate solution onto the AAO substrate; (1-3) The spin-coated PMMA/AAO film is dried to ensure that the PMMA penetrates into the AAO pores; (1-4) Prepare a precursor solution of mesoporous silica and prepolymerize at 60°C; (1-5) Preparation of F127 template agent solution; (1-6) dropping the prepolymerized mesoporous silica into the F127 template solution, stirring at room temperature, to obtain the final mesoporous silica precursor solution; (1-7) spin-coating the mesoporous silicon oxide precursor solution onto the plugged AAO substrate; (1-8) Evaporation-induced self-assembly at 40 °C for 24 h and thermal polymerization at 100 °C for 24 h to obtain the final mesoporous silica/alumina (MS/AAO) composite film. 3. the preparation method of a kind of interface super-assembled polyurea/porous material/alumina functional membrane according to claim 2, is characterized in that, the concrete method of step (1-1) is: the polymethyl methacrylate of 2.3-2.7g is Methyl methacrylate (PMMA) was dissolved in 23ml-27ml of acetone solution, heated and stirred at 40-45°C until dissolved. 4. the preparation method of a kind of interface super-assembly polyurea/porous material/alumina functional film according to claim 2, is characterized in that, step (1-2) spin coating rotation speed is 3000-3500 revolutions, and spin coating time for 30-40 seconds. 5. the preparation method of a kind of interface super-assembly polyurea/porous material/alumina functional film according to claim 2, is characterized in that, the PMMA/AAO film after step (1-3) spin coating is in fume hood Dry for two hours, followed by 5-6 hours in an oven at 200°C. 6. the preparation method of a kind of interface super-assembled polyurea/porous material/alumina functional membrane according to claim 2, is characterized in that, the concrete method of step (1-4) is: prepare prepolymerized mesoporous silica For oligomers, add 2-2.2g of tetraethyl silicate to 10-12g of absolute ethanol, 1.0-1.5g of deionized water and 0.5-0.6g of 0.2M hydrochloric acid mixed solution. Polymerization for 1h. 7. the preparation method of a kind of interface super-assembled polyurea/porous material/alumina functional membrane according to claim 2, is characterized in that, step (1-5) prepares the concrete method of F127 template agent solution as follows: 0.8- 1g of F127 was dissolved in 9-12g of absolute ethanol, and ultrasonically dispersed and dissolved until it became clear. 8 . The method for preparing an interface super-assembled polyurea/porous material/alumina functional film according to claim 2 , wherein in step (1-7), 200-250 μl of mesoporous silica precursor solution is added to Spin-coated on the blocked AAO substrate, the spin-coating speed is 3000-3500 rpm, and the spin-coating time is 40-60 seconds. 9. the preparation method of a kind of interface super-assembled polyurea/porous material/alumina functional membrane according to claim 1, is characterized in that, the concrete method of the water-oil phase solution of step (2) disposing synthetic polyurea monomer is as follows: : Prepare 1.0-1.8w/v% polyethyleneimine (PEI) aqueous solution, dissolve 110-260mg 50wt% PEI solution in 55-65ml deionized water; then prepare 0.3-0.8w/v% 2 ,4-Tolyl diisocyanate (TDI), weigh about 0.01-0.05g of TDI and dissolve it in 55-65ml of n-hexane, and place the prepared two solutions in an oven at 60°C. 10. The method for preparing an interface super-assembled polyurea/porous material/alumina functional membrane according to claim 1, wherein in step (3), 200-250 μL of PEI is added dropwise to the MS/AAO membrane surface, and wait for it to evaporate the water to dryness at 60°C; In step (4), 160-200 μL of TDI solution was added dropwise to the surface of MS/AAO containing PEI polymer chains, and the interfacial polymerization reaction between the amino group and isocyanate between the two phases occurred in an oven at 60° C. The reaction time was 1 min.

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