CN116239819A - Superhydrophobic polyurethane-based Econea composite material and preparation method thereof - Google Patents

Abstract

The application discloses a superhydrophobic polyurethane-based Econea composite material and a preparation method thereof. The preparation method includes dissolving Econea in an organic solvent to obtain a functional liquid, and then dropping the functional liquid into isocyanate to obtain a functional antibacterial agent; configuring polyurethane The foaming component of the sponge is mixed and stirred to obtain a foaming liquid; the functionalized antibacterial agent is mixed with the foaming liquid to obtain a PU‑Econea sponge; the PU‑Econea sponge is soaked in the hydrophobic modification liquid, and then taken out, heated and cured for cleaning, A superhydrophobic polyurethane-based Econea composite was obtained. The application of Econea can effectively improve the antibacterial performance of the material, and at the same time, the surface hydrophobic material further improves the antibacterial performance of the material. The synergistic effect of the two makes the antibacterial performance reach 99.7%, which effectively solves the problem that Econea is easy to hydrolyze; Excellent hydrophobic effect can also be guaranteed in the environment.

Description

Superhydrophobic polyurethane-based Econea composite material and preparation method thereof

technical field

The application belongs to the technical field of hydrophobic materials, and in particular relates to a superhydrophobic polyurethane-based Econea composite material and a preparation method thereof.

Background technique

The massive exploitation of offshore oil leads to frequent occurrence of oil spill accidents, which has caused serious disasters to the marine ecological environment. Among the methods of dealing with marine oil spills, superhydrophobic oil-absorbing materials have been widely studied and applied in solving marine oil spills due to their high absorption efficiency and low application cost.

Polyurethane sponge is considered as an ideal oil-absorbing material due to its advantages such as high oil-absorbing capacity, good mechanical strength, fast rebound performance and easy modification. However, due to the large number of polar groups on the surface of the sponge during the foaming process, it lacks oil-water selectivity. In addition, the oil-absorbing material is immersed in the marine environment, and the surface and internal channels of the porous material are easily eroded by marine organisms, resulting in the destruction of the hydrophobic surface and the decline in oil absorption capacity, which affects the application of polyurethane sponges in solving marine oil spills.

Contents of the invention

The purpose of this application is to provide a kind of superhydrophobic polyurethane-based Econea composite material and preparation method thereof, to solve the polyurethane sponge existing in the prior art because its surface contains a large amount of polar groups and cause it to lack oil-water selectivity, the surface of porous material and internal channels are susceptible to erosion by marine organisms, resulting in technical problems of damage to the hydrophobic surface and reduced oil absorption capacity.

In order to achieve the above object, a technical solution adopted by the application is:

A preparation method of a superhydrophobic polyurethane-based Econea composite material is provided, comprising:

Dissolving Econea in an organic solvent to obtain a functional liquid, and then dropping the functional liquid into isocyanate to obtain a functionalized antibacterial agent;

Configure polyurethane foam foaming components, mix and stir to obtain foaming liquid;

Mixing and reacting the functionalized antibacterial agent with the foaming liquid to obtain PU-Econea sponge;

The PU-Econea sponge is soaked in the hydrophobic modification solution, and then taken out, heated and cured for cleaning to obtain a superhydrophobic polyurethane-based Ecoconea composite material.

In one or more embodiments, the organic solvent includes one or more combinations of dichloromethane, ethyl acetate, toluene, n-hexane, and chloroform.

In one or more embodiments, the polyurethane sponge foaming component includes the following raw materials in parts by weight:

10-60 parts of polyether polyol; 0.1-2 parts of catalyst; 0.1-2 parts of surfactant and 1-5 parts of deionized water.

In one or more embodiments, the catalyst includes one or more combinations of dibutyltin dilaurate, stannous isooctanoate, triethylenediamine, pentamethyldiethylenetriamine, and dimethylpiperazine , the surfactant includes one or more combinations of RC-G108, L-580, PMX-200.

In one or more embodiments, the mixing and stirring to obtain a foaming liquid specifically includes: stirring at a high speed at room temperature for 25 to 35 minutes to obtain a foaming liquid.

In one or more embodiments, the mass ratio of the functionalized antibacterial agent to the foaming liquid is (10-40): (10-70), and the content of Econea in the PU-Econea sponge is 0.1-3wt%, the content of the isocyanate in the PU-Econea sponge is 10-40wt%.

In one or more embodiments, the hydrophobic modification liquid includes hydrophobic nano-silica particles and polydimethylsiloxane.

In one or more embodiments, the mass concentration of the hydrophobic nano-silica particles in the hydrophobic modification liquid is 0.1-1.5 wt%, and the mass concentration of the polydimethylsiloxane is 0.8-1.2 wt%.

In order to achieve the above object, another technical solution adopted by the application is:

A superhydrophobic polyurethane-based Econea composite material prepared by the preparation method described in any one of the above-mentioned embodiments is provided.

In order to achieve the above object, another technical solution adopted by the application is:

An application of the superhydrophobic polyurethane-based Econea composite material prepared by the preparation method described in any one of the above-mentioned embodiments is provided in marine oil spill treatment.

Different from the prior art, the beneficial effects of the present application are:

This application firstly reacts Econea with isocyanate to make Econea chemically grafted on the isocyanate, then mixes the isocyanate grafted with Econea with the foaming liquid to perform a foaming reaction to generate PU-Econea sponge, which realizes the immobilization of Econea, and then PU -Econea sponge immersed in hydrophobic modification solution for surface hydrophobic modification can significantly improve the oil absorption performance of the material, Econea can effectively improve the antibacterial performance of the material, and at the same time, the hydrophobic material attached to the surface of the sponge can also further improve the antibacterial performance of the material, the synergy between the two Make the antibacterial performance of the material of the present application reach 99.7%;

The composite material of this application is immobilized by chemical grafting of Econea, which effectively solves the problem that Econea is easy to hydrolyze, improves the antibacterial performance of the oil-absorbing material on the premise of not containing heavy metal organic matter, and can effectively avoid marine pollution when applied to marine oil spill scenarios. Biological attachment, maintaining strong adsorption performance for a long time;

The composite material of this application has excellent hydrophobic properties, and can also guarantee excellent hydrophobic effects in extreme environments. It has strong adsorption properties for different organic solvents and oil products, and the adsorption capacity for chloroform has reached 133.9g /g, the adsorption capacity of light crude oil reached 63.7g/g.

Description of drawings

Fig. 1 is the schematic flow sheet of the preparation method one embodiment of superhydrophobic polyurethane based Econea composite material of the present application;

Fig. 2 is the scanning electron microscope picture of effect example 1 of the present application;

Fig. 3 is the photo of the superhydrophobic polyurethane-based Econea composite material that the application embodiment 1 prepares;

Fig. 4 is the comparison chart of the antibacterial experiment result of the application effect example 2;

Fig. 5 is the result figure of the oil absorption performance experiment of effect example 3 of the present application;

Fig. 6 is a graph showing the experimental results of the adsorption performance of Effect Example 4 of the present application.

Detailed ways

The present application will be described in detail below in conjunction with various implementations shown in the accompanying drawings. However, these embodiments do not limit the present application, and structural, method, or functional changes made by those skilled in the art according to these embodiments are included within the scope of protection of the present application.

The massive exploitation of offshore oil leads to frequent occurrence of oil spill accidents, which has caused serious disasters to the marine ecological environment. Among the methods of dealing with marine oil spills, superhydrophobic oil-absorbing materials have been widely studied and applied in solving marine oil spills due to their high absorption efficiency and low application cost. Polyurethane sponge is considered to be an ideal oil-absorbing material due to its high oil-absorbing capacity, good mechanical strength, fast rebound performance and easy modification. Due to the large number of polar groups on the surface of the sponge during the foaming process, resulting in It lacks oil-water selectivity.

In addition, the oil-absorbing material is immersed in the marine environment, and the surface and internal channels of the porous material are easily eroded by marine organisms, resulting in the destruction of the hydrophobic surface and the decrease of the oil-absorbing capacity. Since the development of the chemical industry in the late 19th century, humans have provided heavy metal compounds based on copper, mercury, arsenic, lead, etc. as antifouling agents in paints. Cumulative transmission along the food chain poses a serious threat to human health.

To this end, the applicant has developed a superhydrophobic polyurethane-based Econea composite material. On the one hand, this material can ensure its oil absorption performance by hydrophobically modifying the surface of the polyamide sponge. On the other hand, it can effectively improve the surface and The anti-fouling performance of the internal channel prevents marine bio-erosion materials from affecting the water absorption performance, and is environmentally friendly, so the composite material can be applied to the treatment of marine oil spills.

Specifically, please refer to FIG. 1 , which is a schematic flow chart of an embodiment of the preparation method of the superhydrophobic polyurethane-based Econea composite material of the present application.

The preparation method includes:

S100, dissolving Econea in an organic solvent to obtain a functional liquid, and then dropping the functional liquid into isocyanate to obtain a functionalized antibacterial agent.

2-(p-Chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole (Econea) as a novel environmentally friendly marine antifouling agent with a short half-life in seawater , can be deeply explained by marine organisms without accumulation, and is currently widely used in marine antifouling coatings and plays an important role in the global marine antifouling system.

However, Econea is easily degraded in the water environment, and its half-life is about 3 hours. In order to slow down its hydrolysis in seawater and maintain its long-term antifouling performance in complex environments, it needs to be immobilized during use.

Specifically, Econea can be dissolved in an organic solvent and then added dropwise to isocyanate. During the dropwise addition, Econea reacts with isocyanate to chemically graft Econea on isocyanate.

In one application scenario, the mass ratio of the functional antibacterial agent to the foaming liquid is (10-40): (11.2-69).

In an application scenario, the organic solvent may include one or more combinations of dichloromethane, ethyl acetate, toluene, n-hexane, and chloroform, as long as it can realize the dissolution of Econea.

S200, configuring polyurethane foam foaming components, mixing and stirring to obtain a foaming liquid.

In one application scenario, the polyurethane sponge foaming component includes the following raw materials in parts by weight:

10-60 parts of polyether polyol; 0.1-2 parts of catalyst; 0.1-2 parts of surfactant and 1-5 parts of deionized water.

Wherein, the catalyst can include dibutyltin dilaurate, stannous isooctanoate, triethylenediamine, pentamethyldiethylenetriamine, one or more combinations in dimethylpiperazine; surfactant can include RC- One or more combinations of G108, L-580, PMX-200.

In an application scenario, mixing and stirring to obtain a foaming liquid may specifically include: stirring at a high speed at room temperature for 25 to 35 minutes to obtain a foaming liquid.

S300, mixing and reacting the functionalized antibacterial agent with the foaming solution to obtain a PU-Econea sponge.

In the process of mixing the functional antibacterial agent with the foaming liquid, the isocyanate grafted with Econea and the foaming liquid are mixed and foamed to obtain a polyurethane sponge, which realizes the immobilization of Econea, avoids the degradation of Econea in the water environment, and makes Econea able to In the marine environment, the polyurethane surface and porous channels can resist bacterial adhesion for a long time, so that the composite material has better antibacterial properties and prevents marine organisms from affecting the oil absorption performance of the material.

In an application scenario, the mass ratio of the functionalized antibacterial agent to the foaming liquid can be (10-40): (11.2-69), the content of Econea in the PU-Econea sponge can be 0.1-3wt%, and the PU-Econea sponge The content of isocyanate can be 10-40wt%.

S400. Soak the PU-Econea sponge in the hydrophobic modification solution, then take it out, heat and cure it, and clean it to obtain a superhydrophobic polyurethane-based Ecoconea composite material.

Further, after the Econea is immobilized to obtain the PU-Econea sponge, the PU-Econea sponge can be soaked in the hydrophobic modification solution, and the surface of the polyurethane sponge can be hydrophobically modified by the dip coating method, so that it has a better oil-water selection sex.

In an application scenario, the hydrophobic modification liquid may include hydrophobic nano-silica particles and polydimethylsiloxane.

Polydimethylsiloxane (PDMS) is a high molecular polymer with stable physical and chemical properties, colorless and odorless, high transparency, good thermal conductivity, and low surface energy. Used as an additive for defoamers, mold release agents and other materials; SiO ₂ is a chemical substance that exists widely in nature. Hydrophobic silica is obtained by reacting fumed silica with active silane, which has a large specific surface area and can be adsorbed Strong force, good dispersion effect and so on.

By soaking the PU-Econea sponge in the hydrophobic modification solution containing PDMS and _SiO2 , the low surface energy PDMS can be loaded on the surface of the PU-Econea sponge and inside the porous channels, while _SiO2 is attached to the surface of the PU-Econea sponge. On the surface and inside the porous channel, the surface roughness of PU-Econea sponge is improved, thereby significantly improving the hydrophobic performance and oil-water selectivity of the material.

Specifically, the mass concentration of hydrophobic nano-silica particles in the hydrophobic modification solution may be 0.1-1.5 wt%, and the mass concentration of polydimethylsiloxane may be 0.8-1.2 wt%.

The effect of the technical solution of the present application will be further explained in detail below in conjunction with specific examples.

Example 1:

A kind of superhydrophobic polyurethane base Econea composite material, adopts following method to prepare:

Weigh 0.03g of Econea and dissolve it in 5g of dichloromethane to obtain a functional liquid, then weigh 10g of isocyanate, stir it mechanically at 40°C, and drop the functional liquid into the isocyanate to obtain a functional antibacterial agent;

Weigh 10g of polyether polyol, 1g of dibutyltin dilaurate, 0.1g of RC-G108 and 3g of deionized water, stir at room temperature for 30 minutes at high speed to obtain a foaming solution;

Mix and react the functionalized antibacterial agent and foaming solution to obtain PU-Econea sponge;

The PU-Econea sponge is soaked in the hydrophobic modification solution, and then taken out, heated and cured for cleaning to obtain a super-hydrophobic polyurethane-based Ecoconea composite material, wherein the hydrophobic modification solution includes 0.1wt% hydrophobic nano-silica particles and 1wt% polystyrene Dimethicone.

Example 2:

A kind of superhydrophobic polyurethane base Econea composite material, adopts following method to prepare:

Weigh 1g of Econea and dissolve it in 5g of ethyl acetate to obtain a functional liquid, then weigh 20g of isocyanate, stir mechanically at 40°C, drop the functional liquid into the isocyanate to obtain a functional antibacterial agent;

Weigh 60g of polyether polyol, 2g of stannous isooctanoate, 2g of L-580 and 5g of deionized water, and stir at high speed for 30 minutes at room temperature to obtain a foaming solution;

Mix and react the functionalized antibacterial agent and foaming solution to obtain PU-Econea sponge;

Soak the PU-Econea sponge in the hydrophobic modification solution, then take it out, heat and cure it, and wash it to obtain a superhydrophobic polyurethane-based Ecoconea composite material, wherein the hydrophobic modification solution includes 1.5wt% hydrophobic nano-silica particles and 0.8wt% Polydimethylsiloxane.

Example 3:

A kind of superhydrophobic polyurethane base Econea composite material, adopts following method to prepare:

Weigh 2g of Econea and dissolve it in 10g of toluene to obtain a functional liquid, then weigh 25g of isocyanate, stir it mechanically at 40°C, and drop the functional liquid into the isocyanate to obtain a functional antibacterial agent;

Weigh 30g of polyether polyol, 0.1g of pentamethyldiethylenetriamine, 1g of PMX-200 and 1g of deionized water, and stir at high speed for 30 minutes at room temperature to obtain a foaming solution;

Mix and react the functionalized antibacterial agent and foaming solution to obtain PU-Econea sponge;

The PU-Econea sponge is soaked in the hydrophobic modification solution, and then taken out, heated and cured for cleaning to obtain a superhydrophobic polyurethane-based Ecoconea composite material, wherein the hydrophobic modification solution includes 1 wt% of hydrophobic nano-silica particles and 1.2 wt% of polystyrene Dimethicone.

Comparative example 1:

A kind of PU sponge, adopts following method to prepare:

Weigh 10g of isocyanate and stir mechanically at 40°C;

Weigh 10g of polyether polyol, 1g of dibutyltin dilaurate, 0.1g of RC-G108 and 3g of deionized water, stir at room temperature for 30 minutes at high speed to obtain a foaming solution;

The isocyanate and the foaming liquid are mixed and reacted to obtain the PU sponge.

Comparative example 2:

A kind of PU-Econea sponge, adopts following steps to prepare:

Weigh 0.03g of Econea and dissolve it in 5g of dichloromethane to obtain a functional liquid, then weigh 10g of isocyanate, stir it mechanically at 40°C, and drop the functional liquid into the isocyanate to obtain a functional antibacterial agent;

Weigh 10g of polyether polyol, 1g of dibutyltin dilaurate, 0.1g of RC-G108 and 3g of deionized water, stir at room temperature for 30 minutes at high speed to obtain a foaming solution;

Mix and react the functionalized antibacterial agent and the foaming liquid to obtain PU-Econea sponge.

Comparative example 3:

A kind of PDMS-PU-Econea sponge composite material, adopts following steps to prepare:

Weigh 0.03g of Econea and dissolve it in 5g of dichloromethane to obtain a functional liquid, then weigh 10g of isocyanate, stir it mechanically at 40°C, and drop the functional liquid into the isocyanate to obtain a functional antibacterial agent;

Weigh 10g of polyether polyol, 1g of dibutyltin dilaurate, 0.1g of RC-G108 and 3g of deionized water, stir at room temperature for 30 minutes at high speed to obtain a foaming solution;

Mix and react the functionalized antibacterial agent and foaming solution to obtain PU-Econea sponge;

The PU-Econea sponge is soaked in the hydrophobic modification solution, and then taken out, heated and cured for cleaning to obtain a PDMS-PU-Econea sponge composite material, wherein the hydrophobic modification solution includes 1.1 wt% polydimethylsiloxane.

Effect example 1:

The superhydrophobic polyurethane-based Ecoconea composite material prepared in Example 1 and the PU-Econea sponge prepared in Comparative Example 2 were analyzed by scanning electron microscopy, and Figure 2 was obtained.

Please refer to Fig. 2, Fig. 2 is the scanning electron micrograph of the effect example 1 of the present application, wherein a, b are the scanning electron micrographs of the material prepared in the comparative example 2, and c, d are the scanning electron micrographs of the material prepared in the embodiment 1.

As shown in the figure, the materials prepared in Example 1 and Comparative Example 2 all form a three-dimensional porous structure, and the surface of the material prepared in Comparative Example 2 is smooth without attachments; while the material prepared in Example 1 obtained after hydrophobic modification, sponge The surface becomes rough and the surface is covered with _SiO2 nanoparticles.

Therefore, it can be seen that after the hydrophobic modification of PDMS and _SiO2 , the surface of the PU sponge can be loaded with low surface energy PDMS, and _SiO2 nanoparticles can be attached to improve the surface roughness and the oil-water separation performance of the material.

The photo of the superhydrophobic polyurethane-based Econea composite material prepared in Example 1 is shown in Figure 3, and Figure 3 is a photo of the superhydrophobic polyurethane-based Ecoconea composite material prepared in Example 1 of the present application. As shown in the figure, the material has a porous sponge structure with a rough surface.

Effect example 2: Antibacterial experiment

The materials prepared in Example 1, Comparative Example 1, and Comparative Example 2 were cut into samples of 10×10×10 mm ³ and immersed in artificial seawater for 24 hours.

Prepare liquid medium to cultivate Escherichia coli, then remove the samples of Example 1 and Comparative Examples 1 to 3 from artificial seawater and fix them at the bottom of the liquid medium to fully contact with activated Escherichia coli, and cultivate for 24 hours.

After the cultivation, the samples of Example 1, Comparative Example 1, and Comparative Example 2 were taken out to rinse off the E. coli on the surface of the sample with PBS reagent, and the washed E. coli was diluted and cultivated in a solid medium for 24 hours to form colonies. The number of Escherichia coli was measured by the colony method, and the antibacterial properties of the materials prepared in Example 1 and Comparative Example 2 were calculated with reference to the number of colonies in the sample of Comparative Example 1, and Figure 4 was obtained.

Please refer to FIG. 4 , which is a comparison chart of the antibacterial experiment results of Effect Example 2 of the present application. As shown in the figure, compared with the PU sponge of Comparative Example 1, the PU-Econea sponge of Comparative Example 2 has better antibacterial performance, and can inhibit the attachment of E. coli by about 88.96±3.2%, reflecting the antibacterial performance of Econea.

Compared with the PU sponge of Comparative Example 1, the PDMS-PU-Econea sponge of Comparative Example 3 has an excellent antibacterial performance of about 96.03±1.7%, which is related to the good antibacterial performance of Econea and the low surface energy of PDMS.

In addition, by introducing _SiO nanoparticles to increase the surface roughness, the superhydrophobic polyurethane-based Econea composite of Example 1 had the highest antibacterial ability, reaching 99.12 ± 0.6%. Therefore, low surface energy (PDMS), high surface roughness (SiO ₂ ) and antibacterial activity (Econea) can synergistically improve the antifouling and antibacterial properties.

Effect example 3: oil absorption performance experiment

The materials prepared in Example 1 and Comparative Examples 1 to 3 were used for oil absorption performance experiment. Specifically, the materials prepared in Example 1 and Comparative Examples 1 to 3 were cut into 10×10×10 mm samples and immersed in crude oil ^, and the materials were taken out with tweezers at regular intervals to measure the weight, based on the weight of the materials before and after oil absorption Calculate the oil absorption performance of the material by difference, and get Figure 5.

Please refer to FIG. 5 . FIG. 5 is a graph showing the experimental results of the oil absorption performance of Effect Example 3 of the present application. As can be seen from the figure, the process of crude oil entering the PU sponge of Comparative Example 1 and the PU-Econea sponge of Comparative Example 2 is very slow, and after soaking for 10 minutes, it can only absorb about 28g/g (crude oil weight/sponge weight) crude oil.

The PDMS-PU-Econea sponge of Comparative Example 3 can absorb 48g/g crude oil after soaking for 10 minutes. Compared with comparative example 3, the material of Example 1 introduces SiO2 nanoparticles, which greatly enhances the hydrophobicity of the sponge, and absorbs 58.8g/g crude oil within 3 minutes, after which the oil absorption capacity does not increase significantly with time. The maximum adsorption capacity for light crude oil is reached within minutes.

Effect example 4: adsorption performance experiment

Get the superhydrophobic polyurethane-based Econea composite material prepared in Example 2 and cut into 10 × 10 × 10mm ^Samples , respectively immersed in ethanol, methanol, benzene, n-hexane, isopropanol, dichloromethane, chloroform, light crude oil In , after the inside of the material is saturated, the material is taken out with tweezers and weighed. Based on the mass of the material before and after adsorption, the adsorption capacity of the material is calculated, and Figure 6 is obtained.

Please refer to FIG. 6, which is a graph showing the experimental results of the adsorption performance of Effect Example 4 of the present application. As shown in the figure, the material prepared in Example 2 has the largest adsorption capacity in chloroform, reaching 133.9g/g, and the adsorption capacity in light crude oil reaches 63.7g/g.

It can be seen from the above that the superhydrophobic polyurethane-based Econea composite material prepared in Example 2 has good adsorption properties for different organic solvents and oils.

The specific implementation manner described above in conjunction with the accompanying drawings describes exemplary embodiments, but does not represent all embodiments that can be realized or fall within the protection scope of the claims. As used throughout this specification, the term "exemplary" means "serving as an example, instance, or illustration," and does not mean "preferred" or "advantaged" over other embodiments. The detailed description includes specific details for the purpose of providing an understanding of the described technology. However, the techniques may be practiced without these specific details. In some instances, well-known structures and devices are shown in block diagram form in order to avoid obscuring the concepts of the described embodiments.

The above description of the present disclosure is provided to enable any person of ordinary skill in the art to make or use the present disclosure. Various modifications to the present disclosure will be obvious to those skilled in the art, and the corresponding general principles herein can also be applied to other variants without departing from the protection scope of the present disclosure . Thus, the disclosure is not intended to be limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The preparation method of the super-hydrophobic polyurethane-based Econea composite material is characterized by comprising the following steps of:

dissolving Econea in an organic solvent to obtain a functional liquid, and then dripping the functional liquid into isocyanate to obtain a functional antibacterial agent;

preparing polyurethane sponge foaming components, mixing and stirring to obtain foaming liquid;

mixing the functional antibacterial agent with the foaming liquid for reaction to obtain PU-Econea sponge;

and soaking the PU-Econea sponge in the hydrophobic modification liquid, and then taking out, heating, solidifying and cleaning to obtain the super-hydrophobic polyurethane-based Econea composite material.

2. The preparation method according to claim 1, wherein the organic solvent comprises one or more of dichloromethane, ethyl acetate, toluene, n-hexane, and chloroform.

3. The preparation method according to claim 1, wherein the polyurethane sponge foaming component comprises the following raw materials in parts by weight:

10-60 parts of polyether polyol; 0.1-2 parts of catalyst; 0.1 to 2 parts of surfactant and 1 to 5 parts of deionized water.

4. The method of claim 3, wherein the catalyst comprises one or more of dibutyl tin dilaurate, stannous octoate, triethylene diamine, pentamethyl diethylene triamine, and dimethyl piperazine, and the surfactant comprises one or more of RC-G108, L-580, and PMX-200.

5. The preparation method according to claim 3, wherein the mixing and stirring to obtain the foaming liquid comprises the following steps: stirring at high speed for 25-35 min at room temperature to obtain foaming liquid.

6. The preparation method according to claim 1, wherein the mass ratio of the functionalized antimicrobial agent to the foaming liquid is (10-40): (10-70), wherein the content of the Econea in the PU-Econea sponge is 0.1-3 wt%, and the content of the isocyanate in the PU-Econea sponge is 10-40 wt%.

7. The method of claim 1, wherein the hydrophobically modified liquid comprises hydrophobic nanosilica particles and polydimethylsiloxane.

8. The method according to claim 7, wherein the hydrophobic nano silica particles in the hydrophobic modification liquid have a mass concentration of 0.1 to 1.5wt% and the polydimethylsiloxane has a mass concentration of 0.8 to 1.2wt%.

9. A superhydrophobic polyurethane-based ecoea composite prepared by the method of any one of claims 1-8.

10. An application of the super-hydrophobic polyurethane-based ecoea composite material prepared by the preparation method of any one of claims 1 to 8 in marine oil spill treatment.

Images