Preparation method of super-hydrophilic light-heat composite material with underwater oil absorption capacity

Abstract

The present application relates to the technical field of super-hydrophilic / super-oleophilic materials, and particularly to a preparation method of a super-hydrophilic photo-thermal composite material with the ability to absorb heavy oil underwater, which comprises the following steps: first, natural oligomeric amino polysaccharide is used to synergistically aminate raw cotton with amino silane coupling agent; then, based on the synergistic amination system of the raw cotton, polymeric active units and nano-scale heat-conducting particles are introduced into the raw cotton; and finally, the mixed liquid phase is cured by the hyperbranched polymer forming method to complete the construction of the super-hydrophilic photo-thermal composite material with the ability to absorb heavy oil underwater by the one-pot method. The raw materials of the present application are green and environmentally friendly, and the experimental steps are simple, safe and convenient. The prepared product has excellent super-hydrophilicity and super-oleophilicity in an air atmosphere, with a contact angle of 0°. In an underwater atmosphere, the product has super-hydrophilicity and excellent oil absorption performance, and still has stable super-hydrophilicity and oil absorption capacity after cyclic utilization in different atmospheres. In addition, the product has good photo-thermal performance and good absorption and separation capacity for viscous oil phases, which lays a foundation for wider application.

Description

Preparation method of superhydrophilic photothermal composite material with underwater heavy oil absorption capability Technical Field

[0001] This invention relates to the field of superhydrophilic / superoleophilic materials technology, specifically to a method for preparing a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater. Background Technology

[0002] In recent years, with the rapid development of science and technology and industry, the continuous increase in industrial oily wastewater, and the frequent occurrence of marine oil spills, which have brought great harm to the ecological environment and human health, how to achieve continuous, stable, and efficient oil-water separation has become a research hotspot. Heavy oil in wastewater has a large molecular weight and high viscosity. Traditional adsorption and membrane separation methods can effectively adsorb the oil phase in wastewater, but these methods suffer from high costs in manufacturing adsorbent materials and the susceptibility of membrane materials to fouling, leading to low material recycling performance. Therefore, the removal of heavy oil is complex and difficult.

[0003] Current research on materials and methods for constructing underwater heavy oil absorption structures includes, for example, invention patent CN113788970B, a carbon nanotube / microcrystalline cellulose composite membrane and its preparation method and application, which proposes to use a specific ratio of aldehyde-based microcrystalline cellulose and aminated carbon nanotubes to prepare a composite membrane material with good wettability, photothermal effect, and emulsion separation properties through a Schiff base reaction; and invention patent CN113398769B, a CS-CNCs multilayer modified membrane for anti-oil contamination and its preparation method and application, which proposes to use hydroxylated stainless steel mesh as a substrate and chitosan and cellulose nanocrystals for layer-by-layer self-assembly to obtain... Composite materials exhibiting super-amphiphilic properties in air and capable of efficiently separating crude oil / water mixtures and oil-in-water emulsions are being developed. Currently, monolithic solid materials with high porosity are also being widely researched and applied to oil-water separation. Specifically, porous polystyrene monoliths with amphibious super-amphiphilic properties are prepared through emulsion template methods, achieving super-hydrophilicity in both air and underwater environments and exhibiting good adsorption effects on various light and heavy oils. However, these experimental methods require high reaction conditions, involve overly complicated reaction steps, and use materials containing toxic components. Therefore, it is particularly important to construct materials with simpler reaction processes, superior effects, and environmentally friendly heavy oil adsorption capabilities. Summary of the Invention

[0004] In view of the deficiencies of the prior art, the present invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability. The method is based on a cotton synergistic amination system, which modifies the cotton to be hydrophilic, and then places it in an alcohol system. Polymer active units and nanoscale thermally conductive particles are introduced in sequence. Under room temperature conditions, the superhydrophilic photothermal composite material with underwater heavy oil absorption capability is easily and quickly constructed through the gelation effect of multi-acrylate compounds and multi-amino compounds.

[0005] To achieve the above objectives, the present invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps: weighing silicon carbide and placing it in a sodium hydroxide solution, heating it in a water bath, centrifuging and washing it several times, and drying it to obtain modified silicon carbide for later use; completely immersing the purified raw cotton in a sodium hydroxide solution, washing it in an oil bath, drying it, and combing it to obtain hydroxylated raw cotton for later use; weighing chitosan oligosaccharide and completely dissolving it in an equal volume of deionized water and anhydrous ethanol, adding it to the hydroxylated raw cotton, and uniformly dispersing it in the reaction liquid phase, adjusting... Adjust the pH value of the system, add 3-aminopropyltriethoxysilane, and heat it in an oil bath until fully dissolved. Remove the solution and wash it with anhydrous ethanol to obtain amino-functionalized cotton fibers for later use. Place the amino-functionalized cotton fibers in anhydrous ethanol; add a polyacrylate compound and dissolve it completely; add nano-hydroxyapatite and disperse it evenly; add modified nano-silicon carbide and disperse it evenly; add ethylenediamine-terminated polyethyleneimine and disperse it evenly. After the reaction is allowed to complete, a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater is obtained.

[0006] Furthermore, the amount of silicon carbide used is 1g, the amount of sodium hydroxide solution used is 400mL, the concentration of sodium hydroxide solution is 4%, the water bath temperature for silicon carbide treatment is 95℃, the treatment time is 6h, the number of centrifugal washings is 3, the centrifugation speed is 10000r / min, and the treatment time is 10min.

[0007] Further, the amount of raw cotton used is 1g, the amount of sodium hydroxide solution used is 100mL, the concentration of sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, and it is washed with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the mass of chitosan oligosaccharide is 0.2g, the volume of deionized water and anhydrous ethanol is 5mL each, the pH of the system is adjusted to 4-5, the amount of 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and it is washed three times with anhydrous ethanol.

[0008] Further, the volume of the anhydrous ethanol is 10 mL, and the mass ratio of the polyacrylate compound to the amino-functionalized cotton fiber is 30:1; the polyacrylate compound is isoprene tetraacrylate or pentaerythritol triacrylate.

[0009] Furthermore, the mass ratio of the nano-hydroxyapatite to the amino-functionalized cotton fiber is 10:1 to 20:1.

[0010] Furthermore, the mass ratio of the modified nano-silicon carbide to the amino-functionalized cotton fiber is 0.6:1 to 2.4:1.

[0011] Furthermore, the mass ratio of the ethylenediamine-terminated polyethyleneimine to the amino-functionalized cotton fiber is 5:1 to 8:1.

[0012] Furthermore, the final reaction is allowed to stand for 24 hours, and the reaction temperature is room temperature.

[0013] A superhydrophilic photothermal composite material capable of absorbing heavy oil underwater is prepared by any of the above-mentioned methods for preparing a superhydrophilic photothermal composite material capable of absorbing heavy oil underwater.

[0014] The preparation method of the aforementioned superhydrophilic photothermal composite material with underwater heavy oil absorption capability firstly modifies the hydrophilicity of cotton based on a synergistic amination system, then places it in an alcohol-based system, sequentially introducing polymeric active units and nanoscale thermally conductive particles. Under room temperature conditions, the superhydrophilic photothermal composite material with underwater heavy oil absorption capability is easily and quickly constructed through the gelation effect of multi-acrylate and multi-amino compounds. Further investigation is conducted on the water and oil phase wetting and photothermal properties of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability under different atmospheres. Its cyclic water and oil absorption performance under different atmospheres is measured, and its oil absorption performance under different oil / water phase conditions is applied to oil-water separation under water immersion conditions.

[0015] The aforementioned superhydrophilic photothermal composite material with underwater heavy oil absorption capability is used for oil-water separation under different atmospheres.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability. It uses amino-functionalized hydrophilic treated cotton fibers as the physical framework material, and adds nano-photothermal materials to impart good photothermal properties. Utilizing the gelling effect of polyacrylate compounds and multi-amino compounds, a one-pot method is used to construct the superhydrophilic photothermal composite material with underwater heavy oil absorption capability. Compared with other materials, it has advantages such as being environmentally friendly and low-cost, and its preparation steps are simple and safe.

[0018] The superhydrophilic photothermal composite material produced by this invention has the ability to absorb heavy oil underwater, exhibiting good superhydrophilicity and excellent stability.

[0019] The superhydrophilic photothermal composite material produced by this invention has the ability to absorb heavy oil underwater. It is superhydrophilic and superoleophilic in air with a contact angle of 0°. Under water, it is superhydrophilic and has excellent heavy oil absorption capacity. Furthermore, under near-infrared light irradiation, its temperature can rise by 34.6°C in 300s, which is 151.75% higher than that of the composite material. It has good photothermal properties and has significant advantages in the absorption and separation of viscous oil phases.

[0020] The superhydrophilic photothermal composite material produced by this invention has the ability to absorb heavy oil underwater. It can absorb both water and oil phases by a certain multiple in both air and underwater environments, with the maximum oil absorption in underwater environment reaching more than 5 times.

[0021] The superhydrophilic photothermal composite material produced by this invention has excellent recyclability. After six underwater atmospheric cycles for maximum oil absorption, it still exhibits excellent superhydrophilic properties and can be used for oil absorption under continuous and stable water immersion conditions. Attached Figure Description

[0022] Figure 1 is an optical photograph of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1;

[0023] Figure 2 is a schematic diagram of the water and oil wetting effect of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in an air atmosphere in Example 1.

[0024] Figure 3 is a schematic diagram of the water contact angle of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in an air atmosphere in Example 1.

[0025] Figure 4 is a schematic diagram of the oil contact angle of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in an air atmosphere in Example 1.

[0026] Figure 5 is a dynamic schematic diagram of the underwater atmosphere water and oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1.

[0027] Figure 6 is a schematic diagram of the photothermal heating of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1.

[0028] Figure 7 is a schematic diagram of the photothermal temperature increase of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1.

[0029] Figure 8 is a schematic diagram showing the maximum water absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1.

[0030] Figure 9 is a schematic diagram showing the maximum water absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1.

[0031] Figure 10 is a schematic diagram of the test results of the maximum water absorption of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability under different atmospheres in Example 1.

[0032] Figure 11 is a schematic diagram of the test results of the maximum water absorption of a superhydrophilic photothermal composite material with underwater heavy oil absorption capacity under air atmosphere in Example 1, and the wetting characteristics test results after each cycle of the maximum water absorption test.

[0033] Figure 12 is a schematic diagram of the test results of the maximum water absorption of a superhydrophilic photothermal composite material with underwater heavy oil absorption capacity under underwater atmosphere and the wetting characteristics test results after each cycle of the maximum water absorption test in Example 1.

[0034] Figure 13 is a schematic diagram of the test of the maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in air atmosphere and the maximum oil absorption capacity of air atmosphere circulation in Example 1.

[0035] Figure 14 is a schematic diagram of the test of the maximum oil absorption capacity and the maximum oil absorption capacity of the superhydrophilic photothermal composite material with underwater heavy oil absorption capacity in Example 1.

[0036] Figure 15 is a schematic diagram of the test results of the maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in air atmosphere in Example 1.

[0037] Figure 16 is a schematic diagram of the test results of the maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1.

[0038] Figure 17 is a schematic diagram of the test results of the maximum oil absorption of a superhydrophilic photothermal composite material with underwater heavy oil absorption capacity in Example 1, and the wetting characteristics test results after each cycle of the maximum oil absorption test.

[0039] Figure 18 is a schematic diagram of the test results of the maximum oil absorption of a superhydrophilic photothermal composite material with underwater heavy oil absorption capacity in Example 1, and the wetting characteristics test results after each underwater atmosphere cycle.

[0040] Figure 19 is a dynamic schematic diagram of the underwater heavy oil (small amount) absorption performance of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1.

[0041] Figure 20 is a dynamic schematic diagram of the underwater heavy oil (large amount) absorption performance of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in Example 1. Detailed Implementation

[0042] To illustrate the objectives of this invention in detail, the following description, in conjunction with specific embodiments and the accompanying drawings, provides a further detailed explanation. Numerous specific details are set forth in the following description to provide a thorough understanding. However, this invention can be practiced in many ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the invention. Therefore, this invention is not limited to the specific embodiments disclosed below.

[0043] Cotton fiber is naturally biodegradable and abundant. The surface of raw cotton contains a large amount of low surface energy substances such as pectin and wax, thus exhibiting strong hydrophobicity. Treatment with strong alkalis can remove impurities through a simple chemical reaction and introduce a large number of hydroxyl groups, giving it superhydrophilicity. Furthermore, cotton fiber has a strong adsorption capacity for oil. Based on these two properties, it can serve as a high-quality raw material for constructing superhydrophilic materials. Photothermal materials can directly and efficiently convert solar energy into heat energy, causing the material surface to heat up, reducing the viscosity of the viscous oil phase on its surface, increasing its fluidity, and thus accelerating the absorption rate, achieving a highly efficient oil absorption effect. Researchers have found that combining superwetting properties with photothermal effects further improves the separation efficiency of different water-oil mixtures, achieving a more ideal oil-water separation effect.

[0044] This invention employs a "one-pot method," placing the reactants in the same container at room temperature and pressure. The superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater can be constructed "from bottom to top" at room temperature mainly through the gelation effect of multi-acrylate compounds and multi-amino compounds. Furthermore, the experimental process is characterized by mild reaction conditions, a simple experimental procedure, and the use of green and environmentally friendly materials, which both protects the environment and conforms to the concept of sustainable development.

[0045] Example 1

[0046] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0047] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0048] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0049] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0050] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0051] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0052] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0053] Step 4: Add 0.8g of nano-hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0054] Step 5: Add 0.1g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0055] Step Six: Add 0.3g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0056] Example 2

[0057] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0058] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0059] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0060] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the deionized water and anhydrous ethanol volumes are 5mL each, 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The anhydrous ethanol volume is 10mL, and the mass ratio of pentaerythritol triacrylate to aminofunctionalized cotton fiber is 30:1.

[0061] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0062] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0063] Step 3: Add 1.5g of pentaerythritol triacrylate to the container from Step 2 and shake well to dissolve completely;

[0064] Step 4: Add 1.0g of nano hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0065] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0066] Step Six: Add 0.3g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0067] Example 3:

[0068] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0069] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0070] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0071] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the deionized water and anhydrous ethanol volumes are 5mL each, 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The anhydrous ethanol volume is 10mL, and the mass ratio of pentaerythritol triacrylate to aminofunctionalized cotton fiber is 30:1.

[0072] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0073] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0074] Step 3: Add 1.5g of pentaerythritol triacrylate to the container from Step 2 and shake well to dissolve completely;

[0075] Step 4: Add 1.0g of nano hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0076] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0077] Step Six: Add 0.4g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0078] Example 4:

[0079] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0080] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0081] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0082] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0083] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0084] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0085] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0086] Step 4: Add 1.0g of nano hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0087] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0088] Step Six: Add 0.3g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0089] Example 5:

[0090] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0091] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0092] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0093] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0094] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0095] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0096] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0097] Step 4: Add 1.0g of nano hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0098] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0099] Step Six: Add 0.2g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0100] Example 6:

[0101] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0102] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0103] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0104] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0105] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0106] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0107] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0108] Step 4: Add 1.0g of nano hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0109] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0110] Step Six: Add 0.25g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0111] Example 7:

[0112] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0113] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0114] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0115] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0116] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0117] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0118] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0119] Step 4: Add 1.0g of nano hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0120] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0121] Step Six: Add 0.4g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0122] Example 8:

[0123] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0124] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0125] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0126] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0127] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0128] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0129] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0130] Step 4: Add 0.5g of nano hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0131] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0132] Step Six: Add 0.25g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0133] Example 9:

[0134] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0135] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0136] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0137] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0138] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0139] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0140] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0141] Step 4: Add 0.75g of nano-hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0142] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0143] Step Six: Add 0.25g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0144] Example 10:

[0145] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0146] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0147] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0148] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0149] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0150] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0151] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0152] Step 4: Add 0.8g of nano-hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0153] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0154] Step Six: Add 0.25g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0155] Example 11:

[0156] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0157] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After oil bath washing, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use. The amount of silicon carbide used was 1 g, the amount of sodium hydroxide solution used was 400 mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6 h, the number of centrifugation washings was 3, the centrifugation speed was 10000 r / min, and the treatment time was 10 min.

[0158] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0159] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0160] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0161] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0162] Step 4: Add 0.8g of nano-hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0163] Step 5: Add 0.05g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0164] Step Six: Add 0.3g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0165] Example 12:

[0166] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0167] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After oil bath washing, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use. The amount of silicon carbide used was 1 g, the amount of sodium hydroxide solution used was 400 mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6 h, the number of centrifugation washings was 3, the centrifugation speed was 10000 r / min, and the treatment time was 10 min.

[0168] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0169] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0170] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0171] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0172] Step 4: Add 0.8g of nano-hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0173] Step 5: Add 0.03g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0174] Step Six: Add 0.3g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0175] Example 13:

[0176] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0177] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0178] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0179] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0180] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0181] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0182] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0183] Step 4: Add 0.8g of nano-hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0184] Step 5: Add 0.04g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0185] Step Six: Add 0.3g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0186] Example 14:

[0187] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0188] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After oil bath washing, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use. The amount of silicon carbide used was 1 g, the amount of sodium hydroxide solution used was 400 mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6 h, the number of centrifugation washings was 3, the centrifugation speed was 10000 r / min, and the treatment time was 10 min.

[0189] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0190] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0191] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0192] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0193] Step 4: Add 0.8g of nano-hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0194] Step 5: Add 0.08g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0195] Step Six: Add 0.3g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0196] Example 15:

[0197] This invention provides a method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, comprising the following steps:

[0198] A certain mass of silicon carbide was weighed and placed in a sodium hydroxide solution of a certain mass fraction. After heating in a water bath, it was centrifuged and washed several times. It was then transferred to a petri dish and dried to obtain modified silicon carbide for later use. The raw cotton, which had been manually cleaned of impurities, was completely immersed in a sodium hydroxide solution of a certain mass fraction. After an oil bath, it was washed, dried, and combed to obtain hydroxylated raw cotton for later use. A certain mass of chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and evenly dispersed in the reaction liquid phase. Glacial acetic acid was slowly added dropwise while stirring to adjust the pH of the system to 4-5. A certain volume of 3-aminopropyltriethoxysilane was added and fully dissolved. After heating in an oil bath, the solution was removed and washed several times with anhydrous ethanol to obtain amino-functionalized cotton fiber for later use.

[0199] The amount of silicon carbide used was 1g, the amount of sodium hydroxide solution used was 400mL, the concentration of sodium hydroxide solution was 4%, the water bath temperature for silicon carbide treatment was 95℃, the treatment time was 6h, the number of centrifugal washings was 3, the centrifugation speed was 10000r / min, and the treatment time was 10min.

[0200] Preferably, the raw cotton is 1g, the sodium hydroxide solution is 100mL, the concentration of the sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90℃, the treatment time is 1h, followed by washing with tap water and deionized water three times each, the oven temperature is 70℃, the treatment time is 12h, the chitosan oligosaccharide mass is 0.2g, the volumes of deionized water and anhydrous ethanol are 5mL each, the 3-aminopropyltriethoxysilane is 0.5mL, the oil bath temperature is 60℃, the reaction time is 12h, and the cotton is washed three times with anhydrous ethanol. The volume of anhydrous ethanol is 10mL, and the mass ratio of isoprene tetraacrylate to aminofunctionalized cotton fiber is 30:1.

[0201] Step 1: Take 0.05g of amino-functionalized cotton fiber into a flat-bottomed centrifuge tube;

[0202] Step 2: Add 10 mL of anhydrous ethanol to the container from Step 1 and shake to disperse it evenly.

[0203] Step 3: Add 1.5g of isoprene tetraacrylate to the container from Step 2 and shake well to dissolve completely;

[0204] Step 4: Add 0.8g of nano-hydroxyapatite to the container from Step 3 and shake well to disperse it evenly.

[0205] Step 5: Add 0.12g of modified nano-silicon carbide to the container from Step 4, and shake well to disperse it evenly;

[0206] Step Six: Add 0.3g of ethylenediamine-terminated polyethyleneimine to the container from Step Five, shake well to disperse it evenly, and let it stand at room temperature until the reaction is complete to obtain a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater.

[0207] It should be noted that all reagents used in the above examples were of analytical grade.

[0208] It should also be noted that the preparation steps of Examples 1 to 15 are basically the same, except that the amount of some reagents is adjusted and the ratio is different. The wetting characteristics, photothermal properties, aqueous phase absorption performance under different atmospheres, and oil phase absorption performance under different atmospheres of the products of Examples 1 to 15 were measured respectively. The product characteristics are not significantly different. The test process of the product of Example 1 will be used as an example for explanation below.

[0209] I. Wetting characteristics and photothermal properties of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability were determined under different atmospheres. See Figures 1-7, which show the wetting characteristics and photothermal properties of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability.

[0210] Figure 1 shows an optical photograph of the product from step six of the invention.

[0211] Referring to Figure 2, in an air atmosphere, the superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater was placed flat on the test platform, and water droplets and oil droplets were dropped onto the surface of the material respectively. It can be seen that the water droplets wetted and spread after contacting the surface of the material, while the oil droplets spread more rapidly after contacting the surface of the material, demonstrating the product's ability to absorb water and oil.

[0212] Referring to Figure 3, the water contact angle of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability was measured using a contact angle measuring instrument in an air atmosphere (the test water droplet was 5μL). It can be seen that the water droplet gradually penetrates into the interior of the material and eventually spreads out completely, resulting in a water contact angle of 0°. This shows that the product has excellent superhydrophilicity in an air atmosphere.

[0213] Referring to Figure 4, the oil contact angle of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability was measured using a contact angle measuring instrument in an air atmosphere (the oil droplet was 5μL). It can be seen that when the oil droplet comes into contact with the material surface, it is quickly absorbed into the interior, and the oil contact angle is 0°. This shows that the product has excellent superhydrophilicity in an air atmosphere and its oil absorption capacity is stronger than its water absorption capacity.

[0214] Referring to Figure 5, when the superhydrophilic photothermal composite material with underwater heavy oil absorption capability was placed in an aqueous phase stained with gardenia yellow, bubbles were observed to be released. After the aqueous phase reached saturation and the material sank to the bottom of the beaker, three drops of dichloromethane stained with oil-soluble red were added to the surface of the material. It was observed that the oil droplets were immediately absorbed into the material, leaving three red oil marks on its surface. This demonstrates that the product still exhibits excellent water and oil absorption capabilities in an underwater environment.

[0215] Refer to Figures 6-7 for the determination of the photothermal properties of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability. The specific determination methods include:

[0216] S1: Place the near-infrared lamp 10cm away from the surface of the super-hydrophilic photothermal composite material with the ability to absorb heavy oil underwater;

[0217] S2: Record the temperature change of the material from 0s to 300s using an infrared measuring instrument at 50s test intervals;

[0218] S3: Increase = (Temperature when irradiated with infrared spectrum for 300s - Temperature when irradiated with infrared spectrum for 0s) / Temperature when irradiated with infrared spectrum for 0s × 100%.

[0219] The photothermal properties of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability were measured, and the results are shown in Figures 6 and 7:

[0220] The temperature of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability increased from 22.8℃ at 0s to 57.4℃ within 300s, an increase of 151.75%. The temperature increase of the hybrid based on amino-functionalized cotton fiber (without silicon carbide) was 41.13%. The comparison shows that the superhydrophilic photothermal composite material with underwater heavy oil absorption capability has excellent photothermal performance.

[0221] All reagents used in this embodiment are of analytical grade.

[0222] II. A water phase absorption performance test of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in different atmospheres. See Figure 8-12, which shows the water phase absorption performance of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in different atmospheres.

[0223] Referring to Figure 8, the maximum water absorption in air and the maximum water absorption during air circulation of a superhydrophilic photothermal composite material capable of absorbing heavy oil underwater are measured:

[0224] The specific method for determining the maximum water absorption capacity of a superhydrophilic photothermal composite material capable of absorbing heavy oil underwater includes:

[0225] E1: Weigh an appropriate amount of product on an electronic balance and record its mass;

[0226] E2: Use tweezers to pick up the product and transfer it to the test platform. Use a pipette to drip water onto the product surface drop by drop until the product is saturated with water.

[0227] E3: Quickly use tweezers to clamp the product onto the electronic balance, accurately read the value, and record the data. The ratio of the mass after water absorption to the mass before water absorption represents the water absorption capacity of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability in the air atmosphere, i.e., the maximum water absorption per unit volume.

[0228] The specific method for determining the maximum water absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability during air atmosphere circulation includes:

[0229] H1: Weigh an appropriate amount of product on an electronic balance and record its mass;

[0230] H2: Use tweezers to pick up the product and transfer it to the test platform. Use a pipette to drip water onto the product surface drop by drop until the product is saturated with water.

[0231] H3: Quickly use tweezers to clamp the product onto the electronic balance, take an accurate reading, and record the data;

[0232] H4: After weighing, allow the product to air dry naturally, then measure the oil contact angle;

[0233] H5: The product is washed multiple times with anhydrous ethanol and deionized water, and finally air-dried in a natural environment to the dry weight under standard temperature and humidity.

[0234] H6: Repeat steps H1-H5 six times. The ratio of the mass after each water absorption to the mass before water absorption is used to represent the water absorption capacity of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability in the air atmosphere, that is, the maximum water absorption per unit volume.

[0235] Referring to Figure 9, the maximum water absorption capacity of a superhydrophilic photothermal composite material capable of absorbing heavy oil underwater was determined. The specific determination method included:

[0236] P1: Weigh an appropriate amount of product on an electronic balance and record its mass;

[0237] P2: Use tweezers to pick up the product and immerse it in a beaker containing deionized water. Bubbles will continuously be released until the product is saturated with water and sinks to the bottom of the beaker.

[0238] P3: Quickly use tweezers to clamp the product onto the electronic balance, take accurate readings, and record the data. The ratio of the mass after water absorption to the mass before water absorption represents the water absorption capacity of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability in an underwater atmosphere, i.e., the maximum water absorption per unit volume.

[0239] The determination of the maximum water absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability during underwater atmospheric circulation includes the following specific methods:

[0240] K1: Weigh an appropriate amount of product on an electronic balance and record its mass;

[0241] K2: Use tweezers to pick up the product and immerse it in a beaker containing deionized water. Bubbles will continuously be released until the product is saturated with water and sinks to the bottom of the beaker.

[0242] K3: Quickly use tweezers to clamp the product onto the electronic balance, take an accurate reading, and record the data;

[0243] K4: After weighing, allow to air dry in a natural environment, then measure the oil contact angle;

[0244] K5: Wash the product multiple times with anhydrous ethanol and deionized water, and finally air dry it in a natural environment.

[0245] K6: Repeat steps K1-K5 six times. The ratio of the mass after each water absorption to the mass before water absorption is used to represent the water absorption capacity of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability in an underwater atmosphere, i.e., the maximum water absorption per unit volume.

[0246] Figure 10-12 shows the results of tests on the maximum water absorption, cyclic maximum water absorption, and wetting properties of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in air and underwater environments.

[0247] When water droplets are placed on the product surface in an airy atmosphere, they are quickly absorbed. As water continues to drip, the product becomes saturated with water. At this point, the product mass is 3.928 times the initial mass, indicating that the product has good water absorption performance in an airy atmosphere.

[0248] When the product is wetted in an underwater environment, it releases air bubbles and continuously absorbs water until it sinks to the bottom of the cup and reaches saturation. At this point, the product mass is 3.643 times the initial mass, indicating that the product has good water absorption performance in an underwater environment.

[0249] A superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater underwent six maximum water absorption tests. The water absorption capacity decreased in the air atmosphere, but remained basically stable in the water atmosphere, indicating that the product has a certain recycling capacity.

[0250] After each cycle of maximum water absorption tests in both air and underwater environments, the oil contact angle of a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater remained at 0°, indicating that the product has stable and continuous superhydrophilic properties and can be recycled multiple times.

[0251] All reagents used in this embodiment are of analytical grade.

[0252] 3. The oil phase absorption performance of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was tested in different atmospheres. See Figures 13-18, which show the oil phase absorption performance of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in different atmospheres.

[0253] Referring to Figure 13, the maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was determined in an air atmosphere. The specific determination method included:

[0254] A1: The maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was determined in an air atmosphere using six different oils, including n-hexane, kerosene, petroleum ether, dichloromethane, chlorobenzene, and epichlorohydrin.

[0255] A2: Weigh an appropriate amount of product on an electronic balance and record its mass;

[0256] A3: Use tweezers to pick up an appropriate amount of product and place it in a beaker containing an appropriate amount of oil until the product is saturated with oil and is completely stained.

[0257] A4: Quickly use tweezers to clamp the product onto the electronic balance, accurately read the value, and record its mass. The ratio of the mass after oil absorption to the mass before oil absorption represents the oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in the air atmosphere, i.e., the maximum oil absorption per unit volume.

[0258] The maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was determined by circulating it in an air atmosphere. The specific determination method included:

[0259] B1: The maximum oil absorption of the product in an air atmosphere was determined using n-hexane as a representative.

[0260] B2: Weigh an appropriate amount of product on an electronic balance and record its mass;

[0261] B3: Use tweezers to pick up an appropriate amount of product and place it in a beaker containing an appropriate amount of oil until the product is saturated with oil and is completely stained.

[0262] B4: Quickly use tweezers to clamp the product onto the electronic balance, accurately read the value, record its mass, and after weighing, wash the product multiple times with anhydrous ethanol and deionized water.

[0263] B5: Finally, air dry in a natural environment, then measure the water contact angle;

[0264] B6: Repeat steps B2-B5 six times. The ratio of the mass after each oil absorption to the mass before oil absorption is used to represent the oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in the air atmosphere, that is, the maximum oil absorption per unit volume.

[0265] Referring to Figure 14, the maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was determined in an underwater atmosphere. The specific determination method included:

[0266] D1: The maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was determined using three types of heavy oil: dichloromethane, chlorobenzene, and epichlorohydrin.

[0267] D2: Place the beaker on the test bench, add an appropriate amount of deionized water to the beaker, then use a syringe to take an appropriate amount of oil phase, and then insert the needle to the bottom of the beaker to slowly squeeze out the oil.

[0268] D3: Weigh an appropriate amount of product on an electronic balance and record its mass;

[0269] D4: Use tweezers to hold the product and immerse it in a beaker containing deionized water. First, absorb water until saturated, then remove air bubbles while continuously absorbing the oil phase until saturated.

[0270] D5: Quickly use tweezers to clamp the product onto the electronic balance, accurately read the value, and record its mass. The ratio of the mass after oil absorption to the mass before oil absorption represents the oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in an underwater atmosphere, i.e., the maximum oil absorption per unit volume.

[0271] The maximum oil absorption capacity of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was determined by underwater atmospheric cycling. The specific determination method included:

[0272] F1: Taking heavy oil dichloromethane as an example, the maximum cyclic oil absorption of a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater was determined in an underwater atmosphere.

[0273] F2: Place the beaker on the test bench, add an appropriate amount of deionized water to the beaker, then use a syringe to take an appropriate amount of oil phase, and then insert the needle to the bottom of the beaker to slowly squeeze out the oil.

[0274] F3: Weigh an appropriate amount of product on an electronic balance and record its mass;

[0275] F4: Use tweezers to hold the product and immerse it in a beaker containing deionized water. First, absorb water until saturated, then remove air bubbles while continuously absorbing the oil phase until saturated.

[0276] F5: Quickly use tweezers to clamp the product onto the electronic balance, accurately read the value, record its mass, and after weighing, wash the product multiple times with anhydrous ethanol and deionized water.

[0277] F6: Finally, allow to air dry in a natural environment, then measure the water contact angle;

[0278] F7: Repeat steps F2-F6 six times. The ratio of the mass after each oil absorption to the mass before oil absorption represents the oil absorption capacity of a superhydrophilic photothermal composite material capable of absorbing heavy oil underwater, i.e., the maximum oil absorption per unit volume.

[0279] Figure 15-18 shows the results of testing the maximum oil absorption capacity, cyclic maximum oil absorption capacity, and wetting properties of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability in air and underwater environments.

[0280] In an air atmosphere, the surface of the super-hydrophilic photothermal composite material with the ability to absorb heavy oil underwater comes into contact with the oil phase and absorbs it quickly. The color deepens rapidly and extends to the whole surface. It can achieve an oil absorption capacity of 2.489-7.323 times for different oil phases, and the oil absorption capacity for heavy oil dichloromethane is as high as 7.323 times, demonstrating excellent oil absorption effect.

[0281] In an underwater environment, the superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater first absorbs water to saturation until it sinks, and then the absorbed water phase is squeezed out to absorb the oil phase. The absorption of dichloromethane, chlorobenzene and epichlorohydrin per unit volume of the product in an underwater environment was measured to be 7.988, 5.613 and 6.758 times, respectively, indicating that it has excellent oil absorption effect under water immersion conditions.

[0282] A superhydrophilic photothermal composite material with underwater heavy oil absorption capacity underwent six cycles of maximum oil absorption test. In an air atmosphere, the absorption of n-hexane remained above 2 times, and in an underwater atmosphere, the absorption of dichloromethane remained above 6 times. The maximum oil absorption capacity reached 8.5 times the original mass. After the cycle test, the oil absorption capacity remained basically stable, indicating that the product has a certain recycling capacity.

[0283] After each cycle of maximum oil absorption testing in both air and underwater environments, the water contact angle of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability remained at 0°, indicating that the product has stable and continuous superhydrophilicity and can be used for oil absorption under continuous water immersion conditions.

[0284] All reagents used in this embodiment are of analytical grade.

[0285] IV. An application test of an oil-water separation using a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was conducted. See Figures 19-20, which show the oil-water separation performance of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability.

[0286] Referring to Figure 19, the underwater heavy oil (small amount) absorption performance of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was determined. The specific determination method included:

[0287] L1: Add an appropriate amount of deionized water to the beaker;

[0288] L2: Use a pipette to draw up the dichloromethane dyed with oil-soluble red dye, insert it into the bottom of the cup, and squeeze out a drop;

[0289] L3: Use tweezers to pick up a piece of superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater, and slowly insert it into the bottom of the beaker to absorb the dyed dichloromethane until the dyed dichloromethane is fully absorbed by the product.

[0290] L4: Remove the superhydrophilic photothermal composite material with underwater heavy oil absorption capability from the container and observe the surface wetting state of the product and the liquid state inside the beaker.

[0291] Referring to Figure 20, the underwater heavy oil (large quantity) absorption performance of a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was determined. The specific determination method included:

[0292] N1: Add an appropriate amount of deionized water to the beaker;

[0293] N2: Use a pipette to draw up the dichloromethane dyed with oil-soluble red dye, insert it into the bottom of the beaker, and squeeze it out until it covers the bottom of the beaker;

[0294] N3: Use tweezers to pick up a piece of superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater, and slowly insert it into the bottom of the beaker to absorb the dyed dichloromethane until the dyed dichloromethane is fully absorbed by the product.

[0295] N4: Take out a superhydrophilic photothermal composite material with the ability to absorb heavy oil underwater from the container and observe the surface wetting state of the product and the state of the liquid in the beaker.

[0296] Figure 19-20 shows the application test results of an oil-water separation using a superhydrophilic photothermal composite material capable of absorbing heavy oil underwater: underwater dichloromethane oil droplets are completely absorbed by the superhydrophilic photothermal composite material, the deionized water becomes clear, and a red oil stain is left on the surface of the superhydrophilic photothermal composite material; a large amount of underwater dichloromethane oil phase is completely absorbed by the superhydrophilic photothermal composite material, the water phase becomes clear, and the superhydrophilic photothermal composite material is stained red from the inside out.

[0297] In summary, this product demonstrates excellent absorption of both small and large quantities of heavy oil droplets on and underwater, enabling efficient and stable heavy oil absorption under water immersion conditions. All reagents used in this embodiment were of analytical grade.

Claims

1. A method for preparing a superhydrophilic photothermal composite material with underwater heavy oil absorption capability, characterized in that: Includes the following steps: Silicon carbide was weighed and placed in a sodium hydroxide solution, heated in a water bath, centrifuged and washed several times, and dried to obtain modified nano-silicon carbide for later use. The purified raw cotton was completely immersed in a sodium hydroxide solution, washed in an oil bath, dried, and combed to obtain hydroxylated raw cotton for later use. Chitosan oligosaccharide was weighed and completely dissolved in an equal volume of deionized water and anhydrous ethanol. The hydroxylated raw cotton was added to the solution and uniformly dispersed in the reaction liquid phase. The pH of the system was adjusted, and 3-aminopropyltriethoxysilane was added to dissolve it completely. After heating in an oil bath, the solution was removed and washed with anhydrous ethanol to obtain amino-functionalized cotton fibers for later use. The amino-functionalized cotton fibers were placed in anhydrous ethanol. Isopentyl tetraacrylate or pentaerythritol triacrylate was added to dissolve it completely. Nano-hydroxyapatite was added and uniformly dispersed. Modified nano-silicon carbide was added and uniformly dispersed. Ethylenediamine-terminated polyethyleneimine was added and uniformly dispersed. After the reaction was allowed to complete, a superhydrophilic photothermal composite material with underwater heavy oil absorption capability was obtained.

2. The method for preparing the superhydrophilic photothermal composite material with underwater heavy oil absorption capability according to claim 1, characterized in that, The amount of silicon carbide used is 1 g, the amount of sodium hydroxide solution used is 400 mL, the concentration of sodium hydroxide solution is 4%, the water bath temperature for silicon carbide treatment is 95 ℃, the treatment time is 6 h, the number of centrifugal washings is 3, the centrifugation speed is 10000 r / min, and the treatment time is 10 min.

3. The method for preparing the superhydrophilic photothermal composite material with underwater heavy oil absorption capability according to claim 1, characterized in that, The amount of raw cotton used is 1 g, the amount of sodium hydroxide solution used is 100 mL, the concentration of sodium hydroxide solution is 16%, the oil bath temperature for raw cotton treatment is 90 ℃, the treatment time is 1 h, and it is washed with tap water and deionized water three times each, respectively. The oven temperature is 70 ℃, the treatment time is 12 h, the mass of chitosan oligosaccharide is 0.2 g, the volume of deionized water and anhydrous ethanol is 5 mL each, the pH of the system is adjusted to 4~5, the amount of 3-aminopropyltriethoxysilane is 0.5 mL, the oil bath temperature is 60 ℃, the reaction time is 12 h, and it is washed three times with anhydrous ethanol.

4. The method for preparing the superhydrophilic photothermal composite material with underwater heavy oil absorption capability according to claim 1, characterized in that, The volume of anhydrous ethanol is 10 mL, and the mass ratio of isoprene tetraacrylate or pentaerythritol triacrylate to the amino-functionalized cotton fiber is 30:

1.

5. The method for preparing the superhydrophilic photothermal composite material with underwater heavy oil absorption capability according to claim 1, characterized in that, The mass ratio of the nano-hydroxyapatite to the amino-functionalized cotton fiber is 10:1 to 20:

1.

6. The method for preparing the superhydrophilic photothermal composite material with underwater heavy oil absorption capability according to claim 1, characterized in that, The mass ratio of the modified nano-silicon carbide to the amino-functionalized cotton fiber is 0.6:1 to 2.4:

1.

7. The method for preparing the superhydrophilic photothermal composite material with underwater heavy oil absorption capability according to claim 1, characterized in that, The mass ratio of the ethylenediamine-terminated polyethyleneimine to the amino-functionalized cotton fiber is 5:1 to 8:

1.

8. The method for preparing the superhydrophilic photothermal composite material with underwater heavy oil absorption capability according to claim 1, characterized in that, The final reaction was allowed to stand for 24 hours at room temperature.

9. A superhydrophilic photothermal composite material with underwater heavy oil absorption capability, characterized in that: The superhydrophilic photothermal composite material with underwater heavy oil absorption capability was prepared using the preparation method of any one of claims 1-8.

10. The use of the superhydrophilic photothermal composite material with underwater heavy oil absorption capability according to claim 9, characterized in that, The superhydrophilic photothermal composite material with underwater heavy oil absorption capability is used for oil-water separation in both air and underwater environments.

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