Submerged super-amphiphobic oil-water switchable separation material based on photocuring 3D printing and preparation method thereof

Abstract

The invention discloses an under-liquid super-amphiphobic oil-water switchable separation material based on photocuring 3D printing, which is obtained by photocuring 3D printing of a monomer containing conjugated double bonds, an initiator and a precursor of a metal organic framework material, and the water contact angle of the material in air is 90-175 degrees. The underwater oil contact angle in the same oil-water system is 90-180 degrees, the oil-water contact angle in oil is 90-180 degrees, after the material is subjected to abrasive paper friction treatment for 10 cycles, an oil-water mixture can still be separated in a water-passing oil-blocking or oil-passing water-blocking mode, and the separation efficiency is higher than 99.5%. The invention also discloses a preparation method of the composition. The oil-water separation material disclosed by the invention not only can realize submerged super-amphiphobic property in a plurality of oil-water systems and meet the switching between underwater oleophobic property and under-oil hydrophobic property in different types of oil-water systems, but also can be higher than 98.20% in separation efficiency after 50 cycles of oil-water separation, is high in friction resistance, and is low in cost due to the fact that all the raw materials are commercially available raw materials. The preparation is simple and visual, the energy consumption is low, and the popularization and application are facilitated.

Description

Technical Field

[0001] The present invention belongs to the technical field of oil-water switchable separation materials and preparation thereof, and specifically relates to an underwater super-double oleophobic and water switchable separation material based on photocuring 3D printing and a preparation method thereof. Background Art

[0002] Industrial manufacturing, transportation and catering industries will produce a large amount of oily wastewater. These oily wastewaters are mainly composed of petroleum, mineral oil, vegetable oil, animal oil and other impurities. Therefore, they have the characteristics of complex composition, diverse properties and huge production volume, which makes it impossible for the above oily wastewater to be treated in time and effectively and enter the environment. In addition, there are leakages or other accidents in the process of industrial production and transportation, which will also cause these oily wastewaters to enter the environment, which not only causes great damage to the water environment and soil, but also forms a large amount of resource waste. It should be pointed out that many of the oily liquids such as halogenated hydrocarbons will settle to the bottom of the water body because their density is greater than that of water, and they cannot be effectively treated by traditional adsorption, combustion or volatilization methods. In addition, aquatic plants and fish will slowly absorb these wastewaters and enter the human body through the food chain, posing a threat to human health. How to effectively treat these oily wastewaters, improve the purity of their oil phase and then reuse them is a difficult problem that needs to be solved urgently. Among them, using oil-water separation materials to separate oil and water to improve the purity of the oil phase is one of the ideal methods to solve this problem.

[0003] Oil-water separation is usually divided into two methods: passing through oil to block water (oil removal type) and passing through water to block oil (water removal type). Passing through oil to block water means that the oil phase can quickly pass through the material while the water phase is blocked. Therefore, this method is suitable for mixed (heavy oil-water) systems where the density of the water phase is less than that of the oil phase; on the contrary, passing through water to block oil means that the water phase can quickly pass through the material while the oil phase is blocked. Therefore, this method is usually more suitable for oil-water (light oil-water) mixed systems where the density of the water phase is greater than that of the oil phase. Both passing through water to block oil and passing through oil to block water utilize the special wettability of the material surface. The former utilizes the superhydrophilicity and underwater superoleophobicity of the material, while the latter utilizes the superoleophilicity and superhydrophobicity under oil of the material. The wettability of a material is usually characterized by the contact angle (CA) of the liquid on its surface. According to the CA value, superwettability can generally be expanded to superhydrophobicity (i.e., the CA of water is greater than 150°), superoleophobicity (i.e., the CA of oil is greater than 150°), superhydrophilicity (i.e., the CA of water is close to 0°), and superoleophilicity (i.e., the CA of oil is close to 0°). Unfortunately, traditional water-through oil-blocking or oil-through water-blocking materials can only achieve a single function, that is, different oil-water separation materials need to be used for oil-water systems of different densities to achieve rapid and effective separation, which is not only troublesome, but also makes the separation cost extremely high. In addition, in order to achieve superhydrophobicity and superoleophilicity and superhydrophilicity and superoleophobicity, it is often necessary to use fluorinated silicones or fluorinated sodium sulfonates to modify the surface of oil-water separation materials. However, these substances are not only expensive but also have extremely strong biological toxicity, which can cause great damage to the environment and human body.

[0004] Therefore, new materials that can achieve underwater super-oleophobicity and oil-under-super-hydrophobicity in the same oil-water system (i.e., underwater super-amphiphobic materials) have attracted much attention in recent years. For example, Xu Changlian et al. (Underwater oleophobic / oil-under-hydrophobic switchable oil-water separation material and preparation method thereof [P]. Chinese patent: CN114307254A.2022.04.12) used phenolic compounds to modify the oil-water separation material, and then the micro-nanostructure formed by the self-assembly of the compound generated by the organic ligand and the metal ion was attached to the surface of the porous mesh substrate material to form an underwater oleophobic / oil-under-hydrophobic switchable oil-water separation material, which achieved the on-demand selective separation of oil-under-hydrophobicity and underwater oleophobicity. However, the underwater super-amphiphobic-oil-water separation material has the problems of uncontrollable structure and cannot be designed into a solid multi-faceted through-hole structure according to actual needs.

[0005] 3D printing is a method that can convert a three-dimensional model into a physical object. It can quickly construct a material with a complex and regular structure without using a template. It has the advantages of low cost and high precision, and can greatly reduce the consumption of human resources. Therefore, some people try to use it to prepare oil-water switchable separation materials. For example, Yuan et al. (YUAN S, STROBBE D, KRUTH JP, et al. Super-hydrophobic 3D printed polysulfone membranes with a switchablewettability by self-assembled candle soot for efficient gravity-driven oil / water separation [J]. Journal of Materials Chemistry A, 2017, 5 (48): 25401.) used laser sintering (SLS) 3D printing technology to prepare a 3D polysulfone (PSU) membrane, and then soaked it in a n-hexane solution containing candle ash to make the candle ash self-assembled on the surface of the PSU membrane. Modification, so that the material has super oleophilic and super hydrophobic properties in the air, and the material is oil-water separation in an oil-water blocking manner. However, in order to achieve the oil-water separation effect of water-oil blocking, the dry superoleophilic and superhydrophobic PSU membrane must first be soaked in ethanol for a certain period of time to make it completely wetted by ethanol, and then soaked in water for a certain period of time. The PSU membrane soaked in ethanol and water can be successfully used for oil-water separation by water-oil blocking. Therefore, the preparation of the switchable separation of oil-water blocking and water-oil blocking is not only complicated, but also requires the use of organic solvents outside the oil-water system to be separated to achieve switchable separation, and the cycle durability is poor. In addition, the PSU raw material needs to be preheated at 163°C before 3D printing can be used to prepare the PSU membrane, and the preparation conditions are relatively harsh. At the same time, due to the characteristics of the self-assembled coating obtained by modification, it is speculated that the mechanical properties of the material are poor and it is not resistant to friction, which makes it impossible to achieve on-demand separation of oil and water after friction.Yang et al. (YANG Y, REN Z, ZHOU C, et al. 3D-printed robust dual superlyophobic Ti-based porous structure for switchable oil / water emulsion separations [J]. Advanced Functional Materials, 2023, 33 (15): 2212262.) used selective laser melting (SLM) technology to print a Ti-based irregular porous structure (SLM-3D Ti), and integrated the re-enterable texture into the porous framework by melting and solidifying Ti powder, so that the material was endowed with hydrophilicity and oleophilicity in the air, as well as underwater superoleophobicity and oil-under-superhydrophobicity. Although the material has underwater superoleophobicity and oil-under-superhydrophobicity, the material obtained by this method forms a random and intricate framework and tortuous channels inside, so it is not only impossible to prepare it quickly and repeatedly, but also its durability is not ideal when it is reused. In addition, its SLM technology needs to be carried out under high temperature conditions of thousands of degrees and requires the use of expensive high-purity, small-particle-size pure Ti powder, so its preparation cost is high and the conditions are harsh. In summary, the materials that have been reported to be prepared by 3D printing technology and have both underwater superoleophobicity and oil-under-superhydrophobicity in the same oil-water system have the problem of needing to be soaked in an organic solvent (such as ethanol) outside the oil-water system to be separated to achieve wettability switching, poor mechanical properties of the materials and poor resistance to friction, or their preparation methods have the problem of complex preparation process, harsh preparation conditions (need to be in a high temperature environment) and the need to use expensive raw materials. Therefore, there is an urgent need to develop a 3D printing preparation method for underwater super-amphiphobic materials with low economic cost, simple process flow, mild preparation conditions (reaction temperature below 90°C). The prepared material has the characteristics of switchable separation of water-through oil blocking and oil-through water blocking without external stimulation, hydrophobicity in air and excellent durability. At the same time, it can also be designed into a repeatable and sturdy multi-faceted through-hole structure according to actual needs to meet the purification and recycling of oily wastewater of different types and environments. Summary of the invention

[0006] The purpose of the present invention is to address the problems existing in the prior art and first provide an underwater super-double oleophobic and water-switchable separation material based on photocuring 3D printing.

[0007] Another object of the present invention is to provide a method for preparing the above-mentioned underwater super-double oleophobic and water-switchable separation material based on photocuring 3D printing.

[0008] The present invention provides an underwater super-double oleophobic and water switchable separation material based on photocuring 3D printing, characterized in that the material is composed of a multi-faceted through-hole skeleton with a micro-nano structure obtained by photocuring 3D printing of a precursor containing a conjugated double bond monomer, an initiator, and a metal organic framework material under mild conditions. The water contact angle of the material in the air is 90-175°, the underwater oil contact angle in the same oil-water system is 90-180°, and the underwater water contact angle is 90-180°. After the material is rubbed with sandpaper for 10 cycles, it can still separate the oil-water mixture by passing through water to block oil or passing through oil to block water, and the separation efficiency is higher than 99.5%.

[0009] The above underwater super-double oleophobic and water-switchable separation material has a water contact angle of 90 to 175° in the air, an underwater oil contact angle of 150 to 180° and an underwater water contact angle of 90 to 180° in the same oil-water system.

[0010] The above underwater super-double oleophobic and water-switchable separation material has a water contact angle of 90 to 175° in the air, an underwater oil contact angle of 90 to 180° and an underwater water contact angle of 150 to 180° in the same oil-water system.

[0011] The above underwater super-double oleophobic and water-switchable separation material has a water contact angle of 120-175° in the air, an underwater oil contact angle of 150-180° and a underwater water contact angle of 150-180° in the same oil-water system, and a water contact angle of 150-180° under oil.

[0012] The monomer containing conjugated double bonds in the above underwater super-double oleophobic water switchable separation material is at least one of acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, methyl methacrylate, hydroxyethyl acrylate, trimethylolpropane triacrylate, n-butyl methacrylate, bisphenol A (meth) acrylate, butadiene dicarboxylate, styrene, divinylbenzene and stilbene;

[0013] The initiator described in the above underwater super-double oleophobic water switchable separation material is at least one of azobisisobutyronitrile, dibenzoyl peroxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (1- (2,4-difluorophenyl) -3-pyrrolyl) titanocene, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4-phenyl benzophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and benzophenone.

[0014] The metal organic framework material described in the above underwater super-double oleophobic water switchable separation material is at least one of ZIF-4, ZIF-8, ZIF-7, ZIF-67, ZIF-71, ZIF-90, ZIF-L and ZIF-zni.

[0015] The multi-sided through-hole structure described in the above underwater super-double oleophobic water switchable separation material is any one of 2-sided through holes, 4-sided through holes, 6-sided through holes, 8-sided through holes, 10-sided through holes, 12-sided through holes, 14-sided through holes, 16-sided through holes, 18-sided through holes or 20-sided through holes, and its pore diameter or side length is 50 to 3000 μm, preferably 50 to 600 μm.

[0016] The multi-faceted through holes described in the above-mentioned underwater super-double oleophobic and water-switchable separation material refer to a multi-faceted connected hole structure, which runs through the entire material, so that the material has multiple open channels, allowing the fluid to flow through the holes in multiple directions.

[0017] The underwater super dual oleophobic and water switchable separation material described above can be used for oil-through and water-blocking, which means it is used for separation of heavy oil-water mixtures, and can be used for water-through and oil-blocking, which means it is used for separation of light oil-water mixtures.

[0018] The present invention provides a method for preparing the above-mentioned underwater super-double oleophobic water switchable separation material based on photocuring 3D printing, and the process steps and conditions of the method are as follows:

[0019] (1) First, a conjugated double bond-containing monomer, an initiator, and a metal organic framework material are prepared into a photocurable 3D printing precursor solution in a mass ratio of 100:(0.1-10):(0.1-50) for later use;

[0020] (2) using computer graphics software to establish a three-dimensional porous material model containing a multi-faceted through-hole skeleton, wherein the pore size or side length is set to 50 to 3000 μm, and the model is saved in STL format;

[0021] (3) Import the STL format file into the slicing software, set the slicing parameters, and perform slicing, wherein the printing exposure time is set to 0.5-100 s, the bottom layer exposure time is set to 0.5-200 s, and the light wavelength is set to 200-1000 nm and then saved for later use;

[0022] (4) After the prepared light-curing 3D printing precursor solution is poured into the printer tank, light-curing 3D printing is performed at 0-90°C. After printing is completed, it can be washed with ethanol and then dried.

[0023] The conjugated double bond-containing monomer used in the above method is at least one of acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, methyl methacrylate, hydroxyethyl acrylate, trimethylolpropane triacrylate, n-butyl methacrylate, bisphenol A (meth)acrylate, butadiene dicarboxylate, styrene, divinylbenzene and stilbene;

[0024] The initiator used in the above method is at least one of azobisisobutyronitrile, dibenzoyl peroxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (1- (2,4-difluorophenyl) -3-pyrrolyl) titanocene, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4-phenyl benzophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and benzophenone.

[0025] The metal organic framework material used in the above method is at least one of ZIF-4, ZIF-8, ZIF-7, ZIF-67, ZIF-71, ZIF-90, ZIF-L and ZIF-zni.

[0026] The multi-sided through holes described in the above method are any one of 2-sided through holes, 4-sided through holes, 6-sided through holes, 8-sided through holes, 10-sided through holes, 12-sided through holes, 14-sided through holes, 16-sided through holes, 18-sided through holes or 20-sided through holes, preferably 2-sided through holes, 4-sided through holes, 6-sided through holes, 8-sided through holes or 10-sided through holes.

[0027] The mass ratio of the conjugated double bond-containing monomer, the initiator, and the metal organic framework material used in the above method is preferably 100:(0.1-2):(0.1-10).

[0028] The aperture or side length of the multi-faceted through hole described in the above method is preferably 50 to 600 μm.

[0029] The printing exposure time set in the above method is preferably 1 to 10 seconds.

[0030] The bottom layer exposure time set in the above method is preferably 0.5 to 80 seconds.

[0031] The wavelength of light set in the above method is preferably 200 to 450 nm.

[0032] The light-curing 3D printing temperature set in the above method is preferably 10 to 35°C.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. Since the underwater super-amphiphobic and switchable oil-water separation material provided by the present invention is based on photocuring 3D printing and has a multi-faceted through-hole skeleton with a micro-nano structure, the material is not only hydrophobic in the air, but also realizes underwater super-amphiphobicity in multiple oil-water systems, and satisfies the switching of underwater oleophobicity and underwater hydrophobicity in different types of oil-water systems, and avoids the problems of complex preparation process, harsh conditions, high cost, and non-repeatable preparation existing in the existing 3D printing technology.

[0035] 2. Since the underwater super-amphiphobic switchable oil-water separation material provided by the present invention is obtained by photocuring 3D printing of a uniform precursor containing a metal organic framework material and a conjugated polymer monomer, the material not only has a similar micro-nano structure from the inside out, enabling it to stably achieve underwater super-amphiphobicity in multiple oil-water systems, but also can be used for water-through oil-blocking and oil-through water-blocking switchable separation of different types of oil-water systems, and after 50 cycles of oil-water separation, the separation efficiency can be higher than 98.20%.

[0036] 3. Since the underwater super-amphiphobic switchable oil-water separation material provided by the present invention not only has a porous skeleton structure, but also the skeleton structure body is evenly distributed from the inside to the outside with a hierarchical micro-nano structure composed of similar micron or nano-sized spherical or lamellar morphologies, the mechanical properties of the material are greatly improved. After 10 cycles of sandpaper friction, the oil-water separation can still be achieved by a switchable separation method of passing through water to block oil or passing through oil to block water, and the separation efficiency can be higher than 99.5%.

[0037] 4. Since the preparation method of the underwater super-amphiphobic switchable oil-water separation material provided by the present invention adopts a uniform precursor containing a metal organic framework material and a conjugated polymer monomer as the raw material for photocuring 3D printing, it not only avoids the use of expensive reagents such as fluorinated silicones or fluorinated sodium sulfonates compared with the traditional method of preparing superwetting surfaces, thereby reducing the preparation cost and environmental pollution, but also reduces the printing temperature and the preparation process is simpler and faster than the existing 3D printing preparation method, and the prepared material structure has better reproducibility.

[0038] 5. The raw materials used in the preparation method provided by the present invention are all commercially available raw materials and are easy to obtain, thereby greatly reducing the preparation cost and being more conducive to expanding production.

[0039] 6. The preparation process of the method provided by the present invention is simple and visual, with low energy consumption, and is therefore conducive to promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a scanning electron microscope photo of the underwater super-double oleophobic water switchable separation material prepared in Example 14 of the present invention. From the photo, it can be seen that there are two through-hole skeleton structures, and there is a hierarchical micro-nano structure composed of micron or nano-sized spherical or flake morphology on the surface of the skeleton structure.

[0041] Figure 2 This is a photo of the water-oil blocking experiment of the underwater super-double oleophobic water switchable separation material prepared in Example 13 of the present invention. As can be seen from the photo, water successfully passed through the material, while the oil phase was blocked above the material. After 10 minutes, the oil phase was still blocked without leakage, indicating that the water-oil blocking separation of the oil-water mixture was successfully achieved.

[0042] Figure 3 This is a photo of the submerged super-double oleophobic and water-switchable separation material prepared in Example 13 of the present invention, showing an oil-through-water blocking experiment. As can be seen from the photo, the oil successfully passed through the material, while the water phase was blocked above the separator. After 10 minutes, the water phase was still blocked without leakage, indicating that the oil-water mixture was successfully separated by oil-through-water blocking.

[0043] Figure 4 This is a cyclic oil-water separation experiment of the underwater super-double oleophobic and water-switchable separation material prepared in Example 13 of the present invention. As can be seen from the figure, after using the material to perform oil-water separation for fifty cycles, the separation efficiency is still greater than 98.2%, reflecting its excellent cyclic separation durability.

[0044] Figure 5 This is a photo of the friction resistance experiment of the underwater super-double oleophobic water switchable separation material prepared in Example 14 of the present invention. In this experiment, the membrane material is placed on the surface of 1000# sandpaper, and a 200g weight is placed on the material. Then, the weight is dragged with tweezers so that the same surface of the material contacts the sandpaper surface under the pressure of the weight and is rubbed back and forth. Each drag of 20cm is one cycle.

[0045] Figure 6 This is a bar chart of the separation efficiency of the underwater super-double oleophobic water switchable separation material after sandpaper friction prepared in Example 14 of the present invention. As shown in the figure, after the material was rubbed with sandpaper for 10 cycles, its separation efficiency did not decrease significantly and was higher than 99.5%, showing that the material has excellent mechanical friction resistance.

[0046] Figure 7 It is a partial schematic diagram of the square six-sided through-hole skeleton design of the underwater super-double oleophobic and water-switchable separation material prepared in Example 3 of the present invention.

[0047] Figure 8 It is a partial schematic diagram of the circular six-sided through-hole skeleton design of the underwater super-double oleophobic and water-switchable separation material prepared in Example 9 of the present invention. DETAILED DESCRIPTION

[0048] The following embodiments are given to clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0049] In addition, it is worth explaining that 1) the hydrophobicity of the material surface means that the water contact angle of the material in the air environment is greater than 90°; on the contrary, when the material is hydrophilic, its water contact angle in the air environment is less than 90°; similarly, the oleophobicity of the material surface means that its oil contact angle in the air environment is greater than 90°, and when it is lipophilic, its oil contact angle in the air environment is less than 90°. Underwater oleophobicity means that the oil contact angle of the material in water is greater than 90°, and sub-oil hydrophobicity means that the water contact angle of the material in oil is greater than 90°. 2) The water contact angle of the material obtained in the following examples in the air is measured by the following method: the material is placed horizontally on the working platform of the water contact angle tester, 2 to 5 μL of water is dropped on the surface of the material with a micro-injector, the water drop morphology is photographed after 5 seconds, and its water contact angle value is measured, and at least 5 different positions are tested. 3) The underwater oil contact angle of the material obtained in the following examples is measured by the following method: fix the material on a glass slide and invert it in deionized water, add 2 to 5 μL of oil droplets to the material surface with a micro-injector, photograph the oil droplet morphology after 5 seconds, measure the underwater oil contact angle value, and test at least 5 different positions. 4) The underwater water contact angle of the material obtained in the following examples is measured by the following method: place the material in a transparent quartz container, soak it with oil, place the quartz container on the sample working platform of the water contact angle tester, keep the sample horizontal, add 2 to 5 μL of water droplets to the material surface with a micro-injector, photograph the oil droplet morphology after 5 seconds, measure the water contact angle value, and test at least 5 positions. 5) The water-through oil-blocking surface of the material obtained in the following examples is wetted with water, and the oil-through water-blocking surface is wetted with oil. When the oil-water mixture passes through the material, water passes through the water-wetted side and oil passes through the oil-wetted side, and the opposite phase is blocked. 6) The oil-water mixture cyclic separation of the materials obtained in the following examples means that the materials are washed and dried after each separation, and separated again according to the method in 5) above. 7) The oil-water mixture separation efficiency of the materials obtained in the following examples is calculated according to the following formula: η=(m 1 / m 0 )×100%, where η is the separation efficiency, m 0 and m 1 They are respectively the mass of the water phase in the oil-water mixture before and after separation; when the separation efficiency is greater than 98%, it proves that the oil-water separation efficiency of the material is excellent.

[0050] Example 1

[0051] First, acrylic acid containing conjugated double bond monomer, initiator azobisisobutyronitrile, and metal organic framework material ZIF-4 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:0.1:0.1; a 3D printing model with two through holes and a side length of 100μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 2s, the bottom exposure time is set to 60s, and the light wavelength is set to 250nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 5℃. After printing, it can be washed with ethanol and dried.

[0052] The prepared underwater super-amphiphobic material has a water contact angle of 90±5° in air, an underwater oil contact angle of 155±5° in the same oil-water system, and a water contact angle of 147±5° under oil.

[0053] Example 2

[0054] First, the conjugated double bond monomer methyl acrylate, initiator azobisisobutyronitrile, and metal organic framework material ZIF-4 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:0.2:2; a 3D printing model with 4 through holes and a hole size of 200μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 0.5s, the bottom exposure time is set to 60s, and the light wavelength is set to 350nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 7°C. After printing, it can be washed with ethanol and dried.

[0055] The prepared underwater super-amphiphobic material has a water contact angle of 95±5° in air, an underwater oil contact angle of 141±5° in the same oil-water system, and a water contact angle of 144±5° under oil.

[0056] Example 3

[0057] First, prepare the photocurable 3D printing precursor solution of ethyl acrylate containing conjugated double bond monomer, dibenzoyl peroxide initiator, and metal organic framework material ZIF-4 at a mass ratio of 100:0.1:5; use computer drawing software to build a 3D printing model with 6 through holes and a side length of 300μm, and save the model in STL format; import the STL format file into the slicing software, set the slicing parameters, and perform slicing, wherein the printing exposure time is set to 2s, the bottom exposure time is set to 70s, and the light wavelength is set to 405nm, and after the precursor solution is poured into the printer tank, perform photocurable 3D printing at 9℃. After printing, wash with ethanol and dry.

[0058] The prepared underwater super-amphiphobic material has a water contact angle of 100±5° in air, an oil contact angle of 143±5° underwater in the same oil-water system, and a water contact angle of 140±5° under oil.

[0059] Example 4

[0060] First, prepare the light-curing 3D printing precursor solution with a mass ratio of 100:0.4:10 for the conjugated double bond monomer butyl acrylate, the initiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-4; use computer drawing software to build a 3D printing model with 8 through holes and a side length of 400 μm, and save the model in STL format; import the STL format file into the slicing software, set the slicing parameters, and perform slicing, wherein the printing exposure time is set to 4s, the bottom exposure time is set to 80s, and the light wavelength is set to 700nm, and after the precursor solution is poured into the printer tank, light-curing 3D printing is performed at 0°C. After printing, it can be washed with ethanol and dried.

[0061] The prepared underwater super-amphiphobic material has a water contact angle of 131±5° in air, an underwater oil contact angle of 155±5° in the same oil-water system, and a water contact angle of 158±5° under oil.

[0062] Example 5

[0063] First, the conjugated double bond-containing monomer hexyl acrylate, the initiator bis(1-(2,4-difluorophenyl)-3-pyrrolyl) titanocene, and the metal organic framework material ZIF-4 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:0.1:50; a 3D printing model with 10 through holes and a hole size of 500μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 6s, the bottom exposure time is set to 65s, and the light wavelength is set to 400nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 15°C. After printing, it can be washed with ethanol and dried.

[0064] The prepared underwater super-amphiphobic material has a water contact angle of 112±5° in air, an oil contact angle of 90±5° underwater in the same oil-water system, and a water contact angle of 175±5° underwater in oil.

[0065] Example 6

[0066] First, the conjugated double bond-containing monomers hydroxyethyl acrylate and trimethylolpropane triacrylate (the mass ratio of the two is 1:1), the initiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and the metal organic framework material ZIF-8 are prepared in a mass ratio of 100:1:0.1 to form a photocurable 3D printing precursor solution; a 3D printing model with 20 through holes and a hole size of 50μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 8s, the bottom exposure time is set to 40s, and the light wavelength is set to 365nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 17°C. After printing, it can be washed with ethanol and dried.

[0067] The prepared underwater super-amphiphobic material has a water contact angle of 95±5° in air, an underwater oil contact angle of 132±5° in the same oil-water system, and a water contact angle of 121±5° under oil.

[0068] Example 7

[0069] First, the conjugated double bond monomer nonyl acrylate, initiator 4-phenylbenzophenone, and metal organic framework material ZIF-8 were prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1:2; a 3D printing model with 4 through holes and a side length of 200μm was established using computer drawing software, and the model was saved in STL format; the STL format file was imported into the slicing software, and the slicing parameters were set for slicing, in which the printing exposure time was set to 9s, the bottom exposure time was set to 30s, and the light wavelength was set to 350nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 90℃. After printing, it was washed with ethanol and dried.

[0070] The prepared underwater super-amphiphobic material has a water contact angle of 98±5° in air, an underwater oil contact angle of 137±5° in the same oil-water system, and a water contact angle of 140±5° under oil.

[0071] Example 8

[0072] First, the conjugated double bond monomer decyl acrylate, the initiator phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-8 are mixed in a mass ratio of 100:1:5 to form a photocurable 3D printing precursor solution; a 3D printing model with 4 through holes and a hole size of 300 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 1s, the bottom exposure time is set to 60s, and the light wavelength is set to 405nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 20°C. After printing, it can be washed with ethanol and dried.

[0073] The prepared underwater super-amphiphobic material has a water contact angle of 125±5° in air, an underwater oil contact angle of 151±5° in the same oil-water system, and a water contact angle of 156±5° under oil.

[0074] Example 9

[0075] First, the conjugated double bond monomer styrene, initiator benzophenone, and metal organic framework material ZIF-8 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1.2:10; a 3D printing model with 6 through holes and a hole size of 600μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 3s, the bottom exposure time is set to 75s, and the light wavelength is set to 450nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 33°C. After printing, it can be washed with ethanol and dried.

[0076] The prepared underwater super-amphiphobic material has a water contact angle of 127±5° in air, an underwater oil contact angle of 155±5° in the same oil-water system, and a water contact angle of 150±5° under oil.

[0077] Example 10

[0078] First, the conjugated double bond monomer propyl acrylate, the initiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-8 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1.5:50; a 3D printing model with 8 through holes and a side length of 3000 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 100 s, the bottom exposure time is set to 35 s, and the light wavelength is set to 410 nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 34°C. After printing, it can be washed with ethanol and dried.

[0079] The prepared underwater super-amphiphobic material has a water contact angle of 110±5° in air, an underwater oil contact angle of 143±5° in the same oil-water system, and a water contact angle of 142±5° under oil.

[0080] Embodiment 11

[0081] First, the conjugated double bond-containing monomers acrylic acid and butyl acrylate (the mass ratio of the two is 2:1), the initiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-zni are prepared in a mass ratio of 100:2:0.8 to form a photocurable 3D printing precursor solution; a 3D printing model with two through holes and a hole size of 50μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 20s, the bottom exposure time is set to 10s, and the light wavelength is set to 420nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 26°C. After printing, it can be washed with ethanol and dried.

[0082] The prepared underwater super-amphiphobic material has a water contact angle of 92±5° in air, an oil contact angle of 180±5° underwater in the same oil-water system, and a water contact angle of 103±5° underwater in oil.

[0083] Example 12

[0084] First, the conjugated double bond monomer hydroxyethyl acrylate, initiator dibenzoyl peroxide, and metal organic framework material ZIF-zni are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:5:6; a 3D printing model with 4 through holes and a hole size of 150μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 10s, the bottom exposure time is set to 40s, and the light wavelength is set to 350nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 10°C. After printing, it can be washed with ethanol and dried.

[0085] The prepared underwater super-amphiphobic material has a water contact angle of 135±5° in air, an oil contact angle of 155±5° underwater in the same oil-water system, and a water contact angle of 158±5° underwater in oil.

[0086] Embodiment 13

[0087] First, the conjugated double bond-containing monomer methyl methacrylate, the initiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-zni are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:2:5; a 3D printing model with two through holes and a side length of 200 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 5s, the bottom exposure time is set to 65s, and the light wavelength is set to 405nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 25°C. After printing, it can be washed with ethanol and dried.

[0088] The prepared underwater super-amphiphobic material has a water contact angle of 130±5° in air, an underwater oil contact angle of 150±5° in the same oil-water system, and a water contact angle of 161±5° under oil.

[0089] Embodiment 14

[0090] First, the conjugated double bond-containing monomer methyl methacrylate, the initiator phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-zni are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:2:10; a 3D printing model with two through holes and a side length of 300 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 2s, the bottom exposure time is set to 60s, and the light wavelength is set to 405nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 27°C. After printing, it can be washed with ethanol and dried.

[0091] The prepared underwater super-amphiphobic material has a water contact angle of 135±5° in air, an underwater oil contact angle of 163±5° in the same oil-water system, and a water contact angle of 157±5° under oil.

[0092] Embodiment 15

[0093] First, the conjugated double bond monomer n-butyl methacrylate, the initiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and the metal organic framework material ZIF-zni are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:8:50; a 3D printing model with 10 through holes and a side length of 250μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 3s, the bottom exposure time is set to 55s, and the light wavelength is set to 395nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 30°C. After printing, it can be washed with ethanol and dried.

[0094] The prepared underwater super-amphiphobic material has a water contact angle of 175±5° in air, an underwater oil contact angle of 95±5° in the same oil-water system, and a water contact angle of 165±5° under oil.

[0095] Example 16

[0096] First, the conjugated double bond monomer bisphenol A (meth) acrylate, initiator 4-phenylbenzophenone, and metal organic framework material ZIF-7 were prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:7:0.5; a 3D printing model with 4 through holes and a hole size of 350μm was established using computer drawing software, and the model was saved in STL format; the STL format file was imported into the slicing software, and the slicing parameters were set for slicing, wherein the printing exposure time was set to 4s, the bottom exposure time was set to 0.5s, and the light wavelength was set to 377nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 16°C. After printing, it was washed with ethanol and dried.

[0097] The prepared underwater super-amphiphobic material has a water contact angle of 95±5° in air, an underwater oil contact angle of 168±5° in the same oil-water system, and a water contact angle of 90±5° under oil.

[0098] Embodiment 17

[0099] First, the conjugated double bond monomer octyl acrylate, initiator phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, and metal organic framework material ZIF-7 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:0.6:25; a 3D printing model with 8 through holes and a side length of 450 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 6s, the bottom exposure time is set to 30s, and the light wavelength is set to 350nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 35°C. After printing, it can be washed with ethanol and dried.

[0100] The prepared underwater super-amphiphobic material has a water contact angle of 126±5° in air, an oil contact angle of 151±5° underwater in water, and a water contact angle of 152±5° underwater in the same oil-water system.

[0101] Embodiment 18

[0102] First, the conjugated double bond-containing monomer butadiene dicarboxylate, the initiator phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-7 are mixed in a mass ratio of 100:10:35 to form a photocurable 3D printing precursor solution; a 3D printing model with 6 through holes and a hole size of 500 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 7s, the bottom exposure time is set to 60s, and the light wavelength is set to 405nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 32°C. After printing, it can be washed with ethanol and dried.

[0103] The prepared underwater super-amphiphobic material has a water contact angle of 130±5° in air, an underwater oil contact angle of 156±5° in the same oil-water system, and a water contact angle of 153±5° under oil.

[0104] Embodiment 19

[0105] First, the conjugated double bond monomer stilbene, initiator benzophenone, and metal organic framework material ZIF-7 were prepared in a mass ratio of 100:6:4 to form a photocurable 3D printing precursor solution; a computer drawing software was used to establish a 3D printing model with 8 through holes and a hole size of 600μm, and the model was saved in STL format; the STL format file was imported into the slicing software, and the slicing parameters were set for slicing, in which the printing exposure time was set to 8s, the bottom exposure time was set to 80s, and the light wavelength was set to 365nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 31°C. After printing, it was washed with ethanol and dried.

[0106] The prepared underwater super-amphiphobic material has a water contact angle of 135±5° in air, an underwater oil contact angle of 157±5° in the same oil-water system, and a water contact angle of 150±5° under oil.

[0107] Embodiment 20

[0108] First, divinylbenzene, a monomer containing conjugated double bonds, initiator benzophenone, and metal organic framework material ZIF-7 were prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:0.9:50; a 3D printing model with 10 through holes and a hole size of 600 μm was established using computer drawing software, and the model was saved in STL format; the STL format file was imported into the slicing software, and the slicing parameters were set for slicing, wherein the printing exposure time was set to 9s, the bottom exposure time was set to 200s, and the light wavelength was set to 365nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 28°C. After printing, it was washed with ethanol and dried.

[0109] The prepared underwater super-amphiphobic material has a water contact angle of 157±5° in air, an oil contact angle of 93±5° underwater in the same oil-water system, and a water contact angle of 180±5° under oil.

[0110] Embodiment 21

[0111] First, trimethylolpropane triacrylate containing conjugated double bond monomer, azobisisobutyronitrile initiator, and metal organic framework material ZIF-67 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:0.3:4; a 3D printing model with 4 through holes and a hole size of 100μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 1.5s, the bottom exposure time is set to 5s, and the light wavelength is set to 200nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 29°C. After printing, it can be washed with ethanol and dried.

[0112] The prepared underwater super-amphiphobic material has a water contact angle of 99±5° in air, an underwater oil contact angle of 151±5° in the same oil-water system, and a water contact angle of 148±5° under oil.

[0113] Embodiment 22

[0114] First, the conjugated double bond monomer octyl acrylate, initiator azobisisobutyronitrile, and metal organic framework material ZIF-67 are mixed in a mass ratio of 100:0.5:6 to form a photocurable 3D printing precursor solution; a 3D printing model with 6 through holes and a side length of 150μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 2.5s, the bottom exposure time is set to 10s, and the light wavelength is set to 350nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 34°C. After printing, it can be washed with ethanol and dried.

[0115] The prepared underwater super-amphiphobic material has a water contact angle of 125±5° in air, an underwater oil contact angle of 153±5° in the same oil-water system, and a water contact angle of 151±5° under oil.

[0116] Embodiment 23

[0117] First, the conjugated double bond-containing monomers butyl acrylate and nonyl acrylate (the mass ratio of the two is 1:2), the initiator dibenzoyl peroxide, and the metal organic framework material ZIF-67 are prepared in a mass ratio of 100:0.7:8 to form a photocurable 3D printing precursor solution; a computer drawing software is used to establish a 3D printing model with 8 through holes and a side length of 200μm, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 3.5s, the bottom exposure time is set to 15s, and the light wavelength is set to 400nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 33°C. After printing, it can be washed with ethanol and dried.

[0118] The prepared underwater super-amphiphobic material has a water contact angle of 137±5° in air, an underwater oil contact angle of 157±5° in the same oil-water system, and a water contact angle of 159±5° under oil.

[0119] Embodiment 24

[0120] First, the conjugated double bond monomer nonyl acrylate, the initiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-67 are mixed in a mass ratio of 100:8:40 to form a photocurable 3D printing precursor solution; a 3D printing model with four through holes and a hole size of 250 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 4.5s, the bottom exposure time is set to 20s, and the light wavelength is set to 450nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 24°C. After printing, it can be washed with ethanol and dried.

[0121] The prepared underwater super-amphiphobic material has a water contact angle of 132±5° in air, an oil contact angle of 158±5° underwater in the same oil-water system, and a water contact angle of 160±5° underwater in oil.

[0122] Embodiment 25

[0123] First, the conjugated double bond-containing monomer decyl acrylate, the initiator bis(1-(2,4-difluorophenyl)-3-pyrrolyl) titanocene, and the metal organic framework material ZIF-67 are mixed in a mass ratio of 100:10:50 to form a photocurable 3D printing precursor solution; a 3D printing model with 12 through holes and a side length of 300 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 5.5s, the bottom exposure time is set to 25s, and the light wavelength is set to 1000nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 22°C. After printing, it can be washed with ethanol and dried.

[0124] The prepared underwater super-amphiphobic material has a water contact angle of 151±5° in air, an oil contact angle of 98±5° underwater in the same oil-water system, and a water contact angle of 173±5° underwater in oil.

[0125] Embodiment 26

[0126] First, the conjugated double bond monomer hydroxyethyl acrylate, initiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and metal organic framework material ZIF-71 were mixed in a mass ratio of 100:1:1 to form a photocurable 3D printing precursor solution; a 3D printing model with 6 through holes and a side length of 60 μm was established using computer drawing software, and the model was saved in STL format; the STL format file was imported into the slicing software, and the slicing parameters were set for slicing, wherein the printing exposure time was set to 6.5s, the bottom exposure time was set to 30s, and the light wavelength was set to 365nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 19°C. After printing, it was washed with ethanol and dried.

[0127] The prepared underwater super-amphiphobic material has a water contact angle of 113±5° in air, an underwater oil contact angle of 143±5° in the same oil-water system, and a water contact angle of 148±5° under oil.

[0128] Embodiment 27

[0129] First, trimethylolpropane triacrylate containing conjugated double bond monomer, initiator 4-phenylbenzophenone, and metal organic framework material ZIF-71 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:3:2; a 3D printing model with 8 through holes and a hole size of 70μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 7.5s, the bottom exposure time is set to 35s, and the light wavelength is set to 350nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 26°C. After printing, it can be washed with ethanol and dried.

[0130] The prepared underwater super-amphiphobic material has a water contact angle of 117±5° in air, an oil contact angle of 148±5° underwater in the same oil-water system, and a water contact angle of 145±5° under oil.

[0131] Embodiment 28

[0132] First, the conjugated double bond monomer butyl acrylate, the initiator phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, and the metal organic framework material ZIF-71 are mixed in a mass ratio of 100:2:4 to form a photocurable 3D printing precursor solution; a 3D printing model with four through holes and a side length of 80 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 8.5s, the bottom exposure time is set to 40s, and the light wavelength is set to 405nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 20°C. After printing, it can be washed with ethanol and dried.

[0133] The prepared underwater super-amphiphobic material has a water contact angle of 120±4° in air, an underwater oil contact angle of 151±5° in the same oil-water system, and a water contact angle of 155±5° under oil.

[0134] Embodiment 29

[0135] First, the conjugated double bond monomer bisphenol A (meth) acrylate, initiator benzophenone, and metal organic framework material ZIF-71 were prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1:4; a 3D printing model with 6 through holes and a hole size of 90 μm was established using computer drawing software, and the model was saved in STL format; the STL format file was imported into the slicing software, and the slicing parameters were set for slicing, wherein the printing exposure time was set to 9.5s, the bottom exposure time was set to 50s, and the light wavelength was set to 375nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 21°C. After printing, it was washed with ethanol and dried.

[0136] The prepared underwater super-amphiphobic material has a water contact angle of 137±5° in air, an underwater oil contact angle of 159±5° in the same oil-water system, and a water contact angle of 160±5° under oil.

[0137] Embodiment 30

[0138] First, the conjugated double bond monomer heptyl acrylate, initiator azobisisobutyronitrile, and metal organic framework material ZIF-71 were prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1.7:6; a 3D printing model with 8 through holes and a side length of 110μm was established using computer drawing software, and the model was saved in STL format; the STL format file was imported into the slicing software, and the slicing parameters were set for slicing, in which the printing exposure time was set to 23s, the bottom exposure time was set to 72s, and the light wavelength was set to 300nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 36°C. After printing, it was washed with ethanol and dried.

[0139] The prepared underwater super-amphiphobic material has a water contact angle of 143±5° in air, an underwater oil contact angle of 101±5° in the same oil-water system, and a water contact angle of 170±5° under oil.

[0140] Embodiment 31

[0141] First, the conjugated double bond-containing monomer butadiene dicarboxylate, the initiator bis(1-(2,4-difluorophenyl)-3-pyrrolyl) titanocene, and the metal organic framework material ZIF-90 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1:30; a 3D printing model with 8 through holes and a hole size of 120μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 28s, the bottom exposure time is set to 58s, and the light wavelength is set to 355nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 11°C. After printing, it can be washed with ethanol and dried.

[0142] The prepared underwater super-amphiphobic material has a water contact angle of 123±5° in air, an underwater oil contact angle of 140±5° in the same oil-water system, and a water contact angle of 156±5° under oil.

[0143] Embodiment 32

[0144] First, divinylbenzene, a monomer containing conjugated double bonds, dibenzoyl peroxide, an initiator, and ZIF-90, a metal organic framework material, were prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1.2:14. A 3D printing model with four through holes and a hole size of 140 μm was established using computer drawing software, and the model was saved in STL format. The STL format file was imported into the slicing software, and the slicing parameters were set for slicing, wherein the printing exposure time was set to 2.2 s, the bottom exposure time was set to 52 s, and the light wavelength was set to 400 nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 13 ° C. After printing, it was washed with ethanol and dried.

[0145] The prepared underwater super-amphiphobic material has a water contact angle of 135±5° in air, an oil contact angle of 157±5° underwater in the same oil-water system, and a water contact angle of 155±5° under oil.

[0146] Embodiment 33

[0147] First, the conjugated double bond monomer methyl acrylate, initiator benzophenone, and metal organic framework material ZIF-90 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1.9:5.1; a 3D printing model with 6 through holes and a side length of 160μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 2.8s, the bottom exposure time is set to 100s, and the light wavelength is set to 405nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 38°C. After printing, it can be washed with ethanol and dried.

[0148] The prepared underwater super-amphiphobic material has a water contact angle of 125±5° in air, an underwater oil contact angle of 152±5° in the same oil-water system, and a water contact angle of 161±5° under oil.

[0149] Embodiment 34

[0150] First, the conjugated double bond-containing monomer propyl acrylate, the initiator bis(1-(2,4-difluorophenyl)-3-pyrrolyl) titanocene, the metal organic framework materials ZIF-4 and ZIF-90 (the mass ratio of the two is 1:3) are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:2:4; a 3D printing model with 12 through holes and a hole size of 180μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 3.4s, the bottom exposure time is set to 70s, and the light wavelength is set to 375nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 60℃. After printing, it can be washed with ethanol and dried.

[0151] The prepared underwater super-amphiphobic material has a water contact angle of 136±5° in air, an underwater oil contact angle of 153±5° in the same oil-water system, and a water contact angle of 159±5° under oil.

[0152] Embodiment 35

[0153] First, the conjugated double bond monomers butyl acrylate, methyl acrylate and octyl acrylate (the mass ratio of the three is 1:1:1), the initiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and the metal organic framework material ZIF-90 are prepared in a mass ratio of 100:3:27 to form a photocurable 3D printing precursor solution; a 3D printing model with 6 through holes and a hole size of 200μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 30s, the bottom exposure time is set to 15s, and the light wavelength is set to 395nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 70℃. After printing, it can be washed with ethanol and dried.

[0154] The prepared underwater super-amphiphobic material has a water contact angle of 140±5° in air, an oil contact angle of 148±5° underwater in the same oil-water system, and a water contact angle of 156±5° underwater in oil.

[0155] Embodiment 36

[0156] First, the conjugated double bond monomer styrene, initiator 4-phenylbenzophenone and benzophenone (the mass ratio of the two is 2:1), and metal organic framework material ZIF-90 are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1.3:8.7; a 3D printing model with 10 through holes and a hole size of 700μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 40s, the bottom exposure time is set to 45s, and the light wavelength is set to 800nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 13°C. After printing, it can be washed with ethanol and dried.

[0157] The prepared underwater super-amphiphobic material has a water contact angle of 126±5° in air, an underwater oil contact angle of 147±5° in the same oil-water system, and a water contact angle of 145±5° under oil.

[0158] Embodiment 37

[0159] First, the conjugated double bond monomer hexyl acrylate, initiator phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, metal organic framework materials ZIF-L and ZIF-67 (the mass ratio of the two is 1:1) are prepared in a mass ratio of 100:2:10 to form a photocurable 3D printing precursor solution; a 3D printing model with 12 through holes and a hole size of 260 μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 50s, the bottom exposure time is set to 30s, and the light wavelength is set to 350nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 80°C. After printing, it can be washed with ethanol and dried.

[0160] The prepared underwater super-amphiphobic material has a water contact angle of 134±5° in air, an underwater oil contact angle of 151±5° in the same oil-water system, and a water contact angle of 153±5° under oil.

[0161] Embodiment 38

[0162] First, the conjugated double bond monomer pentyl acrylate, initiator benzophenone, and metal organic framework material ZIF-L were prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:1:5; a 3D printing model with 14 through holes and a side length of 1500μm was established using computer drawing software, and the model was saved in STL format; the STL format file was imported into the slicing software, and the slicing parameters were set for slicing, wherein the printing exposure time was set to 70s, the bottom exposure time was set to 110s, and the light wavelength was set to 405nm. After the precursor solution was poured into the printer tank, photocurable 3D printing was performed at 56°C. After printing, it was washed with ethanol and dried.

[0163] The prepared underwater super-amphiphobic material has a water contact angle of 130±5° in air, an oil contact angle of 157±5° underwater in the same oil-water system, and a water contact angle of 155±5° under oil.

[0164] Embodiment 39

[0165] First, the conjugated double bond monomer ethyl acrylate, initiator azobisisobutyronitrile and benzophenone (the mass ratio of the two is 1:1), and metal organic framework material ZIF-L are prepared into a photocurable 3D printing precursor solution at a mass ratio of 100:2:5; a 3D printing model with 16 through holes and a side length of 2500μm is established using computer drawing software, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 90s, the bottom exposure time is set to 140s, and the light wavelength is set to 355nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 40℃. After printing, it can be washed with ethanol and dried.

[0166] The prepared underwater super-amphiphobic material has a water contact angle of 129±5° in air, an oil contact angle of 155±5° underwater in the same oil-water system, and a water contact angle of 152±5° underwater in oil.

[0167] Embodiment 40

[0168] First, the conjugated double bond monomers hexyl acrylate and butadiene dicarboxylate (the mass ratio of the two is 1:3), the initiator azobisisobutyronitrile, and the metal organic framework material ZIF-L are prepared in a mass ratio of 100:2:8 to form a photocurable 3D printing precursor solution; a computer drawing software is used to establish a 3D printing model with 18 through holes and a side length of 2000μm, and the model is saved in STL format; the STL format file is imported into the slicing software, and the slicing parameters are set for slicing, wherein the printing exposure time is set to 2.5s, the bottom exposure time is set to 160s, and the light wavelength is set to 700nm. After the precursor solution is poured into the printer tank, photocurable 3D printing is performed at 16°C. After printing, it can be washed with ethanol and dried.

[0169] The prepared underwater super-amphiphobic material has a water contact angle of 138±5° in air, an underwater oil contact angle of 148±5° in the same oil-water system, and a water contact angle of 165±5° under oil.

[0170] In order to investigate the underwater oleophobicity and underwater hydrophobicity of the underwater super-double oleophobic water switchable separation material prepared by the present invention, application examples are given below to illustrate the practical application of the underwater super-double oleophobic water switchable separation material prepared by the present invention. However, the application examples given are only application examples of materials prepared by a part of the embodiments of the technical solution of the present invention.

[0171] Application Example 1

[0172] The underwater super dual oleophobic water switchable separation material prepared in Example 13 is placed in an oil-water system such as n-hexane / water and petroleum ether / water, and exhibits underwater oleophobicity and oil-water hydrophobicity. It is placed in the center of the separator, and after being wetted with water, the oil-water mixture is separated by passing through water and blocking oil; at the same time, the oil-water mixture is separated by passing through oil and blocking water after being wetted with oil. Figure 2 , 3 As shown in the figure, it can be seen that the material can successfully separate oil-water mixture by using both water-through oil-blocking and oil-through water-blocking methods. Figure 4 As shown, for the same oil-water system (n-hexane / water), both water-through oil blocking and oil-through water blocking can be achieved, and after 50 cycles of separation, the separation efficiency is still greater than 98.20%.

[0173] Application Example 2

[0174] The underwater super dual oleophobic water switchable separation material prepared in Example 14 exhibits underwater oleophobicity and oil-water hydrophobicity in oil-water systems such as n-hexane / water and petroleum ether / water, and also has excellent friction resistance. That is, the material is placed on the surface of 1000# sandpaper and rubbed repeatedly. Figure 5 , 6 As shown, after 10 cycles of friction, the material can still achieve underwater oil repellency and oil-under-water hydrophobicity, and the separation efficiency is still greater than 99.5%.

Claims

1. An underwater super-double oleophobic water switchable separation material based on photocuring 3D printing, characterized in that The material is composed of a multi-faceted through-porous skeleton with a micro-nano structure obtained by photocuring 3D printing under mild conditions from precursors containing conjugated double bond monomers, initiators, and metal organic framework materials. The water contact angle of the material in the air is 90-175°, the underwater oil contact angle in the same oil-water system is 90-180°, and the underwater water contact angle is 90-180°. After 10 cycles of sandpaper friction treatment, the material can still separate the oil-water mixture by passing through water to block the oil or passing through oil to block the water, and the separation efficiency is higher than 99.5%.

2. The underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 1, characterized in that The material has a water contact angle of 90 to 175° in air, an oil contact angle of 150 to 180° underwater and a water contact angle of 90 to 180° underwater in the same oil-water system, or The water contact angle in air is 90-175°, the oil contact angle underwater in the same oil-water system is 90-180°, and the water contact angle under oil is 150-180°, or The contact angle of water in air is 120-175°, the contact angle of oil under water and the contact angle of water under oil in the same oil-water system are 150-180° and 150-180° respectively.

3. The underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 1 or 2, characterized in that The monomer containing conjugated double bonds in the underwater super-amphiphobic water separation material is at least one of acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, methyl methacrylate, hydroxyethyl acrylate, trimethylolpropane triacrylate, n-butyl methacrylate, bisphenol A (meth) acrylate, butadiene dicarboxylate, styrene, divinylbenzene and stilbene; The initiator is at least one of azobisisobutyronitrile, dibenzoyl peroxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (1- (2,4-difluorophenyl) -3-pyrrolyl) titanocene, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4-phenyl benzophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and benzophenone; The metal organic framework material is at least one of ZIF-4, ZIF-8, ZIF-7, ZIF-67, ZIF-71, ZIF-90, ZIF-L and ZIF-zni.

4. The underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 1 or 2, characterized in that The multi-faceted through-hole structure in the underwater super-double oleophobic water separation material is any one of 2-faced through-holes, 4-faced through-holes, 6-faced through-holes, 8-faced through-holes, 10-faced through-holes, 12-faced through-holes, 14-faced through-holes, 16-faced through-holes, 18-faced through-holes or 20-faced through-holes, and its pore diameter or side length is 50 to 3000 μm.

5. The underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 3, characterized in that The multi-faceted through-hole structure in the underwater super-double oleophobic water separation material is any one of 2-faced through-holes, 4-faced through-holes, 6-faced through-holes, 8-faced through-holes, 10-faced through-holes, 12-faced through-holes, 14-faced through-holes, 16-faced through-holes, 18-faced through-holes or 20-faced through-holes, and its pore diameter or side length is 50 to 3000 μm.

6. A method for preparing an underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 1, characterized in that The process steps and conditions of this method are as follows: (1) First, prepare a photocurable 3D printing precursor solution by mixing a conjugated double bond-containing monomer, an initiator, and a metal organic framework material in a mass ratio of 100:(0.1-10):(0.1-50) for later use; (2) using computer graphics software to establish a three-dimensional porous material model containing a multi-faceted through-hole skeleton, wherein the pore size or side length is set to 50 to 3000 μm, and the model is saved in STL format; (3) Import the STL format file into the slicing software, set the slicing parameters, and perform slicing, wherein the printing exposure time is set to 0.5-100 s, the bottom layer exposure time is set to 0.5-200 s, and the light wavelength is set to 200-1000 nm and then saved for later use; (4) After the prepared light-curing 3D printing precursor solution is poured into the printer tank, light-curing 3D printing is performed at 0-90°C. After printing is completed, it can be cleaned with ethanol and dried.

7. The method for preparing an underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 6, characterized in that The conjugated double bond-containing monomer used in the method is at least one of acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, methyl methacrylate, hydroxyethyl acrylate, trimethylolpropane triacrylate, n-butyl methacrylate, bisphenol A (meth)acrylate, butadiene dicarboxylate, styrene, divinylbenzene and stilbene; The initiator used is at least one of azobisisobutyronitrile, dibenzoyl peroxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (1- (2,4-difluorophenyl) -3-pyrrolyl) titanocene, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4-phenyl benzophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and benzophenone; The metal organic framework material used is at least one of ZIF-4, ZIF-8, ZIF-7, ZIF-67, ZIF-71, ZIF-90, ZIF-L and ZIF-zni.

8. The method for preparing the underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 6 or 7, characterized in that The multi-sided through hole described in the method is any one of a 2-sided through hole, a 4-sided through hole, a 6-sided through hole, an 8-sided through hole, a 10-sided through hole, a 12-sided through hole, a 14-sided through hole, a 16-sided through hole, an 18-sided through hole or a 20-sided through hole.

9. The method for preparing an underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 6 or 7, characterized in that The mass ratio of the conjugated double bond-containing monomer, the initiator and the metal organic framework material used in the method is 100:(0.1-2):(0.1-10).

10. The method for preparing an underwater super-double oleophobic water switchable separation material based on photocuring 3D printing according to claim 8, characterized in that The mass ratio of the conjugated double bond-containing monomer, the initiator and the metal organic framework material used in the method is 100:(0.1-2):(0.1-10).

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