CN113559555A - Block polymer modified oil-water separation stainless steel mesh and preparation method thereof - Google Patents

Block polymer modified oil-water separation stainless steel mesh and preparation method thereof Download PDF

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CN113559555A
CN113559555A CN202110864335.8A CN202110864335A CN113559555A CN 113559555 A CN113559555 A CN 113559555A CN 202110864335 A CN202110864335 A CN 202110864335A CN 113559555 A CN113559555 A CN 113559555A
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stainless steel
block polymer
water separation
oil
steel mesh
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CN113559555B (en
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韩霞
刘洪来
王含含
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East China University of Science and Technology
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Abstract

The invention discloses a preparation method of a block polymer modified oil-water separation stainless steel mesh. According to the invention, acyl bromide is used for substituting polyethylene glycol with different chain lengths and dopamine methacrylamide containing adhesive catechol groups to form a block polymer through atom transfer radical polymerization reaction. And soaking the stainless steel net in a Tris buffer solution added with the polymer reaction solution, and oscillating at constant temperature to obtain the block polymer modified oil-water separation stainless steel net. The block polymer modified oil-water separation stainless steel mesh provided by the invention has the characteristics of good oil-water separation effect, good stability and mechanical force resistance; the mussel inspired block polymer material used has biocompatibility, degradability and environmental protection, and the waste material after use can not cause secondary pollution to the environment. The preparation method and process of the mussel inspired block polymer modified oil-water separation stainless steel mesh are simple and convenient, the process is rapid, and the reaction is mild and controllable.

Description

Block polymer modified oil-water separation stainless steel mesh and preparation method thereof
Technical Field
The invention relates to an oil-water separation stainless steel mesh and a preparation method thereof, in particular to a mussel inspired block polymer modified oil-water separation stainless steel mesh and a preparation method thereof.
Background
The discharge of industrial waste water, the leakage of oil production from the seabed and the like cause water pollution worldwide, and bring heavy burden to the ecology, the economy and the health of human beings, and the treatment of the oil stain in the seawater is a major challenge in the world today. Therefore, development of an effective oily sewage treatment technology is urgently required. The traditional oil pollution treatment methods such as fence method, centrifugal method, chemical treatment method, biological treatment method, flotation, oil skimming and the like can solve the requirements of oil-water separation to a certain extent, but the oil-water separation method has the defects of low separation efficiency, high cost, complex process, easy secondary pollution and the like, so that the oil-water separation method is limited in large-scale application.
Inspired by the phenomenon of self-cleaning of the lotus leaf surface in nature, the utilization of a material with special wettability for oil-water separation becomes a research hotspot, and typical super-hydrophobic-super oleophilic oil type oil removing materials and underwater super-hydrophobic oil type water removing materials are successfully applied to oil-water separation. Biocompatible polymers have been reported in the literature as being incorporated as non-toxic surface antifouling coating materials, including polyethylene glycol, polyacrylates, poly (2-hydroxyethyl methacrylate), and polyacrylamides. Among them, polyethylene glycol is widely used due to its high water solubility, chain flexibility and biocompatibility, and produces antifouling and lubricating properties through space exclusion and surface hydration.
Marine mussels can be tightly adsorbed on hard rock, mineral and metal surfaces in a humid environment. This is attributed to the fact that the sequence of the mussel poda protein contains a large amount of unique 3, 4-dihydroxyphenylalanine (L-DOPA), and the catechol group on the L-DOPA provides a main contribution to the durable and strong adsorption of the mussel on the surface of the substance. Inspired by mussel, dopamine is developed into a firm and universal anchoring agent material, and a new strategy is opened up for surface modification.
In recent years, ABA type triblock copolymers in a ring conformation have been studied as advanced antifouling coatings. Unlike brush-like conventional AB type diblock copolymers, cyclic triblock polymers do not have chain ends, have large exclusion volumes and strong steric hindrance, and provide excellent surface steric stability, antifouling properties and lubricating properties. The method injects great vigor to the development of the science and the technology of the material surface interface, and is widely researched and used for the surface interface modification and the functionalization of the material.
The oil-water separation material based on dopamine surface modification super-hydrophilicity/underwater super-lipophobicity reported at present still has some problems. For example, the rate of oxidizing dopamine by air to form a polydopamine coating is slow, the deposition time is long, the stability is poor, severe dopamine waste and environmental pollution are easily caused, and the problems greatly limit the large-scale application of dopamine in actual life and industrial production; secondly, most of the commonly used oil-water separation materials are non-degradable or difficultly degradable high polymer materials, and the waste is easy to cause secondary pollution to the environment after the use.
Disclosure of Invention
According to the defects and shortcomings of the prior art, the technical problem to be solved by the invention is to provide the mussel inspired block polymer modified oil-water separation stainless steel net, the oil-water separation stainless steel net has the characteristics of high oil-water separation efficiency, good stability and mechanical resistance, the used metal stainless steel net has good mechanical and chemical stability and is cheap and easy to obtain, and the block polymer has biocompatibility, degradability and environmental protection.
The invention aims to solve another technical problem of providing a preparation method of the mussel inspired block polymer modified oil-water separation stainless steel mesh, which has the characteristics of simple and convenient process, quick process, mild and controllable reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
the block polymer modified oil-water separation stainless steel net is prepared by modifying the surface of a stainless steel substrate by using a polyethylene glycol-polydopamine methacrylamide block polymer; stainless steel mesh as the base material, the polymer is coated on it; the structural formula of the polyethylene glycol-polydopamine methacrylamide block polymer is shown as follows:
Figure BDA0003186810140000021
wherein a is an integer of 1-10, and b is 4, 6, 8, 10, 13, 22, 33, 45, 67.
The stainless steel net is a net material formed by weaving stainless steel wires, which serves as a base material to which a polymer is applied.
Preferably, the mesh size of the stainless steel mesh is 500-1000 meshes. The net shape is characterized in that: the stainless steel nets with different meshes have different mesh sizes, and the larger the mesh size is, the smaller the mesh size is. The use of 500-mesh and 1000-mesh stainless steel nets is preferred.
The invention also provides a preparation method of the block polymer modified oil-water separation stainless steel mesh, which comprises the following steps:
(1) preparation of dopamine methacrylamide monomer:
dissolving sodium tetraborate decahydrate and sodium bicarbonate in deionized water to form a saturated solution, and introducing nitrogen to remove oxygen; adding dopamine hydrochloride, and continuing nitrogen bubbling; under the state of ice-water bath, dropwise adding methacrylic anhydride diluted by tetrahydrofuran, and replenishing sodium hydroxide at any time; removing the ice water bath and the nitrogen source after 0.2-1 h; stirring the mixture at room temperature overnight to obtain reddish suspension, filtering to obtain aqueous solution, washing with ethyl acetate, adjusting the pH of the solution with hydrochloric acid to 1.5-2.5, and precipitating a large amount of solid; extracting with ethyl acetate, and extracting and washing with water to obtain a light brown clear solution; drying the clear solution by using anhydrous magnesium sulfate or anhydrous sodium sulfate, filtering to remove a drying agent, performing rotary evaporation and concentration, settling in normal hexane to obtain a white solid, and performing vacuum drying to obtain DMA;
(2) synthesizing a double-head initiator Br-PEG-Br:
dissolving polyethylene glycol, placing in an ice water bath, fully cooling, adding triethylamine, adding 2-bromoisobutyryl bromide under the stirring condition, and reacting at room temperature; after the reaction is stopped, treating the reaction solution by using active carbon, performing suction filtration, and collecting filtrate; removing most of solvent by rotary evaporation, settling in cold ether, centrifuging, and vacuum drying to obtain white product;
(3) synthesis of Block Polymer (PDMA-PEG-PDMA):
adding an initiator, a monomer, a ligand and a solvent into a reaction container, adding a catalyst after liquid nitrogen freezing, vacuumizing and nitrogen filling circulation, unfreezing, and placing the mixture into an oil bath pot for reaction; the mol ratio of the initiator, the monomer, the catalyst cuprous bromide and the ligand is 1: 2-20: 1-4: 2-6; the reaction started after thawing.
(4) Preparing an oil-water separation stainless steel net:
and (4) transferring the reaction solution obtained in the step (3) into a Tris buffer solution, adjusting the pH value to 7.5-10 to obtain a modified solution, and placing the pretreated stainless steel net into the modified solution to oscillate at a constant temperature of 20-37 ℃.
The process can be carried out under weakly acidic conditions; the stronger the basicity, the faster the reaction rate. Preferably, a tris buffer solution of pH 8.0 or 8.5 is used, and the reaction can be accelerated at pH 8.0 or more.
Preferably, in the step (2), the molecular weight of the polyethylene glycol is Mw 200-.
Preferably, in the step (2), the molar ratio of the polyethylene glycol to the triethylamine to the 2-bromoisobutyryl bromide is 1-2: 1-4: 2-5.
Preferably, the reaction in step (3) is an atom transfer radical reaction, and the reaction condition is 60-80 ℃ for 15-30 h. And (3) atom transfer radical polymerization, namely the synthesis reaction of the block polymer in the step (3).
Preferably, in the step (4), the modified solution in the step (4) is prepared from 1 to 5mL of the reaction solution, 25 to 100mL of Tris buffer solution, and 0.5 to 5mL of the alkaline solution. The alkaline solution is used for adjusting the pH of the modifying solution. The pH of the reaction solution was around neutral, and therefore, a small amount of an alkaline solution was added to adjust the pH.
The modified solution is prepared from a reaction stock solution, a Tris buffer solution and an alkaline solution. The alkaline solution may be, for example, sodium hydroxide solution.
The Tris buffer is 0.007-0.015M Tris (Tris hydroxymethyl aminomethane) in water, preferably adjusted in pH with a hydrochloric acid solution, e.g., to 8.2-8.8.
Preferably, in the step (4), the mesh size of the stainless steel mesh is 500-1000 meshes.
Preferably, in the step (4), the modification condition is shaking at 20 to 37 ℃ for 0.5 to 48 hours.
In order to improve the oil-water separation effect and stability, the block polymer modified oil-water separation stainless steel mesh provided by the invention selects dopamine methacrylamide as an adhesion block and polyethylene glycol as a hydrophilic block, and is designed and synthesized into an ABA type triblock copolymer with a ring conformation. Increase the steric hindrance and the steric hindrance to provide excellent surface steric stability, antifouling property and lubricating property. When the surface of the base material is grafted with the block polymer, in a water environment condition, the polyethylene glycol with hydrophilicity is exposed on the surface of the water environment, so that the oil-water separation function is realized; and the hydrophobic dopamine methacrylamide exists in the surface polymer coating and plays a role in keeping the surface polymer coating stable.
In the preparation of the oil-water separation stainless steel mesh, a block polymer reaction solution diluted by a Tris buffer solution is used as a modification solution, and the surface modification treatment is carried out on the pretreated stainless steel mesh. The dopamine methacrylamide which is not completely reacted in the reaction liquid has a synergistic effect on the modification of the block polymer, the thickness and the roughness of the coating are enhanced, the oil-water separation efficiency is higher, and the stability is better. The whole base material modification process is simple, convenient, rapid, controllable and high in safety.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the block polymer modified oil-water separation stainless steel mesh provided by the invention is based on the inspiration of mussels, and has the characteristics of high oil-water separation efficiency, good stability and mechanical resistance.
2. The mussel inspiring block polymer material used in the invention has biocompatibility, degradability and environmental protection, and the waste material after use can not cause secondary pollution to the environment.
3. The method for preparing the mussel inspiring block polymer modified oil-water separation stainless steel mesh has the advantages of simple process, quick modification process, mild and controllable reaction conditions and high safety.
Drawings
FIG. 1 is a graph showing the contact angle of underwater oil (1, 2-dichloroethane) of the stainless steel net before and after modification in example 1. (a) The underwater oil contact angle of the surface of the unmodified stainless steel mesh; (b) the block polymer modified oil-water separation stainless steel net surface underwater oil contact angle is inspired by mussel.
FIG. 2 is a diagram showing the oil-water separation process of the mussel-inspired block polymer modified oil-water separation stainless steel net in example 1.
FIG. 3 is a diagram of multiple cycles of oil-water separation of example 1.
Detailed Description
The following describes in further detail embodiments of the present invention with reference to the drawings and examples, wherein the materials used in the examples are shown in table 1.
TABLE 1
Figure BDA0003186810140000051
Figure BDA0003186810140000061
Example 1
(1) Preparation of dopamine methacrylamide monomer:
10g of sodium tetraborate decahydrate and 4g of sodium bicarbonate were dissolved in 100mL of deionized water to form a saturated solution, and nitrogen was introduced to remove oxygen for 30 min. 5g dopamine hydrochloride was added and nitrogen bubbling was continued for 15 min. Under the state of ice-water bath, 5mL of methacrylic anhydride diluted by tetrahydrofuran was added dropwise, and sodium hydroxide was added at any time to maintain the pH of the reaction solution at 8. And removing the ice water bath and the nitrogen source after half an hour. The reaction was stirred at room temperature overnight to give a reddish suspension, which was filtered off with suction. The aqueous solution was washed three times with 100mL ethyl acetate, and the pH of the solution was adjusted to 2 with 6M hydrochloric acid to precipitate a large amount of solid. Extraction was continued three times with 100mL ethyl acetate, the oil phases were combined and washed once with 100mL water extraction to give a light brown clear solution. The oil phase was dried over anhydrous magnesium sulfate, suction filtered to remove the desiccant, rotary evaporated to concentrate, and settled in n-hexane and vigorously stirred to give a white solid which was dried in a vacuum oven and recorded as DMA.
(2) Double-head initiator Br-PEG200Synthesis of-Br:
2g PEG200 dissolved in 10mL ultra dry dichloromethane, placed in ice water bath to cool to 0 ℃, added 2.78mL Triethylamine (TEA), under stirring conditions using a peristaltic pump to add 3.72mL 2-bromine isobutyryl bromide, room temperature reaction for 30 h. After the reaction is stopped, treating the reaction solution by using active carbon, then carrying out suction filtration, and collecting filtrate; and (3) performing rotary evaporation on the filtrate to remove most of dichloromethane, settling in cold ether, centrifuging, collecting a product, and drying in a vacuum drying oven to obtain white powder.
(3) Block Polymer (PDMA-PEG)200-PDMA) synthesis:
weighing Br-PEG200Adding 5mL of ultra-dry DMF (dimethyl formamide) as a solvent into a 25mL Schlenk bottle containing-Br, DMA and bpy, performing ultrasonic treatment to completely dissolve the DMF, performing liquid nitrogen freezing-vacuumizing-nitrogen filling for 3 times of circulation, adding CuBr, continuing the liquid nitrogen freezing-vacuumizing-nitrogen filling circulation once, thawing, and placing the obtained product in a 75 ℃ oil bath for reaction for 30 hours.
(4) Preparing an oil-water separation stainless steel net:
and (3) transferring 2mL of the reaction solution obtained in the step (3) into 47mL of Tris buffer solution, adding 1mL of sodium hydroxide to adjust the pH value to 8.5, respectively carrying out ultrasonic treatment on deionized water, acetone and ethanol for 15min, drying, soaking a stainless steel net treated for 30min by an ultraviolet ozone cleaning machine in the modification solution, and placing the modified oil-water separation stainless steel net of the mussel inspiring block polymer in a constant temperature oscillation box at 25 ℃ for oscillation for 24h to obtain the mussel inspiring block polymer modified oil-water separation stainless steel net.
FIG. 1 is a graph showing the contact angle of the underwater oil (1, 2-dichloroethane) in the stainless steel net before and after modification. FIG. 1(a) is an unmodified stainless steel mesh surface with an underwater oil contact angle of about 108 °; FIG. 1(b) shows the surface of an oil-water separation stainless steel net modified by mussel inspired block polymer, and the underwater oil drop contact angle is about 150 degrees. Therefore, the surface of the modified stainless steel mesh shows super oleophobic property under water in an oil/water/solid three-phase system, and the oil-water separation performance is enhanced.
Fig. 2 is a diagram of the oil-water separation process of the block polymer modified oil-water separation stainless steel mesh inspired by mussel, and it can be seen from the diagram that the modified stainless steel mesh has excellent oil-water separation effect. The first oil-water separation efficiency of the modified stainless steel mesh is 99.8%, the oil-water separation efficiency of the stainless steel mesh can still reach more than 98% after 50 times of repeated oil-water separation experiments, and a repeated oil-water separation cycle chart of example 1 is shown in fig. 3. The sea mussel inspired block polymer modified underwater super-oleophobic oil-water type oil-water separation stainless steel mesh can be repeatedly used, and has high oil-water separation efficiency.
Example 2
(1) Double-head initiator Br-PEG400Synthesis of-Br:
4g PEG400 dissolved in 12mL ultra dry dichloromethane, placed in ice water bath to cool to 0 ℃, added 2.78mL Triethylamine (TEA), under stirring conditions using a peristaltic pump to add 3.71mL 2-bromine isobutyryl bromide, continued ice water bath for 30min after reaction at room temperature for 30 h. After the reaction is stopped, treating the reaction solution by using active carbon, then carrying out suction filtration, and collecting filtrate; and (3) performing rotary evaporation on the filtrate to remove most of dichloromethane, settling in cold ether, centrifuging, collecting a product, and drying in a vacuum drying oven to obtain white powder.
(2) Block Polymer (PDMA-PEG)400-PDMA) synthesis:
weighing Br-PEG400Adding 5mL of ultra-dry DMF (dimethyl formamide) as a solvent into a 25mL Schlenk bottle containing-Br, DMA and bpy, performing ultrasonic treatment to completely dissolve the DMF, performing liquid nitrogen freezing-vacuumizing-nitrogen filling for 3 times of circulation, adding CuBr, continuing the liquid nitrogen freezing-vacuumizing-nitrogen filling circulation once, thawing, and placing the obtained product in an oil bath kettle at 70 ℃ for reaction for 30 hours.
(3) Preparing an oil-water separation stainless steel net:
and (3) transferring 1mL of the reaction solution obtained in the step (2) into 25mL of Tris buffer solution, adding 0.5mL of sodium hydroxide to adjust the pH value to 8.5, respectively performing ultrasonic treatment on deionized water, acetone and ethanol for 25min, drying, soaking a stainless steel net treated for 45min by an ultraviolet ozone cleaning machine in the modification solution, and placing the modified stainless steel net in a constant temperature oscillation box at 25 ℃ for oscillation for 24h to obtain the mussel inspiring block polymer modified oil-water separation stainless steel net.
Example 3
(1) Double-head initiator Br-PEG800Synthesis of-Br:
8g PEG800 dissolved in 15mL ultra dry dichloromethane, placed in ice water bath to cool to 0 ℃, added 2.78mL Triethylamine (TEA), under stirring conditions using a peristaltic pump to add 3.71mL 2-bromine isobutyryl bromide, continued ice water bath for 60min after room temperature reaction for 24 h. After the reaction is stopped, treating the reaction solution by using active carbon, then carrying out suction filtration, and collecting filtrate; and (3) performing rotary evaporation on the filtrate to remove most of dichloromethane, settling in cold ether, centrifuging, collecting a product, and drying in a vacuum drying oven to obtain white powder.
(2) Block Polymer (PDMA-PEG)800-PDMA) synthesis:
weighing Br-PEG800Adding 15mL of ultra-dry DMF (dimethyl formamide) as a solvent into a 25mL Schlenk bottle containing-Br, DMA and bpy, performing ultrasonic treatment to completely dissolve the DMF, performing liquid nitrogen freezing-vacuumizing-nitrogen filling for 3 times of circulation, adding CuBr, continuing the liquid nitrogen freezing-vacuumizing-nitrogen filling circulation once, thawing, and placing the obtained product in an oil bath kettle at 70 ℃ for reaction for 25 hours.
(3) Preparing an oil-water separation stainless steel net:
and (3) transferring 2mL of the reaction solution obtained in the step (2) into 47mL of Tris buffer solution, adding 1mL of sodium hydroxide to adjust the pH value to 8.5, respectively carrying out ultrasonic treatment on deionized water, acetone and ethanol for 15min, drying, soaking a stainless steel net treated by an ultraviolet ozone cleaning machine for 30min in the modification solution, and placing the modified oil-water separation stainless steel net of the mussel inspiring block polymer in a constant temperature oscillation box for oscillation for 30h at 35 ℃ to obtain the mussel inspiring block polymer modified oil-water separation stainless steel net.
Example 4
(1) Double-head initiator Br-PEG1500Synthesis of-Br:
1.5g PEG1500 dissolved in 10mL ultra dry dichloromethane, placed in ice water bath to cool to 0 ℃, added 0.278mL Triethylamine (TEA), under stirring conditions using peristaltic pump added 0.371mL 2-bromine isobutyryl bromide, continued ice water bath for 45min after room temperature reaction for 25 h. After the reaction is stopped, treating the reaction solution by using active carbon, then carrying out suction filtration, and collecting filtrate; and (3) performing rotary evaporation on the filtrate to remove most of dichloromethane, settling in cold ether, centrifuging, collecting a product, and drying in a vacuum drying oven to obtain white powder.
(2) Block Polymer (PDMA-PEG)1500-PDMA) synthesis:
weighing Br-PEG1500adding-Br, DMA and bpy into 25mL Schlenk bottle, adding 10mL of ultra-dry DMF as solvent, performing ultrasonic treatment to completely dissolve, freezing with liquid nitrogen, vacuumizing, and fillingAdding CuBr after 3 cycles of nitrogen, continuing liquid nitrogen freezing, vacuumizing, filling nitrogen for one time, unfreezing, and placing in an oil bath kettle at 80 ℃ for reaction for 15 hours.
(3) Preparing an oil-water separation stainless steel net:
and (3) transferring 1mL of the reaction solution obtained in the step (2) into 25mL of Tris buffer solution, adding 0.5mL of sodium hydroxide to adjust the pH value to 8.5, respectively carrying out ultrasonic treatment on deionized water, acetone and ethanol for 25min, drying, soaking a stainless steel net treated for 60min by an ultraviolet ozone cleaning machine in a modification solution, and placing the modified stainless steel net in a 30 ℃ constant temperature oscillation box to oscillate for 24h to obtain the mussel inspiring block polymer modified oil-water separation stainless steel net.
Example 5
(1) Double-head initiator Br-PEG3000Synthesis of-Br:
3g PEG3000 dissolved in 10mL ultra dry dichloromethane, placed in ice water bath to cool to 0 ℃, added 0.278mL Triethylamine (TEA), under stirring conditions using a peristaltic pump added 0.371mL 2-bromine isobutyryl bromide, continued ice water bath for 60min after room temperature reaction for 20 h. After the reaction is stopped, treating the reaction solution by using active carbon, then carrying out suction filtration, and collecting filtrate; and (3) performing rotary evaporation on the filtrate to remove most of dichloromethane, settling in cold ether, centrifuging, collecting a product, and drying in a vacuum drying oven to obtain white powder.
(2) Block Polymer (PDMA-PEG)3000-PDMA) synthesis:
weighing Br-PEG3000Adding 10mL of ultra-dry DMF (dimethyl formamide) as a solvent into a 25mL Schlenk bottle containing-Br, DMA and bpy, performing ultrasonic treatment to completely dissolve the DMF, performing liquid nitrogen freezing-vacuumizing-nitrogen filling for 3 times of circulation, adding CuBr, continuing the liquid nitrogen freezing-vacuumizing-nitrogen filling circulation once, thawing, and placing the obtained product in an oil bath kettle at 60 ℃ for reaction for 30 hours.
(3) Preparing an oil-water separation stainless steel net:
and (3 mL) of the reaction solution obtained in the step (2) is transferred and added into 55mL of Tris buffer solution, 1.5mL of sodium hydroxide is added to adjust the pH value to 8.5, deionized water, acetone and ethanol are respectively subjected to ultrasonic treatment for 30min, and after drying, the stainless steel mesh treated for 30min by an ultraviolet ozone cleaning machine is soaked in the modification solution and placed in a constant temperature oscillation box at 35 ℃ for oscillation for 15h to obtain the mussel inspiring block polymer modified oil-water separation stainless steel mesh.
Comparative example 1
In the comparative example, PEG200 is directly dissolved in Tris to prepare a modified solution, sodium hydroxide is added to adjust the pH value to 8.5, a stainless steel mesh which is treated by deionized water, acetone and ethanol for 30min is soaked in the modified solution and is placed in a constant temperature oscillation box at 25 ℃ for oscillation for 24h after being dried, and the mussel inspiring block polymer modified oil-water separation stainless steel mesh is obtained.
Comparative example 2
In the comparative example, PEG400 is directly dissolved in Tris to prepare a modified solution, sodium hydroxide is added to adjust the pH value to 8.5, deionized water, acetone and ethanol are respectively subjected to ultrasonic treatment for 30min, and after drying, a stainless steel mesh treated for 45min by an ultraviolet ozone cleaning machine is soaked in the modified solution and placed in a constant temperature oscillation box at 37 ℃ to be oscillated for 12h to obtain the mussel inspiring block polymer modified oil-water separation stainless steel mesh.
Comparative example 3
In the comparative example, PEG800 is directly dissolved in Tris to prepare a modified solution, sodium hydroxide is added to adjust the pH value to 8.5, a stainless steel mesh which is treated by deionized water, acetone and ethanol for 60min is respectively subjected to ultrasonic treatment for 45min, dried and then treated by an ultraviolet ozone cleaning machine is soaked in the modified solution, and the modified oil-water separation stainless steel mesh of the mussel inspiring block polymer is obtained after oscillation in a constant temperature oscillation box at 30 ℃ for 20 h.
Experimental tests show that the underwater oil contact angle of the surface of the mussel inspired block polymer modified oil-water separation stainless steel net is between 105 DEG and 125 DEG, which is lower than the result of the embodiment 1; the first oil-water separation efficiency of the stainless steel net is 96%, and through 10 repeated oil-water separation experiments, the oil-water separation efficiency of the modified stainless steel net is 55%. Therefore, the modification treatment of the stainless steel mesh using the raw materials in the comparative example does not achieve a good oil-water separation effect.

Claims (10)

1. The block polymer modified oil-water separation stainless steel net is characterized in that: the block polymer modified oil-water separation stainless steel mesh is prepared by modifying the surface of a stainless steel substrate by using a polyethylene glycol-polydopamine methacrylamide block polymer; stainless steel mesh as the base material, the polymer is coated on it; the structural formula of the polyethylene glycol-polydopamine methacrylamide block polymer is shown as follows:
Figure FDA0003186810130000011
wherein a is an integer of 1-10, and b is 4, 6, 8, 10, 13, 22, 33, 45, 67.
2. The block polymer modified stainless steel mesh for oil-water separation according to claim 1, wherein: the mesh size of the stainless steel mesh is 500 meshes and 1000 meshes.
3. The method for preparing the block polymer modified oil-water separation stainless steel net according to claim 1, which is characterized by comprising the following steps:
(1) preparation of dopamine methacrylamide monomer:
dissolving sodium tetraborate decahydrate and sodium bicarbonate in deionized water to form a saturated solution, and introducing nitrogen to remove oxygen; adding dopamine hydrochloride, and continuing nitrogen bubbling; under the state of ice-water bath, dropwise adding methacrylic anhydride diluted by tetrahydrofuran, and replenishing sodium hydroxide at any time; removing the ice water bath and the nitrogen source after 0.2-1 h; stirring the mixture at room temperature overnight to obtain reddish suspension, filtering to obtain aqueous solution, washing with ethyl acetate, adjusting the pH of the solution with hydrochloric acid to 1.5-2.5, and precipitating a large amount of solid; extracting with ethyl acetate, and extracting and washing with water to obtain a light brown clear solution; drying the clear solution by using anhydrous magnesium sulfate or anhydrous sodium sulfate, filtering to remove a drying agent, performing rotary evaporation and concentration, settling in normal hexane to obtain a white solid, and performing vacuum drying to obtain DMA;
(2) synthesizing a double-head initiator Br-PEG-Br:
dissolving polyethylene glycol, placing in an ice water bath, fully cooling, adding triethylamine, adding 2-bromoisobutyryl bromide under the stirring condition, and reacting at room temperature; after the reaction is stopped, treating the reaction solution by using active carbon, performing suction filtration, and collecting filtrate; removing most of solvent by rotary evaporation, settling in cold ether, centrifuging, and vacuum drying to obtain white product;
(3) synthesis of Block Polymer (PDMA-PEG-PDMA):
adding an initiator, a monomer, a ligand and a solvent into a reaction container, adding a catalyst after liquid nitrogen freezing, vacuumizing and nitrogen filling circulation, unfreezing, and placing the mixture into an oil bath pot for reaction; the mol ratio of the initiator, the monomer, the catalyst cuprous bromide and the ligand is 1: 2-20: 1-4: 2-6;
(4) preparing an oil-water separation stainless steel net:
and (4) transferring the reaction solution obtained in the step (3) into a Tris buffer solution, adjusting the pH value to 7.5-10 to obtain a modified solution, and placing the pretreated stainless steel net into the modified solution to oscillate at a constant temperature of 20-38 ℃.
4. The method for preparing the block polymer modified oil-water separation stainless steel mesh as claimed in claim 3, wherein the method comprises the following steps: the molecular weight Mw of the polyethylene glycol in the step (2) is 200-.
5. The method for preparing the block polymer modified oil-water separation stainless steel mesh as claimed in claim 3, wherein the method comprises the following steps: in the step (2), the molar ratio of the polyethylene glycol to the triethylamine to the 2-bromoisobutyryl bromide is 1-2: 1-4: 2-5.
6. The method for preparing the block polymer modified oil-water separation stainless steel mesh as claimed in claim 3, wherein the method comprises the following steps: the reaction vessel in the step (3) is a Schlenk bottle.
7. The method for preparing the block polymer modified oil-water separation stainless steel mesh as claimed in claim 3, wherein the method comprises the following steps: the reaction in the step (3) is atom transfer radical reaction, and the reaction condition is 60-80 ℃ for 15-30 h.
8. The method for preparing the block polymer modified oil-water separation stainless steel mesh as claimed in claim 3, wherein the method comprises the following steps: the modified solution in the step (4) is prepared from 1-5mL of reaction solution, 25-100mL of Tris buffer solution and 0.5-5mL of alkaline solution.
9. The method for preparing the block polymer modified oil-water separation stainless steel mesh as claimed in claim 3, wherein the method comprises the following steps: the mesh size of the stainless steel mesh in the step (4) is 500-1000 meshes.
10. The method for preparing the block polymer modified oil-water separation stainless steel mesh as claimed in claim 3, wherein the method comprises the following steps: in the step (4), the modification condition is oscillation for 0.5-48h at 20-38 ℃.
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CN106422421A (en) * 2016-06-29 2017-02-22 西北大学 Method for preparation of oil-water separation membrane by filter paper modification and application thereof
CN108929412A (en) * 2018-07-10 2018-12-04 南昌大学 A kind of preparation method of the adhesiveness injection aquagel of temperature-responsive
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CN106422421A (en) * 2016-06-29 2017-02-22 西北大学 Method for preparation of oil-water separation membrane by filter paper modification and application thereof
CN108929412A (en) * 2018-07-10 2018-12-04 南昌大学 A kind of preparation method of the adhesiveness injection aquagel of temperature-responsive
CN110670056A (en) * 2019-10-10 2020-01-10 泉州师范学院 Polyasparagine derivative modified oil-water separation stainless steel net film and preparation method thereof

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