CN116023703A - Preparation method and application of superhydrophobic porous polymer - Google Patents
Preparation method and application of superhydrophobic porous polymer Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Abstract
The invention provides a preparation method of a super-hydrophobic porous polymer, which comprises the following steps: firstly mixing the dopant solution and cellulose acetate to obtain a mixture; carrying out second mixing and refrigeration on the mixture and the alcohol compound to obtain a refrigerated product; performing solvent exchange on the refrigerated product, and then freeze-drying to obtain a super-hydrophobic porous polymer; the solute in the dopant solution is selected from ZIF-8 and/or graphene. The invention provides a preparation principle and a method of a super-hydrophobic ZIF-8 doped cellulose acetate porous polymer, and the prepared polymer can be used for rapidly, safely and greenly treating greasy dirt in water. In addition, the preparation method of the three-dimensional porous polymer has the advantages of simple process, low cost and the like, and is an excellent way for realizing large-scale production.
Description
Technical Field
The invention belongs to the technical field of oil-water separation, and particularly relates to a preparation method and application of a super-hydrophobic porous polymer.
Background
As a high heat resource, petroleum is widely used in transportation, chemical industry, electric power and steel manufacturing, and is called "industrial blood". With the rapid development of industry, the world has higher and higher dependence on petroleum, and the exploitation of petroleum is also increasing. Marine oil spill accidents also frequently occur, which not only causes huge economic loss, but also seriously affects ecological environment and human health. At present, several methods for solving the problem of oil spill at sea have been known to human beings. These methods mainly include mechanical collection, in situ combustion, biodegradation, dispersant decomposition, precipitation and adsorptive separation. The adsorption separation method is remarkable in that the cost is low, the operation is simple and the separation efficiency is high. The adsorbent materials developed should be hydrophobic and oleophilic in view of the need to recover spilled oil in the ocean. For this reason, scholars have developed various adsorbent materials having specific wettability. The porous polymer material has higher saturated adsorption capacity, high oil absorption speed and good durability, and has a good prospect in practical application.
Inspired by the super-hydrophobic phenomenon of animals and plants in the nature, various methods are proposed at home and abroad for preparing super-hydrophobic three-dimensional porous polymer-based materials, and common methods comprise a template method, a chemical vapor deposition method and the like. The methods have complex processes and severe preparation conditions, and are not suitable for large-scale industrial production. And most of the porous polymers prepared by the methods have poor hydrophobicity and cannot reach the super-hydrophobic level, so that the oil-water separation effect is poor.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method and application of a super-hydrophobic porous polymer.
The invention provides a preparation method of a super-hydrophobic porous polymer, which comprises the following steps:
firstly mixing the dopant solution and cellulose acetate to obtain a mixture;
carrying out second mixing and refrigeration on the mixture and the alcohol compound to obtain a refrigerated product;
performing solvent exchange on the refrigerated product, and then freeze-drying to obtain a super-hydrophobic porous polymer;
the solute in the dopant solution is selected from ZIF-8 and/or graphene.
Preferably, the solvent in the dope solution is selected from DMF and/or acetone;
the concentration of the dopant solution is 16-20%.
Preferably, the mass ratio of the dopant solution to the cellulose acetate is (1-2): 100.
Preferably, the first mixing is performed under stirring, and the temperature of the first mixing is 60-80 ℃.
Preferably, the alcohol compound is selected from ethanol and/or n-butanol;
the dosage ratio of the mixture to the alcohol compound is (10-12): 10-13.
Preferably, the temperature of the refrigeration is-15 to-25 ℃; the refrigerating time is 20-30 hours.
Preferably, the solvent exchange method comprises:
the refrigerated product was placed in water and the water was replaced multiple times until the residual organic solvent was completely replaced.
Preferably, the temperature of the freeze drying is-40 to-60 ℃; the time of freeze drying is 45-80 hours.
The invention provides a material for oil-water separation, which comprises the following components: the super-hydrophobic porous polymer prepared by the method of the technical scheme is prepared.
The invention provides a device for oil-water separation, which comprises: the super-hydrophobic porous polymer prepared by the method is provided.
The invention provides a preparation principle and a method of a super-hydrophobic ZIF-8 doped cellulose acetate porous polymer, and the prepared polymer can be used for rapidly, safely and greenly treating greasy dirt in water. According to the invention, the three-dimensional porous polymer is prepared by adopting a thermal induction non-solvent induction phase separation method, and the hydrophobic property of the porous polymer can be greatly improved by doping ZIF-8 into the porous polymer. In addition, the preparation method of the three-dimensional porous polymer has the advantages of simple process, low cost and the like, and is an excellent way for realizing large-scale production. Therefore, the super-hydrophobic ZIF-8 doped cellulose acetate porous polymer material developed by utilizing the heat-induced non-solvent induced phase separation method is more suitable for industrial application, and has great application potential in the aspect of super-hydrophobic material preparation.
Drawings
FIG. 1 is an SEM image of a ZIF-8 doped cellulose acetate porous polymer prepared according to example 1;
FIG. 2 is a surface water contact angle of a ZIF-8 doped cellulose acetate porous polymer prepared in example 1;
FIG. 3 is a graph showing the comparison of water contact angles of porous polymers with different ZIF-8 addition amounts in example 1;
FIG. 4 is an optical microscope image of an oil-in-water emulsion before and after separation using the ZIF-8 doped cellulose acetate porous polymer prepared in example 1;
FIG. 5 is a schematic view showing the structure of the peristaltic pump assisting device in embodiment 1;
FIG. 6 is a surface water contact angle of graphene doped cellulose acetate porous polymer prepared in example 2;
fig. 7 is an SEM image of the graphene-doped cellulose acetate porous polymer prepared in example 2.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a super-hydrophobic porous polymer, which comprises the following steps:
firstly mixing the dopant solution and cellulose acetate to obtain a mixture;
carrying out second mixing and refrigeration on the mixture and the alcohol compound to obtain a refrigerated product;
and carrying out solvent exchange on the refrigerated product, and then freeze-drying to obtain the super-hydrophobic porous polymer.
In the present invention, the solute in the dopant solution is selected from the group consisting of ZIF-8 (zeolitic imidazolate framework material) and/or graphene; the solvent in the dope solution is preferably selected from DMF (N, N-dimethylformamide) and/or acetone; the concentration (mass concentration) of the dopant solution is preferably 16 to 20%, more preferably 17 to 19%, and most preferably 18%.
In the invention, ZIF-8 is a metal organic framework material with high hydrophobicity and high porosity and has a rhombic dodecahedron structure. In the present invention, the preparation method of ZIF-8 preferably comprises:
mixing a zinc nitrate hexahydrate solution and a 2-methylimidazole solution, standing, centrifuging, and drying to obtain ZIF-8.
In the present invention, the preparation method of the zinc nitrate hexahydrate solution preferably includes:
under the action of ultrasound, zinc nitrate hexahydrate is dissolved in methanol to obtain zinc nitrate hexahydrate solution.
In the present invention, the ratio of the amount of zinc nitrate hexahydrate to methanol is preferably (0.55 to 0.65) g: (20-30) mL, more preferably (0.58-0.62) g: (23-27) mL, most preferably 0.58g:25mL.
In the present invention, the preparation method of the 2-methylimidazole solution preferably includes:
under the action of ultrasound, 2-methylimidazole is dissolved in methanol to obtain 2-methylimidazole solution.
In the present invention, the ratio of the amount of the 2-methylimidazole to the amount of methanol is preferably (0.35 to 0.45) g: (20-30) mL, more preferably (0.38-0.42) g: (23-27) mL, most preferably 0.38g:25mL.
In the present invention, the mixing is preferably performed under the action of ultrasound, and the time of the ultrasound is preferably 25 to 35min, more preferably 28 to 32min, and most preferably 30min; the mixing gives a milky suspension. In the present invention, the placement is preferably in an oven; the temperature of the placement is preferably 35 to 45 ℃, more preferably 38 to 42 ℃, and most preferably 40 ℃; the time of the holding is preferably 20 to 30 hours, more preferably 24 to 26 hours, and most preferably 24 hours. In the present invention, the centrifugation is preferably performed using ethanol; the number of times of centrifugation is preferably 2 to 4 times, more preferably 3 times. In the present invention, the drying is preferably performed in an oven; the drying temperature is preferably 50 to 70 ℃, more preferably 55 to 65 ℃, and most preferably 60 ℃.
In the present invention, the preparation method of the dope solution preferably includes:
the dope was added to a solvent for ultrasonic dispersion to obtain a dope solution.
In the present invention, the time of the ultrasonic dispersion is preferably 10 to 20 minutes, more preferably 15 minutes.
In the present invention, the mass ratio of the dopant solution to the cellulose acetate is preferably (1 to 2): 100, more preferably (1.2 to 1.8): 100, and most preferably (1.4 to 1.6): 100.
In the present invention, the first mixing is preferably performed under stirring, preferably strong stirring, for a period of preferably 20 to 40 minutes, more preferably 25 to 35 minutes, and most preferably 30 minutes; until completely dissolved; the temperature of the first mixing is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, and most preferably 70 ℃.
In the present invention, the alcohol compound is preferably selected from ethanol and/or n-butanol. In the invention, the ratio (mass ratio) of the mixture to the alcohol compound is preferably (10-12): (10-13), more preferably 11: (11-12).
In the present invention, the second mixing is preferably to cool the mixture to room temperature, and the alcohol compound is added dropwise to the mixture until the solution becomes cloudy; the second mixing is preferably carried out under magnetic stirring.
In the invention, the refrigeration is preferably that the mixture obtained after the second mixing is quickly poured into a flat bottom tube (glass test tube) and placed in a refrigerator for refrigeration; the diameter of the flat bottom tube is preferably 1 to 3cm, more preferably 1.5 to 2.5cm, most preferably 2cm; the height is preferably 3 to 7cm, more preferably 4 to 6cm, most preferably 5cm. In the invention, the temperature of the refrigeration is preferably-15 to-25 ℃, more preferably-18 to-22 ℃, and most preferably-20 ℃; the time for the cold storage is preferably 20 to 30 hours, more preferably 22 to 28 hours, and most preferably 24 to 26 hours.
In the present invention, the solvent exchange method preferably comprises:
the refrigerated product was placed in water and the water was replaced multiple times until the residual organic solvent was completely replaced.
In the present invention, the water is preferably deionized water; preferably at least 3 changes of deionized water are made every 24 hours.
In the present invention, it is preferable to place a flat bottom tube containing the refrigerated product in a beaker filled with water.
In the present invention, the freeze-drying is preferably performed in a freeze-dryer, preferably freeze-drying under vacuum; the temperature of the freeze drying is preferably-40 to-60 ℃, more preferably-45 to-55 ℃, and most preferably-50 ℃; the time for the freeze-drying is preferably 45 to 80 hours, more preferably 48 to 72 hours, and most preferably 60 hours.
In the present invention, the preparation method of the superhydrophobic porous polymer preferably includes:
adding ZIF-8 into DMF for ultrasonic dispersion to obtain ZIF-8 solution; then, cellulose acetate was added to the ZIF-8 solution and stirred at 70 ℃ until completely dissolved to obtain a uniform mixture; cooling the solution to room temperature, and then dropwise adding an alcohol compound into the mixed solution under magnetic stirring; pouring the mixture into a flat bottom pipe with the diameter of 2cm and the height of 5cm, and placing the flat bottom pipe in a refrigerator with the temperature of minus 20 ℃ for refrigeration; after 24 hours, the flat bottom test tube was placed in a 500mL beaker filled with water, and the water was replaced multiple times until the remaining organic solvent was completely replaced; the samples were freeze-dried in a freeze-dryer at-50 ℃ for 48 hours to obtain the final ZIF-8 doped cellulose acetate porous polymer.
In the present invention, the preparation method of the superhydrophobic porous polymer preferably includes:
adding graphene into DMF (dimethyl formamide) for ultrasonic dispersion for 15 minutes; then, adding cellulose acetate into the mixture at 70 ℃ and stirring strongly for 30 minutes until the cellulose acetate is completely dissolved; subsequently, the solution was cooled to room temperature and ethanol was added dropwise until the solution became cloudy; afterwards, the mixture in the beaker is poured into a glass test tube and transferred to a refrigerator at-20 ℃ for 24 hours; thereafter, the glass test tube was immersed in deionized water for 72 hours to replace the residual solvent, during which at least 3 deionized water changes were made every 24 hours; finally, the sample was freeze-dried under vacuum for 72 hours to obtain the final graphene-doped cellulose acetate porous polymer.
In the invention, in the actual oil-in-water emulsion, most of the spilled oil can form micron-sized oil drops under the shearing action of ocean waves in the actual oil spill accident, and the traditional oil adsorbing material is difficult to absorb the oil well.
The invention provides a material for oil-water separation, which comprises the following components: the super-hydrophobic porous polymer prepared by the method of the technical scheme is prepared.
The invention provides a device for oil-water separation, which comprises: the super-hydrophobic porous polymer prepared by the method is provided.
According to the invention, ZIF-8 is doped into the cellulose acetate porous polymer skeleton, so that the porous polymer has super-hydrophobic level, and the oil pollution wastewater can be treated by an adsorption method. According to the invention, the three-dimensional porous polymer is prepared by adopting a thermal induction non-solvent induction phase separation method, and the hydrophobic property of the porous polymer can be greatly improved by doping ZIF-8 into the porous polymer. In addition, the preparation method of the three-dimensional porous polymer has the advantages of simple process, low cost and the like, and is an excellent way for realizing large-scale production. Therefore, the super-hydrophobic ZIF-8 doped cellulose acetate porous polymer material developed by utilizing the heat-induced non-solvent induced phase separation method is more suitable for industrial application, and has great application potential in the aspect of super-hydrophobic material preparation.
The preparation method of ZIF-8 adopted in the following examples of the invention comprises the following steps:
0.58g of zinc nitrate hexahydrate (company: alatidine, analytical grade) and 0.38g of 2-methylimidazole (company: alatidine, analytical grade) were dissolved in 25mL of methanol by sonication, respectively, to form a homogeneous solution. Then, under the action of ultrasound, the two solutions were slowly mixed and sonicated for 30min, and the resulting milky suspension was placed in an oven at 40 ℃ for 24h. And finally, centrifuging with ethanol for three times to obtain a product, and drying the product in a 60 ℃ oven.
The graphene is a high-purity multilayer graphene product provided by Shenzhen Hongdaco evolution technology Co.
Example 1
0.04g of ZIF-8 was added to 10 ml of DMF for ultrasonic dispersion to obtain a ZIF-8 solution. Then, 2g of cellulose acetate was added to the ZIF-8 solution and stirred at 70 ℃ until completely dissolved to obtain a homogeneous mixture. After the solution was cooled to room temperature, 13 ml of ethanol (non-solvent) was added dropwise to the mixed solution under magnetic stirring. Next, the mixture was rapidly poured into a flat bottom tube having a diameter of 2cm and a height of 5cm, and placed in a-20℃refrigerator for cold storage. After 24 hours, the flat bottom tube was placed in a 500mL beaker filled with water, and the water was replaced multiple times until the remaining organic solvent was completely replaced. Finally, the samples were freeze-dried in a freeze-dryer at-50 ℃ for 48 hours to obtain the final ZIF-8 doped cellulose acetate porous polymer.
Fig. 1 is an SEM image of the ZIF-8 doped cellulose acetate porous polymer prepared in example 1, and it can be seen that there are a large number of micropores, which can capture a large amount of air to form air pockets, and when water drops contact the surface of the material, the air pockets can act as barriers to reduce the contact area between the surface of the sample and the water drops, so that the cellulose acetate porous polymer obtains super-hydrophobic performance.
The surface water contact angle of the ZIF-8 doped cellulose acetate porous polymer prepared in example 1 (the water contact angle test is carried out on the cross section of the porous polymer at room temperature by using a contact angle tester with the model of Powereach JC 2000C), deionized water is adopted as the test liquid in the whole test process, and in order to ensure the accuracy of the result, the test is carried out at five different position points of the cross section of the sample, and the test result is averaged), and a specific image is shown in figure 2.
FIG. 3 shows a graph of water contact angles of porous polymers with different ZIF-8 addition amounts, and it can be judged that the optimum addition amount of ZIF-8 (mass content of ZIF-8 in cellulose acetate) is 2wt%.
An important advantage of the ZIF-8 doped cellulose acetate porous polymer is that the ZIF-8 doped cellulose acetate porous polymer can adsorb oil-in-water emulsion, and experimental verification is carried out on the ZIF-8 doped cellulose acetate porous polymer, and the specific detection method comprises the following steps:
firstly, preparing emulsion, mixing xylene (3 ml) and water (30 ml) in a ratio of 1:10, carrying out ultrasonic treatment for 30min under the condition of not adding any emulsifying agent to obtain turbid oil-in-water type emulsion, placing porous polymer into the emulsion, slightly oscillating for about 10min at room temperature, and clarifying the emulsion. For clear observation of the separation effect, the emulsion before and after separation was observed with an optical microscope.
The results of the detection are shown in FIG. 4, and FIG. 4 is an optical microscope image of an oil-in-water emulsion before and after separation, and it can be seen that the oil has been adsorbed clean by the porous polymer. Therefore, the ZIF-8 doped cellulose acetate porous polymer is an ideal oil-water separation material in the aspect of actual offshore oil pollution treatment.
The continuous oil-water separation capability of the material has great practical application value, and fig. 5 is a self-made peristaltic pump auxiliary device, wherein the device is composed of a ZIF-8 doped cellulose acetate porous polymer, a silica gel tube, a peristaltic pump and two serially connected beakers, when the peristaltic pump works, water is repelled by the super-hydrophobic porous polymer on the water surface, oil firstly enters the porous polymer, and then is sent to another empty beaker through the kinetic energy provided by the peristaltic pump, by means of the device, the material can continuously and rapidly separate an oil-water mixture, the continuous separation efficiency can reach 98.9%, and a good separation effect is shown. The calculation formula of the continuous oil-water separation efficiency (h) is as follows:
wherein m is 0 And m is the mass of the oil before and after separation in the left beaker, respectively.
Example 2
0.03g of graphene was added to 10 ml of DMF and subjected to ultrasonic dispersion for 15 minutes. Then, 2g of cellulose acetate was added to the above mixture at 70℃and stirred vigorously for 30 minutes until the cellulose acetate was completely dissolved. Subsequently, the solution was cooled to room temperature, and ethanol was added dropwise until the solution became cloudy. Thereafter, the mixture in the beaker was poured into a glass test tube and transferred to a refrigerator at-20 ℃ for 24 hours. Thereafter, the glass test tube was immersed in deionized water for 72 hours to replace the residual solvent, during which time at least 3 deionized water changes were made every 24 hours. Finally, the sample was freeze-dried under vacuum for 72 hours to obtain the final graphene-doped cellulose acetate porous polymer.
FIG. 6 is a surface water contact angle of the graphene doped cellulose acetate porous polymer prepared in example 2, with a value of 151 degrees, showing that the superhydrophobic level is also achieved, the water contact angle (θ) represents the hydrophobicity of the material, the water contact angle is 90 ° < θ < 150 °, the water is hydrophobic, 150 ° - θ, and the superhydrophobic is achieved; fig. 7 is an SEM image of a graphene doped cellulose acetate porous polymer, shown as a porous structure.
According to the invention, the three-dimensional porous polymer is prepared by adopting a thermal induction non-solvent induction phase separation method, and the hydrophobic property of the porous polymer can be greatly improved by doping ZIF-8 into the porous polymer. In addition, the preparation method of the three-dimensional porous polymer has the advantages of simple process, low cost and the like, and is an excellent way for realizing large-scale production. Therefore, the super-hydrophobic ZIF-8 doped cellulose acetate porous polymer material developed by utilizing the heat-induced non-solvent induced phase separation method is more suitable for industrial application, and has great application potential in the aspect of super-hydrophobic material preparation.
While the invention has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the invention. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the invention as defined by the following claims, so as to adapt the objective, spirit and scope of the present application. All such modifications are intended to be within the scope of this appended claims. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (10)
1. A method for preparing a superhydrophobic porous polymer, comprising:
firstly mixing the dopant solution and cellulose acetate to obtain a mixture;
carrying out second mixing and refrigeration on the mixture and the alcohol compound to obtain a refrigerated product;
performing solvent exchange on the refrigerated product, and then freeze-drying to obtain a super-hydrophobic porous polymer;
the solute in the dopant solution is selected from ZIF-8 and/or graphene.
2. The method according to claim 1, wherein the solvent in the dope solution is selected from DMF and/or acetone;
the mass concentration of the dopant solution is 16-20%.
3. The method according to claim 1, wherein the mass ratio of the dopant solution to the cellulose acetate is (1-2): 100.
4. The method according to claim 1, wherein the first mixing is performed under stirring, and the temperature of the first mixing is 60 to 80 ℃.
5. The method according to claim 1, wherein the alcohol compound is selected from ethanol and/or n-butanol;
the mass ratio of the mixture to the alcohol compound is (10-12) and (10-13).
6. The method of claim 1, wherein the temperature of the refrigeration is-15 to-25 ℃; the refrigerating time is 20-30 hours.
7. The method of claim 1, wherein the solvent exchange method comprises:
the refrigerated product was placed in water and the water was replaced multiple times until the residual organic solvent was completely replaced.
8. The method according to claim 1, wherein the freeze-drying temperature is-40 to-60 ℃; the time of freeze drying is 45-80 hours.
9. A material for oil-water separation comprising: the superhydrophobic porous polymer of claim 1.
10. An apparatus for oil-water separation comprising: provided with the superhydrophobic porous polymer prepared by the method of claim 1.
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Citations (2)
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| CN113388155A (en) * | 2021-06-15 | 2021-09-14 | 安徽大学 | Preparation method of super-hydrophobic sponge for efficient oil-water separation |
| CN114028946A (en) * | 2021-10-25 | 2022-02-11 | 浙江工业大学 | Nano composite cellulose acetate forward osmosis membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113388155A (en) * | 2021-06-15 | 2021-09-14 | 安徽大学 | Preparation method of super-hydrophobic sponge for efficient oil-water separation |
| CN114028946A (en) * | 2021-10-25 | 2022-02-11 | 浙江工业大学 | Nano composite cellulose acetate forward osmosis membrane and preparation method thereof |
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| DIANA N. H. TRAN ET A.: ""Selective adsorption of oil–water mixtures using polydimethylsiloxane (PDMS)–graphene sponges"", 《ENVIRONMENTAL SCIENCE WATER RESEARCH & TECHNOLOGY》, pages 298 * |
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