CN113061236B - Super-hydrophobic covalent organic framework material and preparation method and application thereof - Google Patents
Super-hydrophobic covalent organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of super-hydrophobic materials, and particularly relates to a super-hydrophobic covalent organic framework material, a preparation method and application thereof. The invention relates to a super-hydrophobic covalent organic framework material LNUs obtained by Suzuki coupling reaction of tri (4-boric acid frequency farnesyl alcohol ester phenyl) amine serving as a building element and pi conjugated dibromocarbazole monomer. The method provided by the invention has the advantages of easily available raw materials, simple preparation process and capability of meeting the actual production requirements. The contact angle of the super-hydrophobic material prepared by the method can reach more than 150 degrees, stable hydrophobic performance can be kept under severe conditions such as strong acid, strong alkali, high temperature and the like, and the separation efficiency can reach more than 90 percent when the super-hydrophobic material is used for separating mixed liquid of various kinds of water and oil (or organic solvent). After 10 times of recycling, the original separation effect can be still maintained, and the method has good practicability in the field of oil-water separation treatment in environmental sewage.
Description
Technical Field
The invention belongs to the field of super-hydrophobic materials, and particularly relates to a super-hydrophobic covalent organic framework material, a preparation method and application thereof.
Background
Along with continuous exploitation and production of petroleum, frequent oil spilling accidents in transportation and use processes and oily wastewater discharge in daily necessities production seriously threaten human health and ecological environment, and effective oil-water separation is an important problem to be solved at present. In order to reduce the adverse effects of oil pollution on water environments, many methods have been employed to solve the problems of spilled oil and oily wastewater discharge, such as gravity separation, centrifugation, degreasing, flotation, coagulation, in situ combustion, etc., however, the application of these conventional methods is time-consuming or energy-consuming and is limited by low separation efficiency, complicated operation or secondary pollution. In addition, adsorption is a common method of removing oils and organic contaminants from water. However, conventional absorbent materials (e.g., zeolites and activated carbon) for removing oil and organic contaminants from water also have disadvantages such as poor absorption capacity, non-selective absorption, and difficulty in reuse. Therefore, the problem of oil-water separation is effectively solved, the problem of environmental pollution can be treated, and the resources can be recycled.
In real life, superhydrophobic materials are receiving widespread attention from scientists. Inspired by the superhydrophobic performance of lotus leaves, the superhydrophobic material is researched by people. Under the microscope, when the water drops touch the contact surface due to the rough surface, the water drops are subjected to air resistance and are supplied with an outward force, so that the super-hydrophobic effect is achieved. When the contact angle is greater than 90 degrees, it is called hydrophobic, and reaches 150 degrees or more, which may be called superhydrophobic. Currently, many methods for preparing hydrophobic materials have been developed by researchers, such as self-assembly, vapor deposition, electrodeposition, plasma treatment, electrospinning, spraying, and the like. However, most superhydrophobic materials can involve some application technical problems during actual oil-water separation, for example, the durability is poor, especially when they can cause permanent loss of superhydrophobic surface under extreme conditions such as high temperature, low temperature or corrosive environment, and the defects of the materials can seriously prevent the practical application of the superhydrophobic materials in oil-water separation.
Covalent organic framework materials are novel high molecular polymers formed by connecting light elements such as C, H, B, O, N through covalent bonds, and great attention is paid to the abundant synthetic routes and unique physicochemical stability. Covalent organic framework materials are mostly hydrophobic materials, since the hydrophobicity of a material depends on the chemical composition in the material structure and the roughness of the surface topography of the material. When the covalent organic framework material structure contains hydrophobic groups such as fluorine groups, alkyl long chains, carbon-carbon triple bonds, benzene ring structures, aryl-containing functionalized groups and the like, and the rough surface morphology of the material, the covalent organic framework material has certain hydrophobic performance. It would be desirable to be able to improve the above technical problems if covalent organic framework materials with hydrophobic properties were used in oil-water separation applications.
Disclosure of Invention
The invention aims to provide a super-hydrophobic covalent organic framework material, and a preparation method and application thereof. The invention takes tri (4-boric acid frequency farnesyl alcohol ester phenyl) amine as a construction element and pi conjugated dibromocarbazole monomer to obtain the super-hydrophobic covalent organic framework material LNUs through Suzuki coupling reaction. The reaction condition is mild, and the preparation process is simple and reliable. LNUs materials can be loaded on the surface of the flexible fabric through a simple soaking method, and the obtained product super-hydrophobic flexible fabric can be used in the field of oil-water separation under the condition of environmental severity and has good application prospect.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a super-hydrophobic covalent organic framework material is a super-hydrophobic covalent organic framework material LNUs obtained by Suzuki coupling reaction of tri (4-boric acid frequency-farnesyl-alcohol-ester-phenyl) amine serving as a construction element and pi conjugated dibromocarbazole monomer.
The super-hydrophobic covalent organic framework material LNUs has the following structural formula:
the preparation method of the super-hydrophobic covalent organic framework material comprises the following steps: adding tri (4-boric acid frequency farnesyl alcohol ester phenyl) amine and dibromocarbazole monomers into an organic solvent for dissolution, placing the organic solvent into a reaction container, freezing by utilizing liquid nitrogen, vacuumizing by using an oil pump, introducing nitrogen gas for three times repeatedly, rapidly adding a catalyst into a reaction system, repeatedly and circularly degassing, heating the reaction mixture, stirring and refluxing for 48 hours under the protection of nitrogen gas, cooling to room temperature, filtering, washing, purifying, and then vacuum-drying to obtain the powdery covalent organic framework LNUs.
The preparation method of the super-hydrophobic covalent organic framework material comprises the step of preparing a 3, 6-dibromocarbazole monomer, one of 2, 7-dibromocarbazole and 3, 6-dibromo-9-phenylcarbazole monomer.
The preparation method of the super-hydrophobic covalent organic framework material comprises the step of preparing the catalyst by using tetra (triphenylphosphine) palladium and potassium carbonate.
The preparation method of the super-hydrophobic covalent organic framework material comprises the following steps of: the tris (4-boronic acid farnesyl ester phenyl) amine was 3:2.
The preparation method of the super-hydrophobic covalent organic framework material has the heating temperature of 130 ℃.
The preparation method of the super-hydrophobic covalent organic framework material is characterized in that the vacuum drying temperature and the vacuum drying time are respectively 90 ℃ and 12 hours.
A preparation method of a hydrophobic and oleophylic material comprises the steps of placing any super-hydrophobic covalent organic framework material chloroform into the solution, and carrying out ultrasonic homogenization, soaking and drying on the pretreated flexible fabric to obtain the product super-hydrophobic flexible fabric.
The preparation method of the hydrophobic and oleophylic material comprises the steps of placing the flexible fabric in a beaker, respectively adding 40mL of water, ethanol and acetone, carrying out ultrasonic soaking for 30min, taking out, and drying at 60-70 ℃ for later use.
According to the invention, a Suzuki coupling reaction is carried out by using tri (4-boric acid frequency farnesyl alcohol ester phenyl) amine and pi conjugated dibromocarbazole monomer, so that the super-hydrophobic covalent organic framework material LNUs is obtained. LNUs materials can be loaded on the surface of flexible fabrics by a simple soaking method, the water contact angle of the obtained product can reach more than 150 degrees, and stable hydrophobic performance can be maintained under severe environmental conditions. The invention has the advantages of simple preparation process, lower cost, environmental protection, recycling and the like, and can be widely applied to the oil-water separation treatment of the sewage containing oil or organic solvent in petrochemical industry, metallurgy, food and pharmaceutical industries and the like.
The beneficial effects of the invention are as follows:
1. the super-hydrophobic covalent organic framework material disclosed by the invention is easy to obtain raw materials, simple in preparation process and capable of meeting actual production requirements.
2. The super-hydrophobic covalent organic framework material can be loaded on the surface of a flexible fabric through a simple soaking method, and has simple process operation and universal applicability.
3. The contact angle of the super-hydrophobic flexible fabric prepared by the method can reach more than 150 degrees, stable hydrophobic performance can be kept under severe conditions such as strong acid, strong alkali, high temperature and the like, and the separation efficiency can reach more than 90 percent when the mixed liquid of various water and oil (or organic solvent) is separated.
4. The product super-hydrophobic flexible fabric prepared by the invention has excellent oil-water separation stability and good recoverability, can still keep the original separation effect after being recycled for 10 times, and has good practicability in the field of oil-water separation treatment in environmental sewage.
Drawings
FIG. 1-1 is an infrared spectrum of a superhydrophobic covalent organic framework material LNU-40 and a reactive monomer prepared according to the invention;
FIGS. 1-2 are infrared spectra of the superhydrophobic covalent organic framework materials LNU-41 and the reactive monomers prepared by the invention;
FIGS. 1-3 are infrared spectra of the superhydrophobic covalent organic framework materials LNU-42 and the reactive monomers prepared according to the invention;
FIG. 2-1 is a scanning electron microscope image of the superhydrophobic covalent organic framework material LNU-40 prepared by the invention;
FIG. 2-2 is a scanning electron microscope image of the superhydrophobic covalent organic framework material LNU-41 prepared by the invention;
fig. 2-3 are scanning electron microscope images of the superhydrophobic covalent organic framework materials LNU-42 prepared by the invention;
FIG. 3-1 is a transmission electron microscope image of the superhydrophobic covalent organic framework material LNU-40 prepared by the invention;
FIG. 3-2 is a transmission electron microscope image of the superhydrophobic covalent organic framework material LNU-41 prepared by the invention;
FIG. 3-3 is a transmission electron microscope image of the superhydrophobic covalent organic framework material LNU-42 prepared by the invention;
FIG. 4 is a thermogravimetric plot of the superhydrophobic covalent organic framework materials LNUs prepared in accordance with the present invention;
FIG. 5-1 shows the contact angle of the superhydrophobic covalent organic framework material LNU-40 prepared according to the invention;
FIG. 5-2 shows the contact angle of the superhydrophobic covalent organic framework material LNU-41 prepared according to the invention;
FIG. 5-3 shows the contact angle of the superhydrophobic covalent organic framework material LNU-42 prepared according to the invention;
FIG. 6 is a scanning electron microscope image of the superhydrophobic flexible fabric and the original flexible fabric of the product prepared by the invention;
wherein a: an original flexible fabric; b: a superhydrophobic flexible fabric loaded with LNU-40; c: a superhydrophobic flexible fabric loaded with LNU-41; d: a superhydrophobic flexible fabric loaded with LNU-42;
FIG. 7 is a graph showing the effect of contacting the superhydrophobic flexible fabric and the original flexible fabric with water and chloroform;
wherein a: an original flexible fabric; b: a superhydrophobic flexible fabric loaded with LNU-40; c: a superhydrophobic flexible fabric loaded with LNU-41; d: a superhydrophobic flexible fabric loaded with LNU-42;
FIG. 8 is a graph showing the effect of contacting superhydrophobic flexible fabrics of product loading LNU-41 prepared according to the invention with drops of different pH;
FIG. 9 is a graph showing the relationship between the contact angle of the superhydrophobic flexible fabric loaded with LNU-41 products prepared by the invention and different pH values;
FIG. 10 is a graph showing the relationship between the contact angle of the superhydrophobic flexible fabric loaded with LNU-41 products prepared by the invention and different temperatures;
FIG. 11 is a graph showing the separation effect of the superhydrophobic flexible fabric loaded with LNU-40 prepared by the invention on an oil phase and a water phase;
FIG. 12 is a graph showing the separation effect of the superhydrophobic flexible fabric loaded with LNU-41 prepared by the invention on an oil phase and a water phase;
FIG. 13 is a graph showing the separation effect of the superhydrophobic flexible fabric loaded with LNU-42 prepared according to the invention on an oil phase and a water phase;
FIG. 14 is a cycle usage test of the superhydrophobic flexible fabric of the invention with product loading LNU-41 repeated 10 times.
Detailed Description
The invention is further illustrated by the following examples, which are specific to the preparation of superhydrophobic covalent organic framework materials LNU-40, LNU-41, and LNU-42, as follows:
example 1 preparation of superhydrophobic covalent organic framework Material LNU-40
Synthesis of LNU-40
400mg of tris (4-boronic acid farnesyl ester phenyl) amine (0.6418 mmol) and 312.89mg of 3, 6-dibromocarbazole (0.96274 mmol) were dissolved in 60mLN, N' -dimethylformamide, placed in a 100mL round bottom flask, frozen with liquid nitrogen and purged with oil pump and nitrogen gas was repeatedly passed three times, 80mg of tetrakis (triphenylphosphine) palladium and 5mL of potassium carbonate solution (2 moL/L) were rapidly added to the reaction system, and repeated cyclic deaeration was performed, and the reaction mixture was heated to 130℃and stirred under nitrogen protection for 48 hours under reflux.
Post-treatment of LNU-40
The reaction was suction filtered, leaving a solid insoluble, and washed multiple times with tetrahydrofuran, water and acetone solvents, respectively, for removal of unreacted monomer or catalyst residues that may remain. Further purifying the crude product by Soxhlet extraction with tetrahydrofuran, dichloromethane and chloroform. The crude product is dried in vacuum for 12 hours at 90 ℃, and the obtained powdery solid is the superhydrophobic covalent organic framework material LNU-40. The synthetic route is as follows:
example 2 preparation of superhydrophobic covalent organic framework Material LNU-41
Synthesis of LNU-41
400mg of tris (4-boronic acid farnesyl ester phenyl) amine (0.6418 mmol) and 312.89mg of 2, 7-dibromocarbazole (0.96274 mmol) were dissolved in 60mL of N, N' -dimethylformamide, placed in a 100mL round bottom flask, frozen with liquid nitrogen and purged with oil pump and nitrogen was repeated three times, 80mg of tetrakis (triphenylphosphine) palladium and 5mL of potassium carbonate solution (2 moL/L) were rapidly added to the reaction system, and repeated cyclic deaeration was performed, and the reaction mixture was heated to 130℃and refluxed with stirring under nitrogen protection for 48 hours.
Post-treatment of LNU-41
The reaction was suction filtered, leaving a solid insoluble, and washed multiple times with tetrahydrofuran, water and acetone solvents, respectively, for removal of unreacted monomer or catalyst residues that may remain. Further purifying the crude product by Soxhlet extraction with tetrahydrofuran, dichloromethane and chloroform. The crude product is dried in vacuum for 12 hours at 90 ℃, and the obtained powdery solid is the superhydrophobic covalent organic framework material LNU-41. The synthetic route is as follows:
example 3 preparation of superhydrophobic covalent organic framework Material LNU-42
Synthesis of LNU-42
400mg of tris (4-boronic acid farnesyl ester phenyl) amine (0.6418 mmol) and 386.16mg of 3, 6-dibromo-9-phenylcarbazole (0.96274 mmol) were dissolved in 60mL of N, N' -dimethylformamide, placed in a 100mL round bottom flask, frozen with liquid nitrogen and pumped in vacuum with an oil pump and nitrogen gas was repeatedly three times, 80mg of tetrakis (triphenylphosphine) palladium and 5mL of potassium carbonate solution (2 moL/L) were rapidly added to the reaction system, and repeated cyclic deaeration was performed, and the reaction mixture was heated to 130℃and stirred under nitrogen protection for 48 hours under reflux.
Post-treatment of LNU-42
The reaction was suction filtered, leaving a solid insoluble, and washed multiple times with tetrahydrofuran, water and acetone solvents, respectively, for removal of unreacted monomer or catalyst residues that may remain. Further purifying the crude product by Soxhlet extraction with tetrahydrofuran, dichloromethane and chloroform. The crude product is dried in vacuum for 12 hours at 90 ℃, and the obtained powdery solid is the superhydrophobic covalent organic framework material LNU-42. The synthetic route is as follows:
example 4 detection
1. As shown in fig. 1-1 to 1-3, the superhydrophobic covalent organic framework materials LNU-40, LNU-41 and LNU-42 prepared in the embodiments 1-3 and corresponding monomers thereof are subjected to infrared spectrograms obtained by testing with a fourier infrared spectrometer, a curve a belongs to a tris (4-boric acid frequency-farnesyl-ester-phenyl) amine monomer, a curve b belongs to a dibromocarbazole monomer, and a curve c belongs to a polymer obtained by synthesis. 1399cm in tris (4-boronic acid farnesyl ester phenyl) amine -1 The stretching vibration at the position is attributed to the C-B bond, 1359cm -1 The part is B-O bond stretching vibration, and the dibromocarbazole monomer is positioned at 500cm -1 The characteristic peaks are basically disappeared in the covalent organic framework material, and the phenomena prove that the product is polymerized successfully according to the expected reaction route.
2. In order to study the surface morphology of the super-hydrophobic covalent organic framework material prepared in the embodiment 1-3, a scanning electron microscope is used for carrying out morphology characterization. As shown in fig. 2-1 to 2-3, all three polymers exhibited a morphology of small particle packing of the spheroid-like solid. FIGS. 3-1 through 3-3 are transmission electron microscopy images of LNU-40, LNU-41, and LNU-42, respectively, in which it can be observed that the pores of the three materials all exhibit disordered vermiform structures.
3. As shown in FIG. 4, the thermal gravimetric curves of the superhydrophobic covalent organic framework materials prepared in examples 1-3 of the invention are tested under the air condition. From the figure, we can see that the three polymers can keep stable structure under high temperature condition, and the polymer skeleton begins to collapse at about 250-300 ℃, which indicates that LNUs have very good thermal stability. In addition, the three materials are dispersed in common organic solvents (such as methanol, ethanol, tetrahydrofuran, acetone, methylene chloride, chloroform, tetrahydrofuran and the like) and cannot be dissolved or decomposed, so that LNUs have very good solvent stability.
4. FIGS. 5-1 to 5-3 are hydrophobic property tests of covalent organic framework materials prepared in examples 1-3 of the present invention. The data shows that the water contact angles of the covalent organic framework materials LNU-40, LNU-41 and LNU-42 are 152.4 DEG, 156.8 DEG and 151.8 DEG respectively, and the superhydrophobic effect is achieved. According to the property, the super-hydrophobic flexible fabric is further prepared and practically applied.
Example 5 hydrophobic oleophilic Material
1. Preparation method of hydrophobic and oleophilic material
Cutting the flexible fabric into 4cm multiplied by 4cm, placing the flexible fabric in a beaker, respectively soaking the flexible fabric in 40mL of water, ethanol and acetone for 30min in an ultrasonic manner, taking out the flexible fabric, and drying the flexible fabric at 60-70 ℃ for later use. 30mg of the LNUs prepared by the preparation method is dispersed in 40mL of chloroform, and the pretreated flexible fabric is placed in the dispersion liquid to be subjected to ultrasonic homogenization, standing and drying, so that the product super-hydrophobic flexible fabric is obtained.
2. Hydrophobic and oleophilic Material Properties
As shown in fig. 6, scanning electron microscopy images of the superhydrophobic flexible fabric after the original flexible fabric (a) and the loads LNU-40 (b), LNU-41 (c), and LNU-42 (d), respectively. It can be observed that the surface of the original flexible fabric (a) is flat and smooth, and the surfaces of the flexible fabrics (b), (c) and (d) after the LNUs are loaded are roughened and protruded, thus proving the successful loading of the super-hydrophobic covalent organic framework material LNUs on the flexible fabric.
According to fig. 7, it is shown that when water and chloroform droplets are respectively dropped on the original flexible fabric (a), neither can stay on the surface of the flexible fabric, but rapidly infiltrate the flexible fabric. When water and chloroform are dropped on the flexible fabric loaded with LNU-40 (b), LNU-41 (c) and LNU-42 (d), respectively, the chloroform still permeates the flexible fabric, and the water drops exhibit perfect spheres on the surface of the flexible fabric. This demonstrates that the flexible fabric after loading LNUs has hydrophobic and oleophilic properties.
Considering practical complex environmental factors, the stability of the superhydrophobic performance of the material is very critical. Thus, taking LNU-41 as an example, the corrosion resistance of the flexible fabric of load LNU-41 was tested experimentally. As shown in fig. 8, droplets (water, hydrochloric acid, sodium chloride and sodium hydroxide) with different acidity and alkalinity are respectively dripped on the surface of the same piece of super-hydrophobic flexible fabric, and several droplets are found to keep spherical shape on the surface for a long time, so that the corrosion resistance of the super-hydrophobic flexible fabric loaded with LNUs is proved to be very good.
Fig. 9 shows the relationship of the contact angle of the superhydrophobic flexible fabric loaded with LNU-41 as a function of different pH values. At ph=7, the contact angle of the flexible fabric loaded with LNU-41 can reach 156.1 °, the contact angle measured under strong acid and alkali conditions is slightly reduced, but can still be kept above 140 °, which indicates that the flexible fabric loaded with LNUs can still maintain stable hydrophobic performance under severe environmental conditions.
FIG. 10 is a graph showing the effect of temperature on the hydrophobic properties of superhydrophobic flexible fabrics loaded with LNU-41. The superhydrophobic flexible fabric was heated and maintained at 25 ℃, 45 ℃, 65 ℃, 85 ℃, 105 ℃, 125 ℃ and 145 ℃ for 4 hours, respectively, and then its water contact angle was measured. The results show that the contact angle is slightly different at different temperatures, but still varies over 150 degrees, indicating that the temperature has little effect on the hydrophobic properties of the flexible fabric after loading LNUs.
In order to evaluate the oil-water separation performance of the superhydrophobic flexible fabric, the separation efficiency of the flexible fabric loaded with LNUs on the water phase and the oil phase (organic phase) is experimentally studied. The separation efficiency is calculated as: separation efficiency=m 1 /m 0 X 100%, where m 0 For the initial organic solvent mass, m 1 For the purpose of collecting the mass of the organic solvent from the mixed liquor. FIGS. 11, 12 and 13 show the separation efficiency of the superhydrophobic flexible fabrics loaded with LNU-40, LNU-41 and LNU-42, respectively, for methylene chloride, chloroform, 1, 2-dibromoethane, bromobutane, chlorobenzene and carbon tetrachloride. It can be seen that the separation efficiency of the super-hydrophobic flexible fabric on several organic solvents is above 90%.
In the practical application of hydrophobic materials, recycling considerations are also important. In fig. 14, the superhydrophobic flexible fabric loaded with LNU-41 is taken as an example, and the cyclic stability of the product in an oil-water separation experiment is explored. After 10 times of recycling, the super-hydrophobic flexible fabric shows good recycling performance, and the separation efficiency can be kept at about 90%. The data prove that the product super-hydrophobic flexible fabric prepared by the invention has excellent oil-water separation stability and good recoverability, and has good application prospect in the field of oil-water separation treatment in the sewage of petrochemical industry, metallurgy, pharmaceutical industry and the like.
Claims (7)
1. The application of hydrophobic and oleophylic material in oil-water separation, absorption of leaked crude oil or absorption of organic solvent is characterized by that the superhydrophobic covalent organic framework material is dispersed in chloroform to obtain solution, the pretreated flexible fabric is placed in the above-mentioned solution, and uniformly ultrasonic-treated, soaked and dried so as to obtain the invented superhydrophobic flexible fabric, i.e. hydrophobic and oleophylic material,
the super-hydrophobic covalent organic framework material is a super-hydrophobic covalent organic framework material LNUs obtained by Suzuki coupling reaction of tri (4-boric acid frequency-farnesyl-alcohol-ester-phenyl) amine serving as a construction element and pi conjugated dibromocarbazole monomer,
wherein, according to the mole ratio, dibromocarbazole monomer: the tris (4-boronic acid farnesyl ester phenyl) amine was 3:2.
2. The use according to claim 1, wherein the superhydrophobic covalent organic framework materials LNUs have the following structural formula:
or->Or->。
3. The use according to claim 2, wherein the preparation method of the superhydrophobic covalent organic framework material comprises the following steps: adding tri (4-boric acid frequency farnesyl alcohol ester phenyl) amine and dibromocarbazole monomers into an organic solvent for dissolution, placing the organic solvent into a reaction container, freezing by utilizing liquid nitrogen, vacuumizing by using an oil pump, introducing nitrogen gas for three times repeatedly, rapidly adding a catalyst into a reaction system, repeatedly and circularly degassing, heating the reaction mixture, stirring and refluxing for 48 hours under the protection of nitrogen gas, cooling to room temperature, filtering, washing, purifying, and then vacuum-drying to obtain the powdery super-hydrophobic covalent organic framework material LNUs.
4. The use according to claim 3, wherein the dibromocarbazole monomer is one of 3, 6-dibromocarbazole, 2, 7-dibromocarbazole and 3, 6-dibromo-9-phenylcarbazole.
5. The process of claim 4, wherein the catalyst is tetrakis (triphenylphosphine) palladium or potassium carbonate.
6. The use according to claim 5, wherein the heating temperature is 130 ℃.
7. The use according to claim 6, wherein the vacuum drying temperature and time are 90 ℃ and 12 hours, respectively.
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